U.S. patent application number 16/438060 was filed with the patent office on 2020-05-07 for polycyclic aromatic compound.
This patent application is currently assigned to Kwansei Gakuin Educational Foundation. The applicant listed for this patent is Kwansei Gakuin Educational Foundation JNC Corporation. Invention is credited to Takuji HATAKEYAMA, Hiroki HIRAI, Toshiaki IKUTA, Takeshi MATSUSHITA, Kiichi NAKAJIMA, Soichiro NAKATSUKA, Jingping NI, Yohei ONO, Kazushi SHIREN.
Application Number | 20200144514 16/438060 |
Document ID | / |
Family ID | 53798894 |
Filed Date | 2020-05-07 |
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United States Patent
Application |
20200144514 |
Kind Code |
A1 |
HATAKEYAMA; Takuji ; et
al. |
May 7, 2020 |
POLYCYCLIC AROMATIC COMPOUND
Abstract
A novel polycyclic aromatic compound in which plural aromatic
rings are linked via boron atoms, oxygen atoms and the like is
provided, and therefore, the range of selection of the material for
organic electroluminescent elements can be widened. Also, an
excellent organic electroluminescent element is provided by using
the novel polycyclic aromatic compound as a material for an organic
electroluminescent element.
Inventors: |
HATAKEYAMA; Takuji; (Hyogo,
JP) ; NAKATSUKA; Soichiro; (Hyogo, JP) ;
NAKAJIMA; Kiichi; (Hyogo, JP) ; HIRAI; Hiroki;
(Hyogo, JP) ; ONO; Yohei; (Chiba, JP) ;
SHIREN; Kazushi; (Chiba, JP) ; NI; Jingping;
(Chiba, JP) ; MATSUSHITA; Takeshi; (Chiba, JP)
; IKUTA; Toshiaki; (Chiba, JP) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
Kwansei Gakuin Educational Foundation
JNC Corporation |
Nishinomiya
Tokyo |
|
JP
JP |
|
|
Assignee: |
Kwansei Gakuin Educational
Foundation
Nishinomiya
JP
JNC Corporation
Tokyo
JP
|
Family ID: |
53798894 |
Appl. No.: |
16/438060 |
Filed: |
June 11, 2019 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
|
|
14508554 |
Oct 7, 2014 |
10374166 |
|
|
16438060 |
|
|
|
|
Current U.S.
Class: |
1/1 |
Current CPC
Class: |
C07F 5/02 20130101; H01L
51/0054 20130101; H01L 51/0059 20130101; H01L 51/5056 20130101;
H01L 51/5088 20130101; Y02E 10/549 20130101; H01L 51/008 20130101;
H01L 51/0072 20130101; C07F 9/65685 20130101; H01L 51/0071
20130101; H01L 51/5016 20130101; H01L 51/5072 20130101; H01L
51/0052 20130101; H01L 51/5012 20130101 |
International
Class: |
H01L 51/00 20060101
H01L051/00; C07F 9/6568 20060101 C07F009/6568; C07F 5/02 20060101
C07F005/02 |
Foreign Application Data
Date |
Code |
Application Number |
Feb 18, 2014 |
JP |
2014-028750 |
Claims
1.-17. (canceled)
18. An organic device comprising a polycyclic aromatic compound
represented by the following general formula (1), or an oligomer of
a polycyclic aromatic compound having plural structures each
represented by the following general formula (1): ##STR00395##
wherein in formula (1), each of ring A, ring B and ring C
independently represents an aryl ring or a heteroaryl ring, while
at least one hydrogen atom in these rings may be substituted;
Y.sup.1 represents B, P.dbd.O, or P.dbd.S; when Y.sup.1 represents
B, each of X.sup.1 and X.sup.2 independently represents O, N--R, S
or Se, wherein R of the moiety N--R represents an aryl which may be
substituted, a heteroaryl which may be substituted, or an alkyl
which may be substituted, and R of the moiety N--R may be bonded to
a carbon atom adjacent to the position (atom) of bonding to X.sup.1
or X.sup.2 in the ring A, ring B and/or ring C via --O--, --S--,
--C(--R.sup.a).sub.2--, or a single bond, wherein R.sup.a
represents a hydrogen atom or an alkyl, while the adjacent carbon
atom is not a carbon atom that constitutes the central fused
bicyclic structure of the said formula (1) composed of Y.sup.1,
X.sup.1 and X.sup.2; when Y.sup.1 represents P.dbd.O or P.dbd.S,
each of X.sup.1 and X.sup.2 independently represents O, S or Se,
one of X.sup.1 and X.sup.2 represents O while the other represents
S or Se, one of X.sup.1 and X.sup.2 represents N--R while the other
represents Se, or one of X.sup.1 and X.sup.2 represents S while the
other represents Se, wherein R of the moiety N--R represents an
aryl which may be substituted, a heteroaryl which may be
substituted, or an alkyl which may be substituted, and R of the
moiety N--R may be bonded to a carbon atom adjacent to the position
(atom) of bonding to X.sup.1 or X.sup.2 in the ring A, ring B
and/or ring C via --O--, --S--, --C(--R.sup.a).sub.2--, or a single
bond, wherein R.sup.a represents a hydrogen atom or an alkyl, while
the adjacent carbon atom is not a carbon atom that constitutes the
central fused bicyclic structure of the said formula (1) composed
of Y.sup.1, X.sup.1 and X.sup.2; and at least one hydrogen atom in
the compound or structure represented by formula (1) may be
substituted by a halogen atom or a deuterium atom.
19. The organic device described in claim 18, wherein in formula
(1), each of ring A, ring B and ring C each independently
represents an aryl ring or a heteroaryl ring, while at least one
hydrogen atom in these rings may be substituted by a substituted or
unsubstituted aryl, a substituted or unsubstituted heteroaryl, a
substituted or unsubstituted diarylamino, a substituted or
unsubstituted diheteroarylamino, a substituted or unsubstituted
arylheteroarylamino, a substituted or unsubstituted alkyl, a
substituted or unsubstituted alkoxy, or a substituted or
unsubstituted aryloxy, and these rings have a 5-membered or
6-membered ring that shares a bond(s) with the fused bicyclic
structure at the center of the above formula constructed by
Y.sup.1, X.sup.1 and X.sup.2; Y.sup.1 represents B, P.dbd.O, or
P.dbd.S; when Y.sup.1 represents B, each of X.sup.1 and X.sup.2
independently represents O, N--R, S or Se, wherein R of the moiety
N--R represents an aryl which may be substituted by an alkyl, a
heteroaryl which may be substituted by an alkyl, or an alkyl which
may be substituted by an alkyl, R of the moiety N--R may be bonded
to a carbon atom adjacent to the position (atom) of bonding to
X.sup.1 or X.sup.2 in the ring A, ring B and/or ring C via --O--,
--S--, --C(--R.sup.a).sub.2-- or a single bond, wherein R.sup.a
represents a hydrogen atom or an alkyl, while the adjacent carbon
atom is not a carbon atom that constitutes the central fused
bicyclic structure of the said formula (1) composed of Y.sup.1,
X.sup.1 and X.sup.2; when Y.sup.1 represents P.dbd.O or P.dbd.S,
each of X.sup.1 and X.sup.2 independently represents O, S or Se,
one of X.sup.1 and X.sup.2 represents O while the other represents
S or Se, one of X.sup.1 and X.sup.2 represents N--R while the other
represents Se, or one of X.sup.1 and X.sup.2 represents S while the
other represents Se, wherein R of the moiety N--R represents an
aryl which may be substituted by an alkyl, a heteroaryl which may
be substituted by an alkyl, or an alkyl which may be substituted by
an alkyl, R of the moiety N--R may be bonded to a carbon atom
adjacent to the position (atom) of bonding to X.sup.1 or X.sup.2 in
the ring A, ring B and/or ring C via --O--, --S--,
--C(--R.sup.a).sub.2-- or a single bond, wherein R.sup.a represents
a hydrogen atom or an alkyl, while the adjacent carbon atom is not
a carbon atom that constitutes the central fused bicyclic structure
of the said formula (1) composed of Y.sup.1, X.sup.1 and X.sup.2;
at least one hydrogen atom in the compound or structure represented
by formula (1) may be substituted by a halogen atom or a deuterium
atom; and the oligomer is a dimer or a trimer, which has two or
three of the structure represented by general formula (1).
20. The organic device described in claim 18, wherein the above
general formula (1) is represented by the following general formula
(2): ##STR00396## wherein in formula (2), each of R.sup.1, R.sup.2,
R.sup.3, R.sup.4, R.sup.5, R.sup.6, R.sup.7, R.sup.8, R.sup.9,
R.sup.10 and R.sup.11 independently represents a hydrogen atom, an
aryl, a heteroaryl, a diarylamino, a diheteroarylamino, an
arylheteroarylamino, an alkyl, an alkoxy or an aryloxy, while at
least one hydrogen atom in these may be substituted by an aryl, a
heteroaryl or an alkyl, adjacent groups among R.sup.1 to R.sup.11
may be bonded to each other and form an aryl ring or a heteroaryl
ring together with the ring a, ring b or ring c, at least one
hydrogen atom in the ring thus formed may be substituted by an
aryl, a heteroaryl, a diarylamino, a diheteroarylamino, an
arylheteroarylamino, an alkyl, an alkoxy or an aryloxy, and at
least one hydrogen atom in these substituents may be substituted by
an aryl, a heteroaryl or an alkyl; Y.sup.1 represents B, P.dbd.O,
or P.dbd.S; when Y.sup.1 represents B, each of X and X.sup.2
independently represents O, N--R, S or Se, wherein R of the moiety
N--R represents an aryl having 6 to 12 carbon atoms, a heteroaryl
having 2 to 15 carbon atoms, or an alkyl having 1 to 6 carbon
atoms, R of the moiety N--R may be bonded to a carbon atom adjacent
to the position (atom) of bonding to X.sup.1 or X.sup.2 in the ring
a, ring b and/or ring c via --O--, --S--, --C(--R.sup.a).sub.2-- or
a single bond, wherein R.sup.a represents an alkyl having 1 to 6
carbon atoms, while the adjacent carbon atom is not a carbon atom
that constitutes the central fused bicyclic structure of the said
formula (1) composed of Y.sup.1, X.sup.1 and X.sup.2; when Y.sup.1
represents P.dbd.O or P.dbd.S, each of X.sup.1 and X.sup.2
independently represents O, S or Se, one of X.sup.1 and X.sup.2
represents O while the other represents S or Se, one of X.sup.1 and
X.sup.2 represents N--R while the other represents Se, or one of
X.sup.1 and X.sup.2 represents S while the other represents Se,
wherein R of the moiety N--R represents an aryl having 6 to 12
carbon atoms, a heteroaryl having 2 to 15 carbon atoms, or an alkyl
having 1 to 6 carbon atoms, R of the moiety N--R may be bonded to a
carbon atom adjacent to the position (atom) of bonding to X.sup.1
or X.sup.2 in the ring a, ring b and/or ring c via --O--, --S--,
--C(--R.sup.a).sub.2-- or a single bond, wherein R.sup.a represents
an alkyl having 1 to 6 carbon atoms, while the adjacent carbon atom
is not a carbon atom that constitutes the central fused bicyclic
structure of the said formula (1) composed of Y.sup.1, X.sup.1 and
X.sup.2; and at least one hydrogen atom in the compound represented
by formula (2) may be substituted by a halogen atom or a deuterium
atom.
21. The organic device described in claim 20, wherein in formula
(2), each of R.sup.1, R.sup.2, R.sup.3, R.sup.4, R.sup.5, R.sup.6,
R.sup.7, R.sup.8, R.sup.9, R.sup.10 and R.sup.11 independently
represents a hydrogen atom, an aryl having 6 to 30 carbon atoms, a
heteroaryl having 2 to 30 carbon atoms, or a diarylamino (provided
that the aryl is an aryl having 6 to 12 carbon atoms), while
adjacent groups among R.sup.1 to R.sup.11 are bonded to each other
and form an aryl ring having 9 to 16 carbon atoms or a heteroaryl
ring having 6 to 15 carbon atoms together with the ring a, ring b
or ring c, and at least one hydrogen atom in the ring thus formed
may be substituted by an aryl having 6 to 10 carbon atoms; Y.sup.1
represents B, P.dbd.O, or P.dbd.S; when Y.sup.1 represents B, each
of X.sup.1 and X.sup.2 independently represents O, N--R or S,
wherein R in the moiety N--R represents an aryl having 6 to 10
carbon atoms or an alkyl having 1 to 4 carbon atoms; when Y.sup.1
represents P.dbd.O or P.dbd.S, each of X.sup.1 and X.sup.2
independently represents O or S, one of X.sup.1 and X.sup.2
represents O while the other represents S, wherein R in the moiety
N--R represents an aryl having 6 to 10 carbon atoms or an alkyl
having 1 to 4 carbon atoms; and at least one hydrogen atom in the
compound represented by formula (2) may be substituted by a halogen
atom or a deuterium atom.
22. The organic device described in claim 18, wherein the halogen
atom is a fluorine atom.
23. The organic device described in claim 18, wherein the above
formula (1) is represented by the following formula (1-1), the
following formula (1-2), the following formula (1-4), the following
formula (1-10), the following formula (1-49), the following formula
(1-81), the following formula (1-91), the following formula
(1-100), the following formula (1-141), the following formula
(1-151), the following formula (1-176), the following formula
(1-411), the following formula (1-447), the following formula
(1-601), or the following formula (1-701): ##STR00397##
##STR00398## ##STR00399## ##STR00400##
24. The organic device described in claim 18, wherein the above
formula (1) is represented by the following formula (1-21), the
following formula (1-23), the following formula (1-24), the
following formula (1-50), the following formula (1-152), the
following formula (1-201), the following formula (1-401), the
following formula (1-422), the following formula (1-1048), the
following formula (1-1049), the following formula (1-1050), the
following formula (1-1069), the following formula (1-1084), the
following formula (1-1090), the following formula (1-1092), the
following formula (1-1101), the following formula (1-1102), the
following formula (1-1103), the following formula (1-1145), the
following formula (1-1152), the following formula (1-1159), the
following formula (1-1187), the following formula (1-1190), the
following formula (1-1191), the following formula (1-1192), the
following formula (1-1201), the following formula (1-1210), the
following formula (1-1247), the following formula (1-1250), the
following formula (1-1251), the following formula (1-1252), or the
following formula (1-1271): ##STR00401## ##STR00402## ##STR00403##
##STR00404## ##STR00405## ##STR00406## ##STR00407##
##STR00408##
25. The organic device described in claim 18, wherein the above
formula (1) is represented by the following formula (1-1-1), the
following formula (1-79), the following formula (1-142), the
following formula (1-152-2), the following formula (1-158), the
following formula (1-159), the following formula (1-721), the
following formula (1-1006), the following formula (1-1104), the
following formula (1-1149), the following formula (1-1150), the
following formula (1-1301), the following formula (1-1351), the
following formula (1-2305), the following formula (1-2626), the
following formula (1-2657), the following formula (1-2662), the
following formula (1-2665), the following formula (1-2676), the
following formula (1-2678), the following formula (1-2679), the
following formula (1-2680), the following formula (1-2681), the
following formula (1-2682), the following formula (1-2683), the
following formula (1-2691), the following formula (1-2699), the
following formula (1-3588), the following formula (1-3654), the
following formula (1-3690), the following formula (1-3806), the
following formula (1-3824), the following formula (1-4114), the
following formula (1-4150), the following formula (1-4341), the
following formula (1-4346), the following formula (1-4401), or the
following formula (1-4421-1): ##STR00409## ##STR00410##
##STR00411## ##STR00412## ##STR00413## ##STR00414## ##STR00415##
##STR00416## ##STR00417## ##STR00418##
26. The organic device described in claim 18, which is an organic
electroluminescent element, an organic field effect transistor, or
an organic thin film solar cell.
27. An organic electroluminescent element described in claim 26,
comprising a pair of electrodes composed of a positive electrode
and a negative electrode; and a light emitting layer that is
disposed between the pair of electrodes and contains the polycyclic
aromatic compound represented by the following general formula (1)
or the oligomer thereof described in claim 1 as a material for the
light emitting layer.
28. An organic electroluminescent element described in claim 26,
comprising a pair of electrodes composed of a positive electrode
and a negative electrode; a light emitting layer that is disposed
between the pair of electrodes; and an electron injection layer
and/or an electron transport layer that is disposed between the
negative electrode and the light emitting layer and contains the
polycyclic aromatic compound represented by the following general
formula (1) or the oligomer thereof described in claim 1 as a
material for the electron injection layer or electron transport
layer.
29. An organic electroluminescent element described in claim 26,
comprising a pair of electrodes composed of a positive electrode
and a negative electrode; a light emitting layer that is disposed
between the pair of electrodes; and a hole injection layer and/or a
hole transport layer that is disposed between the positive
electrode and the light emitting layer and contains the polycyclic
aromatic compound represented by the following general formula (1)
or the oligomer thereof described in claim 1 as a material for the
hole injection layer or hole transport layer.
30. The organic electroluminescent element described in claim 27,
further comprising an electron transport layer and/or an electron
injection layer that is disposed between the negative electrode and
the light emitting layer, wherein at least one of the electron
transport layer and the electron injection layer contains at least
one selected from the group consisting of a quinolinol-based metal
complex, a pyridine derivative, a phenanthroline derivative, a
borane derivative, and a benzimidazole derivative.
31. The organic electroluminescent element described in claim 30,
wherein the electron transport layer and/or electron injection
layer further contains at least one selected from the group
consisting of an alkali metal, an alkaline earth metal, a rare
earth metal, an oxide of an alkali metal, a halide of an alkali
metal, an oxide of an alkaline earth metal, a halide of an alkaline
earth metal, an oxide of a rare earth metal, a halide of a rare
earth metal, an organic complex of an alkali metal, an organic
complex of an alkaline earth metal, and an organic complex of a
rare earth metal.
32. A display apparatus comprising the organic electroluminescent
element described in claim 27.
33. A lighting apparatus comprising the organic electroluminescent
element described in claim 27.
Description
TECHNICAL FIELD
[0001] The present invention relates to a polycyclic aromatic
compound, and an organic electroluminescent (EL) element, an
organic field effect transistor and an organic thin film solar cell
using the polycyclic aromatic compound, as well as a display
apparatus and a lighting apparatus.
RELATED ART
[0002] Conventionally, since display apparatuses employing light
emitting elements that are electroluminescent can be subjected to
reduction of power consumption and thickness reduction, various
studies have been conducted thereon. Furthermore, organic
electroluminescent elements formed from organic materials have been
a subject of active investigation, from the viewpoint that weight
reduction or size expansion can be easily achieved. Particularly,
active research has been hitherto conducted on the development of
organic materials having luminescence characteristics for blue
light, which is one of the primary colors of light, and the
development of organic materials having charge transport capability
for holes, electrons and the like (having a potential for serving
as a semiconductor or a superconductor), irrespective of whether
the organic materials are high molecular weight compounds or low
molecular weight compounds.
[0003] An organic EL element has a structure having a pair of
electrodes composed of a positive electrode and a negative
electrode, and a single layer or plural layers that are disposed
between the pair of electrodes and contain organic compounds. Those
layers include a layer containing an organic compound, a light
emitting layer, a charge transport/injection layer for transporting
or injecting charges such as holes or electrons, and the like, and
various organic materials suitable for these layers have been
developed.
[0004] Regarding the materials for light emitting layers, for
example, benzofluorene-based compounds and the like have been
developed (WO 2004/061047). Furthermore, regarding hole
transporting materials, for example, triphenylamine-based compounds
and the like have been developed (JP 2001-172232 A). Also,
regarding electron transporting materials, for example,
anthracene-based compounds and the like have been developed (JP
2005-170911 A).
[0005] Furthermore, in recent years, materials obtained by
improving triphenylamine derivatives have also been reported as
materials that are used in organic EL elements and organic thin
film solar cells (WO 2012/118164). These materials are materials
characterized in that
N,N'-diphenyl-N,N'-bis(3-methylphenyl)-1,1'-biphenyl-4,4'-d iamine
(TPD), which has been already put to practical use, is used as a
base material, and flatness thereof is increased by connecting the
aromatic rings that constitute triphenylamine. In this document,
for example, evaluation of the charge transporting characteristics
of a NO-linked system compound (compound 1 of page 63) has been
made; however, there is no description on the method for producing
materials other than the NO-linked system compound. Also, when the
element that connects is different, the overall electron state of
the compound is different; however, in this regard, the
characteristics obtainable from materials other than the NO-linked
system compound are still not known. For example, since a compound
having a conjugated structure involving high energy of triplet
exciton (T1) can emit phosphorescent light having a shorter
wavelength, the compound is useful as a material for blue light
emitting layer. There is also a demand for a novel compound having
a conjugated structure with high T1 as an electron transporting
material or a hole transporting material that interposes a light
emitting layer.
[0006] A host material for organic EL elements is generally a
molecule in which plural existing aromatic rings of benzene,
carbazole or the like are linked via single bonds, phosphorus atoms
or silicon atoms. This is because when a number of aromatic rings
having a relatively small conjugated system are connected, the
large HOMO-LUMO gap required from a host material (band gap Eg in a
thin film) is secured. Furthermore, in a host material for organic
EL elements that use phosphorescent materials or thermally
activated delayed fluorescence materials, high triplet excitation
energy (E.sub.T) is needed; however, the triplet excitation energy
(E.sub.T) can be increased by localizing SOMO1 and SOMO2 in the
triplet excitation state (T1) by connecting a donor-like or
acceptor-like aromatic ring or substituent to the molecule, and
thereby reducing the exchange interaction between the two orbitals.
However, aromatic rings having small conjugated systems do not have
sufficient redox stability, and an element which uses a molecule
obtained by connecting existing aromatic rings as the host
material, does not have a sufficient service life. On the other
hand, polycyclic aromatic compounds having extended 7t-conjugated
systems generally have excellent redox stability; however, since
the HOMO-LUMO gap (band gap Eg in a thin film) or the triplet
excitation energy (E.sub.T) is low, polycyclic aromatic compounds
have been considered to be unsuitable as host materials.
CITATION LIST
Patent Literatures
[0007] Patent Document 1: WO 2004/061047 [0008] Patent Document 2:
JP 2001-172232 A [0009] Patent Document 3: JP 2005-170911 A [0010]
Patent Document 4: WO 2012/118164
SUMMARY
Problems to be Resolved by the Invention
[0011] As described above, various materials that are used in
organic EL elements have been developed; however, in order to
increase the selection range of the material for organic EL
elements, it is desired to develop materials formed from compounds
different from the conventional compounds. Particularly, the
organic EL characteristics obtainable from materials other than the
NO-linked system compounds reported in Patent Documents 1-4, and
the methods for producing such materials are not yet known.
Means of Solving the Problems
[0012] The inventors of the present invention conducted a thorough
investigation in order to solve the problems described above, and
as a result, the inventors found a novel polycyclic aromatic
compound in which plural aromatic rings are linked via boron atoms,
oxygen atoms and the like, and succeeded in production thereof.
Also, the inventors found that when an organic EL element was
configured by disposing a layer containing this polycyclic aromatic
compound between a pair of electrodes, an excellent organic EL
element was obtained, thus completing the present invention. That
is, the present invention provides a polycyclic aromatic compound
such as follows or an oligomer thereof, and a material for organic
EL element containing a polycyclic aromatic compound such as
follows or an oligomer thereof.
[0013] [1] A polycyclic aromatic compound represented by the
following general formula (1), or an oligomer of a polycyclic
aromatic compound having plural structures that are each
represented by the following general formula (1):
##STR00001##
wherein in formula (1),
[0014] ring A, ring B and ring C each independently represent an
aryl ring or a heteroaryl ring, while at least one hydrogen atom in
these rings may be substituted;
[0015] Y.sup.1 represents B, P, P.dbd.O, P.dbd.S, Al, Ga, As, Si--R
or Ge--R, wherein R of the moieties Si--R and Ge--R represents an
aryl or an alkyl;
[0016] X.sup.1 and X.sup.2 each independently represent O, N--R, S
or Se, wherein R of the moiety N--R represents an aryl or alkyl
which may be substituted, and R of the moiety N--R may be bonded to
the ring B and/or ring C by a linking group or a single bond;
and
[0017] at least one hydrogen atom in the compound or structure
represented by formula (1) may be substituted by a deuterium
atom.
[0018] [2] The polycyclic aromatic compound or the oligomer thereof
described in the above item [1], wherein
[0019] ring A, ring B and ring C each independently represent an
aryl ring or a heteroaryl ring, while at least one hydrogen atom in
these rings may be substituted by a substituted or unsubstituted
aryl, a substituted or unsubstituted heteroaryl, a substituted or
unsubstituted diarylamino, a substituted or unsubstituted alkyl, a
substituted or unsubstituted alkoxy, or a substituted or
unsubstituted aryloxy, and these rings have a 5-membered or
6-membered ring that shares a bond(s) with the fused bicyclic
structure at the center of the above formula constructed by
Y.sup.1, X.sup.1 and X.sup.2;
[0020] Y.sup.1 represents B, P, P.dbd.O, P.dbd.S, Al, Ga, As, Si--R
or Ge--R, wherein R of the moieties Si--R and Ge--R represents an
aryl or an alkyl;
[0021] X.sup.1 and X.sup.2 each independently represent O, N--R, S
or Se, wherein R of the moiety N--R represents an aryl or alkyl
which may be substituted by an alkyl, R of the moiety N--R may be
bonded to the ring B and/or ring C by --O--, --S--,
--C(--R).sub.2-- or a single bond, and R of the moiety
--C(--R).sub.2-- represents a hydrogen atom or an alkyl;
[0022] at least one hydrogen atom in the compound or structure
represented by formula (1) may be substituted by a deuterium atom;
and
[0023] the oligomer is a dimer or a trimer, which has two or three
of the structure represented by general formula (1).
[0024] [3] The polycyclic aromatic compound described in the above
item [1], which is represented by the following general formula
(2):
##STR00002##
wherein in formula (2),
[0025] R.sup.1, R.sup.2, R.sup.3, R.sup.4, R.sup.5, R.sup.6,
R.sup.7, R.sup.8, R.sup.9, R.sup.10 and R.sup.11 each independently
represent a hydrogen atom, an aryl, a heteroaryl, a diarylamino, an
alkyl, an alkoxy or an aryloxy, while at least one hydrogen atom in
these may be substituted by an aryl, a heteroaryl or an alkyl,
adjacent groups among R.sup.1 to R.sup.11 may be bonded to each
other and form an aryl ring or a heteroaryl ring together with the
ring a, ring b or ring c, at least one hydrogen atom in the ring
thus formed may be substituted by an aryl, a heteroaryl, a
diarylamino, an alkyl, an alkoxy or an aryloxy, and at least one
hydrogen atom in these substituents may be substituted by an aryl,
a heteroaryl or an alkyl;
[0026] Y.sup.1 represents B, P, P.dbd.O, P.dbd.S, Al, Ga, As, Si--R
or Ge--R, wherein R of the moieties Si--R and Ge--R represents an
aryl having 6 to 12 carbon atoms or an alkyl having 1 to 6 carbon
atoms; and
[0027] X.sup.1 and X.sup.2 each independently represent O, N--R, S
or Se, wherein R of the moiety N--R represents an aryl having 6 to
12 carbon atoms or an alkyl having 1 to 6 carbon atoms, R of the
moiety N--R may be bonded to the ring b and/or ring c by --O--,
--S--, --C(--R).sub.2-- or a single bond, and R of the moiety
--C(--R).sub.2-represents an alkyl having 1 to 6 carbon atoms.
[0028] [4] The polycyclic aromatic compound described in the above
item [3], wherein
[0029] R.sup.1, R.sup.2, R.sup.3, R.sup.4, R.sup.5, R.sup.6,
R.sup.7, R.sup.8, R.sup.9, R.sup.10 and R.sup.11 each independently
represent a hydrogen atom, an aryl having 6 to 30 carbon atoms, a
heteroaryl having 2 to 30 carbon atoms, or a diarylamino (provided
that the aryl is an aryl having 6 to 12 carbon atoms), while
adjacent groups among R.sup.1 to R.sup.11 are bonded to each other
and form an aryl ring having 9 to 16 carbon atoms or a heteroaryl
ring having 6 to 15 carbon atoms together with the ring a, ring b
or ring c, and at least one hydrogen atom in the ring thus formed
may be substituted by an aryl having 6 to 10 carbon atoms;
[0030] Y.sup.1 represents B, P, P.dbd.O, P.dbd.S or Si--R, wherein
R in the moiety Si--R represents an aryl having 6 to 10 carbon
atoms or an alkyl having 1 to 4 carbon atoms; and
[0031] X.sup.1 and X.sup.2 each independently represent O, N--R or
S, wherein R in the moiety N--R represents an aryl having 6 to 10
carbon atoms or an alkyl having 1 to 4 carbon atoms.
[0032] [5] The polycyclic aromatic compound or the oligomer thereof
described in the above item [1], wherein at least one hydrogen atom
in the compound or structure represented by the formula (1) may be
substituted by fluorine atoms.
[0033] [6] The polycyclic aromatic compound described in the above
item [1], which is represented by the following formula (1-1), the
following formula (1-2), the following formula (1-4) the following
formula (1-10), the following formula (1-49), the following formula
(1-81), the following formula (1-91), the following formula
(1-100), the following formula (1-141), the following formula
(1-151), the following formula (1-176), the following formula
(1-411), the following formula (1-447), the following formula
(1-501), the following formula (1-601), or the following formula
(1-701):
##STR00003## ##STR00004## ##STR00005## ##STR00006##
[0034] [7] The polycyclic aromatic compound described in the above
item [1], which is represented by the following formula (1-21), the
following formula (1-23), the following formula (1-24), the
following formula (1-50), the following formula (1-152), the
following formula (1-201), the following formula (1-401), the
following formula (1-422), the following formula (1-1048), the
following formula (1-1049), the following formula (1-1050), the
following formula (1-1069), the following formula (1-1084), the
following formula (1-1090), the following formula (1-1092), the
following formula (1-1101), the following formula (1-1102), the
following formula (1-1103), the following formula (1-1145), the
following formula (1-1152), the following formula (1-1159), the
following formula (1-1187), the following formula (1-1190), the
following formula (1-1191), the following formula (1-1192), the
following formula (1-1201), the following formula (1-1210), the
following formula (1-1247), the following formula (1-1250), the
following formula (1-1251), the following formula (1-1252), or the
following formula (1-1271):
##STR00007## ##STR00008## ##STR00009## ##STR00010## ##STR00011##
##STR00012## ##STR00013## ##STR00014##
[0035] [8] A material for an organic device, containing the
polycyclic aromatic compound or the oligomer thereof described in
any one of the above items [1] to [7].
[0036] [9] The material for an organic device described in the
above item [8], wherein the material for an organic device is a
material for an organic electroluminescent element, a material for
an organic field effect transistor, or a material for an organic
thin film solar cell.
[0037] [10] The material for an organic electroluminescent element
described in the above item [9], which is a material for a light
emitting layer.
[0038] [11] The material for an organic electroluminescent element
described in the above item [9], which is a material for a hole
injection layer or a material for a hole transport layer.
[0039] [12] An organic electroluminescent element, including a pair
of electrodes composed of a positive electrode and a negative
electrode; and a light emitting layer that is disposed between the
pair of electrodes and contains the material for a light emitting
layer described in the above item [10].
[0040] [13] An organic electroluminescent element, including a pair
of electrodes composed of a positive electrode and a negative
electrode; a light emitting layer that is disposed between the pair
of electrodes; and a hole injection layer and/or a hole transport
layer that is disposed between the positive electrode and the light
emitting layer and contains the material for a hole layer described
in the above item [11].
[0041] [14] The organic electroluminescent element described in the
above item [12] or [13], further including an electron transport
layer and/or an electron injection layer that is disposed between
the negative electrode and the light emitting layer, wherein at
least one of the electron transport layer and the electron
injection layer contains at least one selected from the group
consisting of a quinolinol-based metal complex, a pyridine
derivative, a phenanthroline derivative, a borane derivative, and a
benzimidazole derivative.
[0042] [15] The organic electroluminescent element described in the
above [14], wherein the electron transport layer and/or electron
injection layer further contains at least one selected from the
group consisting of an alkali metal, an alkaline earth metal, a
rare earth metal, an oxide of an alkali metal, a halide of an
alkali metal, an oxide of an alkaline earth metal, a halide of an
alkaline earth metal, an oxide of a rare earth metal, a halide of a
rare earth metal, an organic complex of an alkali metal, an organic
complex of an alkaline earth metal, and an organic complex of a
rare earth metal.
[0043] [16] A display apparatus including the organic
electroluminescent element described in any one of the above items
[12] to [15].
[0044] [17] A lighting apparatus including the organic
electroluminescent element described in any one of the above items
[12] to [15].
Advantageous Effect of the Invention
[0045] According to preferred embodiments of the present invention,
a novel polycyclic aromatic compound that can be used as, for
example, a material for an organic EL element can be provided, and
an excellent organic EL element can be provided by using this
polycyclic aromatic compound.
[0046] Specifically, the inventors of the present invention found
that a polycyclic aromatic compound in which aromatic rings are
linked via a heteroelement such as boron, phosphorus, oxygen,
nitrogen or sulfur, has a large HOMO-LUMO gap (band gap Eg in a
thin film) and high triplet excitation energy (E.sub.T). This is
speculated to be because, since a 6-membered ring containing a
heteroelement has low aromaticity, a decrease in the HOMO-LUMO gap
that comes along with extension of the conjugated system is
suppressed, and SOMO1 and SOMO2 of the triplet excitation state
(T1) are localized by electronic perturbation of the heteroelement.
Furthermore, the polycyclic aromatic compound containing a
heteroelement related to the present invention is such that due to
the localization of SOMO1 and SOMO2 in the triplet excitation state
(T1), the exchange interaction between the two orbitals is reduced,
and therefore, the energy difference between the triplet excitation
state (T1) and the single excitation state (Si) is small. Also,
since the polycyclic aromatic compound exhibits thermally activated
delayed fluorescence, the compound is also useful as a fluorescent
material for an organic EL element. Furthermore, a material having
high triplet excitation energy (E.sub.T) is also useful as an
electron transport layer or a hole transport layer of a
phosphorescence organic EL element or an organic EL element using a
thermally activated delayed fluorescence. Also, since these
polycyclic aromatic compounds can have the energy of HOMO and LUMO
arbitrarily shifted by introducing a substituent, the ionization
potential or the electron affinity can be optimized in accordance
with the peripheral materials.
BRIEF DESCRIPTION OF DRAWINGS
[0047] FIG. 1 is a schematic cross-sectional diagram illustrating
an organic EL element related to the present exemplary
embodiment.
DETAILED DESCRIPTION
1. Polycyclic Aromatic Compound and Oligomer Thereof
[0048] The invention of the present application relates to a
polycyclic aromatic compound represented by the following general
formula (1), or an oligomer of a polycyclic aromatic compound
having plural structures each represented by the following general
formula (1). The invention of the present application preferably
relates to a polycyclic aromatic compound represented by the
following general formula (2), or an oligomer of a polycyclic
aromatic compound having plural structures each represented by the
following general formula (2).
##STR00015##
[0049] Ring A, ring B and ring C in the general formula (1) each
independently represent an aryl ring or a heteroaryl ring, and at
least one hydrogen atom in these rings may be substituted by a
substituent. This substituent is preferably a substituted or
unsubstituted aryl, a substituted or unsubstituted heteroaryl, a
substituted or unsubstituted diarylamino, a substituted or
unsubstituted alkyl, a substituted or unsubstituted alkoxy, or a
substituted or unsubstituted aryloxy. Examples of the substituent
in the case in which these groups have a substituent, include an
aryl, a heteroaryl, and an alkyl. Furthermore, the aryl ring or
heteroaryl ring preferably has a 5-membered ring or 6-membered ring
that shares a bond with the fused bicyclic structure at the center
of the general formula (1) constructed by Y.sup.1, X.sup.1 and
X.sup.2 (hereinafter, this structure is also referred to as
"structure D").
[0050] Here, the "fused bicyclic structure (structure D)" means a
structure in which two saturated hydrocarbon rings that are
configured to include Y.sup.1, X.sup.1 and X.sup.2 and indicated at
the center of the general formula (1), are fused. Furthermore, a
"6-membered ring sharing a bond with the fused bicyclic structure"
means, for example, ring a (benzene ring (6-membered ring)) fused
to the structure D as represented by the above general formula (2).
Furthermore, the phrase "aryl ring or heteroaryl ring (which is
ring A) has this 6-membered ring" means that the ring A is formed
from this 6-membered ring only, or the ring A is formed such that
other rings are further fused to this 6-membered ring so as to
include this 6-membered ring. In other words, the "aryl ring or
heteroaryl ring (which is ring A) having a 6-membered ring" as used
herein means that the 6-membered ring that constitutes the entirety
or a portion of the ring A is fused to the structure D. The same
explanation applies to the "ring B (ring b)", "ring C (ring c)",
and the "5-membered ring".
[0051] The ring A (or ring B or ring C) in the general formula (1)
corresponds to the ring a and its substituents R.sup.1 to R.sup.3
in the general formula (2) (or ring b and its substituents R.sup.4
to R.sup.7, or ring c and its substituents R.sup.8 to R.sup.11).
That is, general formula (2) corresponds to a structure in which
"rings A to C having 6-membered rings" have been selected as the
rings A to C of the general formula (1). For this meaning, the
respective rings of general formula (2) are represented by small
letters a to c.
[0052] In general formula (2), adjacent groups among the
substituents R.sup.1 to R.sup.11 of the ring a, ring b and ring c
may be bonded to each other and form an aryl ring or a heteroaryl
ring together with the ring a, ring b or ring c, and at least one
hydrogen atom in the ring thus formed may be substituted by an
aryl, a heteroaryl, a diarylamino, an alkyl, an alkoxy or an
aryloxy, while at least one hydrogen atom in these substituents may
be substituted by an aryl, a heteroaryl or an alkyl. Therefore, the
polycyclic aromatic compound represented by general formula (2) is
such that the ring structure that constitutes the compound changes
as indicated by the following formula (2-1) and formula (2-2), as a
result of the mutual bonding form of the substituents in the ring
a, ring b or ring c. Ring A', ring B' and ring C' in the respective
formulas correspond to ring A, ring B and ring C, respectively, in
the general formula (1).
##STR00016##
[0053] Ring A', ring B' and ring C' in the above formula (2-1) and
formula (2-2) each represent, to be explained in connection with
the general formula (2), an aryl ring or a heteroaryl ring formed
by bonding between adjacent groups among the substituents R.sup.1
to R.sup.11, together with the ring a, ring b and ring c,
respectively (may also be referred to as a fused ring obtained as
another ring structure is fused to the ring a, ring b or ring c).
In addition, although it is not suggested in the formula, there is
also a compound in which all of the ring a, ring b and ring c have
been changed to ring A', ring B' and ring C'. Furthermore, it can
be seen from the above formula (2-1) and formula (2-2), for
example, R.sup.8 of ring b and R.sup.7 of ring c, R.sup.11 of ring
b and R.sup.1 of ring a, R.sup.4 of ring c and R.sup.3 of ring a,
and the like do not correspond to "adjacent groups", and these are
not to be bonded. That is, the expression "adjacent groups" means
adjacent groups on the same ring.
[0054] A compound represented by the above formula (2-1) or formula
(2-2) corresponds to, for example, a compound represented by any
one of formulas (1-2) to (1-17) listed as specific compounds that
are described below. That is, for example, the compound represented
by formula (2-1) or formula (2-2) is a compound having ring A' (or
ring B' or ring C') that is formed when a benzene ring, an indole
ring, a pyrrole ring, a benzofuran ring or a benzothiophene ring is
fused to the benzene ring which is ring a (or ring b or ring c),
and the fused ring A' (or fused ring B' or fused ring C') that
could be formed is a naphthalene ring, a carbazole ring, an indole
ring, a dibenzofuran ring, or a dibenzothiophene ring.
[0055] Y.sup.1 in the general formula (1) represents B, P, P.dbd.O,
P.dbd.S, Al, Ga, As, Si--R or Ge--R, and R of the moieties Si--R
and Ge--R represents an aryl or an alkyl. In the case of P.dbd.O,
P.dbd.S, Si--R or Ge--R, the atom that is bonded to ring A, ring B
or ring C is P, Si or Ge. Y.sup.1 is preferably B, P, P.dbd.O,
P.dbd.S or Si--R, and particularly preferably B. This explanation
also applies to Y.sup.1 in the general formula (2).
[0056] X.sup.1 and X.sup.2 in the general formula (1) each
independently represent O, N--R, S or Se, while R of the moiety
N--R represents an aryl or alkyl which may be substituted, and R of
the moiety N--R may be bonded to the ring B and/or ring C by a
linking group or a single bond. The linking group is preferably
--O--, --S-- or --C(--R).sub.2--. Meanwhile, R of the moiety
"--C(--R).sub.2--" represents a hydrogen atom or an alkyl. This
explanation also applies to X.sup.1 and X.sup.2 in the general
formula (2).
[0057] Here, the provision that "R of the moiety N--R is bonded to
ring B and/or ring C by a linking group or a single bond" for the
general formula (1) corresponds to the provision that "R of the
moiety N--R is bonded to ring b and/or ring c by --O--, --S--,
--C(--R).sub.2-- or a single bond" for the general formula (2).
