JP4604592B2 - Method for producing arylamine derivative and methanol derivative used therefor - Google Patents

Description

  The present invention includes a plurality of arylamine skeleton, in particular, electrophotographic photosensitive member, a method of manufacturing a suitably arylamine derivative used as a charge-transporting material in the organic electroluminescent device or the like, and a manufacturing useful that, arylamine The present invention relates to a methanol derivative having a skeleton.

Conventionally, as a charge transport material in electrophotographic photoreceptors, displays, flat light sources, organic electroluminescence elements, organic thin film transistors, solar cells, etc., hydrazone, stilbene / styryl, triarylamine, phenothiazine, Known are low molecular organic compounds such as oxadiazole, oxazole, pyrazoline, trifuninylmethane, dihydronicotinamide, indoline, and semicarbazole, and high molecular organic compounds such as polyvinylcarbazole. .

Among these, arylamine compounds have been studied energetically as charge transport materials in electrophotographic photoreceptors for a long time since they have excellent charge transport ability and high durability against environmental fluctuations. However, research is progressing as a hole transport material in organic electroluminescence elements that are attracting attention as next-generation display devices, but the element temperature rapidly increases due to Joule heat generated when the organic electroluminescence elements are driven. The molecular motion of the hole transport material becomes active, the molecules start to aggregate and crystallization occurs in the thin film, and the amorphous nature of the thin film collapses.As a result, due to poor contact with the electric field interface or dielectric breakdown, The problem of causing an increase in drive voltage and a decrease in light emission brightness has been raised, and in order to solve the problem, High temperature of the glass transition temperature of arylamine compounds as hole transport material is desired.

On the other hand, as compounds intended to increase the glass transition temperature of charge transport materials including hole transport materials in these organic electroluminescence devices, for example, two structural units having a triarylamine skeleton are a cyclohexane ring or an adamantane ring. The compound having a molecular weight increased by being linked by an alicyclic ring (see, for example, Patent Document 1, Patent Document 2, Patent Document 3, and Patent Document 4), and further increasing its molecular weight by repeating the coupling. Compound (for example, see Patent Document 5 and Patent Document 6) and a compound in which the molecular weight of the triarylamine skeleton is increased and the two structural units are connected by an aromatic ring to increase the molecular weight (for example, , Refer to Patent Document 7).
JP-A-7-145116. JP-A-8-231475. Japanese Patent Application Laid-Open No. 2001-110572. JP 2001-167882 A. JP-A-8-100038. JP-A-8-227165. JP 2001-131541 A. These proposed arylamine compounds are, for example, a method of reacting a bis (aminoaryl) compound linked with an alicyclic ring with a halogenated aromatic compound or the like, or a biscyclic linked with an alicyclic ring. It is produced by a method of reacting a (halogenated aryl) compound with an aromatic amine or the like, a method of reacting an alicyclic compound with a triarylamine, a method of reacting bis (diarylamino) biphenyl with an alicyclic compound, or the like. However, in these conventional production methods, it is difficult to produce a compound having a different triarylamine skeleton linked to an alicyclic ring or an aromatic ring, and the degree of freedom thereof is low, and the structure control is also difficult. At the same time, it is difficult to control the degree of polymerization and the molecular weight, and it is difficult to selectively obtain the intended high molecular weight compound without fluctuation of the reaction. Was Tsu.

The present invention has been made in view of the above-described prior art. Therefore, the present invention makes it easy to produce a compound having a plurality of different arylamine skeletons, and also facilitates structural control thereof. A method for producing an arylamine derivative having a plurality of arylamine skeletons, wherein a compound can be selectively obtained, the molecular weight can be easily controlled, and a high-purity compound can be produced in high yield, and the method thereof An object of the present invention is to provide a methanol derivative having an arylamine skeleton useful for production.

As a result of intensive studies to solve the above problems, the present inventors have found that it is effective to produce a methanol derivative having an arylamine skeleton represented by benzyl alcohol as a raw material, and have completed the present invention. That is, the present invention provides a plurality of aryls represented by the following general formula (II a ) by reacting an aromatic amine with a methanol derivative having an arylamine skeleton represented by the following general formula (I a ). The production method of an arylamine derivative for producing an arylamine derivative having an amine skeleton, and a methanol derivative having an arylamine skeleton used in the production method and represented by the following general formula (I a ) .

