U.S. patent application number 12/432093 was filed with the patent office on 2009-08-20 for method for producing aromatic compound and aromatic compound.
This patent application is currently assigned to Idemitsu Kosan Co., Ltd.. Invention is credited to Tetsuya Inoue, Hidehiro Matsunami, Fumio MORIWAKI.
Application Number | 20090206748 12/432093 |
Document ID | / |
Family ID | 37856197 |
Filed Date | 2009-08-20 |
United States Patent
Application |
20090206748 |
Kind Code |
A1 |
MORIWAKI; Fumio ; et
al. |
August 20, 2009 |
METHOD FOR PRODUCING AROMATIC COMPOUND AND AROMATIC COMPOUND
Abstract
A process for producing an aromatic compound which can
effectively decrease the contents of halogen elements in the
aromatic compound and an aromatic compound which is produced in
accordance with the process and useful as the material for
obtaining an organic electroluminescence device having a long life
are provided. The process for producing an aromatic compound
comprises bringing an aromatic compound which is produced via an
intermediate compound having halogen elements and has contents of
halogen elements of 10 to 1,000 ppm by mass into reaction with a
dehalogenating agent to decrease the contents of halogen elements
to 10 ppm by mass or smaller, and an aromatic compound which is
produced in accordance with the process.
Inventors: |
MORIWAKI; Fumio; (Chiba,
JP) ; Matsunami; Hidehiro; (Chiba, JP) ;
Inoue; Tetsuya; (Chiba, JP) |
Correspondence
Address: |
OBLON, SPIVAK, MCCLELLAND MAIER & NEUSTADT, P.C.
1940 DUKE STREET
ALEXANDRIA
VA
22314
US
|
Assignee: |
Idemitsu Kosan Co., Ltd.
Chiyoda-ku
JP
|
Family ID: |
37856197 |
Appl. No.: |
12/432093 |
Filed: |
April 29, 2009 |
Related U.S. Patent Documents
|
|
|
|
|
|
Application
Number |
Filing Date |
Patent Number |
|
|
11473178 |
Jun 23, 2006 |
7547809 |
|
|
12432093 |
|
|
|
|
Current U.S.
Class: |
313/504 |
Current CPC
Class: |
C09K 2211/1014 20130101;
C07C 209/84 20130101; C07C 7/173 20130101; C09K 2211/1011 20130101;
C09K 11/06 20130101; C07C 7/173 20130101; C07C 15/28 20130101; C07C
209/84 20130101; C07C 211/54 20130101 |
Class at
Publication: |
313/504 |
International
Class: |
H01J 1/63 20060101
H01J001/63 |
Foreign Application Data
Date |
Code |
Application Number |
Sep 14, 2005 |
JP |
2005-267409 |
Claims
1-11. (canceled)
12. An organic electroluminescent device, comprising: an organic
thin film layer; a cathode; and an anode; wherein: the organic thin
film layer is interposed between the cathode and the anode; the
organic thin film layer comprises at least one light emitting
layer; the at least one light emitting layer comprises an aromatic
compound obtained by reacting an aromatic precursor with a
dehalogenating agent to reduce a content of halogen elements in the
aromatic compound to an amount of 10 ppm by mass or less.
13. The organic electroluminescent device according to claim 12,
wherein the aromatic compound is produced via an intermediate
compound having halogen elements.
14. The organic electroluminescent device according to claim 12,
wherein the aromatic compound comprises a condensed aromatic ring
having 14 to 20 ring carbon atoms.
15. The organic electroluminescent device according to claim 12,
wherein the aromatic compound comprises 1 to 12 nitrogen atoms.
16. The organic electroluminescent device according to claim 12,
wherein the halogen element comprises at least one element selected
from the group consisting of bromine and iodine.
17. The organic electroluminescent device according to any one of
claims 12 to 16, wherein the dehalogenating agent comprises at
least one agent selected from the group consisting of Grignard
reagents, organolithium compounds and boronic acid derivatives.
18. The organic electroluminescent device according to claim 17,
wherein the Grignard reagent comprises at least one reagent
selected from the group consisting of phenylmagnesium bromide,
phenylmagnesium iodide, ethylmagnesium bromide and ethylmagnesium
iodide.
19. The organic electroluminescent device according to claim 17,
wherein the organolithium compound comprises at least one compound
selected from the group consisting of n-butyllithium and
phenyllithium.
20. The organic electroluminescent device according to claim 17,
wherein the boronic acid derivative comprises phenylboronic acid.
Description
TECHNICAL FIELD
[0001] The present invention relates to a process for producing an
aromatic compound useful as the organic material for
electroluminescence and an aromatic compound obtained in accordance
with the process. More particularly, the present invention relates
to a process for producing an aromatic compound having decreased
contents of halogen elements and an aromatic compound obtained in
accordance with the process.
BACKGROUND ART
[0002] An organic electroluminescence device (hereinafter, referred
to as an organic EL device occasionally) is a light emitting device
having at least an organic light emitting layer disposed between a
pair of electrodes. The energy generated by recombination of holes
injected from the anode and electrons injected from the cathode in
the light emitting layer is taken out in the form of light
emission.
[0003] The organic EL device is a device spontaneously emitting
light. The organic EL device has various advantageous properties
such as the great current efficiency of light emission, the light
weight and the decreased thickness, and many developments have been
made recently. As the drawback of the organic EL device, the
luminance of the emitted light decreases as the device is driven,
and various improvements are attempted to suppress the decrease in
the luminance.
[0004] For example, it is disclosed that the decrease in the
luminance exhibited by an organic EL device can be suppressed by
controlling the concentration of halogen impurities in the organic
material used for the organic EL device to a value smaller than
1,000 ppm by mass (for example, refer to Patent Reference 1).
[0005] As the process for controlling the concentration of halogen
impurities in the aromatic compound used for the organic EL device
to a desired value, suitable combinations of purification
technologies such as purification by sublimation and purification
by recrystallization are disclosed in the above patent reference.
Recently, a technology for controlling the content of halogen
impurities more effectively is required, and it is necessary that a
production technology enabling a further decrease in the content of
halogen elements in the material for organic EL devices be
developed.
[0006] In general, the material for organic EL devices is produced
in accordance with a process using a halogenated aromatic compound
as the intermediate compound such as the Ullman reaction, the
Grignard reaction and the Suzuki coupling reaction. It is known
that impurities in the used material greatly affect the properties
of organic EL devices such as the decrease in the luminance and the
initial current efficiency. In general, the increase in the purity
is achieved in accordance with a purification process utilizing the
difference in the physical properties of the material such as the
purification by sublimation, the purification using columns and the
purification by recrystallization.
[0007] When the attention is focused on the increase in the purity
of the material for organic EL devices, it is important that the
contents of halogen compounds which are impurities in the material
for organic EL devices be decreased and, in particular, the
contents of bromine compounds and iodine compounds having great
reactivities be decreased. However, the contents of bromine
compounds and iodine compounds cannot be decreased sufficiently in
accordance with conventional processes.
[0008] [Patent Reference 1] Japanese Patent No. 3290432
DISCLOSURE OF THE INVENTION
Problems to be Overcome by the Invention
[0009] The present invention has been made under the above
circumstances and has an object of providing a process for
producing an aromatic compound which can effectively decrease the
contents of halogen elements contained in the aromatic compound,
and an aromatic compound which is produced in accordance with the
process and is useful as the material for obtaining an organic EL
device having a long lifetime.
Means for Overcoming the Problems
[0010] As the result of intensive studies by the present inventors
to overcome the above problem, it was found that an aromatic
compound having contents of halogen elements of a specific value or
smaller could be obtained by a dehalogenating treatment of a crude
product of an aromatic compound having a content of halogen
elements in a specific range using a chemical reaction. The present
invention has been completed based on the knowledge.
[0011] The present invention provides a process for producing an
aromatic compound and an aromatic compound obtained in accordance
with the process, which are shown in the following:
(1) A process for producing an aromatic compound which comprises
bringing an aromatic compound which is produced via an intermediate
compound having halogen elements and has contents of halogen
elements of 10 to 1,000 ppm by mass into reaction with a
dehalogenating agent to decrease the contents of halogen elements
to 10 ppm by mass or smaller; (2) A process for producing an
aromatic compound described in (1), wherein the aromatic compound
is an organic material for electroluminescence; (3) A process for
producing an aromatic compound described in (1) or (2), wherein the
dehalogenating agent is at least one agent selected from Grignard
reagents, organolithium compounds and boronic acid derivatives; (4)
A process for producing an aromatic compound described in (1) to
(3), wherein the aromatic compound is a compound having a condensed
aromatic ring having 14 to 20 ring carbon atoms in a molecule; (5)
A process for producing an aromatic compound described in (1) to
(4), wherein the aromatic compound is a compound having 1 to 12
nitrogen atoms in a molecule; (6) A process for producing an
aromatic compound described in (1) to (5), wherein the halogen
element is at least one element selected from bromine and iodine;
(7) A process for producing an aromatic compound described in any
one of (3) to (6), wherein the Grignard reagent is at least one
reagent selected from phenylmagnesium bromide, phenylmagnesium
iodide, ethylmagnesium bromide and ethylmagnesium iodide; (8) A
process for producing an aromatic compound described in any one of
(3) to (6), wherein the organolithium compound is at least one
compound selected from n-butyllithium and phenyllithium; (9) A
process for producing an aromatic compound described in any one of
(3) to (6), wherein the boronic acid derivative is phenylboronic
acid; (10) An aromatic compound produced in accordance with the
process described in (1) to (9); and (11) An aromatic compound
described in (10), which is an organic material for
electroluminescence.
EFFECTS OF THE INVENTION
[0012] In accordance with the present invention, an aromatic
compound having contents of halogen elements of 10 ppm by mass or
smaller can be obtained. By using the aromatic compound as the
material for an organic EL device, the life of the organic EL
device can be increased.
THE MOST PREFERRED EMBODIMENT TO CARRY OUT THE INVENTION
[0013] The process for producing an aromatic compound comprises
bringing an aromatic compound which is produced via an intermediate
compound having halogen elements and has contents of halogen
elements of 10 to 1,000 ppm by mass into further reaction with a
dehalogenating agent to decrease the contents of halogen elements
to 10 ppm by mass or smaller. The above reaction is the treatment
of making aromatic halogen compounds as the impurities in the
aromatic compound obtained by the synthesis harmless by converting
the aromatic halogen compounds into other compounds.
[0014] As the process for converting aromatic halogen compounds
into other compounds, conventional reactions using a dehalogenating
agent can be used. Grignard reactions, reactions using
organolithium compounds and reactions using boronic acid
derivatives (Suzuki coupling reactions) are preferable due to the
great yield of the reaction.
[0015] The Grignard reaction is a coupling reaction between an
aromatic halogen compound and a Grignard reagent. As the Grignard
reagent, a commercial reagent or an arylmagnesium bromide, an
arylmagnesium iodide, an alkylmagnesium bromide or an
alkylmagnesium iodide which is suitably prepared can be used. Among
the above reagents, phenyl-magnesium bromide, phenylmagnesium
iodide, ethylmagnesium bromide and ethylmagnesium iodide are
preferable. Phenylmagnesium bromide and phenylmagnesium iodide are
more preferable. The Grignard reagent may be used singly or in
combination of two or more.
[0016] As the solvent for the reaction, a conventional solvent can
be used. Specifically, ether-based solvents such as dimethoxyethane
and tetrahydrofuran are preferable. A mixed solvent of these
solvents may be used. It is desirable that the solvent for the
reaction is treated for dehydration in advance.
[0017] The temperature of the reaction is selected, in general, in
the range of -30 to 100.degree. C. and preferably in the range of
-10 to 80.degree. C. The time of the reaction is selected, in
general, in the range of 1 to 48 hours and preferably in the range
of 2 to 8 hours. It is preferable that the reaction in conducted
under a stream of argon.
[0018] The reaction using an organolithium (Li) compound is,
specifically, a coupling reaction between an aromatic halogen
compound and an organolithium reagent. As the organolithium
compound, various commercial reagents can be used. Aryllithiums and
alkyllithiums are preferable. n-Butyllithium and phenyllithium are
more preferable. The organolithium compound may be used singly or
in combination of two or more.
[0019] As the solvent for the reaction, a conventional solvent can
be used. Cyclic hydrocarbon-based solvents such as cyclohexane and
decaline and ether-based solvents such as dimethoxyethane and
tetrahydrofuran are preferable. A mixed solvent of these solvents
may be used.
[0020] The temperature of the reaction is selected, in general, in
the range of -100 to 50.degree. C. and preferably in the range of
-80 to 10.degree. C. The time of the reaction is selected, in
general, in the range of 1 to 48 hours and preferably in the range
of 1 to 8 hours. It is preferable that the reaction is conducted
under a stream of nitrogen or argon.
[0021] The reaction using a boronic acid derivative is also called
the Suzuki coupling reaction and is a coupling reaction between an
aromatic halogen compound and a boronic acid derivative. As the
boronic acid derivative, various commercial boronic acid
derivatives can be used. Phenylboronic acid and derivatives thereof
are preferable. The boronic acid derivative may be used singly or
in combination of two or more.
[0022] The Suzuki coupling reaction is preferable since the
reactivity with halogens is great and, moreover, in the
dehalogenation treatment of a material having a substituent such as
nitro group and methoxy group, no reactions take place with the
substituent.
[0023] As the solvent for the reaction, a conventional solvent can
be used. Examples of the solvent include aromatic hydrocarbon-based
solvents such as toluene and xylene, cyclic hydrocarbon-based
solvents such as cyclohexane and decaline and ether-based solvents
such as dimethoxyethane and tetrahydrofuran. Among these solvents,
aromatic hydrocarbon-based solvents such as toluene and xylene and
ether-based solvents such as dimethoxyethane and tetrahydrofuran
are preferable. A mixed solvent of these solvents may be used.
[0024] It is preferable that the reaction is conducted in the
condition of suspension while a solvent comprising the above
solvent and water and forming two layers is stirred. In general, a
base is used in this reaction. Examples of the base include
carbonates, phosphates and hydroxides of alkali metals and alkaline
earth metals. Potassium carbonate, cesium carbonate and potassium
phosphate are preferable.
[0025] In this reaction, in general, a complex compound of a
transition metal such as Pd and Ni can be used as the catalyst.
Specifically, Pd(PPh.sub.3).sub.4 and palladium acetate are
preferable. A complex compound of a transition metal such as Pd and
Ni may be used in combination with a phosphorus-based ligand. As
the ligand, tris(o-tolyl)phosphine and tri(t-butyl)phosphine are
preferable.
[0026] The temperature of the reaction is selected, in general, in
the range of 50 to 200.degree. C. and preferably in the range of 70
to 150.degree. C. The time of the reaction is selected, in general,
in the range of 4 to 48 hours and preferably in the range of 8 to
16 hours. It is preferable that the reaction is conducted under the
stream of nitrogen or argon.