[0058] This provision can be expressed by a compound having a ring
structure represented by the following formula (2-3), in which
X.sup.1 or X.sup.2 is incorporated into the fused ring B' and the
fused ring C'. That is, for example, the compound is a compound
having ring B' (or ring C') that is formed as another ring is fused
to a benzene ring which is ring b (or ring c) in the general
formula (2) so as to incorporate X.sup.1 (or X.sup.2). This
compound corresponds to, for example, a compound represented by any
one of formulas (1-451) to (1-462) listed as specific examples that
are described below, and the fused ring B' (or fused ring C') that
could be formed is, for example, a phenoxazine ring, a
phenothiazine ring, or an acridine ring.
##STR00017##
[0059] The "aryl ring" as the ring A, ring B or ring C of the
general formula (1) is, for example, an aryl ring having 6 to 30
carbon atoms, and the aryl ring is preferably an aryl ring having 6
to 16 carbon atoms, more preferably an aryl ring having 6 to 12
carbon atoms, and particularly preferably an aryl ring having 6 to
10 carbon atoms. Meanwhile, this "aryl ring" corresponds to the
"aryl ring formed by bonding between adjacent groups among R.sup.1
to R.sup.11, together with ring a, ring b or ring c" defined by
general formula (2). Also, since ring a (or ring b or ring c) is
already configured by a benzene ring having 6 carbon atoms, a
carbon number of 9 in total of a fused ring obtained when a
5-membered ring is fused to this benzene ring, becomes the lower
limit of the carbon number.
[0060] Specific examples of the "aryl ring" include a benzene ring
which is a monocyclic system; a biphenyl ring which is a bicyclic
system; a naphthalene ring which is a fused bicyclic system; a
terphenyl ring (m-terphenyl, o-terphenyl, or p-terphenyl) which is
a tricyclic system; an acenaphthylene ring, a fluorene ring, a
phenalene ring and a phenanthrene ring, which are fused tricyclic
systems; a triphenylene ring, a pyrene ring and a naphthacene ring,
which are fused tetracyclic systems; and a perylene ring and a
pentacene ring, which are fused pentacyclic systems.
[0061] The "heteroaryl ring" as the ring A, ring B or ring C of the
general formula (1) is, for example, a heteroaryl ring having 2 to
30 carbon atoms, and the heteroaryl ring is preferably a heteroaryl
ring having 2 to 25 carbon atoms, more preferably a heteroaryl ring
having 2 to 20 carbon atoms, even more preferably a heteroaryl ring
having 2 to 15 carbon atoms, and particularly preferably a
heteroaryl ring having 2 to 10 carbon atoms. Furthermore, the
"heteroaryl ring" may be, for example, a heterocyclic ring
containing 1 to 5 heteroatoms selected from oxygen, sulfur and
nitrogen in addition to carbon as the ring-constituting atoms.
Meanwhile, this "heteroaryl ring" corresponds to the "heteroaryl
ring formed by bonding between adjacent groups among R.sup.1 to
R.sup.11, together with the ring a, ring b or ring c" defined by
general formula (2), and since the ring a (or ring b or ring c) is
already composed of a benzene ring having 6 carbon atoms, a carbon
number of 6 in total of a fused ring obtained when a 5-membered
ring is fused to this benzene ring, becomes the lower limit of the
carbon number.
[0062] Specific examples of the "heteroaryl ring" include a pyrrole
ring, an oxazole ring, an isoxazole ring, a thiazole ring, an
isothiazole ring, an imidazole ring, an oxadiazole ring, a
thiadiazole ring, a triazole ring, a tetrazole ring, a pyrazole
ring, a pyridine ring, a pyrimidine ring, a pyridazine ring, a
pyrazine ring, a triazine ring, an indole ring, an isoindole ring,
a 1H-indazole ring, a benzimidazole ring, a benzoxazole ring,
abenzothiazole ring, a 1H-benzotriazole ring, a quinoline ring, an
isoquinoline ring, a cinnoline ring, a quinazoline ring, a
quinoxaline ring, a phthalazine ring, a naphthyridine ring, a
purine ring, a pteridine ring, a carbazole ring, an acridine ring,
a phenoxathiin ring, a phenoxazine ring, a phenothiazine ring, a
phenazine ring, an indolizine ring, a furan ring, a benzofuran
ring, an isobenzofuran ring, a dibenzofuran ring, a thiophene ring,
a benzothiophene ring, a dibenzothiophene ring, a furazane ring, an
oxadiazole ring, and a thianthrene ring.
[0063] At least one hydrogen atom in the aforementioned "aryl ring"
or "heteroaryl ring" may be substituted by a substituted or
unsubstituted "aryl", a substituted or unsubstituted "heteroaryl",
a substituted or unsubstituted "diarylamino", a substituted or
unsubstituted "alkyl", a substituted or unsubstituted "alkoxy", or
a substituted or unsubstituted "aryloxy", which is a primary
substituent. Examples of the aryl of the "aryl", "heteroaryl" and
"diarylamino" as these primary substituents, and the aryl of
"aryloxy" include a monovalent group of the "aryl ring" or
"heteroaryl ring" described above.
[0064] Furthermore, the "alkyl" as the primary substituent may be
any of a straight chain or a branched chain, and examples thereof
include a linear alkyl having 1 to 24 carbon atoms and a branched
alkyl having 3 to 24 carbon atoms. The alkyl is preferably an alkyl
having 1 to 18 carbon atoms (branched alkyl having 3 to 18 carbon
atoms), more preferably an alkyl having 1 to 12 carbon atoms
(branched alkyl having 3 to 12 carbon atoms), even more preferably
an alkyl having 1 to 6 carbon atoms (branched alkyl having 3 to 6
carbon atoms), and particularly preferably an alkyl having 1 to 4
carbon atoms (branched alkyl having 3 to 4 carbon atoms).
[0065] Specific examples of the alkyl include methyl, ethyl,
n-propyl, isopropyl, n-butyl, isobutyl, s-butyl, t-butyl, n-pentyl,
isopentyl, neopentyl, t-pentyl, n-hexyl, 1-methylpentyl,
4-methyl-2-pentyl, 3,3-dimethylbutyl, 2-ethylbutyl, n-heptyl,
1-methylhexyl, n-octyl, t-octyl, 1-methylheptyl, 2-ethylhexyl,
2-propylpentyl, n-nonyl, 2,2-dimethylheptyl, 2,6-dimethyl-4-heptyl,
3,5,5-trimethylhexyl, n-decyl, n-undecyl, 1-methyldecyl, n-dodecyl,
n-tridecyl, 1-hexylheptyl, n-tetradecyl, n-pentadecyl, n-hexadecyl,
n-heptadecyl, n-octadecyl, and n-eicosyl.
[0066] Furthermore, the "alkoxy" as a primary substituent may be,
for example, a linear alkoxy having 1 to 24 carbon atoms or a
branched alkoxy having 3 to 24 carbon atoms. The alkoxy is
preferably an alkoxy having 1 to 18 carbon atoms (branched alkoxy
having 3 to 18 carbon atoms), more preferably an alkoxy having 1 to
12 carbon atoms (branched alkoxy having 3 to 12 carbon atoms), even
more preferably an alkoxy having 1 to 6 carbon atoms (branched
alkoxy having 3 to 6 carbon atoms), and particularly preferably an
alkoxy having 1 to 4 carbon atoms (branched alkoxy having 3 to 4
carbon atoms).
[0067] Specific examples of the alkoxy include methoxy, ethoxy,
propoxy, isopropoxy, butoxy, isobutoxy, s-butoxy, t-butoxy,
pentyloxy, hexyloxy, heptyloxy, and octyloxy.
[0068] The substituted or unsubstituted "aryl", substituted or
unsubstituted "heteroaryl", substituted or unsubstituted
"diarylamino", substituted or unsubstituted "alkyl", substituted or
unsubstituted "alkoxy", or substituted or unsubstituted "aryloxy",
which is the primary substituent, is such that at least one
hydrogen atom thereof may be substituted by a secondary
substituent, as it is explained to be substituted or unsubstituted.
Examples of this secondary substituent include an aryl, a
heteroaryl, and an alkyl, and for the details thereof, reference
can be made to the explanations on the monovalent group of the
"aryl ring" or "heteroaryl ring" described above and the "alkyl" as
the primary substituent. Furthermore, regarding the aryl or
heteroaryl as the secondary substituent, an aryl or heteroaryl in
which at least one hydrogen atom thereof has been substituted by an
aryl such as phenyl (specific examples are described above), or an
alkyl such as methyl (specific examples are described above), is
also included in the aryl or heteroaryl as the secondary
substituent. For instance, when the secondary substituent is a
carbazolyl group, a carbazolyl group in which at least one hydrogen
atom at the 9-position has been substituted by an aryl such as
phenyl, or an alkyl such as methyl, is also included in the
heteroaryl as the secondary substituent.
[0069] Examples of the aryl, heteroaryl, the aryl of the
diarylamino, or the aryl of the aryloxy for R.sup.1 to R.sup.11 of
general formula (2) include the monovalent groups of the "aryl
ring" or "heteroaryl ring" explained in the general formula (1).
Furthermore, regarding the alkyl or alkoxy for R.sup.1 to R.sup.11,
reference can be made to the explanation on the "alkyl" or "alkoxy"
as the primary substituent in the explanation of the general
formula (1). In addition, the same also applies to the aryl,
heteroaryl or alkyl as the substituent for these groups.
Furthermore, the same also applies to the heteroaryl, diarylamino,
alkyl, alkoxy or aryloxy in the case of forming an aryl ring or a
heteroaryl ring by bonding between adjacent groups among R.sup.1 to
R.sup.11 together with the ring a, ring b or ring c, and the aryl,
heteroaryl or alkyl as the further substituent.
[0070] R of the moieties Si--R and Ge--R for Y.sup.1 in the general
formula (1) represents an aryl or an alkyl, and examples of this
aryl or alkyl include those described above. Particularly, an aryl
having 6 to 10 carbon atoms (for example, phenyl or naphthyl), and
an alkyl having 1 to 4 carbon atoms (for example, methyl or ethyl)
are preferred. This explanation also applies to Y.sup.1 for the
general formula (2).
[0071] R of the moiety N--R for X.sup.1 and X.sup.2 of the general
formula (1) represents an aryl or an alkyl, both of which may be
substituted by the secondary substituents described above, and at
least one hydrogen in the aryl may be substituted by, for example,
an alkyl. Examples of this aryl or alkyl include those described
above. Particularly, an aryl having 6 to 10 carbon atoms (for
example, phenyl or naphthyl) and an alkyl having 1 to 4 carbon
atoms (for example, methyl or ethyl) are preferred. This
explanation also applies to X.sup.1 and X.sup.2 in the general
formula (2).
[0072] R of the moiety "--C(--R).sub.2--" as a linking group for
the general formula (1) represents a hydrogen atom or an alkyl, and
examples of this alkyl include those described above. Particularly,
an alkyl having 1 to 4 carbon atoms (for example, methyl or ethyl)
is preferred. This explanation also applies to "--C(--R).sub.2--"
as a linking group for general formula (2).
[0073] Furthermore, the invention of the present application is an
oligomer of a polycyclic aromatic compound having plural unit
structures each represented by general formula (1), and preferably
an oligomer of a polycyclic aromatic compound having plural unit
structures each represented by general formula (2). The oligomer is
preferably a dimer to a hexamer, more preferably a dimer to a
trimer, and a particularly preferably a dimer. The oligomer may be
in a form having a plural number of the unit structures described
above in one compound, and for example, the oligomer may be in a
form in which a plural number of the unit structures are linked via
a linking group such as a single bond, an alkylene group having 1
to 3 carbon atoms, a phenylene group, or a naphthylene group, as
well as a form in which a plural number of the unit structures are
linked such that any ring contained in the unit structure (ring A,
ring B or ring C, or ring a, ring b or ring c) is shared by the
plural unit structures, or may be in a form in which the unit
structures are linked such that any rings contained in the unit
structures (ring A, ring B or ring C, or ring a, ring b or ring c)
are fused.
[0074] Examples of such an oligomer include oligomer compounds
represented by the following formula (2-4), formula (2-5-1) to
formula (2-5-4), and formula (2-6). An oligomer compound
represented by the following formula (2-4) corresponds to, for
example, a compound represented by formula (1-21) described below.
That is, to explain this in view of general formula (2), the
oligomer is an oligomer compound in which plural unit structures
each represented by general formula (2) are carried in one compound
such that a benzene ring as ring a is shared. Furthermore, oligomer
compounds represented by the following formula (2-5-1) to formula
(2-5-4) correspond to, for example, compounds represented by the
following formulas (1-22) to (1-25). That is, to explain this in
view of general formula (2), such an oligomer is an oligomer
compound in which plural unit structures each represented by
general formula (2) are carried in one compound such that a benzene
ring as ring b (or ring c) is shared. Furthermore, an oligomer
compound represented by the following formula (2-6) corresponds to,
for example, a compound represented by any one of the following
formulas (1-31) to (1-37). That is, to explain this in view of
general formula (2), for example, the oligomer is an oligomer
compound in which plural unit structures each represented by
general formula (2) are carried out in one compound such that a
benzene ring as ring b (or ring a or ring c) of a certain unit
structure and a benzene ring as ring b (or ring a or ring c) are
fused.
##STR00018## ##STR00019##
[0075] The oligomer compound may be an oligomer in which an
oligomer form represented by formula (2-4) and an oligomer form
represented by any one of formula (2-5-1) to formula (2-5-4) or
formula (2-6) are combined; may be an oligomer in which an oligomer
form represented by any one of formula (2-5-1) to formula (2-5-4)
and an oligomer form represented by formula (2-6) are combined; or
may be an oligomer in which an oligomer form represented by formula
(2-4), an oligomer form represented by any one of formula (2-5-1)
to formula (2-5-4), and an oligomer form represented by formula
(2-6) are combined.
[0076] Furthermore, all or a portion of the hydrogen atoms in the
chemical structures of the polycyclic aromatic compound represented
by general formula (1) or (2) and an oligomer thereof may be
deuterium atoms.
[0077] Also, all or a portion of the hydrogen atoms in the chemical
structures of the polycyclic aromatic compound represented by
general formula (1) or (2) and an oligomer thereof may be fluorine
atoms. For example, in regard to formula (1), the hydrogen atoms in
the ring A, ring B, ring C (ring A to ring C are aryl rings or
heteroaryl rings), substituents of the ring A to ring C, R (=alkyl
or aryl) when Y.sup.1 represents Si--R or Ge--R, and R (=alkyl or
aryl) when X.sup.1 and X.sup.2 each represent N--R, may be
substituted by fluorine atoms, and among these, a form in which all
or a portion of the hydrogen atoms in the aryl or heteroaryl have
been substituted by fluorine atoms may be mentioned.
[0078] More specific examples of the polycyclic aromatic compound
of the present invention and oligomers thereof include, for
example, compounds represented by the following formulas (1-1) to
(1-825) and compounds represented by the following formulas
(1-1001) to (1-1281).
##STR00020## ##STR00021## ##STR00022## ##STR00023## ##STR00024##
##STR00025## ##STR00026## ##STR00027## ##STR00028## ##STR00029##
##STR00030## ##STR00031## ##STR00032## ##STR00033## ##STR00034##
##STR00035## ##STR00036## ##STR00037## ##STR00038## ##STR00039##
##STR00040## ##STR00041## ##STR00042## ##STR00043## ##STR00044##
##STR00045## ##STR00046## ##STR00047## ##STR00048## ##STR00049##
##STR00050## ##STR00051## ##STR00052## ##STR00053##
##STR00054## ##STR00055## ##STR00056## ##STR00057## ##STR00058##
##STR00059## ##STR00060## ##STR00061## ##STR00062## ##STR00063##
##STR00064## ##STR00065## ##STR00066## ##STR00067## ##STR00068##
##STR00069## ##STR00070## ##STR00071## ##STR00072## ##STR00073##
##STR00074## ##STR00075## ##STR00076## ##STR00077##
##STR00078## ##STR00079## ##STR00080## ##STR00081## ##STR00082##
##STR00083## ##STR00084## ##STR00085## ##STR00086## ##STR00087##
##STR00088## ##STR00089## ##STR00090## ##STR00091## ##STR00092##
##STR00093## ##STR00094## ##STR00095## ##STR00096## ##STR00097##
##STR00098## ##STR00099## ##STR00100## ##STR00101## ##STR00102##
##STR00103## ##STR00104## ##STR00105## ##STR00106## ##STR00107##
##STR00108##
##STR00109## ##STR00110## ##STR00111## ##STR00112## ##STR00113##
##STR00114## ##STR00115## ##STR00116## ##STR00117## ##STR00118##
##STR00119## ##STR00120## ##STR00121## ##STR00122## ##STR00123##
##STR00124## ##STR00125## ##STR00126## ##STR00127## ##STR00128##
##STR00129## ##STR00130## ##STR00131## ##STR00132## ##STR00133##
##STR00134## ##STR00135## ##STR00136## ##STR00137## ##STR00138##
##STR00139## ##STR00140## ##STR00141## ##STR00142##
##STR00143##
[0079] Furthermore, a specific example of the polycyclic aromatic
compound of the present invention and oligomers thereof may be a
compound in which at least one hydrogen atom in one or plural
phenyl groups or one phenylene group in the compound has been
substituted by one or plural alkyls each having 1 to 3 carbon atoms
(preferably one or plural methyl groups). A more preferred example
may be a compound in which the hydrogen atoms at the
ortho-positions of one phenyl group (both of the two sites,
preferably any one site) or the hydrogen atoms at the
ortho-positions of one phenylene group (all of the four sites at
maximum, preferably any one site) have been substituted by methyl
groups.
[0080] Examples of such a compound, even among the compounds
represented by the above formulas (1-1) to (1-825) and the
compounds represented by the above formulas (1-1001) to (1-1281),
include compounds containing phenyl groups or phenylene groups, in
which at least one hydrogen atom in one or plural phenyl groups or
one phenylene group has been substituted by one or plural alkyls
each having 1 to 3 carbon atoms (preferably one or plural methyl
groups). More preferred examples of such a compound include
compounds in which the hydrogen atoms at the ortho-positions of one
phenyl group (both of two sites, preferably any one site) or the
hydrogen atoms at the ortho-positions of one phenylene group (all
of four sites at maximum, preferably any one site) have been
substituted by methyl groups.
[0081] Particularly, further examples include compounds in which at
least one hydrogen atom in one or plural phenyl groups or one
phenylene group in the compounds represented by formula (1-41),
formula (1-42), formula (1-45), formula (1-50), formula (1-79),
formula (1-83), formula (1-84), formula (1-91), formula (1-94),
formula (1-95), formula (1-97), formula (1-151), formula (1-152),
formula (1-1021) to formula (1-1036), formula (1-1037), formula
(1-1038), formula (1-1039), formula (1-1048), formula (1-1049),
formula (1-1050), formula (1-1077), formula (1-1078), formula
(1-1079), formula (1-1187), formula (1-1190), formula (1-1191) and
formula (1-1192), has been substituted by one or plural alkyls each
having 1 to 3 carbon atoms (preferably one or plural methyl
groups). More preferred examples include compounds in which the
hydrogen atoms at the ortho-positions of one phenyl group (both of
two sites, preferably any one site) or the hydrogen atoms at the
ortho-positions of one phenylene group (all of four sites at
maximum, preferably any one site) have been substituted by methyl
groups.
[0082] When at least one hydrogen atom at the ortho-positions of
terminal phenyl groups or a p-phenylene group in a compound is
substituted by a methyl group or the like, adjoining aromatic rings
are likely to intersect each other perpendicularly, and conjugation
is weakened. As a result, the triplet excitation energy (E.sub.T)
can be increased.
[0083] Specific examples thereof include compounds represented by
the following formula (1-41-1) to formula (1-1192-9).
##STR00144## ##STR00145## ##STR00146## ##STR00147## ##STR00148##
##STR00149## ##STR00150## ##STR00151## ##STR00152## ##STR00153##
##STR00154## ##STR00155## ##STR00156## ##STR00157## ##STR00158##
##STR00159## ##STR00160## ##STR00161## ##STR00162## ##STR00163##
##STR00164## ##STR00165## ##STR00166## ##STR00167## ##STR00168##
##STR00169## ##STR00170## ##STR00171##
##STR00172## ##STR00173## ##STR00174## ##STR00175## ##STR00176##
##STR00177## ##STR00178## ##STR00179## ##STR00180## ##STR00181##
##STR00182## ##STR00183## ##STR00184## ##STR00185## ##STR00186##
##STR00187## ##STR00188## ##STR00189## ##STR00190## ##STR00191##
##STR00192## ##STR00193## ##STR00194##
2. Method for Producing Polycyclic Aromatic Compound and Oligomer
Thereof
[0084] In regard to the polycyclic aromatic compound represented by
general formula (1) or (2) and an oligomer thereof, basically, an
intermediate is produced by first linking the ring A (ring a), ring
B (ring b) and ring C (ring c) via linking groups (groups
containing X.sup.1 or X.sup.2) (first reaction), and then a final
product can be produced by linking the ring A (ring a), ring B
(ring b) and ring C (ring c) via linking groups (groups containing
Y.sup.1) (second reaction). In the first reaction, for example, in
the case of an etherification reaction, a general reaction such as
a nucleophilic substitution reaction, or the Ullmann reaction can
be utilized, and in the case of an amination reaction, a general
reaction such as the Buchwald-Hartwig reaction can be utilized.
Also, in the second reaction, the Tandem Hetero-Friedel-Crafts
reaction can be utilized.
[0085] The second reaction is a reaction for introducing Y.sup.1
that links the ring A (ring a), ring B (ring b) and ring C (ring c)
as illustrated in the following scheme (1) or (2), and as an
example, the case in which Y.sup.1 represents a boron atom; and
X.sup.1 and X.sup.2 represent oxygen atoms is shown below. First,
the hydrogen atom between X.sup.1 and X.sup.2 is ortho-metalated
with n-butyllithium, sec-butyllithium or t-butyllithium.
Subsequently, boron trichloride, boron tribromide or the like is
added thereto to conduct lithium-boron metal exchange, and then a
Bronsted base such as N, N-diisopropylethylamine is added thereto
to induce a Tandem Bora-Friedel-Crafts reaction. Thus, an intended
product may be obtained. In the second reaction, a Lewis acid such
as aluminum trichloride may also be added in order to accelerate
the reaction.
##STR00195##
##STR00196##
[0086] Meanwhile, the scheme (1) or (2) mainly illustrates the
method for producing a polycyclic aromatic compound represented by
general formula (1) or (2); however, an oligomer thereof can be
produced by using an intermediate having plural ring A's (ring
a's), ring B's (ring b's) and ring C's (ring c's). More
specifically, the production method may be explained by the
following schemes (3) to (5). In this case, the intended product
may be obtained by increasing the amount of the reagent used
therein such as butyllithium to a double amount or a triple
amount.
##STR00197##
##STR00198##
##STR00199##
[0087] In the above schemes, lithium is introduced into a desired
position by ortho-metalation; however, lithium can also be
introduced into a desired position by halogen-metal exchange by
introducing a bromine atom or the like to a position to which it is
wished to introduce lithium, as in the following schemes (6) and
(7).
##STR00200##
##STR00201##
[0088] Furthermore, also in regard to the method for producing an
oligomer described in the scheme (3), lithium can be introduced to
a desired position also by halogen-metal exchange by introducing
halogen such as a bromine atom or a chlorine atom to a position to
which it is wished to introduce lithium, as in the above schemes
(6) and (7) (following schemes (8), (9) and (10)).
##STR00202##
##STR00203##
##STR00204##
[0089] According to this method, an intended product can also be
synthesized even in a case in which ortho-metalation cannot be
achieved due to the influence of substituents, and therefore, the
method is useful.
[0090] By appropriately selecting the synthesis method described
above and appropriately selecting the raw materials to be used, a
polycyclic aromatic compound having substituents at desired
positions, with Y.sup.1 being a boron atom and X.sup.1 and X.sup.2
being oxygen atoms, and an oligomer thereof can be synthesized.
[0091] Next, the case in which Y.sup.1 represents a boron atom and
X.sup.1 and X.sup.2 represent nitrogen atoms, is illustrated as an
example in the following schemes (11) and (12). Similarly to the
case in which X.sup.1 and X.sup.2 are oxygen atoms, first, the
hydrogen atom between X.sup.1 and X.sup.2 is ortho-metalated with
n-butyllithium or the like. Subsequently, boron tribromide or the
like is added thereto to induce lithium-boron metal exchange, and
then a Bronsted base such as N,N-diisopropylethylamine is added
thereto to induce a Tandem Bora-Friedel-Crafts reaction. Thus, an
intended product may be obtained. In this reaction, a Lewis acid
such as aluminum trichloride may also be added in order to
accelerate the reaction.
##STR00205##
##STR00206##
[0092] Furthermore, even for an oligomer in the case in which
Y.sup.1 represents a boron atom; and X and X.sup.2 represent
nitrogen atoms, lithium can be introduced to a desired position
also by halogen-metal exchange by introducing halogen such as a
bromine atom or a chlorine atom to a position to which it is wished
to introduce lithium, as in the case of the schemes (6) and (7)
(following schemes (13), (14) and (15)).
##STR00207##
##STR00208##
##STR00209##
[0093] Next, the case in which Y.sup.1 represents phosphorus
sulfide, phosphorous oxide or a phosphorus atom; and X.sup.1 and
X.sup.2 represent oxygen atoms, is illustrated as an example in the
following schemes (16) to (19). Similarly to the cases explained
thus far, first, the hydrogen atom between X.sup.1 and X.sup.2 is
ortho-metalated with n-butyllithium or the like. Subsequently,
phosphorus trichloride and sulfur are added thereto in this order,
and finally a Lewis acid such as aluminum trichloride and a
Bronsted base such as N,N-diisopropylethylamine are added thereto
to induce the Tandem Phospha-Friedel-Crafts reaction. Thus, a
compound in which Y.sup.1 is phosphorus sulfide can be obtained.
Furthermore, when the phosphorus sulfide compound thus obtained is
treated with m-chloroperbenzoic acid (m-CPBA), a compound in which
Y.sup.1 is phosphorus oxide can be obtained, while the phosphorus
sulfide compound is treated with triethylphosphine, a compound in
which Y.sup.1 is a phosphorus atom can be obtained.
##STR00210##
##STR00211##
##STR00212##
##STR00213##
[0094] Furthermore, also for an oligomer in the case where Y.sup.1
is phosphorus sulfide; and X.sup.1 and X.sup.2 are oxygen atoms,
lithium can be introduced to a desired position also by
halogen-metal exchange by introducing halogen such as a bromine
atom or a chlorine atom to a position to which it is wished to
introduce lithium, similarly to the schemes (6) and (7) (following
schemes (20), (21) and (22)). Furthermore, when the oligomer
obtained in this manner in which Y.sup.1 represents phosphorus
sulfide; and X.sup.1 and X.sup.2 represents oxygen atoms, is
treated with m-chloroperbenzoic acid (m-CPBA) in the same manner as
in the schemes (18) and (19), a compound in which Y.sup.1 is
phosphorus oxide can be obtained, and when the oligomer is treated
with triethylphosphine, a compound in which Y.sup.1 is a phosphorus
atom can be obtained.
##STR00214##
##STR00215##
##STR00216##
[0095] Here, an example in which Y.sup.1 represents B, P, P.dbd.O
or P.dbd.S; and X.sup.1 and X.sup.2 represent O or NR is described;
however, a compound in which Y.sup.1 represents Al, Ga, As, Si--R
or Ge--R; or X.sup.1 and X.sup.2 represent S can also be
synthesized by appropriately modifying the raw materials.
[0096] Specific examples of the solvent used in the above reactions
include t-butylbenzene and xylene.
[0097] Furthermore, in general formula (2), adjacent groups among
the substituents R.sup.1 to R.sup.11 of the ring a, ring b and ring
c may be bonded to each other and form an aryl ring or a heteroaryl
ring together with the ring a, ring b or ring c, and at least one
hydrogen atom in the ring thus formed may be substituted by an aryl
or a heteroaryl. Therefore, the polycyclic aromatic compound
represented by general formula (2) is such that the ring structure
that constitutes the compound changes as represented by formula
(2-1) and formula (2-2) of the following schemes (23) and (24), due
to the mutual bonding form of substituents in the ring a, ring b
and ring c. These compounds can be synthesized by applying the
synthesis methods shown in the above schemes (1) to (19) to the
intermediates shown in the following schemes (23) and (24).
##STR00217##
##STR00218##
[0098] Ring A', ring B' and ring C' in the above formula (2-1) and
formula (2-2) represent aryl rings or heteroaryl rings formed by
bonding between adjacent groups among the substituents R.sup.1 to
R.sup.11 together with the ring a, ring b, and ring c, respectively
(may also be fused rings obtained as other ring structures are
fused to the ring a, ring b or ring c). Meanwhile, although it is
not suggested in the formulas, there is also a compound in which
all of the ring a, ring b and ring c have been converted to ring
A', ring B', and ring C').
[0099] Furthermore, the provision that "R of the moiety N--R is
linked to the ring b and/or ring c via --O--, --S--,
--C(--R).sub.2-- or a single bond" in general formula (2) can be
expressed as a compound having a ring structure represented by
formula (2-3) of the following scheme (25), in which X.sup.1 or
X.sup.2 is incorporated into the fused ring B' and fused ring C'.
Such a compound can be synthesized by applying the synthesis
methods illustrated in the schemes (1) to (19) to the intermediate
represented by the following scheme (25).
##STR00219##
[0100] Furthermore, regarding the synthesis methods of the above
schemes (1) to (17) and (20) to (25), there is shown an example of
carrying out the Tandem Hetero-Friedel-Crafts reaction by
ortho-metalating the hydrogen atom (or a halogen atom) between
X.sup.1 and X.sup.2 with butyllithiumor the like, before boron
trichloride, boron tribromide or the like is added. However, the
reaction may also be carried out by adding boron trichloride, boron
tribromide or the like without conducting ortho-metalation using
buthyllithium or the like.
[0101] The polycyclic aromatic compound of the present invention or
an oligomer thereof also includes compounds in which at least a
portion of hydrogen atoms have been substituted by deuterium atoms
or substituted by fluorine atoms; however, these compounds can be
synthesized as described above by using raw materials that are
deuterated or fluorinated at desired sites.
[0102] The polycyclic aromatic compound according to the present
invention and an oligomer thereof can be used as a material for
organic devices. Examples of the organic devices include an organic
electroluminescent element, an organic field effect transistor, and
an organic thin film solar cell.
3. Organic Electroluminescent Element
[0103] The polycyclic aromatic compound according to the present
invention and an oligomer thereof can be used as, for example, a
material for an organic electroluminescent element. Hereinafter, an
organic EL element related to the present exemplary embodiment will
be described in detail based on the drawings. FIG. 1 is an outline
cross-sectional diagram illustrating an organic EL element related
to the present exemplary embodiment.
<Structure of Organic Electroluminescent Element>
[0104] The organic electroluminescent element 100 illustrated in
FIG. 1 includes a substrate 101; a positive electrode 102 provided
on the substrate 101; a hole injection layer 103 provided on the
positive electrode 102; a hole transport layer 104 provided on the
hole injection layer 103; a light emitting layer 105 provided on
the hole transport layer 104; an electron transport layer 106
provided on the light emitting layer 105; an electron injection
layer 107 provided on the electron transport layer 106; and a
negative electrode 108 provided on the electron injection layer
107.
[0105] The organic electroluminescent element 100 may also be
configured, by reversing the production procedure, to include, for
example, a substrate 101; a negative electrode 108 provided on the
substrate 101; an electron injection layer 107 provided on the
negative electrode 108; an electron transport layer 106 provided on
the electron injection layer 107; a light emitting layer 105
provided on the electron transport layer 106; a hole transport
layer 104 provided on the light emitting layer 105; a hole
injection layer 103 provided on the hole transport layer 104; and a
positive electrode 102 provided on the hole injection layer
103.
[0106] Not all of the various layers are essential, and the
configuration may include a positive electrode 102, a light
emitting layer 105, and a negative electrode 108 as the minimum
constituent units, while the hole injection layer 103, the hole
transport layer 104, the electron transport layer 106, and the
electron injection layer 107 are optionally provided layers. Also,
each of the various layers described above may be composed of a
single layer, or may be composed of plural layers.
[0107] Embodiments of the layers that constitute an organic
electroluminescent element may include, in addition to the
configuration embodiment of "substrate/positive electrode/hole
injection layer/hole transport layer/light emitting layer/electron
transport layer/electron injection layer/negative electrode"
described above, configuration embodiments of "substrate/positive
electrode/hole transport layer/light emitting layer/electron
transport layer/electron injection layer/negative electrode",
"substrate/positive electrode/hole injection layer/light emitting
layer/electron transport layer/electron injection layer/negative
electrode", "substrate/positive electrode/hole injection layer/hole
transport layer/light emitting layer/electron injection
layer/negative electrode", "substrate/positive electrode/hole
injection layer/hole transport layer/light emitting layer/electron
transport layer/negative electrode", "substrate/positive
electrode/light emitting layer/electron transport layer/electron
injection layer/negative electrode", "substrate/positive
electrode/hole transport layer/light emitting layer/electron
injection layer/negative electrode", "substrate/positive
electrode/hole transport layer/light emitting layer/electron
transport layer/negative electrode", "substrate/positive
electrode/hole injection layer/light emitting layer/electron
injection layer/negative electrode", "substrate/positive
electrode/hole injection layer/light emitting layer/electron
transport layer/negative electrode", "substrate/positive
electrode/light emitting layer/electron transport layer/negative
electrode", and "substrate/positive electrode/light emitting
layer/electron injection layer/negative electrode".
<Substrate in Organic Electroluminescent Element>
[0108] The substrate 101 serves as a support of the organic
electroluminescent element 100, and usually, quartz, glass, metals,
plastics and the like are used. The substrate 101 is formed into a
plate shape, a film shape or a sheet shape according to the
purpose, and for example, a glass plate, a metal plate, a metal
foil, a plastic film, and a plastic sheet are used. Among them, a
glass plate, and a plate made of a transparent synthetic resin such
as polyester, polymethacrylate, polycarbonate or polysulfone are
preferred. For the glass substrate, soda lime glass, alkali-free
glass and the like are used, and furthermore, the thickness is
desirably a thickness sufficient for maintaining the mechanical
strength. Therefore, the thickness is desirably 0.2 mm or more. The
upper limit value of the thickness is, for example, 2 mm or less,
and preferably 1 mm or less. Regarding the material of glass, since
a glass having fewer ions eluted from the glass is desirable,
alkali-free glass is preferred. However, since soda lime glass
provided with a barrier coat of SiO.sub.2 or the like is also
commercially available, this can be used. Furthermore, the
substrate 101 may be provided with a gas barrier film such as a
dense silicon oxide film on at least one surface in order to
increase the gas barrier properties, and particularly in the case
of using a plate, a film or a sheet made of a synthetic resin
having low gas barrier properties as the substrate 101, it is
preferable to provide a gas barrier film.
<Positive Electrode in Organic Electroluminescent
Element>
[0109] The positive electrode 102 is a member that accomplishes the
role of injecting holes to the light emitting layer 105. In
addition, when a hole injection layer 103 and/or hole transport
layer 104 is provided between the positive electrode 102 and the
light emitting layer 105, holes are injected into the light
emitting layer 105 through these layers.
[0110] Examples of the material that forms the positive electrode
102 include inorganic compounds and organic compounds. Examples of
the inorganic compounds include metals (aluminum, gold, silver,
nickel, palladium, chromium and the like), metal oxides (oxides of
indium, oxides of tin, indium tin oxide (ITO), indium zinc oxide
(IZO), and the like), metal halides (copper iodide and the like),
copper sulfide, carbon black, ITO glass, and Nesa glass. Examples
of the organic compounds include electrically conductive polymers
such as polythiophene such as poly(3-methylthiophene), polypyrrole,
and polyaniline. In addition to them, the material can be
appropriately selected for use from the materials used as the
positive electrode of organic electroluminescent elements.
[0111] The resistance of a transparent electrode is not limited
because it is desirable if sufficient electric current can be
supplied to the light emission of a light emitting element;
however, from the viewpoint of the consumption power of the light
emitting element, lower resistance is preferred. For example, an
ITO substrate having a resistance of 300.OMEGA./.quadrature. or
less functions as an element electrode; however, since substrates
having a resistance of about 10.OMEGA./.quadrature. can also be
supplied, it is particularly preferable to use a low resistance
product having a resistance of, for example, 100 to
5.OMEGA./.quadrature., and preferably 50 to 5.OMEGA./.quadrature..
The thickness of ITO can be arbitrarily selected according to the
resistance value, but many products having a thickness between 50
nm and 300 nm are usually used.
<Hole Injection Layer and Hole Transport Layer in Organic
Electroluminescent Element>
[0112] The hole injection layer 103 is a layer that accomplishes
the role of efficiently injecting holes that migrate from the
positive electrode 102 into the light emitting layer 105 or into
the hole transport layer 104. The hole transport layer 104 is a
layer that accomplishes the role of efficiently transporting the
holes injected from the positive electrode 102 or the holes
injected from the positive electrode 102 through the hole injection
layer 103, to the light emitting layer 105. The hole injection
layer 103 and the hole transport layer 104 are respectively formed
by laminating and mixing one kind or two or more kinds of hole
injecting/transporting materials, or by a mixture of hole
injecting/transporting materials and a polymer binder. Furthermore,
the layers may also be formed by adding an inorganic salt such as
iron(III) chloride to hole injecting/transporting materials.
[0113] A hole injecting/transporting substance needs to be capable
of efficiently injecting/transporting holes from the positive
electrode between electrodes to which an electric field is applied,
and a substance having high hole injection efficiency and being
capable of efficiently transporting injected holes is desired. For
this purpose, a substance which has low ionization potential, large
hole mobility, and excellent stability, and in which impurities
that serve as traps are not easily generated at the time of
production and at the time of use, is preferred.
[0114] Regarding the material that forms the hole injection layer
103 and the hole transport layer 104, a polycyclic aromatic
compound represented by the above general formula (1) or an
oligomer thereof can be used. Furthermore, in regard to
photoconductive material, any compound can be selected for use
among the compounds that have been conventionally used as charge
transporting materials for holes, p-type semiconductors, and known
compounds that are used in hole injection layers and hole transport
layers of organic electroluminescent elements. Specific examples
thereof include heterocyclic compounds, including carbazole
derivatives (N-phenylcarbazole, polyvinylcarbazole, and the like);
biscarbazole derivatives such as bis(N-arylcarbazole) and
bis(N-alkylcarbazole); triarylamine derivatives (a polymer having
an aromatic tertiary amino in the main chain or a side chain,
1,1-bis(4-di-p-tolylaminophenyl)cyclohexane,
N,N'-diphenyl-N,N'-di(3-methylphenyl)-4,4'-diaminobiphenyl,
N,N'-diphenyl-N,N'-dinaphthyl-4,4'-diaminobiphenyl,
N,N'-diphenyl-N,N'-di(3-methylphenyl)-4,4'-diphenyl-1,1'-di amine,
N,N'-dinaphthyl-N,N'-diphenyl-4,4'-dphenyl-1,1'-diamine,
N.sup.4,N.sup.4'-diphenyl-N.sup.4,N.sup.4'-bis(9-phenyl-9H-carbazol-3-yl)-
-[1,1'-biphenyl]-4,4'-diamine, N.sup.4,N.sup.4,
N.sup.4,N.sup.4'-tetra[1,1'-biphenyl]-4-yl)-[1,1'-biphenyl]-4,4'-diamine,
triphenylamine derivatives such as
4,4',4''-tris(3-methylphenyl(phenyl)amino)triphenylamine, starburst
amine derivatives, and the like); stilbene derivatives;
phthalocyanine derivatives (metal-free, copper phthalocyanine, and
the like); pyrazoline derivatives; hydrazone-based compounds;
benzofuran derivatives; thiophene derivatives; oxadiazole
derivatives; quinoxaline derivatives (for example,
1,4,5,8,9,12-hexaazatriphenylene-2,3,6,7,10,11-hexacarbonit rile,
and the like); and porphyrin derivatives; and polysilanes. In a
polymeric system, a polycarbonate, a styrene derivative, a
polyvinylcarbazole, a polysilane and the like, which have the
above-mentioned monomers in side chains, are preferred; however,
there are no particular limitations as long as the compound is
capable of forming a thin film that is needed for the production of
a light emitting element, injecting holes from a positive
electrode, and transporting holes.
[0115] Furthermore, it is also known that electroconductivity of an
organic semiconductor is strongly affected by doping of the
material. Such an organic semiconductor matrix substance is
composed of a compound having satisfactory electron donating
properties, or a compound having satisfactory electron accepting
properties. For the doping of electron-donating substances, there
are known strong electron acceptors such as
tetracyanoquinonedimethane (TCNQ) and
2,3,5,6-tetrafluorotetracyano-1,4-benzoquinonedimethane (F4TCNQ)
(see, for example, "M. Pfeiffer, A. Beyer, T. Fritz, K. Leo, Appl.
Phys. Lett., 73(22), 3202-3204 (1998)" and "J. Blochwitz, M.
Pfeiffer, T. Fritz, K. Leo, Appl. Phys. Lett., 73(6), 729-731
(1998)"). These compounds produce so-called holes by an electron
transfer process in an electron-donating type base substance (hole
transporting substance). Electroconductivity of the base substance
changes fairly significantly depending on the number and mobility
of the holes. Known examples of a matrix substance having hole
transporting characteristics include benzidine derivatives (TPD and
the like), starburst amine derivatives (TDATA and the like), and
particular metal phthalocyanines (particularly, zinc phthalocyanine
(ZnPc) and the like) (JP 2005-167175 A).
