JPH09216855A - Acenaphthene compound - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain an acenaphthene compound having an excellent charge transporting activity and useful for an electrophotographic photoreceptor, an organic electroluminescent element, etc. SOLUTION: An acenaphthene compound expressed by formula I [Ar1 is an aryl; Ar2 is a phenylene, a naphthylene, etc.; R1 and R2 are each H, an alkoxy, etc.; X is H, an alkyl, etc.; Y is an aryl or a group expressed by formula II; R3 is H, a halogen, etc.; Z is H or an aryl; (m) and (n) is each an integer of 0-4], e.g. 5- N-[4-(2,2-diphenylviinylphenyl)]-N-phenylamino}acenaphthene. A compound of formula I is obtained e.g. by carrying our a condensation reaction of a diarylamine compound of formula III with a halogenated aryl compound expressed by the formula AAr2 H (A is Cl, Br or I), formylating the obtained triarylamine compound with N,N-dimethylformaldehyde, phosphorus oxychloride, etc., to obtain an aldehyde compound and further reacting a phosphoric acid ester with the aldehyde compound.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel acenaphthene compound which is useful as a charge transport agent used in electrophotographic photoreceptors, organic electroluminescent devices and the like.

[0002]

2. Description of the Related Art As an electrophotographic photosensitive member used in an electrophotographic system, an inorganic photosensitive member containing an inorganic photoconductive compound such as selenium, zinc oxide, cadmium sulfide or silicon as a main component, a charge generating agent and a low There is an organic photoconductor using an organic compound in which a charge transporting agent having a molecular weight or a high molecular weight is dispersed in a binder resin. The electrophotographic method mentioned here is
Generally, in the dark on the surface of the photoconductor using a photoconductive material, for example by charging by corona discharge, exposed to this,
This is a type of image forming method in which an electrostatic latent image is obtained by selectively dissipating the electric charge in the exposed portion, visualized using a toner, and then transferred and fixed on paper or the like to obtain an image. Inorganic photoreceptors have many advantages and have been widely used until now,
For example, selenium is difficult to manufacture, has a high manufacturing cost, is vulnerable to heat and mechanical shock, and is easily crystallized, resulting in deterioration in performance. Zinc oxide and cadmium sulfide have problems in moisture resistance and mechanical strength, and the dye added as a sensitizer is deteriorated by electrification and exposure, resulting in poor durability. Silicon is also difficult to manufacture and uses a highly irritating gas, so it is expensive and sensitive to humidity.

In recent years, organic photoreceptors using various organic compounds have been studied and widely used for the purpose of overcoming the drawbacks of these inorganic photoreceptors. Organic photoreceptors include a single-layer photoreceptor in which a charge generating agent and a charge transporting agent are dispersed in a binder resin, and a laminated photoreceptor in which a charge generating layer and a charge transporting layer are functionally separated. The function-separated type organic photoconductor has been extensively researched and widely used because of its wide choice of materials and the fact that a photoconductor having any desired performance can be produced relatively easily by combining them.

Examples of the charge generating agent include azo compounds,
Many organic compounds such as bisazo compounds, trisazo compounds, tetrakisazo compounds, thiapyrylium salts, squarylium salts, azurenium salts, cyanine dyes, perylene compounds, metal-free or metal phthalocyanine compounds, polycyclic quinone compounds, thioindigo compounds, or quinacridone compounds. Pigments and dyes have been proposed and put into practical use.

As the charge transfer agent, for example, Japanese Patent Publication No. 34-
Oxadiazole compounds described in JP-A-5466, JP-A-56
No. 123544, Oxazole Compound, Japanese Examined Patent Publication No. 5
JP-A 2-41880, Pyrazoline Compound, JP-B-55
-42380 gazette and Japanese Patent Publication No. 61-40104 gazette,
JP-B-62-35673, JP-B-63-3597
No. 6, hydrazone compound, Japanese Patent Publication No. 58-32372
Compounds disclosed in Japanese Patent Publication No. 63-18738, Japanese Patent Publication No. 63-19867, and Japanese Patent Publication No. 3-393.
No. 06 stilbene compound, JP-A-62-3025
For example, there is a butadiene compound disclosed in Japanese Patent No. Organic photoconductors using these charge-transporting materials have excellent properties and some have been put into practical use, but those that sufficiently satisfy the properties required for electrophotographic photoconductors have not yet been obtained. The current situation is not.

[0006]

The charge transfer agent used in the organic photoreceptor has not only the sensitivity and other characteristics as a photoreceptor, but also a chemical stability that withstands light, ozone, and electrical loads. Stability and durability are required so that the sensitivity does not decrease even after repeated use or long-term use. An object of the present invention is to provide a novel acenaphthene compound which is useful as a charge transporting agent and has a property of sufficiently satisfying the characteristics as an electrophotosensitive material.