[0027] In the production of the aromatic compound, the contents of
halogen elements in the aromatic compound can be remarkably
decreased by the treatment using the chemical reaction described
above when the aromatic compound is treated in the stage of a crude
product containing at most 1,000 ppm by mass of halogen
elements.
[0028] When the above crude product is purified in accordance with
a conventional process to decrease the contents of halogen elements
in the aromatic compound to 100 ppm by mass or smaller, the
concentrations of halogen impurities can be further decreased by
the above treatment using the chemical reaction described
above.
[0029] The contents of halogen elements in the aromatic compound
can be decreased to 10 ppm by mass or smaller by the above
dehalogenation treatment. It is preferable that the contents are
decreased to 1 ppm by mass or smaller.
[0030] The process of the present invention can be effectively
applied to production of any aromatic compounds. In particular, the
process is advantageously applied to the production of the material
for organic EL devices using a crude product of an aromatic
compound having a condensed aromatic ring having 14 to 20 ring
carbon atoms in the molecule. Examples of the aromatic compound
having a condensed aromatic ring having 14 to 20 ring carbon atoms
in the molecule include anthracene, phenanthrene, pyrene, chrysene,
benzanthracene, perylene, fluoranthene and tetracene.
[0031] As the aromatic compound having a condensed aromatic ring in
the molecule, for example, compounds shown in 1 to 7 in the
following are preferable.
1. Anthracene Derivatives Represented by the Following General
Formula (1):
##STR00001##
[0033] In general formula (1), Ar represents a substituted or
unsubstituted condensed aromatic group having 10 to 50 ring carbon
atoms. Examples of the condensed aromatic group include 1-naphthyl
group, 2-naphthyl group, 1-anthryl group, 2-anthryl group,
9-anthryl group, 1-phenanthryl group, 2-phenanthryl group,
3-phenanthryl group, 4-phenanthryl group, 9-phenanthryl group,
1-naphthacenyl group, 2-naphthacenyl group, 9-naphthacenyl group,
1-pyrenyl group, 2-pyrenyl group, 4-pyrenyl group,
3-methyl-2-naphthyl group and 4-methyl-1-anthryl group. As the
condensed aromatic group represented by Ar, a group selected from
groups represented by the following formulae is preferable.
##STR00002##
In the above formulae, Ar.sub.1 represents a substituted or
unsubstituted aromatic group having 6 to 50 ring carbon atoms.
[0034] Examples of the group represented by Ar.sub.1 include phenyl
group, 1-naphthyl group, 2-naphthyl group, 1-anthryl group,
2-anthryl group, 9-anthryl group, 9-(10-phenyl)anthryl group,
9-(10-naphthyl-1-yl)anthryl group, 9-(10-naphthyl-2-yl)anthryl
group, 1-phenanthryl group, 2-phenanthryl group, 3-phenanthryl
group, 4-phenanthryl group, 9-phenanthryl group, 1-naphthacenyl
group, 2-naphthacenyl group, 9-naphthacenyl group, 1-pyrenyl group,
2-pyrenyl group, 4-pyrenyl group, 2-biphenylyl group, 3-biphenylyl
group, 4-biphenylyl group, p-terphenyl-4-yl group, p-terphenyl-3-yl
group, p-terphenyl-2-yl group, m-terphenyl-4-yl group,
m-terphenyl-3-yl group, m-terphenyl-2-yl group, o-tolyl group,
m-tolyl group, p-tolyl group, p-t-butylphenyl group,
3-methyl-2-naphthyl group, 4-methyl-1-naphthyl group and
4-methyl-1-anthryl group.
[0035] Among these groups, phenyl group, 1-naphthyl group,
2-naphthyl group, 9-(10-phenyl)anthryl group,
9-(10-naphthyl-1-yl)anthryl group, 9-(10-naphthyl-2-yl)anthryl
group, 9-phenanthryl group, 1-pyrenyl group, 2-pyrenyl group,
4-pyrenyl group, 2-biphenylyl group, 3-biphenylyl group,
4-biphenylyl group, o-tolyl group, m-tolyl group, p-tolyl group and
p-t-butylphenyl group are preferable.
[0036] The above aromatic groups may be substituted with
substituents. Examples of the substituent include alkyl groups
(such as methyl group, ethyl group, propyl group, isopropyl group,
n-butyl group, s-butyl group, isobutyl group, t-butyl group,
n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group,
hydroxymethyl group, 1-hydroxyethyl group, 2-hydroxyethyl group,
2-hydroxyisobutyl group, 1,2-dihydroxyethyl group,
1,3-dihydroxyisopropyl group, 2,3-dihydroxy-t-butyl group,
1,2,3-trihydroxypropyl group, chloromethyl group, 1-chloroethyl
group, 2-chloroethyl group, 2-chloroisobutyl group,
1,2-dichloroethyl group, 1,3-dichloroisopropyl group,
2,3-dichloro-t-butyl group, 1,2,3-trichloropropyl group,
bromomethyl group, 1-bromoethyl group, 2-bromoethyl group,
2-bromoisobutyl group, 1,2-dibromoethyl group, 1,3-dibromoisopropyl
group, 2,3-dibromo-t-butyl group, 1,2,3-tribromopropyl group,
iodomethyl group, 1-iodoethyl group, 2-iodoethyl group,
2-iodoisobutyl group, 1,2-diiodoethyl group, 1,3-diiodoisopropyl
group, 2,3-diiodo-t-butyl group, 1,2,3-triiodopropyl group,
aminomethyl group, 1-aminoethyl group, 2-aminoethyl group,
2-aminoisobutyl group, 1,2-diaminoethyl group, 1,3-diaminoisopropyl
group, 2,3-diamino-t-butyl group, 1,2,3-triaminopropyl group,
cyanomethyl group, 1-cyanoethyl group, 2-cyanoethyl group,
2-cyanoisobutyl group, 1,2-dicyanoethyl group, 1,3-dicyanoisopropyl
group, 2,3-dicyano-t-butyl group, 1,2,3-tricyanopropyl group,
nitromethyl group, 1-nitroethyl group, 2-nitroethyl group,
2-nitroisobutyl group, 1,2-dinitroethyl group, 1,3-dinitroisopropyl
group, 2,3-dinitro-t-butyl group, 1,2,3-trinitropropyl group,
cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl
group, 4-methylcyclohexyl group, 1-adamantyl group, 2-adamantyl
group, 1-norbornyl group and 2-norbornyl group), alkoxyl groups
having 1 to 6 carbon atoms (such as ethoxyl group, methoxyl group,
i-propoxyl group, n-propoxyl group, s-butoxyl group, t-butoxyl
group, pentoxyl group, hexyloxyl group, cyclopentoxyl group and
cyclohexyloxyl group), aryl groups having 5 to 40 ring atoms, amino
groups substituted with aryl groups having 5 to 40 ring atoms,
ester groups having aryl groups having 5 to 40 ring atoms, ester
groups having alkyl groups having 1 to 6 carbon atoms, cyano group,
nitro group and halogen atoms.
[0037] Ar' represents a substituted or unsubstituted aromatic group
having 6 to 50 ring carbon atoms. Examples of the aromatic group
include the groups shown above as the examples of the group
represented by Ar.sub.1. As the aromatic group, the groups shown as
the preferable groups among the groups represented by Ar.sub.1 are
preferable.
[0038] In general formula (1), X represents a substituted or
unsubstituted aromatic group having 6 to 50 ring carbon atoms, a
substituted or unsubstituted aromatic heterocyclic group having 5
to 50 ring carbon atoms, a substituted or unsubstituted alkyl
groups having 1 to 50 carbon atoms, a substituted or unsubstituted
cycloalkyl groups, a substituted or unsubstituted alkoxyl group
having 1 to 50 carbon atoms, a substituted or unsubstituted aralkyl
group having 6 to 50 carbon atoms, a substituted or unsubstituted
aryloxyl group having 5 to 50 ring carbon atoms, a substituted or
unsubstituted arylthio group having 5 to 50 ring carbon atoms, a
substituted or unsubstituted alkoxycarbonyl group having 1 to 50
carbon atoms, carboxyl group, halogen atoms, cyano group, nitro
group or hydroxyl group.
[0039] Examples of the substituted or unsubstituted aromatic group
having 6 to 50 ring carbon atoms represented by X include the
groups shown above as the examples of the aromatic group
represented by Ar.sub.1.
[0040] Examples of the substituted or unsubstituted aromatic
heterocyclic group having 5 to 50 ring carbon atoms include
1-pyrrolyl group, 2-pyrrolyl group, 3-pyrrolyl group, pyrazinyl
group, 2-pyridinyl group, 3-pyridinyl group, 4-pyridinyl group,
1-indolyl group, 2-indolyl group, 3-indolyl group, 4-indolyl group,
5-indolyl group, 6-indolyl group, 7-indolyl group, 1-isoindolyl
group, 2-isoindolyl group, 3-isoindolyl group, 4-isoindolyl group,
5-isoindolyl group, 6-isoindolyl group, 7-isoindolyl group, 2-furyl
group, 3-furyl group, 2-benzofuranyl group, 3-benzofuranyl group,
4-benzofuranyl group, 5-benzofuranyl group, 6-benzofuranyl group,
7-benzofuranyl group, 1-isobenzofuranyl group, 3-isobenzofuranyl
group, 4-isobenzofuranyl group, 5-isobenzofuranyl group,
6-isobenzofuranyl group, 7-isobenzofuranyl group, quinolyl group,
3-quinolyl group, 4-quinolyl group, 5-quinolyl group, 6-quinolyl
group, 7-quinolyl group, 8-quinolyl group, 1-isoquinolyl group,
3-isoquinolyl group, 4-isoquinolyl group, 5-isoquinolyl group,
6-isoquinolyl group, 7-isoquinolyl group, 8-isoquinolyl group,
2-quinoxanyl group, 5-quinoxanyl group, 6-quinoxanyl group,
1-carbazolyl group, 2-carbazolyl group, 3-carbazolyl group,
4-carbazolyl group, 9-carbazolyl group, 1-phenanthridinyl group,
2-phenanthridinyl group, 3-phenanthridinyl group, 4-phenanthridinyl
group, 6-phenanthridinyl group, 7-phenanthridinyl group,
8-phenanthridinyl group, 9-phenanthridinyl group,
10-phenanthridinyl group, 1-acridinyl group, 2-acridinyl group,
3-acridinyl group, 4-acridinyl group, 9-acridinyl group,
1,7-phenanthrolin-2-yl group, 1,7-phenanthrolin-3-yl group,
1,7-phenanthrolin-4-yl group, 1,7-phenanthrolin-5-yl group,
1,7-phenanthrolin-6-yl group, 1,7-phenanthrolin-8-yl group,
1,7-phenanthrolin-9-yl group, 1,7-phenanthrolin-10-yl group,
1,8-phenanthrolin-2-yl group, 1,8-phenanthrolin-3-yl group,
1,8-phenanthrolin-4-yl group, 1,8-phenanthrolin-5-yl group,
1,8-phenanthrolin-6-yl group, 1,8-phenanthrolin-7-yl group,
1,8-phenanthrolin-9-yl group, 1,8-phenanthrolin-10-yl group,
1,9-phenanthrolin-2-yl group, 1,9-phenanthrolin-3-yl group,
1,9-phenanthrolin-4-yl group, 1,9-phenanthrolin-5-yl group,
1,9-phenanthrolin-6-yl group, 1,9-phenanthrolin-7-yl group,
1,9-phenanthrolin-8-yl group, 1,9-phenanthrolin-10-yl group,
1,10-phenanthrolin-2-yl group, 1,10-phenanthrolin-3-yl group,
1,10-phenanthrolin-4-yl group, 1,10-phenanthrolin-5-yl group,
2,9-phenanthrolin-1-yl group, 2,9-phenanthrolin-3-yl group,
2,9-phenanthrolin-4-yl group, 2,9-phenanthrolin-5-yl group,
2,9-phenanthrolin-6-yl group, 2,9-phenanthrolin-7-yl group,
2,9-phenanthrolin-8-yl group, 2,9-phenanthrolin-10-yl group,
2,8-phenanthrolin-1-yl group, 2,8-phenanthrolin-3-yl group,
2,8-phenanthrolin-4-yl group, 2,8-phenanthrolin-5-yl group,
2,8-phenanthrolin-6-yl group, 2,8-phenanthrolin-7-yl group,
2,8-phenanthrolin-9-yl group, 2,8-phenanthrolin-10-yl group,
2,7-phenanthrolin-1-yl group, 2,7-phenanthrolin-3-yl group,
2,7-phenanthrolin-4-yl group, 2,7-phenanthrolin-5-yl group,
2,7-phenanthrolin-6-yl group, 2,7-phenanthrolin-8-yl group,
2,7-phenanthrolin-9-yl group, 2,7-phenanthrolin-10-yl group,
1-phenazinyl group, 2-phenazinyl group, 1-phenothiazinyl group,
2-phenothiazinyl group, 3-phenothiazinyl group, 4-phenothiazinyl
group, 10-phenothiazinyl group, 1-phenoxazinyl group,
2-phenoxazinyl group, 3-phenoxazinyl group, 4-phenoxazinyl group,
10-phenoxazinyl group, 2-oxazolyl group, 4-oxazolyl group,
5-oxazolyl group, 2-oxadiazolyl group, 5-oxadiazolyl group,
3-furazanyl group, 2-thienyl group, 3-thienyl group,
2-methylpyrrol-1-yl group, 2-methylpyrrol-3-yl group,
2-methylpyrrol-4-yl group, 2-methyl-pyrrol-5-yl group,
3-methylpyrrol-1-yl group, 3-methyl-pyrrol-2-yl group,
3-methylpyrrol-4-yl group, 3-methylpyrrol-5-yl group,
2-t-butylpyrrol-4-yl group, 3-(2-phenylpropyl)pyrrol-1-yl group,
2-methyl-1-indolyl group, 4-methyl-1-indolyl group,
2-methyl-3-indolyl group, 4-methyl-3-indolyl group,
2-t-butyl-1-indolyl group, 4-t-butyl-1-indolyl group,
2-t-butyl-3-indolyl group and 4-t-butyl-3-indolyl group.
