U.S. patent application number 17/346936 was filed with the patent office on 2022-09-01 for compound for organic electric element, organic electric element comprising the same, and electronic device thereof.
This patent application is currently assigned to DUK SAN NEOLUX CO., LTD.. The applicant listed for this patent is DUK SAN NEOLUX CO., LTD.. Invention is credited to Mi Young CHAE, Hye Min CHO, Min Ji JO, Ga Eun LEE, Hyung Dong LEE, Nam Geol LEE, Sun Hee LEE, Soung Yun MUN, Dae Hwan OH, Sang Yong PARK.
Application Number | 20220278285 17/346936 |
Document ID | / |
Family ID | |
Filed Date | 2022-09-01 |
United States Patent
Application |
20220278285 |
Kind Code |
A1 |
CHAE; Mi Young ; et
al. |
September 1, 2022 |
COMPOUND FOR ORGANIC ELECTRIC ELEMENT, ORGANIC ELECTRIC ELEMENT
COMPRISING THE SAME, AND ELECTRONIC DEVICE THEREOF
Abstract
Provided are a compound represented by Formula 24, an organic
electric element comprising a first electrode, a second electrode,
and an organic material layer formed between the first electrode
and the second electrode and comprising the compound of Formula 24,
and an electronic device thereof, the element and device having
improved driving voltage, luminous efficiency and life time from
the employment of the compound.
Inventors: |
CHAE; Mi Young; (Cheonan-si,
KR) ; CHO; Hye Min; (Cheonan-si, KR) ; JO; Min
Ji; (Cheonan-si, KR) ; MUN; Soung Yun;
(Cheonan-si, KR) ; LEE; Sun Hee; (Cheonan-si,
KR) ; LEE; Nam Geol; (Cheonan-si, KR) ; LEE;
Hyung Dong; (Cheonan-si, KR) ; OH; Dae Hwan;
(Cheonan-si, KR) ; LEE; Ga Eun; (Cheonan-si,
KR) ; PARK; Sang Yong; (Cheonan-si, KR) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
DUK SAN NEOLUX CO., LTD. |
Cheonan-si |
|
KR |
|
|
Assignee: |
DUK SAN NEOLUX CO., LTD.
Cheonan-si
KR
|
Appl. No.: |
17/346936 |
Filed: |
June 14, 2021 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
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16652383 |
Mar 30, 2020 |
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PCT/KR2018/009503 |
Aug 20, 2018 |
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17346936 |
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International
Class: |
H01L 51/00 20060101
H01L051/00; C07D 409/14 20060101 C07D409/14 |
Foreign Application Data
Date |
Code |
Application Number |
Sep 29, 2017 |
KR |
10-2017-0127537 |
Apr 4, 2018 |
KR |
10-2018-0039162 |
Jun 25, 2018 |
KR |
10-2018-0072472 |
Claims
1. A compound of Formula 24: ##STR00318## wherein Ar.sup.4,
Ar.sup.5, Ar.sup.10 and Ar.sup.11 are each independently a
C.sub.6-C.sub.20 aryl group or a fluorenyl group, L.sup.5 is a
C.sub.12-C.sub.20 heterocyclic group containing at least one
heteroatom selected from the group consisting of O and S, wherein
Ar.sup.4, Ar.sup.5, Ar.sup.10, Ar.sup.11 and L.sup.5 may be each
optionally substituted with one or more substituents selected from
the group consisting of deuterium, a C.sub.1-C.sub.20 alkyl group,
a C.sub.6-C.sub.20 aryl group, and a C.sub.6-C.sub.20 aryl group
substituted with deuterium.
2. The compound of claim 1, wherein L.sup.5 is a dibenzofuran or
dibenzothiophene group.
3. The compound of claim 1, wherein Ar.sup.4 and Ar.sup.5 are each
independently a C.sub.6-C.sub.12 aryl group, and Ar.sup.10 and
Ar.sup.11 are each independently a C.sub.6-C.sub.12 aryl group or a
fluorenyl group.
4. The compound of claim 1, wherein Ar.sup.4 and Ar.sup.5 are each
independently a phenyl or biphenyl group, and one of Ar.sup.10 and
Ar.sup.11 is a phenyl or biphenyl group and the other is a
9,9-dimethyl-9H-fluorenyl group.
5. The compound of claim 4, wherein Ar.sup.4 and Ar.sup.5 are each
independently a phenyl group, Ar.sup.10 is a biphenyl group,
Ar.sup.11 is a 9,9-dimethyl-9H-fluorenyl group.
6. The compound of claim 1, wherein either Ar.sup.10 or Ar.sup.11
is a 2-(9,9-dimethyl-9H)-fluorenyl or 2-(9,9-diphenyl-9H)-fluorenyl
group.
7. The compound of claim 1, wherein the compound of Formula 24 is
Compound 15-7 or Compound 15-8: ##STR00319##
8. An organic electric element comprising a first electrode, a
second electrode and an organic material layer formed between the
first and the second electrodes, wherein the organic material layer
comprises the compound of Formula 24 of claim 1.
9. The organic electric element of claim 8, wherein the organic
material layer comprises a light emitting layer, and an
emission-auxiliary layer formed between the light emitting layer
and the first electrode, wherein the emission-auxiliary layer
comprises the compound of Formula 24.
10. The organic electric element of claim 9, wherein the organic
material layer further comprises a hole transport layer formed
between the light emitting layer and the first electrode, and the
hole transport layer comprises a compound of Formula 21 or 22:
##STR00320## wherein: Ar.sup.4, Ar.sup.5 and Ar.sup.9 are each
independently selected from the group consisting of a
C.sub.6-C.sub.20 aryl group, a fluorenyl group, a C.sub.2-C.sub.20
heterocyclic group containing at least one heteroatom selected from
the group consisting of O, N, S, Si, and P, C.sub.3-C.sub.20
aliphatic ring, and a fused ring group formed by a C.sub.3-C.sub.20
aliphatic ring with a C.sub.6-C.sub.20 aromatic ring, of a
C.sub.1-C.sub.20 alkyl group, a C.sub.2-C.sub.20 alkenyl group, a
C.sub.2-C.sub.20 alkynyl group, a C.sub.1-C.sub.20 alkoxyl group, a
C.sub.6-C.sub.20 aryloxy group and -L'-N(R.sub.a)(R.sub.b), L.sup.5
is selected from the group consisting of a C.sub.6-C.sub.20 arylene
group, a fluorenylene group, and a C.sub.2-C.sub.20 heterocyclic
group containing at least one heteroatom selected from the group
consisting of O, N, S, Si, and P, a C.sub.3-C.sub.20 aliphatic ring
and a fused ring group formed by a C.sub.3-C.sub.20 aliphatic ring
with a C.sub.6-C.sub.20 aromatic ring, L.sup.6 is selected from the
group consisting of a single bond, a C.sub.6-C.sub.20 arylene
group, a fluorenylene group, and a C.sub.2-C.sub.20 heterocyclic
group containing at least one heteroatom selected from the group
consisting of O, N, S, Si, and P, a C.sub.3-C.sub.20 aliphatic ring
and a fused ring group formed by a C.sub.3-C.sub.20 aliphatic ring
with a C.sub.6-C.sub.20 aromatic ring, R.sup.6 to R.sup.9 are each
independently selected from the group consisting of hydrogen,
deuterium, halogen, a C.sub.6-C.sub.20 aryl group, a fluorenyl
group, a C.sub.2-C.sub.20 heterocyclic group containing at least
one heteroatom selected from the group consisting of O, N, S, Si,
and P, a C.sub.3-C.sub.20 aliphatic ring, a fused ring group formed
by a C.sub.3-C.sub.20 aliphatic ring with a C.sub.6-C.sub.20
aromatic ring, a C.sub.1-C.sub.20 alkyl group, a C.sub.2-C.sub.20
alkenyl group, a C.sub.2-C.sub.20 alkynyl group, a C.sub.1-C.sub.20
alkoxyl group, a C.sub.6-C.sub.20 aryloxy group and
-L'-N(R.sub.a)(R.sub.b), wherein adjacent groups may be linked to
each other to form a ring, h, i and g are each an integer of 0 to
4, j is an integer of 0 to 3, where each of these is an integer of
2 or more, a plurality of R.sup.6s, a plurality of R.sup.7s, a
plurality of R.sup.8s, and a plurality of R.sup.9s are the same as
or different from each other, L' is selected from the group
consisting of a single bond, a C.sub.6-C.sub.20 arylene group, a
fluorenylene group, and a C.sub.2-C.sub.20 heterocyclic group
containing at least one heteroatom selected from the group
consisting of O, N, S, Si, and P, a C.sub.3-C.sub.20 aliphatic
ring, and a fused ring group formed by a C.sub.3-C.sub.20 aliphatic
ring with a C.sub.6-C.sub.20 aromatic ring, R.sub.a and R.sub.b are
each independently selected from the group consisting of a
C.sub.6-C.sub.20 aryl group, a fluorenyl group, a C.sub.2-C.sub.20
heterocyclic group containing at least one heteroatom selected from
the group consisting of O, N, S, Si, and P, a C.sub.3-C.sub.20
aliphatic ring and a fused ring group formed by a C.sub.3-C.sub.20
aliphatic ring with a C.sub.6-C.sub.20 aromatic ring, wherein
Ar.sup.4, Ar.sup.5, Ar.sup.9, R.sup.6 to R.sup.9, R.sub.a, R.sub.b,
L.sup.5, L.sup.6, L' and the ring formed by adjacent groups may be
each optionally substituted with one or more substituents selected
from the group consisting of deuterium, halogen, a silane group
unsubstituted or substituted with a C.sub.1-C.sub.20 alkyl group or
a C.sub.6-C.sub.20 aryl group, a siloxane group, a boron group, a
germanium group, a cyano group, a nitro group, a phosphine oxide
group unsubstituted or substituted with a C.sub.1-C.sub.20 alkyl
group or a C.sub.6-C.sub.20 aryl group, a C.sub.1-C.sub.20
alkylthio group, a C.sub.1-C.sub.20 alkoxyl group, a
C.sub.1-C.sub.20 alkyl group, a C.sub.2-C.sub.20 alkenyl group, a
C.sub.2-C.sub.20 alkynyl group, a C.sub.6-C.sub.20 aryl group, a
C.sub.6-C.sub.20 aryl group substituted with deuterium, a fluorenyl
group, a C.sub.2-C.sub.20 heterocyclic group containing at least
one heteroatom selected from the group consisting of O, N, S, Si,
and P, a C.sub.3-C.sub.20 cycloalkyl group, a fused ring group
formed by a C.sub.3-C.sub.20 aliphatic ring with a C.sub.6-C.sub.20
aromatic ring, a C.sub.7-C.sub.20 arylalkyl group, a
C.sub.8-C.sub.20 arylalkenyl group and a combination thereof.
11. The organic electric element of claim 9, wherein the light
emitting layer comprises a compound of Formula 12: ##STR00321##
wherein: Z.sup.1 to Z.sup.4, Z.sup.13 to Z.sup.16 are independently
C(R) or N, Z.sup.5 to Z.sup.12 are independently C, C(R) or N,
L.sup.2 is selected from the group consisting of a single bond, a
C.sub.6-C.sub.20 arylene group, a fluorenylene group, a
C.sub.2-C.sub.20 heterocyclic group containing at least one
heteroatom selected from the group consisting of O, N, S, Si, and
P, a C.sub.3-C.sub.20 aliphatic ring, and a fused ring group formed
by a C.sub.3-C.sub.20 aliphatic ring with a C.sub.6-C.sub.20
aromatic ring, W is N(Ar.sub.5), N, O, S, C(R') or C(R')(R''), and
W is N or C(R') where W is combined with L.sup.2, Ar.sub.4 and
Ar.sub.5 are each independently selected from the group consisting
of a C.sub.6-C.sub.20 aryl group, a fluorenyl group, a
C.sub.2-C.sub.20 heterocyclic group containing at least one
heteroatom selected from the group consisting of O, N, S, Si, and
P, a C.sub.3-C.sub.20 aliphatic ring, a fused ring group formed by
a C.sub.3-C.sub.20 aliphatic ring with a C.sub.6-C.sub.20 aromatic
ring, a C.sub.1-C.sub.20 alkyl group, a C.sub.2-C.sub.20 alkenyl
group, a C.sub.2-C.sub.20 alkynyl group, a C.sub.1-C.sub.20 alkoxyl
group, a C.sub.6-C.sub.20 aryloxy group, -L'-N(R.sub.a)(R.sub.b)
and a combination thereof, R, R' and R'' are each independently
selected from the group consisting of hydrogen, deuterium, halogen,
a C.sub.6-C.sub.20 aryl group, a fluorenyl group, a
C.sub.2-C.sub.20 heterocyclic group containing at least one
heteroatom selected from the group consisting of O, N, S, Si, and
P, a C.sub.3-C.sub.20 aliphatic ring, a fused ring group formed by
a C.sub.3-C.sub.20 aliphatic ring with a C.sub.6-C.sub.20 aromatic
ring, a C.sub.1-C.sub.20 alkyl group, a C.sub.2-C.sub.20 alkenyl
group, a C.sub.2-C.sub.20 alkynyl group, a C.sub.1-C.sub.20 alkoxyl
group, a C.sub.6-C.sub.20 aryloxy group and
-L'-N(R.sub.a)(R.sub.b), wherein adjacent R groups may be
optionally linked to each other to form a ring, and R' and R'' may
be optionally linked to each other to form a ring, L' is selected
from the group consisting of a single bond, a C.sub.6-C.sub.20
arylene group, a fluorenylene group, and a C.sub.2-C.sub.20
heterocyclic group containing at least one heteroatom selected from
the group consisting of O, N, S, Si, and P, a C.sub.3-C.sub.20
aliphatic ring, and a fused ring group formed by a C.sub.3-C.sub.20
aliphatic ring with a C.sub.6-C.sub.20 aromatic ring, and R.sub.a
and R.sub.b are each independently selected from the group
consisting of a C.sub.6-C.sub.20 aryl group, a fluorenyl group, a
C.sub.2-C.sub.20 heterocyclic group containing at least one
heteroatom selected from the group consisting of O, N, S, Si, and
P, a C.sub.3-C.sub.20 aliphatic ring, and a fused ring group formed
by a C.sub.3-C.sub.20 aliphatic ring with a C.sub.6-C.sub.20
aromatic ring, wherein L.sup.2, Ar.sub.4, Ar.sub.5, R, R', R'', the
ring formed by adjacent R, and the ring formed by R' and R'' are
each optionally substituted with one or more substituents selected
from the group consisting of deuterium, halogen, a silane group
unsubstituted or substituted with a C.sub.1-C.sub.20 alkyl group or
a C.sub.6-C.sub.20 aryl group, a siloxane group, a boron group, a
germanium group, a cyano group, a nitro group, a phosphine oxide
group unsubstituted or substituted with a C.sub.1-C.sub.20 alkyl
group or a C.sub.6-C.sub.20 aryl group, a C.sub.1-C.sub.20
alkylthio group, a C.sub.1-C.sub.20 alkoxyl group, a
C.sub.1-C.sub.20 alkyl group, a C.sub.2-C.sub.20 alkenyl group, a
C.sub.2-C.sub.20 alkynyl group, a C.sub.6-C.sub.20 aryl group, a
C.sub.6-C.sub.20 aryl group substituted with deuterium, a fluorenyl
group, a C.sub.2-C.sub.20 heterocyclic group containing at least
one heteroatom selected from the group consisting of O, N, S, Si,
and P, a C.sub.3-C.sub.20 cycloalkyl group, a fused ring group
formed by a C.sub.3-C.sub.20 aliphatic ring with a C.sub.6-C.sub.20
aromatic ring, a C.sub.7-C.sub.20 arylalkyl group, a
C.sub.8-C.sub.20 arylalkenyl group and a combination thereof.
12. An electronic device comprising a display device comprising the
organic electric element of claim 8, and a control unit for driving
the display device.
13. The electronic device of claim 12, wherein the organic electric
element is one of an organic light emitting diode, an organic solar
cell, an organic photo conductor, an organic transistor, and an
element for monochromatic or white illumination.
Description
CROSS-REFERENCE TO RELATED APPLICATION
[0001] This patent application is a Divisional Application of U.S.
patent application Ser. No. 16/652,383, filed on Mar. 30, 2020,
which is a 371 of International Patent Application No.
PCT/KR2018/009503, filed on Aug. 20, 2018, and claims priority from
and the benefit under 35 U.S.C. .sctn. 119 to .sctn. 121, and
.sctn. 365 of Korean Patent Application No. 10-2017-0127537, filed
on Sep. 29, 2017, Korean Patent Application No. 10-2018-0039162,
filed on Apr. 4, 2018, Korean Patent Application No.
10-2018-0072472, filed on Jun. 25, 2018, which are hereby
incorporated by reference for all purposes as if fully set forth
herein. Further, this application claims the benefit of priority in
countries other than U.S., which is hereby incorporated by
reference herein.
BACKGROUND
Technical Field
[0002] The present invention relates to compounds for organic
electric elements, organic electric elements comprising the same,
and electronic devices thereof.
Background Art
[0003] In general, an organic light emitting phenomenon refers to a
phenomenon in which electric energy is converted into light energy
of an organic material. An organic electric element utilizing the
organic light emitting phenomenon usually has a structure including
an anode, a cathode, and an organic material layer interposed
therebetween. In many cases, the organic material layer has a
multi-layered structure having respectively different materials in
order to improve efficiency and stability of an organic electric
element, and for example, may include a hole injection layer, a
hole transport layer, a light emitting layer, an electron transport
layer, an electron injection layer, or the like.
[0004] Materials used as an organic material layer in an organic
electric element may be classified into a light emitting material
and a charge transport material, for example, a hole injection
material, a hole transport material, an electron transport
material, an electron injection material, and the like according to
its function.
[0005] Further, the light emitting material may be divided into a
high molecular weight type and a low molecular weight type
according to its molecular weight, and may also be divided into a
fluorescent material derived from excited singlet states of
electron and a phosphorescent material derived from excited triplet
states of electron according to its light emitting mechanism.
Further, the light emitting material may be divided into blue,
green, and red light emitting material and yellow and orange light
emitting material required for better natural color reproduction
according to its light emitting color.
[0006] Meanwhile, when only one material is used as a light
emitting material, there occur problems of shift of a maximum
luminescence wavelength to a longer wavelength due to
intermolecular interactions and lowering of the efficiency of a
corresponding element due to a deterioration in color purity or a
reduction in luminous efficiency. On account of this, a host/dopant
system may be used as the light emitting material in order to
enhance the color purity and increase the luminous efficiency
through energy transfer. This is based on the principle that if a
small amount of dopant having a smaller energy band gap than a host
forming a light emitting layer is mixed in the light emitting
layer, then excitons generated in the light emitting layer are
transported to the dopant, thus emitting light with high
efficiency. With regard to this, since the wavelength of the host
is shifted to the wavelength band of the dopant, light having a
desired wavelength can be obtained according the type of the
dopant.
[0007] Currently, the power consumption is required more than more
as size of display becomes larger and larger in the portable
display market. Therefore, the power consumption is a very
important factor in the portable display with a limited power
source of the battery, and efficiency and life span issue also is
solved.
[0008] Efficiency, life span, driving voltage, and the like are
correlated with each other. For example, if efficiency is
increased, then driving voltage is relatively lowered, and the
crystallization of an organic material due to Joule heating
generated during operation is reduced as driving voltage is
lowered, as a result of which life span shows a tendency to
increase. However, efficiency cannot be maximized only by simply
improving the organic material layer. This is because long life
span and high efficiency can be simultaneously achieved when an
optimal combination of energy levels and T.sub.1 values, inherent
material properties (mobility, interfacial properties, etc.), and
the like among the respective layers included in the organic
material layer is given.
[0009] In addition, in the recent organic electroluminescent
devices, an emission-auxiliary layer (multi-layered hole transport
layer) must be present between the hole transport layer and the
light emitting layer in order to solve the problems of luminescence
in the hole transport layer and the driving voltage, and it is
necessary to develop different emission-auxiliary layers according
to respective light emitting layers.
[0010] In general, an electron is transferred from an electron
transport layer to a light emitting layer and a hole is transferred
from a hole transport layer to the light emitting layer, as a
result, an exciton is formed by the recombination of the electron
and hole within the light emitting layer. However, material used in
a hole transport layer has a low T1 value because the material
should have a low HOMO value. As a result, the exciton generated in
the light emitting layer is transferred to the hole transport layer
and it causes charge unbalance in the light emitting layer, thereby
emitting light at the interface of the hole transport layer.
[0011] When light is emitted from the interface of the hole
transporting layer, the color purity and efficiency of the organic
electric element are lowered and the lifetime is shortened.
Therefore, it is strongly desired to develop materials for the
emission-auxiliary layer having a HOMO level between the HOMO
energy level of the hole transporting layer and the HOMO energy
level of the light emitting layer, a high T1 energy value and a
hole mobility within a suitable driving voltage range (within a
driving voltage range of blue element of a full device).
[0012] However, this cannot be achieved simply by the structural
properties of the core of the emission-auxiliary layer material. An
element having a high efficiency and a long life span can be
realized when the characteristics of core and sub-substituents of
the emission-auxiliary layer material, the proper combination of
the emission-auxiliary layer and the hole transport layer, and the
proper combination of the emission-auxiliary layer and the light
emitting layer.
[0013] In order to fully exhibit the excellent characteristics of
the organic electric element, materials forming the organic
material layer in the element, such as a hole injection material, a
hole transport material, a light emitting material, an electron
transport material, an electron injection material, an
emission-auxiliary layer material, etc. should be prerequisite to
support by a stable and efficient material, and in particular, it
is strongly required to develop material of host of a light
emitting layer, a hole transport layer and an emission-auxiliary
layer.
Object, Technical Solution and Effects of the Invention
[0014] The present invention is to provide a compound lowering a
driving voltage, improving luminous efficiency, color purity,
stability and lifetime of the element, an organic electric element
comprising the same, and an electronic device thereof.
[0015] In an aspect of the present invention, the present invention
provides the compound represented by the following formula 1.
##STR00001##
[0016] In another aspect of the present invention, the present
invention provides the compound represented by the following
Formula A.
##STR00002##
[0017] In another aspect of the present invention, the present
invention provides an organic electric element using the compound
represented by formula 1 or A above and an electronic device
thereof.
[0018] By using the compound according to embodiments of the
present invention, a driving voltage can be lowered and the
luminous efficiency, color purity, stability and lifetime of the
element can be largely improved.
BRIEF DESCRIPTION OF THE DRAWINGS
[0019] The FIGURE illustrates an example of an organic
electroluminescent element according to the present invention: 100
is organic electric element, 110 is substrate, 120 is first
electrode, 130 is hole injection layer, 140 is hole transport
layer, 141 is buffer layer, 150 is light emitting layer, 151 is
emission-auxiliary layer, 160 is electron transport layer, 170 is
electron injection layer, and 180 is second electrode.
DETAILED DESCRIPTION
[0020] Unless otherwise stated, the term "aryl group" or "arylene
group" as used herein has, but not limited to, 6 to 60 carbon
atoms. The aryl group or arylene group in the present invention may
comprise a monocyclic ring, ring assemblies, a fused polycyclic
system, spiro compounds and the like.
[0021] The term "heterocyclic group" as used herein means a
non-aromatic ring as well as an aromatic ring like "heteroaryl
group" or "heteroarylene group", and unless otherwise stated, it
means a ring comprising one or more heteroatoms and having 2 to 60
carbon atoms, but not limited thereto. Unless otherwise stated, the
term "hetero atom" as used herein represents N, O, S, P or Si, and
the heterocyclic group means a monocyclic form, ring assemblies, a
fused polycyclic system or a spiro compound comprising
heteroatom(s).
[0022] The term "heterocyclic group" as used herein means a ring
comprising a heteroatom like N, O, S, P, Si or the like instead of
carbon consisting of a ring, it comprises a non-aromatic ring as
well as an aromatic ring like "heteroaryl group" or "heteroarylene
group" and the compound comprising the heteroatom group like
SO.sub.2, P.dbd.O or the like instead of carbon consisting of a
ring such as the following compound.
##STR00003##
[0023] Unless otherwise stated, the term "fluorenyl group" or
"fluorenylene group" as used herein means univalent or bivalent
functional group in which R, R' and R'' are all hydrogen in the
following structure, "substituted fluorenyl group" or "substituted
fluorenylene group" means that at least any one of R, R' and R'' is
a substituent other than hydrogen, and it comprises spiro compound
formed by linking R and R' together with the carbon bonded to
them.
##STR00004##
[0024] Unless otherwise stated, the term "spiro compound" as used
herein has, a spiro union which means union having one atom as the
only common member of two rings. The common atom is designated as
`spiro atom`. The compounds are defined as `monospiro-`, `dispiro-`
or `trispiro-` depending on the number of spiro atoms in one
compound.
[0025] In the present description, a `group name` corresponding to
an aryl group, an arylene group, a heterocyclic group, and the like
exemplified for each symbol and its substituent may be written in
the name of functional group reflecting the valence, and may also
be described under the name of a parent compound. For example, in
the case of phenanthrene which is a kind of aryl group, it may be
described by distinguishing valence such as `phenanthryl (group)`
when it is `monovalent group`, and as `phenanthrylene (group)` when
it is `divalent group`, and it may also be described as apparent
compound name, `phenanthrene`, regardless of its valence.
Similarly, in the case of pyrimidine, it may be described as
`pyrimidine` regardless of its valence, and it may also be
described as the name of corresponding functional group such as
pyrimidinyl (group) when it is `monovalent group`, and as
`pyrimidylene (group)` when it is `divalent group`.
[0026] Otherwise specified, the formulas used in the present
invention are as defined in the index definition of the substituent
of the following formula:
##STR00005##
[0027] Wherein, the substituent R.sup.1 is absent when a is an
integer of zero, the sole R.sup.1 is bonded to any one of the
carbon atoms constituting the benzene ring when a is an integer of
1, when a is an integer of 2 or 3, the substituent R.sup.1s may be
bonded as follows and the substituents R.sup.1s may be the same or
different each other, and the substituent R.sup.1s may be bonded to
the carbon of the benzene ring in a similar manner when a is an
integer of 4 to 6. Herein, the indication of the hydrogen bonded to
the carbon which forms the benzene ring is omitted.
##STR00006##
[0028] Hereinafter, referring to the FIGURE, a lamination structure
of an organic electric element including the compound of the
present invention will be described.
[0029] The FIGURE illustrates an organic electric element according
to an embodiment of the present invention.
