JPH11189571A - Method for producing stilbene compound - Google Patents

Abstract

(57) [Summary] (Modifications) [PROBLEMS] To provide a novel method for producing a stilbene compound suitable for an electrophotographic photoreceptor. SOLUTION: A corresponding aldehyde of the general formula II is heated and reacted in the presence of a reagent prepared from chlorodiphenylphosphine and sodium hydride to synthesize a stilbene compound of the general formula I. (R ¹ , R ² , R ³ and R ⁴ represent hydrogen, halogen, an alkyl or alkoxy group which may have a substituent, and R ¹ ＲR ² , R ³ ＲR ⁴ and R ¹ And R ²
And the bonding positions of R ³ and R ⁴ in the benzene ring are the same, except when R ¹ , R ² , R ³ and R ⁴ are all hydrogen)

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a stilbene compound suitable for an electrophotographic photoreceptor.

[0002]

2. Description of the Related Art In recent years, a so-called function-separated type electrophotographic photosensitive member in which charge carrier generation and transfer functions are shared by different compounds has been the mainstream of development. It is also being converted. As the charge carrier transfer medium, there are a case where a polymer photoconductive compound such as polyvinyl carbazole is used and a case where a low molecular weight photoconductive compound is dispersed and dissolved in a binder polymer.

In particular, organic low-molecular-weight photoconductive compounds include:
As the binder, a polymer having excellent film properties, flexibility, adhesiveness, and the like can be selected, so that a photosensitive member that is easy and has excellent mechanical properties can be obtained. A stilbene-based compound is known as a suitable organic low-molecular-weight charge carrier transfer medium (for example, JP-A-60-196768). As a method for producing such a stilbene-based compound, titanium trichloride and potassium, titanium trichloride and lithium aluminum hydride, titanium tetrachloride and zinc, A method is known in which a corresponding aryl aldehyde is reacted in the presence of a reagent such as tungsten chloride and butyl lithium.

[0004]

SUMMARY OF THE INVENTION The present invention provides a novel method for producing a stilbene compound suitable for providing a high-sensitivity and high-durability electrophotographic photoreceptor.

[0005]

That is, the gist of the present invention resides in the following general formula [I]:

[0006]

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Wherein R ¹ , R ² , R ³ and R ⁴ are each a hydrogen atom, a halogen atom, an alkyl group which may have a substituent or an alkoxy group which may have a substituent. R ¹ = R ² , wherein R ¹ and R ² have the same bonding position in each benzene ring, R ³ = R ⁴ , and R ³ and R ⁴ And the bonding position in each benzene ring is the same, but R ¹ ,
A method of manufacturing a stilbene compound represented by R ^2, except when R ³ and R ⁴ are all hydrogen atoms), the following general formula [II]

[0008]

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(Wherein R ¹ and R ³ have the same meanings as in the general formula [I]) and react by heating in the presence of a reagent prepared from chlorodiphenylphosphine and sodium hydride. And a method for producing a stilbene compound.

[0010]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below in detail.
In the general formula [I], R ¹ , R ² , R ³ and R
⁴ is a hydrogen atom; a halogen atom such as a chlorine atom, a bromine atom and an iodine atom; an alkyl group such as a methyl group, an ethyl group, a propyl group, a butyl group and a hexyl group; an alkoxy group such as a methoxy group, an ethoxy group and a butoxy group. Represents a group. These alkyl groups and alkoxy groups may have a substituent. Examples of the substituent include a hydroxyl group; a halogen atom such as a chlorine atom, a bromine atom and an iodine atom; a methyl group, an ethyl group, a propyl group and a butyl group. Alkyl groups such as methoxy, ethoxy and butoxy groups; allyl groups; aralkyl groups such as benzyl group, naphthylmethyl group and phenethyl group; aryloxy groups such as phenoxy group and toloxy group; Arylalkoxy groups such as benzyloxy group and phenethyloxy group; aryl groups such as phenyl group and naphthyl group; arylvinyl groups such as styryl group and naphthylvinyl group; dialkylamino groups such as dimethylamino group and diethylamino group; diphenylamino group A diarylamino group such as a dinaphthylamino group; a dibenzylamino group; Diaralkylamino groups such as Nechiruamino group;
Diheterocyclic amino groups such as dipyridylamino group and dithenylamino group; diallylamino group; and disubstituted amino groups obtained by combining the above amino group substituents.

However, in the general formula [I], R ¹
ＲR ² , the bonding positions of R ¹ and R ² in the respective benzene rings are the same, R ³ ＝ R ⁴ ,
The bonding positions of R ³ and R ⁴ in the respective benzene rings are the same, except when all are hydrogen atoms. Hereinafter, typical examples of the stilbene compound represented by the general formula [I] will be described.

In the following examples, R ¹ , R ² ,
Only the chemical formulas of the substituents of R ³ and R ⁴ and the bonding positions on the benzene ring are shown, but unless otherwise specified, these substituents are hydrogen atoms. The bonding positions of the substituents of R ¹ , R ² , R ³ and R ⁴ on the benzene ring are set such that the carbon atom of the benzene ring bonded to the nitrogen atom is 1, the adjacent carbon atom is 2, and 4, 5, and 6 are represented by the numbers.