In [Formula (Ia) and Formula (IIa), each independently of Ar ¹ and Ar ⁴ represents an A arylene group, Ar ^2, Ar ^3, and Ar ⁵ each independently have a substituent An aryl group which may be substituted, the methylene group may have a substituent R ; b is 0, 1, or 2, and when there are a plurality of Ar ¹ , Ar ² , Ar ³ , Ar ⁴ , and Ar ⁵ , each of them may be different from each other. ]

According to the present invention, it is easy to produce a compound having a plurality of different arylamine skeletons, the structure of which is easy to control, and the desired compound can be selectively obtained, and the molecular weight can be easily controlled. And a method for producing an arylamine derivative having a plurality of arylamine skeletons, and a methanol derivative having an arylamine skeleton useful for the production thereof, which can produce a high-purity compound in a high yield. Can do.

Hereinafter, embodiments of the present invention will be described in detail. However, the description of the constituent elements described below is a representative example of the embodiments of the present invention, and is appropriately modified and implemented without departing from the spirit of the present invention. can do.
The method for producing an arylamine derivative according to the present invention comprises a plurality of compounds represented by the above general formula (II) by reacting an aromatic amine with a methanol derivative having an arylamine skeleton represented by the above general formula (I). An arylamine derivative having a plurality of arylamine skeletons is produced.

In the general formulas (I) and (II), X is not particularly limited as long as it contains at least one arylamine skeleton, and any skeleton of a mono, di, or triarylamine skeleton At least one, for example, monoaryl dialkylamino skeleton, monoaryl diaralkylamino skeleton, diaryl monoalkylamino skeleton, diaryl monoaralkylamino skeleton, triarylamino skeleton, etc. An amino skeleton is preferred. These aryl groups and alkyl groups may be bonded to each other to form a cyclic structure.

Examples of the aryl group include a phenyl group, a biphenyl group, a triphenyl group, a naphthyl group, an acenaphthyl group, a fluorenyl group, an anthryl group, a phenanthryl group, and a pyrenyl group. Examples of the substituent of the methylene group include an alkyl group which may further have a substituent, an alkoxy group, an alkenyl group, an aryl group, a cyano group, a nitro group, and a halogen atom. Of these, an alkyl group, an alkenyl group and the like may be bonded to each other to form a cyclic structure, and as a, an integer in the range of 1 to 6 is suitable.

In the general formula (II), examples of the arylene group of Ar ¹ include a phenylene group, a biphenylene group, a triphenylene group, a naphthylene group, an acenaphthylene group, a fluorenylene group, an anthrylene group, a phenanthrylene group, and a pyrenylene group. Examples of the substituent of the amino group include phenyl groups, biphenyl groups, triphenyl groups, naphthyl groups, acenaphthyl groups, fluorenyl groups, anthryl groups, phenanthryl groups, pyrenyl groups and the like, and the like. The adjacent aryl groups may be bonded directly or via a hetero atom such as an oxygen atom or a sulfur atom to form a cyclic structure.

Specific examples of these methanol derivatives having an arylamine skeleton represented by the general formula (I) are shown below.

Specific examples of the arylamine derivatives represented by the general formula (II) having a plurality of arylamine skeletons are shown below.

In the present invention, among the methanol derivative having an arylamine skeleton represented by the general formula (I) and the arylamine derivative having a plurality of arylamine skeletons represented by the general formula (II), Thus, a methanol derivative represented by the following general formula (Ia) and an arylamine derivative represented by the following general formula (IIa) obtained by reacting it with an aromatic amine are preferred.

[In the formula (Ia) and the formula (IIa), Ar ¹ and Ar ⁴ each independently represent an arylene group which may have a substituent, Ar ² , Ar ³ and Ar ⁵ each independently An aryl group which may have a substituent, and a methylene group may have a substituent. b is 0, 1, or 2, and when there are a plurality of Ar ¹ , Ar ² , Ar ³ , Ar ⁴ , and Ar ⁵ , each of them may be different from each other. ]

In the present invention, a methanol derivative having an arylamine skeleton represented by the above general formula (I) and an arylamine derivative having a plurality of arylamine structures represented by the above general formula (II) Among them, a methanol derivative represented by the following general formula (Ib) and an arylamine derivative represented by the following general formula (IIb) obtained by reacting it with an aromatic amine are preferable.