[0041] Examples of the substituted or unsubstituted alkyl group
represented by X include methyl group, ethyl group, propyl group,
isopropyl group, n-butyl group, s-butyl group, isobutyl group,
t-butyl group, n-pentyl group, n-hexyl group, n-heptyl group,
n-octyl group, hydroxymethyl group, 1-hydroxyethyl group,
2-hydroxyethyl group, 2-hydroxyisobutyl group, 1,2-dihydroxyethyl
group, 1,3-dihydroxyisopropyl group, 2,3-dihydroxy-t-butyl group,
1,2,3-trihydroxypropyl group, chloromethyl group, 1-chloroethyl
group, 2-chloroethyl group, 2-chloroisobutyl group,
1,2-dichloroethyl group, 1,3-dichloroisopropyl group,
2,3-dichloro-t-butyl group, 1,2,3-trichloro-propyl group,
bromomethyl group, 1-bromoethyl group, 2-bromoethyl group,
2-bromoisobutyl group, 1,2-dibromoethyl group,
1,3-dibromo-isopropyl group, 2,3-dibromo-t-butyl group,
1,2,3-tribromopropyl group, iodomethyl group, 1-iodoethyl group,
2-iodoethyl group, 2-iodoisobutyl group, 1,2-diiodoethyl group,
1,3-diiodoisopropyl group, 2,3-diiodo-t-butyl group,
1,2,3-triiodopropyl group, aminomethyl group, 1-aminoethyl group,
2-aminoethyl group, 2-aminoisobutyl group, 1,2-diaminoethyl group,
1,3-diaminoisopropyl group, 2,3-diamino-t-butyl group,
1,2,3-triamino-propyl group, cyanomethyl group, 1-cyanoethyl group,
2-cyanoethyl group, 2-cyanoisobutyl group, 1,2-dicyanoethyl group,
1,3-dicyanoisopropyl group, 2,3-dicyano-t-butyl group,
1,2,3-tricyanopropyl group, nitromethyl group, 1-nitroethyl group,
2-nitroethyl group, 2-nitroisobutyl group, 1,2-dinitroethyl group,
1,3-dinitroisopropyl group, 2,3-dinitro-t-butyl group,
1,2,3-trinitropropyl group.
[0042] Examples of the substituted or unsubstituted cycloalkyl
group include cyclopropyl group, cyclobutyl group, cyclopentyl
group, cyclohexyl group, 4-methylcyclohexyl group, 1-adamantyl
group, 2-adamantyl group, 1-norbornyl group and 2-norbornyl
group.
[0043] The substituted or unsubstituted alkoxyl group is a group
represented by --OY. Examples of the group represented by Y include
methyl group, ethyl group, propyl group, isopropyl group, n-butyl
group, s-butyl group, isobutyl group, t-butyl group, n-pentyl
group, n-hexyl group, n-heptyl group, n-octyl group, hydroxymethyl
group, 1-hydroxyethyl group, 2-hydroxyethyl group,
2-hydroxyisobutyl group, 1,2-dihydroxyethyl group,
1,3-dihydroxyisopropyl group, 2,3-dihydroxy-t-butyl group,
1,2,3-trihydroxypropyl group, chloromethyl group, 1-chloroethyl
group, 2-chloroethyl group, 2-chloroisobutyl group,
1,2-dichloroethyl group, 1,3-dichloroisopropyl group,
2,3-dichloro-t-butyl group, 1,2,3-trichloro-propyl group,
bromomethyl group, 1-bromoethyl group, 2-bromoethyl group,
2-bromoisobutyl group, 1,2-dibromoethyl group,
1,3-dibromo-isopropyl group, 2,3-dibromo-t-butyl group,
1,2,3-tribromopropyl group, iodomethyl group, 1-iodoethyl group,
2-iodoethyl group, 2-iodoisobutyl group, 1,2-diiodoethyl group,
1,3-diiodoisopropyl group, 2,3-diiodo-t-butyl group,
1,2,3-triiodopropyl group, aminomethyl group, 1-aminoethyl group,
2-aminoethyl group, 2-aminoisobutyl group, 1,2-diaminoethyl group,
1,3-diaminoisopropyl group, 2,3-diamino-t-butyl group,
1,2,3-triamino-propyl group, cyanomethyl group, 1-cyanoethyl group,
2-cyanoethyl group, 2-cyanoisobutyl group, 1,2-dicyanoethyl group,
1,3-dicyanoisopropyl group, 2,3-dicyano-t-butyl group,
1,2,3-tricyanopropyl group, nitromethyl group, 1-nitroethyl group,
2-nitroethyl group, 2-nitroisobutyl group, 1,2-dinitroethyl group,
1,3-dinitroisopropyl group, 2,3-dinitro-t-butyl group,
1,2,3-trinitropropyl group.
[0044] Examples of the substituted or unsubstituted aralkyl group
include benzyl group, 1-phenylethyl group, 2-phenylethyl group,
1-phenyl-isopropyl group, 2-phenylisopropyl group, phenyl-t-butyl
group, .alpha.-naphthylmethyl group, 1-.alpha.-naphthylethyl group,
2-.alpha.-naphthylethyl group, 1-.alpha.-naphthylisopropyl group,
2-.alpha.-naphthylisopropyl group, .beta.-naphthylmethyl group,
1-.beta.-naphthylethyl group, 2-.beta.-naphthylethyl group,
1-.beta.-naphthylisopropyl group, 2-.beta.-naphthylisopropyl group,
1-pyrrolylmethyl group, 2-(1-pyrrolyl)ethyl group, p-methylbenzyl
group, m-methylbenzyl group, o-methylbenzyl group, p-chlorobenzyl
group, m-chlorobenzyl group, o-chlorobenzyl group, p-bromobenzyl
group, m-bromobenzyl group, o-bromobenzyl group, p-iodobenzyl
group, m-iodobenzyl group, o-iodobenzyl group, p-hydroxybenzyl
group, m-hydroxybenzyl group, o-hydroxybenzyl group, p-aminobenzyl
group, m-aminobenzyl group, o-aminobenzyl group, p-nitrobenzyl
group, m-nitrobenzyl group, o-nitrobenzyl group, p-cyanobenzyl
group, m-cyanobenzyl group, o-cyanobenzyl group,
1-hydroxy-2-phenylisopropyl group and 1-chloro-2-phenylisopropyl
group.
[0045] The substituted or unsubstituted aryloxyl group is
represented by --OY'. Examples of the group represented by Y'
include phenyl group, 1-naphthyl group, 2-naphthyl group, 1-anthryl
group, 2-anthryl group, 9-anthryl group, 1-phenanthryl group,
2-phenanthryl group, 3-phenanthryl group, 4-phenanthryl group,
9-phenanthryl group, 1-naphthacenyl group, 2-naphthacenyl group,
9-naphthacenyl group, 1-pyrenyl group, 2-pyrenyl group, 4-pyrenyl
group, 2-biphenylyl group, 3-biphenylyl group, 4-biphenylyl group,
p-terphenyl-4-yl group, p-terphenyl-3-yl group, p-terphenyl-2-yl
group, m-terphenyl-4-yl group, m-terphenyl-3-yl group,
m-terphenyl-2-yl group, o-tolyl group, m-tolyl group, p-tolyl
group, p-t-butylphenyl group, p-(2-phenylpropyl)phenyl group,
3-methyl-2-naphthyl group, 4-methyl-1-naphthyl group,
4-methyl-1-anthryl group, 4'-methylbiphenylyl group,
4''-t-butyl-p-terphenyl-4-yl group, 2-pyrrolyl group, 3-pyrrolyl
group, pyrazinyl group, 2-pyridinyl group, 3-pyridinyl group,
4-pyridinyl group, 2-indolyl group, 3-indolyl group, 4-indolyl
group, 5-indolyl group, 6-indolyl group, 7-indolyl group,
1-isoindolyl group, 3-isoindolyl group, 4-isoindolyl group,
5-isoindolyl group, 6-isoindolyl group, 7-isoindolyl group, 2-furyl
group, 3-furyl group, 2-benzofuranyl group, 3-benzofuranyl group,
4-benzofuranyl group, 5-benzofuranyl group, 6-benzofuranyl group,
7-benzofuranyl group, 1-isobenzofuranyl group, 3-isobenzofuranyl
group, 4-isobenzofuranyl group, 5-isobenzofuranyl group,
6-isobenzofuranyl group, 7-isobenzofuranyl group, 2-quinolyl group,
3-quinolyl group, 4-quinolyl group, 5-quinolyl group, 6-quinolyl
group, 7-quinolyl group, 8-quinolyl group,
1-isoquinolyl group, 3-isoquinolyl group, 4-isoquinolyl group,
5-isoquinolyl group, 6-isoquinolyl group, 7-isoquinolyl group,
8-isoquinolyl group, 2-quinoxanyl group, 5-quinoxanyl group,
6-quinoxanyl group, 1-carbazolyl group, 2-carbazolyl group,
3-carbazolyl group, 4-carbazolyl group, 1-phenanthridinyl group,
2-phenanthridinyl group, 3-phenanthridinyl group, 4-phenanthridinyl
group, 6-phenanthridinyl group, 7-phenanthridinyl group,
8-phenanthridinyl group, 9-phenanthridinyl group,
10-phenanthridinyl group, 1-acridinyl group, 2-acridinyl group,
3-acridinyl group, 4-acridinyl group, 9-acridinyl group,
1,7-phenanthrolin-2-yl group, 1,7-phenanthrolin-3-yl group,
1,7-phenanthrolin-4-yl group, 1,7-phenanthrolin-5-yl group,
1,7-phenanthrolin-6-yl group, 1,7-phenanthrolin-8-yl group,
1,7-phenanthrolin-9-yl group, 1,7-phenanthrolin-10-yl group,
1,8-phenanthrolin-2-yl group, 1,8-phenanthrolin-3-yl group,
1,8-phenanthrolin-4-yl group, 1,8-phenanthrolin-5-yl group,
1,8-phenanthrolin-6-yl group, 1,8-phenanthrolin-7-yl group,
1,8-phenanthrolin-9-yl group, 1,8-phenanthrolin-10-yl group,
1,9-phenanthrolin-2-yl group, 1,9-phenanthrolin-3-yl group,
1,9-phenanthrolin-4-yl group, 1,9-phenanthrolin-5-yl group,
1,9-phenanthrolin-6-yl group, 1,9-phenanthrolin-7-yl group,
1,9-phenanthrolin-8-yl group, 1,9-phenanthrolin-10-yl group,
1,10-phenanthrolin-2-yl group, 1,10-phenanthrolin-3-yl group,
1,10-phenanthrolin-4-yl group, 1,10-phenanthrolin-5-yl group,
2,9-phenanthrolin-1-yl group, 2,9-phenanthrolin-3-yl group,
2,9-phenanthrolin-4-yl group, 2,9-phenanthrolin-5-yl group,
2,9-phenanthrolin-6-yl group, 2,9-phenanthrolin-7-yl group,
2,9-phenanthrolin-8-yl group, 2,9-phenanthrolin-10-yl group,
2,8-phenanthrolin-1-yl group, 2,8-phenanthrolin-3-yl group,
2,8-phenanthrolin-4-yl group, 2,8-phenanthrolin-5-yl group,
2,8-phenanthrolin-6-yl group, 2,8-phenanthrolin-7-yl group,
2,8-phenanthrolin-9-yl group, 2,8-phenanthrolin-10-yl group,
2,7-phenanthrolin-1-yl group, 2,7-phenanthrolin-3-yl group,
2,7-phenanthrolin-4-yl group, 2,7-phenanthrolin-5-yl group,
2,7-phenanthrolin-6-yl group, 2,7-phenanthrolin-8-yl group,
2,7-phenanthrolin-9-yl group, 2,7-phenanthrolin-10-yl group,
1-phenazinyl group, 2-phenazinyl group, 1-phenothiazinyl group,
2-phenothiazinyl group, 3-phenothiazinyl group, 4-phenothiazinyl
group, 1-phenoxazinyl group, 2-phenoxazinyl group, 3-phenoxazinyl
group, 4-phenoxazinyl group, 2-oxazolyl group, 4-oxazolyl group,
5-oxazolyl group, 2-oxadiazolyl group, 5-oxadiazolyl group,
3-furazanyl group, 2-thienyl group, 3-thienyl group,
2-methylpyrrol-1-yl group, 2-methylpyrrol-3-yl group,
2-methylpyrrol-4-yl group, 2-methyl-pyrrol-5-yl group,
3-methylpyrrol-1-yl group, 3-methyl-pyrrol-2-yl group,
3-methylpyrrol-4-yl group, 3-methylpyrrol-5-yl group,
2-t-butylpyrrol-4-yl group, 3-(2-phenylpropyl)pyrrol-1-yl group,
2-methyl-1-indolyl group, 4-methyl-1-indolyl group,
2-methyl-3-indolyl group, 4-methyl-3-indolyl group,
2-t-butyl-1-indolyl group, 4-t-butyl-1-indolyl group,
2-t-butyl-3-indolyl group and 4-t-butyl-3-indolyl group.
