JP5728860B2 - N-phenyl-diphenylisoindole derivatives and process for producing them - Google Patents

Description

  The present invention relates to a novel and useful N-phenyl-diphenylisoindole derivative as an organic photoconductor, and a method for producing the same.

  In recent years, there has been a remarkable development in information processing system machines using electrophotography. In particular, laser printers and digital copying machines that convert information into digital signals and record information using light have significantly improved print quality and reliability. Furthermore, they have been applied to laser printers or digital copiers capable of full-color printing by fusing with high-speed technology.

As photoconductors used in these electrophotographic laser printers and digital copying machines, those using organic photosensitive materials (OPC) are generally widely used for reasons such as cost, productivity and pollution-free. Applied. The layer structure of the OPC photoreceptor is roughly divided into a single layer type and a function separation type laminated structure. The first practical OPC, the PVK-TNF charge transfer complex type photoreceptor, was the former single layer type.
On the other hand, in 1968, PVK / a-Se laminated photoconductors were invented independently by Hayashi and Regensburger, later by 1977 Melz et al. And 1978 by Schlosser, an organic pigment dispersion layer and an organic low molecular weight dispersion polymer layer. A multi-layer photoconductor in which all photosensitive layers are made of organic materials has been announced. These functions are separated from the concept of a charge generation layer (CGL) that absorbs light and generates charge, and a charge transport layer (CTL) that injects and transports the charge generated by CGL and neutralizes the surface charge. Also called a mold-laminated photoconductor. This development has dramatically improved sensitivity and durability compared to single-layer photoconductors. In addition, materials with different functions, called charge generation materials (CGM) and charge transport materials (CTM), can be designed individually, so the selection range of these materials has greatly increased. For these reasons, the function-separated laminated photoconductor has the mainstream layer structure of the current OPC photoconductor. The mechanism of electrostatic latent image formation in the function-separated type photoconductor is that when the photoconductor is charged and then irradiated with light, the light passes through the charge transport layer and is absorbed by the charge generation material in the charge generation layer to generate a charge. . Charges generated thereby are injected from the interface between the charge generation layer and the charge transport layer to the charge transport layer, and then moved through the charge transport layer by an electric field to form an electrostatic latent image by canceling the surface charge of the photoreceptor. To do.

In recent years, the high-speed response of a photoconductor has become an even more important issue as the diameter of the photoconductor is reduced (the time between exposure and development is shortened) as the electrophotographic apparatus is increased in speed or downsized.
As commercialized charge transport materials, 1,1-bis (p-diethylaminophenyl) -4,4-diphenyl-1,3-butadiene (Japanese Patent Laid-Open No. 62-30255 of Patent Document 1), 5 -[4- (N, N-di-p-tolylamino) benzylidene] -5H-dibenzo [a, d] cycloheptene (Japanese Patent Application Laid-Open No. 63-225660), 9-methylcarbazole-3-aldehyde 1,1-diphenylhydrazone, pyrene-1-aldehyde 1,1-diphenylhydrazone (Japanese Patent Application Laid-Open No. 58-159536 of Patent Document 3), 4′-bis (4-methylphenyl) amino-α-phenylstilbene, N, N′-diphenyl-N, N′-bis (3-methylphenyl)-[1,1′-biphenyl] -4,4′-diamine, 9,9-dimethyl-2- (di-p-to- Arylamino), and the like fluorene. A general charge transport layer is a solid solution film of about 10 to 30 μm in which these low molecular charge transport materials are molecularly dispersed in a binder resin. As the binder resin, bisphenol-based polycarbonate resin, polyarylate resin, or a copolymer of these with other resins is used in most electrophotographic photoreceptors. However, these charge transport materials are not responsive enough to accommodate future faster process speeds.

  Therefore, in view of the above prior art, an object of the present invention is to provide an N-phenyl-diphenylisoindole derivative useful as an organic photoconductor for obtaining a highly responsive photoconductor and a method for producing the same. is there.

This problem is solved by the following (1) to (2).
That is, (1) “the following general formula (1)

（Ｒ^１、Ｒ^２は水素原子、置換もしくは無置換のアルキル基、置換もしくは無置換のアルコキシ基、置換もしくは無置換のフェニルまたは置換もしくは無置換のフェノキシ基を表わし、Ｒ^３は水素原子、置換もしくは無置換のアルキル基、置換もしくは無置換のアルコキシ基、置換もしくは無置換のフェニルまたは置換もしくは無置換のフェノキシ基を表わし、もしくは下記一般式（２）を表わす。）；

(R ¹ and R ² represent a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted phenyl or a substituted or unsubstituted phenoxy group, and R ³ represents a hydrogen atom, a substituted Or an unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted phenyl or a substituted or unsubstituted phenoxy group, or the following general formula (2).