[In the formulas (Ib) and (IIb), Ar ¹ and Ar ⁴ each independently represent an arylene group which may have a substituent, Ar ² , Ar ³ and Ar ⁵ each independently An aryl group that may have a substituent, Ar ⁶ represents an aryl group that may have a substituent, or an arylene group that may have a substituent; It may have a substituent. c is 0 or 1, and d is an integer of 1 to 6, and when there are a plurality of Ar ¹ , Ar ² , Ar ³ , Ar ⁴ , and Ar ⁵ , each of the plurality may be different from each other. ]

Further, in the present invention, a methanol derivative having an arylamine skeleton represented by the above general formula (I), and an arylamine derivative having a plurality of arylamine skeletons represented by the above general formula (II) Among them, a methanol derivative represented by the following general formula (Ic) and an arylamine derivative represented by the following general formula (IIc) obtained by reacting it with an aromatic amine are also preferred.

[In the formulas (Ic) and (IIc), Ar ¹ , Ar ⁴ , and Ar ⁷ each independently represent an arylene group optionally having a substituent, Ar ² , Ar ³ , and Ar ⁵ Each independently represents an aryl group which may have a substituent, and the methylene group may have a substituent. c is 0 or 1, and e is an integer of 1 to 5, and when there are a plurality of Ar ¹ , Ar ² , Ar ³ , Ar ⁴ , and Ar ⁵ , each of the plurality may be different from each other. ]

Further, in the present invention, a methanol derivative having an arylamine skeleton represented by the above general formula (I), and an arylamine derivative having a plurality of arylamine skeletons represented by the above general formula (II) Among them, a methanol derivative represented by the following general formula (Id) and an arylamine derivative represented by the following general formula (IId) obtained by reacting with an aromatic amine are also preferred.

[In Formula (Id) and Formula (IId), Ar ¹ and Ar ¹⁰ each independently represent an arylene group which may have a substituent, Ar ² , Ar ³ , Ar ⁸ and Ar ⁹ are Each independently represents an aryl group which may have a substituent. f is 0, 1 or 2, and when there are a plurality of Ar ⁸ , Ar ⁹ and Ar ¹⁰ , each of the plurality may be different from each other. ]

In the general formulas (Ia) and (IIa), the general formulas (Ib) and (IIb), the general formulas (Ic) and (IIc), and the general formulas (Id) and (IId), Ar ² , Ar ³ , Ar ⁵ , Ar ⁶ , Ar ⁸ , and Ar ⁹ aryl groups include phenyl, biphenyl, triphenyl, naphthyl, acenaphthyl, fluorenyl, anthryl, phenanthryl, pyrenyl Examples of the arylene group of Ar ¹ , Ar ⁴ , Ar ⁶ , Ar ⁷ , and Ar ¹⁰ include, for example, a phenylene group, a biphenylene group, a triphenylene group, a naphthylene group, an acenaphthylene group, a fluorenylene group, and an anthrylene group. , A phenanthrylene group, a pyrenylene group, and the like. Among them, a phenylene group and a biphenylene group are preferable.

In the present invention, the methanol derivative having an arylamine skeleton represented by the general formula (I) includes, for example, a carbonyl compound having an arylamine skeleton, lithium hydride, sodium borohydride, diisobutyllithium aluminum. A method of reducing with a reducing agent such as hydride, a method of reacting with an anionic species such as a Grignard reagent or an organolithium compound, or generating an anionic species from a compound having a halogenated arylamine skeleton, and a carbonyl compound as the anionic species It can be easily produced by a known method such as a method of reacting.

In the present invention, an arylamine having a plurality of arylamine skeletons represented by the following general formula (II) by reacting an aromatic amine with a methanol derivative having an arylamine skeleton represented by the general formula (I): In producing the derivative, the aromatic amine is not particularly limited as long as it contains at least one arylamine skeleton, and at least one skeleton of a mono-, di-, or triarylamine skeleton is used. Specific examples include monoaryldialkylamine, monoaryldialkylamine, diarylmonoalkylamine, diarylmonoaralkylamine, and triarylamine. Among them, triarylamine is preferable. .