[0046] The substituted or unsubstituted arylthio group is a group
represented by --SY''. Examples of the group represented by Y''
include phenyl group, 1-naphthyl group, 2-naphthyl group, 1-anthryl
group, 2-anthryl group, 9-anthryl group, 1-phenanthryl group,
2-phenanthryl group, 3-phenanthryl group, 4-phenanthryl group,
9-phenanthryl group, 1-naphthacenyl group, 2-naphthacenyl group,
9-naphthacenyl group, 1-pyrenyl group, 2-pyrenyl group, 4-pyrenyl
group, 2-biphenylyl group, 3-biphenylyl group, 4-biphenylyl group,
p-terphenyl-4-yl group, p-terphenyl-3-yl group, p-terphenyl-2-yl
group, m-terphenyl-4-yl group, m-terphenyl-3-yl group,
m-terphenyl-2-yl group, o-tolyl group, m-tolyl group, p-tolyl
group, p-t-butylphenyl group, p-(2-phenylpropyl)phenyl group,
3-methyl-2-naphthyl group, 4-methyl-1-naphthyl group,
4-methyl-1-anthryl group, 4'-methylbiphenylyl group,
4''-t-butyl-p-terphenyl-4-yl group, 2-pyrrolyl group, 3-pyrrolyl
group, pyrazinyl group, 2-pyridinyl group, 3-pyridinyl group,
4-pyridinyl group, 2-indolyl group, 3-indolyl group, 4-indolyl
group, 5-indolyl group, 6-indolyl group, 7-indolyl group,
1-isoindolyl group, 3-isoindolyl group, 4-isoindolyl group,
5-isoindolyl group, 6-isoindolyl group, 7-isoindolyl group, 2-furyl
group, 3-furyl group, 2-benzofuranyl group, 3-benzofuranyl group,
4-benzofuranyl group, 5-benzofuranyl group, 6-benzofuranyl group,
7-benzofuranyl group, 1-isobenzofuranyl group, 3-isobenzofuranyl
group, 4-isobenzofuranyl group, 5-isobenzofuranyl group,
6-isobenzofuranyl group, 7-isobenzofuranyl group, 2-quinolyl group,
3-quinolyl group, 4-quinolyl group, 5-quinolyl group, 6-quinolyl
group, 7-quinolyl group, 8-quinolyl group,
1-isoquinolyl group, 3-isoquinolyl group, 4-isoquinolyl group,
5-isoquinolyl group, 6-isoquinolyl group, 7-isoquinolyl group,
8-isoquinolyl group, 2-quinoxanyl group, 5-quinoxanyl group,
6-quinoxanyl group, 1-carbazolyl group, 2-carbazolyl group,
3-carbazolyl group, 4-carbazolyl group, 1-phenanthridinyl group,
2-phenanthridinyl group, 3-phenanthridinyl group, 4-phenanthridinyl
group, 6-phenanthridinyl group, 7-phenanthridinyl group,
8-phenanthridinyl group, 9-phenanthridinyl group,
10-phenanthridinyl group, 1-acridinyl group, 2-acridinyl group,
3-acridinyl group, 4-acridinyl group, 9-acridinyl group,
1,7-phenanthrolin-2-yl group, 1,7-phenanthrolin-3-yl group,
1,7-phenanthrolin-4-yl group, 1,7-phenanthrolin-5-yl group,
1,7-phenanthrolin-6-yl group, 1,7-phenanthrolin-8-yl group,
1,7-phenanthrolin-9-yl group, 1,7-phenanthrolin-10-yl group,
1,8-phenanthrolin-2-yl group, 1,8-phenanthrolin-3-yl group,
1,8-phenanthrolin-4-yl group, 1,8-phenanthrolin-5-yl group,
1,8-phenanthrolin-6-yl group, 1,8-phenanthrolin-7-yl group,
1,8-phenanthrolin-9-yl group, 1,8-phenanthrolin-10-yl group,
1,9-phenanthrolin-2-yl group, 1,9-phenanthrolin-3-yl group,
1,9-phenanthrolin-4-yl group, 1,9-phenanthrolin-5-yl group,
1,9-phenanthrolin-6-yl group, 1,9-phenanthrolin-7-yl group,
1,9-phenanthrolin-8-yl group, 1,9-phenanthrolin-10-yl group,
1,10-phenanthrolin-2-yl group, 1,10-phenanthrolin-3-yl group,
1,10-phenanthrolin-4-yl group, 1,10-phenanthrolin-5-yl group,
2,9-phenanthrolin-1-yl group, 2,9-phenanthrolin-3-yl group,
2,9-phenanthrolin-4-yl group, 2,9-phenanthrolin-5-yl group,
2,9-phenanthrolin-6-yl group, 2,9-phenanthrolin-7-yl group,
2,9-phenanthrolin-8-yl group, 2,9-phenanthrolin-10-yl group,
2,8-phenanthrolin-1-yl group, 2,8-phenanthrolin-3-yl group,
2,8-phenanthrolin-4-yl group, 2,8-phenanthrolin-5-yl group,
2,8-phenanthrolin-6-yl group, 2,8-phenanthrolin-7-yl group,
2,8-phenanthrolin-9-yl group, 2,8-phenanthrolin-10-yl group,
2,7-phenanthrolin-1-yl group, 2,7-phenanthrolin-3-yl group,
2,7-phenanthrolin-4-yl group, 2,7-phenanthrolin-5-yl group,
2,7-phenanthrolin-6-yl group, 2,7-phenanthrolin-8-yl group,
2,7-phenanthrolin-9-yl group, 2,7-phenanthrolin-10-yl group,
1-phenazinyl group, 2-phenazinyl group, 1-phenothiazinyl group,
2-phenothiazinyl group, 3-phenothiazinyl group, 4-phenothiazinyl
group, 1-phenoxazinyl group, 2-phenoxazinyl group, 3-phenoxazinyl
group, 4-phenoxazinyl group, 2-oxazolyl group, 4-oxazolyl group,
5-oxazolyl group, 2-oxadiazolyl group, 5-oxadiazolyl group,
3-furazanyl group, 2-thienyl group, 3-thienyl group,
2-methylpyrrol-1-yl group, 2-methylpyrrol-3-yl group,
2-methylpyrrol-4-yl group, 2-methyl-pyrrol-5-yl group,
3-methylpyrrol-1-yl group, 3-methyl-pyrrol-2-yl group,
3-methylpyrrol-4-yl group, 3-methylpyrrol-5-yl group,
2-t-butylpyrrol-4-yl group, 3-(2-phenylpropyl)pyrrol-1-yl group,
2-methyl-1-indolyl group, 4-methyl-1-indolyl group,
2-methyl-3-indolyl group, 4-methyl-3-indolyl group,
2-t-butyl-1-indolyl group, 4-t-butyl-1-indolyl group,
2-t-butyl-3-indolyl group and 4-t-butyl-3-indolyl group.
[0047] The substituted or unsubstituted alkoxycarbonyl group is
represented by --COOZ. Examples of the group represented by Z
include methyl group, ethyl group, propyl group, isopropyl group,
n-butyl group, s-butyl group, isobutyl group, t-butyl group,
n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group,
hydroxymethyl group, 1-hydroxyethyl group, 2-hydroxyethyl group,
2-hydroxyisobutyl group, 1,2-dihydroxyethyl group,
1,3-dihydroxyisopropyl group, 2,3-dihydroxy-t-butyl group,
1,2,3-trihydroxypropyl group, chloromethyl group, 1-chloroethyl
group, 2-chloroethyl group, 2-chloroisobutyl group,
1,2-dichloroethyl group, 1,3-dichloroisopropyl group,
2,3-dichloro-t-butyl group, 1,2,3-trichloro-propyl group,
bromomethyl group, 1-bromoethyl group, 2-bromoethyl group,
2-bromoisobutyl group, 1,2-dibromoethyl group,
1,3-dibromo-isopropyl group, 2,3-dibromo-t-butyl group,
1,2,3-tribromopropyl group, iodomethyl group, 1-iodoethyl group,
2-iodoethyl group, 2-iodoisobutyl group, 1,2-diiodoethyl group,
1,3-diiodoisopropyl group, 2,3-diiodo-t-butyl group,
1,2,3-triiodopropyl group, aminomethyl group, 1-aminoethyl group,
2-aminoethyl group, 2-aminoisobutyl group, 1,2-diaminoethyl group,
1,3-diaminoisopropyl group, 2,3-diamino-t-butyl group,
1,2,3-triamino-propyl group, cyanomethyl group, 1-cyanoethyl group,
2-cyanoethyl group, 2-cyanoisobutyl group, 1,2-dicyanoethyl group,
1,3-dicyanoisopropyl group, 2,3-dicyano-t-butyl group,
1,2,3-tricyanopropyl group, nitromethyl group, 1-nitroethyl group,
2-nitroethyl group, 2-nitroisobutyl group, 1,2-dinitro-ethyl group,
1,3-dinitroisopropyl group, 2,3-dinitro-t-butyl group,
1,2,3-trinitropropyl group.
[0048] Examples of the divalent group forming the ring include
tetramethylene group, pentamethylene group, hexamethylene group,
diphenylmethane-2,2'-diyl group, diphenylethane-3,3'-diyl group and
diphenylpropane-4,4'-diyl group.
[0049] Examples of the halogen atom include fluorine atom, chlorine
atom, bromine atom and iodine atom.
[0050] In general formula (1), a, b and c each represent an integer
of 0 to 4 and preferably 0 or 1. n represents an integer of 1 to 3.
When n represents 2 or 3, the plurality of groups in [ ] shown in
the following:
##STR00003##
may be the same with or different from each other.
2. Asymmetric Monoanthracene Derivative Represented by the
Following General Formula (2):
##STR00004##
[0052] In general formula (2), m and n each represent an integer of
1 to 4 and preferably 1 or 2.
[0053] When m=n=1 and the positions of bonding of the groups
represented by Ar.sup.1 and Ar.sup.2 to the respective benzene
rings are horizontally symmetrical, Ar.sup.1 and Ar.sup.2 do not
represent the same group. When m or n represents an integer of 2 to
4, m and n represent integers different from each other. In the
present invention, when the groups represented by Ar.sup.1 and
R.sup.9 are bonded at positions X.sup.1 and X.sup.2, respectively,
of the benzene ring bonded to the 9-position of the anthracene
ring, and the groups represented by Ar.sup.2 and R.sup.10 are
bonded at positions X.sup.1 and X.sup.2, respectively, of the
benzene ring bonded to the 10-position of the anthracene ring, the
positions of bonding of the groups are defined as horizontally
symmetrical.
[0054] In other words, in the anthracene derivative represented by
general formula (2), benzene rings each substituted with an
aromatic group and bonded to the anthracene nucleus have a
horizontally asymmetric structure and, therefore, the above
anthracene derivative has an asymmetric structure.
[0055] When the substituents bonded to the 9-position and the
10-position of the anthracene nucleus are the same with each other,
this structure is not included in the asymmetric structure defined
above even when the substituents at the 2-position and the
3-positions of the anthracene nucleus are different from each
other.
[0056] In general formula (2) shown above, it is preferable that m
and/or n represents 1. When m=1, compounds represented by the
following general formulae (3) to (5) are more preferable.
##STR00005##
[0057] In general formulae (3) to (5), Ar.sup.1, Ar.sup.2, n and
R.sup.1 to R.sup.10 are as defined for general formula (2) in the
above. Similarly to the case described above, Ar.sup.1 and Ar.sup.2
do not represent the same group when n=1 and the positions of
bonding of the groups represented by Ar.sup.1 and Ar.sup.2 are
horizontally symmetrical.
[0058] In general formula (2), Ar.sup.1 and Ar.sup.2 each
independently represent a substituted or unsubstituted aromatic
cyclic group having 6 to 50 ring carbon atoms.
[0059] Examples of the substituted or unsubstituted aromatic cyclic
group having 6 to 50 ring carbon atoms represented by Ar.sup.1 and
Ar.sup.2 include the groups shown above as the examples of the
corresponding group in general formula (1). Phenyl group,
1-naphthyl group, 2-naphthyl group, 9-phenanthryl group,
1-naphthacenyl group, 2-naphthacenyl group, 9-naphthacenyl group,
1-pyrenyl group, 2-pyrenyl group, 4-pyrenyl group, 2-biphenylyl
group, 3-biphenylyl group, 4-biphenylyl group, o-tolyl group,
m-tolyl group, p-tolyl group and p-t-butylphenyl group are
preferable.
[0060] In general formula (2), R.sup.1 to R.sup.10 each
independently represent hydrogen atom, a substituted or
unsubstituted aromatic cyclic group having 6 to 50 ring carbon
atoms, a substituted or unsubstituted aromatic heterocyclic group
having 5 to 50 ring carbon atoms, a substituted or unsubstituted
alkyl group having 1 to 50 carbon atoms, a substituted or
unsubstituted cycloalkyl group, a substituted or unsubstituted
alkoxyl group having 1 to 50 carbon atoms, a substituted or
unsubstituted aralkyl group having 6 to 50 carbon atoms, a
substituted or unsubstituted aryloxyl group having 5 to 50 ring
carbon atoms, a substituted or unsubstituted arylthio group having
5 to 50 ring carbon atoms, a substituted or unsubstituted
alkoxycarbonyl group having 1 to 50 carbon atoms, a substituted or
unsubstituted silyl group, carboxyl group, a halogen atom, cyano
group, nitro group or hydroxyl group.
[0061] Examples of the substituted or unsubstituted aromatic cyclic
group, the substituted or unsubstituted aromatic heterocyclic
group, the substituted or unsubstituted alkyl group, the
substituted or unsubstituted cycloalkyl group, the substituted or
unsubstituted alkoxyl group, the substituted or unsubstituted
aralkyl group, the substituted or unsubstituted aryloxyl group, the
substituted or unsubstituted arylthio group and the substituted or
unsubstituted alkoxycarbonyl group represented by R.sup.1 to
R.sup.10 include the groups shown as the examples of the
corresponding groups represented by X in general formula (1).
[0062] Examples of the halogen atom represented by R.sup.1 to
R.sup.10 include fluorine atom, chlorine atom, bromine atom and
iodine atom.
[0063] Examples of the substituent to the above groups represented
by Ar.sup.1, Ar.sup.2 and R.sup.1 to R.sup.10 include halogen
atoms, hydroxyl group, nitro group, cyano group, alkyl groups, aryl
groups, cycloalkyl groups, alkoxyl groups, aromatic heterocyclic
groups, aralkyl groups, aryloxyl groups, arylthio groups,
alkoxycarbonyl groups and carboxyl group.
3. Asymmetric Anthracene Derivatives Represented by the Following
General Formula (6):
##STR00006##
[0065] As the asymmetric anthracene derivative represented by
general formula (6), the case in which groups are bonded to the
9-position and the 10-position of anthracene symmetrically with
respect to the X-Y axis of the anthracene shown above is excluded.
That the case in which groups are bonded symmetrically with respect
to the X-Y axis is excluded preferably means that general formula
(6) has the following structures:
(I) A.sup.3 and A.sup.4 are different from each other. (II) When
A.sup.3 and A.sup.4 are the same with each other,
[0066] (II-i) Ar.sup.3 and Ar.sup.4 are different from each
other.
[0067] (II-ii) R.sup.19 and R.sup.20 are different from each
other.
[0068] (II-iii) When Ar.sup.3 and Ar.sup.4 are the same with each
other, and R.sup.19 and R.sup.20 are the same with each other,
[0069] (II-iii-1) The position of bonding of A.sup.3 to the
9-position of anthracene is different from the position of bonding
of A.sup.4 to the 10-position of anthracene. [0070] (II-iii-2) When
neither Ar.sup.3 nor Ar.sup.4 represents hydrogen atom, the
position of bonding of Ar.sup.3 in A.sup.3 is different from the
position of bonding of Ar.sup.4 in A.sup.4. [0071] (II-iii-3) When
neither of R.sup.19 nor R.sup.20 represents hydrogen atom, the
position of bonding of R.sup.19 in A.sup.3 is different form the
position of bonding of R.sup.20 in A.sup.4.
[0072] In general formula (6), A.sup.3 and A.sup.4 each
independently represent a substituted or unsubstituted condensed
aromatic cyclic group having 10 to 20 ring carbon atoms and
preferably 10 to 16 ring carbon atoms.
[0073] Examples of the substituted or unsubstituted condensed
aromatic cyclic represented by A.sup.3 and A.sup.4 include
1-naphthyl group, 2-naphthyl group, 1-anthryl group, 2-anthryl
group, 9-anthryl group, 1-phenanthryl group, 2-phenanthryl group,
3-phenanthryl group, 4-phenanthryl group, 9-phenanthryl group,
1-naphthacenyl group, 2-naphthacenyl group, 9-naphthacenyl group,
1-pyrenyl group, 2-pyrenyl group, 4-pyrenyl group,
3-methyl-2-naphthyl group, 4-methyl-1-naphthyl group and
4-methyl-1-anthryl group.
[0074] Among these groups, 1-naphthyl group, 2-naphthyl group and
9-phenanthryl group are preferable.
[0075] In general formula (6), Ar.sup.3 and Ar.sup.4 each
independently represent hydrogen atom or a substituted or
unsubstituted aromatic cyclic group having 6 to 50 ring carbon
atoms and preferably 6 to 16 ring carbon atoms.