Ｒ^５，Ｒ^６は置換もしくは無置換のアルキル基、置換もしくは無置換のフェニル基を表わす。また、ｌは１から４の整数、ｍ，ｎは１から５の整数を表わす。）で表わされるＮ−フェニル−ジフェニルイソインドール誘導体。」：

R ⁵ and R ^{6 each} represents a substituted or unsubstituted alkyl group or a substituted or unsubstituted phenyl group. L represents an integer of 1 to 4, and m and n represent integers of 1 to 5. N-phenyl-diphenylisoindole derivatives represented by ":

(2) A process for producing an N-phenyl-diphenylisoindole derivative of the above general formula (1), which comprises reacting a diketone derivative of the following general formula (3) with an aniline derivative of the following general formula (4) ;

（式中、Ｒ^１、Ｒ^２、Ｒ^３、ｌ、ｍ、ｎは前記と同様の基、整数を表す。）。」。

(Wherein R ¹ , R ² , R ³ , l, m, and n represent the same groups and integers as described above). "

As it is apparent from the following detailed and specific description, the novel N- phenyl represented before following general formula (1) - diphenyl isoindole derivatives, organic transistors, organic EL devices, conductivity, such as organic solar cells It is useful as a material, and particularly useful as a photoconductive material in an electrophotographic photoreceptor. Further, this is extremely useful as a charge transport material in a so-called function-separated type photoreceptor using an organic pigment or an inorganic pigment as a charge generation material.

1 is an infrared absorption spectrum diagram (KBr tablet method) of N- (3-methylphenyl) -2,5-diphenylisoindole of the present invention obtained in Example 1. FIG.

Hereinafter, embodiments of the present invention will be described in detail.
As described above, the N-phenyl-diphenylisoindole derivative represented by the general formula (1) is a novel derivative, and the corresponding diketone derivative represented by the general formula (3) and the general formula (4). It can be produced by reacting the aniline derivative represented.
In order to produce these, the raw material mixture is reacted with a catalytic amount of paratoluenesulfonic acid monohydrate and the like in the presence of a solvent at a temperature of about 150 to 250 ° C., and the reaction solution is reacted with dichlorodicyanoquinone or the like. It can be produced by oxidizing with an oxidizing agent. Examples of the reaction solvent include nitrobenzene, chlorobenzene, dichlorobenzene, trichlorobenzene, quinoline, xylene, N, N-dimethylformamide, dimethyl sulfoxide, N-methylpyrrolidone, 1,3-dimethyl-2-imidazolidinone and the like. it can.

N- phenyl represented before following general formula (1) - diphenyl isoindole derivative, diketone derivative represented by the general formula (3), R ¹ in the aniline derivative represented by the general formula ^(4), R ² and R ^As specific examples of the ^three groups, the alkyl group includes a lower alkyl group such as a methyl group, an ethyl group, a propyl group, and a butyl group, and the alkoxy group includes a lower group such as a methoxy group, an ethoxy group, a propoxy group, and a butoxy group. An alkoxy group is mentioned. Further, examples of the substituent in the alkyl group and alkoxy group include a phenyl group, a halogen atom, an alkoxy group, and a phenyloxy group. Examples of the substituent in the phenyl group and phenoxy group include a lower alkyl group such as a methyl group. , Ethyl group, propyl group, butyl group and the like, lower alkoxy groups such as methoxy group, ethoxy group, propoxy group, butoxy group and halogen atoms such as fluorine, bromine and chlorine.

At diphenyl isoindole derivatives, organic transistors, organic EL element, it is also useful as conductive materials such as organic solar cells especially in electrophotographic photoconductor - novel N- phenyl represented before following general formula (1) It is useful as a photoconductive material. Further, this is extremely useful as a charge transport material in a so-called function-separated type photoreceptor using an organic pigment or an inorganic pigment as a charge generation material.