[0030] Referring to the FIGURE, an organic electric element 100
according to an embodiment of the present invention includes a
first electrode 120 formed on a substrate 110, a second electrode
180, and an organic material layer formed between the first
electrode 120 and the second electrode 180 and comprising the
compound of the present invention. Here, the first electrode 120
may be an anode (positive electrode), and the second electrode 180
may be a cathode (negative electrode). In the case of an inverted
organic electric element, the first electrode may be a cathode, and
the second electrode may be an anode.
[0031] The organic material layer may include a hole injection
layer 130, a hole transport layer 140, a light emitting layer 150,
an electron transport layer 160, and an electron injection layer
170 formed in sequence on the first electrode 120. Here, at least
one layer of the organic material layer may be omitted, or the
organic material layer may further include a hole blocking layer,
an electron blocking layer, an emission-auxiliary layer 151, an
electron transport auxiliary layer, a buffer layer 141, etc., and
the electron transport layer 160 or the like may serve as the hole
blocking layer.
[0032] In addition, although not shown, the organic electric
element according to an embodiment of the present invention may
further include at least a protective layer or a layer for
improving luminous efficiency. The layer for improving luminous
efficiency may be formed on a surface that does not face the
organic material layer of both surfaces of the first electrode or
the second electrode.
[0033] The inventive compound employed in the organic material
layer may be used as a material of a hole injection layer 130, a
hole transport layer 140, an emission-auxiliary layer 151, an
electron transport auxiliary layer, an electron transport layer
160, an electron injection layer 170 and the like, as a host or a
dopant material of a light emitting layer 150, or as a material of
a layer for improving luminous efficiency. For example, the
compound according to Formula 1 of the present invention may be
used as material of the light emitting layer 150, preferably, as
host material of the light emitting layer 150, a mixture of the
compound according to Formula 1 of the present invention and the
compound according to Formula 12 of the present invention may be
used as host material, and the compound according to Formula 20 of
the present invention may be used as material of a hole transport
layer or an emission-auxiliary layer. Preferably, the compound
represented by Formula 21 or 22 of the present invention may be
used as material of a hole transport layer, and the compound
represented by Formula 23 or 24 of the present invention may be
used as material of an emission-auxiliary layer. Also, the compound
represented by Formula A of the present invention may be used as
material of an emission-auxiliary layer, specially, a green
emission-auxiliary layer.
[0034] Even if the core is the same core, the band gap, the
electrical characteristics, the interface characteristics, and the
like may be different depending on which substituent is bonded at
which position. Therefore, it is necessary to study the selection
of the core and the combination of the core and the sub-substituent
bonded to the core. Specially, long life span and high efficiency
can be simultaneously achieved when the optimal combination of
energy levels and T.sub.1 values, inherent material properties
(mobility, interfacial properties, etc.), and the like among the
respective layers of an organic material layer is achieved.
[0035] Therefore, according to the present invention, energy level
and T.sub.1 value between the respective layers of the organic
material layer, inherent material properties (mobility, interfacial
properties, etc.) and the like can be optimized by using as a host
material of a light emitting layer a single compound represented by
the Formula 1 or a mixture of the compound represented by the
Formula 1 and the compound represented by the Formula 12, by using
these compounds as a light-emitting layer material and
simultaneously using the compound according to the formula 20 as a
hole transport layer or an emission-auxiliary layer, and thus it is
possible to simultaneously improve the life span and efficiency of
the organic electric element.
[0036] The organic electric element according to an embodiment of
the present invention may be manufactured using various deposition
methods. The organic electric element according to an embodiment of
the present invention may be manufactured using a PVD (physical
vapor deposition) method or CVD (chemical vapor deposition) method.
For example, the organic electric element may be manufactured by
depositing a metal, a conductive metal oxide, or a mixture thereof
on the substrate to form the anode 120, forming the organic
material layer including the hole injection layer 130, the hole
transport layer 140, the light emitting layer 150, the electron
transport layer 160, and the electron injection layer 170 thereon,
and then depositing a material, which can be used as the cathode
180, thereon. Also, an emitting auxiliary layer 151 may be formed
between a hole transport layer 140 and a light emitting layer 150,
and an electron transport auxiliary layer may be formed between a
light emitting layer 150 and an electron transport layer 160.
[0037] Also, the organic material layer may be manufactured in such
a manner that a smaller number of layers are formed using various
polymer materials by a soluble process or solvent process, for
example, spin coating, nozzle printing, inkjet printing, slot
coating, dip coating, roll-to-roll, doctor blading, screen
printing, or thermal transfer, instead of deposition. Since the
organic material layer according to the present invention may be
formed in various ways, the scope of protection of the present
invention is not limited by a method of forming the organic
material layer.
[0038] The organic electric element according to an embodiment of
the present invention may be of a top emission type, a bottom
emission type, or a dual emission type depending on the material
used.
[0039] Also, the organic electric element according to an
embodiment of the present invention may be any one of an organic
light emitting diode, an organic solar cell, an organic photo
conductor, an organic transistor, and an element for monochromatic
or white illumination.
[0040] Another embodiment of the present invention provides an
electronic device including a display device which includes the
above described organic electric element, and a control unit for
controlling the display device. Here, the electronic device may be
a wired/wireless communication terminal which is currently used or
will be used in the future, and covers all kinds of electronic
devices including a mobile communication terminal such as a
cellular phone, a personal digital assistant (PDA), an electronic
dictionary, a point-to-multipoint (PMP), a remote controller, a
navigation unit, a game player, various kinds of TVs, and various
kinds of computers.
[0041] Hereinafter, the compound according to an aspect of the
present invention will be described.
[0042] The compound according to an aspect of the present invention
is represented by formula 1 below.
##STR00007##
[0043] In the formula 1, each of symbols may be defined as
follows.
[0044] X.sub.1 and X.sub.2 are each independently O or S, provided
that X.sub.1 and X.sub.2 are different from each other. That is,
one of X.sub.1 and X.sub.2 is O and the other is S.
[0045] Ar.sub.1 to Ar.sub.3 are each independently selected from
the group consisting of a C.sub.6-C.sub.60 aryl group, a fluorenyl
group, a C.sub.2-C.sub.60 heterocyclic group containing at least
one heteroatom selected from the group consisting of O, N, S, Si,
and P, a C.sub.3-C.sub.60 aliphatic ring, a fused ring group formed
by a C.sub.3-C.sub.60 aliphatic ring with a C.sub.6-C.sub.60
aromatic ring, a C.sub.1-C.sub.50 alkyl group, a C.sub.2-C.sub.20
alkenyl group, a C.sub.2-C.sub.20 alkynyl group, a C.sub.1-C.sub.30
alkoxyl group, a C.sub.6-C.sub.30 aryloxy group and
-L'-N(R.sub.a)(R.sub.b).
[0046] When Ar.sub.1 to Ar.sub.3 are each an aryl group, Ar.sub.1
to Ar.sub.3 may be preferably a C.sub.6-C.sub.30 or a
C.sub.6-C.sub.20 aryl group, more preferably a C.sub.6-C.sub.18
aryl group, for example, phenyl, biphenyl, naphthyl, phenanthryl,
terphenyl or the like. When Ar.sub.1 to Ar.sub.3 are each a
heterocyclic group, Ar.sub.1 to Ar.sub.3 may be preferably a
C.sub.2-C.sub.30 or a C.sub.2-C.sub.20 heterocyclic group, more
preferably a C.sub.2-C.sub.18 heterocyclic group, for example,
pyrazine, thiophene, pyridine, pyrimidoindole,
5-phenyl-5H-pyrimidido[5,4-b]indole, quinazoline, benzoquinazoline,
carbazole, dibenzoquinazole, dibenzofuran, benzothienopyrimidine,
benzofuropyrimidine, phenothiazine, phenylphenothiazine and the
like. When Ar.sub.1 to Ar.sub.3 are each a fluorenyl group,
Ar.sub.1 to Ar.sub.3 may be 9,9-dimethyl-9H-fluorene,
9,9-diphenyl-9H-fluorene or the like.
[0047] When Ar.sub.2 and Ar.sub.3 are each an aryl group, Ar.sub.2
and Ar.sub.3 may be preferably a C.sub.6-C.sub.50 or a
C.sub.6-C.sub.22 aryl group, more preferably a C.sub.6-C.sub.18
aryl group, for example, phenyl, biphenyl, naphthyl, phenanthryl,
terphenyl or the like.
[0048] When Ar.sub.1 to Ar.sub.3 are each a heterocyclic group,
Ar.sub.1 to Ar.sub.3 may be preferably a C.sub.2-C.sub.30 or a
C.sub.2-C.sub.20 heterocyclic group, more preferably a
C.sub.2-C.sub.18 heterocyclic group, for example, pyrazine,
thiophene, pyridine, pyrimidoindole,
5-phenyl-5H-pyrimidido[5,4-b]indole, quinazoline, benzoquinazoline,
carbazole, dibenzoquinazole, dibenzofuran, benzothienopyrimidine,
benzofuropyrimidine, phenothiazine, phenylphenothiazine and the
like. When Ar.sub.1 to Ar.sub.3 are each a fluorenyl group,
Ar.sub.2 and Ar.sub.3 may be, for example,
9,9-dimethyl-9H-fluorene, 9,9-diphenyl-9H-fluorene or the like.
[0049] R.sup.1 to R.sup.4 are each independently selected from the
group consisting of hydrogen, deuterium, halogen, a
C.sub.6-C.sub.60 aryl group, a fluorenyl group, a C.sub.2-C.sub.60
heterocyclic group containing at least one heteroatom selected from
the group consisting of O, N, S, Si, and P, a C.sub.3-C.sub.60
aliphatic ring, a fused ring group formed by a C.sub.3-C.sub.60
aliphatic ring with a C.sub.6-C.sub.50 aromatic ring, a
C.sub.1-C.sub.50 alkyl group, a C.sub.2-C.sub.20 alkenyl group, a
C.sub.2-C.sub.20 alkynyl group, a C.sub.1-C.sub.30 alkoxyl group, a
C.sub.6-C.sub.30 aryloxy group and -L'-N(R.sub.a)(R.sub.b), and
adjacent groups may be optionally linked to each other to form a
C.sub.6-C.sub.60 aromatic ring, a C.sub.2-C.sub.60 heterocyclic
group, a C.sub.3-C.sub.60 aliphatic ring, or a fused ring group
formed by a C.sub.3-C.sub.60 aliphatic ring with a C.sub.6-C.sub.60
aromatic ring. Here, "adjacent groups are linked to each other"
means that adjacent R.sup.1s, adjacent R.sup.2s, adjacent R.sup.3s,
or adjacent R.sup.4s are respectively are linked to each other.
[0050] a to d are each an integer of 0 to 3, where each of these is
an integer of 2 or more, each of R.sup.1s, each of R.sup.2s, each
of R.sup.3s or each of R.sup.4s is the same or different from each
other.
[0051] When R.sup.1 to R.sup.4 are each an aryl group, R.sup.1 to
R.sup.4 may be preferably a C.sub.6-C.sub.30 or a C.sub.6-C.sub.20
aryl group, more preferably a C.sub.6-C.sub.18 aryl group, for
example, phenyl, biphenyl, naphthyl, terphenyl or the like. When
R.sup.1 to R.sup.4 are each a heterocyclic group, R.sup.1 to
R.sup.4 may be preferably a C.sub.2-C.sub.30 or a C.sub.2-C.sub.20
heterocyclic group, more preferably a C.sub.2-C.sub.8 heterocyclic
group, for example, triazine, pyrimidine, pyridine, quinazoline or
the like.
[0052] The ring formed by linking between adjacent R.sup.1s,
between adjacent R.sup.2s, between adjacent R.sup.3, or between
adjacent R.sup.4 may be preferably a C.sub.6-C.sub.20 aromatic ring
group, or a C.sub.2-C.sub.20 heterocyclic group containing at least
one heteroatom selected from the group consisting of O, N, S, Si,
and P, more preferably, a C.sub.6-C.sub.10 aromatic ring group, or
a C.sub.2-C.sub.10 heterocyclic group containing at least one
heteroatom selected from the group consisting of O, N, S, Si, and
P, for example, benzene ring, naphthalene, phenanthrene, thiophene,
benzothiophene, pyridine and the like. Therefore, when adjacent
R.sup.1s to adjacent R.sup.4s are connected to each other to form a
ring, an aromatic ring or a heterocycle comprising a benzene ring
may be formed together with the benzene ring to which they are
attached, preferably a C.sub.6-C.sub.14 aromatic ring or a
C.sub.2-C.sub.14 heterocycle may be formed.
[0053] L' is selected from the group consisting of a single bond, a
C.sub.6-C.sub.60 arylene group, a fluorenylene group, a
C.sub.2-C.sub.60 heterocyclic group containing at least one
heteroatom selected from the group consisting of O, N, S, Si, and
P, a C.sub.3-C.sub.60 aliphatic ring and a fused ring group formed
by a C.sub.3-C.sub.60 aliphatic ring with a C.sub.6-C.sub.60
aromatic ring.
[0054] When L' is an arylene group, L' may be preferably a
C.sub.6-C.sub.30 or C.sub.6-C.sub.20 arylene group, more preferably
a C.sub.6-C.sub.18 arylene group, for example, phenylene, biphenyl,
naphthalene, terphenyl or the like.
[0055] R.sub.a and R.sub.b are each independently selected from the
group consisting of hydrogen, a C.sub.6-C.sub.60 aryl group, a
fluorenyl group, a C.sub.2-C.sub.60 heterocyclic group containing
at least one heteroatom selected from the group consisting of O, N,
S, Si, and P, a C.sub.3-C.sub.60 aliphatic ring and a fused ring
group formed by a C.sub.3-C.sub.60 aliphatic ring with a
C.sub.6-C.sub.60 aromatic ring.
[0056] When R.sub.a and R.sub.b are each an aryl group, R.sub.a and
R.sub.b may be preferably a C.sub.6-C.sub.30 or C.sub.6-C.sub.20
aryl group, more preferably a C.sub.6-C.sub.18 aryl group, for
example, phenyl, biphenyl, naphthyl, terphenyl or the like.
[0057] Ar.sub.1 to Ar.sub.3, R.sup.1 to R.sup.4, L', R.sub.a,
R.sub.b, and the ring formed by bonding between neighboring
R.sup.1s to neighboring R.sup.4s may be each further substituted
with one or more substituents selected from the group consisting of
deuterium, halogen, a silane group unsubstituted or substituted
with a C.sub.1-C.sub.20 alkyl group or a C.sub.6-C.sub.20 aryl
group, a siloxane group, a boron group, a germanium group, a cyano
group, a nitro group, a phosphine oxide group unsubstituted or
substituted with a C.sub.1-C.sub.20 alkyl group or a
C.sub.6-C.sub.20 aryl group, a C.sub.1-C.sub.20 alkylthio group, a
C.sub.1-C.sub.20 alkoxyl group, a C.sub.1-C.sub.20 alkyl group, a
C.sub.2-C.sub.20 alkenyl group, a C.sub.2-C.sub.20 alkynyl group, a
C.sub.6-C.sub.20 aryl group, a C.sub.6-C.sub.20 aryl group
substituted with deuterium, a fluorenyl group, a C.sub.2-C.sub.20
heterocyclic group containing at least one heteroatom selected from
the group consisting of O, N, S, Si, and P, a
C.sub.3-C.sub.20cycloalkyl group, a fused ring group formed by a
C.sub.3-C.sub.50 aliphatic ring with a C.sub.6-C.sub.50 aromatic
ring, a C.sub.7-C.sub.20 arylalkyl group, and a C.sub.8-C.sub.20
arylalkenyl group.
[0058] That is, where Ar.sub.1 to Ar.sub.3, R.sup.1 to R.sup.4, L',
R.sub.a, R.sub.b, and a ring formed by bonding between neighboring
R.sup.1s to neighboring R.sup.4s are each an aryl group, an arylene
group, an aromatic hydrocarbon, a fluorenyl group, a fluorenylene
group, a heterocyclic group, an aliphatic ring (group), a fused
ring (group), an alkyl group, an alkenyl group, an alkynyl group,
an alkoxy group, an aryloxy group and the like, each of these may
be further substituted with one or more substituents selected from
the group consisting of substituents such as deuterium, halogen and
the like.
[0059] For example, where Ar.sub.1 to Ar.sub.3, R.sup.1 to R.sup.4,
L', R.sub.a, R.sub.b, and a ring formed by bonding between
neighboring R.sup.1s to neighboring R.sup.4s are further
substituted with an aryl group, the aryl group is preferably a
C.sub.6-C.sub.20 aryl group, more preferably, a C.sub.6-C.sub.18
aryl group, for example, phenyl, naphthyl, biphenyl, terphenyl, and
the like.
[0060] In addition, where Ar.sub.1 to Ar.sub.3, R.sup.1 to R.sup.4,
L', R.sub.a, R.sub.b, and a ring formed by bonding between
neighboring R.sup.1s to neighboring R.sup.4s are further
substituted with a heterocyclic group, the heterocyclic group is
preferably a C.sub.2-C.sub.20 heterocyclic group, more preferably,
a C.sub.2-C.sub.12 heterocyclic group, for example, pyrazine,
pyrimidine, pyridine, quinazoline, isoindole, carbazole,
dibenzothiophene, and the like.
[0061] In addition, where Ar.sub.1 to Ar.sub.3, R.sup.1 to R.sup.4,
L', R.sub.a, R.sub.b, and a ring formed by bonding between
neighboring R.sup.1s to R.sup.4s are further substituted with an
alkyl group, the alkyl group is preferably a C.sub.1-C.sub.10 alkyl
group, more preferably, a C.sub.1-C.sub.4 alkyl group, for example,
methyl, t-butyl and the like.
[0062] In addition, Ar.sub.1 to Ar.sub.3, R.sup.1 to R.sup.4, L',
R.sub.a, R.sub.b, and a ring formed by bonding between neighboring
R.sup.1s to R.sup.4s may be further substituted with the
substituents such as F, CN, ethen and the like.
[0063] Formula 1 may be represented by one of the following Formula
2 to Formula 11.
##STR00008## ##STR00009##
[0064] In Formulas 2 to 11, each symbol is as defined for Formula
1. For example, X.sub.1, X.sub.2, Ar.sub.1 to Ar.sub.3, R.sup.1 to
R.sup.4, a, b, c and d are the same as defined for Formula 1.
[0065] Preferably, in Formulas 1 to 11, at least one of Ar.sub.1 to
Ar.sub.3 may be a substituted or unsubstituted C.sub.6-C.sub.24
aryl group, more preferably, Ar.sub.1 to Ar.sub.3 may be all a
substituted or unsubstituted C.sub.6-C.sub.12 aryl group, and
Ar.sub.2 and Ar.sub.3 may be different from each other.
[0066] Specifically, the compound represented by formula 1 may be
one of the following compounds, but it is not limited thereto.
##STR00010## ##STR00011## ##STR00012## ##STR00013## ##STR00014##
##STR00015## ##STR00016## ##STR00017## ##STR00018## ##STR00019##
##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##
[0067] In another aspect of the present invention, the present
invention provides an organic electric element comprising a first
electrode, a second electrode, and an organic material layer formed
between the first electrode and the second electrode, wherein the
organic material layer comprises compound represented by Formula 1.
The organic material layer comprises at least one layer of a hole
injection layer, a hole transport layer, an emission-auxiliary
layer, a light emitting layer, an electron transport auxiliary
layer, an electron transport layer and an electron injection layer,
preferably, the compound represented by Formula 1 is comprised in
the light emitting layer, more preferably, a single compound or
compounds of two or more kinds represented by Formula 1 may be used
as host material of the light emitting layer.
[0068] In one embodiment according to the present invention, the
light emitting layer may further comprise the compound represented
by the following Formula 12.
##STR00066##
[0069] In Formula 12, each of symbols may be defined as
follows.
[0070] Z.sup.1 to Z.sup.4, Z.sup.13 to Z.sup.16 are independently
C(R) or N, Z.sup.5 to Z.sup.12 are independently C, C(R) or N.
[0071] L.sup.2 is selected from the group consisting of a single
bond, a C.sub.6-C.sub.60 arylene group, a fluorenylene group, a
C.sub.2-C.sub.60 heterocyclic group containing at least one
heteroatom selected from the group consisting of O, N, S, Si, and
P, a C.sub.3-C.sub.60 aliphatic ring and a fused ring group formed
by a C.sub.3-C.sub.60 aliphatic ring with a C.sub.6-C.sub.60
aromatic ring.
[0072] When L.sup.2 is an arylene group, L.sup.2 may be preferably
a C.sub.0-C.sub.30 or C.sub.6-C.sub.20 arylene group, more
preferably a C.sub.6-C.sub.18 arylene group, for example,
phenylene, naphthalene, biphenyl, terphenyl or the like. When
L.sup.2 is a heterocyclic group, L.sup.2 may be preferably a
C.sub.2-C.sub.30 or C.sub.2-C.sub.20 heterocyclic group, more
preferably a C.sub.2-C.sub.18 heterocyclic group, for example,
carbazole, phenylcarbazole or the like.
[0073] W is N(Ar.sub.5), N, O, S, C(R') or C(R')(R''), and W is N
or C(R') when W is combined with L.sup.2.
[0074] Ar.sub.4 and Ar.sub.5 are each independently selected from
the group consisting of a C.sub.6-Cao aryl group, a fluorenyl
group, a C.sub.2-C.sub.60 heterocyclic group containing at least
one heteroatom selected from the group consisting of O, N, S, Si,
and P, a C.sub.3-C.sub.50 aliphatic ring, a fused ring group formed
by a C.sub.3-C.sub.50 aliphatic ring with a C.sub.6-C.sub.60
aromatic ring, a C.sub.1-C.sub.50 alkyl group, a C.sub.2-C.sub.20
alkenyl group, a C.sub.2-C.sub.2a alkynyl group, a C.sub.1-C.sub.30
alkoxyl group, a C.sub.6-C.sub.30 aryloxy group,
-L'-N(R.sub.a)(R.sub.b) and a combination thereof. Here, the term
"a combination thereof" means, for example, a combination of an
aryl group and a heterocyclic group, a combination of an aryl group
and an aliphatic ring, a combination of a heterocyclic group and an
aliphatic ring group, and the like.
[0075] R, R' and R'' are each independently selected from the group
consisting of hydrogen, deuterium, halogen, a C.sub.6-C.sub.50 aryl
group, a fluorenyl group, a C.sub.2-C.sub.60 heterocyclic group
containing at least one heteroatom selected from the group
consisting of O, N, S, Si, and P, a C.sub.3-C.sub.60 aliphatic
ring, a fused ring group formed by a C.sub.3-C.sub.60 aliphatic
ring with a C.sub.6-C.sub.60 aromatic ring, a C.sub.1-C.sub.60
alkyl group, a C.sub.2-C.sub.20 alkenyl group, a C.sub.2-C.sub.20
alkynyl group, a C.sub.1-C.sub.30 alkoxyl group, a C.sub.6-C.sub.30
aryloxy group and -L'-N(R.sub.a)(R.sub.b), adjacent R groups may be
optionally linked to each other to form a ring, and R' and R'' may
be optionally linked to each other to form a ring.
[0076] The ring formed by linking between adjacent R groups or
between R' and R'' may be a C.sub.6-C.sub.60 aromatic ring group, a
C.sub.2-C.sub.60 heterocyclic group containing at least one
heteroatom selected from the group consisting of O, N, S, Si, and
P, a C.sub.3-C.sub.60 aliphatic ring, or a fused ring group formed
by a C.sub.3-C.sub.60 aliphatic ring with a C.sub.6-C.sub.60
aromatic ring, preferably, a C.sub.6-C.sub.20 aromatic ring group
or a C.sub.2-C.sub.20 heterocyclic group, more preferably, a
C.sub.6-C.sub.10 aromatic ring group or a C.sub.2-C.sub.10
heterocyclic group, for example, benzene, naphthalene,
phenanthrene, thiophene, benzothiophene, pyridine and the like.
[0077] L', R.sub.a and R.sub.b are the same as defined for Formula
1.
[0078] L.sup.2, Ar.sub.4, Ar.sub.5, R, R', R'', the ring formed by
linking between adjacent R groups, and the ring formed by linking
between R' and R'' may be each further substituted with one or more
substituents selected from the group consisting of deuterium,
halogen, a silane group unsubstituted or substituted with a
C.sub.1-C.sub.20 alkyl group or a C.sub.6-C.sub.20 aryl group, a
siloxane group, a boron group, a germanium group, a cyano group, a
nitro group, a phosphine oxide group unsubstituted or substituted
with a C.sub.1-C.sub.20 alkyl group or a C.sub.6-C.sub.20 aryl
group, a C.sub.1-C.sub.20 alkylthio group, a C.sub.1-C.sub.20
alkoxyl group, a C.sub.1-C.sub.20 alkyl group, a C.sub.2-C.sub.20
alkenyl group, a C.sub.2-C.sub.20 alkynyl group, a C.sub.6-C.sub.20
aryl group, a C.sub.6-C.sub.20 aryl group substituted with
deuterium, a fluorenyl group, a C.sub.2-C.sub.20 heterocyclic group
containing at least one heteroatom selected from the group
consisting of O, N, S, Si, and P, a C.sub.3-C.sub.20 cycloalkyl
group, a fused ring group formed by a C.sub.3-C.sub.60 aliphatic
ring with a C.sub.6-C.sub.60 aromatic ring, a C.sub.7-C.sub.20
arylalkyl group, and a C.sub.8-C.sub.20 arylalkenyl group.
[0079] Preferably, Formula 12 is represented by one of Formulas 13
to 17.
##STR00067##
[0080] In Formulas 13 to 17, Ar.sub.4, Ar.sub.5, Z.sup.1 to
Z.sup.16, L.sup.2, R and R are the same as defined for Formula
12.
[0081] Preferably, in Formulas 13 to 17, at least one of Ar.sub.4
and Ar.sub.5 may be a substituted or unsubstituted C.sub.6-C.sub.30
aryl group, more preferably, both Ar.sub.4 and Ar.sub.5 are a
C.sub.6-C.sub.30 aryl group.
[0082] Preferably, Formula 12 may be represented by Formula 18 or
Formula 19.
##STR00068##
[0083] In Formulas 18 and 19, each of symbols may be defined as
follows.
[0084] Ar.sub.4, Z.sup.1 to Z.sup.16, and L.sup.2 are the same as
defined for Formula 12.