[0076] Examples of the substituted or unsubstituted aromatic cyclic
group represented by Ar.sup.3 and Ar.sup.4 include phenyl group,
1-naphthyl group, 2-naphthyl group, 1-anthryl group, 2-anthryl
group, 9-anthryl group, 1-phenanthryl group, 2-phenanthryl group,
3-phenanthryl group, 4-phenanthryl group, 9-phenanthryl group,
1-naphthacenyl group, 2-naphthacenyl group, 9-naphthacenyl group,
1-pyrenyl group, 2-pyrenyl group, 4-pyrenyl group, 2-biphenylyl
group, 3-biphenylyl group, 4-biphenylyl group, p-terphenyl-4-yl
group, p-terphenyl-3-yl group, p-terphenyl-2-yl group,
m-terphenyl-4-yl group, m-terphenyl-3-yl group, m-terphenyl-2-yl
group, o-tolyl group, m-tolyl group, p-tolyl group, p-t-butylphenyl
group, p-(2-phenylpropyl)phenyl group, 3-methyl-2-naphthyl group,
4-methyl-1-naphthyl group, 4-methyl-1-anthryl group,
4'-methylbiphenylyl group and 4''-t-butyl-p-terphenyl-4-yl
group.
[0077] Among these groups, phenyl group, 1-naphthyl group,
2-naphthyl group, 9-phenanthryl group, 1-naphthacenyl group,
2-naphthacenyl group, 9-naphthacenyl group, 1-pyrenyl group,
2-pyrenyl group, 4-pyrenyl group, 2-biphenylyl group, 3-biphenylyl
group, 4-biphenylyl group, o-tolyl group, m-tolyl group, p-tolyl
group and p-t-butylphenyl group are preferable.
[0078] In general formula (6), R.sup.11 to R.sup.20 each
independently represent hydrogen atom, a substituted or
unsubstituted aromatic group having 6 to 50 ring carbon atoms, a
substituted or unsubstituted aromatic heterocyclic group having 5
to 50 ring carbon atoms, a substituted or unsubstituted alkyl
groups having 1 to 50 carbon atoms, a substituted or unsubstituted
cycloalkyl groups, a substituted or unsubstituted alkoxyl group
having 1 to 50 carbon atoms, a substituted or unsubstituted aralkyl
group having 6 to 50 carbon atoms, a substituted or unsubstituted
aryloxyl group having to 50 ring carbon atoms, a substituted or
unsubstituted arylthio group having 5 to 50 ring carbon atoms, a
substituted or unsubstituted alkoxycarbonyl group having 1 to 50
carbon atoms, a substituted or unsubstituted silyl group, carboxyl
group, halogen atoms, cyano group, nitro group or hydroxyl
group.
[0079] Examples of the substituted or unsubstituted aromatic cyclic
group, the substituted or unsubstituted aromatic heterocyclic
group, the substituted or unsubstituted alkyl group, the
substituted or unsubstituted cycloalkyl group, the substituted or
unsubstituted alkoxyl group, the substituted or unsubstituted
aralkyl group, the substituted or unsubstituted aryloxyl group, the
substituted or unsubstituted arylthio group and the substituted or
unsubstituted alkoxycarbonyl group represented by R.sup.11 to
R.sup.20 include the groups shown as the examples of the
corresponding groups represented by X in general formula (1).
[0080] Examples of the halogen atom represented by R.sup.11 to
R.sup.20 include fluorine atom, chlorine atom, bromine atom and
iodine atom.
[0081] Examples of the substituent to the above groups represented
by Ar.sup.3, Ar.sup.4 and R.sup.11 to R.sup.20 include halogen
atoms, hydroxyl group, nitro group, cyano group, alkyl groups, aryl
groups, cycloalkyl groups, alkoxyl groups, aromatic heterocyclic
groups, aralkyl groups, aryloxyl groups, arylthio groups,
alkoxycarbonyl groups and carboxyl group.
[0082] Ar.sup.3, Ar.sup.4 and R.sup.11 to R.sup.20 may each
represent a plurality of atoms or groups. Groups adjacent to each
other may form a saturated or unsaturated cyclic structure.
Examples of the cyclic structure include unsaturated six-membered
rings such as benzene ring and saturated and unsaturated
five-membered and seven-membered cyclic structures.
[0083] In the present invention, it is preferable that the
asymmetric anthracene derivative represented by general formula (6)
has a naphthalen-1-yl group having a substituent at the 4-position
and/or a substituted or unsubstituted condensed aromatic cyclic
group having 12 to 20 ring carbon atoms. Examples of the
substituent include the substituents shown above as the examples of
the substituent to the groups represented by Ar.sup.3, Ar.sup.4 and
R.sup.11 to R.sup.20.
4. An Asymmetric Anthracene Derivative Represented by the Following
General Formula (6'):
##STR00007##
[0085] General formula (6') is the formula obtained by restricting
general formula (6) in a manner such that A.sup.3' and A.sup.4'
each independently represent a substituted or unsubstituted
condensed aromatic cyclic group having 10 to 20 ring carbon atoms,
and at least one of A.sup.3' and A.sup.4' represents
naphthalen-1-yl group having a substituent at the 4-position or a
substituted or unsubstituted condensed aromatic cyclic group having
12 to 20 ring carbon atoms. Since Ar.sup.3, Ar.sup.4 and R.sup.11
to R.sup.20 each independently represent the same atom or group as
that in general formula (6), examples of the atoms, the groups, the
preferable groups and the substituents include the atoms, the
groups, the preferable groups and the substituents shown as the
corresponding examples in general formula (6). Similarly to general
formula (6), the case in which groups are bonded to the 9-position
and the 10-position of anthracene symmetrically with respect to the
X-Y axis of the anthracene shown above is excluded in general
formula (6').
5. Asymmetric Pyrene Derivatives Represented by the Following
General Formula (7):
##STR00008##
[0087] In general formula (7), Ar and Ar' each represents a
substituted or unsubstituted aromatic group having 6 to 50 ring
carbon atoms.
[0088] Examples of the aromatic group include phenyl group,
1-naphthyl group, 2-naphthyl group, 1-anthryl group, 2-anthryl
group, 9-anthryl group, 9-(10-phenyl)anthryl group,
9-(10-naphthyl-1-yl)anthryl group, 9-(10-naphthyl-2-yl)anthryl
group, 1-phenanthryl group, 2-phenanthryl group, 3-phenanthryl
group, 4-phenanthryl group, 9-phenanthryl group, 1-naphthacenyl
group, 2-naphthacenyl group, 9-naphthacenyl group, 1-pyrenyl group,
2-pyrenyl group, 4-pyrenyl group, 2-biphenylyl group, 3-biphenylyl
group, 4-biphenylyl group, p-terphenyl-4-yl group, p-terphenyl-3-yl
group, p-terphenyl-2-yl group, m-terphenyl-4-yl group,
m-terphenyl-3-yl group, m-terphenyl-2-yl group, o-tolyl group,
m-tolyl group, p-tolyl group, p-t-butylphenyl group,
3-methyl-2-naphthyl group, 4-methyl-1-naphthyl group and
4-methyl-1-anthryl group.
[0089] Among these groups, phenyl group, 1-naphthyl group,
2-naphthyl group, 9-(10-phenyl)anthryl group,
9-(10-naphthyl-1-yl)anthryl group, 9-(10-naphthyl-2-yl)anthryl
group, 9-phenanthryl group, 1-pyrenyl group, 2-pyrenyl group,
4-pyrenyl group, 2-biphenylyl group, 3-biphenylyl group,
4-biphenylyl group, o-tolyl group, m-tolyl group, p-tolyl group and
p-t-butylphenyl group are preferable.
[0090] The above aromatic groups may be substituted with
substituents. Examples of the substituent include alkyl groups
(such as methyl group, ethyl group, propyl group, isopropyl group,
n-butyl group, s-butyl group, isobutyl group, t-butyl group,
n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group,
hydroxymethyl group, 1-hydroxyethyl group, 2-hydroxyethyl group,
2-hydroxyisobutyl group, 1,2-dihydroxyethyl group,
1,3-dihydroxyisopropyl group, 2,3-dihydroxy-t-butyl group,
1,2,3-trihydroxypropyl group, chloromethyl group, 1-chloroethyl
group, 2-chloroethyl group, 2-chloroisobutyl group,
1,2-dichloroethyl group, 1,3-dichloroisopropyl group,
2,3-dichloro-t-butyl group, 1,2,3-trichloropropyl group,
bromomethyl group, 1-bromoethyl group, 2-bromoethyl group,
2-bromoisobutyl group, 1,2-dibromoethyl group, 1,3-dibromoisopropyl
group, 2,3-dibromo-t-butyl group, 1,2,3-tribromopropyl group,
iodomethyl group, 1-iodoethyl group, 2-iodoethyl group,
2-iodoisobutyl group, 1,2-diiodoethyl group, 1,3-diiodoisopropyl
group, 2,3-diiodo-t-butyl group, 1,2,3-triiodopropyl group,
aminomethyl group, 1-aminoethyl group, 2-aminoethyl group,
2-aminoisobutyl group, 1,2-diaminoethyl group, 1,3-diaminoisopropyl
group, 2,3-diamino-t-butyl group, 1,2,3-triaminopropyl group,
cyanomethyl group, 1-cyanoethyl group, 2-cyanoethyl group,
2-cyanoisobutyl group, 1,2-dicyanoethyl group, 1,3-dicyanoisopropyl
group, 2,3-dicyano-t-butyl group, 1,2,3-tricyanopropyl group,
nitromethyl group, 1-nitroethyl group, 2-nitroethyl group,
2-nitroisobutyl group, 1,2-dinitroethyl group, 1,3-dinitroisopropyl
group, 2,3-dinitro-t-butyl group, 1,2,3-trinitropropyl group,
cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl
group, 4-methylcyclohexyl group, 1-adamantyl group, 2-adamantyl
group, 1-norbornyl group and 2-norbornyl group), alkoxyl groups
having 1 to 6 carbon atoms (such as ethoxyl group, methoxyl group,
i-propoxyl group, n-propoxyl group, s-butoxyl group, t-butoxyl
group, pentoxyl group, hexyloxyl group, cyclopentoxyl group and
cyclohexyloxyl group), aryl groups having 5 to 40 ring atoms, amino
groups substituted with aryl groups having 5 to 40 ring atoms,
ester groups having aryl groups having 5 to 40 ring atoms, ester
groups having alkyl groups having 1 to 6 carbon atoms, cyano group,
nitro group and halogen atoms.
[0091] In general formula (7), L and L' each represent a
substituted or unsubstituted phenylene group, a substituted or
unsubstituted naphthalenylene group, a substituted or unsubstituted
fluorenylene group, a substituted or unsubstituted
dibenzosilolylene group. Substituted and unsubstituted phenylene
groups and substituted and unsubstituted fluorenylene groups are
preferable.
[0092] Examples of the substituent include the substituents shown
above as the examples of the substituent to the aromatic group.
[0093] In general formula (7), m represents an integer of 0 to 2
and preferably 0 or 1, n represents an integer of 1 to 4 and
preferably 1 or 2, s represents an integer of 0 to 2 and preferably
0 or 1, and t represents an integer of 0 to 4 and preferably 0 to
2.
[0094] In general formula (7), the group represented by L or Ar is
bonded to one of the 1- to 5-positions of pyrene. The group
represented by L' or Ar' is bonded to one of the 6- to 10-positions
of pyrene.
[0095] In general formula (7), when n+t represent an even number,
the groups represented by Ar, Ar', L and L' satisfy the following
condition (1) or (2):
(1) Ar.noteq.Ar' and/or L.noteq.L' (.noteq. means that the groups
have different structures).
(2) When Ar=Ar' and L=L',
[0096] (2-1) m.noteq.s and/or n.noteq.t, or
[0097] (2-2) when m=s and n=t, [0098] (2-2-1) L and L' or pyrene is
bonded to different positions on Ar and Ar', respectively. [0099]
(2-2-2) when L and L' or pyrene is bonded to the same position on
Ar and Ar', the case in which the positions of substitution of L
and L' or Ar and Ar' on pyrene are the 1- and 6-positions or the 2-
and 7-positions is excluded.
[0100] In general formula (7), Ar and Ar' each represent a
substituted or unsubstituted aromatic group having 6 to 50 ring
carbon atoms, and L and L' each represent a substituted or
unsubstituted phenylene group, a substituted or unsubstituted
naphthalenylene group, a substituted or unsubstituted fluorenylene
group, a substituted or unsubstituted dibenzosilolylene group.
[0101] m represents an integer of 0 to 2, n represents an integer
of 1 to 4, s represents an integer of 0 to 21, and t represents an
integer of 0 to 4. The group represented by L or Ar is bonded to
one of the 1- to 5-positions of pyrene. The group represented by L'
or Ar' is bonded to one of the 6- to 10-positions of pyrene.
[0102] When n+t represent an even number, the groups represented by
Ar, Ar', L and L' satisfy the following condition (1) or (2):
(1) Ar.noteq.Ar' and/or L.noteq.L' (.noteq. means that the groups
have different structures).
(2) When Ar=Ar and L=L',
[0103] (2-1) m.noteq.s and/or n.noteq.t, or
[0104] (2-2) when m=s and n=t, [0105] (2-2-1) L and L' or pyrene is
bonded to different positions on Ar and Ar', respectively. [0106]
(2-2-2) when L and L' or pyrene is bonded to the same position on
Ar and Ar', the case in which the positions of substitution of L
and L' or Ar and Ar' on pyrene are the 1- and 6-positions or the 2-
and 7-positions is excluded.
6. Asymmetric Pyrene Derivative Represented by the Following
General Formula (8):
##STR00009##
[0108] In general formula (8), Ar, Ar', L, L', m, s and t are as
defined for general formula (7). Examples of the groups represented
by Ar, Ar', L and L' and examples of the substituents are as shown
for general formula (7). In general formula (8), the group
represented by L' or Ar' is bonded to one of the 2- to 10-positions
of pyrene.
[0109] In general formula (8), when t represents an odd number, Ar,
Ar', L and L' satisfy the following condition (1') or (2'):
(1') Ar.noteq.Ar' and/or L.noteq.L' (.noteq. means that the groups
have different structures).
(2') When Ar=Ar' and L=L',
[0110] (2-1') m.noteq.s and/or t.noteq.1, or
[0111] (2-2') when m=s and t=1, [0112] (2-2-1) L and L' or pyrene
is bonded to different positions on Ar and Ar', respectively.
[0113] (2-2-2) when L and L' or pyrene is bonded to the same
position on Ar and Ar', the case in which the position of
substitution of L' or Ar' on pyrene is the 6-position is
excluded.
7. Asymmetric Pyrene Derivative Represented by the Following
General Formula (9):
##STR00010##
[0115] In general formula (9), Ar, Ar', L, L', m and s are as
defined for general formula (7). Examples of the groups represented
by Ar, Ar', L and L', preferable examples of the groups represented
by Ar, Ar', L and L' and examples of the substituents are as shown
for general formula (7).