The reaction of the aromatic amine with the methanol derivative represented by the general formula (I) is preferably performed in a solvent, and examples of the solvent include aromatic hydrocarbons such as toluene, anisole, diphenylmethane, and methylnaphthalene. , Chlorinated hydrocarbons such as methylene chloride, chloroform, 1,2-dichloroethane, chlorobenzene, dichlorobenzene, chloronaphthalene, aprotic such as dimethyl sulfoxide, N, N-dimethylformamide, N-methylpyrrolidone, hexamethylphosphoric triamide Polar solvents, alcohols such as methanol, ethanol, n-propanol, isopropanol, n-butanol, 2-butanol, polyhydric alcohols such as ethylene glycol, glycerin, diethyl ether, dibutyl ether, tetrahydrofuran Ethers such as ethylene, polyvalent ethers such as tetraethylene glycol dimethyl ether, saturated aliphatic hydrocarbons such as pentane, hexane and heptane, ketones such as acetone, methyl ethyl ketone and cyclohexanone, esters such as ethyl acetate and butyl acetate And acid solvents such as acetic acid. These may be used alone or in combination of two or more. Among these, aromatic hydrocarbons, chlorinated hydrocarbons, aprotic polar solvents, ethers, polyvalent ethers, saturated aliphatic hydrocarbons, acid solvents, and the like are preferable.

The reaction is preferably carried out in the presence of an acid catalyst. Examples of the acid catalyst include mineral acids such as hydrochloric acid, sulfuric acid and nitric acid, carboxylic acids such as trifluoroacetic acid, trichloroacetic acid and acetic acid, p-toluenesulfonic acid, Compatible acid catalysts such as sulfonic acids such as metasulfonic acid and trifluoromethanesulfonic acid, phosphoric acids such as orthophosphoric acid and metaphosphoric acid, Lewis acids such as aluminum chloride and titanium tetrachloride, and silica gel, clay, and proton ion exchange resin , ZSM-5, ZSM-12, erionite, faujasite and other incompatible acid catalysts such as zeolites, and the like, may be used alone or in combination of two or more.

The reaction is carried out rapidly only by mixing the methanol derivative represented by the general formula (I) and the aromatic amine in the solvent, preferably in the presence of the acid catalyst. In order to suppress decomposition by acid catalyst, it is preferable to shorten the contact time between the two as much as possible. For example, first, an aromatic amine and a methanol derivative are charged in a solvent, and an acid catalyst is added last, It is preferable to use a charging order such as adding an aromatic amine and an acid catalyst, and finally adding a methanol derivative.

The reaction temperature is not particularly limited, but is preferably 0 ° C. or higher and more preferably 10 ° C. or higher from the viewpoint of reaction rate. In view of the boiling point of the solvent used and the stability of the methanol derivative of the general formula (I), the temperature is preferably 200 ° C. or lower, more preferably 150 ° C. or lower.

EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to the following examples unless it exceeds the gist.

Example 1
<Production of methanol derivative (A)>
After adding 20 g of anhydrous aluminum chloride and 16 g of isobutyric chloride to 100 ml of chloroform, a solution prepared by dissolving 20 g of N, N-di-p-tolylaniline in 50 ml of chloroform was added dropwise with stirring and reacted at room temperature for 4 hours. The reaction solution was poured into 300 ml of ice water, the organic phase was separated, then washed with water, saturated aqueous sodium carbonate solution and concentrated under reduced pressure. The crude N, N-di-p-tolyl-4-isopropylcarbonylaniline obtained by concentration was dissolved in a mixed solvent of 60 ml of tetrahydrofuran and 40 ml of methanol, and 2.2 g of sodium borohydride was added to the solution. After reacting for 30 minutes at room temperature with stirring, 100 ml of toluene was added, the organic phase was separated, then washed with water and saturated aqueous sodium chloride solution, concentrated under reduced pressure, and purified by silica gel chromatography. When the obtained product was confirmed by ¹ H-NMR spectrum, it was the following methanol derivative (A) which was the target substance. The yield at that time was 22.9 g, and the yield was 90.7%. A ¹ H-NMR spectrum of the resulting methanol derivative (A) is shown in FIG.