<Light Emitting Layer in Organic Electroluminescent
Element>
[0116] The light emitting layer 105 is a layer that is disposed
between electrodes to which an electric field is applied, and emits
light by recombining the holes injected from the positive electrode
102 and the electron injected from the negative electrode 108. The
material that forms the light emitting layer 105 may be any
compound that is excited by recombination of holes and electrons
and emits light (luminescent compound), and is preferably a
compound that can form a stable thin film shape, and exhibits
strong light emission (fluorescence) efficiency in a solid state.
In the present invention, the polycyclic aromatic compound
represented by the above general formula (1) or an oligomer thereof
can be used as the material for light emitting layer.
[0117] The light emitting layer may be any of a single layer or
plural layers, and each layer is formed by a material for light
emitting layer (a host material and a dopant material). The host
material and the dopant material may be respectively composed of a
single kind, or may be respectively a combination of plural kinds.
The dopant material may be included wholly in the host material, or
may be partially included. Regarding the doping method, the light
emitting layer can be formed by a co-deposition method with a host
material; or alternatively, a dopant material may be mixed in
advance with a host material, and then deposition may be carried
out simultaneously.
[0118] The amount of use of the host material may vary with the
kind of the host material, and the amount of use maybe determined
according to the characteristics of the host material. The
reference of the amount of use of the host material is preferably
50 to 99.999% by weight, more preferably 80 to 99.95% by weight,
and even more preferably 90 to 99.9% by weight, relative to the
total amount of the material for light emitting layer. The
polycyclic aromatic compound represented by the above general
formula (1) or an oligomer thereof can also be used as the host
material.
[0119] The amount of use of the dopant material may vary with the
kind of the dopant material, and the amount of use may be
determined according to the characteristics of the dopant material.
The reference of the amount of use of the dopant is preferably
0.001 to 50% by weight, more preferably 0.05 to 20% by weight, and
even more preferably 0.1 to 10% by weight, relative to the total
amount of the material for light emitting layer. When the amount of
use is in the range described above, for example, it is preferable
from the viewpoint that a concentration quenching phenomenon can be
prevented. The polycyclic aromatic compound represented by the
above general formula (1) or an oligomer thereof can also be used
as the dopant material.
[0120] Examples of the host material that can be used in
combination with the polycyclic aromatic compound represented by
the above general formula (1) or an oligomer thereof include fused
ring derivatives of anthracene, pyrene and the like that have been
traditionally known as luminous bodies, bisstyryl derivatives such
as bisstyrylanthracene derivatives and distyrylbenzene derivatives,
tetraphenylbutadiene derivatives, cyclopentadiene derivatives,
fluorene derivatives, and benzofluorene derivatives.
[0121] Furthermore, the dopant material that can be used in
combination with the polycyclic aromatic compound represented by
the above general formula (1) or an oligomer thereof is not
particularly limited, and existing compounds can be used. The
dopant material can be selected from various materials depending on
the desired color of emitted light. Specific examples thereof
include fused ring derivatives of phenanthrene, anthracene, pyrene,
tetracene, pentacene, perylene, naphthopyrene, dibenzopyrene,
rubrene, chrysene and the like; benzoxazole derivatives,
benzothiazole derivatives, benzimidazole derivatives, benzotriazole
derivatives, oxazole derivatives, oxadiazole derivatives, thiazole
derivatives, imidazole derivatives, thiadiazole derivatives,
triazole derivatives, pyrazoline derivatives, stilbene derivatives,
thiophene derivatives, tetraphenylbutadiene derivatives,
cyclopentadiene derivatives, bisstyryl derivatives such as
bisstyrylanthracene derivatives and distyrylbenzene derivatives (JP
1-245087 A), bisstyrylarylene derivatives (JP 2-247278 A),
diazaindacene derivatives, furan derivatives, benzofuran
derivatives; isobenzofuran derivatives such as phenylisobenzofuran,
dimesitylisobenzofuran, di(2-methylphenyl)isobenzofuran,
di(2-trifluoromethylphenyl)isobenzofuran, and phenylisobenzofuran;
dibenzofuran derivatives; coumarin derivatives such as
7-dialkylaminocoumarin derivatives, 7-piperidinocoumarin
derivatives, 7-hydroxycoumarin derivatives, 7-methoxycoumarin
derivatives, 7-acetoxycoumarin derivatives,
3-benzothiazolylcoumarin derivatives, 3-benzimidazolylcoumarin
derivatives, and 3-benzoxazolylcoumarin derivatives;
dicyanomethylenepyran derivatives, dicyanomethylenethiopyran
derivatives, polymethine derivatives, cyanine derivatives,
oxobenzoanthracene derivatives, xanthene derivatives, rhodamine
derivatives, fluorescein derivatives, pyrylium derivatives,
carbostyryl derivatives, acridine derivatives, oxazine derivatives,
phenylene oxide derivatives, quinacridone derivatives, quinazoline
derivatives, pyrrolopyridine derivatives, furopyridine derivatives,
1,2,5-thiadiazolopyrene derivatives, pyromethene derivatives,
perinone derivatives, pyrrolopyrrole derivatives, squarylium
derivatives, violanthrone derivatives, phenazine derivatives,
acridone derivatives, deazaflavine derivatives, fluorene
derivatives, and benzofluorene derivatives.
[0122] To list the examples of each of the light colors, examples
of blue to bluish green dopant materials include aromatic
hydrocarbon compounds and derivatives thereof, such as naphthalene,
anthracene, phenanthrene, pyrene, triphenylene, perylene, fluorene,
indene, and chrysene; aromatic heterocyclic compounds and
derivatives thereof, such as furan, pyrrole, thiophene, silole,
9-silafluorene, 9,9'-spirobisilafluorene, benzothiophene,
benzofuran, indole, dibenzothiophene, dibenzofuran,
imidazopyridine, phenanthroline, pyrazine, naphthyridine,
quinoxaline, pyrrolopyridine, and thioxanthene; distyrylbenzene
derivatives, tetraphenylbutadiene derivatives, stilbene
derivatives, aldazine derivatives, coumarin derivatives; azole
derivatives such as imidazole, thiazole, thiadiazole, carbazole,
oxazole, oxadiazole, and triazole, and metal complexes thereof; and
aromatic amine derivatives represented by
N,N'-diphenyl-N,N'-di(3-methylphenyl)-4,4'-diphenyl-1,1'-di
amine.
[0123] Furthermore, examples of green-yellow dopant materials
include coumarin derivatives, phthalimide derivatives,
naphthalimide derivatives, perinone derivatives, pyrrolopyrrole
derivatives, cyclopentadiene derivatives, acridone derivatives,
quinacridone derivatives, and naphthacene derivatives such as
rubrene. Furthermore, suitable examples thereof include compounds
in which substituents capable of shifting to a longer wavelength,
such as an aryl, a heteroaryl, an arylvinyl, an amino, and a cyano
are introduced to the above compounds listed as an example of blue
to bluish green dopant materials.
[0124] Furthermore, examples of orange to red dopant materials
include naphthalimide derivatives such as
bis(diisopropylphenyl)perylene tetracarboxylic acid imide; perinone
derivatives; rare earth complexes such as Eu complexes containing
acetylacetone, benzoylacetone and phenanthroline as ligands;
4-(dicyanomethylene)-2-methyl-6-(p-dimethylaminostyryl)-4H-pyran
and analogues thereof; metal phthalocyanine derivatives such as
magnesium phthalocyanine and aluminum chlorophthalocyanine;
rhodamine compounds; deazaflavine derivatives; coumarin
derivatives; quinacridone derivatives; phenoxazine derivatives;
oxazine derivatives; quinazoline derivatives; pyrrolopyridine
derivatives; squarylium derivatives; violanthrone derivatives,
phenazine derivatives; phenoxazone derivatives, and
thiadiazolopyrene derivatives. Furthermore, suitable examples
thereof include compounds in which substituents capable of shifting
to a longer wavelength, such as an aryl, a heteroaryl, an
arylvinyl, an amino, and a cyano are introduced to the above
compounds listed as an example of blue to bluish green and
green-yellow dopant materials.
[0125] In addition to them, dopants can be appropriately selected
for used from the compounds described in "Kagaku Kogyo (Chemical
Industry)", June 2004, p. 13, and reference documents described
therein.
[0126] Among the dopant materials described above, particularly an
amine having a stilbene structure, a perylene derivative, a borane
derivative, an aromatic amine derivative, a coumarin derivative, a
pyran derivative, and a pyrene derivative are preferred.
[0127] An amine having a stilbene structure is represented by the
following formula:
##STR00220##
wherein Ar.sup.1 represents an m-valent group derived from an aryl
having 6 to 30 carbon atoms; Ar.sup.2 and Ar.sup.3 each
independently represent an aryl having 6 to 30 carbon atoms, while
at least one of Ar.sup.1 to Ar.sup.3 has a stilbene structure;
Ar.sup.1 to Ar.sup.3 may be substituted; and m represents an
integer from 1 to 4.
[0128] The amine having a stilbene structure is more preferably a
diaminostilbene represented by the following formula:
##STR00221##
wherein Ar.sup.2 and Ar.sup.3 each independently represent an aryl
having 6 to 30 carbon atoms, and Ar.sup.2 and Ar.sup.3 may be
substituted.
[0129] Specific examples of the aryl having 6 to 30 carbon atoms
include benzene, naphthalene, acenaphthylene, fluorene, phenalene,
phenanthrene, anthracene, fluoranthene, triphenylene, pyrene,
chrysene, naphthacene, perylene, stilbene, distyrylbenzene,
distyrylbiphenyl, and distyrylfluorene.
[0130] Specific examples of the amine having a stilbene structure
include N,N,N',N'-tetra(4-biphenylyl)-4,4'-diaminostilbene,
N,N,N',N'-tetra(1-naphthyl)-4,4'-diaminostilbene,
N,N,N',N'-tetra(2-naphthyl)-4,4'-diaminostilbene,
N,N'-di(2-naphthyl)-N,N'-diphenyl-4,4'-diaminostilbene,
N,N'-di(9-phenanthryl)-N,N'-diphenyl-4,4'-diaminostilbene,
4,4'-bis[4''-bis(diphenylamino)styryl]-biphenyl,
1,4-bis[4'-bis(diphenylamino)styryl]-benzene,
2,7-bis[4'-bis(diphenylamino)styryl]-9,9-dimethylfluorene,
4,4'-bis(9-ethyl-3-carbazovinylene)-biphenyl, and
4,4'-bis(9-phenyl-3-carbazovinylene)-biphenyl.
[0131] Furthermore, the amines having a stilbene structure
described in JP 2003-347056 A, JP 2001-307884 A and the like may
also be used.
[0132] Examples of the perylene derivative include
3,10-bis(2,6-dimethylphenyl)perylene,
3,10-bis(2,4,6-trimethylphenyl)perylene, 3,10-diphenylperylene,
3,4-diphenylperylene, 2,5,8,11-tetra-t-butylperylene,
3,4,9,10-tetraphenylperylene,
3-(1'-pyrenyl)-8,11-di(t-butyl)perylene,
3-(9'-anthryl)-8,11-di(t-butyl)perylene, and
3,3'-bis(8,11-di(t-butyl)perylenyl).
[0133] Furthermore, the perylene derivatives described in JP
11-97178 A, JP 2000-133457 A, JP 2000-26324 A, JP 2001-267079 A, JP
2001-267078 A, JP 2001-267076 A, JP 2000-34234 A, JP 2001-267075 A,
JP 2001-217077 A and the like may also be used.
[0134] Examples of the borane derivative include
1,8-diphenyl-10-(dimesitylboryl)anthracene,
9-phenyl-10-(dimesitylboryl)anthracene,
4-(9'-anthryl)dimesitylborylnaphthalene,
4-(10'-phenyl-9'-anthryl)dimesitylboryl naphthalene,
9-(dimesitylboryl)anthracene,
9-(4'-biphenylyl)-10-(dimesitylboryl)anthracene, and
9-(4'-(N-carbazolyl)phenyl)-10-(dimesitylboryl)anthracene.
[0135] Furthermore, the borane derivatives described in WO
2000/40586 may also be used.
[0136] An aromatic amine derivative is represented by, for example,
the following formula:
##STR00222##
wherein Ar.sup.4 represents an n-valent group derived from an aryl
having 6 to 30 carbon atoms; Ar.sup.5 and Ar.sup.6 each
independently represent an aryl having 6 to 30 carbon atoms, while
Ar.sup.4 to Ar.sup.6 may be substituted; and n represents an
integer from 1 to 4.
[0137] Particularly, an aromatic amine derivative in which Ar.sup.4
represents a divalent group derived from anthracene, chrysene,
fluorene, benzofluorene or pyrene; Ar.sup.5 and Ar.sup.6 each
independently represent an aryl having 6 to 30 carbon atoms;
Ar.sup.4 to Ar.sup.6 may be substituted; and n represents 2, is
more preferred.
[0138] Specific examples of the aryl having 6 to 30 carbon atoms
include benzene, naphthalene, acenaphthylene, fluorene phenalene,
phenanthrene, anthracene, fluoranthene, triphenylene, pyrene,
chrysene, naphthacene, perylene, and pentacene.
[0139] Examples of chrysene-based aromatic amine derivatives
include N,N,N',N'-tetraphenylchrysene-6,12-diamine,
N,N,N',N'-tetra(p-tolyl)chrysene-6,12-diamine,
N,N,N',N'-tetra(m-tolyl)chrysene-6,12-diamine,
N,N,N',N'-tetrakis(4-isopropylphenyl)chrysene-6,12-diamine,
N,N,N',N'-tetra(naphthalen-2-yl)chrysene-6,12-dimine,
N,N'-diphenyl-N,N'-di(p-tolyl)chrysene-6,12-diamine,
N,N'-diphenyl-N,N'-bis(4-ethylphenyl)chrysene-6,12-diamine,
N,N'-diphenyl-N,N'-bis(4-isopropylphenyl)chrysene-6,12-diam ine,
N,N'-diphenyl-N,N'-bis(4-t-butylphenyl)chrysene-6,12-diamin e, and
N,N'-bis(4-isopropylphenyl)-N,N'-di(p-tolyl)chrysene-6,12-d
iamine.
[0140] Furthermore, examples of pyrene-based aromatic diamine
derivatives include N,N,N',N'-tetraphenylpyrene-1,6-diamine,
N,N,N',N'-tetra(p-tolyl)pyrene-1,6-diamine,
N,N,N',N'-tetra(m-tolyl)pyrene-1,6-diamine,
N,N,N',N'-tetrakis(4-isopropyophenyl)pyrene-1,6-diamine,
N,N,N',N'-tetrakis(3,4-dimethylphenyl)pyrene-1,6-diamine,
N,N'-diphenyl-N,N'-di(p-tolyl)pyrene-1,6-diamine,
N,N'-diphenyl-N,N'-bis(4-ethylphenyl)pyrene-1,6-diamine,
N,N'-diphenyl-N,N'-bis(4-isopropylphenyl)pyrene-1,6-diamine,
N,N'-diphenyl-N,N'-bis(4-t-butylphenyl)pyrene-1,6-diamine,
N,N'-bis(4-isopropylphenyl)-N,N'-di(p-tolyl)pyrene-1,6-diam ine,
and
N,N,N',N'-tetrakis(3,4-dimethylphenyl)-3,8-diphenylpyrene-1,6-diamine.
[0141] Furthermore, examples of anthracene-based aromatic amine
derivatives include N,N,N,N-tetraphenylanthracene-9,10-diamine,
N,N,N',N'-tetra(p-tolyl)anthracene-9,10-diamine,
N,N,N',N'-tetra(m-tolyl)anthracene-9,10-diamine,
N,N,N',N'-tetrakis(4-isopropylphenyl)anthracene-9,10-diamin e,
N,N'-diphenyl-N,N'-di(p-tolyl)anthracene-9,10-diamine,
N,N'-diphenyl-N,N'-di(m-tolyl)anthracene-9,10-diamine,
N,N'-diphenyl-N,N'-bis(4-ethylphenyl)anthracene-9,10-diamin e,
N,N'-diphenyl-N,N'-bis(4-isopropylphenyl)anthracene-9,10-di amine,
N,N'-diphenyl-N,N'-bis(4-t-butylphenyl)anthracene-9,10-diam ine,
N,N'-bis(4-isopropylphenyl)-N,N'-di(p-tolyl)anthracene-9,10-diamine,
2,6-di-t-butyl-N,N,N',N'-tetra(p-tolyl)anthracene-9,10-diam ine,
2,6-di-t-butyl-N,N'-diphenyl-N,N'-bis(4-isopropylphenyl)ant
hracene-9,10-diamine,
2,6-di-t-butyl-N,N'-bis(4-isopropylphenyl)-N,N'-di(p-tolyl)
anthracene-9,10-diamine,
2,6-dicyclohexyl-N,N'-bis(4-isopropylphenyl)-N,N'-di(p-toly
l)anthracene-9,10-diamine,
2,6-dicyclohexyl-N,N'-bis(4-isopropylphenyl)-N,N'-bis(4-t-b
utylphenyl)anthracene-9,10-diamine,
9,10-bis(4-diphenylaminophenyl)anthracene-9,10-bis(4-di(1-n
aphthylamino)phenyl)anthracene,
9,10-bis(4-di(2-naphthylamino)phenyl)anthracene,
10-di-p-tolylamino-9-(4-di-p-tolylamino-1-naphthyl)anthrace ne,
10-diphenylamino-9-(4-diphenylamino-1-naphthyl)anthracene, and
10-diphenylamino-9-(6-diphenylamino-2-naphthyl)anthracene.
[0142] Furthermore, examples of pyrene-based aromatic amine
derivatives include N,N,N,N-tetraphenyl-1,8-pyrene-1,6-diamine,
N-biphenyl-4-yl-N-biphenyl-1,8-pyrene-1,6-diamine, and
N.sup.1,N.sup.6-diphenyl-N',N.sup.6-bis(4-trimethylsilanyl-phenyl)-1H,8H--
py rene-1,6-diamine.
[0143] Furthermore, other examples include
[4-(4-diphenylaminophenyl)naphthalene-1-yl]-diphenylamine,
[6-(4-diphenylaminophenyl)naphthalen-2-yl]-diphenylamine,
4,4'-bis[4-diphenylaminonaphthalen-1-yl]biphenyl,
4,4'-bis[6-diphenylaminonaphthalen-2-yl]biphenyl,
4,4''-bis[4-diphenylaminonaphthalen-1-yl]-p-terphenyl, and
4,4''-bis[6-diphenylaminonaphthalen-2-yl]-p-terphenyl.
[0144] Furthermore, the aromatic amine derivatives described in JP
2006-156888 A and the like may also be used.
[0145] Examples of the coumarin derivatives include coumain-6 and
coumarin-334.
[0146] Furthermore, the coumarin derivatives described in JP
2004-43646 A, JP 2001-76876 A, JP 6-298758 A and the like may also
be used.
[0147] Examples of the pyran derivatives include DCM and DCJTB
described below.
##STR00223##
[0148] Furthermore, the pyran derivatives described in JP
2005-126399 A, JP 2005-097283 A, JP 2002-234892 A, JP 2001-220577
A, JP 2001-081090 A, JP 2001-052869 A, and the like may also be
used.
<Electron Injection Layer and Electron Transport Layer in
Organic Electroluminescent Element>
[0149] The electron injection layer 107 is a layer that
accomplishes the role of efficiently injecting the electrons
migrating from the negative electrode 108 into the light emitting
layer 105 or the electron transport layer 106. The electron
transport layer 106 is a layer that accomplishes the role of
efficiently transporting the electrons injected from the negative
electrode 108, or the electrons injected from the negative
electrode 108 through the electron injection layer 107, to the
light emitting layer 105. The electron transport layer 106 and the
electron injection layer 107 are respectively formed by laminating
and mixing one kind or two or more kinds of electron
transporting/injecting materials, or by a mixture of an electron
transporting/injecting material and a polymeric binder.
[0150] An electron injection/transport layer is a layer that
manages injection of electrons from the negative electrode and
transport of electrons, and is preferably a layer that has high
electron injection efficiency and is capable of efficiently
transporting injected electrons. In order to do so, a substance
which has high electron affinity, large electron mobility, and
excellent stability, and in which impurities that serve as traps
are not easily generated at the time of production and at the time
of use, is preferred. However, when the transport balance between
holes and electrons is considered, in a case in which the electron
injection/transport layer mainly accomplishes the role of
efficiently preventing holes coming from the positive electrode
from flowing toward the negative electrode side without being
recombined, even if the electron transporting ability is not so
high, the effect of enhancing the light emission efficiency is
equal to that of a material having high electron transporting
ability. Therefore, the electron injection/transport layer
according to the present exemplary embodiment may also include the
function of a layer that can efficiently prevent migration of
holes.
[0151] As the material that forms the electron transport layer 106
or the electron injection layer 107 (electron transporting
material), the polycyclic aromatic compound represented by the
above general formula (1) or an oligomer thereof can be used.
Furthermore, the material can be arbitrarily selected for use from
compounds that have been conventionally used as electron
transferring compounds in photoconducting materials, and known
compounds that are used in electron injection layers and electron
transport layers of organic electroluminescent elements.
[0152] Regarding the material that is used in the electron
transport layer or electron injection layer, it is preferable that
the material includes at least one selected from compounds formed
from aromatic rings or heteroaromatic rings composed of one or more
kinds of atoms selected from carbon, hydrogen, oxygen, sulfur,
silicon and phosphorus; pyrrole derivatives and fused ring
derivatives thereof; and metal complexes having electron-accepting
nitrogen. Specific examples thereof include fused ring-based
aromatic ring derivatives such as naphthalene and anthracene;
styryl-based aromatic ring derivatives represented by
4,4'-bis(diphenylethenyl)biphenyl; perinone derivatives; coumarin
derivatives; naphthalimide derivatives; quinone derivatives such as
anthraquinone and diphenoquinone; phosphorus oxide derivatives;
carbazole derivatives; and indole derivatives. Examples of a metal
complex having electron-accepting nitrogen include hydroxyazole
complexes such as hydroxyphenyloxazole complexes, azomethine
complexes, tropolone-metal complexes, flavonol-metal complexes, and
benzoquinoline-metal complexes. These materials are used singly,
but may also be used as mixtures with other materials.
[0153] Furthermore, specific examples of other electron
transferring compounds include pyridine derivatives, naphthalene
derivatives, anthracene derivatives, phenanthroline derivatives,
perinone derivatives, coumarin derivatives, naphthalimide
derivatives, anthraquinone derivatives, diphenoquinone derivatives,
diphenylquinone derivatives, perylene derivatives, oxadiazole
derivatives (1,3-bis[(4-t-butylphenyl)-1,3,4-oxadiazolyl]phenylene,
and the like), thiophene derivatives, triazole derivatives
(N-naphthyl-2,5-diphenyl-1,3,4-triazole, and the like), thiadiazole
derivatives, metal complexes of oxine derivatives, quinolinol-based
metal complexes, quinoxaline derivatives, polymers of quinoxaline
derivatives, benzazole compounds, gallium complexes, pyrazole
derivatives, perfluorinated phenylene derivatives, triazine
derivatives, pyrazine derivatives, benzoquinoline derivatives
(2,2'-bis(benzo[h]quinolin-2-yl)-9,9'-spirobifluorene, and the
like), imidazopyridine derivatives, borane derivatives,
benzimidazole derivatives (tris(N-phenylbenzimidazol-2-yl)benzene,
and the like), benzoxazole derivatives, benzothiazole derivatives,
quinoline derivatives, oligopyridine derivatives such as
terpyridine, bipyridine derivatives, terpyridine derivatives
(1,3-bis(4'-(2,2':6'2''-terpyridinyl))benzene, and the like),
naphthyridine derivatives
(bis(1-naphthyl)-4-(1,8-naphthyridin-2-yl)phenylphosphine oxide,
and the like), aldazine derivatives, carbazole derivatives, indole
derivatives, phosphorus oxide derivatives, and bisstyryl
derivatives.
[0154] Furthermore, metal complexes having electron-accepting
nitrogen can also be used, and examples thereof include
quinolinol-based metal complexes, hydroxyazole complexes such as
hydroxyphenyloxazole complexes, azomethine complexes,
tropolone-metal complexes, flavonol-metal complexes, and
benzoquinoline-metal complexes.
[0155] The materials described above are used singly, but may also
be used as mixtures with other materials.
[0156] Among the materials described above, quinolinol-based metal
complexes, bipyridine derivatives, phenanthroline derivatives, and
borane derivatives are preferred.
[0157] A quinolinol-based metal complex is a compound represented
by the following general formula (E-1):
##STR00224##
wherein R.sup.1 to R.sup.6 each represent a hydrogen atom or a
substituent; M represents Li, Al, Ga, Be, or Zn; and n represents
an integer from 1 to 3.
[0158] Specific examples of the quinolinol-based metal complex
include 8-quinolinollithium, tris(8-quinolinolato)aluminum,
tris(4-methyl-8-quinolinolato)aluminum,
tris(5-methyl-8-quinolinolato)aluminum,
tris(3,4-dimethyl-8-quiolinolato)aluminum,
tris(4,5-dimethyl-8-quinolinolato)aluminum,
tris(4,6-dimethyl-8-quinolinolato)aluminum,
bis(2-methyl-8-quinolinolato) (phenolato)aluminum,
bis(2-methyl-8-quinolinolato) (2-methylphenolato)aluminum,
bis(2-methyl-8-quinolinolato) (3-methylphenolato)aluminum,
bis(2-methyl-8-quinolinolato) (4-methylphenolato)aluminum,
bis(2-methyl-8-quinolinolato) (2-phenylphenolato)aluminum,
bis(2-methyl-8-quinolinolato) (3-phenylphenolato)aluminum,
bis(2-methyl-8-quinolinolato) (4-phenylphenolato)aluminum,
bis(2-methyl-8-quinolinolato) (2,3-dimethylphenolato)aluminu m,
bis(2-methyl-8-quinolinolato) (2,6-dimethylphenolato)aluminu m,
bis(2-methyl-8-quinolinolato) (3,4-dimethylphenolato)aluminu m,
bis(2-methyl-8-quinolinolato) (3,5-dimethylphenolato)aluminu m,
bis(2-methyl-8-quinolinolato) (3,5-di-t-butylphenolato)alumi num,
bis(2-methyl-8-quinolinolato) (2,6-diphenylphenolato)aluminu m,
bis(2-methyl-8-quinolinolato) (2,4,6-triphenylphenolato)alum inum,
bis(2-methyl-8-quinolinolato) (2,4,6-trimethylphenolato)alum inum,
bis(2-methyl-8-quinolinolato) (2,4,5,6-tetramethylphenolato)
aluminum, bis(2-methyl-8-quinolinolato) (1-naphtholato)aluminum,
bis(2-methyl-8-quinolinolato) (2-naphtholato)aluminum,
bis(2,4-dimethyl-8-quinolinolato) (2-phenylphenolato)aluminu m,
bis(2,4-dimethyl-8-quinolinolato) (3-phenylphenolato)aluminu m,
bis(2,4-dimethyl-8-quinolinolato) (4-phenylphenolato)aluminu m,
bis(2,4-dimethyl-8-quinolinolato) (3,5-dimethylphenolato)alu minum,
bis(2,4-dimethyl-8-quinolinolato) (3,5-di-t-butylphenolato)a
luminum,
bis(2-methyl-8-quinolinolato)aluminum-.mu.-oxo-bis(2-methyl-8-quinolinola-
to)aluminum,
bis(2,4-dimethyl-8-quinolinolato)aluminum-.mu.-oxo-bis(2,4-dim
ethyl-8-quinolinolato)aluminum,
bis(2-methyl-4-ethyl-8-quinolinolato)aluminum-.mu.-oxo-bis(2-e
thyl-4-ethyl-8-quinolinolato)aluminum,
bis(2-methyl-4-methoxy-8-quinolinolato)aluminum-.mu.-oxo-bis(2-methyl-4-m-
ethoxy-8-quinolinolato)aluminum,
bis(2-methyl-5-cyano-8-quinolinolato)aluminum-.mu.-oxo-bis(2-m
ethyl-5-cyano-8-quinolinolato)aluminum,
bis(2-methyl-5-trifluoromethyl-8-quinolinolato)aluminum-.mu.-o
xo-bis(2-methy-5-trifluoromethyl-8-quiolinolato)aluminum, and
bis(10-hydroxybenzo[h]quinoline)beryllium.
[0159] A bipyridine derivative is a compound represented by the
following general formula (E-2):
##STR00225##
wherein G represents a simple linking bond or an n-valent linking
group; n represents an integer from 2 to 8; and the carbon atoms
that are not used in the pyridine-pyridine linkage or pyridine-G
linkage may be substituted.
[0160] Examples of G of the general formula (E-2) include groups
represented by the following structural formulas. Meanwhile, R's in
the following structural formulas each independently represent a
hydrogen atom, methyl, ethyl, isopropyl, cyclohexyl, phenyl,
1-naphthyl, 2-naphthyl, biphenylyl, or terphenylyl.
##STR00226## ##STR00227## ##STR00228##
[0161] Specific examples of the pyridine derivative include
2,5-bis(2,2'-pyridin-6-yl)-1,1-dimethyl-3,4-diphenylsilole,
2,5-bis(2,2'-pyridin-6-yl)-1,1-dimethyl-3,4-dimesitylsilole,
2,5-bis(2,2'-pyridin-5-yl)-1,1-dimethyl-3,4-diphenylsilole,
2,5-bis(2,2'-pyridin-5-yl)-1,1-dimethyl-3,4-dimesitylsilole,
9,10-di(2,2'-pyridin-6-yl)anthracene,
9,10-di(2,2'-pyridin-5-yl)anthracene,
9,10-di(2,3'-pyridin-6-yl)anthracene,
9,10-di(2,3'-pyridin-5-yl)anthracene,
9,10-di(2,3'-pyridin-6-yl)-2-phenylanthracene,
9,10-di(2,3'-pyridin-5-yl)-2-phenylanthracene,
9,10-di(2,2'-pyridin-6-yl)-2-phenylanthracene,
9,10-di(2,2'-pyridin-5-yl)-2-phenylanthracene,
9,10-di(2,4'-pyridin-6-yl)-2-phenylanthracene,
9,10-di(2,4'-pyridin-5-yl)-2-phenylanthracene,
9,10-di(3,4'-pyridin-6-yl)-2-phenylanthracene,
9,10-di(3,4'-pyridin-5-yl)-2-phenylanthracene,
3,4-diphenyl-2,5-di(2,2'-pyridin-6-yl)thiophene,
3,4-diphenyl-2,5-di(2,3'-pyridin-5-yl)thiophene, and,
6',6''-di(2-pyridyl)-2,2':4',4'':2'',2'''-quaterpyridine.
[0162] A phenanthroline derivative is a compound represented by the
following general formula (E-3-1) or (E-3-2):
##STR00229##
wherein R.sup.1 to R.sup.8 each represent a hydrogen atom or a
substituent; adjacent groups may be bonded to each other and form a
fused ring; G represents a simple linking bond or an n-valent
linking group; and n represents an integer from 2 to 8. Examples of
G of the general formula (E-3-2) include the same groups as those
described in the section of the bipyridine derivative.
[0163] Specific examples of the phenanthroline derivative include
4,7-diphenyl-1,10-phenanthroline,
2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline,
9,10-di(1,10-phenanthrolin-2-yl)anthracene,
2,6-di(1,10-phenanthrolin-5-yl)pyridine,
1,3,5-tri(1,10-phenanthrolin-5-yl)benzene,
9,9'-difluoro-bis(1,10-phenanthrolin-5-yl), bathocuproine, and
1,3-bis(2-phenyl-1,10-phenanthrolin-9-yl)benzene.
[0164] Particularly, the case of using a phenanthroline derivative
in an electron transport layer or an electron injection layer will
be explained. In order to obtain stable light emission over a long
time, a material having excellent thermal stability or thin film
formability is preferred, and among phenanthroline derivatives, a
phenanthroline derivative in which a substituent itself has a
three-dimensional steric structure, or the derivative has a
three-dimensional steric structure as a result of steric repulsion
between a substituent and the phenanthroline skeleton or between a
substituent and an adjacent substituent, or a phenanthroline
derivative having plural phenanthroline skeletons linked together,
is preferred. Furthermore, in the case of linking plural
phenanthroline skeletons, a compound containing conjugated bonds, a
substituted or unsubstituted aromatic hydrocarbon, or a substituted
or unsubstituted heterocyclic aromatic ring in the linked units, is
more preferred.
[0165] A borane derivative is a compound represented by the
following general formula (E-4), and specific examples are
disclosed in JP 2007-27587 A.
##STR00230##
wherein R.sup.11 and R.sup.12 each independently represent at least
one of a hydrogen atom, an alkyl, an aryl which may be substituted,
a silyl which may be substituted, a nitrogen-containing
heterocyclic ring which may be substituted, and cyano; R.sup.13 to
R.sup.16 each independently represent an alkyl which may be
substituted, or an aryl which may be substituted; X represents an
arylene which may be substituted; Y represents an aryl having 16 or
fewer carbon atoms which may be substituted, a boryl which may be
substituted, or a carbazolyl which may be substituted; and n's each
independently represent an integer from 0 to 3.
[0166] Among compounds represented by the above general formula
(E-4), compounds represented by the following general formula
(E-4-1), and compounds represented by the following general
formulas (E-4-1-1) to (E-4-1-4), are preferred. Specific examples
thereof include
9-[4-(4-dimesitylborylnaphthalen-1-yl)phenyl]carbazole and
9-[4-(4-dimesitylborylnaphthalen-1-yl)naphthalen-1-yl]carba
zole.
##STR00231##
wherein R.sup.11 and R.sup.12 each independently represent at least
one of a hydrogen atom, an alkyl, an aryl which may be substituted,
a silyl which may be substituted, a nitrogen-containing
heterocyclic ring which may be substituted, and cyano; R.sup.13 to
R.sup.16 each independently represent an alkyl which may be
substituted, or an aryl which may be substituted; R.sup.21 and
R.sup.22 each independently represent at least one of a hydrogen
atom, an alkyl, an aryl which may be substituted, a silyl which may
be substituted, a nitrogen-containing heterocyclic ring which may
be substituted, and cyano; X.sup.1 represents an arylene having 20
or fewer carbon atoms which may be substituted; n's each
independently represent an integer from 0 to 3; and m's each
independently represent an integer from 0 to 4.
##STR00232##
wherein in the respective formulas, R.sup.31 to R.sup.34 each
independently represent any one of methyl, isopropyl or phenyl; and
R.sup.35 and R.sup.36 each independently represent any one of a
hydrogen atom, methyl, isopropyl or phenyl.
[0167] Among compounds represented by the above general formula
(E-4), compounds represented by the following general formula
(E-4-2), and a compound represented by the following general
formula (E-4-2-1) are preferred.
##STR00233##
wherein R.sup.11 and R.sup.12 each independently represent at least
one of a hydrogen atom, an alkyl, an aryl which may be substituted,
a silyl which may be substituted, a nitrogen-containing
heterocyclic ring which may be substituted, and cyano; R.sup.13 to
R.sup.16 each independently represent an alkyl which may be
substituted, or an aryl which may be substituted; X.sup.1
represents an arylene having 20 or fewer carbon atoms which may be
substituted; and n's each independently represent an integer from 0
to 3.
##STR00234##
wherein R.sup.31 to R.sup.34 each independently represent any one
of methyl, isopropyl, or phenyl; and R.sup.35 and R.sup.36 each
independently represent any one of a hydrogen atom, methyl,
isopropyl, or phenyl.
[0168] Among compounds represented by the above general formula
(E-4), compounds represented by the following general formula
(E-4-3), and compounds represented by the following general
formulas (E-4-3-1) and (E-4-3-2) are preferred.
##STR00235##
wherein R.sup.11 and R.sup.12 each independently represent at least
one of a hydrogen atom, an alkyl, an aryl which may be substituted,
a silyl which may be substituted, a nitrogen-containing
heterocyclic ring which may be substituted, or cyano; R.sup.13 to
R.sup.16 each independently represent an alkyl which may be
substituted, or an aryl which may be substituted; X.sup.1
represents an arylene having 10 or fewer carbon atoms which may be
substituted; Y.sup.1 represents an aryl having 14 or fewer carbon
atoms which may be substituted; and n's each independently
represent an integer from 0 to 3.
##STR00236##
wherein R.sup.31 to R.sup.34 each independently represent any one
of methyl, isopropyl, or phenyl; and R.sup.35 and R.sup.36 each
independently represent any one of a hydrogen atom, methyl,
isopropyl, or phenyl.
[0169] A benzimidazole derivative is a compound represented by the
following general formula (E-5):
##STR00237##
wherein Ar.sup.1 to Ar.sup.3 each independently represent a
hydrogen atom or an aryl having 6 to 30 carbon atoms which may be
substituted. Particularly, a benzimidazole derivative in which
Ar.sup.1 represents an anthryl which may be substituted is
preferred.
[0170] Specific examples of the aryl having 6 to 30 carbon atoms
include phenyl, 1-naphthyl, 2-naphthyl, acenaphthylen-1-yl,
acenaphthylen-3-yl, acenaphthylen-4-yl, acenaphthylen-5-yl,
fluoren-1-yl, fluoren-2-yl, fluoren-3-yl, fluoren-4-yl,
fluoren-9-yl, phenalen-1-yl, phenalen-2-yl, 1-phenanthryl,
2-phenanthryl, 3-phenanthryl, 4-phenanthryl, 9-phenanthryl,
1-anthryl, 2-anthryl, 9-anthryl, fluoranthen-1-yl,
fluoranthen-2-yl, fluoranthen-3-yl, fluoranthen-7-yl,
fluoranthen-8-yl, triphenylen-1-yl, triphenylen-2-yl, pyren-1-yl,
pyren-2-yl, pyren-4-yl, chrysen-1-yl, chrysen-2-yl, chrysen-3-yl,
chrysen-4-yl, chrysen-5-yl, chrysen-6-yl, naphthacen-1-yl,
naphthacen-2-yl, naphthacen-5-yl, perylen-1-yl, perylen-2-yl,
perylen-3-yl, pentacen-1-yl, pentacen-2-yl, pentacen-5-yl, and
pentacen-6-yl.
[0171] Specific examples of the benzimidazole derivative include
1-phenyl-2-(4-(10-phenylanthracen-9-yl)phenyl)-1H-benzo[d]i
midazole,
2-(4-(10-(naphthalen-2-yl)anthracen-9-yl)phenyl)-1-phenyl-1H-benzo[d]imid-
azole,
2-(3-(10-(naphthalen-2-yl)anthracen-9-yl)phenyl)-1-phenyl-1H-benzo[-
d]imidazole,
5-(10-(naphthlen-2-yl)anthracen-9-yl)-1,2-diphenyl-1H-benzo
[d]imidazole,
1-(4-(10-(naphthalen-2-yl)anthracen-9-yl)phenyl)-2-phenyl-1H-benzo[d]imid-
azole, 2-(4-(9,10-di(naphthalen-2-yl)anthracen-2-yl)phenyl)-1-phen
yl-1H-benzo[d]imidazole,
1-(4-(9,10-di(naphthalen-2-yl)anthracen-2-yl)phenyl)-2-phen
yl-1H-benzo[d]imidazole, and
5-(9,10-di(naphthalen-2-yl)anthracen-2-yl)-1,2-diphenyl-1H-benzo[d]imidaz-
ole.
[0172] The electron transport layer or the electron injection layer
may further contain a substance that can reduce the material that
forms the electron transport layer or electron injection layer.
Regarding this reducing substance, various substances may be used
as long as they have reducibility to a certain extent. For example,
at least one selected from the group consisting of alkali metals,
alkaline earth metals, rare earth metals, oxides of alkali metals,
halides of alkali metals, oxides of alkaline earth metals, halides
of alkaline earth metals, oxides of rare earth metals, halides of
rare earth metals, organic complexes of alkali metals, organic
complexes of alkaline earth metals, and organic complexes of rare
earth metals, can be suitably used.
[0173] Preferred examples of the reducing substance include alkali
metals such as Na (work function 2.36 eV), K (work function 2.28
eV), Rb (work function 2.16 eV), and Cs (work function 1.95 eV);
and alkaline earth metals such as Ca (work function 2.9 eV), Sr
(work function 2.0 to 2.5 eV), and Ba (work function 2.52 eV). A
reducing substance having a work function of 2.9 eV or less is
particularly preferred. Among these, more preferred examples of the
reducing substance include alkali metals such as K, Rb and Cs; even
more preferred examples include Rb and Cs; and the most preferred
example is Cs. These alkali metals have particularly high reducing
ability, and can promote an enhancement of the emission luminance
or lengthening of the service life in organic EL elements when the
alkali metals are added in a relatively small amount to the
material that forms the electron transport layer or electron
injection layer. Furthermore, as the reducing substance having a
work function of 2.9 eV or less, a combination of two or more kinds
of these alkali metals is also preferred, and particularly, a
combination including Cs, for example, a combination of Cs with Na,
a combination of Cs with K, a combination of Cs with Rb, or a
combination of Cs with Na and K, is preferred. When Cs is
incorporated, the reducing ability can be efficiently manifested,
and an enhancement of the emission luminance or lengthening of the
service life in organic EL elements can be promoted by adding Cs to
the material that forms the electron transport layer or electron
injection layer.
<Negative Electrode in Organic Electroluminescent
Element>
[0174] The negative electrode 108 is a member that accomplishes the
role of injecting electrons to the light emitting layer 105 through
the electron injection layer 107 and the electron transport layer
106.