[0013]

TABLE 1 Compound No. Compound Example 1 R ¹ and R ² ; -Cl (position 4) R ³ and R ⁴ ; -Cl (position 4) 2 R ¹ and R ² ; -Cl (position ³ ) R ³ and R ⁴ ; Cl (position 4) 3 R ¹ and R ² ; -CH ₃ (position 4) R ³ and R ⁴ ; -CH ₃ (position 4) 4 R ¹ and R ² ; -C ₂ H ₅ (position 4 Position) 5 R ¹ and R ² ; -CH ₃ (position 3) R ³ and R ⁴ ; -OCH ₃ (position 4) 6 R ¹ and R ² ; -OCH ₃ (position 4) 7 R ¹ and R ² ; —OC ₂ H ₅ (position 4) 8 R ¹ and R ² ; —OC ₃ H ₇ (position 3) In the present invention, the stilbene compound represented by the above general formula [I] is converted to A target compound is obtained by subjecting the corresponding aldehyde compound to a two-molecule condensation reaction in the presence of a reaction reagent.

This method will be described in detail below.

[0015]

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An aldehyde represented by the general formula [II] (wherein R ¹ and R ³ have the same meaning as in the general formula [I]) is tetrahydrofuran,
The compound represented by the general formula [I] can be obtained by reacting with a reagent prepared from chlorodiphenylphosphine and sodium hydride in a known organic solvent inert to the reaction such as dioxane under heating. At this time, any one of a cis form, a trans form and a mixture of the cis form and the trans form is obtained. (In the following formula, the general formula [I] represents one of a cis-form, a trans-form, and a mixture of the cis-form and the trans-form.) In order to suppress a side reaction, pyridine, triethylamine, tri-n -Butylamine,
A tertiary amine such as 1,8-bis (dimethylamino) naphthalene may be added.

In these reactions, in some cases,
After completion of each step or after completion of all the steps, a highly purified product can be obtained by a known purification means such as recrystallization purification, sublimation purification, and column purification. The stilbene compound represented by the general formula [I] exhibits extremely excellent performance as an organic photoconductor. Particularly, when used as a charge transfer medium, a photosensitive member having high sensitivity and excellent durability can be provided.

[0018]

EXAMPLES Next, the present invention will be described more specifically with reference to Examples, but the present invention is not limited to the following Production Examples and Examples as long as the gist of the present invention is not exceeded. In the examples, “parts” means “parts by weight”. Example 1 To a solution of 3.7 g of chlorodiphenylphosphine in 17 ml of diethylene glycol dimethyl ether was added 0.3 g of water, and then 1.3 g of sodium hydride (60%). Then, 4-methoxy-triphenylamine aldehyde

[0019]

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After adding 4.0 g, the mixture was heated under reflux for 30 minutes. After cooling, 10 ml of water was added to the reaction system.
By performing extraction, concentration and purification treatments in the usual manner,
1.5 g of yellow crystals (melting point: 157-159 ° C.) were obtained. This compound was found to be a stilbene compound (Compound No. 6) represented by the following structural formula by the following elemental analysis, mass spectrometry, and infrared absorption spectrum measurement (FIG. 1). (Elemental analysis value) C% H% N% as C ₄₀ H ₃₄ N ₂ O ₂ Measured value 83.60 5.96 4.87 Actual value 83.51 6.07 4.98 (Mass spectrometry result) C ₄₀ as _{H 34 N 2 O 2, M} . W. = 574 M + = 574

[0021]

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Application Example 1.0 part of a titanium oxyphthalocyanine pigment and 0.5 part of polyvinyl butyral (polyvinyl butyral # 6000, manufactured by Denki Kagaku Kogyo KK) are mixed with 30 parts of 4-
Methoxy-4-methylpentanone-2 (Mitsubishi Chemical Corporation)
(Manufactured by K.K.).

This dispersion was applied to a 100 μm-thick aluminum film deposited on a polyester film with a wire bar so that the weight after drying was 0.2 g / m ² , and then dried to form a charge. A generator layer was formed. On top of this, 70 parts of the stilbene compound produced in Example 1 and the polycarbonate resin shown below

[0024]

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A coating solution prepared by dissolving 100 parts in 900 parts of dioxane was applied and dried to form a charge transfer layer having a thickness of 17 μm. The sensitivity, that is, half-exposure amount of the electrophotographic photosensitive member having the photosensitive layer composed of two layers obtained as described above was 2.6 μW / cm ² . The half-exposure amount is determined by first charging the photoreceptor in a dark place by a corona discharge of -4.8 kV, and then exposing it to light of 775 nm, and measuring the exposure amount required for the surface potential to attenuate from 500 V to 250 V. I asked.

[0026]

According to the present invention, a stilbene compound suitable for an electrophotographic photosensitive member can be economically synthesized.

[Brief description of the drawings]

FIG. 1 is an infrared absorption spectrum of a stilbene compound obtained in Example 1.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁶ Identification symbol FI C09B 23/00 C09B 23/00 J G03G 5/06 313 G03G 5/06 313 312

Claims (1)

[Claims] 1. A compound represented by the following general formula [I] (Wherein, R ¹ , R ² , R ³ and R ⁴ each represent a hydrogen atom, a halogen atom, an alkyl group which may have a substituent or an alkoxy group which may have a substituent. And R ¹ = R ² , wherein the bonding positions of R ¹ and R ² in the respective benzene rings are the same, and R ³ =
R ⁴ and R ³ and R ⁴ have the same bonding position in the respective benzene rings, except that R ¹ , R ² , R ³ and R ⁴ are all hydrogen atoms) A method for producing a stilbene compound represented by the following general formula [I
I] embedded image Wherein R ¹ and R ³ are as defined in the general formula [I], and reacted by heating in the presence of a reagent prepared from chlorodiphenylphosphine and sodium hydride. For producing a stilbene compound.