[0085] L.sup.1 is selected from the group consisting of a single
bond, a C.sub.6-C.sub.60 arylene group, a fluorenylene group, a
C.sub.2-C.sub.60 heterocyclic group containing at least one
heteroatom selected from the group consisting of O, N, S, Si, and
P, a C.sub.3-C.sub.60 aliphatic ring and a fused ring group formed
by a C.sub.3-C.sub.60 aliphatic ring with a C.sub.6-C.sub.60
aromatic ring.
[0086] When L.sup.1 is an arylene group, L.sup.1 may be preferably
a C.sub.6-C.sub.30 or C.sub.6-C.sub.20 arylene group, more
preferably a C.sub.6-C.sub.12 arylene group, for example,
phenylene, naphthalene, biphenyl or the like,
[0087] Y is O, S or N--Ar.sub.6.
[0088] R.sup.a and R.sup.b are each independently selected from the
group consisting of deuterium, halogen, a C.sub.6-C.sub.20 aryl
group, a C.sub.6-C.sub.20 aryl group substituted with deuterium, a
fluorenyl group, a C.sub.2-C.sub.20 heterocyclic group containing
at least one heteroatom selected from the group consisting of O, N,
S, Si, and P, a C.sub.3-C.sub.20 cycloalkyl group, a fused ring
group formed by a C.sub.3-C.sub.60 aliphatic ring with a
C.sub.6-C.sub.60 aromatic ring, a C.sub.7-C.sub.20 arylalkyl group
and a C.sub.8-C.sub.20 arylalkenyl group, and adjacent groups may
be optionally linked to each other to form a C.sub.6-C.sub.60
aromatic ring, a C.sub.2-C.sub.60 heterocyclic group, a
C.sub.3-C.sub.60 aliphatic ring, or a fused ring group formed by a
C.sub.3-C.sub.60 aliphatic ring with a C.sub.6-C.sub.60 aromatic
ring.
[0089] y is an integer of 0 to 3, and z is an integer of 0 to 4,
where each of these is an integer of 2 or more, each of R.sup.as,
each of R.sup.bs is the same or different from each other.
[0090] Ar.sub.6 is selected from the group consisting of a
C.sub.6-C.sub.60 aryl group, a C.sub.6-C.sub.60 aryl group
substituted with deuterium, a fluorenyl group, a C.sub.2-C.sub.60
heterocyclic group containing at least one heteroatom selected from
the group consisting of O, N, S, Si, and P, a C.sub.3-C.sub.60
cycloalkyl group, a fused ring group formed by a C.sub.3-C.sub.50
aliphatic ring with a C.sub.6-C.sub.60 aromatic ring, a
C.sub.1-C.sub.60 alkyl group, a C.sub.2-C.sub.20 alkenyl group, a
C.sub.2-C.sub.20 alkynyl group, a C.sub.1-C.sub.30 alkoxyl group, a
C.sub.6-C.sub.30 aryloxy group, a C.sub.7-C.sub.20 arylalkyl group
and a C.sub.8-C.sub.20 arylalkenyl group. Preferably, Ar.sub.6 is
selected from the group consisting of a C.sub.6-C.sub.20 aryl
group, a C.sub.6-C.sub.20 aryl group substituted with deuterium, a
fluorenyl group, a C.sub.2-C.sub.20 heterocyclic group containing
at least one heteroatom selected from the group consisting of O, N,
S, Si, and P, a C.sub.3-C.sub.20 cycloalkyl group, a fused ring
group formed by a C.sub.3-C.sub.60 aliphatic ring with a
C.sub.6-C.sub.60 aromatic ring, a C.sub.7-C.sub.20 arylalkyl group
and a C.sub.8-C.sub.20 arylalkenyl group.
[0091] Specifically, the compound represented by formula 12 may be
one of the following compounds, but it is not limited thereto.
##STR00069## ##STR00070## ##STR00071## ##STR00072## ##STR00073##
##STR00074## ##STR00075## ##STR00076## ##STR00077##
##STR00078## ##STR00079## ##STR00080## ##STR00081## ##STR00082##
##STR00083## ##STR00084## ##STR00085## ##STR00086## ##STR00087##
##STR00088## ##STR00089## ##STR00090##
[0092] Preferably, the organic material layer of an organic element
according to the present invention comprises a light emitting
layer, a hole transport layer formed between the first electrode
and the light emitting layer, and an emission-auxiliary layer
formed between the light emitting layer and the hole transport
layer, the light emitting layer comprises the compound represented
by Formula 1, and the hole transport layer or the
emission-auxiliary layer comprises the compound represented by
Formula 20.
##STR00091##
[0093] In Formula 20, each of symbols may be defined as
follows.
[0094] Ar.sup.4 and Ar.sup.5 are each independently selected from
the group consisting of a C.sub.6-C.sub.50 aryl group, a fluorenyl
group, a C.sub.2-C.sub.60 heterocyclic group containing at least
one heteroatom selected from the group consisting of O, N, S, Si,
and P, a C.sub.3-C.sub.60 aliphatic ring, a fused ring group formed
by a C.sub.3-C.sub.60 aliphatic ring with a C.sub.6-C.sub.60
aromatic ring, a C.sub.1-C.sub.50 alkyl group, a C.sub.2-C.sub.20
alkenyl group, a C.sub.2-C.sub.20 alkynyl group, a C.sub.1-C.sub.30
alkoxyl group, a C.sub.6-C.sub.30 aryloxy group and
-L'-N(R.sub.a)(R.sub.b), and Ar.sup.4 and Ar.sup.5 may be combined
with each other to form a ring.
[0095] Ar.sup.6 is selected from the group consisting of a
C.sub.6-C.sub.60 aryl group, a fluorenyl group, and a
C.sub.2-C.sub.50 heterocyclic group containing at least one
heteroatom selected from the group consisting of O, N, S, Si, and
P; or Ar.sup.6 is selected from the group consisting of the
following Formulas 1-a to 1-c.
##STR00092##
[0096] In Formula 1-a to 1-c, each of symbols may be defined as
follows.
[0097] Ar.sup.9 to Ar.sup.11 are each independently selected from
the group consisting of a C.sub.6-C.sub.50 aryl group, a fluorenyl
group, a C.sub.2-C.sub.60 heterocyclic group containing at least
one heteroatom selected from the group consisting of O, N, S, Si,
and P, a C.sub.3-C.sub.60 aliphatic ring, a fused ring group formed
by a C.sub.3-C.sub.60 aliphatic ring with a C.sub.6-C.sub.60
aromatic ring, a C.sub.1-C.sub.50 alkyl group, a C.sub.2-C.sub.20
alkenyl group, a C.sub.2-C.sub.20 alkynyl group, a C.sub.1-C.sub.30
alkoxyl group, a C.sub.6-C.sub.30 aryloxy group and
-L'-N(R.sub.a)(R.sub.b).
[0098] L.sup.5 is selected from the group consisting of a
C.sub.6-C.sub.60 arylene group, a fluorenylene group, and a
C.sub.2-C.sub.60 heterocyclic group containing at least one
heteroatom selected from the group consisting of O, N, S, Si, and
P, a C.sub.3-C.sub.60 aliphatic ring and a fused ring group formed
by a C.sub.3-C.sub.60 aliphatic ring with a C.sub.6-C.sub.60
aromatic ring.
[0099] L.sup.6 is selected from the group consisting of a single
bond, a C.sub.6-C.sub.60 arylene group, a fluorenylene group, and a
C.sub.2-C.sub.60 heterocyclic group containing at least one
heteroatom selected from the group consisting of O, N, S, Si, and
P, a C.sub.3-C.sub.60 aliphatic ring and a fused ring group formed
by a C.sub.3-C.sub.60 aliphatic ring with a C.sub.6-C.sub.50
aromatic ring.
[0100] R.sup.6 to R.sup.9 are each independently selected from the
group consisting of hydrogen, deuterium, halogen, a
C.sub.6-C.sub.60 aryl group, a fluorenyl group, a C.sub.2-C.sub.60
heterocyclic group containing at least one heteroatom selected from
the group consisting of O, N, S, Si, and P, a C.sub.3-C.sub.60
aliphatic ring, a fused ring group formed by a C.sub.3-C.sub.60
aliphatic ring with a C.sub.6-C.sub.50 aromatic ring, a
C.sub.1-C.sub.50 alkyl group, a C.sub.2-C.sub.20 alkenyl group, a
C.sub.2-C.sub.20 alkynyl group, a C.sub.1-C.sub.30 alkoxyl group, a
C.sub.6-C.sub.30 aryloxy group and -L'-N(R.sub.a)(R.sub.b).
[0101] h, i and g are each an integer of 0 to 4, j is an integer of
0 to 3, where each of these is an integer of 2 or more, a plurality
of R.sup.6s, a plurality of R.sup.7s, a plurality of R.sup.8s, a
plurality of R.sup.9s are the same as or different from each other.
In addition, when h, i, j and g are each an integer of 2 or more,
adjacent R.sup.6 groups, adjacent R.sup.7 groups, adjacent R.sup.8
groups, or adjacent R.sup.9 groups may be linked to each other to
form a ring. Here, the ring formed by linking between adjacent
groups may be a C.sub.6-C.sub.60 aromatic ring group, a
C.sub.2-C.sub.50 heterocyclic group, a C.sub.3-C.sub.50 aliphatic
ring, or a fused ring group formed by a C.sub.3-C.sub.60 aliphatic
ring with a C.sub.6-C.sub.60 aromatic ring.
[0102] L', R.sub.a and R.sub.b are the same as defined for Formula
1.
[0103] Ar.sup.4 to Ar.sup.6, Ar.sup.9 to Ar.sup.11, R.sup.6 to
R.sup.9, L.sup.5, L.sup.6, and the ring formed by bonding between
neighboring groups may be each further substituted with one or more
substituents selected from the group consisting of deuterium,
halogen, a silane group unsubstituted or substituted with a
C.sub.1-C.sub.20 alkyl group or a C.sub.6-C.sub.20 aryl group, a
siloxane group, a boron group, a germanium group, a cyano group, a
nitro group, a phosphine oxide group unsubstituted or substituted
with a C.sub.1-C.sub.20 alkyl group or a C.sub.6-C.sub.20 aryl
group, a C.sub.1-C.sub.20 alkylthio group, a C.sub.1-C.sub.20
alkoxyl group, a C.sub.1-C.sub.20 alkyl group, a C.sub.2-C.sub.20
alkenyl group, a C.sub.2-C.sub.20 alkynyl group, a C.sub.6-C.sub.20
aryl group, a C.sub.6-C.sub.20 aryl group substituted with
deuterium, a fluorenyl group, a C.sub.2-C.sub.20 heterocyclic group
containing at least one heteroatom selected from the group
consisting of O, N, S, Si, and P, a C.sub.3-C.sub.20 cycloalkyl
group, a fused ring group formed by a C.sub.3-C.sub.60 aliphatic
ring with a C.sub.6-C.sub.60 aromatic ring, a C.sub.7-C.sub.20
arylalkyl group, a C.sub.8-C.sub.20 arylalkenyl group and a
combination thereof.
[0104] Preferably, the light emitting layer may further comprise
the compound represented by Formula 12.
[0105] Preferably, the hole transport layer comprises the compound
represented by the following Formula 21 or Formula 22 and the
emission-auxiliary layer comprises the compound represented by the
following Formula 23 or Formula 24.
##STR00093##
[0106] In Formulas 21 to 24, Ar.sup.4, Ar.sup.5, Ar.sup.9 to
Ar.sup.11, h, i, g, j, L.sup.5, L.sup.6, R.sup.6 to R.sup.9 are the
same as defined above, Ar.sup.7 is selected from the group
consisting of a C.sub.6-C.sub.60 aryl group, a fluorenyl group, a
C.sub.2-C.sub.60 heterocyclic group containing at least one
heteroatom selected from the group consisting of O, N, S, Si, and
P, and a C.sub.3-C.sub.60 aliphatic ring. Preferably, in Formula
24, at least one of Ar.sup.4, Ar.sup.5, Ar.sup.10 and Ar.sup.11 may
be represented by Formula 24-1.
##STR00094##
[0107] In Formula 24-1, each of symbols may be defined as
follows.
[0108] R.sup.a', R.sup.b' and R.sup.c' are each independently
selected from the group consisting of hydrogen, deuterium, halogen,
a C.sub.1-C.sub.20 alkyl group, a C.sub.2-C.sub.20 alkenyl group, a
C.sub.2-C.sub.20 alkynyl group, a C.sub.6-C.sub.20 aryl group, a
fluorenyl group, a C.sub.2-C.sub.20 heterocyclic group containing
at least one heteroatom selected from the group consisting of O, N,
S, Si, and P, C.sub.3-C.sub.20 cycloalkyl group, and a fused ring
group formed by a C.sub.3-C.sub.50 aliphatic ring with a
C.sub.6-C.sub.60 aromatic ring, and adjacent groups may be
optionally linked to each other to form a ring. When adjacent
R.sup.a' groups, adjacent R.sup.b' groups, or adjacent R.sup.c'
groups are linked to each other to form a ring, the ring may be a
C.sub.6-C.sub.60 aromatic ring group, a C.sub.2-C.sub.60
heterocyclic group, a C.sub.3-C.sub.60 aliphatic ring, or a fused
ring group formed by a C.sub.3-C.sub.60 aliphatic ring with a
C.sub.6-C.sub.60 aromatic ring.
[0109] I', m' and n' are each an integer of 0 to 4, where each of
these is an integer of 2 or more, a plural of R.sup.a's, a plural
of R.sup.b's or a plural of R.sup.c's are each the same or
different from each other.
[0110] Ar.sub.1' is selected from the group consisting of a
C.sub.1-C.sub.20 alkyl group, a C.sub.2-C.sub.20 alkenyl group, a
C.sub.2-C.sub.20 alkynyl group, a C.sub.6-C.sub.20 aryl group, a
fluorenyl group, a C.sub.2-C.sub.20 heterocyclic group containing
at least one heteroatom selected from the group consisting of O, N,
S, Si, and P, C.sub.3-C.sub.20 cycloalkyl group, and a fused ring
group formed by a C.sub.3-C.sub.60 aliphatic ring with a
C.sub.6-C.sub.60 aromatic ring.
[0111] R.sub.a', R.sup.b', R.sup.c', Ar.sub.1' and the ring formed
by bonding between neighboring may be each further substituted with
one or more substituents selected from the group consisting of
deuterium, halogen, a silane group unsubstituted or substituted
with a C.sub.1-C.sub.20 alkyl group or a C.sub.6-C.sub.20 aryl
group, a siloxane group, a boron group, a germanium group, a cyano
group, a nitro group, a phosphine oxide group unsubstituted or
substituted with a C.sub.1-C.sub.20 alkyl group or a
C.sub.6-C.sub.20 aryl group, a C.sub.1-C.sub.20 alkylthio group, a
C.sub.1-C.sub.20 alkoxyl group, a C.sub.1-C.sub.20 alkyl group, a
C.sub.2-C.sub.20 alkenyl group, a C.sub.2-C.sub.20 alkynyl group, a
C.sub.6-C.sub.20 aryl group, a C.sub.6-C.sub.20 aryl group
substituted with deuterium, a fluorenyl group, a C.sub.2-C.sub.20
heterocyclic group containing at least one heteroatom selected from
the group consisting of O, N, S, Si, and P, a C.sub.3-C.sub.20
cycloalkyl group, a fused ring group formed by a C.sub.3-C.sub.60
aliphatic ring with a C.sub.6-C.sub.60 aromatic ring, a
C.sub.7-C.sub.20 arylalkyl group, a C.sub.8-C.sub.20 arylalkenyl
group and a combination thereof.
[0112] In addition, preferably, in Formula 24, Ar.sub.1' and
L.sup.5 are each independently a C.sub.6-C.sub.60 arylene group,
for example, phenyl, biphenyl, o-terphenyl, m-terphenyl,
p-terphenyl or naphthalene.
[0113] Preferably, Formula 24 may be represented by the following
Formula A.
[0114] <Formula A>
##STR00095##
[0115] In Formula A, R.sub.a', R.sup.b', R.sup.c', Ar.sub.1', l',
m' and n' are the same as defined for Formula 24-1, Ar.sub.2' is
the same as defined for Ar.sup.11 in Formula 24, Ar.sub.3' is the
same as defined for Ar.sup.4 in Formula 24, Ar.sub.4, is the same
as defined for Ar.sup.5 in Formula 24, and a' is an integer of 1 to
3. That is, in Formula A, each of symbols may be defined as
follows.
[0116] R.sup.a', R.sup.b' and R.sup.c' are each independently
selected from the group consisting of hydrogen, deuterium, halogen,
a C.sub.1-C.sub.20 alkyl group, a C.sub.2-C.sub.20 alkenyl group, a
C.sub.2-C.sub.20 alkynyl group, a C.sub.6-C.sub.20 aryl group, a
fluorenyl group, a C.sub.2-C.sub.20 heterocyclic group containing
at least one heteroatom selected from the group consisting of O, N,
S, Si, and P, C.sub.3-C.sub.20 cycloalkyl group, and a fused ring
group formed by a C.sub.3-C.sub.60 aliphatic ring with a
C.sub.6-C.sub.50 aromatic ring, and adjacent groups may be
optionally linked to each other to form a ring. When adjacent
R.sup.a' groups, adjacent R.sup.b' groups, or adjacent R.sup.c'
groups are linked to each other to form a ring, the ring may be a
C.sub.6-C.sub.60 aromatic ring group, a C.sub.2-C.sub.50
heterocyclic group, a C.sub.3-C.sub.50 aliphatic ring, or a fused
ring group formed by a C.sub.3-C.sub.60 aliphatic ring with a
C.sub.6-C.sub.60 aromatic ring.
[0117] l', m' and n' are each an integer of 0 to 4, where each of
these is an integer of 2 or more, a plural of R.sup.a's, a plural
of R.sup.b's or a plural of R.sup.c's are each the same or
different from each other.
[0118] Ar.sub.1' is selected from the group consisting of a
C.sub.1-C.sub.20 alkyl group, a C.sub.2-C.sub.20 alkenyl group, a
C.sub.2-C.sub.20 alkynyl group, a C.sub.6-C.sub.20 aryl group, a
fluorenyl group, a C.sub.2-C.sub.20 heterocyclic group containing
at least one heteroatom selected from the group consisting of O, N,
S, Si, and P, C.sub.3-C.sub.20 cycloalkyl group, and a fused ring
group formed by a C.sub.3-C.sub.60 aliphatic ring with a
C.sub.6-C.sub.60 aromatic ring.
[0119] Where Ar.sub.1' is an aryl group, Ar.sub.1' may be
preferably a C.sub.6-C.sub.18 aryl group, more preferably a
C.sub.6-C.sub.12 aryl group, for example, phenyl, biphenyl,
terphenyl, naphthyl or the like.
[0120] Ar.sub.2', Ar.sub.3' and Ar.sub.4' are each independently
selected from the group consisting of a C.sub.6-C.sub.60 aryl
group, a fluorenyl group, a C.sub.2-C.sub.60 heterocyclic group
containing at least one heteroatom selected from the group
consisting of O, N, S, Si, and P, a C.sub.3-C.sub.60 aliphatic
ring, a fused ring group formed by a C.sub.3-C.sub.60 aliphatic
ring with a C.sub.6-C.sub.60 aromatic ring, a C.sub.1-C.sub.60
alkyl group, a C.sub.2-C.sub.20 alkenyl group, a C.sub.2-C.sub.20
alkynyl group, a C.sub.1-C.sub.30 alkoxyl group, a C.sub.6-C.sub.30
aryloxy group and -L'-N(R.sub.a)(R.sub.b), Ar.sup.4 and Ar.sup.5
may be linked to each other to form a ring.
[0121] Where Ar.sub.2' is an aryl group, Ar.sub.2' may be
preferably a C.sub.6-C.sub.30 aryl group, more preferably a
C.sub.6-C.sub.18 aryl group, for example, phenyl, naphthyl,
biphenyl, terphenyl or the like. Where Ar.sub.2' is a heterocyclic
group, Ar.sub.2' may be preferably a C.sub.2-C.sub.30 heterocyclic
group, more preferably a C.sub.2-C.sub.16 heterocyclic group, for
example, dibenzofuran, dibenzothiophene and the like. Where
Ar.sub.2' is a fluorenyl group, Ar.sub.2' may be
9,9-dimethylfluorene, 9,9-diphenylfluorene, 9,9'-spirobifluorene
and the like.
[0122] Where Ar.sub.3' and Ar.sub.4' are each an aryl group,
Ar.sub.3' and Ar.sub.4' may be preferably a C.sub.6-C.sub.30 aryl
group, more preferably a C.sub.6-C.sub.18 aryl group, for example,
phenyl, biphenyl, terphenyl, naphthyl, triphenylene, phenanthrene
or the like. Where Ar.sub.3' and Ar.sub.4' are each a heterocyclic
group, Ar.sub.3' and Ar.sub.4' may be preferably a C.sub.2-C.sub.30
heterocyclic group, more preferably a C.sub.2-C.sub.12 heterocyclic
group, for example, dibenzofuran, dibenzothiophene and the like.
Where Ar.sub.3' and Ar.sub.4' are each a fluorenyl group, Ar.sub.3'
and Ar.sub.4' may be 9,9-dimethylfluorene, 9,9-diphenylfluorene,
9,9'-spirobifluorene and the like.
[0123] L' is selected from the group consisting of a single bond, a
C.sub.6-C.sub.60 arylene group, a fluorenylene group, a
C.sub.2-C.sub.60 heterocyclic group containing at least one
heteroatom selected from the group consisting of O, N, S, Si, and
P, a C.sub.3-C.sub.60 aliphatic ring and a fused ring group formed
by a C.sub.3-C.sub.60 aliphatic ring with a C.sub.6-C.sub.60
aromatic ring,
[0124] R.sub.a and R.sub.b are each independently selected from the
group consisting of hydrogen, a C.sub.6-C.sub.60 aryl group, a
fluorenyl group, a C.sub.2-C.sub.60 heterocyclic group containing
at least one heteroatom selected from the group consisting of O, N,
S, Si, and P, a C.sub.3-C.sub.60 aliphatic ring and a fused ring
group formed by a C.sub.3-C.sub.60 aliphatic ring with a
C.sub.6-C.sub.60 aromatic ring.
[0125] R.sup.a', R.sup.b', R.sup.c', R.sub.a, R.sub.b, Ar.sub.1' to
Ar.sub.4', L' and a ring formed by bonding between neighboring
groups may be each further substituted with one or more
substituents selected from the group consisting of deuterium,
halogen, a silane group unsubstituted or substituted with a
C.sub.1-C.sub.20 alkyl group or a C.sub.6-C.sub.20 aryl group, a
siloxane group, a boron group, a germanium group, a cyano group, a
nitro group, a phosphine oxide group unsubstituted or substituted
with a C.sub.1-C.sub.20 alkyl group or a C.sub.6-C.sub.20 aryl
group, a C.sub.1-C.sub.20 alkylthio group, a C.sub.1-C.sub.20
alkoxyl group, a C.sub.1-C.sub.20 alkyl group, a C.sub.2-C.sub.20
alkenyl group, a C.sub.2-C.sub.20 alkynyl group, a C.sub.6-C.sub.20
aryl group, a C.sub.6-C.sub.20 aryl group substituted with
deuterium, a fluorenyl group, a C.sub.2-C.sub.20 heterocyclic group
containing at least one heteroatom selected from the group
consisting of O, N, S, Si, and P, a C.sub.3-C.sub.20 cycloalkyl
group, a fused ring group formed by a C.sub.3-C.sub.60 aliphatic
ring with a C.sub.6-C.sub.60 aromatic ring, a C.sub.7-C.sub.20
arylalkyl group, a C.sub.8-C.sub.20 arylalkenyl group and a
combination thereof.
[0126] Formula A may be represented by one of Formula B to Formula
D.
##STR00096##
[0127] In Formulas B to D, R.sup.a', R.sup.b', R.sup.c', l', m',
n', Ar.sub.1' to Ar.sub.4' are the same as defined for Formula
A.
[0128] In addition, Formula A may be represented by one of Formula
E to Formula G.
##STR00097##
[0129] In Formulas E to G, R.sup.a', R.sup.b', R.sup.c', l', m',
n', Ar.sub.1' to Ar.sub.4' are the same as defined for Formula
A.
[0130] In addition, Formula A may be represented by one of Formula
H to Formula K.
##STR00098##
[0131] In Formulas H to K, R.sup.a', R.sup.b', R.sup.c', l', m',
n', Ar.sub.1' to Ar.sub.3' are the same as defined for Formula
A.
[0132] X is independently O, S or C(R')(R''),
[0133] R.sup.d', R.sup.e', R' and R'' are each independently
selected from the group consisting of hydrogen, deuterium, halogen,
a C.sub.1-C.sub.20 alkyl group, a C.sub.2-C.sub.20 alkenyl group, a
C.sub.2-C.sub.20 alkynyl group, a C.sub.6-C.sub.20 aryl group, a
fluorenyl group, a C.sub.2-C.sub.20 heterocyclic group containing
at least one heteroatom selected from the group consisting of O, N,
S, Si, and P, C.sub.3-C.sub.20 cycloalkyl group, and a fused ring
group formed by a C.sub.3-C.sub.60 aliphatic ring with a
C.sub.6-C.sub.60 aromatic ring, and adjacent groups may be
optionally linked to each other to form a ring. Where adjacent
R.sup.d' groups or adjacent R.sup.e' groups are linked to each
other to form a ring, the ring may be a C.sub.6-C.sub.60 aromatic
ring group, a C.sub.2-C.sub.60 heterocyclic group, a
C.sub.3-C.sub.60 aliphatic ring, or a fused ring group formed by a
C.sub.3-C.sub.60 aliphatic ring with a C.sub.6-C.sub.60 aromatic
ring, and when R' group and R'' group are linked to each other to
form a ring, a spiro compound may be formed together with C to
which they are attached.
[0134] o' is independently an integer of 0 to 3, p' is
independently an integer of 0 to 4, where o' is an integer of 2 or
more, a plural of R.sup.d's are each the same or different from
each other, where p' is an integer of 2 or more, a plural of
R.sup.e's are each the same or different from each other.