[0175] The material that forms the negative electrode 108 is not
particularly limited as long as it is a substance capable of
efficiently injecting electrons to an organic layer; however, the
same materials as the materials that form the positive electrode
102 can be used. Among them, preferred examples include metals such
as tin, indium, calcium, aluminum, silver, copper, nickel,
chromium, gold, platinum, iron, zinc, lithium, sodium, potassium,
cesium and magnesium, and alloys thereof (a magnesium-silver alloy,
a magnesium-indium alloy, an aluminum-lithium alloy such as lithium
fluoride/aluminum, and the like). In order to enhance the element
characteristics by increasing the electron injection efficiency,
lithium, sodium, potassium, cesium, calcium, magnesium, or alloys
thereof containing low work function-metals are effective. However,
many of these low work function-metals are generally unstable in
air. In order to ameliorate this, for example, a method of using an
electrode having high stability obtained by doping a trace amount
of lithium, cesium or magnesium to an organic layer, is known.
Other examples of the dopant that can be used include inorganic
salts such as lithium fluoride, cesium fluoride, lithium oxide, and
cesium oxide. However, the present invention is not intended to be
limited to these.
[0176] Furthermore, in order to protect the electrode, a metal such
as platinum, gold, silver, copper, iron, tin, aluminum or indium;
an alloy using these metals; an inorganic substance such as silica,
titania or silicon nitride; polyvinyl alcohol, vinyl chloride, a
hydrocarbon-based polymer compound; or the like may be laminated
thereon according to a preferred embodiment. The method for
producing these electrodes is not particularly limited as long as
the method is capable of conduction, such as resistance heating,
electron beam, sputtering, ion plating and coating.
<Binder that May be Used in Various Layers>
[0177] The materials used in the above-described hole injection
layer, hole transport layer, light emitting layer, electron
transport layer, and electron injection layer can form the various
layers by being used singly; however, it is also possible to use
the materials after dispersing them in a solvent-soluble resin such
as polyvinyl chloride, polycarbonate, polystyrene,
poly(N-vinylcarbazole), polymethyl methacrylate, polybutyl
methacrylate, polyester, polysulfone, polyphenylene oxide,
polybutadiene, a hydrocarbon resin, a ketone resin, a phenoxy
resin, polyamide, ethyl cellulose, a vinyl acetate resin, an ABS
resin, or a polyurethane resin; or a curable resin such as a
phenolic resin, a xylene resin, a petroleum resin, a urea resin, a
melamine resin, an unsaturated polyester resin, an alkyd resin, an
epoxy resin, or a silicone resin.
<Method for Producing Organic Electroluminescent Element>
[0178] The various layers that constitute an organic
electroluminescent element can be formed by forming thin films of
the materials that will constitute the various layers, by methods
such as a vapor deposition method, resistance heating deposition,
electron beam deposition, sputtering, a molecular lamination
method, a printing method, a spin coating method, a casting method,
and a coating method. There are no particular limitations on the
film thickness of the various layers thus formed, and the film
thickness can be appropriately set depending on the properties of
the material, but the film thickness is usually in the range of 2
nm to 5000 nm. The film thickness can be usually measured using a
crystal oscillation type film thickness analyzer or the like. In
the case of forming a thin film using a vapor deposition method,
the deposition conditions vary with the kind of the material, the
intended crystal structure and association structure of the film,
and the like. It is preferable to appropriately set the vapor
deposition conditions generally in the ranges of a boat heating
temperature of +50.degree. C. to +400.degree. C., a degree of
vacuum of 10.sup.-6 to 10.sup.-3 Pa, a rate of deposition of 0.01
to 50 nm/second, a substrate temperature of -150.degree. C. to
+300.degree. C., and a film thickness of 2 nm to 5 .mu.m.
[0179] Next, a method for producing an organic electroluminescent
element configured to include positive electrode/hole injection
layer/hole transport layer/light emitting layer formed from a host
material and a dopant material/electron transport layer/electron
injection layer/negative electrode, is explained as an example of
the method for producing an organic electroluminescent element. On
an appropriate substrate, a positive electrode is produced by
forming a thin film of a positive electrode material by a vapor
deposition method or the like, and then thin films of a hole
injection layer and a hole transport layer are formed on this
positive electrode. A thin film is formed thereon by co-depositing
a host material and a dopant material, and thereby a light emitting
layer is obtained. An electron transport layer and an electron
injection layer are formed on this light emitting layer, and a thin
film formed from a substance for negative electrode is formed by a
vapor deposition method or the like as a negative electrode.
Thereby, an intended organic electroluminescent element is
obtained. Furthermore, in regard to the production of the organic
electroluminescent element described above, it is also possible to
produce the element by reversing the order of production, that is,
in the order of a negative electrode, an electron injection layer,
an electron transport layer, a light emitting layer, a hole
transport layer, a hole injection layer, and a positive
electrode.
[0180] In a case in which a direct current voltage is applied to an
organic electroluminescent element obtained in this manner, it is
desirable to apply the positive polarity to the positive electrode
and the negative polarity to the negative electrode, and when a
voltage of 2 to 40 V is applied, light emission can be observed
from a transparent or semitransparent electrode side (the positive
electrode or the negative electrode, or both). Also, this organic
electroluminescent element also emits light even when a pulse
current or an alternating current is applied. The waveform of the
alternating current applied may be any waveform.
<Application Examples of Organic Electroluminescent
Element>
[0181] Furthermore, the present invention can also be applied to a
display apparatus including an organic electroluminescent element,
or a lighting apparatus including an organic electroluminescent
element.
[0182] A display apparatus or lighting apparatus including an
organic electroluminescent element can be produced according to a
known method such as connecting the organic electroluminescent
element according to the present exemplary embodiment and a known
driving apparatus. The organic electroluminescent element can be
driven by appropriately using a known driving method such as direct
current driving, pulse driving or alternating current driving.
[0183] Examples of the display apparatus include panel displays
such as color flat panel displays; and flexible displays such as
flexible organic electroluminescent (EL) displays (see, for
example, JP 10-335066 A, JP 2003-321546 A, JP 2004-281086 A, and
the like). Furthermore, the display mode of the display may be, for
example, a matrix and/or segment mode. Meanwhile, the matrix
display and the segment display may co-exist in the same panel.
[0184] A matrix refers to a system in which pixels for display are
arranged two-dimensionally as in a lattice form or a mosaic form,
and characters or images are displayed by collections of pixels.
The shape or size of the pixel is determined according to the use.
For example, in the display of images and characters of personal
computers, monitors and televisions, square pixels each having a
size of 300 m or less on each side are usually used, and in the
case of large-sized displays such as display panels, pixels having
a size in the order of millimeters on each side are used. In the
case of monochromic display, it is desirable to arrange pixels of
the same color; however, in the case of color display, display is
achieved by arranging pixels of red, green and blue colors. In this
case, typically, there are available delta type displays and stripe
type displays. Regarding this matrix driving method, any of a line
sequential driving method or an active matrix method may be
employed. Line sequential driving has an advantage of having a
simpler structure; however, there are occasions in which the active
matrix method is superior when the operation characteristics are
taken into consideration. Therefore, it is necessary to use the
driving method appropriately according to the use.
[0185] In the segment mode (type), a pattern is formed so as to
display predetermined information, and the determined regions are
induced to emit light. Examples thereof include the display of time
or temperature in a digital clock or a digital thermometer, the
display of the state of operation in an audio instrument or an
electronic cooker, and the panel display in an automobile.
[0186] Examples of the lighting apparatus include the light
apparatuses for indoor lighting or the like, and the backlight of a
liquid crystal display apparatus (see, for example, JP 2003-257621
A, JP 2003-277741 A, and JP 2004-119211 A). A backlight is mainly
used for the purpose of enhancing visibility of a display apparatus
that is not self-luminous, and is used in liquid crystal display
apparatuses, timepieces, audio apparatuses, automotive panels,
display panels, signs, and the like. Particularly, regarding the
backlight for the use in liquid crystal display apparatuses, among
others, for the use in personal computers where thickness reduction
has been a problem to be solved, when it is considered that
thickness reduction is difficult because the backlights of
conventional types are constructed from fluorescent lamps or light
waveguides, a backlight employing the luminescent element according
to the present exemplary embodiment is characterized by its
thinness and lightweightness.
4. Other Organic Devices
[0187] The polycyclic aromatic compound according to the present
invention and an oligomer thereof can be used in the production of
an organic field effect transistor, an organic thin film solar cell
or the like, in addition to the organic electroluminescent element
described above.
[0188] An organic field effect transistor is a transistor that
controls the electric current by means of an electric field
generated by voltage input, and is provided with a source
electrode, a drain electrode, and a gate electrode. When a voltage
is applied to the gate electrode, an electric field is generated,
and the field effect transistor can control the electric current by
arbitrarily damming the flow of electrons (or holes) that flow
between the source electrode and the drain electrode. The field
effect transistor can be easily miniaturized compared with simple
transistors (bipolar transistors), and can be effectively used as
elements that constitute an integrated circuit or the like.
[0189] The structure of an organic field effect transistor is
usually such that a source electrode and a drain electrode are
provided in contact with an organic semiconductor active layer that
is formed using the polycyclic aromatic compound according to the
present invention and an oligomer thereof, and it is desirable if a
gate electrode is provided so as to interpose an insulating layer
(dielectric layer) that is in contact with the organic
semiconductor active layer. Examples of the element structure
include the following structures.
[0190] (1) Substrate/gate electrode/insulator layer/source
elctrode.drain electrode/organic semiconductor active layer
[0191] (2) Substrate/gate electrode/insulator layer/organic
semiconductor active layer/source electrode.drain electrode
[0192] (3) Substrate/organic semiconductor active layer/source
electrode.drain electrode/insulator layer/gate electrode
[0193] (4) Substrate/source electrode.drain electrode/organic
semiconductor active layer/insulator layer/gate electrode.
[0194] An organic field effect transistor configured as such can be
applied as a pixel driving switching element of a liquid crystal
display or organic electroluminescent display of active
matrix-driven type, or the like.
[0195] An organic thin film solar cell has a structure in which a
positive electrode such as ITO, a hole transport layer, a
photoelectric conversion layer, an electron transport layer, and a
negative electrode are laminated on a transparent substrate of
glass or the like. The photoelectric conversion layer has a p-type
semiconductor layer on the positive electrode side, and has an
n-type semiconductor layer on the negative electrode side. The
polycyclic aromatic compound according to the present invention and
an oligomer thereof can be used as the materials of a hole
transport layer, a p-type semiconductor layer, an n-type
semiconductor layer, or an electron transport layer, depending on
the properties. The polycyclic aromatic compound according to the
present invention and an oligomer thereof can function as a hole
transporting material or an electron transporting material in an
organic thin film solar cell. The organic thin film solar cell may
appropriately include a hole blocking layer, an electron blocking
layer, an electron injection layer, a hole injection layer, a
smoothing layer and the like, in addition to the members described
above. In the organic thin film solar cell, existing materials that
are conventionally used in organic thin film solar cells can be
appropriately selected and used in combination.
EXAMPLES
[0196] Hereinafter, the present invention will be explained more
specifically by way of Examples, but the present invention is not
intended to be limited to these. First, Synthesis Examples of
polycyclic aromatic compounds are described below.
Synthesis Example (1)
Synthesis of 5,9-dioxa-13b-boranaphtho[3,2,1-de]anthracene
##STR00238##
[0198] First, a 1.6 M n-butyllithium hexane solution (0.75 ml) was
introduced at 0.degree. C. into a flask containing diphenoxybenzene
(0.26 g) and ortho-xylene (3.0 ml) in a nitrogen atmosphere. After
the contents were stirred for 30 minutes, the temperature was
increased to 70.degree. C., and the mixture was further stirred for
4 hours. Hexane was distilled off by heating and stirring the
mixture at 100.degree. C. under a nitrogen gas stream, and then the
mixture was cooled to -20.degree. C. Boron tribromide (0.114 ml)
was added thereto, and the mixture was stirred for one hour. The
temperature of the mixture was raised to room temperature, the
mixture was stirred for one hour, subsequently
N,N-diisopropylethylamine (0.342 ml) was added thereto, and the
resulting mixture was heated and stirred at 120.degree. C. for 5
hours. Thereafter, N,N-diisopropylethylamine (0.171 ml) was added
thereto, and the mixture was filtered using a Florisil short pass
column. The solvent was distilled off under reduced pressure, and
thus a crude purification product was obtained. The crude product
was washed using methanol, and thus a compound (0.121 g)
represented by formula (1-1) was obtained as a white solid.
##STR00239##
[0199] The structure of the compound thus obtained was identified
by an NMR analysis.
[0200] .sup.1H-NMR (400 MHz, CDCl.sub.3): .delta.=8.69 (dd, 2H),
7.79 (t, 1H), 7.70 (ddd, 2H), 7.54 (dt, 2H), 7.38 (ddd, 2H), 7.22
(d, 2H).
Synthesis Example (2)
Synthesis of 15b-bora-5,9-dioxaphenanthro[1,2,3-ij]tetraphene
##STR00240##
[0202] First, 1-bromonaphthalene (0.154 ml) was introduced into a
flask containing copper(I) iodide (19.7 mg), .alpha.-picolinic acid
(26.2 mg), potassium phosphate (0.429 g), resorcinol (57.5 mg) and
dimethyl sulfoxide (2.0 ml), at room temperature in a nitrogen
atmosphere. The contents were heated and stirred for 33.5 hours at
90.degree. C., 1 Normal aqueous ammonia (3.0 ml) was subsequently
added thereto at room temperature, and the aqueous layer was
extracted three times with toluene. Subsequently, the solvent was
distilled off under reduced pressure. A solid thus obtained was
purified by silica gel column chromatography (developing liquid:
toluene), and thus 1,3-bis(1-naphthyloxy)benzene (0.155 g) was
obtained as a white solid.
##STR00241##
[0203] A 1.6 M n-butyllithiumhexane solution (9.0 ml) was added
dropwise to a flask containing 1,3-bis(1-naphthyloxy)benzene (4.45
g) and ortho-xylene (36 ml), at 0.degree. C. in a nitrogen
atmosphere. The temperature was increased to 70.degree. C., and the
contents were stirred for 4 hours. Subsequently, the temperature
was increased to 100.degree. C., and hexane was distilled off. The
residue was cooled to 0.degree. C., boron tribromide (1.37 ml) was
added thereto, and the mixture was stirred for 2 hours.
Subsequently, the temperature of the mixture was increased to room
temperature, and the mixture was stirred for 12 hours. The mixture
as cooled again to 0.degree. C., N,N-diisopropylethylamine (6.16
ml) was added thereto, subsequently the temperature of the mixture
was increased to 120.degree. C., and the mixture was stirred for 8
hours. N,N-diisopropylethylamine (3.08 ml) was added to the mixture
at 0.degree. C., and then the mixture was filtered using a Florisil
short pass column. The solvent was distilled off under reduced
pressure, and thus a crude product was obtained. The crude product
was washed using methanol and acetonitrile, and thereby a compound
(0.405 g) represented by formula (1-2) was obtained as white
solid.
##STR00242##
[0204] The structure of the compound thus obtained was identified
by an NMR analysis.
[0205] .sup.1H-NMR (400 MHz, CDCl.sub.3): .delta.=8.82-8.85 (m,
2H), 8.71 (d, 2H), 7.94-7.97 (m, 2H), 7.89 (t, 1H), 7.78 (d, 2H),
7.66-7.71 (m, 4H), 7.48 (d, 2H).
Synthesis Example (3)
Synthesis of
2,12-diphenyl-5,9-dioxa-13b-boranaphtho[3,2,1-de]anthracene
##STR00243##
[0207] Copper(I) iodide (1.0 g) and iron(III) acetylacetonate (3.7
g) were added to an NMP (120 ml) solution of 1,3-dibromobenzene (25
g), [1,1'-biphenyl]-4-ol (39.7 g) and potassium carbonate (58.6 g)
in a nitrogen atmosphere, the temperature of the mixture was
increased to 150.degree. C., and the mixture was stirred for 4
hours. The reaction liquid was cooled to room temperature, and a
salt precipitated by adding ethyl acetate and aqueous ammonia
thereto was removed by suction filtration using a Hirsch funnel
covered with Celite. The filtrate was partitioned, and the solvent
of the organic layer was distilled off under reduced pressure.
Subsequently, the residue was dissolved in ethyl acetate, and the
residue was reprecipitated by adding heptane thereto. The
precipitate was further passed through a silica gel short pass
column (developing liquid: heated chlorobenzene), and a solid
obtained by distilling off the solvent under reduced pressure was
reprecipitated from ethyl acetate/heptane. Thus,
1,3-bis([1,1'-biphenyl]-4-yloxy)benzene (33.0 g) was obtained.
##STR00244##
[0208] A 2.6 M n-butyllithium hexane solution (29.2 ml) was
introduced into a flask containing
1,3-bis([1,1'-biphenyl]-4-yloxy)benzene (30.0 g) and ortho-xylene
(500 ml), at 0.degree. C. in a nitrogen atmosphere. After
completion of dropwise addition, the temperature of the mixture was
increased to 70.degree. C., and the mixture was stirred for one
hour. The temperature of the mixture was further increased to
100.degree. C., andhexanewas distilled off. The mixture was stirred
overnight at room temperature, and then the mixture was cooled to
-30.degree. C. Boron tribromide (8.4 ml) was added thereto, the
temperature of the mixture was increased to room temperature, and
the mixture was stirred for one hour. Thereafter, the mixture was
cooled to 0.degree. C. again, N,N-diisopropylethylamine (25.0 ml)
was added thereto, and the mixture was stirred at room temperature
until heat generation was settled, and then was heated and stirred
for 4 hours at 120.degree. C. The reaction liquid was cooled to
room temperature, and crystals thus precipitated were collected by
suction filtration and washed with an aqueous solution of sodium
acetate. Furthermore, the crystals were washed with heptane, ethyl
acetate and methanol in this order, and thereby a compound (16.6 g)
represented by formula (1-151) was obtained.
##STR00245##
[0209] The structure of a compound thus obtained was identified by
an NMR analysis.
[0210] .sup.1H-NMR (400 MHz, CDCl.sub.3): .delta.=8.96 (m, 2H),
7.97 (dd, 2H), 7.83 (t, 1H), 7.74 (m, 4H), 7.64 (d, 2H), 7.51 (t,
4H), 7.40 (t, 2H), 7.28 (d, 2H).
Synthesis Example (4)
Synthesis of
6,8-diphenyl-5,9-dioxa-13b-boranaphtho[3,2,1-de]anthracene
##STR00246##
[0212] A flask containing 1,5-dibromo-2,4-difluorobenzene (30.0 g),
phenol (31.2 g), potassium carbonate (45.7 g) and NMP (150 ml) was
heated with stirring at 160.degree. C. The reaction liquid was
cooled to room temperature, and NMP was distilled off under reduced
pressure. Subsequently, water and toluene were added thereto, and
the reaction liquid was partitioned. The solvent was distilled off
under reduced pressure, and then the residue was purified using a
silica gel short pass column (developing liquid: heptane/toluene=1
(volume ratio)). Thus,
((4,6-dibromo-1,3-phenylene)bis(oxy))dibenzene (44.0 g) was
obtained.
##STR00247##
[0213] In a nitrogen atmosphere, Pd(PPh.sub.3).sub.4 (5.5 g) was
added to a suspension solution of
((4,6-dibromo-1,3-phenylene)bis(oxy))dibenzene (40.0 g),
phenylboronic acid (34.8 g), sodium carbonate (60.6 g), toluene
(500 ml), isopropanol (100 ml) and water (100 ml), and the mixture
was stirred for 8 hours at the reflux temperature. The reaction
liquid was cooled to room temperature, water and toluene were added
thereto, and then the mixture was partitioned. The solvent of the
organic layer was distilled off under reduced pressure. A solid
thus obtained was dissolved in heated chlorobenzene, and the
solution was passed through a silica gel short pass column
(developing liquid: toluene). An appropriate amount of the solvent
was distilled off, and then reprecipitation was carried out by
adding heptane to the residue. Thus,
4',6'-diphenoxy-1,1':3',1''-terphenyl (41.0 g) was obtained.
##STR00248##
[0214] A 2.6 M n-butyllithium hexane solution (29.0 ml) was
introduced into a flask containing
4',6'-diphenoxy-1,1':3',1''-terphenyl (30.0 g) and ortho-xylene
(300 ml), at 0.degree. C. in a nitrogen atmosphere. After
completion of dropwise addition, the temperature of the mixture was
increased to 70.degree. C., and the mixture was stirred for 4
hours. The temperature of the mixture was further increased to
100.degree. C., and hexane was distilled off. The mixture was
cooled to -50.degree. C., and boron tribromide (8.4 ml) was added
thereto. The temperature of the mixture was increased to room
temperature, and the mixture was stirred for one hour. Thereafter,
the mixture was cooled again to 0.degree. C.,
N,N-diisopropylethylamine (25.0 ml) was added thereto, and the
mixture was stirred at room temperature until heat generation was
settled, and then was heated and stirred for 4 hours at 120.degree.
C. The reaction liquid was cooled to room temperature, and an
organic material was extracted with toluene. Water was added to the
toluene solution thus obtained, the mixture was partitioned, and
the solvent was distilled off under reduced pressure. A solid thus
obtained was dissolved in chlorobenzene, subsequently an
appropriate amount was distilled off under reduced pressure, and
reprecipitation was carried out by adding heptane thereto.
Reprecipitation was further carried out in the same manner except
that heptane was replaced with ethyl acetate. Thus, a compound (4.2
g) represented by formula (1-91) was obtained.
##STR00249##
[0215] The structure of the compound thus obtained was identified
by an NMR analysis.
[0216] .sup.1H-NMR (400 MHz, CDCl.sub.3): .delta.=8.74 (d, 2H),
8.00 (s, 1H), 7.81 (d, 4H), 7.69 (t, 2H), 7.54 (t, 4H), 7.49 (m,
2H), 7.37-7.46 (m, 4H).
Synthesis Example (5)
Synthesis of
6,8-di(9H-carbazol-9-yl)-5,9-dioxa-13b-boranaphtho[3,2,1-de]anthracene
##STR00250##
[0218] In a nitrogen atmosphere, a solution of
1,5-dibromo-2,4-difluorobenzene (600.0 g), carbazole (81.1 g),
potassium carbonate (91.0 g) and NMP (300 ml) was heated to
155.degree. C., and the mixture was stirred for 4 hours. The
reaction liquid was cooled to room temperature, water was added
thereto to dissolve inorganic salts, and an organic material was
collected by suction filtration. The organic material was washed
with ethyl acetate, and then was dissolved in heated
ortho-dichlorobenzene. The solution was passed through a silica gel
short pass column (developing liquid: ortho-dichlorobenzene). The
solvent was distilled off under reduced pressure, and then the
residue was further washed with ethyl acetate. Thus,
9,9'-(4,6-dibromo-1,3-phenylene)bis(9H-carbazole) (108.0 g) was
obtained.
##STR00251##
[0219] Copper(I) iodide (0.84 g) and iron(III) acetylacetonate (3.1
g) were added to an NMP (200 ml) solution of
9,9'-(4,6-dibromo-1,3-phenylene)bis(9H-carbazole) (50.0 g), phenol
(10.0 g) and potassium carbonate (49.0 g) in a nitrogen atmosphere,
and the temperature of the mixture was increased to 150.degree. C.
The mixture was stirred for 4 hours. The reaction liquid was cooled
to room temperature, ethyl acetate and aqueous ammonia were added
thereto, and then the mixture was partitioned. The solvent of the
organic layer was distilled off under reduced pressure.
Subsequently, the residue was purified by silica gel column
chromatography (developing liquid: toluene/heptane=1 (volume
ratio)), and then a solid obtained by distilling off the solvent
under reduced pressure was washed with heptane. Thus,
9,9'-(4,6-diphenoxy-1,3-phenylene)bis(9H-carbazole) (16.8 g) was
obtained.
##STR00252##
[0220] A 2.6 M n-butyllithium hexane solution (11.2 ml) was
introduced into a flask containing
9,9'-(4,6-diphenoxy-1,3-phenylene)bis(9H-carbazole) (16.5 g) and
ortho-xylene (150 ml), at 0.degree. C. in a nitrogen atmosphere.
After completion of dropwise addition, the temperature of the
mixture was increased to 70.degree. C., and the mixture was stirred
for 4 hours. The temperature of the mixture was further increased
to 100.degree. C., and hexane was distilled off under reduced
pressure. The mixture was cooled to -50.degree. C., boron
tribromide (3.2 ml) was added thereto, the temperature of the
mixture was increased to room temperature, and the mixture was
stirred for one hour. Thereafter, the mixture was cooled again to
0.degree. C., and N,N-diisopropylethylamine (25.0 ml) was added
thereto. The mixture was stirred at room temperature until heat
generation was settled, and then the mixture was heated and stirred
for 4 hours at 120.degree. C. The reaction liquid was cooled to
room temperature, an aqueous solution of sodium acetate and ethyl
acetate were added thereto, and then the mixture was partitioned. A
solid precipitated by distilling off the solvent under reduced
pressure was collected by suction filtration, and the solid was
washed with heptane. From a chlorobenzene solution of the solid
thus obtained, an appropriate amount of the solvent was distilled
off under reduced pressure, and the solid was reprecipitated by
further adding ethyl acetate. Thus, a compound (9.5 g) represented
by formula (1-100) was obtained.
##STR00253##
[0221] The structure of the compound thus obtained was identified
by an NMR analysis.
[0222] .sup.1H-NMR (400 MHz, CDCl.sub.3): .delta.=8.77 (d, 2H),
8.25 (s, 1H), 8.21 (d, 4H), 7.61 (t, 2H), 7.42 (m, 6H), 7.33 (m,
8H), 7.10 (d, 2H).
Synthesis Example (6)
Synthesis of
N.sup.6,N.sup.6,N.sup.8,N.sup.8-tetraphenyl-5,9-dioxa-13b-boranaphtho[3,2-
,1-de]a nthracene-6,8-diamine
##STR00254##
[0224] A flask containing
((4,6-dibromo-1,3-phenylene)bis(oxy))dibenzene (45.0 g),
diphenylamine (45.0 g), Pd(dba).sub.2 (1.2 g),
(4-(N,N-dimethylamino)phenyl)-di-t-butylphosphine (A-.sup.taphos)
(1.1 g), NaOtBu (25.7 g) and toluene (250 ml) was heated to
100.degree. C. and stirred for 4 hours. The reaction liquid was
cooled to room temperature, water and ethyl acetate were added
thereto, the mixture was partitioned, and then the solvent was
distilled off under reduced pressure. Subsequently, the residue was
purified by silica gel column chromatography (developing liquid:
toluene/heptane=1 (volume ratio)), and was dissolved in ethyl
acetate. The residue was reprecipitated by adding heptane thereto.
Thus, 4,6-diphenoxy-N.sup.1,N.sup.1,
N.sup.3,N.sup.3-tetrapheylbenzene-1,3-diamine (17.6 g) was
obtained.
##STR00255##
[0225] A 2.6 M n-butyllithium hexane solution (11.8 ml) was
introduced into a flask containing 4,6-diphenoxy-N.sup.1,N.sup.1,
N.sup.3,N.sup.3-tetraphenylbenzene-1,3-diamine (17.5 g) and
ortho-xylene (130 ml), at 0.degree. C. in a nitrogen atmosphere.
After completion of dropwise addition, the temperature of the
mixture was increased to 70.degree. C., and the mixture was stirred
for 4 hours. Furthermore, the temperature of the mixture was
increased to 100.degree. C., and hexane was distilled off. The
mixture was cooled to -50.degree. C., boron tribromide (3.4 ml) was
added thereto, the temperature of the mixture was increased to room
temperature, and the mixture was stirred for one hour. Thereafter,
the mixture was cooled again to 0.degree. C.,
N,N-diisopropylethylamine (10.0 ml) was added thereto, and the
mixture was stirred at room temperature until heat generation was
settled. Subsequently, the mixture was heated and stirred for 4
hours at 120.degree. C. The reaction liquid was cooled to room
temperature, an aqueous solution of sodium acetate and ethyl
acetate were added thereto, and then the mixture was partitioned.
Precipitation was induced by distilling off the solvent under
reduced pressure, and then the precipitate was purified by silica
gel column chromatography (developing liquid: heptane/toluene=3/2
(volume ratio)). Furthermore, the product was dissolved in
chlorobenzene, and then was reprecipitated by distilling off an
appropriate amount of the solvent under reduced pressure. Thus, a
compound (5.5 g) represented by formula (1-141) was obtained.
##STR00256##
[0226] The structure of the compound thus obtained was identified
by an NMR analysis.
[0227] .sup.1H-NMR (400 MHz, CDCl.sub.3): .delta.=8.60 (d, 2H),
7.80 (s, 1H), 7.55 (t, 2H), 7.30 (t, 2H), 7.22 (m, 8H), 7.12 (m,
8H), 7.02 (d, 2H), 6.94 (t, 4H).
Synthesis Example (7)
Synthesis of
5,13-diphenyl-7,11-dioxa-18b-boraphenaleno[2,1-b:8,9-b]dic
arbazole
##STR00257##
[0229] In a nitrogen atmosphere, a flask containing
9H-carbazol-2-ol (25.0 g), iodobenzene (30.6 g), Pd(dba).sub.2 (2.4
g), a 1M tri-t-butylphosphine toluene solution (8.2 ml), NaOtBu
(33.0 g), and 1,2,4-trimethylbenzene (250 ml) was heated to
120.degree. C. and stirred for 6 hours. The reaction liquid was
cooled to room temperature, water and ethyl acetate were added
thereto, and the mixture was neutralized by adding dilute
hydrochloric acid. The solvent was distilled off under reduced
pressure, and then the residue was purified by silica gel column
chromatography (developing liquid: toluene/heptane=1 (volume
ratio)) and was further washed with heptane. Thus,
9-phenyl-9H-carbazol-2-ol (30.8 g) was obtained.
##STR00258##
[0230] Copper(I) iodide (0.51 g) and iron(III) acetylacetonate (1.9
g) were added to an NMP (150 ml) solution of
9-phenyl-9H-carbazol-2-ol (30.7 g), 1,3-dibromobenzene (12.7 g) and
potassium carbonate (30.0 g) in a nitrogen atmosphere, and the
temperature of the mixture was increased to 150.degree. C. and
stirred for 8 hours. The reaction liquid was cooled to room
temperature, ethyl acetate and aqueous ammonia were added thereto,
and then the mixture was partitioned. The solvent of the organic
layer was distilled off under reduced pressure. Subsequently, the
residue was purified by silica gel column chromatography
(developing liquid: toluene/heptane=4/6 (volume ratio)), and thus
1,3-bis((9-phenyl-9H-carbazol-2-yl)oxy)benzene (22.0 g) was
obtained.
##STR00259##
[0231] A 2.6 M n-butyllithium hexane solution (15.0 ml) was
introduced into a flask containing
1,3-bis((9-phenyl-9H-carbazol-2-yl)oxy)benzene (22.0 g) and
t-butylbenzene (120 ml), at 0.degree. C. in a nitrogen atmosphere.
After completion of dropwise addition, the temperature of the
mixture was increased to 70.degree. C., and the mixture was stirred
for 4 hours. The temperature of the mixture was further increased
to 100.degree. C., and hexane was distilled off. The residue was
cooled to -50.degree. C., boron tribromide (11 g) was added
thereto, and the temperature of the mixture was increased to room
temperature. The mixture was stirred for one hour. Thereafter, the
mixture was cooled again to 0.degree. C., N,N-diisopropylethylamine
(9.6 g) was added thereto, and the mixture was stirred at room
temperature until heat generation was settled. Subsequently, the
mixture was heated and stirred for 2 hours at 120.degree. C. The
reaction liquid was cooled to room temperature, and a precipitate
generated by adding an aqueous solution of sodium acetate thereto
was collected by suction filtration. The precipitate was washed
with heptane, ethyl acetate and methanol in this order, and was
further washed with refluxed chlorobenzene. Thus, a compound (6.8
g) represented by formula (1-10) was obtained.
##STR00260##
[0232] The structure of the compound thus obtained was identified
by an NMR analysis.
[0233] .sup.1H-NMR (400 MHz, CDCl.sub.3): .delta.=9.61 (s, 2H),
8.42 (m, 2H), 7.64-7.77 (m, 9H), 7.52-7.58 (m, 2H), 7.42-7.51 (m,
8H), 7.13 (d, 2H).
Synthesis Example (8)
Synthesis of N.sup.3,N.sup.3,
N.sup.11N,N.sup.11-tetraphenyl-5,9-dioxa-13b-boranaphtho[3,2,1-de]anthrac-
ene-3,11-diamine
##STR00261##
[0235] A flask containing diphenylamine (41.0 g), 3-bromophenol
(40.0 g), Pd(dba).sub.2 (0.7 g), A-.sup.taPhos (0.6 g), NaOtBu
(56.0 g), and toluene (400 ml) was heated to 80.degree. C. and
stirred for one hour. The reaction liquid was cooled to room
temperature, subsequently water and ethyl acetate were added
thereto, and then the mixture was partitioned. The solvent was
distilled off under reduced pressure. The residue was purified by
silica gel column chromatography (developing liquid:
toluene/heptane=1 (volume ratio)), and a solid thus obtained was
washed with heptane. Thus, 3-(diphenylamino)phenol (69.5 g) was
obtained.
##STR00262##
[0236] Copper(I) iodide (0.56 g) and iron(III) acetylacetonate (2.1
g) were added to an NMP (150 ml) solution of
3-(diphenylamino)phenol (34.1 g), 1,3-dibromobenzene (14.0 g) and
potassium carbonate (33.0 g) in a nitrogen atmosphere. The
temperature of the mixture was increased to 150.degree. C., and the
mixture was stirred for 10 hours. The reaction liquid was cooled to
room temperature, ethyl acetate and aqueous ammonia were added
thereto, and then the mixture was partitioned. The solvent of the
organic layer was distilled off under reduced pressure.
Subsequently, the residue was purified by silica gel column
chromatography (developing liquid: toluene/heptane=4/6 (volume
ratio)), and 3,3'-(1,3-phenylenebis(oxy))bis(N,N-diphenylaniline)
(27.0 g was obtained.
##STR00263##
[0237] A 2.6 M n-butyllithium hexane solution (18.3 ml) was
introduced into a flask containing
3,3'-(1,3-phenylenebis(oxy))bis(N,N-diphenylaniline) (27.0 g) and
xylene (150 ml), at 0.degree. C. in a nitrogen atmosphere. After
completion of dropwise addition, the temperature of the mixture was
increased to 70.degree. C., and the mixture was stirred for 4
hours. The temperature of the mixture was further increased to
100.degree. C., and hexane was distilled off. The mixture was
cooled to -50.degree. C., boron tribromide (13.6 g) was added
thereto, the temperature of the mixture was increased to room
temperature, and the mixture was stirred for one hour. Thereafter,
the mixture was cooled again to 0.degree. C.,
N,N-diisopropylethylamine (11.7 g) was added thereto, and the
mixture was stirred at room temperature until heat generation was
settled. Subsequently, the mixture was heated and stirred for 2
hours at 120.degree. C. The reaction liquid was cooled to room
temperature, and a precipitate generated by adding an aqueous
solution of sodium acetate was collected by suction filtration. The
solid thus obtained was dissolved in ortho-dichlorobenzene, and
reprecipitation was carried out by concentrating the solution.
Thus, a compound (6.2 g) represented by formula (1-176) was
obtained.
##STR00264##
[0238] The structure of the compound thus obtained was identified
by an NMR analysis.
[0239] .sup.1H-NMR (400 MHz, CDCl.sub.3): .delta.=8.35 (d, 2H),
7.61 (t, 1H), 7.34 (t, 8H), 7.23 (d, 8H), 7.15 (t, 4H), 7.02 (m,
4H), 6.98 (m, 2H).
Synthesis Example (9)
Synthesis of
9-(5,9-dioxa-13b-boranaphtho[3,2,1-de]anthracen-7-yl)-9H-ca
rbazole
##STR00265##
[0241] In a nitrogen atmosphere, a flask containing
1,3-dibromo-5-fluorobenzene (50.0 g), carbazole (39.5 g), cesium
carbonate (96.2 g) and DMSO (500 ml) was heated to 150.degree. C.
and stirred for 10 hours. The reaction liquid was cooled to room
temperature, and a precipitate precipitated by adding water thereto
was collected by suction filtration. A solid thus obtained was
purified by silica gel column chromatography (developing liquid:
toluene/heptane=1/10 (volume ratio)), and then the solid was
recrystallized from a mixed solvent of toluene/heptane. Thus,
9-(3,5-dibromophenyl)-9H-carbazole (49.0 q) was obtained.
##STR00266##
[0242] Copper(I) iodide (0.71 g) and iron(III) acetylacetonate (2.6
g) were added to an NMP (240 ml) solution of phenol (21.1 g),
9-(3,5-dibromophenyl)-9H-carbazole (30.0 g) and potassium carbonate
(41.3 g) in a nitrogen atmosphere. The temperature of the mixture
was increased to 150.degree. C., and the mixture was stirred for 6
hours. The reaction liquid was cooled to room temperature,
subsequently toluene was added thereto, and the mixture was suction
filtered using a Hirsch funnel covered with Celite. A saturated
sodium chloride solution was added to the filtrate, and the mixture
was partitioned. The organic layer was distilled off under reduced
pressure, and the residue was purified by silica gel column
chromatography (developing liquid: toluene/heptane=2/1 (volume
ratio)). Thus, 9-(3,5-diphenoxyphenyl)-9H-carbazole (27.3 q) was
obtained.
##STR00267##
[0243] A 1.6 M n-butyllithium hexane solution (16.1 ml) was
introduced into a flask containing
9-(3,5-diphenoxyphenyl)-9H-carbazole (10.0 g) and xylene (100 ml),
at 0.degree. C. in a nitrogen atmosphere. After completion of
dropwise addition, the temperature of the mixture was increased to
70.degree. C., and the mixture was stirred for 4 hours. The
temperature of the mixture was further increased to 100.degree. C.,
and hexane was distilled off. The mixture was cooled to -50.degree.
C., boron tribromide (2.7 ml) was added thereto, the temperature of
the mixture was increased to room temperature, and the mixture was
stirred for one hour. Thereafter, the mixture was cooled again to
0.degree. C., N,N-diisopropylethylamine (8.1 ml) was added thereto,
and the mixture was stirred at room temperature until heat
generation was settled. Subsequently, the mixture was heated and
stirred for 8 hours at 120.degree. C. The reaction liquid was
cooled to room temperature, an aqueous solution of sodium acetate
and toluene were added thereto, and then the mixture was
partitioned. Subsequently, the solvent was distilled off under
reduced pressure. A solid thus obtained was recrystallized from
toluene, and thus a compound (1.7 g) represented by formula (1-49)
was obtained.
##STR00268##
[0244] The structure of the compound thus obtained was identified
by an NMR analysis.
[0245] .sup.1H-NMR (400 MHz, CDC.sub.3): .delta.=8.75 (d, 2H), 8.18
(d, 2H), 7.75 (t, 2H), 7.71 (d, 2H), 7.58 (d, 2H), 7.50 (s, 2H),
7.42-7.49 (m, 4H), 7.35 (t, 2H).
Synthesis Example (10)
Synthesis of
10-(5,9-dioxa-13b-boranaphtho[3,2,1-de]anthracen-7-yl)-10H-phenoxazine
##STR00269##
[0247] In a nitrogen atmosphere, a solution of
1-bromo-3,5-difluorobenzene (23.0 g), phenol (33.6 g), potassium
carbonate (49.4 g) and NMP (150 ml) was heated to 170.degree. C.
and was stirred for 10 hours. The reaction liquid was cooled to
room temperature, toluene and a saturated aqueous solution of
sodium chloride were added thereto, and then the mixture was
partitioned. The solvent was distilled off under reduced pressure.
Subsequently, the residue was purified by silica gel column
chromatography (developing liquid: heptane), and
((5-bromo-1,3-phenylene)bis(oxy))dibenzene (35.9 g) was
obtained
##STR00270##
[0248] In a nitrogen atmosphere, a flask containing
((5-bromo-1,3-phenylene)bis(oxy))dibenzene (14.0 g), phenoxazine
(8.3 g), Pd(dba).sub.2 (0.71 g), A-.sup.taPhos (0.98 g), NaOtBu
(5.9 g), and ortho-xylene (100 ml) was heated to 120.degree. C. and
stirred for one hour. The reaction liquid was cooled to room
temperature, subsequently water and toluene were added thereto, and
then the mixture was partitioned. The solvent was distilled off
under reduced pressure. A solid thus obtained was purified by
silica gel column chromatography (developing liquid:
toluene/heptane=1/5 (volume ratio)) was purified, and thus
10-(3,5-diphenoxyphenyl)-10H-phenoxazine (18.0 g) was obtained.
##STR00271##
[0249] A 1.6 M n-butyllithium hexane solution (15.5 ml) was
introduced into a flask containing
10-(3,5-diphenoxyphenyl)-10H-phenoxazine (10.0 g) and xylene (100
ml), at 0.degree. C. in a nitrogen atmosphere. After completion of
dropwise addition, the temperature was increased to 70.degree. C.,
and the mixture was stirred for 4 hours. The temperature of the
mixture was further increased to 100.degree. C., and hexane was
distilled off. The mixture was cooled to -50.degree. C., boron
tribromide (2.6 ml) was added thereto, the temperature of the
mixture was increased to room temperature, and the mixture was
stirred for one hour. Thereafter, the mixture was cooled again to
0.degree. C., N,N-diisopropylethylamine (7.8 ml) was added thereto,
and the mixture was stirred at room temperature until heat
generation was settled. Subsequently, the mixture was heated and
stirred for 8 hours at 120.degree. C. The reaction liquid was
cooled to room temperature, an aqueous solution of sodium acetate
and toluene were added thereto, and then the mixture was
partitioned. Subsequently, the solvent was distilled off under
reduced pressure. A solid thus obtained was purified by silica gel
column chromatography (developing liquid: toluene/heptane=1/10
(volume ratio)) and was recrystallized from toluene. Thus, a
compound (1.8 g) represented by formula (1-81) was obtained.