  Examples of organic pigments include CI Pigment Blue 25 (Color Index CI 21180), CI Pigment Red 41 (CI 21200), CI Acid Red 52 (CI 45100), CI Basic Red 3 (CI 45210), and azo pigments having a carbazole skeleton ( JP-A-53-95033), azo pigments having a distyrylbenzene skeleton (JP-A-53-133445), azo pigments having a triphenylamine skeleton (described in JP-A-53-132347) ), An azo pigment having a dibenzothiophene skeleton (described in JP-A-54-21728), an azo pigment having an oxadiazole skeleton (described in JP-A-54-12742), an azo pigment having a fluorenone skeleton ( Described in JP-A-54-22834), azo pigments having a bis-stilbene skeleton (described in JP-A-54-17733), azo having a distyryloxadiazole skeleton Fee (described in JP-A-54-2129), (described in JP 54-14967 JP) azo pigments having a distyryl carbazole skeleton, azo pigments such as azo pigments having a benzanthrone skeleton. For example, CI Pigment Blue 16 (CI 74100), Y-type oxotitanium phthalocyanine (Japanese Patent Laid-Open No. 64-17066), A (β) -type oxotitanium phthalocyanine, B (α) -type oxotitanium phthalocyanine, I-type oxotitanium phthalocyanine (Described in JP-A-11-21466), type II chlorogallium phthalocyanine (Iijima et al., Chemical Society of Japan, 67th Spring Annual, 1B4, 04 (1994)), type V hydroxygallium phthalocyanine (Damon et al., Chemical Society of Japan) 67th Spring Annual, 1B4, 05 (1994)), phthalocyanine pigments such as X-type metal-free phthalocyanine (US Pat. No. 3,816,118), C-Ibat Brown 5 (CI 73410), C-I Vat Die (CI 73030), etc. Indigo pigment, Argo Scarlet B (manufactured by Bayer), Intense Scar Tsu door R (manufactured by Bayer Co., Ltd.) perylene pigments such as. These materials may be used alone or in combination of two or more. In addition, inorganic pigments such as selenium, selenium-tellurium, cadmium sulfide, and α-silicon can also be used.

  Hereinafter, the present invention will be described in detail with reference to examples.

[Production of N- (3-methylphenyl) -2,5-diphenylisoindole]

  A diketone derivative of the following structural formula (5) (4.36 g, 15.0 mmol), 3-methyltoluidine (4.82 g, 45.0 mmol), 1,2,4-trichlorobenzene were mixed and mixed at 200 ° C. with 3 Stir for hours. After cooling to room temperature, the reaction solution was poured into methanol to precipitate a precipitate. The precipitate was collected by filtration, dissolved in 100 ml of dichloromethane, 2,3-dicyano 4,5-dichloroquinone (3.0 g, 13.2 mmol) was added, and the mixture was stirred at room temperature for 30 minutes. Water was added thereto, extracted with dichloromethane, and washed with water. The black solid obtained by concentrating the organic layer under reduced pressure was subjected to silica gel column treatment [eluent: dichloromethane], and light yellow powder N- (3-methylphenyl) -2,5- represented by the following structural formula (5) 1.0 g (yield 30.6%) of diphenylisoindole was obtained.

The melting point of the obtained derivative was 201.5 to 202.0 ° C., and the elemental analysis value thereof was as follows as C ₂₇ H ₂₁ N.
C H N
Actual value 90.2 5.9 3.9
Calculated value 90.2 5.9 3.8
The infrared absorption spectrum (KBr tablet method) of this derivative is shown in FIG.

[Production of N- (4-methylphenyl) -2,5-diphenylisoindole]
The other N-phenylisoindole derivative was obtained under the same conditions as in Example 1. Table 1 shows chemical structural formulas, melting points, and elemental analysis values of the obtained derivatives.

[Production of N- (3-methoxymethylphenyl) -2,5-diphenylisoindole]
The other N-phenylisoindole derivative was obtained under the same conditions as in Example 1. Table 1 shows chemical structural formulas, melting points, and elemental analysis values of the obtained derivatives.

[Production of N- (4-methoxymethylphenyl) -2,5-diphenylisoindole]
The other N-phenylisoindole derivative was obtained under the same conditions as in Example 1. Table 1 shows chemical structural formulas, melting points, and elemental analysis values of the obtained derivatives.

[Application Example 1]
Dissolve 1 part of N-phenyl-diphenylisoindole derivative represented by the above formula (Chemical Formula 5) as a charge transport material in a resin solution of 1 part of polycarbonate resin [Panlite K-1300 manufactured by Teijin Ltd.] and 8 parts of tetrahydrofuran. This solution was applied onto an aluminum plate with a doctor blade and dried at 80 ° C. for 5 minutes and then at 135 ° C. for 20 minutes to form a thin film having a thickness of about 15 μm. A gold electrode was further deposited on the film to prepare a sandwich cell. When the carrier mobility was measured by the time-of-flight method using the element configured as described above, a high-speed carrier mobility of 7.6 × 10 ⁻⁴ cm ² V ⁻¹ s ^{−1 at} an electric field strength of 250,000 Vcm ⁻¹ . showed that.

[Comparative Example 1]
When an amine compound represented by the following structural formula (7) was subjected to the same operation as in the application example, a thin film, a sandwich cell was prepared, and carrier mobility was measured, and 1.2 × 10 ⁻⁴ cm at an electric field strength of 250,000 Vcm ⁻¹ . ² V ⁻¹ s ⁻¹ .

JP 62-30255 A JP-A-63-225660 JP 58-159536 A

Claims (2)

Structural formula (8)

Diphenyl isoindole derivative - N- phenyl represented in.
A process for producing an N-phenyl-diphenylisoindole derivative of the above structural formula (8) , wherein a diketone derivative of the following structural formula (5) is reacted with an aniline derivative of the following structural formula (9) .

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