[0135] R.sup.d', R.sup.e', R', R'' and the ring formed by bonding
between neighboring groups may be each further substituted with one
or more substituents selected from the group consisting of
deuterium, halogen, a silane group unsubstituted or substituted
with a C.sub.1-C.sub.20 alkyl group or a C.sub.6-C.sub.20 aryl
group, a siloxane group, a boron group, a germanium group, a cyano
group, a nitro group, a phosphine oxide group unsubstituted or
substituted with a C.sub.1-C.sub.20 alkyl group or a
C.sub.6-C.sub.20 aryl group, a C.sub.1-C.sub.20 alkylthio group, a
C.sub.1-C.sub.20 alkoxyl group, a C.sub.1-C.sub.20 alkyl group, a
C.sub.2-C.sub.20 alkenyl group, a C.sub.2-C.sub.20 alkynyl group, a
C.sub.6-C.sub.20 aryl group, a C.sub.6-C.sub.20 aryl group
substituted with deuterium, a fluorenyl group, a C.sub.2-C.sub.20
heterocyclic group containing at least one heteroatom selected from
the group consisting of O, N, S, Si, and P, a C.sub.3-C.sub.20
cycloalkyl group, a fused ring group formed by a C.sub.3-C.sub.60
aliphatic ring with a C.sub.6-C.sub.60 aromatic ring, a
C.sub.7-C.sub.20 arylalkyl group, a C.sub.8-C.sub.20 arylalkenyl
group and a combination thereof.
[0136] Formula A may be represented by one of Formula L to Formula
O.
##STR00099## ##STR00100##
[0137] In Formulas H to K, R.sup.a', R.sup.b', R.sup.c', l', m',
n', Ar.sub.3' and Ar.sub.4' are the same as defined for Formula
A.
[0138] R.sup.e', R.sup.f', R.sup.g', R.sup.h' and R.sup.l' are each
independently selected from the group consisting of hydrogen,
deuterium, halogen, a C.sub.1-C.sub.20 alkyl group, a
C.sub.2-C.sub.20 alkenyl group, a C.sub.2-C.sub.20 alkynyl group, a
C.sub.6-C.sub.20 aryl group, a fluorenyl group, a C.sub.2-C.sub.20
heterocyclic group containing at least one heteroatom selected from
the group consisting of O, N, S, Si, and P, C.sub.3-C.sub.20
cycloalkyl group, and a fused ring group formed by a
C.sub.3-C.sub.50 aliphatic ring with a C.sub.6-C.sub.60 aromatic
ring, and adjacent groups may be optionally linked to each other to
form a ring. Where adjacent R.sup.e' groups, adjacent R.sup.f'
groups, adjacent R.sup.g' groups, adjacent R.sup.h' groups, or
adjacent R.sup.l' groups are linked to each other to form a ring,
the ring may be a C.sub.6-C.sub.60 aromatic ring group, a
C.sub.2-C.sub.60 heterocyclic group, a C.sub.3-C.sub.50 aliphatic
ring, or a fused ring group formed by a C.sub.3-C.sub.50 aliphatic
ring with a C.sub.6-C.sub.60 aromatic ring.
[0139] p', r' and t' are each independently an integer of 0 to 3,
q' and s' are each independently an integer of 0 to 4, where each
of these is an integer of 2 or more, each of R.sup.e's, each of
R.sup.f's, each of R.sup.g's, each of R.sup.h's, and each of
R.sup.l's is each the same or different from each other.
[0140] b' is an integer of 0 to 3.
[0141] R.sup.e', R.sup.f', R.sup.g', R.sup.h', R.sup.l' and the
ring formed by bonding between neighboring groups may be each
further substituted with one or more substituents selected from the
group consisting of deuterium, halogen, a silane group
unsubstituted or substituted with a C.sub.1-C.sub.20 alkyl group or
a C.sub.6-C.sub.20 aryl group, a siloxane group, a boron group, a
germanium group, a cyano group, a nitro group, a phosphine oxide
group unsubstituted or substituted with a C.sub.1-C.sub.20 alkyl
group or a C.sub.6-C.sub.20 aryl group, a C.sub.1-C.sub.20
alkylthio group, a C.sub.1-C.sub.20 alkoxyl group, a
C.sub.1-C.sub.20 alkyl group, a C.sub.2-C.sub.20 alkenyl group, a
C.sub.2-C.sub.20 alkynyl group, a C.sub.6-C.sub.20 aryl group, a
C.sub.6-C.sub.20 aryl group substituted with deuterium, a fluorenyl
group, a C.sub.2-C.sub.20 heterocyclic group containing at least
one heteroatom selected from the group consisting of O, N, S, Si,
and P, a C.sub.3-C.sub.20 cycloalkyl group, a fused ring group
formed by a C.sub.3-C.sub.60 aliphatic ring with a C.sub.6-C.sub.60
aromatic ring, a C.sub.7-C.sub.20 arylalkyl group, a
C.sub.8-C.sub.20 arylalkenyl group and a combination thereof.
[0142] Specifically, the compound represented by formula 20 may be
one of the following compounds, but it is not limited thereto.
##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##
[0143] Specifically, the compound represented by formula A may be
one of the following compounds, but it is not limited thereto.
##STR00131## ##STR00132## ##STR00133## ##STR00134## ##STR00135##
##STR00136## ##STR00137## ##STR00138## ##STR00139## ##STR00140##
##STR00141## ##STR00142## ##STR00143## ##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##
[0144] In another aspect of the present invention, the present
invention provides an organic electric element comprising a first
electrode, a second electrode, and an organic material layer formed
between the first electrode and the second electrode, wherein the
organic material layer comprises a single compound or compounds of
two or more kinds represented by Formula 1.
[0145] In another aspect of the present invention, the present
invention provides an organic electric element comprising a first
electrode, a second electrode, and an organic material layer formed
between the first electrode and the second electrode, wherein the
organic material layer comprises a single compound or compounds of
two or more kinds represented by Formula A.
[0146] The organic material layer comprises at least one layer of a
hole injection layer, a hole transport layer, an emission-auxiliary
layer, a light emitting layer, an electron transport auxiliary
layer, an electron transport layer and an electron injection layer,
and preferably, the compound represented by Formula 1 may be
comprised in a light emitting layer and the compound represented by
Formula A may be comprised in an emission-auxiliary layer, in
particular, a green emission-auxiliary layer.
[0147] In another aspect of the present invention, the present
invention provides an electronic device comprising a display device
comprising the organic electric element, and a control unit for
driving the display device, wherein the organic electric element
comprises the compound represented by Formula 1 or A.
[0148] Hereinafter, synthesis examples of the compounds represented
by Formulas 1, 12, 20 and A, respectively, and preparation methods
of an organic electric element according to one embodiment of the
present invention will be described in detail by way of examples.
However, the present invention is not limited to the following
examples.
Synthesis Example
Synthesis Example 1
[0149] As shown in Reaction Scheme 1 below, the compound
represented by Formula according to the present invention can be
synthesized by reacting Sub 1 with Sub 2.
##STR00187##
1. Synthesis Example of Sub 1
[0150] Sub 1 of the Reaction Scheme 1 can be synthesized according
to the reaction route of the following Reaction Scheme 2, but there
is no limitation thereto.
##STR00188##
[0151] Synthesis of Sub 1-2
##STR00189##
[0152] After 2,4-dichloro-6-phenyl-1,3,5-triazine (25 g, 110.59
mmol) and
(6-([1,1'-biphenyl]-3-yl)dibenzo[b,d]thiophen-4-yl)boronic acid
(92.52 g, 243.30 mmol) were dissolved in THF (590 ml),
Pd(PPh.sub.3).sub.4 (5.11 g, 4.42 mmol), K.sub.2CO.sub.3 (45.85 g,
331.77 mmol) and water (295 ml) were added thereto and the mixture
was stirred under reflux. When the reaction was completed, the
reaction product was extracted with ether and water and the organic
layer was concentrated. The concentrated organic layer was dried
with MgSO.sub.4 and concentrated. Thereafter, the concentrate was
applied to a silica gel column to obtain 46.54 g (yield: 80%) of
the product.
[0153] Synthesis of Sub 1-12
##STR00190##
[0154]
(6-([1,1'-biphenyl]-3-yl)benzo[b]naphtho[1,2-d]thiophen-8-yl)boroni-
c acid (104.70 g, 243.30 mmol), Pd(PPh.sub.3).sub.4 (0.04 eq.),
K.sub.2CO.sub.3 (3 eq.), anhydrous THE and a small amount of water
were added to 2,4-dichloro-6-phenyl-1,3,5-triazine (25 g, 110.59
mmol), and then 44.60 g (yield: 70%) of the product was obtained by
the same method as in synthesis of Sub 1-2.
[0155] Synthesis of Sub 1-15
##STR00191##
[0156] (7-(2-(pyrazin-2-yl)phenyl)dibenzo[b,d]thiophen-4-yl)boronic
acid (76.14 g, 199.19 mmol), Pd(PPh.sub.3).sub.4 (0.04 eq.),
K.sub.2CO.sub.3 (3 eq.), anhydrous THE and a small amount of water
were added to 2,4-dichloro-6-(naphthalen-2-yl)-1,3,5-triazine (25
g, 90.54 mmol), and then 35.59 g (yield: 68%) of the product was
obtained by the same method as in synthesis of Sub 1-2.
[0157] Synthesis of Sub 1-22
##STR00192##
[0158]
(8-(2-(2H-isoindol-2-yl)phenyl)dibenzo[b,d]thiophen-4-yl)boronic
acid (116.77 g, 278.47 mmol), Pd(PPh.sub.3).sub.4 (0.04 eq.),
K.sub.2CO.sub.3 (3 eq.), anhydrous THE and a small amount of water
were added to 2,4-dichloro-6-(perfluorophenyl)-1,3,5-triazine (40
g, 126.58 mmol), and then 49.75 g (yield: 60%) of the product was
obtained by the same method as in synthesis of Sub 1-2.
[0159] Synthesis of Sub 1-37
##STR00193##
[0160] (7-(9H-carbazol-9-yl)dibenzo[b,d]furan-4-yl)boronic acid
(157.85 g, 418.47 mmol), Pd(PPh.sub.3).sub.4 (0.04 eq.),
K.sub.2CO.sub.3 (3 eq.), anhydrous THE and a small amount of water
were added to 2,4-dichloro-6-phenyl-1,3,5-triazine (43 g, 190.21
mmol), and then 64.66 g (yield: 65%) of the product was obtained by
the same method as in synthesis of Sub 1-2.
[0161] Synthesis of Sub 1-67
##STR00194##
[0162] (6-(phenyl-d5)dibenzo[b,d]thiophen-4-yl)boronic acid (135.41
g, 437.94 mmol), Pd(PPh.sub.3).sub.4 (0.04 eq.), K.sub.2CO.sub.3 (3
eq.), anhydrous THE and a small amount of water were added to
2,4-dichloro-6-phenyl-1,3,5-triazine (45 g, 199.06 mmol), and then
68.83 g (yield: 76%) of the product was obtained by the same method
as in synthesis of Sub 1-2.
[0163] Synthesis of Sub 1-70
##STR00195##
[0164]
5-([1,1'-biphenyl]-3-yl)benzo[b]naphtho[1,2-d]thiophen-10-yl)boroni-
c acid (188.46 g, 437.94 mmol), Pd(PPh.sub.3).sub.4 (0.04 eq.),
K.sub.2CO.sub.3 (3 eq.), anhydrous THE and a small amount of water
were added to
2,4-dichloro-6-(dibenzo[b,d]furan-3-yl)-1,3,5-triazine (45 g,
199.06 mmol), and then 72.25 g (yield: 63%) of the product was
obtained by the same method as in synthesis of Sub 1-2.
[0165] Synthesis of Sub 1-74
##STR00196##
[0166] (8-([1,1'-biphenyl]-3-yl)dibenzo[b,d]furan-3-yl)boronic acid
(177.22 g, 486.60 mmol), Pd(PPh.sub.3).sub.4 (0.04 eq.),
K.sub.2CO.sub.3 (3 eq.), anhydrous THE and a small amount of water
were added to 2,4-dichloro-6-phenyl-1,3,5-triazine (50 g, 221.18
mmol), and then 81.22 g (yield: 72%) of the product was obtained by
the same method as in synthesis of Sub 1-2.
[0167] The compound belonging to Sub 1 may be, but not limited to,
the following compounds, and Table 1 shows FD-MS (Field
Desorption-Mass Spectrometry) values of compounds belonging to Sub
1.
##STR00197## ##STR00198## ##STR00199## ##STR00200## ##STR00201##
##STR00202## ##STR00203## ##STR00204## ##STR00205## ##STR00206##
##STR00207## ##STR00208## ##STR00209## ##STR00210## ##STR00211##
##STR00212## ##STR00213## ##STR00214## ##STR00215## ##STR00216##
##STR00217## ##STR00218##
TABLE-US-00001 TABLE 1 Compound FD-MS Compound FD-MS Sub 1-1 m/z =
449.08 (C.sub.27H.sub.16ClN.sub.3S = 449.96) Sub 1-2 m/z = 525.11
(C.sub.33H.sub.20ClN.sub.3S = 526.05) Sub 1-4 m/z = 499.09
(C.sub.31H.sub.18ClN.sub.3S = 500.02) Sub 1-6 m/z = 575.12
(C.sub.37H.sub.22ClN.sub.3S = 576.11) Sub 1-7 m/z = 606.17
(C.sub.39H.sub.19D.sub.5ClN.sub.3S = 607.18) Sub 1-8 m/z = 544.09
(C.sub.32H.sub.18ClFN.sub.4S = 545.03) Sub 1-9 m/z = 505.14
(C.sub.31H.sub.24ClN.sub.3S = 506.06) Sub 1-10 m/z = 557.05
(C.sub.31H.sub.16ClN.sub.5S.sub.2 = 558.07) Sub 1-11 m/z = 599.12
(C.sub.39H.sub.22ClN.sub.3S = 600.14) Sub 1-12 m/z = 575.12
(C.sub.37H.sub.22ClN.sub.3S = 576.11) Sub 1-15 m/z = 577.11
(C.sub.35H.sub.20ClN.sub.5S = 578.09) Sub 1-16 m/z = 575.12
(C.sub.37H.sub.22ClN.sub.3S = 576.11) Sub 1-17 m/z = 601.11
(C.sub.37H.sub.20ClN.sub.5S = 602.11) Sub 1-20 m/z = 617.11
(C.sub.37H.sub.20ClN.sub.5OS = 618.11) Sub 1-21 m/z = 601.14
(C.sub.39H.sub.24ClN.sub.3S = 602.15) Sub 1-22 m/z = 654.07
(C.sub.35H.sub.16ClF.sub.5N.sub.4S = 655.04) Sub 1-25 m/z = 526.10
(C.sub.32H.sub.19ClN.sub.4S = 527.04) Sub 1-26 m/z = 666.16
(C.sub.43H.sub.27ClN.sub.4S = 667.23) Sub 1-27 m/z = 536.09
(C.sub.31H.sub.13D.sub.5ClN.sub.3S.sub.2 = 537.11) Sub 1-28 m/z =
499.09 (C.sub.31H.sub.18ClN.sub.3S = 500.02) Sub 1-31 m/z = 518.08
(C.sub.30H.sub.16ClFN.sub.4S = 518.99) Sub 1-32 m/z = 455.12
(C.sub.27H.sub.22ClN.sub.3S = 456.00) Sub 1-34 m/z = 509.13
(C.sub.33H.sub.20ClN.sub.3O = 509.99) Sub 1-35 m/z = 433.10
(C.sub.27H.sub.16ClN.sub.3O = 433.90) Sub 1-36 m/z = 635.18
(C.sub.43H.sub.26ClN.sub.3O = 636.15) Sub 1-37 m/z = 522.12
(C.sub.33H.sub.19ClN.sub.4O = 522.99) Sub 1-38 m/z = 603.13
(C.sub.37H.sub.22ClN.sub.5S = 604.13) Sub 1-41 m/z = 483.11
(C.sub.31H.sub.18ClN.sub.3O = 483.96) Sub 1-43 m/z = 561.14
(C.sub.35H.sub.20ClN.sub.5O = 562.03) Sub 1-44 m/z = 626.13
(C.sub.40H.sub.23ClN.sub.4S = 627.16) Sub 1-46 m/z = 615.12
(C.sub.39H.sub.22ClN.sub.3OS = 616.14) Sub 1-50 m/z = 611.15
(C.sub.39H.sub.22ClN.sub.5O = 612.09) Sub 1-52 m/z = 632.14
(C.sub.39H.sub.25ClN.sub.4OS = 633.17) Sub 1-54 m/z = 655.22
(C.sub.43H.sub.22D.sub.5ClN.sub.4O = 656.20) Sub 1-55 m/z = 527.10
(C.sub.31H.sub.18ClN.sub.5S = 528.03) Sub 1-56 m/z = 559.15
(C.sub.37H.sub.22ClN.sub.3O = 560.05) Sub 1-60 m/z = 576.12
(C.sub.36H.sub.21ClN.sub.4S = 577.10) Sub 1-61 m/z = 509.13
(C.sub.33H.sub.20ClN.sub.3O = 509.99) Sub 1-62 m/z = 605.13
(C.sub.38H.sub.24ClN.sub.3OS = 606.14) Sub 1-63 m/z = 599.14
(C.sub.39H.sub.22ClN.sub.3O.sub.2 = 600.07) Sub 1-65 m/z = 602.13
(C.sub.38H.sub.23ClN.sub.4S = 603.14) Sub 1-66 m/z = 680.15
(C.sub.42H.sub.25ClN.sub.6S = 681.21) Sub 1-67 m/z = 454.11
(C.sub.27H.sub.11D.sub.5ClN.sub.3S = 454.99) Sub 1-68 m/z = 525.11
(C.sub.33H.sub.20ClN.sub.3S = 526.05) Sub 1-69 m/z = 544.09
(C.sub.32H.sub.18ClFN.sub.4S = 545.03) Sub 1-70 m/z = 575.12
(C.sub.37H.sub.22ClN.sub.3S = 576.11) Sub 1-71 m/z = 449.08
(C.sub.27H.sub.16ClN.sub.3S = 449.96) Sub 1-71 m/z = 525.11
(C.sub.33H.sub.20ClN.sub.3S = 526.05) Sub 1-73 m/z = 449.08
(C.sub.27H.sub.16ClN.sub.3S = 449.96) Sub 1-74 m/z = 509.13
(C.sub.33H.sub.20ClN.sub.3O = 509.99)
2. Synthesis Example of Sub 2
[0168] Sub 2 of the Reaction Scheme 1 can be synthesized according
to the reaction route of the following Reaction Scheme 3, but there
is no limitation thereto.
##STR00219##
[0169] Synthesis of Sub 2-3
##STR00220##
[0170] After 4-([1,1'-biphenyl]-3-yl)-6-bromodibenzo[b,d]furan (CAS
Registry Number: 1010068-89-9) (50 g, 125.22 mmol) were dissolved
in THF (522 ml), the temperature of the reactant was lowered to
-78.degree. C. Thereafter, n-BuLi (2.5M in hexane) (12.03 g, 187.83
mmol) was added slowly thereto and the mixture was stirred at
0.degree. C. for 1 hour. Thereafter, the temperature of the
reactant was lowered to -78.degree. C., triisopropyl borate (28.26
g, 150.27 mmol) and water (261 ml) were added thereto and the
mixture was stirred at room temperature for 12 hour. When reaction
was completed, the product was extracted with ether and water.
Then, the organic layer was dried with MgSO.sub.4 and concentrated.
The concentrate was applied to silica gel column and recrystallized
to obtain 36.49 g (yield: 80%) of the product.
[0171] Synthesis of Sub 2-7
##STR00221##
[0172] (1) Synthesis of Sub 2-1-1
[0173] After dibenzo[b,d]furan-4-ylboronic acid (50 g, 235.84 mmol)
and 7-bromo-5-phenyl-5H-pyrimido[5,4-b]indole (91.74 g, 283.01
mmol) were dissolved in THF (865 mL), Pd(PPh.sub.3).sub.4 (10.90 g,
9.43 mmol), K.sub.2CO.sub.3 (97.79 g, 707.51 mmol) and water (432
ml) were added thereto and the mixture was stirred under reflux.
When reaction was completed, the product was extracted with ether
and water. Then, the organic layer was concentrated and dried with
MgSO.sub.4 and concentrated. Thereafter, concentrate was applied to
silica gel column and recrystallized to obtain 53.37 g (yield: 55%)
of the product.
[0174] (2) Synthesis of Sub 2-1-2
[0175] After
7-(dibenzo[b,d]furan-4-yl)-5-phenyl-5H-pyrimido[5,4-b]indole (53.37
g, 129.71 mmol) were dissolved in THF (476 mL), the temperature of
the reactant was lowered to -75.degree. C. Thereafter, n-BuLi(2.5M
in hexane) (9.97 g, 155.65 mmol) was added slowly thereto and the
solution was stirred at room temperature for 1 hour. Thereafter,
the temperature of the reactant was lowered to -75.degree. C.,
l.sub.2 (49.38 g, 194.56 mmol) and water (238 mL) were added
thereto and the mixture was stirred at room temperature for 17
hour. Thereafter, aqueous solution of sodium thiosulfate was added
thereto and the mixture was stirred for 1 hour. When reaction was
completed, the product was extracted with ether and water. Then,
the organic layer was dried with MgSO.sub.4 and concentrated. The
concentrate was applied to silica gel column and recrystallized to
41.82 g (yield: 60%) of the product.
[0176] (3) Synthesis of Sub 2-7
[0177] THF (324 mL), n-BuLi(2.5M in hexane) (7.48 g, 116.74 mmol),
triisopropyl borate (17.56 g, 93.39 mmol) and water (162 mL) were
added to
6-(5-phenyl-5H-pyrimido[5,4-b]indol-7-yl)dibenzo[b,d]furan-4-yl)boroni-
c acid (41.82 g, 77.82 mmol), and then, 24.80 g (yield: 70%) of the
product was obtained by the same method as in synthesis of Sub
2-3.
[0178] Synthesis of Sub 2-50
##STR00222##
[0179] After dibenzofuran, 1-bromo-8-phenyl-(CAS Registry Number:
1822310-20-2) (45 g, 139.24 mmol) were dissolved in THF (580 ml),
the temperature of the reactant was lowered to -78.degree. C.
Thereafter, n-BuLi (2.5M in hexane) (13.38 g, 208.86 mmol) was
added slowly thereto and the mixture was stirred at 0.degree. C.
for 1 hour. Thereafter, the temperature of the reactant was lowered
to -78.degree. C., triisopropyl borate (31.42 g, 167.08 mmol) and
water (290 ml) were added thereto and the mixture was stirred at
room temperature for 12 hour. When reaction was completed, the
organic layer was dried with MgSO.sub.4 and concentrated. The
concentrate was applied to silica gel column and recrystallized to
obtain 26.88 g (yield: 67%) of the product.
[0180] The compound belonging to Sub 2 may be, but not limited to,
the following compounds, and Table 2 shows FD-MS values of
compounds belonging to Sub 2.
##STR00223## ##STR00224## ##STR00225## ##STR00226## ##STR00227##
##STR00228## ##STR00229## ##STR00230## ##STR00231##
##STR00232##
TABLE-US-00002 TABLE 2 Compound FD-MS Compound FD-MS Sub 2-1 m/z =
288.10 (C.sub.18H.sub.13BO.sub.3 = 288.11) Sub 2-3 m/z = 364.13
(C.sub.24H.sub.17BO.sub.3 = 364.21) Sub 2-5 m/z = 388.13
(C.sub.26H.sub.17BO.sub.3 = 388.23) Sub 2-6 m/z = 313.09
(C.sub.19H.sub.12BNO.sub.3 = 313.12) Sub 2-7 m/z = 455.14
(C.sub.28H.sub.18BN.sub.3O.sub.3 = 455.28) Sub 2-8 m/z = 340.10
(C.sub.20H.sub.13BN.sub.2O.sub.3 = 340.15) Sub 2-9 m/z = 338.11
(C.sub.22H.sub.15BO.sub.3 = 338.17) Sub 2-11 m/z = 416.13
(C.sub.26H.sub.17BN.sub.2O.sub.3 = 416.24) Sub 2-13 m/z = 404.16
(C.sub.27H.sub.21BO.sub.3 = 404.27) Sub 2-17 m/z = 466.15
(C.sub.30H.sub.19BN.sub.2O.sub.3 = 466.30) Sub 2-20 m/z = 366.12
(C.sub.22H.sub.15BN.sub.2O.sub.3 = 366.18) Sub 2-30 m/z = 380.10
(C.sub.24H.sub.17BO.sub.2S = 380.27) Sub 2-38 m/z = 365.12
(C.sub.23H.sub.16BNO.sub.3 = 365.20) Sub 2-39 m/z = 440.13
(C.sub.28H.sub.17BN.sub.2O.sub.3 = 440.27) Sub 2-40 m/z = 454.12
(C.sub.30H.sub.19BO.sub.2S = 454.35) Sub 2-42 m/z = 354.09
(C.sub.22H.sub.15BO.sub.2S = 354.23) Sub 2-45 m/z = 430.12
(C.sub.28H.sub.19BO.sub.2S = 430.33) Sub 2-46 m/z = 388.13
(C.sub.26H.sub.17BO.sub.3 = 388.23) Sub 2-47 m/z = 365.12
(C.sub.23H.sub.16BNO.sub.3 = 365.20) Sub 2-49 m/z = 293.13
(C.sub.18H.sub.8D.sub.5BO.sub.3 = 293.14)
3. Synthesis Example of Final Product
[0181] Synthesis of Compound 1-3
##STR00233##
[0182] After Sub 1-1 (60 g, 133.35 mmol) in a round bottom flask
was dissolved in THF (489 mL), Sub 2-3 (58.28 g, 160.01 mmol),
Pd(PPh.sub.3).sub.4 (6.16 g, 5.33 mmol), K.sub.2CO.sub.3 (55.29 g,
400.04 mmol) and water (244 mL) were added thereto and the mixture
was stirred under reflux. When reaction was completed, the product
was extracted with ether and water. Thereafter, the organic layer
was dried with MgSO.sub.4 and concentrated. The concentrate was
applied to silica gel column and recrystallized to obtain 73.40 g
(yield: 75%) of the product.
[0183] Synthesis of Compound 1-6
##STR00234##
[0184] THF (418 mL), Sub 2-1 (39.43 g, 136.87 mmol),
Pd(PPh.sub.3).sub.4 (5.27 g, 4.56 mmol), K.sub.2CO.sub.3 (47.29 g,
342.17 mmol), water (209 mL) were added to Sub 1-3 (60 g, 114.06
mmol), and then 61.11 g (yield: 73%) of the product was obtained by
the same method as in synthesis of 1-3.