##STR00272##
[0250] The structure of the compound thus obtained was identified
by an NMR analysis.
[0251] .sup.1H-NMR (400 MHz, CDCl.sub.3): .delta.=8.73 (d, 2H),
7.75 (t, 2H), 7.56 (d, 2H), 7.44 (t, 2H), 7.25 (s, 2H), 6.57-6.80
(m, 6H), 6.13 (br, 2H).
Synthesis Example (11)
Synthesis of
5,9-dimethyl-5,9-diaza-13b-boranaphtho[3,2,1-de]anthracene
##STR00273##
[0253] A 1.6 M n-butyllithiumhexane solution (25.0 ml) was added to
a t-butylbenzene (20 ml) solution of
N.sup.1,N.sup.3-dimethyl-N.sup.1,N.sup.3-diphenylbenzene-1,3-diamine
(2.9 g) at 0.degree. C. in a nitrogen atmosphere. The temperature
of the mixture was increased to 100.degree. C., hexane was
distilled off, and the residue was further heated and stirred for
21 hours. The mixture was cooled to -40.degree. C., THF (10 ml) was
added thereto, and then boron tribromide (1.9 ml) was added
thereto. The temperature of the mixture was increased to room
temperature over one hour, and then the mixture was cooled to
0.degree. C. N,N-diisopropylamine (5.2 ml) was added thereto, and
the mixture was filtered using a Florisil short pass column. The
solvent was distilled off under reduced pressure, and then the
residue was washed with acetonitrile. Thus, a compound (0.96 g)
represented by formula (1-411) was obtained as a yellowish green
solid.
##STR00274##
[0254] The structure of the compound thus obtained was identified
by an NMR analysis.
[0255] .sup.1H-NMR (400 MHz, CDCl.sub.3): .delta.=8.73 (dd, 2H),
7.75 (t, 1H), 7.67 (m, 2H), 7.57 (dd, 2H), 7.29 (m, 2H), 7.00 (d,
2H), 3.91 (s, 6H).
Synthesis Example (12)
Synthesis of
5,9-dioxa-13b-thiophosphanaphtho[3,2,1-de]anthracene
##STR00275##
[0257] A 1.6 Mn-butyllithiumhexane solution (15.0 mL) was added to
a benzene (60 mL) solution of m-diphenoxybenzene (5.25 g) at
0.degree. C. in a nitrogen atmosphere. The temperature of the
mixture was increased to 70.degree. C., the mixture was stirred for
4 hours, and then phosphorus trichloride (4.12 g) that had been
cooled to 0.degree. C. was added thereto. The mixture was heated to
80.degree. C. and stirred for one hour, and then sulfur (1.15 g)
was added thereto. The mixture was further stirred for one hour at
80.degree. C. The mixture was cooled again to 0.degree. C.,
aluminum trichloride (18.7 g) and N,N-diisopropylethylamine (6.20
g) were added thereto. Then, the temperature of the mixture was
increased to 80.degree. C., and the mixture was stirred for 20
hours. The mixture was cooled to room temperature, and then the
reaction liquid was added to a dichloromethane (300 ml) solution of
1,4-diazabicyclo[2.2.2]octane (31.4 g). Subsequently, the mixture
was suction filtered using a Hirsch funnel covered with Celite, and
the solvent was distilled off under reduced pressure. A yellowish
brown oily substance thus obtained was purified using a silica gel
short pass column (developing liquid: dichloromethane). The solvent
was distilled off under reduced pressure, and a crude product was
washed using acetonitrile. Thus, a compound (3.56 g) represented by
formula (1-701) was obtained as a white solid.
##STR00276##
[0258] The structure of the compound thus obtained was identified
by an NMR analysis.
[0259] .sup.1H-NMR (400 MHz, CDCl.sub.3): .delta.=8.14 (m, 2H),
7.55 (m, 2H), 7.53 (t, 1H), 7.35-7.37 (m, 4H), 7.12 (dd, 2H).
[0260] .sup.1H NMR (.delta. ppm in CDCl.sub.3); 7.13 (dd, 2H, J=4.4
Hz, 8.0 Hz), 7.34-7.40 (m, 4H), 7.53 (t, 1H, J=8.0 Hz), 7.55 (ddd,
2H, J=0.8 Hz, 1.6, 7.6 Hz), 8.15 (ddd, 2H, J=1.6 Hz, 7.6 Hz, 13.2
Hz).
[0261] .sup.13C NMR (.delta. ppm in CDCl.sub.3); 102.5 (d, 1C,
J=82.8 Hz), 112.8 (d, 2C, J=4.8 Hz), 119.7 (d, 2C, J=92.4 Hz),
119.8 (d, 2C, J=5.8 Hz), 125.1 (d, 2C, J=10.6 Hz), 129.0 (d, 2C,
J=6.7 Hz), 132.9 (2C), 133.2, 155.7 (2C), 156.1 (2C).
Synthesis Example (13)
Synthesis of
5,9-dioxa-13b-oxophosphanaphtho[3,2,1-de]anthracene
##STR00277##
[0263] m-Chloroperbenzoic acid (m-CPBA) (1.61 g) was added to a
dichloromethane (100 ml) solution of
5,9-dioxa-13b-thiophosphanaphtho[3,2,1-de]anthracene (1.79 g) at
0.degree. C., and then the mixture was stirred for 22 hours at room
temperature. A saturated aqueous solution of sodium sulfite (10.0
ml) was added thereto, and the mixture was stirred at room
temperature. Insoluble materials were separated by filtration, and
the mixture was partitioned. The solvent was distilled off under
reduced pressure, and the residue was purified using a silica gel
short pass column (developing liquid: dichloromethane/ethyl
acetate=1 (volume ratio)). Subsequently, a crude product thus
obtained was washed using hexane, and a compound (1.07 g)
represented by formula (1-601) was obtained
##STR00278##
[0264] The structure of the compound thus obtained was identified
by an NMR analysis.
[0265] .sup.1H-NMR (400 MHz, CDCl.sub.3): .delta.=8.22 (m, 2H),
7.64 (dd, 2H), 7.62 (t, 1H), 7.39-7.43 (m, 4H), 7.17 (dd, 2H).
[0266] Furthermore, m-chloroperbenzoic acid (1.24 g, 77 wt %, 5.55
mmol) was added to
13b-thiophospha-5,9-dioxanaphtho[3,2,1-de]anthracene (1.79 g, 5.55
mmol) and dichloromethane (100 mL) at 0.degree. C., and the mixture
was stirred at room temperature. After 22 hours, m-chloroperbenzoic
acid (0.373 g, 77 wt %, 1.66 mmol) was added thereto at 0.degree.
C., and the mixture was stirred at room temperature. After one
hour, a saturated solution of sodium sulfite (10.0 ml) was added
thereto, and the mixture was stirred at room temperature. Insoluble
materials were removed by filtration, the filtrate was partitioned
into a dichloromethane layer, and then the aqueous layer was
extracted with dichloromethane. The organic layers thus obtained
were combined and concentrated, and then the combined organic layer
was passed through a silica gel short pass column using
dichloromethane and ethyl acetate as developing solvents. The
solvent of the filtrate was distilled off under reduced pressure. A
crude product thus obtained was washed using hexane, and thus a
compound represented by formula (1-601) was obtained as a white
solid (1.07 g, yield 63%).
[0267] The structure of the compound thus obtained was identified
by an NMR analysis.
[0268] .sup.1H NMR (.delta. ppm in CDCl.sub.3); 7.16 (dd, 2H, J=4.0
Hz, 8.4 Hz), 7.37-7.44 (m, 4H), 7.61 (t, 1H, J=8.4 Hz), 7.62 (dd,
2H, J=1.6 Hz, 7.6 Hz), 8.21 (ddd, 2H, J=1.6 Hz, 7.6 Hz, 12.0
Hz).
[0269] .sup.13C NMR (.delta. ppm in CDCl.sub.3); 103.7 (d, 1C,
J=98.2 Hz), 112.2 (d, 2C, J=4.8 Hz), 117.6 (d, 2C, J=116.3 Hz),
119.9 (d, 2C, J=5.8 Hz), 124.5 (d, 2C, J=11.5 Hz), 129.4 (d, 2C,
J=4.8 Hz), 133.6 (2C), 134.1, 156.6 (2C), 157.4 (2C).
Synthesis Example (14)
Synthesis of 5,9-dioxa-13b-phosphanaphtho[3,2,1-de]anthracene
##STR00279##
[0271] Triethylphosphine (0.168 g) was introduced into a flask
containing 5,9-dioxa-13b-thiophosphanaphtho[3,2,1-de]anthracene
(0.32 g) and degassed o-xylene (3.0 mL) in a nitrogen atmosphere,
and then the mixture was stirred for 21 hours at 120.degree. C. The
solvent and triethylphosphine sulfide that was produced as a side
product were distilled off under reduced pressure, and thus a
compound (0.08 g) represented by formula (1-501) was obtained.
##STR00280##
[0272] The structure of the compound thus obtained was identified
by an NMR analysis.
[0273] .sup.1H-NMR (400 MHz, CDCl.sub.3): .delta.=7.77 (m, 2H),
7.33 (m, 2H), 7.25 (m, 1H), 7.18-7.22 (m, 4H), 6.93 (dd, 2H).
[0274] Furthermore, triethylphosphine (0.130 g, 1.10 mmol) was
added to 5,9-dioxa-13b-thiophosphanaphtho[3,2,1-de]anthracene
(0.322 g, 1.00 mmol) and degassed o-xylene (6.0 mL) in a nitrogen
atmosphere, and the mixture was stirred at 120.degree. C. After 14
hours, the solvent and triethylphosphine sulfide that was produced
as a side product were distilled off under reduced pressure, and
thus a compound represented by formula (1-501) was obtained as a
white solid (0.283 g, yield 97%).
[0275] The structure of the compound thus obtained was identified
by an NMR analysis.
[0276] .sup.1H NMR (.delta. ppm in CDCl.sub.3); 6.94 (dd, 2H, J=2.0
Hz, 8.4 Hz), 7.18-7.22 (m, 4H), 7.25 (dt, 1H, J=1.2 Hz, 8.4 Hz),
7.33 (ddd, 2H, J=0.8 Hz, 1.6 Hz, 7.6 Hz), 7.77 (ddd, 2H, J=1.6 Hz,
6.4 Hz, 7.6 Hz).
[0277] .sup.13C NMR (.delta. ppm in CDCl.sub.3); 107.2 (d, 1C,
J=4.8 Hz), 112.5 (2C), 118.7 (2C), 121.5 (d, 2C, J=28.0 Hz), 124.6
(d, 2C, J=3.8 Hz), 129.7 (d, 2C, J=4.8 Hz), 129.8, 129.9 (2C),
153.7 (d, 2C, J=8.7 Hz), 154.5 (d, 2C, J=6.8 Hz).
Synthesis Example (15)
Synthesis of 7,11-dioxa-17c-boraphenanthro[2,3,4-no]tetraphene
##STR00281##
[0279] First, 2-bromonaphthalene (50.6 g) was added to a flask
containing copper iodide (4.9 g), .alpha.-picolinic acid (6.3 g),
potassium phosphate (101.9 g), resorcinol (12.8 g) and dimethyl
sulfoxide (DMSO) (400 ml) in a nitrogen atmosphere, and the mixture
was heated and stirred for 17 hours at 1300. After the reaction was
terminated, the reaction liquid was cooled to 0.degree. C., 1
Normal aqueous ammonia (160 ml) was added thereto, toluene was
added thereto, and then the mixture was partitioned. The solvent
was distilled off under reduced pressure, and a solid thus obtained
was washed with methanol. Thus, 1,3-bis(2-naphthyloxy)benzene (34.5
g) was obtained as a white solid.
##STR00282##
[0280] In a nitrogen atmosphere, a flask containing
1,3-bis(2-naphthyloxy)benzene (1.8 g) and t-butylbenzene (15 ml)
was cooled at 0.degree. C., and a 1.6 M n-butyllithiumhexane
solution (4.7 ml) was added dropwise thereto. After completion of
dropwise addition, hexane was distilled off by heating and stirring
the mixture for 0.5 hours at 90.degree. C., and the residue was
further heated and stirred for 3.5 hours at this temperature.
Thereafter, the reaction liquid was cooled to -40.degree. C., boron
tribromide (0.95 ml) was added thereto, and the mixture was stirred
for 2 hours. Furthermore, the mixture was stirred for 13 hours at
room temperature, and then was cooled to 0.degree. C.
N,N-diisopropylethylamine (1.74 ml) was added thereto. Furthermore,
the mixture was heated and stirred for 24 hours at 100.degree. C.,
and then the mixture was filtered using a Florisil short pass
column. The solvent was distilled off under reduced pressure. A
solid thus obtained was washed using acetonitrile, and thus a
compound (0.6 g) represented by formula (1-4) was obtained.
##STR00283##
[0281] The structure of the compound thus obtained was identified
by an NMR analysis.
[0282] .sup.1H-NMR (400 MHz, CDCl.sub.3): .delta.=8.16 (d, 2H),
7.91 (d, 2H), 7.80 (t, 1H), 7.76 (d, 2H), 7.74 (d, 2H), 7.42 (dd,
2H), 7.39 (d, 2H), 7.09 (dd, 2H).
Synthesis Example (16)
Synthesis of
5,9-diphenyl-7-(N,N-diphenylamino)-5,9-diaza-13b-boranaphth
o[3,2,1-de]anthracene
##STR00284##
[0284] In a nitrogen atmosphere, boron tribromide (0.06 ml) was
introduced into a flask containing
N.sup.1,N.sup.1,N.sup.3,N.sup.3,N.sup.5,N.sup.5-hexaphenylbenzene-1,3,5-t-
riamine (0.29 g) and t-butylbenzene (3 ml) at room temperature, and
then the mixture was heated for 37 hours at 90.degree. C. The
mixture was further heated for 37 hours at 170.degree. C.,
subsequently the reaction liquid was cooled to 0.degree. C., and
N,N-diisopropylethylamine (0.26 ml) was added thereto. The solution
was filtered using a Florisil short pass column, and a solid
obtained by distilling off the solvent under reduced pressure was
washed with diethyl ether. Thus, a compound (0.16 g) represented by
formula (1-447) was obtained as a greenish yellow solid.
##STR00285##
[0285] The structure of the compound thus obtained was identified
by an NMR analysis.
[0286] .sup.1H-NMR (400 MHz, CDCl.sub.3): .delta.=8.89 (dd, 2H),
7.47 (t, 4H), 7.39 (m, 4H), 7.24 (m, 6H), 7.10 (m, 4H), 6.94 (m,
6H), 6.72 (d, 2H), 5.22 (m, 2H).
[0287] Furthermore, boron tribromide (3.78 mL, 40 mmol) was added
to
N.sup.1,N.sup.1,N.sup.3,N.sup.3,N.sup.5,N.sup.5-hexaphenylbenzene-1,3,5-t-
riamine (11.6 g, 20 mmol) and ortho-dichlorobenzene (ODCB, 120 mL)
at room temperature in a nitrogen atmosphere, and then the mixture
was heated and stirred for 48 hours at 170.degree. C. Thereafter,
the reaction solution was distilled off under reduced pressure at
60.degree. C. The reaction solution was filtered using a Florisil
short pass column, the solvent was distilled off under reduced
pressure, and a crude product was obtained. The crude product was
washed using hexane, and thus a compound represented by formula
(1-447) was obtained as a yellow solid (11.0 g, yield 94%).
[0288] The structure of the compound thus obtained was identified
by an NMR analysis.
[0289] .sup.1H NMR (400 MHz, CDCl.sub.3) .delta. 5.62 (brs, 2H),
6.71 (d, 2H), 6.90-6.93 (m, 6H), 7.05-7.09 (m, 4H), 7.20-7.27 (m,
6H), 7.33-7.38 (m, 4H), 7.44-7.48 (m, 4H), 8.90 (dd, 2H).
[0290] .sup.13C NMR (101 MHz, CDCl.sub.3) .delta. 98.4 (2C), 116.8
(2C), 119.7 (2C), 123.5 (2C), 125.6 (4C), 128.1 (2C), 128.8 (4C),
130.2 (4C), 130.4 (2C), 130.7 (4C), 134.8 (2C), 142.1 (2C), 146.6
(2C), 147.7 (2C), 147.8 (2C), 151.1.
Synthesis Example (17)
Synthesis of
3,11-diphenyl-5,9-dioxa-13b-boranaphtho[3,2,1-de]anthracene
##STR00286##
[0292] A flask containing 2-bromo-1,3-difluorobenzene (12.0 g),
[1,1'-biphenyl]-3-ol (23.0 g), potassium carbonate (34.0 g) and NMP
(130 ml) was heated and stirred for 10 hours at 170.degree. C. in a
nitrogen atmosphere. After the reaction was terminated, the
reaction liquid was cooled to room temperature, water and toluene
were added thereto, and then the mixture was partitioned. The
solvent was distilled off under reduced pressure, and then the
residue was purified by silica gel column chromatography
(developing liquid: heptane/toluene=7/3 (volume ratio)). Thus,
3,3''-((2-bormo-1,3-phenylene)bis(oxy))di-1,1'-biphenyl (26.8 g)
was obtained.
##STR00287##
[0293] In a nitrogen atmosphere, a flask containing
3,3''-((2-bromo-1,3-phenylene)bis(oxy))di-1,1'-biphenyl (14.0 g)
and xylene (100 ml) was cooled to -40.degree. C., and a 2.6 M
n-butyllithium hexane solution (11.5 ml) was added dropwise
thereto. After completion of the dropwise addition, the temperature
of the mixture was increased to room temperature, and then was
decreased again to -40.degree. C. Boron tribromide (3.3 ml) was
added thereto. The temperature of the mixture was increased to room
temperature, the mixture was stirred for 13 hours, and then the
mixture was cooled to 0.degree. C. N,N-diisopropylethylamine (9.7
ml) was added thereto, and the mixture was heated and stirred for 5
hours at 130.degree. C. The reaction liquid was cooled to room
temperature, an aqueous solution of sodium acetate that had been
cooled in an ice bath was added thereto, and the mixture was
stirred. A solid thus precipitated was collected by suction
filtration. The solid thus obtained was washed with water,
methanol, and heptane in this order, and was further recrystallized
from chlorobenzene. Thus, a compound (8.9 g) represented by formula
(1-152) was obtained.
##STR00288##
[0294] The structure of the compound thus obtained was identified
by an NMR analysis.
[0295] .sup.1H-NMR (400 MHz, CDCl.sub.3): .delta.=8.75 (d, 2H),
7.75-7.84 (m, 7H), 7.65 (d, 2H), 7.53 (t, 4H), 7.44 (t, 2H), 7.25
(d, 2H).
Synthesis Example (18)
Synthesis of
2,6,8,12-tetraphenyl-5,9-dioxa-13b-boranaphtho[3,2,1-de]ant
hracene
##STR00289##
[0297] A flask containing 1,5-bromo-2,4-difluorobenzene (90.0 g),
phenylboronic acid (88.6 g), tripotassium phosphate (154.0 g),
Pd-132 (Johnson Matthey) (1.6 g), toluene (900 ml), isopropanol
(300 ml) and water (150 ml) was heated and stirred for one hour at
the reflux temperature in a nitrogen atmosphere. After the reaction
was terminated, the reaction liquid was cooled to room temperature,
water was added thereto, and then the mixture was partitioned. The
solvent was distilled off under reduced pressure, and then the
residue was purified using a silica gel short pass column
(developing liquid: heptane/toluene=1 (volume ratio)), and thus
4',6'-difluoro-1,1':3,1''-terphenyl (86.0 q) was obtained.
##STR00290##
[0298] In a nitrogen atmosphere, a flask containing
4',6'-difluoro-1,1':3',1''-terphenyl (35.0 g) and THF (200 ml) was
cooled to -78.degree. C., and a 1 M sec-butyllithium cyclohexane
solution (138 ml) was added dropwise thereto. The mixture was
stirred for 30 minutes, and then bromine (23.0 g) was added
dropwise. After completion of the dropwise addition, an aqueous
solution of sodium sulfite was added thereto, and the mixture was
stirred at room temperature. Water and toluene were added thereto,
and then the mixture was partitioned. The solvent was distilled off
under reduced pressure, and an oily crude purification product thus
obtained was reprecipitated by adding heptane thereto. Thus,
5'-bromo-4',6'-difluoro-1,1': 3',1''-terphenyl (41.7 g) was
obtained.
##STR00291##
[0299] A flask containing 5'-bromo-4',6'-difluoro-1,1':
3',1''-terphenyl (23.0 g), [1,1'-biphenyl]-4-ol (25.0 g), potassium
carbonate (37.0 g) and NMP (120 ml) was heated and stirred for 2
hours at 200.degree. C. in a nitrogen atmosphere. After the
reaction was terminated, the reaction liquid was cooled to room
temperature, NMP was distilled off under reduced pressure,
subsequently water and toluene were added thereto, and then the
mixture was partitioned. The solvent was distilled off under
reduced pressure, and then the residue was purified by silica gel
column chromatography (developing liquid: heptane/toluene=7/3
(volume ratio)). The residue was dissolved in ethyl acetate, and
then was reprecipitated by adding heptane thereto. Thus,
4',6'-bis([1,1'-biphenyl]-4-yloxy)-5'-bromo-1,1':3',1''-terp henyl
(38.2 q) was obtained.
##STR00292##
[0300] In a nitrogen atmosphere, a flask containing
4',6'-bis([1,1'-biphenyl]-4-yloxy)-5'-bromo-1,1':3',1''-terp henyl
(19.0 g) and xylene (200 ml) was cooled to -40.degree. C., and a
1.0 M sec-butyllithium cyclohexane solution (31.0 ml) was added
dropwise thereto. After completion of the dropwise addition, the
temperature of the mixture was increased to about 60.degree. C.,
and distillation was carried out under reduced pressure. The
reaction liquid was cooled again to -40.degree. C., and boron
tribromide (3.3 ml) was added thereto. The temperature of the
mixture was increased to room temperature, and the mixture was
stirred for 0.5 hours. Subsequently, the mixture was cooled to
0.degree. C., N,N-diisopropylethylamine (9.7 ml) was added thereto,
the temperature of the mixture was increased to 130.degree. C., and
the mixture was heated and stirred for 3 hours. The reaction liquid
was cooled to room temperature, an aqueous solution of sodium
acetate that had been cooled in an ice bath was added thereto, and
the mixture was stirred. A solid thus precipitated was collected by
suction filtration. The solid thus obtained was washed with water,
methanol and heptane in this order, and was further washed with
toluene that had been heated to the reflux temperature, and with
chlorobenzene that had been heated to the reflux temperature. Thus,
a compound (9.2 g) represented by formula (1-1048) was
obtained.
##STR00293##
[0301] The structure of the compound thus obtained was identified
by an NMR analysis.
[0302] .sup.1H-NMR (400 MHz, CDC.sub.3): .delta.=9.00 (m, 2H), 8.03
(s, 1H), 7.96 (dd, 2H), 7.84 (d, 4H), 7.75 (d, 4H), 7.50-7.60 (m,
10H), 7.46 (t, 2H), 7.40 (t, 2H).
Synthesis Example (19)
Synthesis of
3,6,8,11-tetraphenyl-5,9-dioxa-13b-boranaphtho[3,2,1-de]ant
hracene
##STR00294##
[0304] A flask containing 5'-bromo-4',6'-difluoro-1,1':
3',1''-terphenyl (23.0 g), [1,1'-biphenyl]-3-ol (25.0 g), potassium
carbonate (37.0 g) and NMP (120 ml) was heated and stirred for 2
hours at 200.degree. C. in a nitrogen atmosphere. After the
reaction was terminated, the reaction liquid was cooled to room
temperature, NMP was distilled off under reduced pressure, water
and toluene were added thereto, and then the mixture was
partitioned. The solvent was distilled off under reduced pressure,
and then the residue was purified by silica gel column
chromatography (developing liquid: heptane/toluene=7/3 (volume
ratio)). The purification product was further washed with heptane,
and thus 4',6'-bis([1,1'-biphenyl]-3-yloxy)-5'-bromo-1,1':
3',1''-terp henyl (40.0 g) was obtained.
##STR00295##
[0305] In a nitrogen atmosphere, a flask containing
4',6'-bis([1,1'-biphenyl]-3-yloxy)-5'-bromo-1,1': 3',1''-terp henyl
(20.0 g) and xylene (150 ml) was cooled to -40.degree. C., and a
1.0 M sec-butyllithium cyclohexane solution (33.0 ml) was added
dropwise thereto. After completion of the dropwise addition, the
temperature of the mixture was increased to about 60.degree. C.,
and distillation was carried out under reduced pressure. The
resultant was cooled again to -40.degree. C., and boron tribromide
(3.5 ml) was added thereto. The temperature of the mixture was
increased to room temperature, and the mixture was stirred for 0.5
hours. Subsequently, the mixture was cooled to 0.degree. C.,
N,N-diisopropylethylamine (10.8 ml) was added thereto, the
temperature of the mixture was increased to 120.degree. C., and the
mixture was heated and stirred for 3 hours. The reaction liquid was
cooled to room temperature, an aqueous solution of sodium acetate
that had been cooled in an ice bath was added thereto, and then the
mixture was stirred. A solid thus precipitated was collected by
suction filtration. The solid thus obtained was washed with water,
methanol and heptane in this order, and was further washed with
ethyl acetate that had been heated to the reflux temperature, and
with chlorobenzene that had been heated to the reflux temperature.
Thus, a compound (10.0 g) represented by formula (1-1049) was
obtained.
##STR00296##
[0306] The structure of the compound thus obtained was identified
by an NMR analysis.
[0307] .sup.1H-NMR (400 MHz, CDCl.sub.3): .delta.=8.76 (d, 2H),
7.98 (s, 1H), 7.82 (d, 4H), 7.71 (d, 4H), 7.64 (m, 4H), 7.55 (t,
4H), 7.50 (t, 4H), 7.40-7.47 (m, 4H).
Synthesis Example (20)
Synthesis of
3,6,8,11-tetraphenyl-5,9-dioxa-13b-boranaphtho[3,2,1-de]ant
hracene
##STR00297##
[0309] A flask containing 5'-bromo-4',6'-difluoro-1,1':
3',1''-terphenyl (23.0 g), [1,1'-biphenyl]-2-ol (25.0 g), potassium
carbonate (37.0 g) and NMP (120 ml) was heated and stirred for 4
hours at 200.degree. C. in a nitrogen atmosphere. After the
reaction was terminated, the reaction liquid was cooled to room
temperature, NMP was distilled off under reduced pressure,
subsequently water and toluene were added thereto, and then the
mixture was partitioned. The solvent was distilled off under
reduced pressure, and then the residue was purified by silica gel
column chromatography (developing liquid: heptane/toluene=7/3
(volume ratio)). Thus,
4',6'-bis([1,1'-biphenyl]-2-yloxy)-5'-bromo-1,1': 3',1''-terp henyl
(38.2 g) was obtained.
##STR00298##
[0310] In a nitrogen atmosphere, a flask containing
4',6'-bis([1,1'-biphenyl]-2-yloxy)-5'-bromo-1,1': 3',1''-terp henyl
(20.0 g) and xylene (150 ml) was cooled to -40.degree. C., and a
1.0 M sec-butyllithium cyclohexane solution (33.0 ml) was added
dropwise thereto. After completion of the dropwise addition, the
temperature of the mixture was increased to about 60.degree. C.,
and components having boiling points lower than that of xylene were
distilled off under reduced pressure. The residue was cooled again
to -40.degree. C., and boron tribromide (3.5 ml) was added thereto.
The temperature of the mixture was increased to room temperature,
the mixture was stirred for 0.5 hours, and then the mixture was
cooled to 0.degree. C. N,N-diisopropylethylamine (10.8 ml) was
added thereto, the temperature of the mixture was increased to
130.degree. C., and the mixture was heated and stirred for 4 hours.
The reaction liquid was cooled to room temperature, an aqueous
solution of sodium acetate that had been cooled in an ice bath was
added thereto, and the mixture was stirred. A solid thus
precipitated was collected by suction filtration. The solid thus
obtained was washed with water, methanol and heptane in this order,
and was further recrystallized from toluene. Thus, a compound (14.1
g) represented by formula (1-1050) was obtained.
##STR00299##
[0311] The structure of the compound thus obtained was identified
by an NMR analysis.
[0312] .sup.1H-NMR (400 MHz, CDCl.sub.3): .delta.=8.78 (d, 2H),
7.81 (s, 1H), 7.68 (d, 2H), 7.48 (t, 2H), 7.38 (d, 4H), 7.35 (d,
4H), 7.27 (m, 2H), 7.19 (m, 6H), 7.10 (t, 4H).
Synthesis Example (21)
Synthesis of 6,8-diphenyl-N.sup.3,N.sup.3,
N.sup.11,N.sup.11-tetra-p-tolyl-5,9-dioxa-13b-borana
phtho[3,2,1-de]anthracene-3,11-diamine
##STR00300##
[0314] A flask containing di-p-tolylamine (36.0 g), 3-bromophenol
(30.0 g), Pd-132 (Johnson Matthey) (0.6 g), NaOtBu (42.0 g), and
toluene (300 ml) was heated to 90.degree. C. and stirred for one
hour. The reaction liquid was cooled to room temperature,
subsequently water and ethyl acetate were added thereto, and the
mixture was partitioned. Furthermore, the resultant was purified by
silica gel column chromatography (developing liquid:
toluene/heptane=1/1 (volume ratio)), and a solid thus obtained was
washed with heptane. Thus, 3-(di-p-tolylamino)phenol (60.0 g) was
obtained.
##STR00301##
[0315] In a nitrogen atmosphere, a flask containing
1,5-dibromo-2,4-difluorobenzene (30.0 g), phenylboronic acid (29.6
g), Pd(PPh3)4 (2.6 g), tripotassium phosphate (51.0 g), toluene
(400 ml), isopropanol (100 ml) and water (50 ml) was heated and
stirred for 5 hours at the reflux temperature. The reaction liquid
was cooled to room temperature, water and toluene were added to the
mixture, and the mixture was partitioned. Subsequently, the
resultant was purified by silica gel column chromatography
(developing liquid: heptane), and thus 4',6'-difluoro-1,1':
3',1''-terphenyl (25.0 g) was obtained.
##STR00302##
[0316] In a nitrogen atmosphere, a flask containing
3-(di-p-tolylamino)phenol (28.7 g), 4',6'-difluoro-1,1':
3',1''-terphenyl (12.0 g), potassium carbonate (19.0 g), and NMP
(120 ml) was heated and stirred for 5 hours at 200.degree. C. The
reaction liquid was cooled to room temperature, water and ethyl
acetate were added to the reaction liquid, and the mixture was
partitioned. Subsequently, the resultant was purified by silica gel
column chromatography (developing liquid: toluene/heptane=4/6
(volume ratio)), and thus 3,3'-([1,1':
3',1''-terphenyl]-4',6'-diylbis(oxy))bis(N,N-di-p-tolylaniline)
(33.0 g) was obtained.
##STR00303##
[0317] A 2.6 M n-butyllithium hexane solution (18.3 ml) was
introduced into a flask containing 3,3'-([1,1':
3',1''-terphenyl]-4',6'-diylbis(oxy))bis(N,N-di-p-tolylaniline)
(27.0 g) and xylene (150 ml), at 0.degree. C. in a nitrogen
atmosphere. After completion of dropwise addition, the temperature
of the mixture was increased to 70.degree. C., and the mixture was
stirred for 4 hours. The temperature of the mixture was further
increased to 100.degree. C., and hexane was distilled off. The
mixture was cooled to -50.degree. C., boron tribromide (13.6 g) was
added thereto, the temperature of the mixture was increased to room
temperature, and the mixture was stirred for one hour. Thereafter,
the mixture was cooled again to 0.degree. C.,
N,N-diisopropylethylamine (11.7 g) was added thereto, and the
mixture was stirred at room temperature until heat generation was
settled. Subsequently, the temperature of the mixture was increased
to 120.degree. C., and the mixture was heated and stirred for one
hour. The reaction liquid was cooled to room temperature, an
aqueous solution of sodium acetate and ethyl acetate were added
thereto, and the mixture was partitioned. Subsequently, the
resultant was purified by silica gel column chromatography
(developing liquid: toluene/heptane=3/7 (volume ratio)), and was
further purified by activated carbon column chromatography
(developing liquid: toluene). A solid obtained by distilling off
the solvent under reduced pressure was dissolved in chlorobenzene,
and was reprecipitated by adding heptane thereto. Thus, a compound
(2.5 g) represented by formula (1-1145) was obtained.
##STR00304##
[0318] The structure of the compound thus obtained was identified
by an NMR analysis.
[0319] .sup.1H-NMR (400 MHz, CDCl.sub.3): .delta.=8.34 (d, 2H),
7.79 (s, 1H), 7.71 (d, 4H), 7.43 (t, 4H), 7.34 (t, 2H), 7.05-7.15
(m, 16H), 6.90 (m, 4H), 2.34 (s, 12H).
Synthesis Example (22)
Synthesis of
9-(4-(5,9-dioxa-13b-boranaphtho[3,2,1-de]anthracen-7-yl)phe
nyl)-9H-carbazole
##STR00305##
[0321] In a nitrogen atmosphere, a flask containing
((5-bromo-1,3-phenylene)bis(oxy))dibenzene (27.0 g),
(4-(9H-carbazol-9-yl)phenyl)boronic acid (25.0 g), tripotassium
phosphate (34.0 g), Pd-132 (Johnson Matthey) (0.3 g), toluene (400
ml), isopropanol (100 ml) and water (50 ml) was heated and stirred
for one hour at the reflux temperature. After the reaction was
terminated, the reaction liquid was cooled to room temperature,
water was added thereto, and the mixture was partitioned. The
solvent was distilled off under reduced pressure, and then the
residue was purified using a silica gel short pass column
(developing liquid: toluene). Thus,
9-(3',5'-diphenoxy[1,1'-biphenyl]-4-yl)-9H-carbazole (38.0 g) was
obtained.
##STR00306##
[0322] A 1.0 M sec-butyllithium cyclohexane solution (39.6 ml) was
introduced to a flask containing
9-(3',5'-diphenoxy[1,1'-biphenyl]-4-yl)-9H-carbazole (19.0 g) and
xylene (130 ml), at 0.degree. C. in a nitrogen atmosphere. After
completion of dropwise addition, the temperature of the mixture was
increased to 70.degree. C., the mixture was stirred for 3 hours,
and then components having boiling points lower than that of xylene
were distilled off under reduced pressure. The mixture was cooled
to -50.degree. C., boron tribromide (4.3 ml) was added thereto, the
temperature of the mixture was increased to room temperature, and
the mixture was stirred for 0.5 hours. Thereafter, the mixture was
cooled again to 0.degree. C., N,N-diisopropylethylamine (13.1 ml)
was added thereto, and the mixture was stirred at room temperature
until heat generation was settled. Subsequently, the temperature of
the mixture was increased to 120.degree. C., and the mixture was
heated and stirred for 2 hours. The reaction liquid was cooled to
room temperature, and a solid produced by adding an aqueous
solution of sodium acetate that had been cooled in an ice bath and
then adding heptane thereto was collected by suction filtration.
The solid thus obtained was washed with water and then with
toluene, and then was washed with refluxed ethyl acetate. The solid
was further recrystallized from chlorobenzene, and thus a compound
(15.6 g) represented by formula (1-50) was obtained.
##STR00307##
[0323] The structure of the compound thus obtained was identified
by an NMR analysis.
[0324] .sup.1H-NMR (400 MHz, CDCl.sub.3): .delta.=8.73 (d, 2H),
8.17 (d, 2H), 8.01 (d, 2H), 7.74 (m, 4H), 7.60 (d, 2H), 7.58 (s,
2H), 7.53 (d, 2H), 7.40-7.48 (m, 4H), 7.32 (t, 2H).
Synthesis Example (23)
Synthesis of
9-(4-(5,9-dioxa-13b-boranaphtho[3,2,1-de]anthracen-2-yl)phe
nyl)-9H-carbazole
##STR00308##
[0326] In a nitrogen atmosphere, copper(I) iodide (1.6 g) and
iron(III) acetylacetonate (6.1 g) were added to an NMP (300 ml)
solution of 1-bromo-3-fluorobenzene (50.0 g), phenol (30.0 g) and
potassium carbonate (79.0 g) in a nitrogen atmosphere. The
temperature of the mixture was increased to 150.degree. C., and the
mixture was stirred for 4 hours. The reaction liquid was cooled to
room temperature, and a salt precipitated by adding ethyl acetate
and aqueous ammonia thereto was removed by suction filtration using
a Hirsch funnel covered with Celite. The filtrate was partitioned,
and the solvent of the organic layer was distilled off under
reduced pressure. Subsequently, the residue was purified using a
silica gel short pass column (developing liquid:
toluene/heptane=2/8 (volume ratio)), and thus
1-fluoro-3-phenoxybenzene (41.0 g) was obtained.
##STR00309##
[0327] A flask containing 4'-bromo-[1,1'-biphenyl]-4-ol (25.0 g),
carbazole (18.5 g), Pd(dba).sub.2, a 1 M tri-t-butylphosphine
toluene solution (4.0 ml), NaOtBu (24.0 g) and
1,2,4-trimethylbenzene (300 ml) was heated and stirred for 2 hours
at 150.degree. C. The reaction liquid was cooled to room
temperature, and then a solid precipitated by adding dilute
hydrochloric acid was collected by suction filtration. The solid
thus obtained was washed with water, and was purified using a
silica gel short pass column (chlorobenzene/ethyl
acetate/ethanol=5/4/1 (volume ratio)). The solvent was distilled
off under reduced pressure, and a solid thus obtained was washed
with chlorobenzene. Furthermore, the solid was dissolved in
chlorobenzene, and was reprecipitated by adding ethyl acetate and
ethanol thereto. Thus, 4'-(9H-carbazol-9-yl)-[1,1'-biphenyl]-4-ol
(29.3 g) was obtained.
##STR00310##
[0328] A flask containing 1-fluoro-3-phenoxybenzene (16.3 g),
4'-(9H-carbazol-9-yl)-[1,1'-biphenyl]-4-ol (29.0 g), potassium
carbonate (29.0 g), and NMP (150 ml) was heated and stirred for 4
hours at 200.degree. C. in a nitrogen atmosphere. Since the
progress of the reaction was slow at this time point, cesium
carbonate (31.0 g) was added thereto, and the mixture was further
heated and stirred for 8 hours. After the reaction was terminated,
the reaction liquid was cooled to room temperature, NMP was
distilled off under reduced pressure, subsequently water and ethyl
acetate were added to the residue, and the mixture was partitioned.
The solvent was distilled off under reduced pressure, and then the
residue was purified by silica gel column chromatography
(developing liquid: heptane/toluene=8/2 (volume ratio)). Thus,
9-(4'-(3-phenoxyphenoxy)-[1,1'-biphenyl]-4-yl)-9H-carbazole (37.1
g) was obtained.
##STR00311##
[0329] A 1.0 M sec-butyllithium cyclohexane solution (37.5 ml) was
introduced into a flask containing
9-(4'-(3-phenoxyphenoxy)-[1,1'-biphenyl]-4-yl)-9H-carbazole (18.0
g) and xylene (130 ml), at 0.degree. C. in a nitrogen atmosphere.
After completion of dropwise addition, the temperature of the
mixture was increased to 70.degree. C., the mixture was stirred for
4 hours, and then components having boiling points lower than that
of xylene were distilled off under reduced pressure. The mixture
was cooled to -50.degree. C., boron tribromide (4.0 ml) was added
thereto, the temperature of the mixture was increased to room
temperature, and the mixture was stirred for 0.5 hours. Thereafter,
the mixture was cooled again to 0.degree. C.,
N,N-diisopropylethylamine (13.4 ml) was added thereto, and the
mixture was stirred at room temperature until heat generation was
settled. Subsequently, the temperature of the mixture was increased
to 120.degree. C., and the mixture was heated and stirred for 2
hours. The reaction liquid was cooled to room temperature, and a
solid produced by adding an aqueous solution of sodium acetate that
had been cooled in an ice bath and then ethyl acetate was collected
by suction filtration. The solid thus obtained was washed with
refluxed ethyl acetate, and then was purified using a silica gel
short pass column (developing liquid: heated chlorobenzene). The
solid was further recrystallized from chlorobenzene, and thus a
compound (6.9 g) represented by formula (1-1101) was obtained.
##STR00312##
[0330] The structure of the compound thus obtained was identified
by an NMR analysis.
[0331] .sup.1H-NMR (400 MHz, CDCl.sub.3): .delta.=8.98 (m, 1H),
8.80 (d, 1H), 8.18 (d, 2H), 8.04 (dd, 1H), 7.96 (d, 2H), 7.84 (t,
1H), 7.72-7.78 (m, 3H), 7.70 (d, 1H), 7.60 (d, 1H), 7.54 (d, 2H),
7.43-7.48 (m, 3H), 7.26-7.34 (m, 4H).
Synthesis Example (24)
Synthesis of
9-(4-(5,9-dioxa-13b-boranaphtho[3,2,1-de]anthracen-3-yl)phe
nyl)-9H-carbazole
##STR00313##
[0333] In a nitrogen atmosphere, a flask containing
1-bromo-3-fluorobenzene (50.0 g), phenol (30.0 g), potassium
carbonate (80.0 g) and NMP (300 ml) was heated and stirred for 12
hours at 200.degree. C. The reaction liquid was cooled to room
temperature, NMP was distilled off under reduced pressure,
subsequently water and ethyl acetate were added thereto, and the
mixture was partitioned. The solvent of the organic layer was
distilled off under reduced pressure, and then the residue was
purified using a silica gel short pass column (developing liquid:
toluene/heptane=2/8 (volume ratio)). Thus, 1-bromo-3-phenoxybenzene
(58.2 g) was obtained.