<Production of arylamine derivative (A)>
2 g of the methanol derivative (A) obtained above and 1.7 g of N, N-di-3,4-xylylaniline were stirred in a mixed solution of 30 ml of acetic acid, 15 ml of toluene and 0.15 g of methanesulfonic acid. The mixture was reacted at 65 ° C. for 2 hours, 150 ml of toluene was added, the organic phase was separated, then washed with water, saturated aqueous sodium hydrogen carbonate solution and saturated aqueous sodium chloride solution, concentrated under reduced pressure, and subjected to silica gel chromatography. Purification gave a colorless crystalline product. When the obtained product was confirmed by IR spectrum, it was the following arylamine derivative (A) having a plurality of arylamine skeletons as a target substance, and the purity calculated from the area percentage of the peak area using LC was It was 97.2%. The yield at that time was 2.2 g, and the yield was 58.2%. The IR spectrum of the resulting arylamine derivative (A) is shown in FIG.

Example 2
<Production of methanol derivative (B)>
To 250 ml of chloroform was added 51.3 g of anhydrous aluminum chloride and 41.1 g of isobutyric chloride, and with stirring, a solution of 20 g of N, N-diphenyl-p-toluidine dissolved in 50 ml of chloroform was added dropwise and reacted at room temperature for 1 hour. After the reaction, the reaction solution was poured into 500 ml of ice water, the organic phase was separated, then washed with water, saturated aqueous sodium carbonate solution, and concentrated under reduced pressure. The crude N, N-4-diisopropylcarbonylphenyl-p-toluidine obtained by concentration was dissolved in a mixed solvent of 200 ml of tetrahydrofuran and 100 ml of methanol, and 5.7 g of sodium borohydride was added to the solution. After reacting for 30 minutes at room temperature under stirring, 250 ml of toluene was added and the organic phase was separated, then washed with water and saturated aqueous sodium chloride solution, concentrated under reduced pressure, and purified by silica gel chromatography. When the obtained product was confirmed by ¹ H-NMR spectrum, it was the following methanol derivative (B) which was the target substance. The yield at that time was 31.1 g, and the yield was 73.8%. The ¹ H-NMR spectrum of the resulting methanol derivative (B) is shown in FIG.

<Production of arylamine derivative (B)>
5 g of the methanol derivative (B) obtained above and 20 g of N, N-di-p-tolylaniline
Is reacted in a mixed solution of 140 ml of acetic acid, 50 ml of chloroform and 0.9 g of methanesulfonic acid at 65 ° C. for 1 hour with stirring, 150 ml of toluene is added, the organic phase is separated, and then water, saturated carbonate The product was washed with an aqueous sodium hydrogen solution and a saturated aqueous sodium chloride solution, concentrated under reduced pressure, and purified by silica gel chromatography to obtain a colorless crystal product. When the obtained product was confirmed by IR spectrum, it was the following arylamine derivative (B) having a plurality of arylamine skeletons as a target substance, and the purity calculated from the area percentage of the peak area using LC was It was 97.7%. The yield at that time was 6.2 g, and the yield was 69.7%. The IR spectrum of the resulting arylamine derivative (B) is shown in FIG.

Example 3
<Production of methanol derivative (C)>
To 200 ml of chloroform, 14.7 g of anhydrous aluminum chloride and 11.8 g of n-butyric chloride are added, and 15 g of N, N′-diphenyl-N, N′-di-3,4-xylylbenzidine is added to 150 ml of chloroform under stirring. The dissolved solution was added dropwise and reacted at room temperature for 1 hour. The reaction solution was poured into 500 ml of ice water, the organic phase was separated, then washed with water and saturated aqueous sodium carbonate solution, and concentrated under reduced pressure. The crude N-phenyl-N′-4-n-propylcarbonylphenyl-N, N′-di-3,4-xylylbenzidine obtained by concentration was dissolved in a mixed solvent of 100 ml of tetrahydrofuran and 50 ml of methanol. After adding 0.63 g of sodium borohydride to the solution and reacting at room temperature with stirring for 30 minutes, 100 ml of toluene was added, the organic phase was separated, and then washed with water and saturated aqueous sodium chloride solution, Concentrated under reduced pressure and purified by silica gel chromatography. When the obtained product was confirmed by ¹ H-NMR spectrum, it was the following methanol derivative (C) which was the target substance. The yield at that time was 10.2 g, and the yield was 60.1%. The ¹ H-NMR spectrum of the resulting methanol derivative (C) is shown in FIG.