[0185] Synthesis of Compound 1-11
##STR00235##
[0186] THF (382 mL), Sub 2-6 (39.13 g, 124.98 mmol),
Pd(PPh.sub.3).sub.4 (4.81 g, 4.17 mmol), K.sub.2CO.sub.3 (43.18 g,
312.44 mmol) and water (191 mL) were added to Sub 1-6 (60 g, 104.15
mmol), and then 54.76 g (yield: 65%) of the product was obtained by
the same method as in synthesis of 1-3.
[0187] Synthesis of Compound 1-14
##STR00236##
[0188] THF (404 mL), Sub 2-1 (288.11 g, 132.10 mmol),
Pd(PPh.sub.3).sub.4 (5.09 g, 4.40 mmol), K.sub.2CO.sub.3 (45.64 g,
330.26 mmol) and water (202 mL) were added to Sub 1-8 (60 g, 110.09
mmol), and then 52.21 g (yield: 63%) of the product was obtained by
the same method as in synthesis of 1-3.
[0189] Synthesis of Compound 1-22
##STR00237##
[0190] THF (381 mL), Sub 2-1 (35.88 g, 124.55 mmol),
Pd(PPh.sub.3).sub.4 (4.80 g, 4.15 mmol), K.sub.2CO.sub.3 (43.03 g,
311.37 mmol) and water (190 mL) were added to Sub 1-15 (60 g,
103.79 mmol), and then 55.47 g (yield: 68%) of the product was
obtained by the same method as in synthesis of 1-3.
[0191] Synthesis of Compound 1-44
##STR00238##
[0192] THF (410 mL), Sub 2-1 (38.62 g, 134.05 mmol),
Pd(PPh.sub.3).sub.4 (5.16 g, 4.47 mmol), K.sub.2CO.sub.3 (46.32 g,
335.13 mmol) and water (205 mL) were added to Sub 1-27 (60 g,
111.71 mmol), and then 49.93 g (yield: 60%) of the product was
obtained by the same method as in synthesis of 1-3.
[0193] Synthesis of Compound 1-74
##STR00239##
[0194] THF (359 mL), Sub 2-26 (35.78 g, 117.63 mmol),
Pd(PPh.sub.3).sub.4 (4.53 g, 3.92 mmol), K.sub.2CO.sub.3 (40.64 g,
294.07 mmol) and water (180 mL) were added to Sub 1-50 (60 g, 98.02
mmol), and then 46.71 g (yield: 57%) of the product was obtained by
the same method as in synthesis of 1-3.
[0195] Synthesis of Compound 1-98
##STR00240##
[0196] THF (484 mL), Sub 2-1 (45.59 g, 158.25 mmol),
Pd(PPh.sub.3).sub.4 (6.10 g, 5.27 mmol), K.sub.2CO.sub.3 (54.68 g,
395.61 mmol) and water (242 mL) were added to Sub 1-67 (60 g,
131.87 mmol), and then 70.80 g (yield: 81%) of the product was
obtained by the same method as in synthesis of 1-3.
[0197] Synthesis of Compound 2-15
##STR00241##
[0198] THF (489 mL), (8-phenyldibenzo[b,d]furan-1-yl)boronic acid
(46.10 g, 160.01 mmol), Pd(PPh.sub.3).sub.4 (6.16 g, 5.33 mmol),
K.sub.2CO.sub.3 (55.29 g, 400.04 mmol) and water (244 mL) were
added to Sub 1-1 (60 g, 133.35 mmol), and then 58.77 g (yield: 67%)
of the product was obtained by the same method as in synthesis of
1-3.
[0199] Synthesis of Compound 3-22
##STR00242##
[0200] THE (424 mL), (7-phenyldibenzo[b,d]furan-2-yl)boronic acid
(39.97 g, 138.73 mmol), Pd(PPh.sub.3).sub.4 (5.34 g, 4.62 mmol),
K.sub.2CO.sub.3 (47.94 g, 346.83 mmol) and water (212 mL) were
added to
2-chloro-4-(3-fluoronaphthalen-1-yl)-6-(7-(pyridin-3-yl)dibenzo[b,d]thiop-
hen-3-yl)-1,3,5-triazine (60 g, 115.61 mmol), and then 51.26 g
(yield: 61%) of the product was obtained by the same method as in
synthesis of 1-3.
[0201] Synthesis of Compound 4-11
##STR00243##
[0202] THF (382 mL), (6-phenylnaphtho[2,3-b]benzofuran-2-yl)boronic
acid (42.26 g, 124.98 mmol), Pd(PPh.sub.3).sub.4 (4.81 g, 4.17
mmol), K.sub.2CO.sub.3 (43.18 g, 312.44 mmol) and water (191 mL)
were added to Sub 1-70 (60 g, 104.15 mmol), and then 50.38 g
(yield: 58%) of the product was obtained by the same method as in
synthesis of 1-3.
[0203] Synthesis of Compound 4-38
##STR00244##
[0204] THF (85 mL),
(8-([1,1'-biphenyl]-3-yl)dibenzo[b,d]thiophen-1-yl)boronic acid
(10.52 g, 27.7 mmol), Pd(PPh.sub.3).sub.4 (1.33 g, 1.2 mmol),
K.sub.2CO.sub.3 (9.56 g, 69.1 mmol) and water (42 mL) were added to
2-chloro-4-phenyl-6-(6-phenyldibenzo[b,d]furan-4-yl)-1,3,5-triazine
(10 g, 23.0 mmol), and then 14.38 g (yield: 85%) of the product was
obtained by the same method as in synthesis of 1-3.
[0205] Synthesis of Compound 4-41
##STR00245##
[0206] THF (180 mL), (7-phenyldibenzo[b,d]furan-3-yl)boronic acid
(16.9 g, 58.7 mmol), Pd(PPh.sub.3).sub.4 (2.82 g, 2.4 mmol),
K.sub.2CO.sub.3 (20.27 g, 146.7 mmol) and water (90 mL) were added
to
2-chloro-4-phenyl-6-(6-phenyldibenzo[b,d]thiophen-4-yl)-1,3,5-triazine
(22 g, 48.9 mmol), and then 25.73 g (yield: 80%) of the product was
obtained by the same method as in synthesis of 1-3.
[0207] Synthesis of Compound 4-43
##STR00246##
[0208] THF (285 mL), (8-phenyldibenzo[b,d]furan-1-yl)boronic acid
(26.89 g, 93.3 mmol), Pd(PPh.sub.3).sub.4 (4.49 g, 3.9 mmol),
K.sub.2CO.sub.3 (32.25 g, 233.4 mmol) and water (143 mL) were added
to
2-chloro-4-phenyl-6-(6-phenyldibenzo[b,d]thiophen-3-yl)-1,3,5-triazine
(35 g, 77.8 mmol), and then 36.84 g (yield: 72%) of the product was
obtained by the same method as in synthesis of 1-3.
[0209] The FD-MS values of the compounds represented by Formula 1
of the present invention prepared according to the above synthesis
examples are shown in Table 3 below.
TABLE-US-00003 TABLE 3 Compound FD-MS Compound FD-MS 1-1 m/z =
657.19 (C.sub.45H.sub.27N.sub.3OS = 657.79) 1-2 m/z = 733.22
(C.sub.51H.sub.31N.sub.3OS = 733.89) 1-3 m/z = 733.22
(C.sub.51H.sub.31N.sub.3OS = 733.89) 1-4 m/z = 733.22
(C.sub.51H.sub.31N.sub.3OS = 733.89) 1-7 m/z = 707.20
(C.sub.49H.sub.29N.sub.3OS = 707.85) 1-8 m/z = 757.22
(C.sub.53H.sub.31N.sub.3OS = 757.91) 1-9 m/z = 859.27
(C.sub.61H.sub.37N.sub.3OS = 860.05) 1-10 m/z = 707.20
(C.sub.49H.sub.29N.sub.3OS = 707.85) 1-11 m/z = 808.23
(C.sub.56H.sub.32N.sub.4OS = 808.96) 1-12 m/z = 890.31
(C.sub.63H.sub.34D.sub.5N.sub.3OS = 891.12) 1-13 m/z = 824.24
(C.sub.35H.sub.32N.sub.6OS = 824.96) 1-14 m/z = 752.20
(C.sub.50H.sub.29FN.sub.4OS = 752.87) 1-15 m/z = 765.26
(C.sub.51H.sub.35N.sub.5OS = 765.94) 1-16 m/z = 765.17
(C.sub.49H.sub.27N.sub.5OS.sub.2 = 765.91) 1-17 m/z = 807.23
(C.sub.57H.sub.33N.sub.3OS = 807.97) 1-18 m/z = 833.25
(C.sub.59H.sub.35N.sub.3OS = 834.01) 1-19 m/z = 733.22
(C.sub.51H.sub.31N.sub.3OS = 733.89) 1-20 m/z = 733.22
(C.sub.51H.sub.31N.sub.3OS = 733.89) 1-21 m/z = 783.23
(C.sub.55H.sub.33N.sub.3OS = 783.95) 1-22 m/z = 785.22
(C.sub.53H.sub.31N.sub.5OS = 785.93) 1-23 m/z = 859.27
(C.sub.61H.sub.37N.sub.3OS = 860.05) 1-24 m/z = 785.22
(C.sub.53H.sub.31N.sub.5OS = 785.93) 1-25 m/z = 809.22
(C.sub.55H.sub.31N.sub.5OS = 809.95) 1-26 m/z = 849.28
(C.sub.60H.sub.39N.sub.3OS = 850.05) 1-27 m/z = 783.23
(C.sub.55H.sub.33N.sub.3OS = 783.95) 1-28 m/z = 657.19
(C.sub.45H.sub.27N.sub.3OS = 657.79) 1-29 m/z = 809.25
(C.sub.57H.sub.35N.sub.3OS = 809.99) 1-32 m/z = 900.27
(C.sub.61H.sub.36N.sub.6OS = 901.06) 1-33 m/z = 835.24
(C.sub.57H.sub.33N.sub.5OS = 835.99) 1-34 m/z = 901.25
(C.sub.61H.sub.35N.sub.5O2S = 902.04) 1-35 m/z = 809.25
(C.sub.37H.sub.33N.sub.3OS = 809.99) 1-36 m/z = 938.21
(C.sub.59H.sub.31F.sub.5N.sub.4OS = 938.98) 1-37 m/z = 783.23
(C.sub.55H.sub.33N.sub.3OS = 783.95) 1-42 m/z = 812.24
(C.sub.54H.sub.32N.sub.6OS = 812.95) 1-43 m/z = 950.31
(C.sub.67H.sub.42N.sub.4OS = 951.16) 1-44 m/z = 744.21
(C.sub.49H.sub.24D.sub.5N.sub.3OS.sub.2 = 744.94) 1-50 m/z = 726.19
(C.sub.48H.sub.27FN.sub.4OS = 726.83) 1-51 m/z = 791.27
(C.sub.53H.sub.37N.sub.5OS = 791.97) 1-58 m/z = 897.28
(C.sub.64H.sub.39N.sub.3OS = 898.10) 1-59 m/z = 822.25
(C.sub.57H.sub.34N.sub.4OS = 822.99) 1-60 m/z = 887.27
(C.sub.61H.sub.37N.sub.5OS = 888.06) 1-64 m/z = 885.28
(C.sub.63H.sub.39N.sub.3OS = 886.09) 1-68 m/z = 911.27
(C.sub.63H.sub.37N.sub.5OS = 912.08) 1-69 m/z = 885.26
(C.sub.61H.sub.35N.sub.5OS = 886.05) 1-70 m/z = 989.25
(C.sub.69H.sub.39N.sub.3OS.sub.2 = 990.21) 1-75 m/z = 909.28
(C.sub.65H.sub.39N.sub.3OS = 910.11) 1-76 m/z = 856.23
(C.sub.57H.sub.36N.sub.4OS.sub.2 = 857.06) 1-78 m/z = 929.32
(C.sub.65H.sub.35D.sub.5N.sub.4OS = 930.15) 1-79 m/z = 735.21
(C.sub.49H.sub.29N5OS = 735.87) 1-90 m/z = 784.23
(C.sub.54H.sub.32N.sub.4OS = 784.94) 1-92 m/z = 889.28
(C.sub.62H.sub.39N.sub.3O.sub.2S = 890.07) 1-96 m/z = 888.27
(C.sub.60H.sub.36N.sub.6OS = 889.05) 1-98 m/z = 662.22
(C.sub.45H.sub.22D.sub.5N.sub.3OS = 662.82) 1-99 m/z = 667.25
(C.sub.45H.sub.17D.sub.10N.sub.3OS = 667.85) 1-100 m/z = 733.22
(C.sub.51H.sub.31N.sub.3OS = 733.89) 2-15 m/z = 657.19
(C.sub.45H.sub.27N.sub.3OS = 657.79)
Synthesis Example 2
[0210] As shown in Reaction Schemes 4-1 and 4-2 below, the compound
represented by Formula 12 according to the present invention can be
synthesized by reacting Sub with Sub 4-1, but there is no
limitation thereto.
[0211] <Reaction Scheme 4-1> (where L.sup.2 in Formula 12 is
not a single bond)
##STR00247##
##STR00248##
[0212] Synthesis of Compound 5-1
##STR00249##
[0213] After 3-bromo-9-phenyl-9H-carbazole (6.4 g, 20 mmol) was
dissolved in THF,
(9-(4,6-diphenyl-1,3,5-triazin-2-yl)-9H-carbazol-3-yl)boronic acid
(8.8 g, 20 mmol), Pd(PPh.sub.3).sub.4 (0.03 eq.), K.sub.2CO.sub.3
(3 eq.) and water were added thereto and the mixture was stirred
under reflux. When reaction was completed, the product was
extracted with ether and water. Thereafter, the organic layer was
dried with MgSO.sub.4 and concentrated. The concentrate was applied
to silica gel column and recrystallized to obtain 9.2 g (yield:
72%) of the product.
[0214] Synthesis of Compound 5-21
##STR00250##
[0215] Dibenzo[b,d]furan-2-ylboronic acid (4.2 g, 20 mmol) were
added to 10-bromo-7-(pyridin-2-yl)-7H-benzo[c]carbazole (7.5 g, 20
mmol), and then 6.5 g (yield: 71%) of the product was obtained by
the same method as in synthesis of 5-1.
[0216] Synthesis of Compound 5-25
##STR00251##
[0217] (9-(naphthalen-2-yl)-9H-carbazol-3-yl)boronic acid (6.7 g,
20 mmol) were added to
9-([1,1'-biphenyl]-4-yl)-3-bromo-9H-carbazole (8.0 g, 20 mmol), and
then 9.2 g (yield: 75%) of the product was obtained by the same
method as in synthesis of 5-1.
[0218] Synthesis of Compound 5-31
##STR00252##
[0219] (9-phenyl-9H-carbazol-3-yl)boronic acid (5.7 g, 20 mmol)
were added to 3'-bromo-9-phenyl-9H-2,9'-bicarbazole (9.7 g, 20
mmol), and then 9.5 g (yield: 73%) of the product was obtained by
the same method as in synthesis of 5-1.
[0220] Synthesis of Compound 5-32
##STR00253##
[0221]
(12-([1,1':4',1''-terphenyl]-4-yl)-12H-benzo[4,5]thieno[2,3-a]carba-
zol-3-yl)boronic acid (10.9 g, 20 mmol) were added to
3-bromo-9-(dibenzo[b,d]furan-2-yl)-9H-carbazole (8.2 g, 20 mmol),
and then 11.5 g (yield: 69%) of the product was obtained by the
same method as in synthesis of 5-1.
[0222] Synthesis of Compound 5-34
##STR00254##
[0223] (4-(dibenzo[b,d]thiophen-3-yl)phenyl)boronic acid (6.1 g, 20
mmol) were added to 4-bromo-9-phenyl-9H-carbazole (6.4 g, 20 mmol),
and then 6.7 g (yield: 67%) of the product was obtained by the same
method as in synthesis of 5-1.
[0224] Synthesis of Compound 5-35
##STR00255##
[0225] 9(9,9-dimethyl-9H-fluoren-3-yl)boronic acid (4.8 g, 20 mmol)
were added to 3-bromo-9-phenyl-9H-carbazole (6.4 g, 20 mmol), and
then 6.1 g (yield: 70%) of the product was obtained by the same
method as in synthesis of 5-1.
[0226] The FD-MS values of the compounds according to Formula 1 of
the present invention prepared according to the above synthesis
examples are shown in the following Table 4.
TABLE-US-00004 TABLE 4 Compound FD-MS Compound FD-MS 5-1 m/z =
639.24 (C.sub.45H.sub.29N.sub.5 = 639.75) 5-2 m/z = 715.27
(C.sub.51H.sub.33N.sub.5 = 715.84) 5-3 m/z = 780.33
(C.sub.57H.sub.40N.sub.4 = 780.95) 5-4 m/z = 639.24
(C.sub.45H.sub.29N.sub.5 = 639.75) 5-5 m/z = 715.27
(C.sub.51H.sub.33N.sub.5 = 715.84) 5-6 m/z = 780.33
(C.sub.57H.sub.40N.sub.4 = 780.95) 5-7 m/z = 612.23
(C.sub.44H.sub.28N.sub.4 = 612.72) 5-8 m/z = 612.23
(C.sub.44H.sub.28N.sub.4 = 612.72) 5-9 m/z = 662.25
(C.sub.48H.sub.30N.sub.4 = 662.78) 5-10 m/z = 484.19
(C.sub.36H.sub.24N.sub.2 = 484.59) 5-11 m/z = 639.24
(C.sub.45H.sub.29N.sub.5 = 639.75) 5-12 m/z = 715.27
(C.sub.51H.sub.33N.sub.5 = 715.84) 5-13 m/z = 715.27
(C.sub.51H.sub.33N.sub.5 = 715.84) 5-14 m/z = 638.25
(C.sub.46H.sub.30N.sub.4 = 638.76) 5-15 m/z = 579.18
(C.sub.40H.sub.25N.sub.3S = 579.71) 5-16 m/z = 410.14
(C.sub.29H.sub.18N.sub.2S = 410.47) 5-17 m/z = 486.17
(C.sub.35H.sub.22N.sub.2O = 486.56) 5-18 m/z = 486.17
(C.sub.35H.sub.22N.sub.2O = 486.56) 5-19 m/z = 486.17
(C.sub.35H.sub.22N.sub.2O = 486.56) 5-20 m/z = 563.20
(C.sub.40H.sub.25N.sub.3O = 563.65) 5-21 m/z = 460.16
(C.sub.33H.sub.20N.sub.2O = 460.52) 5-22 m/z = 536.19
(C.sub.39H.sub.24N.sub.2O = 536.62) 5-23 m/z = 689.26
(C.sub.49H.sub.31N.sub.5 = 689.80) 5-24 m/z = 585.22
(C.sub.43H.sub.27N.sub.3 = 585.69) 5-25 m/z = 610.24
(C.sub.46H.sub.30N.sub.2 = 610.76) 5-26 m/z = 610.24
(C.sub.46H.sub.30N.sub.2 = 610.76) 5-27 m/z = 636.26
(C.sub.48H.sub.32N.sub.2 = 636.80) 5-28 m/z = 636.26
(C.sub.48H.sub.32N.sub.2 = 636.80) 5-29 m/z = 610.24
(C.sub.46H.sub.30N.sub.2 = 610.76) 5-30 m/z = 610.24
(C.sub.46H.sub.30N.sub.2 = 610.76) 5-31 m/z = 649.25
(C.sub.48H.sub.31N.sub.3 = 649.80) 5-32 m/z = 832.25
(C.sub.60H.sub.36N.sub.2OS = 833.02) 5-33 m/z = 560.23
(C.sub.42H.sub.28N.sub.2 = 560.70) 5-34 m/z = 501.16
(C.sub.36H.sub.23NS = 501.65) 5-35 m/z = 435.20 (C.sub.33H.sub.25N
= 435.57) 5-36 m/z = 725.28 (C.sub.54H.sub.35N.sub.3 = 725.90) 5-37
m/z = 650.24 (C.sub.48H.sub.30N.sub.2O = 650.78) 5-38 m/z = 650.24
(C.sub.48H.sub.30N.sub.2O = 650.78) 5-39 m/z = 650.24
(C.sub.48H.sub.30N.sub.2O = 650.78) 5-40 m/z = 650.24
(C.sub.48H.sub.30N.sub.2O = 650.78) 5-41 m/z = 666.21
(C.sub.48H.sub.30N.sub.2S = 666.84) 5-42 m/z = 666.21
(C.sub.48H.sub.30N.sub.2S = 666.84) 5-43 m/z = 666.21
(C.sub.48H.sub.30N.sub.2S = 666.84) 5-44 m/z = 666.21
(C.sub.48H.sub.30N.sub.2S = 666.84) 5-45 m/z = 650.24
(C.sub.48H.sub.30N.sub.2O = 650.78) 5-46 m/z = 650.24
(C.sub.48H.sub.30N.sub.2O = 650.78) 5-47 m/z = 650.24
(C.sub.48H.sub.30N.sub.2O = 650.78) 5-48 m/z = 650.24
(C.sub.48H.sub.30N.sub.2O = 650.78) 5-49 m/z = 666.21
(C.sub.48H.sub.30N.sub.2S = 666.84) 5-50 m/z = 666.21
(C.sub.48H.sub.30N.sub.2S = 666.84) 5-51 m/z = 666.21
(C.sub.48H.sub.30N.sub.2S = 666.84) 5-52 m/z = 666.21
(C.sub.48H.sub.30N.sub.2S = 666.84) 5-57 m/z = 636.26
(C.sub.48H.sub.32N.sub.2 = 636.80) 5-58 m/z = 725.28
(C.sub.54H.sub.35N.sub.3 = 725.90)
Synthesis Example 3
[0227] The compound represented by Formula 20 according to the
present invention can be synthesized as follows, but is not limited
thereto.
[0228] Synthesis of Compound 13-17
##STR00256##
[0229] After 9-(4'-bromo-[1,1'-biphenyl]-4-yl)-9H-carbazole(9.6 g,
24 mmol) was dissolved in toluene,
di([1,1'-biphenyl]-4-yl)amine(6.4 g, 20 mmol), Pd.sub.2(dba).sub.3
(0.05 eq.), PPh.sub.3 (0.1 eq.) and NaOt-Bu (3 eq.) were added
thereto and the mixture was stirred under reflux at 100.degree. C.
for 24. When reaction was completed, the product was extracted with
ether and water. Thereafter, the organic layer was dried with
MgSO.sub.4 and concentrated. The concentrate was applied to silica
gel column and recrystallized to obtain 12.9 g (yield: 84%) of the
product.
[0230] Synthesis of Compound 13-32
##STR00257##
[0231] After 3-(4-bromophenyl)-9-phenyl-9H-carbazole (9.6 g, 24
mmol) was dissolved in toluene,
N-([1,1'-biphenyl]-4-yl)-9,9-dimethyl-9H-fluoren-2-amine (7.2 g, 20
mmol), Pd.sub.2(dba).sub.3 (0.05 eq.), PPh.sub.3 (0.1 eq.) and
NaOt-Bu (3 eq.) were added thereto and then 13.8 g (yield: 85%) of
the product was obtained by the same method as in synthesis of
13-17.
[0232] Synthesis of Compound 14-34
##STR00258##
[0233] After Sub 5(4) (4.7 g, 20 mmol), Pd.sub.2(dba).sub.3 (0.5 g,
0.6 mmol), P(t-Bu).sub.3 (0.2 g, 2 mmol), t-BuONa (5.8 g, 60 mmol)
and toluene (300 mL) were added to Sub 4(19) (9.5 g, mmol) and the
reaction was carried out at 100.degree. C. When reaction was
completed, the product was extracted with CH.sub.2Cl.sub.2 and
water. Thereafter, the organic layer was dried with MgSO.sub.4 and
concentrated. The concentrate was applied to silica gel column and
recrystallized to obtain 9.8 g (yield: 78%) of the product.
[0234] Synthesis of Compound 14-58
##STR00259##
[0235] Sub 5(7) (5.7 g, 20 mmol), Pd.sub.2(dba).sub.3 (0.5 g, 0.6
mmol), P(t-Bu).sub.3 (0.2 g, 2 mmol), t-BuONa (5.8 g, 60 mmol) and
toluene (300 mL) were added to Sub 4(35) (8.4 g, 20 mmol), and then
10.4 g (yield: 83%) of the product was obtained by the same method
as in synthesis of 14-34.
[0236] Synthesis of Compound 14-59
##STR00260##
[0237] Sub 5(11) (7.9 g, 20 mmol), Pd.sub.2(dba).sub.3 (0.5 g, 0.6
mmol), P(t-Bu).sub.3 (0.2 g, 2 mmol), t-BuONa (5.8 g, 60 mmol) and
toluene (300 mL) were added to Sub 4(32) (12.9 g, mmol), and then
5.2 g (yield: 79%) of the product was obtained by the same method
as in synthesis of 14-34.
[0238] Synthesis of Compound 14-69
##STR00261##
[0239] 4-(0.parallel.p (0.5 g, 0.6 mmol), P(t-Bu).sub.3 (0.2 g, 2
mmol), t-BuONa (5.8 g, 60 mmol) and toluene (300 mL) were added to
N-([1,1'-biphenyl]-4-yl)-9,9-dimethyl-9H-fluoren-2-amine (7.2 g, 20
mmol), and then 12.2 g (yield: 81%) of the product was obtained by
the same method as in synthesis of 14-34.
[0240] Synthesis of Compound 14-71
##STR00262##
[0241]
N-(3-bromophenyl)-N-(9,9-dimethyl-9H-fluoren-2-yl)dibenzo[b,d]furan-
-1-amine (10.6 g, 20 mmol), Pd.sub.2(dba).sub.3 (0.5 g, 0.6 mmol),
P(t-Bu).sub.3 (0.2 g, 2 mmol), t-BuONa (5.8 g, mmol) and toluene
(300 mL) were added to
N-(9,9-dimethyl-9H-fluoren-2-yl)dibenzo[b,d]furan-1-amine (7.5 g,
20 mmol), and then 12.9 g (yield: 78%) of the product was obtained
by the same method as in synthesis of 14-34.
[0242] Synthesis of Compound 14-72
##STR00263##
[0243] 2-bromo-9,9-dimethyl-9H-fluorene (5.5 g, 20 mmol),
Pd.sub.2(dba).sub.3 (0.5 g, 0.6 mmol), P(t-Bu).sub.3 (0.2 g, 2
mmol), t-BuONa (5.8 g, 60 mmol) and toluene (300 mL) were added to
N-(3-(9-phenyl-9H-fluoren-9-yl)phenyl)dibenzo[b,d]furan-1-amine
(10.0 g, 20 mmol), and then 11.1 g (yield: 80%) of the product was
obtained by the same method as in synthesis of 14-34.