##STR00314##
[0334] A flask containing 3-bromophenol (10.0 g),
(4-(9H-carbazol-9-yl)phenyl)boronic acid (18.5 g), Pd-132 (Johnson
Matthey) (0.2 g), tripotassium phosphate (25.0 g), toluene (200
ml), isopropanol (50 ml), and water (25 ml) was heated and stirred
for one hour at the reflux temperature. The reaction liquid was
cooled to room temperature, subsequently water and toluene were
added thereto, and the mixture was partitioned. Subsequently, the
reaction liquid was purified using a silica gel short pass column
(developing liquid: heated chlorobenzene), and a solid obtained by
distilling off the solvent under reduced pressure was washed with
refluxed heptane. Thus, 4'-(9H-carbazol-9-yl)-[1,1'-biphenyl]-3-ol
(18.5 g) was obtained.
##STR00315##
[0335] Copper(I) iodide (0.3 g) and iron(III) acetylacetonate (1.1
g) were added to an NMP (100 ml) solution of
1-bromo-3-phenoxybenzene (12.5 g),
4'-(9H-carbazol-9-yl)-[1,1'-biphenyl]-3-ol (18.5 g) and potassium
carbonate (14.0 g) in a nitrogen atmosphere. The temperature of the
mixture was increased to 160.degree. C., and the mixture was
stirred for 6 hours. The reaction liquid was cooled to room
temperature, NMP was distilled off under reduced pressure, and then
a solid precipitated by adding ethyl acetate and aqueous ammonia
thereto was removed by suction filtration using a Hirsch filter
covered with Celite. The filtrate was partitioned, the solvent of
the organic layer was distilled off under reduced pressure, and
then the residue was purified by silica gel column chromatography
(developing liquid: toluene/heptane=3/7 (volume ratio)). Thus,
9-(3'-(3-phenoxyphenoxy)-[1,1'-biphenyl]-4-yl)-9H-carbazole (21.0
g) was obtained.
##STR00316##
[0336] A 1.0 M sec-butyllithium cyclohexane solution (43.8 ml) was
introduced into a flask containing
9-(3'-(3-phenoxyphenoxy)-[1,1'-biphenyl]-4-yl)-9H-carbazole (21.0
g) and xylene (130 ml), at 0.degree. C. in a nitrogen atmosphere.
After completion of dropwise addition, the temperature of the
mixture was increased to 70.degree. C., the mixture was stirred for
3 hours, and then components having boiling points lower than that
of xylene were distilled off under reduced pressure. The reaction
liquid was cooled to -50.degree., boron tribromide (4.7 ml) was
added thereto, the temperature of the mixture was increased to room
temperature, and the mixture was stirred for 0.5 hours. Thereafter,
the mixture was cooled again to 0.degree. C.,
N,N-diisopropylethylamine (14.6 ml) was added thereto, and the
mixture was stirred at room temperature until heat generation was
settled. Subsequently, the temperature of the mixture was increased
to 130.degree. C., and the mixture was heated and stirred for 2
hours. The reaction liquid was cooled to room temperature, and a
solid produced by adding an aqueous solution of sodium acetate that
had been cooled in an ice bath and then adding heptane thereto was
collected by suction filtration. The solid thus obtained was washed
with refluxed ethyl acetate, and then was recrystallized from
chlorobenzene. Thus, a compound (13.6 q) represented by formula
(1-1102) was obtained.
##STR00317##
[0337] The structure of the compound thus obtained was identified
by an NMR analysis.
[0338] .sup.1H-NMR (400 MHz, CDCl.sub.3): .delta.=8.81 (d, 1H),
8.75 (d, 1H), 8.18 (d, 2H), 8.00 (d, 2H), 7.89 (m, 1H), 7.83 (t,
1H), 7.71-7.77 (m, 4H), 7.58 (d, 1H), 7.53 (d, 2H), 7.41-7.48 (m,
3H), 7.26-7.34 (m, 4H).
Synthesis Example (25)
Synthesis of
9-(4-(5,9-dioxa-13b-boranaphtho[3,2,1-de]anthracen-4-yl)phe
nyl)-9H-carbazole
##STR00318##
[0340] A flask containing 2-bromophenol (10.0 g),
(4-(9H-carbazol-9-yl)phenyl)boronic acid (18.2 g), Pd-132 (Johnson
Matthey) (0.2 g), tripotassium phosphate (25.0 g), toluene (200
ml), isopropanol (50 ml), and water (25 ml) was heated and stirred
for one hour at the reflux temperature. The reaction liquid was
cooled to room temperature, subsequently water and toluene were
added thereto, and the mixture was partitioned. Subsequently, the
reaction liquid was purified using a silica gel short pass column
(developing liquid: heated toluene), and then a solid obtained by
distilling off the solvent under reduced pressure was washed with
refluxed heptane. Thus, 4'-(9H-carbazol-9-yl)-[1,1'-biphenyl]-2-ol
(18.7 g) was
##STR00319##
[0341] Copper(I) iodide (0.5 g) and iron(III) acetylacetonate (1.8
g) were added to an NMP (100 ml) solution of
1-bromo-3-phenoxybenzene (12.6 g),
4'-(9H-carbazol-9-yl)-[1,1'-biphenyl]-2-ol (18.7 g) and potassium
carbonate (14.0 g) in a nitrogen atmosphere. The temperature of the
mixture was increased to 150.degree. C., and the mixture was
stirred for 6 hours. The reaction liquid was cooled to room
temperature, NMP was distilled off under reduced pressure, and then
a solid precipitated by adding ethyl acetate and aqueous ammonia
thereto was removed by suction filtration using a Hirsch funnel
covered with Celite. The filtrate was partitioned, and the solvent
of the organic layer was distilled off under reduced pressure.
Subsequently, the residue was purified by silica gel column
chromatography (developing liquid: toluene/heptane=3/7 (volume
ratio)), and thus
9-(2'-(3-phenoxyphenoxy)-[1,1'-biphenyl]-4-yl)-9H-carbazole (20.0
g) was obtained.
##STR00320##
[0342] A 1.0 M sec-butyllithium cyclohexane solution (41.7 ml) was
introduced into a flask containing
9-(2'-(3-phenoxyphenoxy)-[1,1'-biphenyl]-4-yl)-9H-carbazole (20.0
g) and xylene (130 ml), at 0.degree. C. in a nitrogen atmosphere.
After completion of dropwise addition, the temperature of the
mixture was increased to 70.degree. C., the mixture was stirred for
3 hours, and then components having boiling points lower than that
of xylene were distilled off under reduced pressure. The mixture
was cooled to -50.degree. C., boron tribromide (4.5 ml) was added
thereto, the temperature of the mixture was increased to room
temperature, and the mixture was stirred for 0.5 hours. Thereafter,
the mixture was cooled again to 0.degree. C.,
N,N-diisopropylethylamine (13.9 ml) was added thereto, and the
mixture was stirred at room temperature until heat generation was
settled. Subsequently, the temperature of the mixture was increased
to 130.degree. C., and the mixture was heated and stirred for 3
hours. The reaction liquid was cooled to room temperature, and a
solid produced by adding an aqueous solution of sodium acetate that
had been cooled in an ice bath and then adding heptane was
collected by suction filtration. The solid thus obtained was washed
with refluxed ethyl acetate, and then was dissolved in
chlorobenzene. Reprecipitation was carried out by adding heptane to
the solution, and thus a compound (8.5 g) represented by formula
(1-1103) was obtained.
##STR00321##
[0343] The structure of the compound thus obtained was identified
by an NMR analysis.
[0344] .sup.1H-NMR (400 MHz, CDCl.sub.3): .delta.=8.77 (t, 2H),
8.19 (d, 2H), 7.96 (d, 2H), 7.86 (d, 1H), 7.80 (t, 1H), 7.72-7.77
(m, 3H), 7.59 (d, 3H), 7.54 (t, 1H), 7.47 (t, 2H), 7.44 (t, 1H),
7.33 (t, 2H), 7.26 (m, 1H), 7.19 (d, 1H).
Synthesis Example (26)
Synthesis of
9-(4-(5,9-dioxa-13b-boranaphtho[3,2,1-de]anthracen-8-yl)phe
nyl)-9H-carbazole
##STR00322##
[0346] In a nitrogen atmosphere, a flask containing
1-bromo-2,4-difluorobenzene (46.6 g), phenol (50.0 g), potassium
carbonate (133.0 g) and NMP (300 ml) was heated and stirred for 8
hours at 200.degree. C. The reaction liquid was cooled to room
temperature, NMP was distilled off under reduced pressure,
subsequently water and ethyl acetate were added thereto, and the
mixture was partitioned. The solvent of the organic layer was
distilled off under reduced pressure, and then the residue was
purified by silica gel column chromatography (developing liquid:
toluene/heptane=2/8 (volume ratio)). Thus,
((4-bromo-1,3-phenylene)bis(oxy))dibenzene (58.2 g) was
obtained.
##STR00323##
[0347] A flask containing
((4-bromo-1,3-phenylene)bis(oxy))dibenzene (15.0 g),
(4-(9H-carbazol-9-yl)phenyl)boronic acid (13.9 g), Pd-132 (Johnson
Matthey) (0.2 g), tripotassium phosphate (19.0 g), toluene (200
ml), isopropanol (50 ml) and water (25 ml) was heated and stirred
for 2 hours at the reflux temperature. The reaction liquid was
cooled to room temperature, subsequently water and toluene were
added thereto, and the mixture was partitioned. Subsequently, the
resultant was purified by silica gel column chromatography
(developing liquid: toluene/heptane mixed solvent), and thus
9-(2',4'-diphenoxy[1,1'-biphenyl]-4-yl)-9H-carbazole (20.0 g) was
obtained. At this time, the proportion of toluene in the developing
liquid was gradually increased by making reference to the method
described in "Introduction to Organic Chemical Experiments
(1)--Handling of Materials and Separation/Purification", published
by Kagaku-Dojin Publishing Co., Inc., p. 94, and thereby the target
substance was eluted.
##STR00324##
[0348] A 1.0 M sec-butyllithium cyclohexane solution (41.7 ml) was
introduced into a flask containing
9-(2',4'-diphenoxy[1,1'-biphenyl]-4-yl)-9H-carbazole (20.0 g) and
xylene (130 ml), at 0.degree. C. in a nitrogen atmosphere. After
completion of dropwise addition, the temperature of the mixture was
increased to 70.degree. C., the mixture was stirred for 3 hours,
and then components having boiling points lower than that of xylene
were distilled off under reduced pressure. The mixture was cooled
to -50.degree. C., boron tribromide (4.5 ml) was added thereto, the
temperature of the mixture was increased to room temperature, and
the mixture was stirred for 0.5 hours. Thereafter, the mixture was
cooled again to 0.degree. C., N,N-diisopropylethylamine (13.9 ml)
was added thereto, and the mixture was stirred at room temperature
until heat generation was settled. Subsequently, the temperature of
the mixture was increased to 130.degree. C., and the mixture was
heated and stirred for 3 hours. The reaction liquid was cooled to
room temperature, and a solid produced by adding an aqueous
solution of sodium acetate that had been cooled in an ice bath and
then adding heptane thereto was collected by suction filtration.
The solid thus obtained was washed with refluxed ethyl acetate, and
then was recrystallized from chlorobenzene. Thus, a compound (12.9
g) represented by formula (1-1092) was obtained.
##STR00325##
[0349] The structure of the compound thus obtained was identified
by an NMR analysis.
[0350] .sup.1H-NMR (400 MHz, CDC.sub.3): .delta.=8.75 (d, 2H), 8.19
(d, 2H), 8.02 (m, 3H), 7.70-7.78 (m, 4H), 7.54-7.62 (m, 4H),
7.38-7.50 (m, 5H), 7.32 (t, 2H).
Synthesis Example (27)
Synthesis of
9-(5,9-dioxa-13b-boranaphtho[3,2,1-de]anthracen-7-yl)-9'-ph
enyl-9H,9'H-3,3'-bicarbazole
##STR00326##
[0352] A flask containing (9-phenyl-9H-carbazol-3-yl)boronic acid
(50.0 g), 3-bromo-9H-carbazole (39.0 g), Pd-132 (Johnson Matthey)
(1.2 g), sodium carbonate (46.1 g), toluene (400 ml), ethanol (100
ml) and water (100 ml) was heated and stirred for 2 hours at the
reflux temperature. The reaction liquid was cooled to room
temperature, subsequently water and toluene were added thereto, and
the mixture was partitioned. Subsequently, the resultant was
purified by amino group-modified silica gel (NH DM1020:
manufactured by Fuji Silysia Chemical, Ltd.) column chromatography
(developing liquid: toluene). Thus,
9-phenyl-9H,9'H-3,3'-bicarbazole (52.0 g) was obtained.
##STR00327##
[0353] A flask containing
((5-bromo-1,3-phenylene)bis(oxy))dibenzene (29.2 g),
9-phenyl-9H,9'H-3,3'-bicarbazole (35.0 g), Pd(dba).sub.2 (0.5 g),
dicyclohexyl(1-methyl-2,2-diphenylcyclopropyl)phosphine (Cy-cBRIDP)
(0.9 g), NaOtBu (24.7 g), and xylene (300 ml) was heated to
150.degree. C., and the mixture was stirred for 17 hours. The
reaction liquid was cooled to room temperature, water was added
thereto, and the mixture was partitioned. Subsequently, the solvent
was distilled off under reduced pressure. Subsequently, the residue
was purified by silica gel column chromatography (developing
liquid: toluene/heptane=1/4 (volume ratio)), and thus
9-(3,5-diphenoxyphenyl)-9'-phenyl-9H,9'H-3,3'-bicarbazole (46.5 g)
was obtained.
##STR00328##
[0354] A 1.0 M sec-butyllithium cyclohexane solution (28.5 ml) was
introduced into a flask containing
9-(3,5-diphenoxyphenyl)-9'-phenyl-9H,9'H-3,3'-bicarbazole (20.0 g)
and xylene (100 ml), at 0.degree. C. in a nitrogen atmosphere.
After completion of dropwise addition, the temperature of the
mixture was increased to 70.degree. C., the mixture was stirred for
3 hours, and then components having boiling points lower than that
of xylene were distilled off under reduced pressure. The mixture
was cooled to -50.degree. C., boron tribromide (3.4 ml) was added
thereto, the temperature of the mixture was increased to room
temperature, and the mixture was stirred for 0.5 hours. Thereafter,
the mixture was cooled again to 0.degree. C.,
N,N-diisopropylethylamine (10.4 ml) was added thereto, and the
mixture was stirred at room temperature until heat generation was
settled. Subsequently, the temperature of the mixture was increased
to 130.degree. C., and the mixture was heated and stirred for 4
hours. The reaction liquid was cooled to room temperature, an
aqueous solution of sodium acetate that had been cooled in an ice
bath and then toluene were added thereto, and the mixture was
partitioned. The resultant was purified by silica gel column
chromatography (developing liquid: toluene/heptane=1/1 (volume
ratio)), and then a solid obtained by distilling off the solvent
under reduced pressure was dissolved in toluene. The solid was
reprecipitated by adding heptane to the solution, and thus a
compound (1.0 g) represented by formula (1-1069) was obtained.
##STR00329##
[0355] The structure of the compound thus obtained was identified
by an NMR analysis.
[0356] .sup.1H-NMR (400 MHz, CDCl.sub.3): .delta.=8.76 (dd, 2H),
8.48 (s, 2H), 8.26 (t, 2H), 7.73-7.86 (m, 6H), 7.58-7.67 (m, 6H),
7.41-7.57 (m, 9H), 7.38 (t, 1H), 7.33 (m, 1H).
Synthesis Example (28)
Synthesis of
8-(naphthalen-1-yl)-5,9-dioxa-13b-boranaphtho[3,2,1-de]anth
racene
##STR00330##
[0358] A flask containing
((4-bromo-1,3-phenylene)bis(oxy))dibenzene (25.0 g),
1-naphthaleneboronic acid (13.9 g), Pd-132 (Johnson Matthey) (0.1
g), potassium carbonate (20.2 g), tetrabutylammonium bromide (TBAB)
(0.7 g), SOLMIX A-11 (200 ml) and water (50 ml) was heated and
stirred for 2 hours at the reflux temperature. The reaction liquid
was cooled to room temperature, subsequently water and toluene were
added thereto, and the mixture was partitioned. Subsequently, the
resultant was purified by silica gel column chromatography
(developing liquid: toluene/heptane mixed solvent). At this time,
the proportion of toluene in the developing liquid was gradually
increased, and thereby the target substance was eluted. The target
substance was further recrystallized from a SOLMIX A-11/toluene
mixed solvent, and thus 1-(2,4-diphenoxyphenyl)naphthalene (22.9 g)
was obtained.
##STR00331##
[0359] A 1.6 M n-butyllithium hexane solution (22.6 ml) was
introduced into a flask containing
1-(2,4-diphenoxyphenyl)naphthalene (13.0 g) and xylene (100 ml), at
0.degree. C. in a nitrogen atmosphere. After completion of dropwise
addition, the temperature of the mixture was increased to
80.degree. C., the mixture was stirred for 4 hours, and then
components having boiling points lower than that of xylene were
distilled off under reduced pressure. The mixture was cooled to
-50.degree. C., boron tribromide (3.8 ml) was added thereto, the
temperature of the mixture was increased to room temperature, and
the mixture was stirred for 0.5 hours. Thereafter, the mixture was
cooled again to 0.degree. C., N,N-diisopropylethylamine (11.7 ml)
was added thereto, and the mixture was stirred at room temperature
until heat generation was settled. Subsequently, the temperature of
the mixture was increased to 120.degree. C., and the mixture was
heated and stirred for 4 hours. The reaction liquid was cooled to
room temperature, an aqueous solution of sodium acetate that had
been cooled in an ice bath and then toluene were added thereto, and
the mixture was partitioned. Subsequently, recrystallization from
toluene/heptane was carried out, and then a compound (4.0 g)
represented by formula (1-1084) was obtained.
##STR00332##
[0360] The structure of the compound thus obtained was identified
by an NMR analysis.
[0361] .sup.1H-NMR (400 MHz, CDCl.sub.3): .delta.=8.87 (m, 2H),
7.98 (d, 2H), 7.85 (d, 1H), 7.75 (t, 1H), 7.67 (d, 1H), 7.62 (m,
3H), 7.51 (m, 2H), 7.30-7.43 (m, 4H), 7.02 (d, 1H).
Synthesis Example (29)
Synthesis of
8-(pyren-1-yl)-5,9-dioxa-13b-boranaphtho[3,2,1-de]anthracen e
##STR00333##
[0363] A flask containing
((4-bromo-1,3-phenylene)bis(oxy))dibenzene (12.0 g),
1-pyreneboronic acid (9.5 g), Pd-132 (Johnson Matthey) (0.03 g),
potassium carbonate (9.7 g), TBAB (3.4 g), SOLMIX A-11 (60 ml) and
water (24 ml) was heated and stirred for one hour at the reflux
temperature. The reaction liquid was cooled to room temperature,
subsequently water and toluene were added thereto, and the mixture
was partitioned. Subsequently, the reaction liquid was purified
using a silica gel short pass column (developing liquid: toluene),
and was recrystallized from a SOLMIX A-11/ethyl acetate mixed
solvent. Thus, 1-(2,4-diphenoxyphenyl)pyrene (13.3 q) was
obtained.
##STR00334##
[0364] A 1.6 M n-butyllithium hexane solution (18.2 ml) was
introduced into a flask containing 1-(2,4-diphenoxyphenyl)pyrene
(12.5 g) and xylene (100 ml), at 0.degree. C. in a nitrogen
atmosphere. After completion of dropwise addition, the temperature
of the mixture was increased to 80.degree. C., the mixture was
stirred for 4 hours, and then components having boiling points
lower than that of xylene were distilled off under reduced
pressure. The mixture was cooled to -50.degree. C., boron
tribromide (3.1 ml) was added thereto, the temperature of the
mixture was increased to room temperature, and the mixture was
stirred for 0.5 hours. Thereafter, the mixture was cooled again to
0.degree. C., N,N-diisopropylethylamine (9.4 ml) was added thereto,
and the mixture was stirred at room temperature until heat
generation was settled. Subsequently, the temperature of the
mixture was increased to 1200, and the mixture was heated and
stirred for 4 hours. The reaction liquid was cooled to room
temperature, and a solid precipitated by adding an aqueous solution
of sodium acetate that had been cooled in an ice bath and then
adding heptane was collected by suction filtration. The solid was
washed with water and SOLMIX A-11 in this order, and then was
recrystallized from xylene. The resultant was further
recrystallized from chlorobenzene, and thus a compound (3.3 g)
represented by formula (1-1090) was obtained.
##STR00335##
[0365] The structure of the compound thus obtained was identified
by an NMR analysis.
[0366] .sup.1H-NMR (400 MHz, CDCl.sub.3): .delta.=8.76 (d, 1H),
8.71 (d, 1H), 8.32 (d, 1H), 8.23 (d, 1H), 8.18 (m, 4H), 7.95-8.05
(m, 4H), 7.79 (t, 1H), 7.64 (d, 1H), 7.45 (m, 3H), 7.35 (t, 1H),
6.97 (d, 1H).
Synthesis Example (30)
Synthesis of
3,6,8,11-tetraphenyl-5,9-dioxa-13b-thiophosphanaphtho[3,2,1-de]anthracene
##STR00336##
[0368] In a nitrogen atmosphere, a flask containing
4',6'-bis([1,1'-biphenyl]-2-yloxy)-5'-bromo-1,1': 3',1''-terp henyl
(17.0 g) and xylene (150 ml) was cooled to -40.degree. C., and a
1.0 M sec-butyllithium cyclohexane solution (27.1 ml) was added
dropwise thereto. After completion of the dropwise addition, the
temperature of the mixture was increased to about 80.degree. C.,
and components having boiling points lower than that of xylene were
distilled under reduced pressure. Subsequently, the mixture was
cooled to -10.degree. C., and phosphorus trichloride (3.5 ml) was
added thereto. The temperature of the mixture was increased to
80.degree. C., the mixture was stirred for one hour, subsequently
sulfur (12.2 g) was added thereto, and the mixture was heated and
stirred for another one hour. Subsequently, the mixture was first
cooled to -10.degree. C., and aluminum chloride (24.6 g) and
N,N-diisopropylethylamine (11.0 ml) were added thereto. The
temperature of the mixture was increased to 120.degree. C., and
then the mixture was heated and stirred for 12 hours. The reaction
liquid was cooled to room temperature, the reaction liquid was
added to a toluene solution of 1,4-diazabicyclo[2.2.2]octane, and
the mixture was stirred. Water, toluene and ethyl acetate were
added thereto, the mixture was partitioned, and the solvent was
distilled off under reduced pressure. Subsequently, the product
thus obtained was dissolved in toluene, and a solid precipitated by
adding heptane thereto was separated by filtration. The filtrate
was purified by silica gel column chromatography (developing
liquid: toluene/heptane mixed solvent). At this time, the
proportion of toluene in the developing liquid was gradually
increased, and the intended substance was eluted. The resultant was
further washed with ethyl acetate, and thus a compound (4.7 g)
represented by formula (1-1252) was obtained.
##STR00337##
Synthesis Example (31)
Synthesis of
3,6,8,11-tetraphenyl-5,9-dioxa-13b-oxophosphanaphtho[3,2,1-de]anthracene
##STR00338##
[0370] m-CPBA (1.9 g) was added to a dichloromethane (150 mL)
solution of the compound (4.7 g) represented by the above formula
(1-1252) at 0.degree. C., subsequently the temperature of the
mixture was increased to room temperature, and the mixture was
stirred for 5 hours. A saturated aqueous solution of sodium sulfite
was added thereto, the mixture was stirred at room temperature,
subsequently insoluble materials were separated by filtration, and
the filtrate was further partitioned. The solvent was distilled off
under reduced pressure, and the residue was purified by silica gel
column chromatography (developing liquid: toluene/ethyl acetate
mixed solvent). At this time, the proportion of ethyl acetate in
the developing liquid was gradually increased, and the intended
substance was eluted. The solvent was distilled off under reduced
pressure, a solid thus obtained was dissolved in toluene, and the
solid was reprecipitated by adding heptane thereto. Thus, a
compound (1.1 q) represented by formula (1-1192) was obtained.
##STR00339##
[0371] The structure of the compound thus obtained was identified
by an NMR analysis.
[0372] .sup.1H-NMR (400 MHz, CDCl.sub.3): .delta.=8.29 (m, 2H),
7.56 (d, 2H), 7.53 (s, 1H), 7.47 (t, 2H), 7.16-7.23 (m, 12H),
7.07-7.10 (m, 8H).
Synthesis Example (32)
Synthesis of
5,9-diphenyl-5,9-diaza-13b-boranaphtho[3,2,1-de]anthracene
##STR00340##
[0374] In a nitrogen atmosphere, a flask containing diphenylamine
(66.0 g), 1-bromo-2,3-dichlorobenzene (40.0 g), Pd-132 (Johnson
Matthey) (1.3 g), NaOtBu (43.0 g) and xylene (400 ml) was heated
and stirred for 2 hours at 80.degree. C. Subsequently, the
temperature of the mixture was increased to 120.degree. C., and the
mixture was heated and stirred for 3 hours. The reaction liquid was
cooled to room temperature, and then a solid precipitated by adding
water and ethyl acetate was collected by suction filtration.
Subsequently, the solid was purified using a silica gel short pass
column (developing liquid: heated toluene). The solvent was
distilled off under reduced pressure, and a solid thus obtained was
washed with heptane. Thus,
2-chloro-N.sup.1,N.sup.1,N.sup.3,N.sup.3-tetraphenylbenzene-1,3-diamine
(65.0 g) was obtained.
##STR00341##
[0375] A 1.7 M tert-butyllithium pentane solution (27.6 ml) was
introduced into a flask containing
2-chloro-N.sup.1,N.sup.1,N.sup.3,N.sup.3-tetraphenylbenzene-1,3-diamine
(20.0 g) and tert-butylbenzene (150 ml), at -30.degree. C. in a
nitrogen atmosphere. After completion of dropwise addition, the
temperature of the mixture was increased to 60.degree. C., the
mixture was stirred for 2 hours, and then components having boiling
points lower than that of tert-butylbenzene were distilled off
under reduced pressure. The mixture was cooled to -30.degree. C.,
boron tribromide (5.1 ml) was added thereto, the temperature of the
mixture was increased to room temperature, and the mixture was
stirred for 0.5 hours. Thereafter, the mixture was cooled again to
0.degree. C., N,N-diisopropylethylamine (15.6 ml) was added
thereto, and the mixture was stirred at room temperature until heat
generation was settled. Subsequently, the temperature of the
mixture was increased to 120.degree. C., and the mixture was heated
and stirred for 3 hours. The reaction liquid was cooled to room
temperature, an aqueous solution of sodium acetate that had been
cooled in an ice bath and then heptane were added thereto, and the
mixture was partitioned. Subsequently, the reaction liquid was
purified using a silica gel short pass column (additive liquid:
toluene), and then a solid obtained by distilling off the solvent
under reduced pressure was dissolved in toluene and reprecipitated
by adding heptane thereto. Thus, a compound (6.0 g) represented by
formula (1-401) was obtained.
##STR00342##
[0376] The structure of the compound thus obtained was identified
by an NMR analysis.
[0377] .sup.1H-NMR (400 MHz, CDCl.sub.3): .delta.=8.94 (d, 2H),
7.70 (t, 4H), 7.60 (t, 2H), 7.42 (t, 2H), 7.38 (d, 4H), 7.26 (m,
3H), 6.76 (d, 2H), 6.14 (d, 2H).
Synthesis Example (33)
Synthesis of
9-([1,1'-biphenyl]-4-yl)-5,12-diphenyl-5,9-diaza-13b-borana
phtho[3,2,1-de]anthracene
##STR00343##
[0379] In a nitrogen atmosphere, a flask containing diphenylamine
(37.5 g), 1-bromo-2,3-dichlorobenzene (50.0 g), Pd-132 (Johnson
Matthey) (0.8 g), NaOtBu (32.0 g) and xylene (500 ml) was heated
and stirred for 4 hours at 80.degree. C., subsequently the
temperature of the mixture was increased to 120.degree. C., and the
mixture was heated and stirred for 3 hours. The reaction liquid was
cooled to room temperature, water and ethyl acetate were added
thereto, and the mixture was partitioned. Subsequently, the
resultant was purified by silica gel column chromatography
(developing liquid: toluene/heptane=1/20 (volume ratio)), and thus
2,3-dichloro-N,N-diphenylaniline (63.0 g) was obtained.
##STR00344##
[0380] In a nitrogen atmosphere, a flask containing
2,3-dichloro-N,N-diphenylaniline (16.2 g),
di([1,1'-biphenyl]-4-yl)amine (15.0 g), Pd-132 (Johnson Matthey)
(0.3 g), NaOtBu (6.7 g) and xylene (150 ml) was heated and stirred
for one hour at 120.degree. C. The reaction liquid was cooled to
room temperature, subsequently water and ethyl acetate were added
thereto, and the mixture was partitioned. Subsequently, the
reaction liquid was purified using a silica gel short pass column
(developing liquid: heated toluene) and was further washed with a
heptane/ethyl acetate=1 (volume ratio) mixed solvent. Thus,
N.sup.1,N.sup.1-di([1,1'-bipheyl]-4-yl)-2-chloro-N.sup.3,N.sup.3-diphenyl-
benzene
##STR00345##
[0381] A 1.6 M tert-butyllithium pentane solution (37.5 ml) was
introduced into a flask containing
N.sup.1,N.sup.1-di([1,1'-biphenyl]-4-yl)-2-chloro-N.sup.3,N.sup.3-dipheny-
lbenzen e-1,3-diamine (22.0 g) and tert-butylbenzene (130 ml), at
-30.degree. C. in a nitrogen atmosphere. After completion of
dropwise addition, the temperature of the mixture was increased to
60.degree. C., the mixture was stirred for one hour, and then
components having boiling points lower than that of
tert-butylbenzene were distilled off under reduced pressure. The
mixture was cooled to -30.degree. C., boron tribromide (6.2 ml) was
added thereto, the temperature of the mixture was increased to room
temperature, and the mixture was stirred for 0.5 hours. Thereafter,
the mixture was cooled again to 0.degree. C.,
N,N-diisopropylethylamine (12.8 ml) was added thereto, and the
mixture was stirred at room temperature until heat generation was
settled. Subsequently, the temperature of the mixture was increased
to 120.degree. C., and the mixture was heated and stirred for 2
hours. The reaction liquid was cooled to room temperature, an
aqueous solution of sodium acetate that had been cooled in an ice
bath and then ethyl acetate were added thereto, and the mixture was
partitioned. Subsequently, the reaction liquid was purified using a
silica gel short pass column (developing liquid: heated
chlorobenzene). The resultant was washed with refluxed heptane and
refluxed ethyl acetate, and then was reprecipitated from
chlorobenzene. Thus, a compound (5.1 g) represented by formula
(1-1152) was obtained.
##STR00346##
[0382] The structure of the compound thus obtained was identified
by an NMR analysis.
[0383] .sup.1H-NMR (400 MHz, CDCl.sub.3): .delta.=9.17 (s, 1H),
8.99 (d, 1H), 7.95 (d, 2H), 7.68-7.78 (m, 7H), 7.60 (t, 1H),
7.40-7.56 (m, 10H), 7.36 (t, 1H), 7.30 (m, 2H), 6.95 (d, 1H), 6.79
(d, 1H), 6.27 (d, 1H), 6.18 (d, 1H).
Synthesis Example (34)
Synthesis of
5,9,11,15-tetraphenyl-5,9,11,15-tetraaza-19b,20b-diboranaph
tho[3,2,1-de:1',2',3'-jk]pentacene
##STR00347##
[0385] In a nitrogen atmosphere, a flask containing
2,3-dichloro-N,N-diphenylaniline (36.0 g),
N.sup.1,N.sup.3-diphenylbenzene-1,3-diamine (12.0 g), Pd-132
(Johnson Matthey) (0.3 g), NaOtBu (11.0 g) and xylene (150 ml) was
heated and stirred for 3 hours at 120.degree. C. The reaction
liquid was cooled to room temperature, subsequently water and ethyl
acetate were added thereto, and the mixture was partitioned.
Subsequently, the resultant was purified by silica gel column
chromatography (developing liquid: toluene/heptane mixed solvent).
At this time, the proportion of toluene in the developing liquid
was gradually increased, and thereby the intended substance was
eluted. The intended substance was further purified by activated
carbon column chromatography (developing liquid: toluene), and thus
N.sup.1,N.sup.1'-(1,3-phenylene)bis(2-chloro-N,
N.sup.3,N.sup.3-triphenylbenzene-1,3-diamine) (22.0 g) was
obtained.
##STR00348##
[0386] A 1.6 M tert-butyllithium pentane solution (42.0 ml) was
introduced into a flask containing
N.sup.1,N.sup.1'-(1,3-phenylene)bis(2-chloro-N,
N.sup.3,N.sup.3-triphenylbenzene-1,3-diamine) (22.0 g) and
tert-butylbenzene (150 ml), at -30.degree. C. in a nitrogen
atmosphere. After completion of dropwise addition, the temperature
of the mixture was increased to 60.degree. C., the mixture was
stirred for 5 hours, and components having boiling points lower
than that of tert-butylbenzene were distilled off under reduced
pressure. The mixture was cooled to -30.degree. C., boron
tribromide (7.6 ml) was added thereto, the temperature of the
mixture was increased to room temperature, and the mixture was
stirred for 0.5 hours. Thereafter, the mixture was cooled again to
0.degree. C., N,N-diisopropylethylamine (18.9 ml) was added
thereto, and the mixture was stirred at room temperature until heat
generation was settled. Subsequently, the temperature of the
mixture was increased to 120.degree. C., and the mixture was heated
and stirred for 2 hours. The reaction liquid was cooled to room
temperature, an aqueous solution of sodium acetate that had been
cooled in an ice bath was added thereto, and a solid thus
precipitated was separated by filtration. A filtrate was
partitioned, and the organic layer was purified by silica gel
column chromatography (developing liquid: toluene/heptane=1 (volume
ratio)). The solvent was distilled off under reduced pressure, a
solid thus obtained was dissolved in chlorobenzene, and the solid
was reprecipitated by adding ethyl acetate. Thus, a compound (0.6
g) represented by formula (1-422) was obtained.
##STR00349##
[0387] The structure of the compound thus obtained was identified
by an NMR analysis.
[0388] .sup.1H-NMR (400 MHz, DMSO-d6): .delta.=10.38 (s, 1H), 9.08
(d, 2H), 7.81 (t, 4H), 7.70 (t, 2H), 7.38-7.60 (m, 14H), 7.30 (t,
2H), 7.18 (d, 4H), 6.74 (d, 2H), 6.07 (d, 2H), 6.02 (d, 2H), 5.78
(s, 1H).
Synthesis Example (35)
Synthesis of
N.sup.1-(5,9-diphenyl-5,9-diaza-13b-boranaphtho[3,2,1-de]anthrac
en-3-yl)-N.sup.1,N.sup.3,N.sup.3-triphenylbenzene-1,3-diamine
##STR00350##
[0390] During the silica gel column chromatographic purification of
the compound (0.6 g) represented by formula (1-422), a fraction
containing the relevant derivative was fractionated. The fraction
was further washed with refluxed heptane, and then was
reprecipitated from chlorobenzene/ethyl acetate. Thus, a compound
(1.1 g) represented by formula (1-1159) was obtained.
##STR00351##
[0391] The structure of the compound thus obtained was identified
by an NMR analysis.
[0392] .sup.1H-NMR (400 MHz, DMSO-d6): .delta.=8.78 (d, 1H), 8.66
(d, 1H), 7.69 (t, 2H), 7.59 (t, 1H), 7.59 (t, 2H), 7.49 (m, 2H),
7.40 (d, 2H), 7.22-7.32 (m, 10H), 7.18 (t, 1H), 6.97-7.07 (m, 9H),
6.89 (d, 1H), 6.60-6.70 (m, 4H), 6.11 (s, 1H), 5.96 (m, 2H).
Synthesis Example (36)
Synthesis of
9-phenyl-9H-5-oxa-9-aza-13b-boranaphtho[3,2,1-de]anthracene
##STR00352##
[0394] In a nitrogen atmosphere, a flask containing
1-bromo-2-chloro-3-fluorobenzene (25.0 g), phenol (12.3 g),
potassium carbonate (33.0 g) and NMP (150 ml) was heated and
stirred for 4 hours at 180.degree. C. The reaction liquid was
cooled to room temperature, NMP was distilled off under reduced
pressure, subsequently water and ethyl acetate were added thereto,
and the mixture was partitioned. Subsequently, the reaction liquid
was purified using a silica gel short pass column (developing
liquid: toluene/heptane=1/1 (volume ratio)), and thus
1-bromo-2-chloro-3-phenoxybenzene (32.0 g) was obtained.
##STR00353##
[0395] In a nitrogen atmosphere, a flask containing diphenylamine
(21.0 g), 1-bromo-2-chloro-3-phenoxybenzene (32.0 g), Pd-132
(Johnson Matthey) (0.4 g), NaOtBu (16.0 g) and xylene (200 ml) was
heated and stirred for 4 hours at 80.degree. C. The reaction liquid
was cooled to room temperature, subsequently water and ethyl
acetate were added thereto, and the mixture was partitioned.
Subsequently, the resultant was purified by silica gel column
chromatography (developing liquid: toluene/heptane=2/8 (volume
ratio), and was further reprecipitated from heptane. Thus,
2-chloro-3-phenoxy-N,N-diphenylaniline (35.0 g) was obtained.
##STR00354##
[0396] A 1.7 M tert-butyllithium pentane solution (26.5 ml) was
introduced into a flask containing
2-chloro-3-phenoxy-N,N-diphenylaniline (16.0 g) and
tert-butylbenzene (150 ml), at -30.degree. C. in a nitrogen
atmosphere. After completion of dropwise addition, the temperature
of the mixture was increased to 15.degree. C., and the mixture was
stirred for 2 hours. The mixture was cooled again to -30.degree.
C., and boron tribromide (4.9 ml) was added thereto. Subsequently,
the temperature of the mixture was increased to 60.degree. C. while
pressure was reduced, and components having boiling points lower
than that of tert-butylbenzene were distilled off under reduced
pressure. Thereafter, the mixture was cooled to 0.degree. C.,
N,N-diisopropylethylamine (15.0 ml) was added thereto, and the
mixture was stirred at room temperature until heat generation was
settled. Subsequently, the temperature of the mixture was increased
to 120.degree. C., and the mixture was heated and stirred for one
hour. The reaction liquid was cooled to room temperature, an
aqueous solution of sodium acetate that had been cooled in an ice
bath and then ethyl acetate were added thereto, and the mixture was
partitioned. The resultant was purified by silica gel column
chromatography (developing liquid: toluene/heptane mixed solvent).
At this time, the proportion of toluene in the developing liquid
was gradually increased, and thereby the intended substance was
eluted. The intended substance was further purified by activated
carbon column chromatography (developing liquid: toluene), and thus
a compound (0.8 g) represented by formula (1-1201) was
obtained.
##STR00355##
[0397] The structure of the compound thus obtained was identified
by an NMR analysis.
[0398] .sup.1H-NMR (400 MHz, CDCl.sub.3): .delta.=8.92 (d, 1H),
8.78 (d, 1H), 7.70 (t, 2H), 7.66 (t, 1H), 7.61 (t, 1H), 7.53 (m,
2H), 7.47 (t, 1H), 7.37 (m, 3H), 7.27 (t, 1H), 7.11 (d, 1H), 6.80
(d, 1H), 6.31 (d, 1H).
Synthesis Example (37)
Synthesis of
N,N,9-triphenyl-9H-5-oxa-9-aza-13b-boranaphtho[3,2,1-de]ant
hracene-3-amine
##STR00356##
[0400] In a nitrogen atmosphere, a flask containing
1-bromo-2-chloro-3-fluorobenzene (20.0 g), 3-(diphenylamino) phenol
(27.4 g), potassium carbonate (26.4 g) and NMP (150 ml) was heated
and stirred for 6 hours at 180.degree. C. The reaction liquid was
cooled to room temperature, NMP was distilled off under reduced
pressure, subsequently water and toluene were added thereto, and
the mixture was partitioned. Subsequently, the resultant was
purified by silica gel column chromatography (developing liquid:
toluene/heptane=2/1 (volume ratio)), and thus
3-(3-bromo-2-chlorophenoxy)-N,N'-diphenylaniline (31.6 g)
##STR00357##
[0401] In a nitrogen atmosphere, a flask containing diphenylamine
(13.0 g), 3-(3-bromo-2-chlorophenoxy)-N,N'-diphenylaniline (31.6
g), Pd-132 (Johnson Matthey) (0.5 g), NaOtBu (10.1 g), and
1,2,4-trimethylbenzene (150 ml) was heated and stirred for one hour
at the reflux temperature. The reaction liquid was cooled to room
temperature, and then insoluble salts were removed by suction
filtration. Subsequently, the filtrate was purified using an
activated carbon short pass column (developing liquid: toluene),
and was further purified by silica gel column chromatography
(developing liquid: toluene/heptane=1/6 (volume ratio)). Thus,
2-chloro-3-(3-diphenylamino)phenoxy-N,N-diphenylaniline (26.3 g)
was obtained.