<Production of arylamine derivative (C)>
2 g of the methanol derivative (C) obtained above and 4.4 g of N, N-di-p-tolylaniline were stirred at 65 ° C. with stirring in a mixed solution of 70 ml of acetic acid, 15 ml of chloroform and 0.45 g of methanesulfonic acid. The reaction is allowed to proceed for 1 hour, 150 ml of toluene is added, the organic phase is separated, then washed with water, saturated aqueous sodium bicarbonate and saturated aqueous sodium chloride, concentrated under reduced pressure, and purified by silica gel chromatography. Gave a colorless crystalline product. When the obtained product was confirmed by IR spectrum, it was the following arylamine derivative (C) having a plurality of arylamine skeletons as a target substance, and the purity calculated from the area percentage of the peak area using LC was It was 95.4%. The yield at that time was 1.9 g, and the yield was 66.7%. FIG. 7 shows the IR spectrum of the resulting arylamine derivative (C).

Example 4
<Production of methanol derivative (D)>
To 200 ml of chloroform, 14.7 g of anhydrous aluminum chloride and 11.8 g of n-butyric chloride are added, and 15 g of N, N′-diphenyl-N, N′-di-3,4-xylylbenzidine is added to 150 ml of chloroform under stirring. The dissolved solution was added dropwise and reacted at room temperature for 1 hour. The reaction solution was poured into 500 ml of ice water, the organic phase was separated, then washed with water and saturated aqueous sodium carbonate solution, and concentrated under reduced pressure. The crude N, N′-4-di-n-propylcarbonylphenyl-N, N′-di-3,4-xylylbenzidine obtained by concentration was dissolved in a mixed solvent of 100 ml of tetrahydrofuran and 50 ml of methanol. After adding 0.63 g of sodium borohydride to the solution and reacting at room temperature with stirring for 30 minutes, 100 ml of toluene was added, the organic phase was separated, and then washed with water and saturated aqueous sodium chloride solution, Concentrated under reduced pressure and purified by silica gel chromatography. When the obtained product was confirmed by ¹ H-NMR spectrum, it was the following methanol derivative (D) which was the target substance. The yield at that time was 7.4 g, and the yield was 39.1%. The ¹ H-NMR spectrum of the resulting methanol derivative (D) is shown in FIG.

<Production of arylamine derivative (D)>
4 g of the methanol derivative (D) obtained above and 8 g of N, N-di-p-tolylaniline were mixed in a mixed solution of 140 ml of acetic acid, 35 ml of chloroform and 0.9 g of methanesulfonic acid at 65 ° C. with stirring. After reacting for hours, 150 ml of toluene are added and the organic phase is separated, then washed with water, saturated aqueous sodium bicarbonate, saturated aqueous sodium chloride, concentrated under reduced pressure, and purified by silica gel chromatography, A colorless crystalline product was obtained. When the obtained product was confirmed by IR spectrum, it was the following arylamine derivative (D) having a plurality of arylamine skeletons as a target substance, and the purity calculated from the area percentage of the peak area using LC was It was 96.3%. The yield at that time was 5.33 g, and the yield was 76.6%. The IR spectrum of the resulting arylamine derivative (D) is shown in FIG.

Example 5
<Production of arylamine derivative (E)>
2.2 g of the methanol derivative (D) obtained above and 3.7 g of the following arylamine derivative having a plurality of arylamine skeletons in a mixed solution of 70 ml of acetic acid, 20 ml of chloroform, and 0.45 g of methanesulfonic acid, After reacting at 65 ° C. for 1 hour with stirring, 150 ml of toluene is added and the organic phase is separated, then washed with water, saturated aqueous sodium hydrogen carbonate solution and saturated aqueous sodium chloride solution, concentrated under reduced pressure, and chromatographed on silica gel. Purification by chromatography gave a colorless crystalline product. When the obtained product was confirmed by IR spectrum, it was the following arylamine derivative (E) having a plurality of arylamine skeletons as a target substance, and the purity calculated from the area percentage of the peak area using LC was It was 98.4%. The yield at that time was 3.2 g, and the yield was 55.5%. FIG. 9 shows the IR spectrum of the resulting arylamine derivative (E).