Synthesis Example 4
[0244] As shown in Reaction Scheme 5 below, the compound
represented by Formula A according to the present invention can be
synthesized by reacting Sub a with Sub b, but there is no
limitation thereto.
##STR00264##
Synthesis Example of Sub a
[0245] Sub a of the Reaction Scheme 5 can be synthesized according
to the reaction route of the following Reaction Scheme 5-1, but
there is no limitation thereto.
##STR00265##
##STR00266##
[0246] 1-bromo-3-chlorobenzene (50 g, 261.2 mmol),
N-([1,1'-biphenyl]-4-yl)-[1,1'-biphenyl]-2-amine (125.92 g, 391.7
mmol), Pd.sub.2(dba).sub.3 (7.17 g, 7.8 mmol), P(t-Bu).sub.3 (4.23
g, 20.9 mmol), NaO(t-Bu) (75.30 g, 783.5 mmol) and toluene (3200
mL) were placed in a round bottom flask and then the mixture was
heated under reflux at 80.degree. C. for 4 hours. When the reaction
is completed, the resultant was diluted with distilled water at
room temperature and was extracted with CH.sub.2Cl.sub.2 and water.
Thereafter, the organic layer was dried with MgSO.sub.4 and
concentrated. The concentrate was recrystallized with methylene
chloride and hexane to obtain Sub a-3 (93.63 g, 83%) of the
product.
[0247] Synthesis of Sub a-29
##STR00267##
[0248] 1-Bromo-3-chlorobenzene (50 g, 261.2 mmol),
N-(9,9-dimethyl-9H-fluoren-2-yl)dibenzo[b,d]furan-1-amine (147.09
g, 391.7 mmol), Pd.sub.2(dba).sub.3 (7.17 g, 7.8 mmol),
P(t-Bu).sub.3 (4.23 g, 20.9 mmol), NaO(t-Bu) (75.30 g, 783.5 mmol)
and toluene (3200 mL) were placed in a round bottom flask and then
the mixture was heated under reflux at 80.degree. C. for 4 hours.
When the reaction is completed, the resultant was diluted with
distilled water at room temperature and was extracted with
CH.sub.2Cl.sub.2 and water. Thereafter, the organic layer was dried
with MgSO.sub.4 and concentrated. The concentrate was
recrystallized with methylene chloride and hexane to obtain Sub
a-29 (107.89 g, 85%) of the product.
[0249] Synthesis of Sub a-39
##STR00268##
[0250] 4-Bromo-4'-chloro-1,1'-biphenyl (50 g, 186.9 mmol),
N-(9,9-dimethyl-9H-fluoren-2-yl)dibenzo[b,d]furan-4-amine (105.25
g, 280.3 mmol), Pd.sub.2(dba).sub.3 (5.13 g, 5.6 mmol),
P(t-Bu).sub.3 (3.02 g, 15.0 mmol), NaO(t-Bu) (53.88 g, 560.6 mmol)
and toluene (2300 mL) were placed in a round bottom flask and then
the mixture was heated under reflux at 80.degree. C. for 4 hours.
When the reaction is completed, the resultant was diluted with
distilled water at room temperature and was extracted with
CH.sub.2Cl.sub.2 and water. Thereafter, the organic layer was dried
with MgSO.sub.4 and concentrated. The concentrate was
recrystallized with methylene chloride and hexane to obtain Sub
a-39 (87.19 g, 83%) of the product.
[0251] The example of the compound belonging to Sub a may be, but
not limited to, the following compounds, and Table 5 shows ED-MS
values of the following compounds.
##STR00269## ##STR00270## ##STR00271## ##STR00272## ##STR00273##
##STR00274## ##STR00275## ##STR00276## ##STR00277## ##STR00278##
##STR00279## ##STR00280## ##STR00281## ##STR00282## ##STR00283##
##STR00284## ##STR00285## ##STR00286## ##STR00287## ##STR00288##
##STR00289## ##STR00290## ##STR00291## ##STR00292## ##STR00293##
##STR00294## ##STR00295## ##STR00296## ##STR00297## ##STR00298##
##STR00299##
TABLE-US-00005 TABLE 5 Compound FD-MS Compound FD-MS Sub a-1 m/z =
279.08 (C.sub.18H.sub.14ClN = 279.77) Sub a-2 m/z = 355.11
(C.sub.24H.sub.18ClN = 355.87) Sub a-3 m/z = 431.14
(C.sub.30H.sub.22ClN = 431.96) Sub a-4 m/z = 507.18
(C.sub.36H.sub.26ClN = 508.06) Sub a-5 m/z = 507.18
(C.sub.36H.sub.26ClN = 508.06) Sub a-6 m/z = 329.10
(C.sub.22H.sub.16ClN = 329.83) Sub a-7 m/z = 405.13
(C.sub.28H.sub.20ClN = 405.93) Sub a-8 m/z = 395.14
(C.sub.27H.sub.22ClN = 395.93) Sub a-9 m/z = 471.18
(C.sub.33H.sub.26ClN = 472.03) Sub a-10 m/z = 471.18
(C.sub.33H.sub.26ClN = 472.03) Sub a-11 m/z = 511.21
(C.sub.36H.sub.30ClN = 512.09) Sub a-12 m/z = 471.18
(C.sub.33H.sub.26ClN = 472.03) Sub a-13 m/z = 471.18
(C.sub.33H.sub.26ClN = 472.03) Sub a-14 m/z = 511.21
(C.sub.36H.sub.30ClN = 512.09) Sub a-15 m/z = 595.21
(C.sub.43H.sub.30ClN = 596.17) Sub a-16 m/z = 635.24
(C.sub.46H.sub.34ClN = 636.24) Sub a-17 m/z = 519.18
(C.sub.37H.sub.26ClN = 520.07) Sub a-18 m/z = 595.21
(C.sub.43H.sub.30ClN = 596.17) Sub a-19 m/z = 671.24
(C.sub.49H.sub.34ClN = 672.27) Sub a-20 m/z = 519.18
(C.sub.37H.sub.26ClN = 520.07) Sub a-21 m/z = 593.19
(C.sub.43H.sub.28ClN = 594.15) Sub a-22 m/z = 595.21
(C.sub.43H.sub.30ClN = 596.17) Sub a-23 m/z = 671.24
(C.sub.49H.sub.34ClN = 672.27) Sub a-24 m/z = 635.24
(C.sub.46H.sub.34ClN = 636.24) Sub a-25 m/z = 595.21
(C.sub.43H.sub.30ClN = 596.17) Sub a-26 m/z = 369.09
(C.sub.24H.sub.16ClNO = 369.85) Sub a-27 m/z = 445.12
(C.sub.30H.sub.20ClNO = 445.95) Sub a-28 m/z = 445.12
(C.sub.30H.sub.20ClNO = 445.95) Sub a-29 m/z = 485.15
(C.sub.33H.sub.24ClNO = 486.01) Sub a-30 m/z = 609.19
(C.sub.43H.sub.28ClNO = 610.15) Sub a-31 m/z = 369.09
(C.sub.24H.sub.16ClNO = 369.85) Sub a-32 m/z = 419.11
(C.sub.28H.sub.18ClNO = 419.91) Sub a-33 m/z = 609.19
(C.sub.43H.sub.28ClNO = 610.15) Sub a-34 m/z = 445.12
(C.sub.30H.sub.20ClNO = 445.95) Sub a-35 m/z = 445.12
(C.sub.30H.sub.20ClNO = 445.95) Sub a-36 m/z = 495.14
(C.sub.34H.sub.22ClNO = 496.01) Sub a-37 m/z = 485.15
(C.sub.33H.sub.24ClNO = 486.01) Sub a-38 m/z = 369.09
(C.sub.24H.sub.16ClNO = 369.85) Sub a-39 m/z = 561.1
(C.sub.39H.sub.28ClNO = 562.11) Sub a-40 m/z = 461.10
(C.sub.30H.sub.20ClNS = 462.01) Sub a-41 m/z = 577.16
(C.sub.39H.sub.28ClNS = 578.17) Sub a-42 m/z = 461.10
(C.sub.30H.sub.20ClNS = 462.01) Sub a-43 m/z = 435.08
(C.sub.28H.sub.18ClNS = 435.97) Sub a-44 m/z = 501.13
(C.sub.33H.sub.24ClNS = 502.07) Sub a-45 m/z = 385.07
(C.sub.24H.sub.16ClNS = 385.91) Sub a-46 m/z = 625.16
(C.sub.43H.sub.28ClNS = 626.21) Sub a-47 m/z = 431.14
(C.sub.30H.sub.22ClN = 431.96) Sub a-48 m/z = 355.11
(C.sub.24H.sub.18ClN = 355.87) Sub a-49 m/z = 507.18
(C.sub.36H.sub.26ClN = 508.06) Sub a-50 m/z = 405.13
(C.sub.28H.sub.20ClN = 405.93) Sub a-51 m/z = 547.21
(C.sub.39H.sub.30ClN = 548.13) Sub a-52 m/z = 395.14
(C.sub.27H.sub.22ClN = 395.93) Sub a-53 m/z = 561.22
(C.sub.40H.sub.32ClN = 562.15) Sub a-54 m/z = 759.27
(C.sub.56H.sub.38ClN = 760.38) Sub a-55 m/z = 671.24
(C.sub.49H.sub.34ClN = 672.27) Sub a-56 m/z = 419.11
(C.sub.28H.sub.18ClNO = 419.91) Sub a-57 m/z = 609.19
(C.sub.43H.sub.28ClNO = 610.15) Sub a-58 m/z = 369.09
(C.sub.24H.sub.16ClNO = 369.85) Sub a-59 m/z = 485.15
(C.sub.33H.sub.24ClNO = 486.01) Sub a-60 m/z = 445.12
(C.sub.30H.sub.20ClNO = 445.95) Sub a-61 m/z = 445.12
(C.sub.30H.sub.20ClNO = 445.95) Sub a-62 m/z = 435.08
(C.sub.28H.sub.18ClNS = 435.97) Sub a-63 m/z = 501.13
(C.sub.33H.sub.24ClNS = 502.07) Sub a-64 m/z = 461.10
(C.sub.30H.sub.20ClNS = 462.01) Sub a-65 m/z = 511.12
(C.sub.34H.sub.22ClNS = 512.07) Sub a-66 m/z = 431.14
(C.sub.30H.sub.22ClN = 431.96) Sub a-67 m/z = 569.19
(C.sub.41H.sub.28ClN = 570.13) Sub a-68 m/z = 485.15
(C.sub.33H.sub.24ClNO = 486.01) Sub a-69 m/z = 355.11
(C.sub.24H.sub.18ClN = 355.87) Sub a-70 m/z = 405.13
(C.sub.28H.sub.20ClN = 405.93) Sub a-71 m/z = 521.19
(C.sub.37H.sub.28ClN = 522.09) Sub a-72 m/z = 547.21
(C.sub.39H.sub.30ClN = 548.13) Sub a-73 m/z = 395.14
(C.sub.27H.sub.22ClN = 395.93) Sub a-74 m/z = 517.16
(C.sub.37H.sub.24ClN = 518.06) Sub a-75 m/z = 595.21
(C.sub.43H.sub.30ClN = 596.17) Sub a-76 m/z = 609.19
(C.sub.43H.sub.28ClNO = 610.15) Sub a-77 m/z = 485.15
(C.sub.33H.sub.24ClNO = 486.01) Sub a-78 m/z = 385.07
(C.sub.24H.sub.16ClNS = 385.91) Sub a-79 m/z = 577.16
(C.sub.39H.sub.28ClNS = 578.17) Sub a-80 m/z = 431.14
(C.sub.30H.sub.22ClN = 431.96) Sub a-81 m/z = 395.14
(C.sub.27H.sub.22ClN = 395.93) Sub a-82 m/z = 569.19
(C.sub.41H.sub.28ClN = 570.13) Sub a-83 m/z = : 485.15
(C.sub.33H.sub.24ClNO = 486.01) Sub a-84 m/z = 495.14
(C.sub.34H.sub.22ClNO = 496.01) Sub a-85 m/z = 501.13
(C.sub.33H.sub.24ClNS = 502.07) Sub a-86 m/z = 435.08
(C.sub.28H.sub.18ClNS = 435.97) Sub a-87 m/z = 547.21
(C.sub.39H.sub.30ClN = 548.13) Sub a-88 m/z = 519.18
(C.sub.37H.sub.26ClN = 520.07) Sub a-89 m/z = 595.21
(C.sub.43H.sub.30ClN = 596.17) Sub a-90 m/z = 609.19
(C.sub.43H.sub.28ClNO = 610.15) Sub a-91 m/z = 431.14
(C.sub.30H.sub.22ClN = 431.96) Sub a-92 m/z = 471.18
(C.sub.33H.sub.26ClN = 472.03) Sub a-93 m/z = 385.07
(C.sub.24H.sub.16ClNS = 385.91) Sub a-94 m/z = 431.14
(C.sub.30H.sub.22ClN = 431.96) Sub a-95 m/z = 329.10
(C.sub.22H.sub.16ClN = 329.83) Sub a-96 m/z = 471.18
(C.sub.33H.sub.26ClN = 472.03) Sub a-97 m/z = 501.13
(C.sub.33H.sub.24ClNS = 502.07) Sub a-98 m/z = 471.18
(C.sub.33H.sub.26ClN = 472.03) Sub a-99 m/z = 759.27
(C.sub.56H.sub.38ClN = 760.38) Sub a-100 m/z = 609.19
(C.sub.43H.sub.28ClNO = 610.15) Sub a-101 m/z = 360.14
(C.sub.24H.sub.13D.sub.5ClN = 360.90) Sub a-102 m/z = 405.13
(C.sub.28H.sub.20ClN = 405.93) Sub a-103 m/z = 471.18
(C.sub.33H.sub.26ClN = 472.03) Sub a-104 m/z = 519.18
(C.sub.37H.sub.26ClN = 520.07) Sub a-105 m/z = 609.19
(C.sub.43H.sub.28ClNO = 610.15) Sub a-106 m/z = 355.11
(C.sub.24H.sub.18ClN = 355.87) Sub a-107 m/z = 507.18
(C.sub.36H.sub.26ClN = 508.06) Sub a-108 m/z = 519.18
(C.sub.37H.sub.26ClN = 520.07) Sub a-109 m/z = 481.16
(C.sub.34H.sub.24ClN = 482.02) Sub a-110 m/z = 609.19
(C.sub.43H.sub.28ClNO = 610.15) Sub a-111 m/z = 445.12
(C.sub.30H.sub.20ClNO = 445.95) Sub a-112 m/z = 461.10
(C.sub.30H.sub.20ClNS = 462.01) Sub a-113 m/z = 429.13
(C.sub.30H.sub.20ClN = 429.95) Sub a-114 m/z = 379.11
(C.sub.26H.sub.18ClN = 379.89) Sub a-115 m/z = 519.18
(C.sub.37H.sub.26ClN = 520.07) Sub a-116 m/z = 635.24
(C.sub.46H.sub.34ClN = 636.24) Sub a-117 m/z = 445.12
(C.sub.30H.sub.20ClNO = 445.95) Sub a-118 m/z = 575.24
(C.sub.44H.sub.23ClN = 576.18) Sub a-119 m/z = 561.19
(C.sub.39H.sub.28ClNO = 562.11)
Synthesis Example of Sub b
[0252] Sub b of the Reaction Scheme 5 can be synthesized according
to the reaction route of the following Reaction Scheme 5-2, but
there is no limitation thereto.
##STR00300##
[0253] Synthesis of Sub b-1
##STR00301##
[0254] 9-(3-bromophenyl)-9-phenyl-9H-fluorene (100 g, 251.7 mmol),
aniline (35.16 g, 377.5 mmol), Pd.sub.2(dba).sub.3 (6.91 g, 7.6
mmol), P(t-Bu).sub.3 (4.07 g, 20.1 mmol), NaO(t-Bu) (72.57 g, 755.1
mmol) and toluene (3150 mL) were placed in a round bottom flask and
then the mixture was heated under reflux at 60.degree. C. for 4
hours. When the reaction is completed, the resultant was diluted
with distilled water at room temperature and was extracted with
CH.sub.2Cl.sub.2 and water. Thereafter, the organic layer was dried
with MgSO.sub.4 and concentrated. The concentrate was
recrystallized with methylene chloride and hexane to obtain Sub b-1
(82.46 g, 80%) of the product.
[0255] Synthesis of Sub b-17
##STR00302##
[0256] 9-(3-bromophenyl)-9-phenyl-9H-fluorene (100 g, 251.7 mmol),
9,9-dimethyl-9H-fluoren-3-amine (79.01 g, 377.5 mmol),
Pd.sub.2(dba).sub.3 (6.91 g, 7.6 mmol), P(t-Bu).sub.3 (4.07 g, 20.1
mmol), NaO(t-Bu) (72.57 g, 755.1 mmol) and toluene (3150 mL) were
placed in a round bottom flask and then the mixture was heated
under reflux at 60.degree. C. for 4 hours. When the reaction is
completed, the resultant was diluted with distilled water at room
temperature and was extracted with CH.sub.2Cl.sub.2 and water.
Thereafter, the organic layer was dried with MgSO.sub.4 and
concentrated. The concentrate was recrystallized with methylene
chloride and hexane to obtain Sub b-17 (101.88 g, 77%) of the
product.
[0257] Synthesis of Sub b-26
##STR00303##
[0258] 9-(3-bromophenyl)-9-phenyl-9H-fluorene (100 g, 251.7 mmol),
9,9-dimethyl-9H-fluoren-4-amine (69.17 g, 377.5 mmol),
Pd.sub.2(dba).sub.3 (6.91 g, 7.6 mmol), P(t-Bu).sub.3 (4.07 g, 20.1
mmol), NaO(t-Bu) (72.57 g, 755.1 mmol) and toluene (3150 mL) were
placed in a round bottom flask and then the mixture was heated
under reflux at 60.degree. C. for 4 hours. When the reaction is
completed, the resultant was diluted with distilled water at room
temperature and was extracted with CH.sub.2Cl.sub.2 and water.
Thereafter, the organic layer was dried with MgSO.sub.4 and
concentrated. The concentrate was recrystallized with methylene
chloride and hexane to obtain Sub b-26 (99.34 g, 79%) of the
product.
[0259] Example of the compounds belonging to Sub b may be, but not
limited to, the following compounds, and Table 6 shows the FD-MS
values of the following compounds.
##STR00304## ##STR00305## ##STR00306## ##STR00307## ##STR00308##
##STR00309##
TABLE-US-00006 TABLE 6 Compound FD-MS Compound FD-MS Sub b-1 m/z =
409.18 (C.sub.31H.sub.23N = 409.53) Sub b-2 m/z = 409.18
(C.sub.31H.sub.23N = 409.53) Sub b-3 m/z = 409.18
(C.sub.31H.sub.23N = 409.53) Sub b-4 m/z = 414.21
(C.sub.31H.sub.18D.sub.5N = 414.56) Sub b-5 m/z = 485.21
(C.sub.37H.sub.27N = 485.63) Sub b-6 m/z = 485.21
(C.sub.37H.sub.27N = 485.63) Sub b-7 m/z = 485.21
(C.sub.37H.sub.27N = 485.63) Sub b-8 m/z = 485.21
(C.sub.37H.sub.27N = 485.63) Sub b-9 m/z = 485.21
(C.sub.37H.sub.27N = 485.63) Sub b-10 m/z = 485.21
(C.sub.37H.sub.27N = 485.63) Sub b-11 m/z = 525.25
(C.sub.40H.sub.31N = 525.70) Sub b-12 m/z = 525.25
(C.sub.40H.sub.31N = 525.70) Sub b-13 m/z = 527.26
(C.sub.40H.sub.33N = 527.71) Sub b-14 m/z = 525.25
(C.sub.40H.sub.31N = 525.70) Sub b-15 m/z = 525.25
(C.sub.40H.sub.31N = 525.70) Sub b-16 m/z = 525.25
(C.sub.40H.sub.31N = 525.70) Sub b-17 m/z = 525.25
(C.sub.40H.sub.31N = 525.70) Sub b-18 m/z = 525.25
(C.sub.40H.sub.31N = 525.70) Sub b-19 m/z = 649.28
(C.sub.50H.sub.35N = 649.84) Sub b-20 m/z = 647.26
(C.sub.50H.sub.33N = 647.82) Sub b-21 m/z = 649.28
(C.sub.50H.sub.35N = 649.84) Sub b-22 m/z = 649.28
(C.sub.50H.sub.35N = 649.84) Sub b-23 m/z = 649.28
(C.sub.50H.sub.35N = 649.84) Sub b-24 m/z = 649.28
(C.sub.50H.sub.35N = 649.84) Sub b-25 m/z = 649.28
(C.sub.50H.sub.35N = 649.84) Sub b-26 m/z = 499.19
(C.sub.37H.sub.25NO = 499.61) Sub b-27 m/z = 549.21
(C.sub.41H.sub.27NO = 549.67) Sub b-28 m/z = 499.19
(C.sub.37H.sub.25NO = 499.61) Sub b-29 m/z = 499.19
(C.sub.37H.sub.25NO = 499.61) Sub b-30 m/z = 575.22
(C.sub.43H.sub.29NO = 575.71) Sub b-31 m/z = 575.22
(C.sub.43H.sub.29NO = 575.71) Sub b-32 m/z = 499.19
(C.sub.37H.sub.25NO = 499.61) Sub b-33 m/z = 437.18
(C.sub.32H.sub.23NO = 437.54)
Synthesis Example of Final Product
[0260] Synthesis of compound G-3
##STR00310##
[0261] Sub a-3 (10 g, 23.2 mmol), Sub b-1 (9.48 g, 23.2 mmol),
Pd.sub.2(dba).sub.3 (0.64 g, 0.7 mmol), P(t-Bu).sub.3 (0.37 g, 1.9
mmol), NaO(t-Bu) (6.67 g, 69.5 mmol) and toluene (230 mL) were
placed in a round bottom flask and then the mixture was heated
under reflux at 110.degree. C. for 3 hours. When the reaction is
completed, the resultant was diluted with distilled water at room
temperature and was extracted with CH.sub.2C.sub.2 and water.
Thereafter, the organic layer was dried with MgSO.sub.4 and
concentrated. The concentrate was dissolved in toluene and filtered
with a silica gel filter. After concentrating the filtered
solution, the concentrate was recrystallized with toluene and
acetone to obtain G-3 (17.0 g, 89%) of the product.
[0262] Synthesis of Compound G-29
##STR00311##
[0263] Sub a-29 (10 g, 20.6 mmol), Sub b-1 (8.43 g, 20.6 mmol),
Pd.sub.2(dba).sub.3 (0.57 g, 0.6 mmol), P(t-Bu).sub.3 (0.33 g, 1.6
mmol), NaO(t-Bu) (5.93 g, 61.7 mmol) and toluene (210 mL) were
placed in a round bottom flask and then the mixture was heated
under reflux at 110.degree. C. for 3 hours. When the reaction is
completed, the resultant was diluted with distilled water at room
temperature and was extracted with CH.sub.2Cl.sub.2 and water.
Thereafter, the organic layer was dried with MgSO.sub.4 and
concentrated. The concentrate was dissolved in toluene and filtered
with a silica gel filter. After concentrating the filtered
solution, the concentrate was recrystallized with toluene and
acetone to obtain G-29 (15.20 g, 86%) of the product.
[0264] Synthesis of Compound G-81
##STR00312##
[0265] Sub a-116 (10 g, 15.7 mmol), Sub b-8 (7.63 g, 15.7 mmol),
Pd.sub.2(dba).sub.3 (0.43 g, 0.5 mmol), P(t-Bu).sub.3 (0.25 g, 1.3
mmol), NaO(t-Bu) (4.53 g, 47.2 mmol) and toluene (160 mL) were
placed in a round bottom flask and then the mixture was heated
under reflux at 110.degree. C. for 3 hours. When the reaction is
completed, the resultant was diluted with distilled water at room
temperature and was extracted with CH.sub.2Cl.sub.2 and water.
Thereafter, the organic layer was dried with MgSO.sub.4 and
concentrated. The concentrate was dissolved in toluene and filtered
with a silica gel filter. After concentrating the filtered
solution, the concentrate was recrystallized with toluene and
acetone to obtain G-81 (13.99 g, 82%) of the product.
[0266] Synthesis of Compound G-88
##STR00313##
[0267] Sub a-69 (10 g, 28.1 mmol), Sub b-12 (14.77 g, 28.1 mmol),
Pd.sub.2(dba).sub.3 (0.77 g, 0.8 mmol), P(t-Bu).sub.3 (0.45 g, 2.2
mmol), NaO(t-Bu) (8.10 g, 84.3 mmol) and toluene (280 mL) were
placed in a round bottom flask and then the mixture was heated
under reflux at 110.degree. C. for 3 hours. When the reaction is
completed, the resultant was diluted with distilled water at room
temperature and was extracted with CH.sub.2Cl.sub.2 and water.
Thereafter, the organic layer was dried with MgSO.sub.4 and
concentrated. The concentrate was dissolved in toluene and filtered
with a silica gel filter. After concentrating the filtered
solution, the concentrate was recrystallized with toluene and
acetone to obtain G-88 (19.47 g, 82%) of the product.
[0268] Synthesis of Compound G-137
##STR00314##
[0269] Sub a-90 (10 g, 16.4 mmol), Sub b-21 (10.65 g, 16.4 mmol),
Pd.sub.2(dba).sub.3 (0.45 g, 0.5 mmol), P(t-Bu).sub.3 (0.27 g, 1.3
mmol), NaO(t-Bu) (4.73 g, 49.2 mmol) and toluene (170 mL) were
placed in a round bottom flask and then the mixture was heated
under reflux at 110.degree. C. for 3 hours. When the reaction is
completed, the resultant was diluted with distilled water at room
temperature and was extracted with CH.sub.2Cl.sub.2 and water.
Thereafter, the organic layer was dried with MgSO.sub.4 and
concentrated. The concentrate was dissolved in toluene and filtered
with a silica gel filter. After concentrating the filtered
solution, the concentrate was recrystallized with toluene and
acetone to obtain G-137 (16.24 g, 81%) of the product.