[0116] The process of the present invention can be advantageously
applied to production of a material for organic EL devices using a
crude product of an aromatic compound having 1 to 12 nitrogen atoms
in the molecule.
[0117] Examples of the aromatic compound having 1 to 12 nitrogen
atoms include amine-based compounds such as aromatic diamines,
aromatic triamines and aromatic tetraamines; carbazole-based
compounds such as dicarbazole derivatives, tricarbazole derivatives
and tetracarbazole derivatives; benzimidazole-based compounds;
phenanthroline-based compounds; quinoxaline-based compounds;
hexaazatriphenylene-based compounds; indolidine-based compounds;
bipyridyl-based compounds; pyrimidine-based compounds;
triazine-based compounds; and phthalocyanine-based compounds.
[0118] Among the aromatic compounds described above, compounds
having a low symmetry have a tendency that halogen impurities are
left remaining in the material for organic EL devices since many
types of aromatic halogenated compounds are used and complicated
reactions are conducted utilizing the difference in reactivity of
halogen atoms. Compounds having nitrogen atom in the molecule tend
to form an intramolecular complex with an isolated halogen, and
halogen impurities tend to be left remaining in the molecule. Due
to these reasons, the process comprising the treatment using
chemical reaction such as the process of the present invention is
very effective for decreasing the contents of halogens in the
material for organic EL devices in the high purity region.
[0119] Examples of the aromatic compound having 1 to 12 nitrogen
atoms in the molecule include the compounds represented by the
following general formulae (10) to (14):
##STR00011##
[0120] In general formula (10), Ar.sup.5 to Ar.sup.13 and Ar.sup.21
to Ar.sup.23 each independently represent a group selected from
substituted and unsubstituted aromatic groups having 6 to 50 ring
carbon atoms and aromatic heterocyclic groups having 5 to 50 ring
carbon atoms. The pair of groups represented by Ar.sup.5 and
Ar.sup.6, Ar.sup.7 and Ar.sup.8 or Ar.sup.9 and Ar.sup.10 may be
bonded to each other to form a saturated or unsaturated ring. a to
c and p to r each represent an integer of 0 to 3. Examples of the
substituted or unsubstituted aromatic group having 6 to 50 ring
carbon atoms include the groups shown as the examples of the
corresponding group in general formula (7). Examples of the
aromatic heterocyclic group having 5 to 50 ring carbon atoms
include the groups shown as the examples of the group represented
by X in general formula (1).
##STR00012##
[0121] In general formula (11), Ar.sup.25 to Ar.sup.28 each
independently represent a group selected from substituted and
unsubstituted aromatic groups having 6 to 50 ring carbon atoms and
substituted and unsubstituted aromatic heterocyclic groups having 5
to 50 ring carbon atoms. The groups represented by Ar.sup.26 and
Ar.sup.27 may be bonded to each other to form a saturated or
unsaturated ring. L.sup.1 represents the single bond or a group
selected from substituted and unsubstituted aromatic group 6 to 50
ring carbon atoms and substituted and unsubstituted aromatic
heterocyclic groups having 5 to 50 ring carbon atoms. x represents
an integer of 0 to 5. Examples of the substituted or unsubstituted
aromatic group having 6 to 50 ring carbon atoms and aromatic
heterocyclic group having 5 to 50 ring carbon atoms include the
groups described above for general formula (10).
HAr-L.sup.2-Ar.sup.31--Ar.sup.32 (12)
[0122] In general formula (12), HAr represents a substituted or
unsubstituted heterocyclic group having 3 to 40 carbon atoms and
nitrogen atom, L.sup.2 represents the single bond or a group
selected from substituted and unsubstituted arylene groups having 6
to 60 carbon atoms, substituted and unsubstituted heteroarylene
groups having 3 to 60 carbon atoms and substituted or unsubstituted
fluorenylene groups, Ar.sup.31 represents a substituted or
unsubstituted divalent aromatic hydrocarbon group having 6 to 60
carbon atoms, and Ar.sup.32 represents a group selected from
substituted and unsubstituted aryl groups having 6 to 60 carbon
atoms and substituted and unsubstituted heteroaryl groups having 3
to 60 carbon atoms.
##STR00013##
[0123] In general formulae (13) and (14), R represents hydrogen
atom or a group selected from substituted and unsubstituted aryl
groups having 6 to 60 carbon atoms, substituted and unsubstituted
pyridyl group, substituted and unsubstituted quinolyl group,
substituted and unsubstituted alkyl groups having 1 to 20 carbon
atoms and substituted and unsubstituted alkoxyl groups having 1 to
20 carbon atoms. n represents an integer of 0 to 4. R.sup.31
represents a group selected from substituted and unsubstituted aryl
groups having 6 to 60 carbon atoms, substituted and unsubstituted
pyridyl group, substituted and unsubstituted quinolyl group,
substituted and unsubstituted alkyl groups having 1 to 20 carbon
atoms and substituted and unsubstituted alkoxyl groups having 1 to
20 carbon atoms. R.sup.32 represents hydrogen atom or a group
selected from substituted and unsubstituted aryl groups having 6 to
60 carbon atoms, substituted and unsubstituted pyridyl group,
substituted and unsubstituted quinolyl group, substituted and
unsubstituted alkyl groups having 1 to 20 carbon atoms and
substituted and unsubstituted alkoxyl groups having 1 to 20 carbon
atoms. L.sup.3 represents a group selected from substituted and
unsubstituted arylene groups having 6 to 60 carbon atoms,
substituted and unsubstituted pyridinylene groups, substituted and
unsubstituted quinolynylene groups and substituted and
unsubstituted fluorenylene groups. Ar.sup.31 represents a group
selected from substituted and unsubstituted arylene group having 6
to 60 carbon atoms, substituted and unsubstituted pyridinylene
groups and substituted and unsubstituted quinolynylene groups.
Ar.sup.32 represents a group selected from substituted and
unsubstituted aryl groups having 6 to 60 carbon atoms, substituted
and unsubstituted pyridyl group, substituted and unsubstituted
quinolyl group, substituted and unsubstituted alkyl groups having 1
to 20 carbon atoms and substituted and unsubstituted alkoxyl groups
having 1 to 20 carbon atoms.
[0124] The aromatic compound of the present invention is
advantageously used as the material for organic EL devices, organic
semiconductors and electronic photosensitive materials. Typical
examples of the construction of the organic EL device using the
aromatic compound of the present invention include:
(1) An anode/a light emitting layer/a cathode; (2) An anode/a hole
injecting layer/a light emitting layer/a cathode; (3) An anode/a
light emitting layer/an electron injecting layer/a cathode; (4) An
anode/a hole injecting layer/a light emitting layer/an electron
injecting layer/a cathode; (5) An anode/an organic semiconductor
layer/a light emitting layer/a cathode; (6) An anode/an organic
semiconductor layer/an electron barrier layer/a light emitting
layer/a cathode; (7) An anode/an organic semiconductor layer/a
light emitting layer/an adhesion improving layer/a cathode; (8) An
anode/a hole injecting layer/a hole transporting layer/a light
emitting layer/an electron injecting layer/a cathode; (9) An
anode/an insulating layer/a light emitting layer/an insulating
layer/a cathode; (10) An anode/an inorganic semiconductor layer/an
insulating layer/a light emitting layer/an insulating layer/a
cathode; (11) An anode/an organic semiconductor layer/an insulating
layer/a light emitting layer/an insulating layer/a cathode; (12) An
anode/an insulating layer/a hole injecting layer/a hole
transporting layer/a light emitting layer/an insulating layer/a
cathode; and (13) An anode/an insulating layer/a hole injecting
layer/a hole transporting layer/a light emitting layer/an electron
injecting layer/a cathode.
[0125] Among the above constructions, construction (8) is
preferable. However, the construction of the organic EL device is
not limited to those shown above as the examples. The aromatic
compound of the present invention may be used in any of the above
organic layers. Among the above constructions, the constructions
using the aromatic compound of the present invention in the light
emitting zone or the hole transporting zone are preferable.
EXAMPLES
[0126] The present invention will be described more specifically
with reference to examples in the following. However, the present
invention is not limited to the examples.
Synthesis Example 1
Synthesis of
9-(naphthyl-2-yl)-10-(4-(naphthyl-1-yl)phenyl-1-yl)anthracene
(BH1)
(1) Synthesis of 9-(naphthyl-2-yl)anthracene
[0127] Under the stream of nitrogen, 30.0 kg of 9-bromoanthracene
(manufactured by Tokyo Chemical Industry Co., Ltd.), 24.1 kg of
2-naphthylboronic acid, 2.157 kg of
tetrakis(triphenylphosphine)palladium, 48.4 kg of potassium
carbonate (manufactured by NIPPON SODA Co., Ltd.), 150 liters of
toluene and 150 liters of Solmix were placed into a 1,000 liter
reactor, and the reaction was allowed to proceed at 78.degree. C.
for 50 hours.
[0128] After the reaction mixture was cooled to the room
temperature, 188 liters of tetrahydrofuran and 188 liters of water
were added, and the obtained mixture was fractionated. The obtained
organic layer was washed with 115 liters of a 5% by mass aqueous
solution of sodium hydroxide, 115 liters of a 5% by mass aqueous
solution of sodium hydrogencarbonate and 115 liters of a 5% by mass
aqueous solution of sodium chloride, successively, and the washed
organic layer was concentrated under a reduced pressure.
[0129] The organic layer was purified using a column packed with
300 kg of silica gel and toluene as the developing solvent and
concentrated under a reduced pressure. Then, 590 liters of heptane
was added until a slurry was obtained, and the obtained slurry was
filtered at the room temperature. The obtained residue was dried,
and 33.2 kg of 9-(naphthyl-2-yl)anthracene was obtained.
(2) Synthesis of 9-bromo-10-(naphthyl-2-yl)anthracene
[0130] Under the stream of nitrogen, 33.2 kg of
9-(naphthyl-2-yl)-anthracene obtained above in (1) and 265 liters
of dimethylformamide were placed into a 1,000 liter reactor, and a
solution obtained by dissolving 21.36 kg of N-bromosuccimide
(manufactured by MIDORI KAGAKU Co., Ltd.) in 100 liters of
dimethylformamide was added dropwise at a temperature in the range
of 30 to 35.degree. C.
[0131] After the reaction was allowed to proceed for 4 hours, 454
liters of water was added dropwise. The obtained reaction product
was filtered, and the obtained crystals were washed with 60 liters
of water. The washed crystals were dissolved into 276 liters of
chloroform, and the resultant solution was washed with 80 liters of
water and dried with 7 kg of magnesium sulfate. The organic layer
was concentrated under a reduced pressure, and 590 liters of
n-heptane was added until a slurry was obtained. The slurry was
filtered at the room temperature, and the obtained crystals were
dissolved into 57 liters of toluene. After 230 liters of n-heptane
was added, the resultant mixture was cooled to -5.degree. C. The
temperature was then elevated to 60.degree. C., and the crystals
were separated by filtration. The separated crystals were dried,
and 34.6 kg of 9-bromo-10-(naphthyl-2-yl)anthracene was
obtained.
(3) Synthesis of (9-(naphthyl-2-yl)anthracene-10-yl)boronic
acid
[0132] Under the stream of nitrogen, 17.3 kg of
9-bromo-10-(naphthyl-2-yl)anthracene obtained above in (2) and 138
liters of tetrahydrofuran were placed into a 200 liter reactor. The
mixture was cooled at -70.degree. C., and 20.4 kg of a 17% by mass
hexane solution of n-butyllithium (manufactured by ASIA LITHIUM Co.
Ltd.) was added dropwise at a temperature in the range of -64 to
-70.degree. C., and the reaction was allowed to proceed at the same
temperature for 2 hours. To the obtained reaction mixture, 9.38 kg
of trimethyl borate (manufactured by Daihachi Chemical Industry
Co., Ltd.) was added dropwise at a temperature in the range of -64
to -70.degree. C., and the reaction was allowed to proceed at the
same temperature for 2 hours. To the obtained reaction mixture, 103
liters of a 5 moles/liter hydrochloric acid was added dropwise at a
temperature of 5.degree. C. or lower. The obtained product was
fractionated at the room temperature, and the organic layer was
washed with 60 liters of a 5% by mass solution of sodium
hydrogencarbonate and treated by extraction with 60 liters of
toluene.
[0133] The step having the same procedures as those described above
was conducted once more, and the products in the two steps were
combined. The combined product was washed with 120 liters of a 10%
by mass aqueous solution of sodium chloride and concentrated under
a reduced pressure. To the concentrated product, 200 liters of
n-heptane was added until a slurry was obtained. The crystals in
the slurry were separated by filtration, washed in 30 liters of
toluene heated at 50.degree. C., cooled to the room temperature,
separated by filtration and dried, and 20.3 kg of
(9-(naphthyl-2-yl)anthracene-10-yl)boronic acid was obtained.
(4) Synthesis of 1-(4-bromophenyl-1-yl)naphthalene
[0134] Under the stream of nitrogen, 14.7 kg of 1-naphthylboronic
acid, 22.0 kg of 4-bromoiodobenzene, 1.797 kg of
tetrakis(triphenylphosphine)-palladium, 24.7 kg of potassium
carbonate (manufactured by NIPPON SODA Co., Ltd.) and 220 liters of
toluene were placed into a reactor having an inner volume of 500
liters, and the reaction was allowed to proceed at 75.degree. C.
for 32 hours.
[0135] To the obtained reaction mixture, 220 liters of water was
added, and the resultant product was fractionated. The obtained
organic layer was washed with 130 liters of a 5% by mass aqueous
solution of sodium hydroxide, 130 liters of a 5% by mass aqueous
solution of sodium hydrogencarbonate and 130 liters of a 5% by mass
aqueous solution of sodium chloride, successively. The washed
product was concentrated under a reduced pressure and purified
using a column packed with 220 kg of silica gel and n-heptane as
the developing solvent. After the purified product was concentrated
under a reduced pressure and distilled under a reduced pressure,
16.9 kg of 1-(4-bromophenyl-1-yl)naphthalene was obtained.
(5) Synthesis of
9-(naphthyl-2-yl)-10-(4-(naphthyl-1-yl)phenyl-1-yl)-anthracene
(BH1)
[0136] Under the stream of nitrogen, 5.0 kg of
(9-(naphthyl-2-yl)-anthracene-10-yl)boronic acid obtained above in
(3), 4.07 kg of 1-(4-bromophenyl-1-yl)naphthalene obtained above in
(4), 332 g of tetrakis(triphenylphosphine)palladium, 5.95 kg of
potassium carbonate (manufactured by NIPPON SODA Co., Ltd.), 50
liters of water and 50 liters of dimethoxyethane were placed into a
reactor having an inner volume of 200 liters, and the reaction was
allowed to proceed at 75.degree. C. for 18 hours.