Comparative Example 1
To 35 ml of acetic acid, 10 g of N, N-diphenyl-p-toluidine, 7 g of n-caprinaldehyde and 0.5 g of methanesulfonic acid were added and reacted at 65 ° C. for 8 hours with stirring. Cool, add 100 ml of toluene and stir for 10 minutes to separate the organic phase, then wash with water, saturated aqueous sodium carbonate, concentrate under reduced pressure and purify by silica gel chromatography to produce colorless crystals. I got a thing. The obtained product was subjected to LC-MS analysis. The following compounds were found to be 1: 7 wt%, 2:26 wt%, 3: 3% wt, 4:48 wt%, 5: 4 wt%, 6: It was confirmed that the mixture was 12% by weight. The yield at that time was 51.6%. Compounds 1 to 6 were not separable by silica gel chromatography.

Application example 1
Using a conductive support in which an aluminum vapor deposition layer (thickness 70 nm) is formed on the surface of a biaxially stretched polyethylene terephthalate resin film (thickness 75 μm), the following undercoat layer dispersion is barred on the vapor deposition layer of the support. The coater was applied so that the film thickness after drying was 1.25 μm and dried to form an undercoat layer.
<Dispersion for undercoat layer>
Rutile type titanium oxide having an average primary particle size of 40 nm (“TTO55N” manufactured by Ishihara Sangyo Co., Ltd.), 3% by weight of methyldimethoxysilane with respect to the titanium oxide, and 2% with respect to the titanium oxide.
The slurry obtained by mixing with methanol by weight in a ball mill was dried, then heat-treated at 120 ° C. to 140 ° C. for 30 minutes, further washed with methanol and dried to obtain hydrophobically treated titanium oxide. A dispersion slurry of hydrophobized titanium oxide was obtained by dispersing with a ball mill in a mixed solvent of 1-propanol. The dispersion slurry, a mixed solvent of methanol / 1-propanol / toluene (weight ratio 7/1/2), and ε-caprolactam [following formula A] / bis (4-amino-3-methylcyclohexyl) methane [below The composition molar ratio of formula B] / hexamethylene diamine [following formula C] / decamethylene dicarboxylic acid [following formula D] / octadecamethylene dicarboxylic acid [following formula E] is 75% / 9.5% / 3% / 9.5% / 3% copolymerized polyamide pellets are heated and stirred and mixed to dissolve the polyamide pellets, and then subjected to ultrasonic dispersion treatment to obtain a hydrophobically treated titanium oxide / copolymerized polyamide. Was used as an undercoat layer dispersion with a solid content concentration of 18.0%.

Next, on the formed undercoat layer, the following charge generation layer coating solution was applied by a bar coater so that the film thickness after drying was 0.4 μm and dried to form a charge generation layer. <Coating liquid for charge generation layer>
As a charge generation material, 10 parts by weight of oxytitanium phthalocyanine having a powder X-ray diffraction spectrum by CuKα characteristic X-ray shown in FIG. 10 and 150 parts by weight of 4-methoxy-4-methylpentanone-2 are mixed, and a sand grind mill is mixed. And pulverized and dispersed for 1 hour, 160 parts by weight of the phthalocyanine dispersion and 5% by weight of polyvinyl butyral (“Denka Butyral # 6000C” manufactured by Denki Kagaku Kogyo Co., Ltd.) as a binder resin. A mixed solution of 100 parts by weight of a dimethoxyethane solution and 100 parts by weight of a 1,2-dimethoxyethane solution of 5% by weight of a phenoxy resin (“PKHH” manufactured by Union Carbide) was mixed, and 1,2-dimethoxyethane was further added. In addition, the solid content concentration was adjusted to 4.0 wt% to prepare a charge generation layer coating solution.