[0270] Synthesis of Compound G-168
##STR00315##
[0271] Sub a-117 (10 g, 22.4 mmol), Sub b-26 (11.20 g, 22.4 mmol),
Pd.sub.2(dba).sub.3 (0.62 g, 0.7 mmol), P(t-Bu).sub.3 (0.36 g, 1.8
mmol), NaO(t-Bu) (6.47 g, 67.3 mmol) and toluene (230 mL) were
placed in a round bottom flask and then the mixture was heated
under reflux at 110.degree. C. for 3 hours. When the reaction is
completed, the resultant was diluted with distilled water at room
temperature and was extracted with CH.sub.2Cl.sub.2 and water.
Thereafter, the organic layer was dried with MgSO.sub.4 and
concentrated. The concentrate was dissolved in toluene and filtered
with a silica gel filter. After concentrating the filtered
solution, the concentrate was recrystallized with toluene and
acetone to obtain G-168 (16.92 g, 83%) of the product.
[0272] The FD-MS values of the compounds according to Formula A of
the present invention prepared according to the above synthesis
examples are shown in the following Table 7.
TABLE-US-00007 TABLE 7 Compound FD-MS Compound FD-MS G-1 m/z =
652.29 (C.sub.49H.sub.36N.sub.2 = 652.84) G-2 m/z = 728.32
(C.sub.55H.sub.40N.sub.2 = 728.94) G-3 m/z = 804.35
(C.sub.61H.sub.44N.sub.2 = 805.04) G-4 m/z = 880.38
(C.sub.67H.sub.48N.sub.2 = 881.14) G-5 m/z = 880.38
(C.sub.67H.sub.48N.sub.2 = 881.14) G-6 m/z = 702.30
(C.sub.53H.sub.38N.sub.2 = 702.90) G-7 m/z = 778.33
(C.sub.59H.sub.42N.sub.2 = 779.00) G-8 m/z = 768.35
(C.sub.58H.sub.44N.sub.2 = 769.00) G-9 m/z = 844.38
(C.sub.64H.sub.48N.sub.2 = 845.10) G-10 m/z = 844.38
(C.sub.64H.sub.48N.sub.2 = 845.10) G-11 m/z = 884.41
(C.sub.67H.sub.52N.sub.2 = 885.17) G-12 m/z = 844.38
(C.sub.64H.sub.48N.sub.2 = 845.10) G-13 m/z = 844.38
(C.sub.64H.sub.48N.sub.2 = 845.10) G-14 m/z = 884.41
(C.sub.67H.sub.52N.sub.2 = 885.17) G-15 m/z = 968.41
(C.sub.74H.sub.52N.sub.2 = 969.24) G-16 m/z = 1008.44
(C.sub.77H.sub.56N.sub.2 = 1009.31) G-17 m/z = 892.38
(C.sub.68H.sub.48N.sub.2 = 893.15) G-18 m/z = 968.41
(C.sub.74H.sub.52N.sub.2 = 969.24) G-19 m/z = .sub.1044.44
(C.sub.80H.sub.56N.sub.2 = 1045.34) G-20 m/z = 892.38
(C.sub.68H.sub.48N.sub.2 = 893.15) G-21 m/z = 966.40
(C.sub.74H.sub.50N.sub.2 = 967.23) G-22 m/z = 968.41
(C.sub.74H.sub.52N.sub.2 = 969.24) G-23 m/z = 1044.44
(C.sub.80H.sub.56N.sub.2 = 1045.34) G-24 m/z = 1008.44
(C.sub.77H.sub.56N.sub.2 = 1009.31) G-25 m/z = 968.41
(C.sub.74H.sub.52N.sub.2 = 969.24) G-26 m/z = 742.30
(C.sub.55H.sub.38N.sub.2O = 742.92) G-27 m/z = 823.36
(C.sub.61H.sub.37D.sub.5N.sub.2O = 824.05) G-28 m/z = 818.33
(C.sub.61H.sub.42N.sub.2O = 819.02) G-29 m/z = 858.36
(C.sub.64H.sub.46N.sub.2O = 859.09) G-30 m/z = 982.39
(C.sub.74H.sub.50N.sub.2O = 983.23) G-31 m/z = 742.30
(C.sub.55H.sub.38N.sub.2O = 742.92) G-32 m/z = 792.31
(C.sub.59H.sub.40N.sub.2O = 792.98) G-33 m/z = 982.39
(C.sub.74H.sub.50N.sub.2O = 983.23) G-34 m/z = 818.33
(C.sub.61H.sub.42N.sub.2O = 819.02) G-35 m/z = 818.33
(C.sub.61H.sub.42N.sub.2O = 819.02) G-36 m/z = 868.35
(C.sub.65H.sub.44N.sub.2O = 869.08) G-37 m/z = 858.36
(C.sub.64H.sub.46N.sub.2O = 859.09) G-38 m/z = 742.30
(C.sub.55H.sub.38N.sub.2O = 742.92) G-39 m/z = 934.39
(C.sub.70H.sub.50N.sub.2O = 935.18) G-40 m/z = 834.31
(C.sub.61H.sub.42N.sub.2S = 835.08) G-41 m/z = 950.37
(C.sub.70H.sub.50N.sub.2S = 951.24) G-42 m/z = 834.31
(C.sub.61H.sub.42N.sub.2S = 835.08) G-43 m/z = 808.29
(C.sub.59H.sub.40N.sub.2S = 809.04) G-44 m/z = 874.34
(C.sub.64H.sub.46N.sub.2S = 875.15) G-45 m/z = 758.28
(C.sub.55H.sub.38N.sub.2S = 758.98) G-46 m/z = 998.37
(C.sub.74H.sub.50N.sub.2S = 999.29) G-47 m/z = 880.38
(C.sub.67H.sub.48N.sub.2 = 881.14) G-48 m/z = 804.35
(C.sub.61H.sub.44N.sub.2 = 805.04) G-49 m/z = 804.35
(C.sub.61H.sub.44N.sub.2 = 805.04) G-50 m/z = 880.38
(C.sub.67H.sub.48N.sub.2 = 881.14) G-51 m/z = 854.37
(C.sub.65H.sub.46N.sub.2 = 855.10) G-52 m/z = 844.38
(C.sub.64H.sub.48N.sub.2 = 845.10) G-53 m/z = 996.44
(C.sub.76H.sub.56N.sub.2 = 997.30) G-54 m/z = 920.41
(C.sub.70H.sub.52N.sub.2 = 921.20) G-55 m/z = 844.38
(C.sub.64H.sub.48N.sub.2 = 845.10) G-56 m/z = 920.41
(C.sub.70H.sub.52N.sub.2 = 921.20) G-57 m/z = 1010.46
(C.sub.77H.sub.58N.sub.2 = 1011.33) G-58 m/z = 1044.44
(C.sub.80H.sub.56N.sub.2 = 1045.34) G-59 m/z = 1208.51
(C.sub.93H.sub.64N.sub.2 = 1209.55) G-60 m/z = 1118.46
(C.sub.86H.sub.58N.sub.2 = 1119.42) G-61 m/z = 968.41
(C.sub.74H.sub.52N.sub.2 = 969.24) G-62 m/z = 1120.48
(C.sub.86H.sub.60N.sub.2 = 1121.44) G-63 m/z = 868.35
(C.sub.65H.sub.44N.sub.2O = 869.08) G-64 m/z = 1058.42
(C.sub.80H.sub.54N.sub.2O = 1059.33) G-65 m/z = 818.33
(C.sub.61H.sub.42N.sub.2O = 819.02) G-66 m/z = 934.39
(C.sub.70H.sub.50N.sub.2O = 935.18) G-67 m/z = 894.36
(C.sub.67H.sub.46N.sub.2O = 895.12) G-68 m/z = 894.36
(C.sub.67H.sub.46N.sub.2O = 895.12) G-69 m/z = 884.32
(C.sub.65H.sub.44N.sub.2S = 885.14) G-70 m/z = 950.37
(C.sub.70H.sub.50N.sub.2S = 951.24) G-71 m/z = 910.34
(C.sub.67H.sub.46N.sub.2S = 911.18) G-72 m/z = 960.35
(C.sub.71H.sub.48N.sub.2S = 961.24) G-73 m/z = 1074.40
(C.sub.80H.sub.54N.sub.2S = 1075.39) G-74 m/z = 652.29
(C.sub.49H.sub.36N.sub.2 = 652.84) G-75 m/z = 880.38
(C.sub.67H.sub.48N.sub.2 = 881.14) G-76 m/z = 880.38
(C.sub.67H.sub.48N.sub.2 = 881.14) G-77 m/z = 844.38
(C.sub.64H.sub.48N.sub.2 = 845. 10) G-78 m/z = 920.41
(C.sub.70H.sub.52N.sub.2 = 921.20) G-79 m/z = 920.41
(C.sub.70H.sub.52N.sub.2 = 921.20) G-80 m/z = 960.44
(C.sub.73H.sub.56N.sub.2 = 961.27) G-81 m/z = 1084.48
(C.sub.83H.sub.60N.sub.2 = 1085.41) G-82 m/z = 1018.43
(C.sub.78H.sub.54N.sub.2 = 1019.30) G-83 m/z = 1044.44
(C.sub.80H.sub.56N.sub.2 = 1045.34) G-84 m/z = 894.36
(C.sub.67H.sub.46N.sub.2O = 895.12) G-85 m/z = 818.33
(C.sub.61H.sub.42N.sub.2O = 819.02) G-86 m/z = 1058.42
(C.sub.80H.sub.54N.sub.2O = 1059.33) G-87 m/z = 934.39
(C.sub.70H.sub.50N.sub.2O = 935.18) G-88 m/z = 844.38
(C.sub.64H.sub.48N.sub.2 = 845.10) G-89 m/z = 844.38
(C.sub.64H.sub.48N.sub.2 = 845.10) G-90 m/z = 920.41
(C.sub.70H.sub.52N.sub.2 = 921.20) G-91 m/z = 896.41
(C.sub.68H.sub.52N.sub.2 = 897.18) G-92 m/z = 1010.46
(C.sub.77H.sub.58N.sub.2 = 1011.33) G-93 m/z = .sub.1036.48
(C.sub.79H.sub.60N.sub.2 = 1037.36) G-94 m/z = 884.41
(C.sub.67H.sub.52N.sub.2 = 885.17) G-95 m/z = 1006.43
(C.sub.77H.sub.54N.sub.2 = 1007.29) G-96 m/z = 1084.48
(C.sub.83H.sub.60N.sub.2 = 1085.41) G-97 m/z = 1084.48
(C.sub.83H.sub.60N.sub.2 = 1085.41) G-98 m/z = 858.36
(C.sub.64H.sub.46N.sub.2O = 859.09) G-99 m/z = 974.42
(C.sub.73H.sub.54N.sub.2O = 975.25) G-100 m/z = 908.38
(C.sub.68H.sub.48N.sub.2O = 909.15) G-101 m/z = 934.39
(C.sub.70H.sub.50N.sub.2O = 935.18) G-102 m/z = 1098.45
(C.sub.83H.sub.58N.sub.2O = 1099.39) G-103 m/z = 974.42
(C.sub.73H.sub.54N.sub.2O = 975.25) G-104 m/z = 874.34
(C.sub.64H.sub.46N.sub.2S = 875.15) G-105 m/z = 1066.43
(C.sub.79H.sub.58N.sub.2S = 1067.41) G-106 m/z = 768.35
(C.sub.58H.sub.44N.sub.2 = 769.00) G-107 m/z = 844.38
(C.sub.64H.sub.48N.sub.2 = 845.10) G-108 m/z = 920.41
(C.sub.70H.sub.52N.sub.2 = 921.20) G-109 m/z = 996.44
(C.sub.76H.sub.56N.sub.2 = 997.30) G-110 m/z = 818.37
(C.sub.62H.sub.46N.sub.2 = 819.06) G-111 m/z = 894.40
(C.sub.68H.sub.50N.sub.2 = 895.16) G-112 m/z = 960.44
(C.sub.73H.sub.56N.sub.2 = 961.27) G-113 m/z = 884.41
(C.sub.67H.sub.52N.sub.2 = 885.17) G-114 m/z = 960.44
(C.sub.73H.sub.56N.sub.2 = 961.27) G-115 m/z = 1058.46
(C.sub.81H.sub.58N.sub.2 = 1059.37) G-116 m/z = 1084.48
(C.sub.83H.sub.60N.sub.2 = 1085.41) G-117 m/z = 1160.51
(C.sub.89H.sub.64N.sub.2 = 1161.51) G-118 m/z = 1084.48
(C.sub.83H.sub.60N.sub.2 = 1085.41) G-119 m/z = 934.39
(C.sub.70H.sub.50N.sub.2O = 935.18) G-120 m/z = 974.42
(C.sub.73H.sub.54N.sub.2O = 975.25) G-121 m/z = 934.39
(C.sub.70H.sub.50N.sub.2O = 935.18) G-122 m/z =.sub.: 984.41
(C.sub.74H.sub.52N.sub.2O = 985.24) G-123 m/z = 990.40
(C.sub.73H.sub.54N.sub.2S = 991.31) G-124 m/z = 924.35
(C.sub.68H.sub.48N.sub.2S = 925.21) G-125 m/z = 874.34
(C.sub.64H.sub.46N.sub.2S = 875.15) G-126 m/z = 968.41
(C.sub.74H.sub.52N.sub.2 = 969.24) G-127 m/z = 1044.44
(C.sub.80H.sub.56N.sub.2 = 1045.34) G-128 m/z = 940.38
(C.sub.72H.sub.48N.sub.2 = 941.19) G-129 m/z = 1008.44
(C.sub.77H.sub.56N.sub.2 = 1009.31) G-130 m/z = 1084.48
(C.sub.83H.sub.60N.sub.2 = 1085.41) G-131 m/z = 1160.51
(C.sub.89H.sub.64N.sub.2 = 1161.51) G-132 m/z = 1132.48
(C.sub.87H.sub.60N.sub.2 = 1133.45) G-133 m/z = 1208.51
(C.sub.93H.sub.64N.sub.2 = 1209.55) G-134 m/z = 1208.51
(C.sub.93H.sub.64N.sub.2 = 1209.55) G-135 m/z = 1098.45
(C.sub.83H.sub.58N.sub.2O = 1099.39) G-136 m/z = 982.39
(C.sub.74H.sub.50N.sub.2O = 983.23) G-137 m/z = 1222.49
(C.sub.93H.sub.62N.sub.2O = 1223.53) G-138 m/z = 1048.39
(C.sub.78H.sub.52N.sub.2S = 1049.35) G-139 m/z = 892.38
(C.sub.68H.sub.48N.sub.2 = 893.15) G-140 m/z = 1044.44
(C.sub.80H.sub.56N.sub.2 = 1045.34) G-141 m/z = 1084.48
(C.sub.83H.sub.60N.sub.2 = 1085.41) G-142 m/z = 982.39
(C.sub.74H.sub.50N.sub.2O = 983.23) G-143 m/z = 1058.42
(C.sub.80H.sub.54N.sub.2O = 1059.33) G-144 m/z = 998.37
(C.sub.74H.sub.50N.sub.2S = 999.29) G-145 m/z = 1044.44
(C.sub.80H.sub.56N.sub.2 = 1045.34) G-146 m/z = 1120.48
(C.sub.86H.sub.60N.sub.2 = 1121.44) G-147 m/z = 942.40
(C.sub.72H.sub.50N.sub.2 = 943.21) G-148 m/z = 1084.48
(C.sub.83H.sub.60N.sub.2 = 1085.41) G-149 m/z = 1084.48
(C.sub.83H.sub.60N.sub.2 = 1085.41) G-150 m/z = 1132.48
(C.sub.87H.sub.60N.sub.2 = 1133.45) G-151 m/z = 1248.54
(C.sub.96H.sub.68N.sub.2 = 1249.61) G-152 m/z = 982.39
(C.sub.74H.sub.50N.sub.2O = 983.23) G-153 m/z = 1058.42
(C.sub.80H.sub.54N.sub.2O = 1059.33) G-154 m/z = 1112.42
(C.sub.83H.sub.56N.sub.2S = 1113.44) G-155 m/z = 998.37
(C.sub.74H.sub.50N.sub.2S = 999.29) G-156 m/z = 742.30
(C.sub.55H.sub.38N.sub.2O = 742.92) G-157 m/z = 818.33
(C.sub.61H.sub.42N.sub.2O = 819.02) G-158 m/z = 868.35
(C.sub.65H.sub.44N.sub.2O = 869.08) G-159 m/z = 1010.42
(C.sub.76H.sub.54N.sub.2O = 1011.28) G-160 m/z = 934.39
(C.sub.70H.sub.50N.sub.2O = 935.18) G-161 m/z = 984.41
(C.sub.74H.sub.52N.sub.2O = 985.24) G-162 m/z = 982.39
(C.sub.74H.sub.50N.sub.2O = 983.23) G-163 m/z = 1222.49
(C.sub.93H.sub.62N.sub.2O = 1223.53) G-164 m/z = 908.34
(C.sub.67H.sub.44N.sub.2O.sub.2 = 909.10) G-165 m/z = 1072.40
(C.sub.80H.sub.52N.sub.2O.sub.2 = 1073.31) G-166 m/z = 832.31
(C.sub.61H.sub.40N.sub.2O.sub.2 = 833.00) G-167 m/z = 948.37
(C.sub.70H.sub.48N.sub.2O.sub.2 = 949.17) G-168 m/z = 908.34
(C.sub.67H.sub.44N.sub.2O.sub.2 = 909.10) G-169 m/z = 823.36
(C.sub.61H.sub.37D.sub.5N.sub.2O = 824.05) G-170 m/z = 894.36
(C.sub.67H.sub.46N.sub.2O = 895.12) G-171 m/z = 970.39
(C.sub.73H.sub.50N.sub.2O = 971.22) G-172 m/z = 868.35
(C.sub.65H.sub.44N.sub.2O = 869.08) G-173 m/z = 858.36
(C.sub.64H.sub.46N.sub.2O = 859.09) G-174 m/z =: 934.39
(C.sub.70H.sub.50N.sub.2O = 935.18) G-175 m/z = 934.39
(C.sub.70H.sub.50N.sub.2O = 935.18) G-176 m/z = 1058.42
(C.sub.80H.sub.54N.sub.2O = 1059.33) G-177 m/z = 982.39
(C.sub.74H.sub.50N.sub.2O = 983.23) G-178 m/z = 908.34
(C.sub.67H.sub.44N.sub.2O.sub.2 = 909.10) G-179 m/z = 1072.40
(C.sub.80H.sub.52N.sub.2O.sub.2 = 1073.31) G-180 m/z = 908.34
(C.sub.67H.sub.44N.sub.2O.sub.2 = 909.10) G-181 m/z = 818.33
(C.sub.61H.sub.42N.sub.2O = 819.02) G-182 m/z = 970.39
(C.sub.73H.sub.50N.sub.2O = 971.22) G-183 m/z = 858.36
(C.sub.64H.sub.46N.sub.2O = 859.09) G-184 m/.sub.7 = 1058.42
(C.sub.80H.sub.54N.sub.2O = 1059.33) G-185 m/z = 982.39
(C.sub.74H.sub.50N.sub.2O = 983.23) G-186 m/z = 882.32
(C.sub.65H.sub.42N.sub.2O.sub.2 = 883.06) G-187 m/z = 908.34
(C.sub.67H.sub.44N.sub.2O.sub.2 = 909.10) G-188 m/z = 970.39
(C.sub.73H.sub.50N.sub.2O = 971.22) G-189 m/z = 1020.41
(C.sub.77H.sub.52N.sub.2O = 1021.28) G-190 m/z = 1010.42
(C.sub.76H.sub.54N.sub.2O = 1011.28) G-191 m/z = 974.42
(C.sub.73H.sub.54N.sub.2O = 975.25) G-192 m/z = 982.39
(C.sub.74H.sub.50N.sub.2O = 983.23) G-193 m/z = 1134.45
(C.sub.86H.sub.58N.sub.2O = 1135.42) G-194 m/z = 982.39
(C.sub.74H.sub.50N.sub.2O = 983.23) G-195 m/z = 908.34
(C.sub.67H.sub.44N.sub.2O.sub.2 = 909.10) G-196 m/z = 948.37
(C.sub.70H.sub.48N.sub.2O.sub.2 = 949.17) G-197 m/z = 924.32
(C.sub.67H.sub.44N.sub.2OS = 925.16) G-198 m/z = 802.33
(C.sub.61H.sub.42N.sub.2 = 803.02) G-199 m/z = 752.32
(CS.sub.7H.sub.40N.sub.2 = 752.96) G-200 m/z = 892.38
(C.sub.68H.sub.48N.sub.2 = 893.15) G-204 m/z = 934.39
(C.sub.70H.sub.50N.sub.2O = 935.18)
[0273] Fabrication and Evaluation of Organic Electric element
[Example 1] Green OLED (a Phosphorescent Host)
[0274]
N.sup.1-(naphthalen-2-yl)-N.sup.4,N.sup.4-bis(4-(naphthalen-2-yl(ph-
enyl)amino)phenyl)-N.sup.1-phenylbenzene-1,4-diamine (hereinafter,
"2-TNATA") was vacuum-deposited on the ITO layer formed on a glass
substrate to form a hole injection layer with a thickness of
nm.
[0275] Next, 4,4'-bis[N-(1-naphthyl)-N-phenylamino]biphenyl
(hereinafter, "NPD") was vacuum-deposited on the hole injection
layer to form a hole transport layer with a thickness of 60 nm.
[0276] Subsequently, a light emitting layer with a thickness of 30
nm was vacuum-deposited on the hole transport layer by using
compound 1-1 of the present invention as a host material and
tris(2-phenylpyridine)-iridium (hereinafter, "Ir(ppy).sub.3") as a
dopant material in a weight ratio of 95:5.
[0277] Subsequently,
(1,1'-biphenyl-4-olato)bis(2-methyl-8-quinolinolato)aluminum
(hereinafter, "BAlq") was vacuum-deposited with a thickness of 10
nm on the light emitting layer to form a hole blocking layer, and
tris-(8-hydroxyquinoline)aluminum (hereinafter, "Alq.sub.3") was
vacuum-deposited with a thickness of 40 nm on the hole blocking
layer to form an electron transport layer.
[0278] Next, LiF was deposited with a thickness of 0.2 nm on the
electron transport layer to form an electron injection layer, and
then Al was deposited with a thickness of nm on the electron
injection layer to form a cathode.
[Example 2] to [Example 15]
[0279] The OLED was fabricated in the same manner as described in
Example 1 except that compounds of the present invention described
in Table 5 instead of the compound 1-1 of the present invention was
used as host material of a light emitting layer.
[Comparative Example 1] to [Comparative Example 3]
[0280] The OLEDs were fabricated in the same manner as described in
Example 1 except that one of the comparative compounds 1 to 3
instead of compound 1-1 of the present invention was used as host
material of a light emitting layer.
##STR00316##
[0281] Electroluminescence (EL) characteristics were measured with
PR-650 (Photoresearch) by applying a forward bias DC voltage to the
OLEDs prepared in Examples 1 to 15 of the present invention and
Comparative Examples 1 to 3. And, the T95 life time was measured
using a life time measuring apparatus manufactured by Mcscience
Inc. at reference brightness of 5000 cd/m.sup.2. The measurement
results are shown in Tables 8 below.
TABLE-US-00008 TABLE 8 Current Voltage Density Brightness
Efficiency Lifetime CIE Compound (V) (mA/cm.sup.2) (cd/m.sup.2)
(cd/A) T(95) x y comp.Ex(1) comp.Com 1 5.9 21.2 5000 23.6 56.1 0.33
0.61 comp.Ex(2) comp.Com 2 5.8 15.9 5000 31.5 75.4 0.33 0.61
comp.Ex(3) comp.Com 3 5.8 15.1 5000 33.2 77.1 0.33 0.61 Ex.(1) Com.
1-1 5.7 13.8 5000 36.2 84.3 0.33 0.62 Ex.(2) Com. 1-2 5.6 14.1 5000
35.4 85.1 0.33 0.61 Ex.(3) Com. 1-98 5.6 13.7 5000 36.4 84.8 0.33
0.62 Ex.(4) Com. 1-100 5.7 14.2 5000 35.2 82.1 0.33 0.62 Ex.(5)
Com. 2-1 5.6 13.3 5000 37.6 85.6 0.33 0.61 Ex.(6) Com. 2-3 5.5 13.4
5000 37.2 86.6 0.33 0.61 Ex.(7) Com. 2-15 5.5 12.9 5000 38.9 87.5
0.33 0.62 Ex.(8) Com. 2-35 5.5 13.3 5000 37.7 87.2 0.33 0.62 Ex.(9)
Com. 3-6 5.5 13.7 5000 36.5 85.9 0.33 0.61 Ex.(10) Com. 4-33 5.7
14.2 5000 35.1 80.7 0.33 0.62 Ex.(11) Com. 4-37 5.5 13.1 5000 38.2
87.8 0.33 0.61 Ex.(12) Com. 4-39 5.7 14.2 5000 35.3 81.5 0.33 0.61
Ex.(13) Com. 4-42 5.7 14.2 5000 35.2 81.0 0.33 0.61 Ex.(14) Com.
4-43 5.7 14.2 5000 35.1 81.2 0.33 0.61 Ex.(15) Com. 4-45 5.7 14.1
5000 35.4 80.9 0.33 0.61
[Example 16] to [Example 55]
[0282] The OLED was fabricated in the same manner as described in
Example 1 except that a mixture of the compound represented by
Formula 1 and the compound represented by Formula 12 of the present
invention described in Table 6 instead of compound 1-1 of the
present invention was used as host material of a light emitting
layer.
[Comparative Example 4] and [Comparative Example 6]
[0283] The OLEDs were fabricated in the same manner as described in
Example 1 except that a mixture of comparative compound 2 and
compound 5-27 of the present invention (Comparative Example 4), or
a mixture of comparative compound 3 and compound 5-27 of the
present invention instead of compound 1-1 of the present invention
was used as host material of a light emitting layer.
[0284] Electroluminescence (EL) characteristics were measured with
PR-650 (Photoresearch) by applying a forward bias DC voltage to the
OLEDs prepared in Examples 16 to 55 of the present invention and
Comparative Examples 4 and 5. And, the T95 life time was measured
using a life time measuring apparatus manufactured by Mcscience
Inc. at reference brightness of 5000 cd/m.sup.2. The measurement
results are shown in Tables 9 below.
TABLE-US-00009 TABLE 9 Current Voltage Density Brightness
Efficiency Lifetime Host 1 Host 2 (V) (mA/cm.sup.2) (cd/m.sup.2)
(cd/A) T(95) comp.Ex(4) comp.Com 2 Com. 5-27 5.6 14.8 5000 33.8
83.7 comp.Ex(5) comp.Com 3 Com. 5-27 5.6 14.0 5000 35.7 86.3
Ex.(16) Com. 1-1 Com. 5-27 5.0 11.9 5000 42.1 105.3 Ex.(17) Com.