##STR00358##
[0402] A 1.6 M tert-butyllithium pentane solution (31.4 ml) was
introduced into a flask containing
2-chloro-3-(3-diphenylamino)phenoxy-N,N-diphenylaniline (26.3 g)
and tert-butylbenzene (150 ml), at -30.degree. C. in a nitrogen
atmosphere. After completion of dropwise addition, the temperature
of the mixture was increased to room temperature, and the mixture
was stirred overnight. The mixture was cooled again to -30.degree.
C., and boron tribromide (5.4 ml) was added thereto. Subsequently,
the temperature of the mixture was increased to 60.degree. C. while
pressure was reduced, and components having boiling points lower
than that of tert-butylbenzene were distilled off under reduced
pressure. Thereafter, the mixture was cooled to 0.degree. C.,
N,N-diisopropylethylamine (17.0 ml) was added thereto, and the
mixture was stirred at room temperature until heat generation was
settled. Subsequently, the temperature of the mixture was increased
to 120.degree. C., and the mixture was heated and stirred for 5.5
hours. The reaction liquid was cooled to room temperature, an
aqueous solution of sodium acetate that had been cooled in an ice
bath and then ethyl acetate were added thereto, and the mixture was
partitioned. The mixture was purified by silica gel column
chromatography (developing liquid: toluene), and recrystallization
from toluene was carried out. Thus, a compound (0.6 q) represented
by formula (1-1210) was obtained.
##STR00359##
[0403] The structure of the compound thus obtained was identified
by an NMR analysis.
[0404] .sup.1H-NMR (400 MHz, CDCl.sub.3): .delta.=8.81 (d, 1H),
8.57 (d, 1H), 7.70 (t, 2H), 7.61 (t, 1H), 7.44 (m, 2H), 7.37 (t,
6H), 7.12-7.30 (m, 7H), 7.03 (m, 2H), 6.92 (d, 1H), 6.76 (d, 1H),
6.26 (d, 1H).
Synthesis Example (38)
Synthesis of
5,11-diphenyl-6,10-dioxa-16b-boraanthra[3,2,1-de]tetracene
##STR00360##
[0406] Copper(I) iodide (0.8 g) and iron(III) acetylacetonate (3.0
g) were added to an NMP (100 ml) solution of
1-phenylnaphthalen-2-ol (20.0 g) synthesized by the method
described in Angew. Chem. Int. Ed. 2013, 52, 10598-10601,
1,3-dibromobenzene (9.7 g) and potassium carbonate (23.0 g) in a
nitrogen atmosphere. The temperature of the mixture was increased
to 150.degree. C., and the mixture was stirred for 6 hours. The
reaction liquid was cooled to room temperature, and a salt
precipitated by adding aqueous ammonia thereto was removed by
suction filtration using a Hirsch funnel covered with Celite. Ethyl
acetate was added to the filtrate, and the mixture was partitioned.
Subsequently, the resultant was purified by silica gel column
chromatography (developing liquid: toluene/heptane=3/7), and thus
1,3-bis((1-phenylnaphthalen-2-yl)oxy)benzene (12.0 g) was
obtained.
##STR00361##
[0407] A 2.6 M n-butyllithium hexane solution (24.5 ml) was
introduced into a flask containing
1,3-bis((1-phenylnaphthalen-2-yl)oxy)benzene (12.0 g) and
ortho-xylene (100 ml), at 0.degree. C. in a nitrogen atmosphere.
After completion of dropwise addition, the temperature of the
mixture was increased to 70.degree. C., the mixture was stirred for
2 hours, and then components having boiling points lower than that
of xylene were distilled off under reduced pressure. The mixture
was cooled to -50.degree. C., boron tribromide (4.9 ml) was added
thereto, the temperature of the mixture was increased to room
temperature, and the mixture was stirred for 0.5 hours. Thereafter,
the mixture was cooled again to 0.degree. C.,
N,N-diisopropylethylamine (8.1 ml) was added thereto, and the
mixture was stirred at room temperature until heat generation was
settled. Subsequently, the temperature of the mixture was increased
to 120.degree. C., and the mixture was heated and stirred for 3
hours. In order to further accelerate the reaction, aluminum
chloride (6.2 g) was added thereto, and the mixture was heated and
stirred for 2 hours at 130.degree. C. The reaction liquid was
cooled to room temperature, and a suspension produced by adding an
aqueous solution of sodium acetate that had been cooled in an ice
bath was directly partitioned. Subsequently, a solid produced by
adding heptane to the organic layer was collected by suction
filtration. The solid thus obtained was washed with refluxed ethyl
acetate, toluene and chlorobenzene in this order, and thus a
compound (5.3 g) represented by formula (1-1271) was obtained.
##STR00362##
[0408] The structure of the compound thus obtained was identified
by an NMR analysis.
[0409] .sup.1H-NMR (400 MHz, CDCl.sub.3): .delta.=9.56 (s, 2H),
8.28 (d, 2H), 7.74 (m, 2H), 7.50-7.66 (m, 15H), 6.90 (d, 2H).
Synthesis Example (39)
Synthesis of 5,9-dithia-13b-boranaphtho[3,2,1-de]anthracene
##STR00363##
[0411] In a nitrogen atmosphere, a solution of
2-bromo-1,3-difluorobenzene (23.6 g), benzenethiol (27.2 g),
potassium carbonate (67.0 g) and NMP (150 ml) was heated to
180.degree. C. and stirred for 12 hours. The reaction liquid was
cooled to room temperature, NMP was distilled off under reduced
pressure, subsequently water and ethyl acetate were added thereto,
and the mixture was partitioned. Subsequently, the resultant was
purified by silica gel column chromatography (developing liquid:
toluene/heptane=1/9 (volume ratio)). A crude purification product
thus obtained was dissolved in toluene and was reprecipitated by
adding heptane. Thus, (2-bromo-1,3-phenylene)bis(phenylsulfane)
(9.5 g) was obtained.
##STR00364##
[0412] In a nitrogen atmosphere, a flask containing
(2-bromo-1,3-phenylene)bis(phenylsulfane) (9.5 g) and xylene (100
ml) was cooled to -40.degree. C., and a 1.0 M sec-butyllithium
cyclohexane solution (26.7 ml) was added dropwise thereto. After
completion of dropwise addition, the temperature of the mixture was
increased to about 60.degree. C., and components having boiling
points lower than that of xylene were distilled off under reduced
pressure. The mixture was cooled again to -40.degree. C., and boron
tribromide (2.9 ml) was added thereto. The temperature of the
mixture was increased to room temperature, and the mixture was
stirred for 0.5 hours. Subsequently, the mixture was cooled to
0.degree. C., and N,N-diisopropylethylamine (8.9 ml) was added
thereto. The temperature of the mixture was increased to
120.degree. C., and the mixture was heated and stirred for 2 hours.
The reaction liquid was cooled to room temperature, an aqueous
solution of sodium acetate that had been cooled in an ice bath and
ethyl acetate were added thereto, and the mixture was partitioned.
The solvent was distilled off under reduced pressure, and
reprecipitation was carried out by adding heptane to an oily
substance thus obtained. A solid thus obtained was washed with
ethyl acetate, and thus a compound (4.6 g) represented by formula
(1-201) was obtained.
##STR00365##
[0413] The structure of the compound thus obtained was identified
by an NMR analysis.
[0414] .sup.1H-NMR (400 MHz, CDCl.sub.3): .delta.=8.30 (d, 2H),
7.72 (d, 2H), 7.54-7.62 (m, 4H), 7.50 (t, 1H), 7.43 (t, 2H).
Synthesis Example (40)
Synthesis of
9,10,19,20-tetraoxa-4b,14b-diboradinaphtho[1,2,3-fg:1',2',3'-gr]pentacene
##STR00366##
[0416] In a nitrogen atmosphere, a flask containing
1,4-dibromo-2,3,5,6-tetrafluorobenzene (6.24 g), phenol (9.53 g),
potassium carbonate (14.0 g) and NMP (20 ml) was heated and stirred
for 18 hours at 140.degree. C. The reaction liquid was cooled to
room temperature, saturated brine and toluene were added thereto,
and the mixture was partitioned. The solvent was distilled off
under reduced pressure, and then the residue was purified using a
silica gel short pass column (developing liquid: toluene). The
solvent was distilled off under reduced pressure, and a crude
purification product was washed using methanol. Thus,
1,4-dibromo-2,3,5,6-tetraphenoxybenzene (9.64 g) was obtained.
##STR00367##
[0417] A 1.6 M n-butyllithium hexane solution (0.610 ml) was added
to a t-butylbenzene (3.0 ml) solution of
1,4-dibromo-2,3,5,6-tetraphenoxybenzene (0.604 g), at 0.degree. C.
in a nitrogen atmosphere. The mixture was stirred for one hour,
subsequently the temperature of the mixture was increased to room
temperature, and t-butylbenzene (4.0 ml) was added thereto. The
mixture was cooled to -50.degree. C., boron tribromide (0.105 ml)
was added thereto, and the mixture was stirred for 30 minutes. The
temperature of the mixture was increased to 0.degree. C., the
mixture was stirred for 30 minutes, subsequently the temperature of
the mixture was increased to 60.degree. C., and the mixture was
stirred for 10 hours. Thereafter, the mixture was cooled to
0.degree. C., N,N-diisopropylethylamine (0.350 ml) was added
thereto, and the mixture was heated and stirred for 17 hours at the
reflux temperature. The reaction liquid was cooled to room
temperature, and was filtered using a Florisil short pass column.
The solvent was distilled off under reduced pressure, and then the
residue was washed with hexane. Thus,
7-bromo-6,8-diphenoxy-5,9-dioxa-13b-boranaphtho[3,2,1-de]an
thracene (0.106 g) was obtained as a pale orange-colored
product.
##STR00368##
[0418] A 1.1 M sec-butyllithium hexane solution (1.98 ml) was added
to a t-butylbenzene (2.5 ml) solution of
7-bromo-6,8-diphenoxy-5,9-dioxa-13b-boranaphtho[3,2,1-de]an
thracene (0.103 g), at -50.degree. C. in a nitrogen atmosphere.
After the mixture was stirred for 30 minutes, the temperature of
the mixture was increased to 0.degree. C., and the mixture was
stirred for 2 hours. The mixture was cooled again to -50.degree.
C., boron tribromide (0.220 ml) was added thereto, the temperature
of the mixture was increased to room temperature, and the mixture
was stirred for 30 minutes. Thereafter, N,N-diisopropylethylamine
(65.9 .mu.l) was added thereto, and the mixture was heated and
stirred for 11 hours at the reflux temperature. The reaction liquid
was cooled to room temperature, and was suction filtered using a
glass filter covered with Celite. The solvent was distilled off
under reduced pressure, and a crude product was obtained. The crude
product was washed using hexane and chloroform, and thereby a
compound (4.10 mg) represented by formula (1-21) was obtained as an
orange-colored solid.
##STR00369##
[0419] The structure of the compound thus obtained was identified
by an NMR analysis.
[0420] .sup.1H NMR (.delta. ppm in CDCl.sub.3); 8.80 (dd, J=1.6,
7.8 Hz, 4H), 7.83 (ddd, J=1.6, 6.0, 8.4 Hz, 4H), 7.81 (dd, J=2.0,
8.4 Hz, 4H), 7.46 (ddd, J=2.0, 6.0, 7.8 Hz, 4H).
[0421] LRMS (EI+) m/z 462 (M.sup.+)
Synthesis Examples (41) and (42)
Synthesis of
19b,20b-dibora-5,9,11,15-tetraoxadinaphtho[3,2,1-de:1',2',3'-j
k]pentacene
##STR00370##
[0422] Synthesis of
4b,13b-dibora-5,9,16,20-tetraoxadinaphtho[3,2,1-de:3',2',1'
-pq]pentaphene
##STR00371##
[0424] 1-Bromo-2,6-difluorobenzene (25.2 g, 0.130 mol) was added to
phenol (12.3 g, 0.130 mol), potassium carbonate (18.0 g, 0.130 mol)
and N-methylpyrrolidone (NMP, 250 mL) at room temperature in a
nitrogen atmosphere, and the mixture was heated and stirred for 160
hours at 120.degree. C. Thereafter, NMP was distilled off under
reduced pressure, and then toluene was added thereto. The mixture
was filtered using a silica gel short pass column, and the solvent
was distilled off under reduced pressure. Thus,
2-bromo-1-fluoro-3-phenoxybenzene was obtained as a pale red liquid
(2-64 g, yield 76%)
##STR00372##
[0425] 2-Bromo-1-fluoro-3-phenoxybenzene (7.67 g, 28.7 mmol) was
added to resorcinol (14.4 g, 14.4 mmol), potassium carbonate (3.97
g, 28.7 mmol), and NMP (57.4 mL) at room temperature in a nitrogen
atmosphere, and the mixture was heated and stirred for 160 hours at
150.degree. C. and then heated and stirred for 22 hours at
160.degree. C. Thereafter, NMP was distilled off under reduced
pressure, and then toluene was added thereto. The mixture was
filtered using a Florisil short pass column, the solvent was
distilled off under reduced pressure, and a crude product was
obtained. The crude product was recrystallized using toluene, and
thus 1,3-bis(2-bromo-3-phenoxyphenoxy)benzene was obtained as a
white solid (5.35 g, yield 62%).
##STR00373##
[0426] A hexane solution of butyllithium (0.688 mL, 1.64 M, 1.1
mmol) was added to 1,3-bis(2-bromo-3-phenoxyphenoxy)benzene (0.302
g, 0.50 mmol) and tert-butylbenzene (5.0 mL), at -42.degree. C. in
a nitrogen atmosphere, and then the mixture was stirred for 22
hours at room temperature. Boron tribromide (0.142 mL, 1.5 mmol)
was added thereto at -42.degree. C., and the mixture was stirred
for 3 hours at 50.degree. C. The mixture was stirred for another 17
hours at 70.degree. C., and then 10% of the reaction solution was
distilled off at 0.degree. C. under reduced pressure.
N,N-diisopropylethylamine (0.348 mL, 2.0 mmol) was added thereto at
0.degree. C., and the mixture was heated and stirred for 20 hours
at 150.degree. C. Subsequently, the mixture was filtered using a
Florisil short pass column, the solvent was distilled off under
reduced pressure, and a crude product was obtained. The crude
product was washed using dichloromethane and acetonitrile, and
thereby a white solid was obtained. Next, the white solid was
recrystallized using ethyl acetate, and thereby a compound
represented by formula (1-24) was obtained as a white solid (19.2
mg, yield 8.3%). Furthermore, the solvent of the filtrate was
distilled off under reduced pressure, and thereby a compound
represented by formula (1-24) as a pale yellow-colored solid and a
compound represented by formula (1-23) was obtained as a mixture at
a ratio of 1:5 (30.8 mg, yield 13%). From these results, the yield
of the compound represented by formula (1-24) was calculated to be
11% (24.3 mg), and the yield of the compound represented by formula
(1-23) was calculated to be 11% (25.7 mg).
##STR00374##
[0427] The structure of the compound represented by formula (1-24)
was identified by an NMR analysis.
[0428] .sup.1H NMR (.delta. ppm in CDCl.sub.3); 10.13 (s, 1H), 8.92
(dd, J=1.6, 8.0 Hz, 2H), 7.82 (t, J=8.0 Hz, 2H), 7.78 (ddd, J=1.6,
6.8, 8.0 Hz, 2H), 7.62 (d, J=7.6 Hz, 4H), 7.51-7.54 (m, 4H), 6.98
(s, 1H).
[0429] LRMS (EI+) m/z 462 (M+)
[0430] The structure of the compound represented by formula (1-23)
was identified by an NMR analysis.
[0431] .sup.1H NMR (.delta. ppm in DMSO-D6); 8.92 (d, J=8.8 Hz,
1H), 8.77 (dd, J=1.6, 7.6 Hz, 1H), 8.57 (d, J=8.4 Hz, 1H), 7.93 (t,
J=8.0 Hz, 1H), 7.81 (ddd, J=1.6, 7.2, 8.4 Hz, 1H), 7.67 (t, J=8.0
Hz, 1H), 7.58-7.63 (m, 2H), 7.47-7.50 (m, 3H), 7.35 (dd, J=1.6, 8.4
Hz, 1H), 7.31 (t, J=8.0 Hz, 1H), 7.28 (d, J=8.4 Hz, 1H), 7.19 (t,
J=8.0 Hz, 2H).
[0432] LRMS (EI+) m/z 462 (M+)
Synthesis Example (43)
Synthesis of
2,6,8,12-tetraphenyl-5,9-dioxa-13b-thiophosphanaphtho[3,2,1-de]anthracene
##STR00375##
[0434] First, a hexane solution of butyllithium (12.2 mL, 1.64 M,
20.0 mmol) was added to
4',6'-bis([1,1'-biphenyl]-4-yloxy)-5'-bromo-1,1':3',1''-terp henyl
(12.9 g, 20.0 mmol) and benzene (36 mL), at 0.degree. C. in a
nitrogen atmosphere, and the mixture was stirred for one hour at
room temperature. Phosphorus trichloride (1.90 mL, 22.0 mmol) was
added thereto at 0.degree. C., and the mixture was stirred for one
hour at 80.degree. C. The solvent was distilled off under reduced
pressure, sulfur (0.770 g, 24.0 mmol) and o-dichlorobenzene (60 mL)
were added thereto, and the mixture was stirred for one hour at
80.degree. C. Aluminum trichloride (18.6 g, 0.140 mol) at
-70.degree. C. and N,N-diisopropylethylamine (8.20 mL, 48.0 mmol)
at 0.degree. C. were added thereto, and the mixture was stirred for
16 hours at 100.degree. C. The mixture was cooled to room
temperature, and then the reaction liquid was added to a
dichloromethane (300 ml) solution of 1,4-diazabicyclo[2.2.2]octane
(31.4 g, 0.280 mol). Subsequently, the mixture was suction filtered
using a glass filter covered with Celite, and the solvent of the
filtrate was distilled off under reduced pressure. The residue was
dissolved in toluene, the solution was suction filtered using a
glass filter covered with silica gel, and then the solvent of the
filtrate was distilled off under reduced pressure. The residue was
dissolved in dichloromethane, water was added thereto, and then the
dichloromethane layer was separated, while the aqueous layer was
extracted with dichloromethane. The solvent was distilled off under
reduced pressure, and a crude product was washed using hexane,
methanol, acetonitrile, and ethyl acetate. Thus, a compound (0.723
g) represented by formula (1-1250) was obtained as a white
solid.
##STR00376##
[0435] The structure of the compound thus obtained was identified
by an NMR analysis.
[0436] .sup.1H NMR (.delta. ppm in CDCl.sub.3); 7.33 (dd,
J.sub.HP=6.2 Hz, J=8.7 Hz, 2H), 7.38-7.55 (m, 12H), 7.68 (d, J=7.2
Hz, 4H), 7.63 (d, J=7.3 Hz, 4H), 7.71 (s, 1H), 7.74 (dd,
J.sub.HP=2.2 Hz, J=8.7 Hz, 2H), 8.41 (dd, J.sub.HP=13.4 Hz, J=2.2
Hz, 2H).
[0437] .sup.13C NMR (.delta. ppm in CDCl.sub.3); 103.2 (d,
J.sub.CP=81.9 Hz), 119.9 (d, J.sub.CP=81.4 Hz, 2C), 120.3 (2C),
126.9 (2C), 127.0 (4C), 127.3 (d, J.sub.CP=7.3 Hz, 2C), 127.8 (2C),
128.0 (2C), 128.4 (4C), 129.1 (4C), 129.6 (4C), 131.7 (2C), 135.9,
136.0 (2C), 138.6 (d, J.sub.CP=10.1 Hz, 2C), 139.3 (2C), 151.8
(2C), 155.2 (2C).
Synthesis Example (44)
Synthesis of
2,6,8,12-tetraphenyl-5,9-dioxa-13b-oxophosphanaphtho[3,2,1-de]anthracene
##STR00377##
[0439] m-Chloroperbenzoic acid (0.247 g, 77 wt %, 1.10 mmol) at
0.degree. C. was added to the compound represented by the above
formula (1-1250) (0.633 g, 1.01 mmol) and dichloromethane (100 mL),
and the mixture was stirred at room temperature. After 6 hours,
m-chloroperbenzoic acid (44.9 mg, 77 wt %, 0.200 mmol) was added
thereto at 0.degree. C., and the mixture was stirred at room
temperature. After 14 hours, a saturated solution of sodium sulfite
(10.0 ml) was added thereto, and the mixture was stirred at room
temperature. Insoluble materials were removed by filtration, a
dichloromethane layer was separated, and then the aqueous layer was
extracted with dichloromethane. The organic layers thus obtained
were combined and concentrated, and the combined organic layer was
subjected to a silica gel short pass column using dichloromethane
and ethyl acetate as developing solvents. The solvent of the
filtrate was distilled off under reduced pressure. A crude product
thus obtained was washed using methanol, and thus a compound (0.580
g) represented by formula (1-1190) was obtained as a white
solid.
##STR00378##
[0440] The structure of the compound thus obtained was identified
by an NMR analysis.
[0441] 1H NMR (.delta. ppm in CDCl.sub.3); 7.37-7.56 (m, 14H), 7.62
(d, J=7.3 Hz, 4H), 7.69 (d, J=7.9 Hz, 4H), 7.79 (s, 1H), 7.80 (dd,
J=2.3, 8.7 Hz, 2H), 8.44 (dd, J=2.3 Hz, 2H).
[0442] .sup.13C NMR (.delta. ppm in CDCl.sub.3); 104.0 (d,
J.sub.CP=97.3 Hz), 117.6 (d, J.sub.CP=116.6 Hz, 2C), 120.4 (2C),
126.3 (2C), 127.0 (4C), 127.4 (d, J.sub.CP=4.8 Hz, 2C), 127.7 (2C),
127.9 (2C), 128.4 (4C), 129.0 (4C), 129.6 (4C), 132.4 (2C), 136.0,
136.7 (2C), 138.0 (d, J.sub.CP=10.6 Hz, 2C), 139.3 (2C), 152.1
(2C), 156.7 (2C).
Synthesis Example (45)
Synthesis of
2,12-diphenyl-5,9-dioxa-13b-thiophosphanaphtho[3,2,1-de]ant
hracene
##STR00379##
[0444] First, a hexane solution of butyllithium (11.0 mL, 1.64 M,
18.0 mmol) was added to 1,3-bis([1,1'-biphenyl]-4-yloxy)benzene
(6.22 g, 15.0 mmol) and benzene (120 mL), at 0.degree. C. in a
nitrogen atmosphere, and the mixture was stirred for 18 hours at
70.degree. C. Phosphorus trichloride (1.76 mL, 22.5 mmol) was added
thereto at 0.degree. C., and the mixture was stirred for 2 hours at
80.degree. C. The solvent was distilled off under reduced pressure,
and then sulfur (0.866 g, 27.0 mmol) and o-dichlorobenzene (60 mL)
were added thereto, and the mixture was stirred for one hour at
80.degree. C. Aluminum trichloride (14.0 g, 105 mmol) at
-95.degree. C. and N,N-diisopropylethylamine (6.18 mL, 36.0 mmol)
at 0.degree. C. were added thereto, and the mixture was stirred for
16 hours at 80.degree. C. The mixture was cooled to room
temperature, and then the reaction mixed liquid was added to a
dichloromethane (300 ml) solution of 1,4-diazabicyclo[2.2.2]octane
(23.6 g, 210 mmol). Subsequently, the mixture was suction filtered
using a glass filter covered with Celite, and was purified using a
silica gel short pass column (developing liquid: dichloromethane).
The solvent was distilled off under reduced pressure, and a crude
product was washed using methanol and toluene. Thus, a compound
(1.31 g) represented by formula (1-1247) was obtained as a white
solid.
##STR00380##
[0445] The structure of the compound thus obtained was identified
by an NMR analysis.
[0446] .sup.1H NMR (.delta. ppm in CDCl.sub.3); 7.17 (dd,
J.sub.HP=4.1 Hz, J=8.2 Hz, 2H), 7.41 (tt, J=1.4, 7.3 Hz, 2H), 7.46
(dd, J.sub.HP=2.3 Hz, J=8.7 Hz, 2H), 7.49 (dd, J=7.3, 8.0 Hz, 4H),
7.57 (t, J=8.2 Hz 1H), 7.63 (d, J=8.0 Hz, 4H), 7.78 (dd, J=2.3, 8.7
Hz, 2H), 8.39 (dd J=2.3 Hz, J.sub.HP=13.5 Hz, 2H).
[0447] .sup.13C NMR (.delta. ppm in CDCl.sub.3); 102.4 (d,
J.sub.CP=82.4 Hz), 112.9 (d, J.sub.CP=4.8 Hz, 2C), 120.1 (d,
J.sub.CP=92 Hz, 2C), 120.3 (d, J.sub.CP=6.7 Hz 2C), 127.0 (4C),
127.5 (d, J.sub.CP=5.8 Hz, 2C), 127.9 (2C), 129.1 (4C), 131.7
(J.sub.CP=1.9 Hz, 2C), 133.3, 138.5 (J.sub.CP=11.5 Hz, 2C), 139.3
(2C), 155.1 (J.sub.CP=2.9 Hz, 2C), 156.2 (2C).
Synthesis Example (46)
Synthesis of
2,12-diphenyl-5,9-dioxa-13b-oxophosphanaphtho[3,2,1-de]anth
racene
##STR00381##
[0449] m-Chloroperbenzoic acid (1.16 g, 77 wt %, 5.16 mmol) at
0.degree. C. was added to the compound represented by formula
(1-1247) (2.45 g, 5.17 mmol) and dichloromethane (500 mL), and the
mixture was stirred at room temperature. After 5 hours,
m-chloroperbenzoic acid (0.350 g, 77 wt %, 1.56 mmol) was added
thereto at 0.degree. C., and the mixture was stirred at room
temperature. After 16 hours, a saturated solution of sodium sulfite
(20.0 ml) was added thereto, and the mixture was stirred at room
temperature. A dichloromethane layer was separated, and then the
aqueous layer was extracted with dichloromethane. The organic
layers thus obtained were combined and concentrated, and then the
combined organic layer was purified using a silica gel short pass
column using dichloromethane and dichloromethane/ethyl acetate=1
(volume ratio) as developing solvents. A filtrate thus obtained was
distilled off under reduced pressure, and thus a compound (2.32 g)
represented by formula (1-1187) was obtained.
##STR00382##
[0450] The structure of the compound thus obtained was identified
by an NMR analysis.
[0451] .sup.1H NMR (.delta. ppm in CDCl.sub.3); 7.20 (dd,
J.sub.HP=4.1 Hz, J=8.5 Hz, 2H), 7.41 (tt, J=1.4, 7.4 Hz, 2H), 7.48
(d, J=7.4 Hz, 2H), 7.52 (d, J=8.7, Hz, 4H), 7.62 (dd, J=1.4, 7.5
Hz, 4H), 7.64 (t, J=8.5 Hz, 1H), 7.83 (dd, J=2.2, 8.7 Hz, 2H), 8.41
(dd, J.sub.HP=12.4 Hz, J=2.2 Hz, 2H). .sup.13C NMR (.delta. ppm in
CDCl.sub.3); 103.6 (d, J.sub.CP=97.8 Hz), 112.4 (d, J.sub.CP=4.8
Hz, 2C), 118.0 (d, J.sub.CP=116.0 Hz, 2C), 120.5 (d, J.sub.CP=6.7
Hz, 2C), 127.1 (4C), 127.5 (d, J.sub.CP=5.8 Hz, 2C), 128.0 (2C),
129.2 (4C), 132.6 (2C), 134.3, 138.0 (d, J.sub.CP=10.5 Hz, 2C),
139.5 (2C), 156.8 (2C), 156.8 (d, J.sub.CP=6.9 Hz, 2C).
Synthesis Example (47)
Synthesis of
3,6,8,11-tetraphenyl-5,9-dioxa-13b-thiophosphanaphtho[3,2,1-de]anthracene
##STR00383##
[0453] First, a hexane solution of butyllithium (12.2 mL, 1.64 M,
20.0 mmol) was added to
4',6'-bis([1,1'-biphenyl-3yloxy])-5'-bromo-1,1': 3',1''-terp henyl
(12.9 g, 20.0 mmol) and benzene (70 mL), at 0.degree. C. in a
nitrogen atmosphere, and the mixture was stirred for 2 hours.
Phosphorus trichloride (1.92 mL, 22.0 mmol) was added thereto at
0.degree. C., and the mixture was stirred for one hour at
80.degree. C. The solvent was distilled off under reduced pressure,
sulfur (0.768 g, 24.0 mmol) and o-dichlorobenzene (60 mL) were
added thereto, and the mixture was stirred for one hour at
80.degree. C. Aluminum trichloride (18.7 g, 140 mmol) at
-95.degree. C. and N,N-diisopropylethylamine (8.20 mL, 48.0 mmol)
at 0.degree. C. were added thereto, and the mixture was stirred for
16 hours at 100.degree. C. The mixture was cooled to room
temperature, and then the reaction liquid was added to a
dichloromethane (300 ml) solution of 1,4-diazabicyclo[2.2.2]octane
(31.4 g, 280 mmol). Subsequently, the mixture was suction filtered
using a glass filter covered with Celite, and the filtrate was
concentrated under reduced pressure and was diluted using toluene.
Insoluble materials were removed by filtration. The solvent of the
filtrate was distilled off under reduced pressure, and then the
residue was purified using a silica gel short pass column
(developing liquid: dichloromethane). The solvent was distilled off
under reduced pressure, and then the residue was purified using a
silica gel short pass column (developing liquid: toluene). The
solvent was distilled off under reduced pressure, and a crude
product was washed using acetonitrile and hexane. Thus, a compound
(1.22 g) represented by formula (1-1251) was obtained as a white
solid.
##STR00384##
[0454] The structure of the compound thus obtained was identified
by an NMR analysis.
[0455] .sup.1H NMR (.delta. ppm in CDCl.sub.3); 7.40-7.50 (m, 10H),
7.52 (dd, J=7.2 Hz, 7.6 Hz, 4H), 7.59 (d, J=7.2 Hz, 4H), 7.63 (ddd,
J.sub.HP=1.8 Hz, J=1.8 Hz, 8.0 Hz, 2H), 7.67-7.70 (m, 5H), 8.26
(dd, J.sub.HP=12.8 Hz, J=8.0 Hz, 2H).
[0456] .sup.13C NMR (.delta. ppm in CDCl.sub.3); 103.5 (d,
J.sub.CP=80.5 Hz), 117.9 (d, J.sub.CP=93.9 Hz, 2C), 118.2 (d,
J.sub.CP=5.8 Hz, 2C), 124.2 (d, J.sub.CP=11.5 Hz, 2C), 126.9 (d,
J.sub.CP=5.8 Hz, 2C), 127.3 (4C), 127.7 (2C), 128.4 (4C), 128.6
(2C), 129.0 (4C), 129.3 (d, J.sub.CP=5.8 Hz, 2C), 129.6 (4C),
135.9, 136.1 (2C), 139.0 (2C), 146.3 (2C), 151.7 (2C), 156.1
(2C).
Synthesis Example (48)
Synthesis of
3,6,8,11-tetraphenyl-5,9-dioxa-13b-oxophosphanaphtho[3,2,1-de]anthracene
##STR00385##
[0458] m-Chloroperbenzoic acid (0.404 g, 77 wt %, 1.79 mmol) at
0.degree. C. was added to the compound represented by the above
formula (1-1251) (1.12 g, 1.79 mmol) and dichloromethane (150 mL),
and the mixture was stirred at room temperature. After 5 hours,
m-chloroperbenzoic acid (0.674 g, 77 wt %, 0.391 mmol) was added
thereto at 0.degree. C., and the mixture was stirred at room
temperature. After 16 hours, a saturated solution of sodium sulfite
(10 ml) and water (40 ml) were added thereto, and the mixture was
stirred at room temperature. Insoluble materials were removed by
filtration, a dichloromethane layer was separated, and then the
aqueous layer was extracted with dichloromethane. The organic
layers thus obtained were combined and concentrated, and then the
combined organic layer was subjected to a silica gel short pass
column using dichloromethane and dichloromethane/ethyl acetate=1
(volume ratio) as developing solvents. The solvent of the filtrate
was distilled off under reduced pressure. A crude product thus
obtained was washed using methanol, and thus a compound (1.04 g)
represented by formula (1-1191) was obtained as a white solid.
##STR00386##
[0459] The structure of the compound thus obtained was identified
by an NMR analysis.
[0460] .sup.1H NMR (.delta. ppm in CDCl); 7.40-7.50 (m, 10H), 7.53
(t, J=7.1 Hz, 4H), 7.61 (d, J=6.9 Hz, 4H), 7.64 (dt, J.sub.HP=1.9
Hz, J=1.9 Hz, 8.0 Hz, 2H), 7.69 (d, J=7.1 Hz, 4H), 7.77 (s, 1H),
8.32 (dd, J.sub.HP=11.7 Hz, J=8.0 Hz, 2H).
[0461] .sup.13C NMR (.delta. ppm in CDCl); 104.3 (d, J.sub.CP=96.8
Hz), 115.9 (d, J.sub.CP=117.9 Hz, 2C), 118.2 (d, J.sub.CP=5.8 Hz,
2C), 123.5 (d, J.sub.CP=10.5 Hz, 2C), 126.3 (d, J.sub.CP=4.8 Hz,
2C), 127.3 (4C), 127.7 (2C), 128.5 (4C), 128.6 (2C), 129.0 (4C),
129.6 (4C), 129.7 (d, J.sub.CP=8.6 Hz, 2C), 136.1, 136.7 (2C),
139.0 (2C), 146.9 (2C), 152.2 (2C), 157.7 (2C).
[0462] Other polycyclic aromatic compounds of the present invention
can be synthesized by methods according to the Synthesis Examples
described above, by appropriately changing the compounds of raw
materials.
[0463] Hereinafter, various Examples will be described in order to
explain the present invention in more detail, but the present
invention is not intended to be limited to these.
[0464] Organic EL elements related to Examples 1 and 2 were
produced, and the external quantum efficiency obtainable when each
of the organic EL elements was driven at a current density capable
of giving a luminance of 100 cd/m.sup.2 was measured. The material
configurations of the various layers in the organic EL elements
thus produced are shown in the following Table 1.
TABLE-US-00001 TABLE 1 Hole Hole Hole Electron Electron Injection
Injection Transport Light Emitting Layer Transport Transport
Negative Layer 1 Layer 2 Layer (25 nm) Layer 2 Layer 1 Electrode
(65 nm) (5 nm) (60 nm) Host Dopant (20 nm) (10 nm) (1 nm/100 nm)
Ex. 1 HI HAT-CN HT BH1 Compound ET2 ET1 LiF/Al (1-176) Ex. 2 HI
HAT-CN HT BH1 Compound ET2 ET1 LiF/Al (1-100)
[0465] In Table 1, "HI" means
N.sup.4,N.sup.4'-diphenyl-N.sup.4,N.sup.4'-bis(9-phenyl-9H-carbazol-3-yl)-
-[1,1'-biphenyl]-4,4'-diamine; "HAT-CN" means
1,4,5,8,9,12-hexaazatriphenylenehexacarbonitrile; "HT" means
N-([1,1'-biphenyl]-4-yl)-N-(4-(9-phenyl-9H-carbazol-3-yl)ph
enyl)-[1,1'-biphenyl]-4-amine; "BH1" means
9-phenyl-10-(4-phenylnaphthalen-1-yl)anthracene; "ET2" means
9-(4'-(dimesitylboryl)-[1,1'-binaphthalen]-4-yl)-9H-carbazo le; and
"ET1" means 5,5''-(2-phenylanthracene-9,10-diyl) di-2,2'-bipyridine
(the same in the following tables). Chemical structures thereof are
shown below.
##STR00387## ##STR00388##
Example 1
[0466] <Element Using Compound (1-176) as Dopant Material of
Light Emitting Layer>
[0467] A glass substrate (manufactured by Opto Science, Inc.)
having a size of 26 mm.times.28 mm.times.0.7 mm, which was obtained
by forming a film of ITO having a thickness of 180 nm by
sputtering, and polishing the ITO film to 150 nm, was used as a
transparent supporting substrate. This transparent supporting
substrate was fixed to a substrate holder of a commercially
available vapor deposition apparatus (manufactured by Showa Shinku
Co., Ltd.), and a vapor deposition boat made of molybdenum and
containing HI, a vapor deposition boat made of molybdenum and
containing HAT-CN, a vapor deposition boat made of molybdenum and
containing HT, a vapor deposition boat made of molybdenum and
containing BH1, a vapor deposition boat made of molybdenum and
containing compound (1-176) of the present invention, a vapor
deposition boat made of molybdenum and containing ET2, a vapor
deposition boat made of molybdenum and containing ET1, a vapor
deposition boat made of molybdenum and containing LiF, and a vapor
deposition boat made of tungsten and containing aluminum, were
mounted in the apparatus.
[0468] Various layers as described below were formed sequentially
on the ITO film of the transparent supporting substrate. The
pressure in a vacuum chamber was reduced to 5.times.10.sup.-4 Pa,
and first, a hole injection layer 1 was formed by heating the vapor
deposition boat containing HI and thereby performing vapor
deposition to obtain a film thickness of 65 nm. Subsequently, a
hole injection layer 2 was formed by heating the vapor deposition
boat containing HAT-CN and thereby performing deposition to obtain
a film thickness of 5 nm. Furthermore, a hole transport layer was
formed by heating the vapor deposition boat containing HT and
thereby performing deposition to obtain a film thickness of 60 nm.
Next, a light emitting layer was formed by simultaneously heating
the vapor deposition boat containing BH1 and the vapor deposition
boat containing compound (1-176) and thereby performing deposition
to obtain a film thickness of 25 nm. The rate of deposition was
regulated such that the weight ratio of BH1 and the compound
(1-176) would be approximately 80:20. Next, an electron transport
layer 2 was formed by heating the vapor deposition boat containing
ET2 and thereby conducting deposition to obtain a film thickness of
20 nm, and an electron transport layer 1 was formed by heating the
vapor deposition boat containing ET1 and thereby performing
deposition to obtain a film thickness of 10 nm. The rate of
deposition for each layer was 0.01 to 1 nm/second.
[0469] Thereafter, the vapor deposition boat containing LiF was
heated, and thereby vapor deposition was conducted at a rate of
deposition of 0.01 to 0.1 nm/second so as to obtain a film
thickness of 1 nm. Subsequently, a negative electrode was formed by
heating the vapor deposition boat containing aluminum and thereby
performing deposition at a rate of deposition of 0.01 to 2
nm/second so as to obtain a film thickness of 100 nm. Thus, an
organic EL element was obtained.
[0470] When a direct current voltage was applied to the ITO
electrode as the positive electrode and the LiF/aluminum electrode
as the negative electrode, blue light emission having a peak top at
about 437 nm was obtained. The external quantum efficiency at a
luminance of 100 cd/m.sup.2 was 3.39%.
Example 2
[0471] <Element Using Compound (1-100) as Dopant Material of
Light Emitting Layer>
[0472] An organic EL element was obtained by a method equivalent to
that of Example 1, except that the compound (1-176) as the dopant
material of the light emitting layer was changed to compound
(1-100). When a direct current voltage was applied to the two
electrodes, blue light emission having a peak top at about 457 nm
was obtained. The external quantum efficiency at a luminance of 100
cd/m.sup.2 was 2.78%.
[0473] Furthermore, organic EL elements related to Examples 3 and 4
were produced, and the external quantum efficiency obtainable when
each element was driven at a current density that could give a
luminance of 100 cd/m.sup.2, was measured. The material
configurations of the various layers in the organic EL elements
thus produced are shown in the following Table 2.
TABLE-US-00002 TABLE 2 Hole Hole Electron Injection Transport Light
Emitting Layer Transport Negative Layer Layer (30 nm) Layer
Electrode (10 nm) (30 nm) Host Dopant (50 nm) (1 nm/100 nm) Ex. 3
HAT-CN TBB CBP Compound TPBi LiF/Al (1-141) Ex. 4 HAT-CN TBB CBP
Compound TPBi LiF/Al (1-81)
[0474] In Table 2, "TBB" means
N.sup.4,N.sup.4,N.sup.4',N.sup.4'-tetra([1,1'-biphenyl]-4-yl)-[1,1'-biphe-
nyl]-4, 4'-diamine; "CBP" means
4,4'-di(9H-carbazolyl-9-yl)-1,1'-biphenyl; and "TPBi" means
1,3,5-tris(1-phenyl-1H-benzo[d]imidazol-2-yl)benzene. The chemical
structures thereof are shown below.
##STR00389##
Example 3
[0475] <Element Using Compound (1-141) as Dopant Material of
Light Emitting Layer>
[0476] A glass substrate (manufactured by Opto Science, Inc.)
having a size of 26 mm.times.28 mm.times.0.7 mm, which was obtained
by forming a film of ITO having a thickness of 180 nm by
sputtering, and polishing the ITO film to 150 nm, was used as a
transparent supporting substrate. This transparent supporting
substrate was fixed to a substrate holder of a commercially
available vapor deposition apparatus (manufactured by Showa Shinku
Co., Ltd.), and a vapor deposition boat made of molybdenum and
containing HAT-CN, a vapor deposition boat made of molybdenum and
containing TBB, a vapor deposition boat made of molybdenum and
containing CBP, a vapor deposition boat made of molybdenum and
containing compound (1-141) of the present invention, a vapor
deposition boat made of molybdenum and containing TPBi, a vapor
deposition boat made of molybdenum and containing LiF, and a vapor
deposition boat made of tungsten and containing aluminum, were
mounted in the apparatus.