Next, on the formed charge generation layer, the following charge transport layer coating solution is applied by a film applicator so that the film thickness after drying becomes 25 μm, and dried to form a charge transport layer, thereby forming a laminated type. An electrophotographic photoreceptor having a photosensitive layer was produced.
<Coating liquid for charge transport layer>
Constituent repeating units having 40 parts by weight of the arylamine derivative B prepared in Example 2 as a charge transport material and 2,2-bis (4-hydroxy-3-methylphenyl) propane as an aromatic diol component as a binder resin Polycarbonate resin comprising 51 mol% and 49 mol% of structural repeating units having 1,1-bis (4-hydroxyphenyl) -1-phenylethane as an aromatic diol component, and having a terminal structure derived from pt-butylphenol (Viscosity average molecular weight 30,000) 100 parts by weight and 0.03 part by weight of silicone oil as a leveling agent are dissolved in 640 parts by weight of a tetrahydrofuran / toluene mixed solvent (weight ratio 8/2) to form a charge transport layer coating solution. Was prepared.

An electrophotographic characteristic evaluation apparatus produced according to the standard of the electrophotographic society for the obtained electrophotographic photoreceptor ["Basics and Applications of Secondary Electrophotographic Technology" (Edited by Electrophotographic Society, Corona Publishing, pages 404-405)] The photoconductor is charged so that the initial surface potential is −700 V, and the light from the halogen lamp is made to be monochromatic light of 780 nm by the interference filter as exposure light, and the LED light of 660 nm is charged as charge eliminating light. The electrical characteristics were evaluated by the cycle of exposure, potential measurement, and static elimination. At that time, the exposure light irradiation energy (μJ / cm ² ) required for the surface potential to be −350 V was measured as sensitivity, and the surface potential after irradiation with static elimination light was measured as a residual potential. The sensitivity was 0.101 μJ / cm. ^{2. The} residual potential was −36 V, and it was confirmed that the arylamine derivative B produced in Example 2 was an excellent charge transport material.

1 is a ¹ H-NMR spectrum of a methanol derivative (A) obtained in Example 1. 2 is a ¹ H-NMR spectrum of a methanol derivative (B) obtained in Example 2. 2 is a ¹ H-NMR spectrum of a methanol derivative (C) obtained in Example 3. 2 is a ¹ H-NMR spectrum of a methanol derivative (D) obtained in Example 4. 2 is an IR spectrum of the arylamine derivative (A) obtained in Example 1. 3 is an IR spectrum of the arylamine derivative (B) obtained in Example 2. 3 is an IR spectrum of the arylamine derivative (C) obtained in Example 3. 4 is an IR spectrum of the arylamine derivative (D) obtained in Example 4. 3 is an IR spectrum of the arylamine derivative (E) obtained in Example 5. 3 is a powder X-ray diffraction spectrum by CuKα characteristic X-ray of oxytitanium phthalocyanine as a charge generation material used in Application Example 1. FIG.

Claims (3)

An aromatic amine is reacted with a methanol derivative having an arylamine skeleton represented by the following general formula (Ia) to produce an arylamine derivative having a plurality of arylamine skeletons represented by the following general formula (IIa) A process for producing an arylamine derivative, characterized in that

[In the formulas (Ia) and (IIa), Ar ¹ and Ar ⁴ each independently represent an arylene group, and Ar ² , Ar ³ , and Ar ⁵ each independently have a substituent. The methylene group may have a substituent R; b is 0, 1, or 2, and when there are a plurality of Ar ¹ , Ar ² , Ar ³ , Ar ⁴ , and Ar ⁵ , each of them may be different from each other. ] The methanol derivative having an arylamine skeleton represented by the general formula (Ia) is represented by the following general formula (Ib), and a plurality of arylamine skeletons represented by the general formula (IIa) The method for producing an arylamine derivative according to claim 1, wherein the arylamine derivative having the formula is represented by the following general formula (IIb).

[In Formula (Ib) and Formula (IIb), Ar ¹ and Ar ⁴ each independently represent an arylene group, and Ar ² , Ar ³ , and Ar ⁵ each independently have a substituent. Ar ⁶ represents an aryl group which may have a substituent, or an arylene group which may have a substituent, and the methylene group may have a substituent R. Good. c is 0 or 1, and d is an integer of 1 to 6, and when there are a plurality of Ar ¹ , Ar ² , Ar ³ , Ar ⁴ , and Ar ⁵ , each of the plurality may be different from each other. ] 3. The method for producing an arylamine derivative according to claim 1, wherein an acid catalyst is present in the reaction of the aromatic amine.

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