[0137] After the reaction mixture was cooled to the room
temperature, the crystals were separated by filtration and washed
with 24 liters of water, 24 liters of methanol and 24 liters of
n-heptane and then in 44 liters of n-heptane heated at 50.degree.
C. After being cooled to the room temperature, the crystals were
separated by filtration.
[0138] The obtained crystals were purified using a column packed
with 25 kg of silica gel and a mixed solvent of hexane and toluene
(hexane/toluene=3/1), concentrated under a reduced pressure,
filtered after adding 2.5 liters of acetone and washed with 2.5
liters of acetone and 2.5 liters of hexane. After the washed
product was dried, the product was purified by sublimation under
the condition of a degree of vacuum of 3.times.10.sup.-3 Pa and a
temperature of the boat of 270 to 280.degree. C., and 4.81 kg of
9-(naphthyl-2-yl)-10-(4-(naphthyl-1-yl)phenyl-1-yl)anthracene (BH1)
was obtained.
[0139] The purity of BH1 obtained above measured in accordance with
the high performance liquid chromatography (HPLC) was 99.98% as the
ratio of BH1 peak area to all peak area. When the content of
bromine present in BH1 was measured in accordance with the ICP-MS
(burning) method, the content was found to be 28 ppm by mass.
Example 1
Treatment of BH1 by the Grignard Reaction
[0140] Under the stream of argon, 600 g of BH1 was suspended in 9
liters of anhydrous tetrahydrofuran (THF). To the resultant
suspension, 60 ml of a 32% by mass tetrahydrofuran solution of
phenylmagnesium bromide (manufactured by Tokyo Chemical Industry
Co., Ltd.) was slowly added dropwise under cooling with ice, and
the obtained mixture was stirred at 50 to 60.degree. C. for 30
minutes. To the obtained mixture, a dilute sulfuric acid was added
to decompose the unreacted substances. The reaction product was
treated by extraction with toluene, and the organic layer was
washed with a 5% by mass aqueous solution of NaOH, a 5% by mass
aqueous solution of sodium hydrogencarbonate and a 10% by mass
aqueous solution of sodium chloride and concentrated under a
reduced pressure. Toluene was added to the residue of the
concentration to form a material fluid. The material fluid was
purified using a column packed with silica gel and alumina, and the
obtained fluid was concentrated under a reduced pressure. When a
slurry was obtained, 2 liters of heptane was slowly added, and the
resultant mixture was cooled. After being cooled to 5.degree. C.,
the crystals were separated by filtration, and 490 g of yellow
crystals were obtained.
[0141] The obtained yellow crystals were purified by sublimation
under the condition of a degree of vacuum of 3.times.10.sup.-3 Pa
and a temperature of the boat of 270 to 280.degree. C., and 415 g
of BH1 treated by the Grignard reaction (referred to as GBH1,
hereinafter) was obtained.
[0142] The purity of GBH1 obtained above measured in accordance
with HPLC was 99.99% or greater as the ratio of GBH1 peak area to
all peak area. When the content of bromine present in GBH1 was
measured in accordance with the ICP-MS (burning) method, the
content was found to be smaller than 1 ppm by mass.
Example 2
Treatment of BH1 by the Reaction with an Organolithium Reagent
[0143] Under purging with nitrogen, 600 g of BH1 was dissolved into
5 liters of anhydrous toluene and 5 liters of anhydrous ether. To
the obtained solution, 75 ml of a 15% by mass hexane solution of
n-butyllithium (manufactured by Tokyo Chemical Industry Co., Ltd.)
was slowly added at -78.degree. C. The reaction mixture was stirred
at 0.degree. C. for 1 hour, and then the reaction was stopped by
adding water. The reaction product was treated by extraction with
toluene. The organic layer was washed with a 5% by mass aqueous
solution of NaOH, a 5% by mass aqueous solution of sodium
hydrogencarbonate and a 10% by mass aqueous solution of sodium
chloride and then concentrated under a reduced pressure. Toluene
was added to the residue of the concentration to form a material
fluid. The material fluid was purified using a column packed with
silica gel and alumina, and the obtained fluid was concentrated
under a reduced pressure. When a slurry was obtained, 2 liters of
heptane was slowly added, and the resultant mixture was cooled.
After being cooled to 5.degree. C., the crystals were separated by
filtration, and 495 g of yellow crystals were obtained.
[0144] The obtained yellow crystals were purified by sublimation
under the condition of a degree of vacuum of 3.times.10.sup.-3 Pa
and a temperature of the boat of 270 to 280.degree. C., and 421 g
of BH1 treated by the reaction with an organolithium reagent
(referred to as LBH1, hereinafter) was obtained.
[0145] The purity of LBH1 obtained above measured in accordance
with HPLC was 99.99% or greater as the ratio of LBH1 peak area to
all peak area. When the content of bromine present in LBH1 was
measured in accordance with the ICP-MS (burning) method, the
content was found to be smaller than 1 ppm by mass.
Example 3
Treatment of BH1 by the Suzuki Coupling Reaction
[0146] Under purging with nitrogen, 600 g of BH1, 9 liters of
toluene, 14.4 g of phenylboronic acid, 49.2 g of potassium
carbonate, 3 liters of water and 26 g of Pd(PPh.sub.3).sub.4 were
placed into a reactor, and the temperature was elevated to
75.degree. C. After the reaction mixture was aged at the same
temperature for one night, the aqueous layer was removed. The
organic layer was washed with a 5% by mass aqueous solution of
NaOH, a 5% by mass aqueous solution of sodium hydrogencarbonate and
a 10% by mass aqueous solution of sodium chloride and then
concentrated under a reduced pressure. Toluene was added to the
residue of the concentration to form a material fluid. The material
fluid was purified using a column packed with silica gel and
alumina, and the obtained fluid was concentrated under a reduced
pressure. When a slurry was obtained, 1,920 ml of heptane was
slowly added, and the resultant mixture was cooled. After being
cooled to 5.degree. C., the crystals were separated by filtration,
and 540 g of yellow crystals were obtained.
[0147] The obtained yellow crystals were purified by sublimation
under the condition of a degree of vacuum of 3.times.10.sup.-3 Pa
and a temperature of the boat of 270 to 280.degree. C., and 475 g
of BH1 treated by the Suzuki reaction (referred to as SBH1,
hereinafter) was obtained.
[0148] The purity of SBH1 obtained above measured in accordance
with HPLC was 99.99% or greater as the ratio of SBH1 peak area to
all peak area. When the content of bromine present in SBH1 was
measured in accordance with the ICP-MS (burning) method, the
content was found to be smaller than 1 ppm by mass.
Synthesis Example 2
Synthesis of N,N,N',N'-tetra(4-biphenylyl)-benzidine (HT1)
[0149] Into a three-necked flask having an inner volume of 1,000
ml, 100 g of 4-bromobiphenyl (manufactured by Tokyo Chemical
Industry Co., Ltd.), 23.1 g of benzamide (manufactured by Tokyo
Chemical Industry Co., Ltd.), 3.6 g of cuprous iodide (manufactured
by Kanto Chemical Co., Inc.) and 58 g of anhydrous potassium
carbonate (manufactured by Kanto Chemical Co., Inc.) were placed.
Then, a stirrer was placed into the flask, and rubber caps were set
at the two side inlets. A curled tube condenser for refluxing was
set at the central inlet of the flask. A three-way stopcock was set
above the condenser, and a balloon filled with argon gas was set
above the three-way stopcock. The system was purged with the argon
gas in the balloon three times using a vacuum pump.
[0150] Then, 500 ml of diethylbenzene was added by a syringe
through a rubber septum. The flask was set in an oil bath, and the
temperature was slowly elevated to 200.degree. C. while the
solution was stirred. After 6 hours, the flask was removed from the
oil bath to complete the reaction and left standing for 12 hours
under the atmosphere of argon.
[0151] The reaction solution was transferred to a separation
funnel, and 1,000 ml of dichloromethane was added to dissolve
precipitates. The organic layer was washed with 600 ml of a
saturated aqueous solution of sodium chloride and dried with
anhydrous potassium carbonate. Potassium carbonate was removed from
the organic layer by filtration, and the solvent in the obtained
organic layer was removed by distillation. To the obtained residue,
2,000 ml of toluene and 400 ml of ethanol were added. After
attaching a drying tube, the mixture was heated at 80.degree. C.,
and the residue was completely dissolved. After being left standing
for 12 hours, the solution was slowly cooled to the room
temperature so that recrystallization could be achieved.
[0152] The obtained crystals were separated by filtration and dried
in vacuum at 60.degree. C., and 74 g of
N,N-di-(4-biphenylyl)benzamide was obtained.
[0153] Into a three-necked flask having an inner volume of 3
liters, 70 g of N,N-di-(4-biphenylyl)benzamide, 31.5 g of
4,4'-diiodobiphenyl (manufactured by Wako Pure Chemical Industries
Ltd.), 1.5 g of cuprous iodide and 36 g of potassium hydroxide were
placed. A rubber cap was attached to one of the side inlets. A
curled tube condenser for refluxing was set at the central inlet of
the flask. A three-way stopcock was set above the condenser, and a
balloon filled with argon gas was set above the three-way stopcock.
The system was purged with the argon gas in the balloon three times
using a vacuum pump.
[0154] Then, 1,000 ml of xylene was added by a syringe through a
rubber septum. The flask was set in an oil bath, and the
temperature was slowly elevated to 140.degree. C. while the
solution was stirred. After stirring at 140.degree. C. for 6 hours,
the flask was removed from the oil bath and left standing for 12
hours.
[0155] After the formed precipitates were completely dissolved by
adding 3 liters of dichloromethane, the resultant solution was
transferred to a separation funnel. After washing with 3 liters of
a saturated aqueous solution of sodium chloride, the separated
organic layer was dried with anhydrous potassium carbonate. After
filtration, the solvent was removed by distillation. To the
obtained residue, 10 liters of toluene and 3 liters of ethanol were
added. After a drying tube was attached, the mixture was heated at
80.degree. C., and the residue was completely dissolved. The
resultant solution was slowly cooled to the room temperature. Then,
the precipitates were separated by filtration, washed with small
amounts of toluene and ethanol, dried in a vacuum dryer at
60.degree. C. for 3 hours and purified by sublimation under the
condition of a degree of vacuum of 3.times.10.sup.-3 Pa and a
temperature of the boat of 360 to 370.degree. C., and 70 g of
N,N,N'.N'-tetra(4-biphenylyl)benzidine (HT1) was obtained. The
purity of HT1 obtained above measured in accordance with HPLC was
99.98% as the ratio of HT1 peak area to all peak area. When the
content of bromine present in HT1 was measured in accordance with
the ICP-MS (burning) method, the content was found to be 20 ppm by
mass.
Example 4
Treatment of HT1 by Chemical Reaction
[0156] Under purging with nitrogen, 50 g of HT1, 5 liters of
toluene, 0.8 g of phenylboronic acid, 2.7 g of potassium carbonate
and 1.4 g of Pd(PPh.sub.3).sub.4 were placed into a reactor, and
the temperature was elevated to 75.degree. C. After the reaction
mixture was aged at the same temperature for one night, the
reaction mixture was cooled, and the aqueous layer was removed. The
precipitates were separated by filtration, washed with water,
methanol and acetone and purified by recrystallization using
toluene, and 47 g of yellow crystals were obtained.
[0157] The obtained yellow crystals were purified by sublimation
under the condition of a degree of vacuum of 3.times.10.sup.-3 Pa
and a temperature of the boat of 350 to 360.degree. C., and 41 g of
HT1 treated by chemical reaction (referred to as SHT1, hereinafter)
was obtained.
[0158] The purity of SHT1 obtained above measured in accordance
with HPLC was 99.99% or greater as the ratio of SHT1 peak area to
all peak area. When the content of bromine present in SHT1 was
measured in accordance with the ICP-MS (burning) method, the
content was found to be smaller than 1 ppm by mass.
Example 5
Evaluation of GBH1
[0159] A glass substrate having a size of 25 mm.times.75
mm.times.1.1 mm thickness and an ITO transparent electrode
(manufactured by GEOMATEC Company) was cleaned by application of
ultrasonic wave in isopropyl alcohol for 5 minutes and then by
exposure to ozone generated by ultraviolet light for 30
minutes.
[0160] The cleaned glass substrate having the transparent electrode
was attached to a substrate holder of a vacuum vapor deposition
apparatus. On the surface of the cleaned substrate at the side
having the transparent electrode, a film of HT1 having a thickness
of 80 nm was formed in a manner such that the formed film covered
the transparent electrode. The formed film of HT1 worked as the
hole transporting layer.
[0161] Then, a film of GBH1 having a thickness of 40 nm was formed
by vapor deposition. At the same time, an amine compound D1
expressed by the formula shown in the following as the dopant was
vapor deposited in an amount such that the ratio of the amounts by
mass of GBH1 to D1 was 40:2. The formed film worked as the light
emitting layer.
[0162] On the formed film, a film of Alq
(tris(8-hydroxyquinoline)-aluminum expressed by the formula shown
in the following) having a thickness of 20 nm was formed. The film
of Alq worked as the electron transporting layer. Thereafter, LiF
was vapor deposited to form a film having a thickness of 1 nm so
that an electron injecting layer was formed. Metallic Al was vapor
deposited on the formed film of LiF to form a metal cathode, and an
organic EL device was obtained. The color of the light emitted from
the organic EL device was blue.
[0163] The result of the measurement of the half lifetime of the
light emission when the device was driven under a constant DC
current at an initial luminance of 5,000 nit at the room
temperature is shown in Table 1.
##STR00014##
Example 6
Evaluation of LBH1
[0164] An organic EL device was prepared in accordance with the
same procedures as those conducted in Example 5 except that LBH1
was used in place of GBH1. The prepared organic EL device emitted
blue light. The result of the measurement of the half lifetime of
the light emission when the device was driven under a constant DC
current at an initial luminance of 5,000 nit at the room
temperature is shown in Table 1.
Example 7
Evaluation of SBH1
[0165] An organic EL device was prepared in accordance with the
same procedures as those conducted in Example 5 except that SBH1
was used in place of GBH1. The prepared organic EL device emitted
blue light. The result of the measurement of the half lifetime of
the light emission when the device was driven under a constant DC
current at an initial luminance of 5,000 nit at the room
temperature is shown in Table 1.
Example 8
Evaluation of SHT1
[0166] An organic EL device was prepared in accordance with the
same procedures as those conducted in Example 5 except that SHT1
was used in place of HT1, and BH1 was used in place of GBH1. The
prepared organic EL device emitted blue light. The result of the
measurement of the half lifetime of the light emission when the
device was driven under a constant DC current at an initial
luminance of 5,000 nit at the room temperature is shown in Table
1.