[0477] Various layers as described below were formed sequentially
on the ITO film of the transparent supporting substrate. The
pressure in a vacuum chamber was reduced to 5.times.10.sup.-4 Pa,
and first, a hole injection layer was formed by heating the vapor
deposition boat containing HAT-CN and thereby performing vapor
deposition to obtain a film thickness of 10 nm. Subsequently, a
hole transport layer was formed by heating the vapor deposition
boat containing TBB and thereby performing deposition to obtain a
film thickness of 30 nm. Next, a light emitting layer was formed by
simultaneously heating the vapor deposition boat containing CBP and
the vapor deposition boat containing compound (1-141) and thereby
performing deposition to obtain a film thickness of 30 nm. The rate
of deposition was regulated such that the weight ratio of CBP and
the compound (1-141) would be approximately 80:20. Next, an
electron transport layer was formed by heating the vapor deposition
boat containing TPBi and thereby performing deposition to obtain a
film thickness of 50 nm. The rate of deposition for each layer was
0.01 to 1 nm/second.
[0478] Thereafter, the vapor deposition boat containing LiF was
heated, and thereby vapor deposition was conducted at a rate of
deposition of 0.01 to 0.1 nm/second so as to obtain a film
thickness of 1 nm. Subsequently, a negative electrode was formed by
heating the vapor deposition boat containing aluminum and thereby
performing deposition at a rate of deposition of 0.01 to 2
nm/second so as to obtain a film thickness of 100 nm. Thus, an
organic EL element was obtained.
[0479] When a direct current voltage was applied to the ITO
electrode as the positive electrode and the LiF/aluminum electrode
as the negative electrode, green light emission having a peak top
at about 534 nm was obtained. The external quantum efficiency at a
luminance of 100 cd/m.sup.2 was 6.29%.
Example 4
[0480] <Element Using Compound (1-81) as Dopant Material of
Light Emitting Layer>
[0481] An organic EL element was obtained by a method equivalent to
that of Example 3, except that the compound (1-141) as the dopant
material of the light emitting layer was changed to compound
(1-81). When a direct current voltage was applied to the two
electrodes, green light emission having a peak top at about 512 nm
was obtained. The external quantum efficiency at a luminance of 100
cd/m.sup.2 was 8.37%.
[0482] Furthermore, an organic EL element related to Example 5 was
produced, and the external quantum efficiency obtainable when the
organic EL element was driven at a current density that could give
a luminance of 1000 cd/m.sup.2 or 100 cd/m.sup.2, was measured. The
material configurations of the various layers in the organic EL
element thus produced are shown in the following Table 3.
TABLE-US-00003 TABLE 3 Hole Hole Electron Injection Transport Light
Emitting Layer Transport Negative Layer Layer (30 nm) Layer
Electrode (10 nm) (30 nm) Host Dopant (50 nm) (1 nm/100 nm) Ex. 5
HAT-CN TBB Compound Ir(PPy).sub.3 TPBi LiF/Al (1-91)
[0483] In Table 3, "Ir(PPy).sub.3" means
tris(2-phenylpyridine)iridium(III). The chemical structure thereof
is shown below.
##STR00390##
Example 5
[0484] <Element Using Compound (1-91) as Host Material of Light
Emitting Layer>
[0485] A glass substrate (manufactured by Opto Science, Inc.)
having a size of 26 mm.times.28 mm.times.0.7 mm, which was obtained
by forming a film of ITO having a thickness of 180 nm by
sputtering, and polishing the ITO film to 150 nm, was used as a
transparent supporting substrate. This transparent supporting
substrate was fixed to a substrate holder of a commercially
available vapor deposition apparatus (manufactured by Showa Shinku
Co., Ltd.), and a vapor deposition boat made of molybdenum and
containing HAT-CN, a vapor deposition boat made of molybdenum and
containing TBB, a vapor deposition boat made of molybdenum and
containing compound (1-91) of the present invention, a vapor
deposition boat made of molybdenum and containing Ir(PPy).sub.3, a
vapor deposition boat made of molybdenum and containing TPBi, a
vapor deposition boat made of molybdenum and containing LiF, and a
vapor deposition boat made of tungsten and containing aluminum,
were mounted in the apparatus.
[0486] Various layers as described below were formed sequentially
on the ITO film of the transparent supporting substrate. The
pressure in a vacuum chamber was reduced to 5.times.10.sup.-4 Pa,
and first, a hole injection layer was formed by heating the vapor
deposition boat containing HAT-CN and thereby performing vapor
deposition to obtain a film thickness of 10 nm. Subsequently, a
hole transport layer was formed by heating the vapor deposition
boat containing TBB and thereby performing deposition to obtain a
film thickness of 30 nm. Next, a light emitting layer was formed by
simultaneously heating the vapor deposition boat containing
compound (1-91) and the vapor deposition boat containing
Ir(PPy).sub.3 and thereby performing deposition to obtain a film
thickness of 30 nm. The rate of deposition was regulated such that
the weight ratio of the compound (1-91) and Ir(PPy).sub.3 would be
approximately 95:5. Next, an electron transport layer was formed by
heating the vapor deposition boat containing TPBi and thereby
performing deposition to obtain a film thickness of 50 nm. The rate
of deposition for each layer was 0.01 to 1 nm/second.
[0487] Thereafter, the vapor deposition boat containing LiF was
heated, and thereby vapor deposition was conducted at a rate of
deposition of 0.01 to 0.1 nm/second so as to obtain a film
thickness of 1 nm. Subsequently, a negative electrode was formed by
heating the vapor deposition boat containing aluminum and thereby
performing deposition at a rate of deposition of 0.01 to 2
nm/second so as to obtain a film thickness of 100 nm. Thus, an
organic EL element was obtained.
[0488] When a direct current voltage was applied to the ITO
electrode as the positive electrode and the LiF/aluminum electrode
as the negative electrode, green light emission having a peak top
at about 512 nm was obtained. The external quantum efficiency at a
luminance of 1000 cd/m.sup.2 was 10.88%. Also, the external quantum
efficiency at a luminance of 100 cd/m.sup.2 was 14.76%.
[0489] Furthermore, organic EL elements related to Examples 6 to 14
were produced, and the external quantum efficiency obtainable when
each of the organic EL elements was driven at a current density
that could give a luminance of 1000 cd/m.sup.2 or 100 cd/m.sup.2,
was measured. The material configurations of the various layers in
the organic EL elements thus produced are shown in the following
Table 4.
TABLE-US-00004 TABLE 4 Hole Hole Electron Injection Transport Light
Emitting Layer Transport Negative Layer Layer (30 nm) Layer
Electrode (10 nm) (30 nm) Host Dopant (50 nm) (1 nm/100 nm) Ex. 6
HAT-CN TBB Compound Ir(PPy).sub.3 TPBi LiF/Al (1-152) Ex. 7 HAT-CN
TBB Compound Ir(PPy).sub.3 TPBi LiF/Al (1-1048) Ex. 8 HAT-CN TBB
Compound Ir(PPy).sub.3 TPBi LiF/Al (1-1049) Ex. 9 HAT-CN TBB
Compound Ir(PPy).sub.3 TPBi LiF/Al (1-1050) Ex. 10 HAT-CN TBB
Compound Ir(PPy).sub.3 TPBi LiF/Al (1-100) Ex. 11 HAT-CN TBB
Compound Ir(PPy).sub.3 TPBi LiF/Al (1-49) Ex. 12 HAT-CN TBB
Compound Ir(PPy).sub.3 TPBi LiF/Al (1-176) Ex. 13 HAT-CN TBB
Compound Ir(PPy).sub.3 TPBi LiF/Al (1-1069) Ex. 14 HAT-CN TBB
Compound Ir(PPy).sub.3 TPBi LiF/Al (1-1201)
Example 6
[0490] <Element Using Compound (1-152) as Host Material of Light
Emitting Layer>
[0491] An organic EL element was obtained by a method equivalent to
that of Example 5, except that the compound (1-91) as the host
material of the light emitting layer was changed to compound
(1-152). When a direct current voltage was applied to the two
electrodes, green light emission having a peak top at about 512 nm
was obtained. The external quantum efficiency at a luminance of
1000 cd/m.sup.2 was 9.36%. The external quantum efficiency at a
luminance of 100 cd/m.sup.2 was 13.26%.
Example 7
[0492] <Element Using Compound (1-1048) as Host Material of
Light Emitting Layer>
[0493] An organic EL element was obtained by a method equivalent to
that of Example 5, except that the compound (1-91) as the host
material of the light emitting layer was changed to compound
(1-1048). When a direct current voltage was applied to the two
electrodes, green light emission having a peak top at about 512 nm
was obtained. The external quantum efficiency at a luminance of
1000 cd/m.sup.2 was 9.50%. The external quantum efficiency at a
luminance of 100 cd/m.sup.2 was 12.43%.
Example 8
[0494] <Element Using Compound (1-1049) as Host Material of
Light Emitting Layer>
[0495] An organic EL element was obtained by a method equivalent to
that of Example 5, except that the compound (1-91) as the host
material of the light emitting layer was changed to compound
(1-1049). When a direct current voltage was applied to the two
electrodes, green light emission having a peak top at about 512 nm
was obtained. The external quantum efficiency at a luminance of
1000 cd/m.sup.2 was 6.54%. The external quantum efficiency at a
luminance of 100 cd/m.sup.2 was 7.44%.
Example 9
[0496] <Element Using Compound (1-1050) as Host Material of
Light Emitting Layer>
[0497] An organic EL element was obtained by a method equivalent to
that of Example 5, except that the compound (1-91) as the host
material of the light emitting layer was changed to compound
(1-1050). When a direct current voltage was applied to the two
electrodes, green light emission having a peak top at about 512 nm
was obtained. The external quantum efficiency at a luminance of
1000 cd/m.sup.2 was 10.98%. The external quantum efficiency at a
luminance of 100 cd/m.sup.2 was 12.32%.
Example 10
[0498] <Element Using Compound (1-100) as Host Material of Light
Emitting Layer>
[0499] An organic EL element was obtained by a method equivalent to
that of Example 5, except that the compound (1-91) as the host
material of the light emitting layer was changed to compound
(1-100). When a direct current voltage was applied to the two
electrodes, green light emission having a peak top at about 512 nm
was obtained. The external quantum efficiency at a luminance of
1000 cd/m.sup.2 was 5.73%. The external quantum efficiency at a
luminance of 100 cd/m.sup.2 was 8.75%.
Example 11
[0500] <Element Using Compound (1-49) as Host Material of Light
Emitting Layer>
[0501] An organic EL element was obtained by a method equivalent to
that of Example 5, except that the compound (1-91) as the host
material of the light emitting layer was changed to compound
(1-49). When a direct current voltage was applied to the two
electrodes, green light emission having a peak top at about 512 nm
was obtained. The external quantum efficiency at a luminance of
1000 cd/m.sup.2 was 7.33%. The external quantum efficiency at a
luminance of 100 cd/m.sup.2 was 10.36%.
Example 12
[0502] <Element Using Compound (1-176) as Host Material of Light
Emitting Layer>
[0503] An organic EL element was obtained by a method equivalent to
that of Example 5, except that the compound (1-91) as the host
material of the light emitting layer was changed to compound
(1-176). When a direct current voltage was applied to the two
electrodes, green light emission having a peak top at about 512 nm
was obtained. The external quantum efficiency at a luminance of
1000 cd/m.sup.2 was 10.74%. The external quantum efficiency at a
luminance of 100 cd/m.sup.2 was 11.77%.
Example 13
[0504] <Element Using Compound (1-1069) as Host Material of
Light Emitting Layer>
[0505] An organic EL element was obtained by a method equivalent to
that of Example 5, except that the compound (1-91) as the host
material of the light emitting layer was changed to compound
(1-1069). When a direct current voltage was applied to the two
electrodes, green light emission having a peak top at about 512 nm
was obtained. The external quantum efficiency at a luminance of
1000 cd/m.sup.2 was 8.96%. The external quantum efficiency at a
luminance of 100 cd/m.sup.2 was 11.80%.
Example 14
[0506] <Element Using Compound (1-1201) as Host Material of
Light Emitting Layer>
[0507] An organic EL element was obtained by a method equivalent to
that of Example 5, except that the compound (1-91) as the host
material of the light emitting layer was changed to compound
(1-1201). When a direct current voltage was applied to the two
electrodes, green light emission having a peak top at about 512 nm
was obtained. The external quantum efficiency at a luminance of
1000 cd/m.sup.2 was 10.14%. The external quantum efficiency at a
luminance of 100 cd/m.sup.2 was 12.17%.
[0508] Furthermore, organic EL elements related to Examples 15 and
16 were produced, and the external quantum efficiency obtainable
when each of the organic EL elements was driven at a current
density that could give a luminance of 1000 cd/m.sup.2, was
measured. The material configurations of the various layers in the
organic EL elements thus produced are shown in the following Table
5.
TABLE-US-00005 TABLE 5 Hole Hole Hole Electron Electron Injection
Injection Transport Light Emitting Layer Transport Transport
Negative Layer 1 Layer 2 Layer (20 nm) Layer 2 Layer 1 Electrode
(40 nm) (5 nm) (25 nm) Host Dopant (20 nm) (10 nm) (1 nm/100 nm)
Ex. 15 HI HAT-CN HT BH1 Compound ET2 ET1 LiF/Al (1-1145) Ex. 16 HI
HAT-CN HT BH1 Compound ET2 ET1 LiF/Al (1-401)
Example 15
[0509] <Element Using Compound (1-1145) as Dopant Material of
Light Emitting Layer>
[0510] A glass substrate (manufactured by Opto Science, Inc.)
having a size of 26 mm.times.28 mm.times.0.7 mm, which was obtained
by forming a film of ITO having a thickness of 180 nm by
sputtering, and polishing the ITO film to 150 nm, was used as a
transparent supporting substrate. This transparent supporting
substrate was fixed to a substrate holder of a commercially
available vapor deposition apparatus (manufactured by Showa Shinku
Co., Ltd.), and a vapor deposition boat made of molybdenum and
containing HI, a vapor deposition boat made of molybdenum and
containing HAT-CN, a vapor deposition boat made of molybdenum and
containing HT, a vapor deposition boat made of molybdenum and
containing BH1, a vapor deposition boat made of molybdenum and
containing compound (1-1145) of the present invention, a vapor
deposition boat made of molybdenum and containing ET2, a vapor
deposition boat made of molybdenum and containing ET1, a vapor
deposition boat made of molybdenum and containing LiF, and a vapor
deposition boat made of tungsten and containing aluminum, were
mounted in the apparatus.
[0511] Various layers as described below were formed sequentially
on the ITO film of the transparent supporting substrate. The
pressure in a vacuum chamber was reduced to 5.times.10.sup.-4 Pa,
and first, a hole injection layer 1 was formed by heating the vapor
deposition boat containing HI and thereby performing vapor
deposition to obtain a film thickness of 40 nm. Subsequently, a
hole injection layer 2 was formed by heating the vapor deposition
boat containing HAT-CN and thereby performing deposition to obtain
a film thickness of 5 nm. Furthermore, a hole transport layer was
formed by heating the vapor deposition boat containing HT and
thereby performing deposition to obtain a film thickness of 25 nm.
Next, a light emitting layer was formed by simultaneously heating
the vapor deposition boat containing BH1 and the vapor deposition
boat containing compound (1-1145) and thereby performing deposition
to obtain a film thickness of 20 nm. The rate of deposition was
regulated such that the weight ratio of BH1 and the compound
(1-1145) would be approximately 95:5. Next, an electron transport
layer 2 was formed by heating the vapor deposition boat containing
ET2 and thereby performing deposition to obtain a film thickness of
20 nm, and an electron transport layer 1 was formed by heating the
vapor deposition boat containing ET1 and thereby performing
deposition to obtain a film thickness of 10 nm. The rate of
deposition for each layer was 0.01 to 1 nm/second.
[0512] Thereafter, the vapor deposition boat containing LiF was
heated, and thereby vapor deposition was conducted at a rate of
deposition of 0.01 to 0.1 nm/second so as to obtain a film
thickness of 1 nm. Subsequently, a negative electrode was formed by
heating the vapor deposition boat containing aluminum and thereby
performing deposition at a rate of deposition of 0.01 to 2
nm/second so as to obtain a film thickness of 100 nm. Thus, an
organic EL element was obtained.
[0513] When a direct current voltage was applied to the ITO
electrode as the positive electrode and the LiF/aluminum electrode
as the negative electrode, blue light emission having a peak top at
about 449 nm was obtained. The external quantum efficiency at a
luminance of 1000 cd/m.sup.2 was 4.75%.
Example 16
[0514] <Element Using Compound (1-401) as Dopant Material of
Light Emitting Layer>
[0515] An organic EL element was obtained by a method equivalent to
that of Example 15, except that the compound (1-1145) as the dopant
material of the light emitting layer was changed to compound
(1-401). When a direct current voltage was applied to the two
electrodes, blue light emission having a peak top at about 458 nm
was obtained. The external quantum efficiency at a luminance of
1000 cd/m.sup.2 was 4.33%.
[0516] Furthermore, organic EL elements related to Examples 17 to
19 were produced, and the external quantum efficiency obtainable
when each of the organic EL elements was driven at a current
density that could give a luminance of 1000 cd/m.sup.2, was
measured. The material configurations of the various layers in the
organic EL elements thus produced are shown in the following Table
6.
TABLE-US-00006 TABLE 6 Hole Hole Hole Electron Injection Transport
Transport Light Emitting Layer Transport Negative Layer Layer 1
Layer 2 (30 nm) Layer Electrode (10 nm) (20 nm) (10 nm) Host Dopant
(50 nm) (1 nm/100 nm) Ex. 17 HAT-CN TBB TcTa Compound Ir(PPy).sub.3
TPBi LiF/Al (1-1101) Ex. 18 HAT-CN TBB TcTa Compound Ir(PPy).sub.3
TPBi LiF/Al (1-1102) Ex. 19 HAT-CN TBB TcTa Compound Ir(PPy).sub.3
TPBi LiF/Al (1-1103)
[0517] In Table 6, "TcTa" means tris(4-carbazolyl-9-ylphenyl)amine.
The chemical structure thereof is shown below.
##STR00391##
Example 17
[0518] <Element Using Compound (1-1101) as Host Material of
Light Emitting Layer>
[0519] A glass substrate (manufactured by Opto Science, Inc.)
having a size of 26 mm.times.28 mm.times.0.7 mm, which was obtained
by forming a film of ITO having a thickness of 180 nm by
sputtering, and polishing the ITO film to 150 nm, was used as a
transparent supporting substrate. This transparent supporting
substrate was fixed to a substrate holder of a commercially
available vapor deposition apparatus (manufactured by Choshu
Industry Co., Ltd.), and a vapor deposition crucible made of
tantalum and containing HAT-CN, a vapor deposition crucible made of
tantalum and containing TBB, a vapor deposition crucible made of
tantalum and containing TcTa, a vapor deposition crucible made of
tantalum and containing compound (1-1101) of the present invention,
a vapor deposition crucible made of tantalum and containing
Ir(PPy).sub.3, a vapor deposition crucible made of tantalum and
containing TPBi, a vapor deposition crucible made of tantalum and
containing LiF, and a vapor deposition crucible made of aluminum
nitride and containing aluminum, were mounted in the apparatus.
[0520] Various layers as described below were formed sequentially
on the ITO film of the transparent supporting substrate. The
pressure in a vacuum chamber was reduced to 2.0.times.10.sup.-4 Pa.
First, the vapor deposition crucible containing HAT-CN was heated,
and thereby vapor deposition was performed so as to obtain a film
thickness of 10 nm. Subsequently, the vapor deposition crucible
containing TBB was heated, and thereby vapor deposition was
performed so as to obtain a film thickness of 20 nm. Further, the
vapor deposition crucible containing TcTa was heated, and thereby
vapor deposition was performed so as to obtain a film thickness of
20 nm. Thus, hole injection layers and hole transport layers
composed of three layers were formed. Next, the vapor deposition
crucible containing compound (1-1101) of the present invention and
the vapor deposition crucible containing Ir(PPy).sub.3 were
simultaneously heated, and thereby vapor deposition was performed
so as to obtain a film thickness of 30 nm. Thus, a light emitting
layer was formed. The rate of deposition was regulated such that
the weight ratio of the compound (1-1101) of the present invention
and Ir(PPy).sub.3 would be approximately 95:5. Next, the vapor
deposition crucible containing TPBi was heated, and thereby vapor
deposition was performed so as to obtain a film thickness of 50 nm.
Thus, an electron transport layer was formed. The rate of
deposition for each layer was 0.01 to 1 nm/second.
[0521] Thereafter, the vapor deposition crucible containing LiF was
heated, and thereby vapor deposition was performed at a rate of
deposition of 0.01 to 0.1 nm/second so as to obtain a film
thickness of 1 nm. Subsequently, the vapor deposition crucible
containing aluminum was heated, and thereby vapor deposition was
performed so as to obtain a film thickness of 100 nm. Thus, a
negative electrode was formed. At this time, the negative electrode
was formed by performing vapor deposition at a rate of deposition
of 0.1 nm/sec to 2 nm/sec, and thus an organic electroluminescent
element was obtained.
[0522] When a direct current voltage was applied to the ITO
electrode as the positive electrode and the LiF/aluminum electrode
as the negative electrode, green light emission having a peak top
at about 512 nm was obtained. The external quantum efficiency at a
luminance of 1000 cd/m.sup.2 was 10.09%.
Example 18
[0523] <Element Using Compound (1-1102) as Host Material of
Light Emitting Layer>
[0524] An organic EL element was obtained by a method equivalent to
that of Example 17, except that the compound (1-1101) as the host
material of the light emitting layer was changed to compound
(1-1102). When a direct current voltage was applied to the two
electrodes, green light emission having a peak top at about 512 nm
was obtained. The external quantum efficiency at a luminance of
1000 cd/m.sup.2 was 7.99%.
Example 19
[0525] <Element Using Compound (1-1103) as Host Material of
Light Emitting Layer>
[0526] An organic EL element was obtained by a method equivalent to
that of Example 17, except that the compound (1-1101) as the host
material of the light emitting layer was changed to compound
(1-1103). When a direct current voltage was applied to the two
electrodes, green light emission having a peak top at about 512 nm
was obtained. The external quantum efficiency at a luminance of
1000 cd/m.sup.2 was 9.05%.
[0527] Furthermore, organic EL elements related to Examples 20 and
21 were produced, and the external quantum efficiency obtainable
when each of the organic EL elements was driven at a current
density that could give a luminance of 1000 cd/m.sup.2, was
measured. The material configurations of the various layers in the
organic EL elements thus produced are shown in the following Table
7.
TABLE-US-00007 TABLE 7 Hole Hole Hole Injection Transport Transport
Light Emitting Layer Electron Electron Negative Layer Layer 1 Layer
2 (30 nm) Transport Transport Electrode (10 nm) (20 nm) (10 nm)
Host Dopant Layer 1 Layer 2 (1 nm/100 nm) Ex. 20 HAT-CN TBB TcTa
CBP Ir(PPy).sub.3 Compound -- LiF/Al (1-1192) 50 nm Ex. 21 HAT-CN
TBB TcTa CBP Ir(PPy).sub.3 Compound ET-3 LiF/Al (1-1192) 40 nm 10
nm
[0528] In Table 7, "ET-3" means
3-(3-10-(naphthalen-2-yl)anthracen-9-yl)phenyl)pyridine. The
chemical structure thereof is shown below.
##STR00392##
Example 20
[0529] <Element Using Compound (1-1192) in Electron Transport
Layer>
[0530] A glass substrate (manufactured by Opto Science, Inc.)
having a size of 26 mm.times.28 mm.times.0.7 mm, which was obtained
by forming a film of ITO having a thickness of 180 nm by
sputtering, and polishing the ITO film to 150 nm, was used as a
transparent supporting substrate. This transparent supporting
substrate was fixed to a substrate holder of a commercially
available vapor deposition apparatus (manufactured by Choshu
Industry Co., Ltd.), and a vapor deposition crucible made of
tantalum and containing HAT-CN, a vapor deposition crucible made of
tantalum and containing TBB, a vapor deposition crucible made of
tantalum and containing TcTa, a vapor deposition crucible made of
tantalum and containing CBP, a vapor deposition crucible made of
tantalum and containing Ir(PPy).sub.3, a vapor deposition crucible
made of tantalum and containing compound (1-1192) of the present
invention, a vapor deposition crucible made of tantalum and
containing ET-3, a vapor deposition crucible made of tantalum and
containing LiF, and a vapor deposition crucible made of aluminum
nitride and containing aluminum, were mounted in the apparatus.
[0531] Various layers as described below were formed sequentially
on the ITO film of the transparent supporting substrate. The
pressure in a vacuum chamber was reduced to 2.0.times.10.sup.-4 Pa.
First, the vapor deposition crucible containing HAT-CN was heated,
and thereby vapor deposition was performed so as to obtain a film
thickness of 10 nm. Subsequently, the vapor deposition crucible
containing TBB was heated, and thereby vapor deposition was
performed so as to obtain a film thickness of 20 nm. Further, the
vapor deposition crucible containing TcTa was heated, and thereby
vapor deposition was performed so as to obtain a film thickness of
10 nm. Thus, hole injection layers and hole transport layers
composed of three layers were formed. Next, the vapor deposition
crucible containing CBP and the vapor deposition crucible
containing Ir(PPy).sub.3 were simultaneously heated, and thereby
vapor deposition was performed so as to obtain a film thickness of
30 nm. Thus, a light emitting layer was formed. The rate of
deposition was regulated such that the weight ratio of CBP and
Ir(PPy).sub.3 would be approximately 95:5. Next, the vapor
deposition crucible containing the compound (1-1192) of the present
invention was heated, and thereby vapor deposition was performed so
as to obtain a film thickness of 50 nm. Thus, an electron transport
layer was formed. The rate of deposition for each layer was 0.01 to
1 nm/second.
[0532] Thereafter, the vapor deposition crucible containing LiF was
heated, and thereby vapor deposition was performed at a rate of
deposition of 0.01 to 0.1 nm/second so as to obtain a film
thickness of 1 nm. Subsequently, the vapor deposition crucible
containing aluminum was heated, and thereby vapor deposition was
performed so as to obtain a film thickness of 100 nm. Thus, a
negative electrode was formed. At this time, the negative electrode
was formed by performing vapor deposition at a rate of deposition
of 0.1 nm/sec to 2 nm/sec, and thus an organic electroluminescent
element was obtained.
[0533] When a direct current voltage was applied to the ITO
electrode as the positive electrode and the LiF/aluminum electrode
as the negative electrode, green light emission having a peak top
at about 512 nm was obtained. The external quantum efficiency at a
luminance of 1000 cd/m.sup.2 was 13.49%.
Example 21
[0534] <Element Using Compound (1-1192) in Electron Transport
Layer 1 and ET-3 in Electron Transport Layer 2>
[0535] An organic EL element was obtained by a method equivalent to
that of Example 20, except that the compound (1-1192) was deposited
to a thickness of 10 nm as an electron transport layer 1, and then
ET-3 was deposited to a thickness of 40 nm as an electron transport
layer 2 so that the electron transport layer was changed to two
layers. When a direct current voltage was applied to the two
electrodes, green light emission having a peak top at about 512 nm
was obtained. The external quantum efficiency at a luminance of
1000 cd/m.sup.2 was 11.54%.
[0536] Furthermore, an organic EL element related to Example 22 was
produced, and the external quantum efficiency obtainable when the
organic EL element was driven at a current density that could give
a luminance of 1000 cd/m.sup.2, was measured. The material
configurations of the various layers in the organic EL element thus
produced is shown in the following Table 8.
TABLE-US-00008 TABLE 8 Hole Hole Hole Electron Electron Injection
Injection Transport Light Emitting Layer Transport Transport
Negative Layer 1 Layer 2 Layer (20 nm) Layer 1 Layer 2 Electrode
(40 nm) (5 nm) (25 nm) Host Dopant (20 nm) (10 nm) (1 nm/100 nm)
Ex. 22 HI HAT-CN HT BH2 Compound ET-4 ET-3 LiF/Al (1-447)
[0537] In Table 8, "BH2" means 1,3-di(pyren-1-yl)benzene, and
"ET-4" means
3,9-di(naphthalen-2-yl)spiro[benzo[a]fluorene-11,9'-fluoren e]. The
chemical structures thereof are shown below.
##STR00393##
Example 22
[0538] <Element Using Compound (1-447) as Dopant of Light
Emitting Layer>
[0539] A glass substrate (manufactured by Opto Science, Inc.)
having a size of 26 mm.times.28 mm.times.0.7 mm, which was obtained
by forming a film of ITO having a thickness of 180 nm by
sputtering, and polishing the ITO film to 150 nm, was used as a
transparent supporting substrate. This transparent supporting
substrate was fixed to a substrate holder of a commercially
available vapor deposition apparatus (manufactured by Choshu
Industry Co., Ltd.), and a vapor deposition crucible made of
tantalum and containing HI, a vapor deposition crucible made of
tantalum and containing HAT-CN, a vapor deposition crucible made of
tantalum and containing HT, a vapor deposition crucible made of
tantalum and containing BH2, a vapor deposition crucible made of
tantalum and containing compound (1-447) of the present invention,
a vapor deposition crucible made of tantalum and containing ET-4, a
vapor deposition crucible made of tantalum and containing ET-3, a
vapor deposition crucible made of tantalum and containing LiF, and
a vapor deposition crucible made of aluminum nitride and containing
aluminum, were mounted in the apparatus.
[0540] Various layers as described below were formed sequentially
on the ITO film of the transparent supporting substrate. The
pressure in a vacuum chamber was reduced to 2.0.times.10.sup.-4 Pa.
First, the vapor deposition crucible containing HI was heated, and
thereby vapor deposition was performed so as to obtain a film
thickness of 40 nm. Subsequently, the vapor deposition crucible
containing HAT-CN was heated, and thereby vapor deposition was
performed so as to obtain a film thickness of 5 nm. Further, the
vapor deposition crucible containing HT was heated, and thereby
vapor deposition was performed so as to obtain a film thickness of
25 nm. Thus, hole injection layers and hole transport layers
composed of three layers were formed. Next, the vapor deposition
crucible containing BH2 and the vapor deposition crucible
containing the compound (1-447) of the present invention were
simultaneously heated, and thereby vapor deposition was performed
so as to obtain a film thickness of 20 nm. Thus, a light emitting
layer was formed. The rate of deposition was regulated such that
the weight ratio of BH2 and compound (1-447) of the present
invention would be approximately 95:5. Next, the vapor deposition
crucible containing ET-4 was heated, and thereby vapor deposition
was performed so as to obtain a film thickness of 20 nm.
Subsequently, the vapor deposition crucible containing ET-3 was
heated, and thereby vapor deposition was performed so as to obtain
a film thickness of 10 nm. Thus, an electron transport layer
composed of two layers was formed. The rate of deposition for each
layer was 0.01 to 1 nm/second.
[0541] Thereafter, the vapor deposition crucible containing LiF was
heated, and thereby vapor deposition was performed at a rate of
deposition of 0.01 to 0.1 nm/second so as to obtain a film
thickness of 1 nm. Subsequently, the vapor deposition crucible
containing aluminum was heated, and thereby vapor deposition was
performed so as to obtain a film thickness of 100 nm. Thus, a
negative electrode was formed. At this time, the negative electrode
was formed by performing vapor deposition at a rate of deposition
of 0.1 nm/sec to 2 nm/sec, and thus an organic electroluminescent
element was obtained.
[0542] When a direct current voltage was applied to the ITO
electrode as the positive electrode and the LiF/aluminum electrode
as the negative electrode, blue light emission having a peak top at
about 457 nm was obtained. The external quantum efficiency at a
luminance of 1000 cd/m.sup.2 was 6.15%.
[0543] Furthermore, organic EL elements related to Examples 23 to
27 were produced, and the external quantum efficiency obtainable
when each of the organic EL elements was driven at a current
density that could give a luminance of 1000 cd/m.sup.2, was
measured. The material configurations of the various layers in the
organic EL elements thus produced are shown in the following Table
9.
TABLE-US-00009 TABLE 9 Hole Hole Hole Electron Electron Injection
Injection Transport Light Emitting Layer Transport Transport
Negative Layer 1 Layer 2 Layer (20 nm) Layer 1 Layer 2 Electrode
(40 nm) (5 nm) (25 nm) Host Dopant (20 nm) (10 nm) (1 nm/100 nm)
Ex. 23 HI HAT-CN HT BH1 BD1 Compound ET-1 LiF/Al (1-50) Ex. 24 HI
HAT-CN HT BH1 BD1 Compound ET-1 LiF/Al (1-49) Ex. 25 HI HAT-CN HT
BH1 BD1 Compound ET-3 LiF/Al (1-50) Ex. 26 HI HAT-CN HT BH1 BD1
Compound ET-3 LiF/Al (1-49) Ex. 27 HI HAT-CN HT BH1 BD1 Compound --
LiF/Al (1-50) (30 nm) Ex. 28 HI HAT-CN HT BH1 BD1 Compound --
LiF/Al (1-1050) (30 nm) Ex. 29 HI HAT-CN HT BH1 BD1 Compound --
LiF/Al (1-1102) (30 nm) Ex. 30 HI HAT-CN HT BH1 BD1 Compound ET-1
LiF/Al (1-1050) Ex. 31 HI HAT-CN HT BH1 BD1 Compound ET-1 LiF/Al
(1-1102)
[0544] In Table 9, "BD1" means
7,7-dimethyl-N.sup.5,N.sup.9-diphenyl-N.sup.5,N.sup.9-bis(4-(trimethylsil-
yl) phen yl)-7H-benzo[c]fluorene-5,9-diamine. The chemical
structure thereof is shown below.
##STR00394##
Example 23
[0545] <Element Using Compound (1-50) in Electron Transport
Layer 1 and ET-1 in Electron Transport Layer 2>
[0546] A glass substrate (manufactured by Opto Science, Inc.)
having a size of 26 mm.times.28 mm.times.0.7 mm, which was obtained
by forming a film of ITO having a thickness of 180 nm by
sputtering, and polishing the ITO film to 150 nm, was used as a
transparent supporting substrate. This transparent supporting
substrate was fixed to a substrate holder of a commercially
available vapor deposition apparatus (manufactured by Choshu
Industry Co., Ltd.), and a vapor deposition crucible made of
tantalum and containing HI, a vapor deposition crucible made of
tantalum and containing HAT-CN, a vapor deposition crucible made of
tantalum and containing HT, a vapor deposition crucible made of
tantalum and containing BH1, a vapor deposition crucible made of
tantalum and containing BD1, a vapor deposition crucible made of
tantalum and containing the compound (1-50) of the present
invention, a vapor deposition crucible made of tantalum and
containing ET-1, a vapor deposition crucible made of tantalum and
containing ET-3, a vapor deposition crucible made of tantalum and
containing LiF, and a vapor deposition crucible made of aluminum
nitride and containing aluminum, were mounted in the apparatus.
[0547] Various layers as described below were formed sequentially
on the ITO film of the transparent supporting substrate. The
pressure in a vacuum chamber was reduced to 2.0.times.10.sup.-4 Pa.
First, the vapor deposition crucible containing HI was heated, and
thereby vapor deposition was performed so as to obtain a film
thickness of 40 nm. Subsequently, the vapor deposition crucible
containing HAT-CN was heated, and thereby vapor deposition was
performed so as to obtain a film thickness of 5 nm. Further, the
vapor deposition crucible containing HT was heated, and thereby
vapor deposition was performed so as to obtain a film thickness of
25 nm. Thus, hole injection layers and hole transport layers
composed of three layers were formed. Next, the vapor deposition
crucible containing BH1 and the vapor deposition crucible
containing BD1 were simultaneously heated, and thereby vapor
deposition was performed so as to obtain a film thickness of 20 nm.
Thus, a light emitting layer was formed. The rate of deposition was
regulated such that the weight ratio of BH1 and BD1 would be
approximately 95:5. Next, the vapor deposition crucible containing
the compound (1-50) of the present invention was heated, and
thereby vapor deposition was performed so as to obtain a film
thickness of 20 nm. Subsequently, the vapor deposition crucible
containing ET-1 was heated, and thereby vapor deposition was
performed so as to obtain a film thickness of 10 nm. Thus, an
electron transport layer composed of two layers was formed. The
rate of deposition for each layer was 0.01 to 1 nm/second.
[0548] Thereafter, the vapor deposition crucible containing LiF was
heated, and thereby vapor deposition was performed at a rate of
deposition of 0.01 to 0.1 nm/second so as to obtain a film
thickness of 1 nm. Subsequently, the vapor deposition crucible
containing aluminum was heated, and thereby vapor deposition was
performed so as to obtain a film thickness of 100 nm. Thus, a
negative electrode was formed. At this time, the negative electrode
was formed by performing vapor deposition at a rate of deposition
of 0.1 nm/sec to 2 nm/sec, and thus an organic electroluminescent
element was obtained.
[0549] When a direct current voltage was applied to the ITO
electrode as the positive electrode and the LiF/aluminum electrode
as the negative electrode, blue light emission having a peak top at
about 456 nm was obtained. The external quantum efficiency at a
luminance of 1000 cd/m.sup.2 was 8.08%.
Example 24
[0550] <Element Using Compound (1-49) in Electron Transport
Layer 1 and ET-1 in Electron Transport Layer 2>
[0551] An organic EL element was obtained by a method equivalent to
that of Example 23, except that the material of the electron
transport layer 1 was changed to compound (1-49). When a direct
current voltage was applied to the two electrodes, blue light
emission having a peak top at about 456 nm was obtained. The
external quantum efficiency at a luminance of 1000 cd/m.sup.2 was
8.86%.
Example 25
[0552] <Element Using Compound (1-50) in Electron Transport
Layer 1 and ET-3 in Electron Transport Layer 2>
[0553] An organic EL element was obtained by a method equivalent to
that of Example 23, except that the material of the electron
transport layer 2 was changed to ET-3. When a direct current
voltage was applied to the two electrodes, blue light emission
having a peak top at about 456 nm was obtained. The external
quantum efficiency at a luminance of 1000 cd/m.sup.2 was 8.16%.
Example 26
[0554] <Element Using Compound (1-49) in Electron Transport
Layer 1 and ET-3 in Electron Transport Layer 2>
[0555] An organic EL element was obtained by a method equivalent to
that of Example 23, except that the material of the electron
transport layer 1 was changed to the compound (1-49), and the
material of the electron transport layer 2 to ET-3. When a direct
current voltage was applied to the two electrodes, blue light
emission having a peak top at about 456 nm was obtained. The
external quantum efficiency at a luminance of 1000 cd/m.sup.2 was
8.94%.
Example 27
[0556] <Element Using Compound (1-50) in Electron Transport
Layer 1>
[0557] An organic EL element was obtained by a method equivalent to
that of Example 23, except that the electron transport layer 2 was
removed, and the film thickness of the electron transport layer 1
was changed to 30 nm. When a direct current voltage was applied to
the two electrodes, blue light emission having a peak top at about
456 nm was obtained. The external quantum efficiency at a luminance
of 1000 cd/m.sup.2 was 4.63%.
Example 28
[0558] <Element Using Compound (1-1050) in Electron Transport
Layer 1>
[0559] An organic EL element was obtained by a method equivalent to
that of Example 23, except that the electron transport layer 2 was
removed, and the film thickness of the electron transport layer 1
was changed to 30 nm. When a direct current voltage was applied to
the two electrodes, blue light emission having a peak top at about
456 nm was obtained. The external quantum efficiency at a luminance
of 1000 cd/m.sup.2 was 3.39%.
Example 29
[0560] <Element Using Compound (1-1102) in Electron Transport
Layer 1>
[0561] An organic EL element was obtained by a method equivalent to
that of Example 23, except that the electron transport layer 2 was
removed, and the film thickness of the electron transport layer 1
was changed to 30 nm. When a direct current voltage was applied to
the two electrodes, blue light emission having a peak top at about
456 nm was obtained. The external quantum efficiency at a luminance
of 1000 cd/m.sup.2 was 4.54%.
Example 30
[0562] <Element Using Compound (1-1050) in Electron Transport
Layer 1 and ET-1 in Electron Transport Layer 2>
[0563] An organic EL element was obtained by a method equivalent to
that of Example 23, except that the material of the electron
transport layer 1 was changed to compound (1-1050). When a direct
current voltage was applied to the two electrodes, blue light
emission having a peak top at about 456 nm was obtained. The
external quantum efficiency at a luminance of 1000 cd/m.sup.2 was
7.88%.
Example 31
[0564] <Element Using Compound (1-1102) in Electron Transport
Layer 1 and ET-1 in Electron Transport Layer 2>
[0565] An organic EL element was obtained by a method equivalent to
that of Example 23, except that the material of the electron
transport layer 1 was changed to compound (1-1102). When a direct
current voltage was applied to the two electrodes, blue light
emission having a peak top at about 456 nm was obtained. The
external quantum efficiency at a luminance of 1000 cd/m.sup.2 was
8.54%.
INDUSTRIAL APPLICABILITY
[0566] According to the present invention, since a novel polycyclic
aromatic compound is provided, the range of selection of the
material for organic EL elements can be widened. Also, when a novel
polycyclic aromatic compound is used as a material for an organic
electroluminescent element, an excellent organic EL element, a
display apparatus including the EL element, and a lighting
apparatus including the EL element can be provided.
REFERENCE SIGNS LIST
[0567] 100 Organic electroluminescent element [0568] 101 Substrate
[0569] 102 Positive electrode [0570] 103 Hole injection layer
[0571] 104 Hole transport layer [0572] 105 Light emitting layer
[0573] 106 Electron transport layer [0574] 107 Electron injection
layer [0575] 108 Negative electrode
* * * * *