1-2 5.0 11.9 5000 41.9 106.4 Ex.(18) Com. 1-98 5.0 11.9 5000 42.0
106.0 Ex.(19) Com. 1-100 5.1 12.0 5000 41.8 105.1 Ex.(20) Com. 2-3
5.0 11.8 5000 42.4 106.9 Ex.(21) Com. 2-15 5.0 11.7 5000 42.9 107.0
Ex.(22) Com. 2-35 5.0 11.7 5000 42.6 106.7 Ex.(23) Com. 3-6 5.0
11.9 5000 42.0 106.5 Ex.(24) Com. 4-33 5.1 12.0 5000 41.8 104.9
Ex.(25) Com. 4-37 5.0 11.7 5000 42.7 107.2 Ex.(26) Com. 1-1 Com.
5-25 5.1 12.3 5000 40.6 103.2 Ex.(27) Com. 1-2 5.1 12.3 5000 40.7
103.9 Ex.(28) Com. 1-98 5.1 12.1 5000 41.2 103.5 Ex.(29) Com. 1-100
5.2 12.2 5000 40.9 102.8 Ex.(30) Com. 2-3 5.1 12.0 5000 41.5 104.6
Ex.(31) Com. 2-15 5.1 12.0 5000 41.7 104.7 Ex.(32) Com. 2-35 5.1
12.1 5000 41.2 104.2 Ex.(33) Com. 3-6 5.1 12.2 5000 41.1 104.0
Ex.(34) Com. 4-33 5.2 12.3 5000 40.6 102.5 Ex.(35) Com. 4-37 5.1
12.0 5000 41.6 104.8 Ex.(36) Com. 1-1 Com. 5-31 4.9 11.5 5000 43.6
107.7 Ex.(37) Com. 1-2 4.9 11.5 5000 43.3 108.2 Ex.(38) Com. 1-98
4.9 11.5 5000 43.5 107.9 Ex.(39) Com. 1-100 5.0 11.6 5000 43.1
107.2 Ex.(40) Com. 2-3 4.9 11.4 5000 43.9 109.0 Ex.(41) Com. 2-15
4.9 11.3 5000 44.2 109.2 Ex.(42) Com. 2-35 4.9 11.4 5000 44.0 108.8
Ex.(43) Com. 3-6 4.9 11.4 5000 43.8 108.5 Ex.(44) Com. 4-33 5.0
11.6 5000 43.0 107.1 Ex.(45) Com. 4-37 4.9 11.4 5000 44.0 109.3
Ex.(46) Com. 1-1 Com. 5-42 5.2 12.7 5000 39.5 101.0 Ex.(47) Com.
1-2 5.2 12.5 5000 40.0 101.5 Ex.(48) Com. 1-98 5.2 12.5 5000 39.9
101.2 Ex.(49) Com. 1-100 5.2 12.7 5000 39.4 100.7 Ex.(50) Com. 2-3
5.2 12.6 5000 39.7 102.1 Ex.(51) Com. 2-15 5.2 12.4 5000 40.3 102.4
Ex.(52) Com. 2-35 5.2 12.5 5000 40.1 102.0 Ex.(53) Com. 3-6 5.2
12.6 5000 39.6 101.7 Ex.(54) Com. 4-33 5.2 12.7 5000 39.4 100.5
Ex.(55) Com. 4-37 5.2 12.5 5000 40.0 102.4
Example 56
[0285] After 2-TNATA was vacuum-deposited on the ITO layer formed
on a glass substrate to form a hole injection layer with a
thickness of 60 nm, NPD was vacuum-deposited on the hole injection
layer to form a hole transport layer with a thickness of 60 nm.
[0286] Next, compound 14-69 of the present invention was
vacuum-deposited to a thickness of 20 nm on the hole transport
layer to form an emission-auxiliary layer, and a light emitting
layer with a thickness of 30 nm was vacuum-deposited on the hole
transport layer by using a mixture of compound 1-1(the first host)
and compound 5-27 (the second host) of the present invention in the
ratio of 6:4 as a host material and Ir(ppy).sub.3) as a dopant
material in a weight ratio of 95:5.
[0287] Subsequently, BAlq was vacuum-deposited with a thickness of
10 nm on the light emitting layer to form a hole blocking layer,
Alq.sub.3 was vacuum-deposited with a thickness of 40 nm on the
hole blocking layer to form an electron transport layer. Next, LiF
was deposited with a thickness of 0.2 nm on the electron transport
layer to form an electron injection layer, and then Al was
deposited with a thickness of 150 nm on the electron injection
layer to form a cathode.
[Example 57] to [Example 73]
[0288] The OLEDs were fabricated in the same manner as described in
Example 56 except that the compounds of the present invention
described in the following Table 7 were used as an
emission-auxiliary layer material and the first host material.
[Comparative Example 6] and [Comparative Example 7]
[0289] The OLEDs were fabricated in the same manner as described in
Example 56 except that Comparative compound 2 or 3 was used as the
first host material.
[0290] Electroluminescence (EL) characteristics were measured with
a PR-650 (Photoresearch) by applying a forward bias DC voltage to
the OLEDs prepared in Examples 56 to 73 of the present invention
and Comparative Examples 6 and 7. And, the T95 life time was
measured using a life time measuring apparatus manufactured by
Mcscience Inc. at reference brightness of 5000 cd/m.sup.2. The
measurement results are shown in Tables 10 below.
TABLE-US-00010 TABLE 10 Current Voltage Density Brightness
Efficiency Lifetime EAL Host 1 Host 2 (V) (mA/cm.sup.2)
(cd/m.sup.2) (cd/A) T(95) comp.Ex(6) 14-69 comp.Com 2 5-27 5.4 13.6
5000 36.8 88.4 comp.Ex(7) comp.Com 3 5.4 13.1 5000 38.1 91.5
Ex.(56) Com. 1-1 5.1 9.8 5000 51.0 123.5 Ex.(57) Com. 1-2 5.1 9.3
5000 53.6 125.6 Ex.(58) Com. 1-98 5.1 9.5 5000 52.6 124.4 Ex.(59)
Com. 2-3 5.0 9.2 5000 54.1 127.4 Ex.(60) Com. 2-15 4.9 9.1 5000
54.7 128.0 Ex.(61) Com. 4-37 4.9 9.2 5000 54.5 128.2 comp.Ex(8)
14-72 comp.Com 2 5.4 12.6 5000 39.6 92.6 comp.Ex(9) comp.Com 3 5.3
12.0 5000 41.6 95.1 Ex.(62) Com. 1-1 4.9 9.0 5000 55.8 128.8
Ex.(63) Com. 1-2 4.9 8.8 5000 56.7 130.2 Ex.(64) Com. 1-98 4.9 8.9
5000 56.4 129.7 Ex.(65) Com. 2-3 4.8 8.4 5000 59.7 131.6 Ex.(66)
Com. 2-15 4.8 8.3 5000 60.5 133.8 Ex.(67) Com. 4-37 4.8 8.3 5000
60.1 134.0 comp.Ex(10) 14-74 comp.Com 2 5.3 11.6 5000 43.1 96.7
comp.Ex(11) comp.Com 3 5.3 10.8 5000 46.3 99.2 Ex.(68) Com. 1-1 4.8
8.1 5000 61.7 134.2 Ex.(69) Com. 1-2 4.8 8.0 5000 62.4 137.6
Ex.(70) Com. 1-98 4.8 8.1 5000 62.0 135.2 Ex.(71) Com. 2-3 4.7 7.9
5000 63.2 138.1 Ex.(72) Com. 2-15 4.7 7.8 5000 64.1 138.8 Ex.(73)
Com. 4-37 4.7 7.8 5000 63.9 139.6
Example 74
[0291] After 2-TNATA was vacuum-deposited on the ITO layer formed
on a glass substrate to form a hole injection layer with a
thickness of 60 nm, the compound 14-69 of the present invention was
vacuum-deposited on the hole injection layer to form a hole
transport layer with a thickness of 60 nm. Next, the compound 14-72
of the present invention was vacuum-deposited to a thickness of 20
nm on the hole transport layer to form an emission-auxiliary layer
and a light emitting layer with a thickness of 30 nm was
vacuum-deposited on the hole transport layer by using a mixture of
the compound 1-1(the first host) and the compound 5-27(the second
host) of the present invention at 6:4 as a host material and
Ir(ppy).sub.3) as a dopant material in a weight ratio of 95:5.
[0292] Subsequently, BAlq was vacuum-deposited with a thickness of
10 nm on the light emitting layer to form a hole blocking layer,
Alq.sub.3 was vacuum-deposited with a thickness of 40 nm on the
hole blocking layer to form an electron transport layer. Next, LiF
was deposited with a thickness of 0.2 nm on the electron transport
layer to form an electron injection layer, and then Al was
deposited with a thickness of 150 nm on the electron injection
layer to form a cathode.
[Example 75] to [Example 85]
[0293] The OLEDs were fabricated in the same manner as described in
Example 74 except that the compounds of the present invention
described in the following Table 8 were used as an
emission-auxiliary layer material and the first host material.
[0294] Electroluminescence (EL) characteristics were measured with
a PR-650 (Photoresearch) by applying a forward bias DC voltage to
the OLEDs prepared in Examples 74 to 85 of the present invention.
And, the T95 life time was measured using a life time measuring
apparatus manufactured by Mcscience Inc. at reference brightness of
5000 cd/m.sup.2. The measurement results are shown in Tables 11
below.
TABLE-US-00011 TABLE 11 Current Voltage Density Brightness
Efficiency Lifetime HTL EAL Host 1 Host 2 (V) (mA/cm.sup.2)
(cd/m.sup.2) (cd/A) T(95) Ex.(74) 14-69 14-72 Com. 1-1 5-27 4.6 7.9
5000 63.2 135.2 Ex.(75) Com. 1-2 4.5 7.6 5000 65.6 138.4 Ex.(76)
Com. 1-98 4.5 7.7 5000 65.2 137.1 Ex.(77) Com. 2-3 4.4 7.4 5000
67.6 139.4 Ex.(78) Com. 2-15 4.4 7.3 5000 68.2 140.0 Ex.(79) Com.
4-37 4.3 7.4 5000 68.0 140.6 Ex.(80) 14-74 Com. 1-1 4.5 7.7 5000
65.3 141.2 Ex.(81) Com. 1-2 4.4 7.4 5000 67.8 145.2 Ex.(82) Com.
1-98 4.4 7.5 5000 67.1 144.0 Ex.(83) Com. 2-3 4.3 7.3 5000 68.4
146.4 Ex.(84) Com. 2-15 4.3 7.2 5000 69.0 147.0 Ex.(85) Com. 4-37
4.2 7.3 5000 68.7 147.3
[0295] From Tables 5 to 8, it can be seen that the driving voltage
of the organic electroluminescent device can be lowered and the
luminous efficiency and lifespan are significantly improved when
the material for an organic electroluminescent device of the
present invention is used as a phosphorescent host material.
[0296] In particular, referring to Table 5, it can be seen that
even when the compound represented by Formula 1 of the present
invention is used as a single host, device characteristics are
superior to that using a comparative compound.
[0297] These results can be explained by the LUMO value of Compound
1-1 of the present invention. Referring to Table 9A below, it can
be seen that the LUMO level of Comparative Compound 2 is the
highest, the LUMO level of Comparative Compound is the lowest, and
the LUMO level of Compound 1-1 of the present invention is located
in the middle.
TABLE-US-00012 TABLE 9A comp. Com2 comp. Com3 Com. 1-1 LUMO 1.939
1.839 1.877
[0298] When comparing Comparative Compounds 2 and 3, Comparative
Compound 2 is different in that the heteroatom of both heterocycles
attached to the triazine is S, while in case of Comparative
Compound 3, the heteroatom is O. From Table 9 above, it can be seen
that when heteroatoms S are introduced into both heterocycles, the
LUMO value is highest (comparative compound 2), and when O is
introduced, the LUMO value is lowest (comparative compound 3), the
LUMO value is located in the middle when S as a heteroatom is
introduced into one heterocycle and O is introduced into the other
heterocycle as the compound of the present invention.
[0299] When comparative compound 2 having the highest LUMO level is
used as the phosphorescent host material, the LUMO level is too
high, and thus the LUMO level acts as a barrier to electron
movement. Therefore, the electron transfer from the electron
transport layer to the light emitting layer is not easy, and the
charge balance in the light emitting layer is reduced.
[0300] In addition, when comparative compound 3 having the lowest
LUMO level is used as a phosphorescent host material, the energy
gap between the electron transport layer and the LUMO level becomes
too large, so that electrons cannot be smoothly transferred from
the electron transport layer to the light emitting layer, as a
result, the charge balance within the light emitting layer is
reduced.
[0301] On the other hand, when the compound of the present
invention in which the LUMO level is located in the middle of the
LUMO level of the comparative compounds is used as a phosphorescent
host material, it has an appropriate LUMO level for electron
transfer, so the biased electron transfer characteristics of
Comparative Compound 2 and Comparative Compound 3 can be
complemented. Therefore, when the compound of the present invention
is used as a phosphorescent host material, the charge balance in
the light-emitting layer increases, so that the luminous efficiency
and lifetime of the organic electroluminescent device are
improved.
[0302] In Table 9A, compound 1-1 of the present invention is used
as an example, but the same conclusion can be reached with the
compounds of the present invention used in Examples 2 to 15 as a
phosphorescent host material.
[0303] On the other hand, referring to the device results of the
embodiments of the present invention, it can be seen that
performance is improved in all aspects of driving voltage,
efficiency, and lifetime when 1-dibenzofuran is substituted rather
than 4-dibenzofuran, and when 2-position of 1-dibenzofuran is
substituted rather than 4-position.
[0304] In more detail, it can be seen that the device result of
Example 5 in which 1-dibenzofuran is substituted in triazine is
better than Example 1 in which 4-dibenzofuran is substituted in
triazine, and the electrical properties of the device of Example 7
in which a substituent is attached at 2-position in benzene of
1-dibenzofuran instead of 4-position are improved.
[0305] This suggests that the energy level of the compound (HOMO,
LUMO, T.sub.1, etc.) and deposition conditions (for example,
T.sub.d, etc.) are changed because the physical properties of the
compound change depending on the substitution position, and this
acts as a major factor (e.g. energy balance) in improving device
performance, which can lead to different device results.
[0306] The above description can be equally applied to the case of
using one compound of the present invention as a host, as well as
when using two or more hosts and even when used in combination with
other layers.
[0307] In addition, as can be seen from the device measurement
results of Examples 1, 2, 5 and 6 of the present invention, it can
be seen that when a substituent (Ar.sub.2, Ar.sub.3) attached to a
heterocycle (dibenzofuran, dibenzothiophene) attached to a triazine
is mutually asymmetric, device performance is further improved. It
is believed that when Ar.sub.2 and Ar.sub.3 are mutually
asymmetric, due to the non-planarity of the compound, charges are
appropriately localized and the flow of the conjugate system is
effectively controlled to improve the lifetime of the device.
[Example 86] Green OLED (an Emission-Auxiliary Layer)
[0308] After 2-TNATA was vacuum-deposited on the ITO(anode) layer
formed on a glass substrate to form a hole injection layer with a
thickness of 60 nm, NPD was vacuum-deposited on the hole injection
layer to form a hole transport layer with a thickness of 60 nm.
Next, compound G-1 of the present invention was vacuum-deposited to
a thickness of 20 nm on the hole transport layer to form an
emission-auxiliary layer and a light emitting layer with a
thickness of 30 nm was vacuum-deposited on the hole transport layer
by using 4,4'-N,N'-dicarbazole-biphenyl (hereinafter, "CBP") and
Ir(ppy).sub.3) as a dopant material in a weight ratio of 95:5.
Subsequently, BAlq was vacuum-deposited with a thickness of 10 nm
on the light emitting layer to form a hole blocking layer,
Alq.sub.3 was vacuum-deposited with a thickness of 40 nm on the
hole blocking layer to form an electron transport layer. Next, LiF
was deposited with a thickness of 0.2 nm on the electron transport
layer to form an electron injection layer, and then Al was
deposited with a thickness of 150 nm on the electron injection
layer to form a cathode.
[Example 87] to [Example 116]
[0309] The OLEDs were fabricated in the same manner as described in
Example 86 except that the compounds of the present invention
described in the following Table 12, instead of compound G-1 of the
present invention, were used as an emission-auxiliary layer
material.
Comparative Example 12
[0310] The OLED was fabricated in the same manner as described in
Example 86 except that an emission-auxiliary layer was not
formed.
[Comparative Example 13] to [Comparative Example 16]
[0311] The OLEDs were fabricated in the same manner as described in
Example 86 except that the following Comparative compounds ref 1 to
ref 4, respectively, instead of compound P-1 of the present
invention, were used as an emission-auxiliary layer material.
##STR00317##
[0312] Electroluminescence (EL) characteristics were measured with
PR-650 (Photoresearch) by applying a forward bias DC voltage to the
OLEDs prepared in Examples 86 to 116 of the present invention and
Comparative Examples 12 to 16. And, the T95 life time was measured
using a life time measuring apparatus manufactured by Mcscience
Inc. at reference brightness of 5000 cd/m.sup.2. The measurement
results are shown in Tables 12 below.
TABLE-US-00013 TABLE 12 Current Voltage Density Brightness
Efficiency Lifetime CIE Compound (V) (mA/cm.sup.2) (cd/m.sup.2)
(cd/A) T(95) x y comp.Ex(12) -- 5.9 13.6 5000 36.8 116.9 0.33 0.61
comp.Ex(13) ref 1 5.8 12.9 5000 38.9 119.2 0.33 0.61 comp.Ex(14)
ref 2 5.6 11.3 5000 44.2 121.3 0.33 0.61 comp.Ex(15) ref 3 5.5 9.8
5000 50.8 125.4 0.33 0.60 comp.Ex(16) ref 4 5.7 11.4 5000 43.9
121.8 0.33 0.61 Ex.(86) Com. G-1 4.8 7.0 5000 71.9 143.0 0.33 0.63
Ex.(87) Com. G-9 4.9 7.3 5000 68.5 139.7 0.33 0.62 Ex.(88) Com.
G-14 4.8 6.9 5000 72.3 143.4 0.33 0.63 Ex.(89) Com. G-15 5.0 7.4
5000 67.5 137.8 0.33 0.63 Ex.(90) Com. G-27 4.6 6.6 5000 75.3 144.7
0.33 0.62 Ex.(91) Com. G-29 4.5 6.6 5000 76.3 145.5 0.33 0.63
EL(92) Com. G-39 4.9 7.2 5000 69.8 141.9 0.33 0.63 EL(93) Com. G-42
4.6 6.6 5000 75.6 144.5 0.33 0.63 Ex.(94) Com. G-47 5.1 7.5 5000
67.0 137.5 0.33 0.63 Ex.(95) Com. G-50 4.8 7.0 5000 71.1 142.8 0.33
0.63 Ex.(96) Com. G-51 4.9 7.4 5000 67.7 138.3 0.33 0.62 EL(97)
Com. G-52 4.5 6.7 5000 74.9 144.9 0.33 0.62 EL(98) Com. G-55 4.9
7.3 5000 68.4 139.5 0.33 0.62 EL(99) Com. G-58 5.2 7.6 5000 65.8
136.8 0.33 0.63 Ex.(100) Com. G-66 4.5 6.6 5000 76.0 145.1 0.33
0.63 Ex.(101) Com. G-71 5.2 7.7 5000 65.1 135.3 0.33 0.62 Ex.(102)
Com. G-74 4.9 7.3 5000 68.8 141.2 0.33 0.62 Ex.(103) Com. G-82 5.1
7.5 5000 66.4 137.3 0.33 0.63 Ex.(104) Com. G-99 5.2 7.6 5000 66.1
135.6 0.33 0.63 Ex.(105) Com. G-101 4.9 7.2 5000 69.3 141.6 0.33
0.63 Ex.(106) Com. G-115 5.2 7.7 5000 64.9 137.0 0.33 0.62 Ex.(107)
Com. G-176 5.2 7.7 5000 65.3 135.0 0.33 0.63 Ex.(108) Com. G-190
5.0 7.4 5000 68.0 138.6 0.33 0.63 Ex.(109) Com. G-193 5.2 7.7 5000
65.0 136.0 0.33 0.63 Ex.(110) Com. G-198 4.8 7.1 5000 70.7 142.4
0.33 0.63 Ex.(111) Com. G-199 4.8 7.1 5000 70.3 142.1 0.33 0.62
Ex.(112) Com. G-200 4.9 7.3 5000 68.2 139.0 0.33 0.63 Ex.(113) Com.
G-201 4.7 6.7 5000 74.3 144.3 0.33 0.62 Ex.(114) Com. G-202 4.7 6.8
5000 73.8 144.1 0.33 0.62 Ex.(115) Com. G-203 4.7 6.8 5000 73.1
143.8 0.33 0.62 Ex.(116) Com. G-204 4.7 6.9 5000 72.6 143.6 0.33
0.63
[0313] As can be seen from the results of Table 12, when a green
organic electroluminescent device was manufactured by using the
compounds of the present invention as material for an
emission-auxiliary layer, the driving voltage of the organic
electroluminescent device is lowered, and luminous efficiency and
lifetime can be improved, compared to the comparative examples not
forming an emission-auxiliary layer, or using Ref 1 to Ref 4 as
material of an emission-auxiliary layer. That is, in the case of
Comparative Examples 13 to 16 in which the emission-auxiliary layer
was formed using one of the comparative compounds ref 1 to ref 4
rather than Comparative Example 12 in which an emission-auxiliary
layer was not formed, the driving voltage, efficiency, and lifetime
of the device were improved.
[0314] Ref 1, Ref 3 and Ref 4 differ in the substituents connected
to the nitrogen atom of the amine group in the NPB type. A phenyl
derivative (biphenyl) is attached to the nitrogen atom of the amine
group in Ref 1, while diphenyl fluorene is attached to the nitrogen
atom in Ref 3 and Ref 4. Looking at the device characteristics of
Comparative Example 13, 15, and 16 using these compounds as
material of an emission-auxiliary layer, it can be seen that the
device characteristics of Comparative Example 15 and are superior
to those of Comparative Example 13.
[0315] In addition, comparing Ref 2 and Ref 4, Ref 4 contains one
additional amine group and carbazole is bound to the additional
amine group, compared to Ref 2. Looking at the device
characteristics of Comparative Example 14 and 16 using these
compounds as material of an emission-auxiliary layer, it can be
seen that efficiency and lifetime are similar, but the driving
voltage is better in Comparative Example 14.
[0316] From these results, it can be seen that even if compounds
having similar structures are used for devices, the characteristics
of the devices may vary depending on the substitution position of
the substituent and the type of the substituent. This seems to be
due to differences in the properties of the compounds when they
have different types of substituents and the position substituted,
and due to these differences, the physical properties of the
compound act as a major factor in improving device performance
(e.g., energy balance) when depositing the compound in the device
manufacturing process.
[0317] Comparing the compound of the present invention and Ref 3,
it is the same in that the two amine groups are bonded through an
arylene linking group, and diphenylfluorene is bonded to the
nitrogen atom of the amine group, but there is a difference in that
the position where the nitrogen of the amine group is bonded is
reverse phenyl(i.e., refers to the phenyl of the diphenyl position
rather than the fluorene backbone of the 9,9-diphenyl-fluorene
structure) in case of the present invention, while the position is
the backbone benzene in case of Ref 3. Due to this difference, it
can be seen that the driving voltage, lifetime, and efficiency are
significantly improved when the compound of the present invention
is used as material of an emission-auxiliary layer, compared to
Comparative Example 15 using Ref 3.
[0318] It appears that this is because the physical properties of
the compound including LUMO, HOMO, band gap and T.sub.1 value are
changed depending on where the amine group is attached to the
diphenylfluorene and this difference in physical properties serves
as a major factor influencing device characteristics when
depositing a compound for forming an emission-auxiliary layer in a
device manufacturing process.
[0319] In addition, comparing the device results of Examples 86,
90, 91, and 97 of the present invention, it can be seen that the
driving voltage, efficiency, and lifetime of the device when a
specific substituent other than a simple aryl group is substituted
with a substituent of an amine group. That is, the device results
of Examples 90 and 97 showed better values than Example 86, wherein
a compound (G-27 or G-52) substituted with dibenzofuran or fluorene
containing a hetero atom is used in Examples 90 and 97 and Compound
G-1 in which a simple phenyl group was substituted with a
substituent of an amine group was used as material of an
emission-auxiliary layer in Example 86, and the device results of
Examples 91 showed better values than Examples 90 and 97, wherein a
compound G-29 in which fluorene and dibenzofuran are linked to one
nitrogen atom of the amine group is used in Example 91.
[0320] Further, comparing Examples 100 and 106 of the present
invention, it can be seen that the device results of Example 100
are further improved than Example 105, wherein fluorene-substituted
compound G-101 at a nitrogen atom connected to diphenylfluorene is
used as material of an emission-auxiliary layer in Example 105, and
compound G-66 in which fluorene is substituted at a nitrogen atom
of another amine group other than the nitrogen atom connected to
diphenylfluorene is used as material of an emission-auxiliary layer
in Example 100.
[0321] In addition, comparing Examples 86 and 102 of the present
invention, it can be seen that the device results of Example 86 are
further improved than Example 102 when two amine groups of the
compound of the present invention are linked to each other through
a phenyl linker, wherein a compound G-1 in which two amine groups
are linked to the linker phenyl in a meta position is used as
material of an emission-auxiliary layer in Example 86 and compound
G-74 in which two amine groups are para-linked to phenyl is used as
material of an emission-auxiliary layer in Example 102.
[0322] It appears that this is because when the structure of the
compound is changed according to the type of substituent, the
position of substitution and the method of substitution, the
physical properties of the compound are changed, and as a result,
physical properties are changed to improve the properties of the
device when an emission-auxiliary layer is formed.
[0323] Although exemplary embodiments of the present invention have
been described for illustrative purposes, those skilled in the art
will appreciate that various modifications can be made without
departing from the essential characteristics of the present
invention. Therefore, the embodiments disclosed in the present
invention are intended to illustrate the present invention, and the
scope of the present invention is not limited by the embodiments.
The scope of the present invention shall be construed on the basis
of the accompanying claims, and it shall be construed that all of
the technical ideas included within the scope equivalent to the
claims belong to the present invention.
* * * * *