Example 9
Evaluation of GBH1 and SHT1
[0167] An organic EL device was prepared in accordance with the
same procedures as those conducted in Example 5 except that SHT1
was used in place of HT1. The prepared organic EL device emitted
blue light. The result of the measurement of the half lifetime of
the light emission when the device was driven under a constant DC
current at an initial luminance of 5,000 nit at the room
temperature is shown in Table 1.
Comparative Example 1
[0168] An organic EL device was prepared in accordance with the
same procedures as those conducted in Example 5 except that BH1 was
used in place of GBH1. The prepared organic EL device emitted blue
light. The result of the measurement of the half lifetime of the
light emission when the device was driven under a constant DC
current at an initial luminance of 5,000 nit AT the room
temperature is shown in Table 1.
TABLE-US-00001 TABLE 1 Light emitting Half lifetime, Hole
transporting layer (host initial layer material) luminance content
of Br content of Br 5,000 nit (ppm by mass) (ppm by mass) (h)
Example 5 HT1 GBH1 450 28 <1 Example 6 HT1 LBH1 440 28 <1
Example 7 HT1 SBH1 440 28 <1 Example 8 SHT1 BH1 460 <1 20
Example 9 SHT1 GBH1 590 <1 <1 Comparative HT1 BH1 280 Example
1 28 20
[0169] It is shown by the above results that the half lifetime was
remarkably improved when the material obtained by the
dehalogenation treatment using chemical reaction was used for the
organic EL device. In particular, the effect was more remarkable
when the materials obtained by the dehalogenation treatment were
used for both of the hole transporting layer and the light emitting
layer.
Synthesis Example 3
Synthesis of
2-(2-biphenylyl)-9,10-bis(3-(1-naphthyl)phenyl)anthracene
(BH2))
[0170] BH2 expressed by the following formula (A) was synthesized
in accordance with the following route of synthesis:
##STR00015##
(1) Synthesis of 2-biphenylyl-9,10-anthraquinone [Compound
(A-1)]
[0171] Under the atmosphere of argon, 3.4 g (14 mmole) of
2-chloro-anthraquinone, 5 g (17 mmole, 1.2 eq) of
2-biphenylylboronic acid, 0.32 g (0.35 mmole; 5% by mass Pd) of
tris(dibenzylideneacetone)dipalladium(0) and 14 g (43 mmole; 2.5
eq) of cesium carbonate were suspended in 40 ml of anhydrous
dioxane. Then, 1.1 ml (25% by mass; 0.98 mmole; 1.4 eq to Pd) of a
toluene solution of tricyclohexylphosphine was added, and the
resultant mixture was stirred at 80.degree. C. for 10 hours.
[0172] The obtained reaction mixture was diluted with 100 ml of
water and 300 ml of toluene, and insoluble components were removed
by filtration with zeolite. The organic layer was separated from
the filtrate, washed with 50 ml of a saturated aqueous solution of
sodium chloride and dried with anhydrous magnesium sulfate. The
solvent was removed by distillation, and a deep red oily substance
was obtained. The obtained oily substance was purified in
accordance with the column chromatography (the column packed with
silica gel). The purification was conducted with a mixed solvent of
hexane and 33% by mass of dichloromethane and then with a mixed
solvent of hexane and 50% by mass of dichloromethane. After the
purification, 7.1 g (the yield: 94%) of a light yellow solid
substance was obtained. The obtained solid substance was identified
to be Compound (A-1) described above in accordance with .sup.1H-NMR
and the field desorption mass analysis (FDMS). The results of the
measurements of .sup.1H-NMR and FDMS are shown in the
following.
[0173] .sup.1H-NMR (CDCl.sub.3, TMS) .delta.: 7.18 (5H, s), 7.49
(5H, s), 7.76 (2H, dd, J=6 Hz, 3 Hz), 8.08 (1H, d, J=8 Hz), 8.2-8.3
(3H, m)
[0174] FDMS calcd. for C.sub.26H.sub.16O.sub.2=360; found: m/z=360
(M.sup.+, 100)
(2) Synthesis of
2-(2-biphenylyl)-9,10-bis(3-(1-naphthyl)phenyl)-9,10-dihydroxy-9,10-dihyd-
roanthracene [Compound (A-2)]
[0175] Under the atmosphere of argon, 4.2 g (15 mmole, 2.7 eq) of
3-(1-naphthyl)-1-bromobenzene was dissolved into 25 ml of anhydrous
toluene and 25 ml of anhydrous THF, and the resultant solution was
cooled at -20.degree. C. in a dry ice/methanol bath. To the cooled
solution, 10 ml (1.59 moles/liter, 15.9 mmole, 1.06 eq) of a hexane
solution of n-butyl-lithium was added, and the obtained mixture was
stirred at -20.degree. C. for 1 hour. To the resultant mixture, 2.0
g (5.6 mmole) of 2-(2-biphenylyl)-9,10-anthraquinone [Compound
(A-1)] was added. The resultant mixture was stirred at the room
temperature for 2 hours and left standing at the room temperature
for one night.
[0176] The obtained reaction mixture was deactivated with 50 ml of
a saturated aqueous solution of ammonium chloride. The organic
layer was separated, washed with 50 ml of a saturated aqueous
solution of sodium chloride and dried with magnesium sulfate. After
the solvent was removed by distillation, a yellow oily substance
was obtained. The oily substance was purified in accordance with
the column chromatography (the column packed with silica gel). In
the purification, the elution was conducted with a mixed solvent of
hexane and 50% by mass of dichloromethane, then with
dichloromethane and with a mixed solvent of dichloromethane and 3%
by mass of methanol. After the purification, 3.1 g (the yield: 74%)
of a light yellow amorphous solid compound was obtained. The
obtained solid compound was identified to be Compound (A-2)
described above in accordance with .sup.1H-NMR. The result of the
measurements of .sup.1H-NMR is shown in the following.
[0177] .sup.1H-NMR (CDCl.sub.3, TMS) .delta.: 2.36 (1H, s), 2.89
(1H, s), 6.7-7.9 (38H, m)
(3) Synthesis of
2-(2-biphenylyl)-9,10-bis(3-(1-naphthyl)phenyl)-anthracene
(BH2)
[0178] Into 25 ml of THF, 1.1 g (1.4 mmole) of
2-(2-biphenylyl)-9,10-bis(3-(1-naphthyl)phenyl)-9,10-dihydroxy-9,10-dihyd-
roanthracene [Compound (A-2)] and 6.5 g (29 mmole, 20 eq) of
stannic chloride dihydrate were suspended. After 15 ml of a
concentrated hydrochloric acid was added, the resultant mixture was
heated under the refluxing condition for 10 hours.
[0179] The obtained reaction mixture was separated by filtration,
washed with water and methanol, successively, and dried, and a
light yellow solid substance was obtained. The obtained solid
substance was purified in accordance with the column chromatography
(the column packed with silica gel). In the purification, the
elution was conducted with a mixed solvent of hexane and 20% by
mass of dichloromethane. After the purification, 1.0 g (the yield:
97%) of a light yellow solid substance was obtained. The obtained
solid substance was identified to be BH2 described above in
accordance with .sup.1H-NMR and FDMS. The results of the
measurements of .sup.1H-NMR and FDMS are shown in the following.
The contents of halogen elements in BH2 were measured in accordance
with the ICP-MS (burning) method and found to be as follows: the
content of I: 5 ppm by mass; the content of Br: 21 ppm by mass; and
the content of Cl: 41 ppm by mass.
[0180] .sup.1H-NMR (CDCl.sub.3, TMS) .delta.: 6.93 (5H, bs),
7.2-7.9 (31H, m), 8.0-8.1 (2H, m)
[0181] FDMS calcd. for C.sub.58H.sub.38=734; found: m/z=734
(M.sup.+, 100)
[0182] .lamda.max: 407, 385, 366 nm (PhMe)
[0183] Fmax: 426, 446 nm (PhMe, .lamda.ex-405 nm)
[0184] Ip=5.69 eV (500 nW, 82 Y/eV)
[0185] Eg=2.92 eV
[0186] Tg=130.degree. C.
Example 10
Treatment of BH2 by Chemical Reaction with an Organolithium
Reagent
[0187] Under the atmosphere of argon, 2.0 g of BH2 was dissolved
into a mixed solvent of 10 ml of anhydrous THF and 10 ml of
toluene, and the obtained solution was cooled at -30.degree. C. To
the cooled solution, 1.0 ml of a 1.6 moles/liter hexane solution of
n-butyllithium was slowly added, and the resultant mixture was
stirred at -30.degree. C. for 5 hours. After 1.0 ml of water was
slowly added to the reaction fluid, the obtained mixture was
concentrated by an evaporator under a reduced pressure. The
obtained solid substance was washed with methanol and dried under a
reduced pressured. The residue was purified in accordance with the
column chromatography (the column packed with silica gel). In the
purification, the elution was conducted with a mixed solvent of
hexane and toluene (hexane/toluene=3/1 (the ratio of the amounts by
mass)). The obtained solid substance was washed with methanol and
dried under a reduced pressure, and 1.6 g (the recovery: 80%) of a
yellow solid substance was obtained. The obtained solid substance
will be referred to as LBH2.
[0188] The contents of halogen elements in the solid substance were
measured in accordance with the ICP-MS (burning) method, and it was
found that the contents of I, Br and Cl were all smaller than 5 ppm
by mass.
Example 11
Treatment of BH2 by Chemical Reaction
[0189] Under the atmosphere of argon, 2.0 g of BH2, 40 mg (0.1 eq
of BH2) of phenylboronic acid and 10 mg (0.03 eq of phenylboronic
acid) of tetrakis(triphenylphosphino)palladium(0) were dissolved
into 10 ml of anhydrous toluene, and the resultant solution was
cooled at -30.degree. C. To the cooled solution, 1.3 ml of a 2
moles/liter aqueous solution of sodium carbonate was added, and the
resultant mixture was stirred at 80.degree. C. for 6 hours. After
1.0 ml of water was slowly added to the obtained reaction fluid,
the resultant mixture was concentrated by an evaporator under a
reduced pressure. The obtained solid substance was washed with
methanol and dried under a reduced pressure. The residue was
purified in accordance with the column chromatography (the column
packed with silica gel). In the purification, the elution was
conducted with toluene and then with methylene chloride. The
obtained solid substance was washed with methanol and dried under a
reduced pressure, and 2.0 g (the recovery: 100%) of a yellow solid
substance was obtained. The obtained solid substance will be
referred to as SBH2.
[0190] The contents of halogen elements in the solid substance were
measured in accordance with the ICP-MS (burning) method, and it was
found that the contents of I, Br and Cl were all smaller than 5 ppm
by mass.
Example 12
Evaluation of LBH2
[0191] A glass substrate having a size of 25 mm.times.75
mm.times.1.1 mm thickness and an ITO transparent electrode
(manufactured by GEOMATEC Company) was cleaned by application of
ultrasonic wave in isopropyl alcohol for 5 minutes and then by
exposure to ozone generated by ultraviolet light for 30
minutes.
[0192] The cleaned glass substrate having the transparent electrode
was attached to a substrate holder of a vacuum vapor deposition
apparatus. On the surface having the transparent electrode, a film
of
N,N'-bis(4-diphenylaminophenyl)-N,N'-diphenyl-4,4'-diaminobiphenyl
(TPD232) having a thickness of 40 nm was formed in a manner such
that the formed film covered the transparent electrode. The formed
film of TPD232 worked as the hole injecting layer.
[0193] On the film of TPD232, a film of
N,N,N',N'-tetrakis(4-biphenyl)-4,4'-benzidine (BPTPD) having a
thickness of 40 nm was formed by vapor deposition. The film of
BPTPD worked as the hole transporting layer.
[0194] LBH2 and 1,6-bis(diphenylamino)pyrene in amounts such that
the ratio of the amounts by mass was 20:1 were dissolved into a
mixed solvent of dioxane and isopropyl alcohol (1:8 as the ratio of
the amounts by volume), and a 3% by mass coating solution was
prepared. Using the prepared coating solution, a light emitting
layer having a thickness of 40 nm was formed on the film of BPTPD
in accordance with the spin coating process. The obtained laminated
substrate was heated by an infrared heat source (a halogen lamp)
under a vacuum of about 10.sup.-6 Pa so that the temperature of the
substrate was elevated at 120.degree. C.
[0195] It was confirmed from the result of the measurement by the
quadrupole mass spectrometer that the residual solvents in the
films could be removed by the heating for 30 minutes. Thereafter,
the laminated substrate was transferred to the inside of the vacuum
vapor deposition apparatus by an apparatus for transfer of the
substrate while the laminated substrate was kept without contacting
the outside atmosphere. A film of Alq
(tris(8-hydroxyquinoline)aluminum, expressed by the formula shown
above) having a thickness of 30 nm was formed in accordance with
the vacuum vapor deposition process. The film of Alq worked as the
electron transporting layer.
[0196] Then, a film of lithium fluoride having a thickness of 1
.mu.m was formed in accordance with the vacuum vapor deposition
process as the electron injecting layer. On the electron injecting
layer, metallic aluminum was vapor deposited to form a metal
cathode, and an organic EL device was prepared. When a voltage of
5.0 V was applied to the device, an electric current of 2.3
mA/cm.sup.2 passed, and blue light having chromaticity coordinates
of (0.15, 0.26) was emitted at a luminance of 94 cd/m.sup.2. The
current efficiency was 4.1 cd/A and 2.61 m/W. When the device was
driven at the room temperature with a small electric current at an
initial luminance of 100 cd/m.sup.2, the half lifetime of the
luminance was 13,000 hours.
Example 13
Evaluation of SBH2
[0197] An organic EL device was prepared in accordance with the
same procedures as those conducted in Example 12 except that SBH2
was used in place of LBH2. When a voltage of 5.0 V was applied to
the device, an electric current of 2.3 mA/cm.sup.2 passed, and blue
light having chromaticity coordinates of (0.15, 0.26) was emitted
at a luminance of 92 cd/m.sup.2. The current efficiency was 4.0
cd/A and 2.51 m/W. When the device was driven at the room
temperature with a small electric current at an initial luminance
of 100 cd/m.sup.2, the half lifetime of the luminance was 12,000
hours.
Comparative Example 2
Evaluation of BH2
[0198] An organic EL device was prepared in accordance with the
same procedures as those conducted in Example 12 except that BH2
was used in place of LBH2. When a voltage of 5.0 V was applied to
the device, an electric current of 2.5 mA/cm.sup.2 passed, and blue
light having chromaticity coordinates of (0.15, 0.26) was emitted
at a luminance of 93 cd/m.sup.2. The current efficiency was 3.7
cd/A and 2.31 m/W. When the device was driven at the room
temperature with a small electric current at an initial luminance
of 100 cd/m.sup.2, the half lifetime of the luminance was 9,800
hours.
INDUSTRIAL APPLICABILITY
[0199] The aromatic compound obtained in accordance with the
process of the present invention can be advantageously used as the
material for organic EL devices, organic semiconductors and
electronic photosensitive substances.
* * * * *