[0007]

According to the present invention, there is provided an acenaphthene compound represented by the following general formula (1).

[0008]

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[In the formula, Ar ₁ represents an aryl group which may have a substituent, and Ar ₂ represents a phenylene group, a naphthylene group, a biphenylene group or an anthrylene group which may have a substituent; ₁ represents a hydrogen atom, a lower alkyl group or a lower alkoxy group, X represents a hydrogen atom, an alkyl group which may have a substituent or an aryl group which may have a substituent, and Y represents a substituent. An aryl group which may be used or the following general formula (2)

[0010]

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(Wherein R ₂ represents a hydrogen atom, a lower alkyl group or a lower alkoxy group, R ₃ represents a hydrogen atom, a halogen atom or a lower alkyl group, Z represents a hydrogen atom or a substituent) Represents an aryl group, and m and n represent an integer of 0 to 4). ]

The acenaphthene compound represented by the above general formula (1) of the present invention is a novel compound, and these compounds are generally synthesized from the corresponding amino compounds by N-arylation reaction such as Ullmann reaction. The triarylamine compound is formylated and synthesized by a modified Wittig reaction with the corresponding phosphonate ester. Formylation is generally performed by the Vilsmeier reaction. For example, the following general formula (3)

[0013]

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[In the formula, R ₁ and Y are represented by the general formula (1)
Has the same meaning as ] A diarylamine compound represented by the following general formula (4)

[0015]

[Chemical 6]

[In the formula, Ar ₂ has the same meaning as in the general formula (1), and A represents a chlorine atom, a bromine atom or an iodine atom. ] The following general formula (5) obtained by subjecting a halogenated aryl compound represented by

[0017]

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[In the formula, Ar ₂ , R ₁ and Y have the same meanings as in the general formula (1). ] The triarylamine compound represented by the formula [6] is subjected to formylation with N, N-dimethylformaldehyde and phosphorus oxychloride.

[0019]

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[In the formula, Ar ₂ , R ₁ and Y have the same meaning as in the general formula (1). ] The aldehyde compound represented by this is obtained. Next, the following general formula (7) is added to the aldehyde compound.

[0021]

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[In the formula, Ar ₁ and X have the same meanings as in the general formula (1), and R ₄ represents a lower alkyl group. ] The acenaphthene compound of the present invention represented by the general formula (1) is obtained by reacting the phosphonate represented by In the amine compound of the present invention represented by the general formula (1), the following general formula (8)

[0023]

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[In the formula, Ar ₁ , Ar ₂ , R ₁ , R ₂ , X and m have the same meanings as in the general formulas (1) and (2). ] The N-aryl aniline compound represented by the following formula is used as a starting material to carry out the formylation reaction as described above, and the following general formula (9)

[0025]

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[Wherein Ar ₁ , Ar ₂ , R ₁ , R ₂ and X are
And m have the same meaning as in the general formulas (1) and (2). ] The aldehyde compound represented by
The following general formula (10)

[0027]

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[In the formula, R ₃ , R ₄ , Z and n have the same meanings as in the general formula (1). ] In the general formula (1), Y is the following general formula (2)

[0029]

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The acenaphthene compound of the present invention represented by the above general formula (1) when represented by the following formula is obtained.

The condensation reaction of the above-mentioned diarylamine compound and the halogenated tetralin compound is a reaction known as the Ullmann reaction, and is carried out without solvent or in the presence of a solvent. As the solvent, a high boiling point solvent such as nitrobenzene, dichlorobenzene or dimethyl sulfoxide is used. Further, potassium carbonate, sodium carbonate, sodium hydrogen carbonate, potassium hydroxide, sodium hydroxide and the like are used as a deoxidizing agent. Further, usually, the reaction is carried out using a catalyst such as copper powder or copper halide. The reaction temperature is usually 160 to 230 ° C.

The condensation reaction between the above-mentioned aldehyde compound and phosphonate ester is a reaction known as a modified Wittig reaction, preferably in the presence of a basic catalyst. In this case, potassium hydroxide, sodium amide, sodium methylate, potassium-t-butoxide, etc. are used as the basic catalyst. As the solvent, methyl alcohol, ethyl alcohol, t-butyl alcohol, toluene, tetrahydrofuran, dioxane, dimethyl sulfoxide, N, N-dimethylformamide and the like are used. The reaction temperature is usually from room temperature to 100
° C. The phosphonate represented by the general formula (7) or (10) used as a raw material in the present invention is obtained by directly reacting the corresponding halogen compound and trialkyl phosphite with toluene, xylene, N, N-dimethylformamide. It is easily synthesized by heating the reaction in an organic solvent such as.

In the above general formula (1), when Ar ₁ is an aryl group having a substituent, the substituent is a lower alkyl group having 1 to 4 carbon atoms or a lower alkoxy group having 1 to 4 carbon atoms. , A cycloalkyl group having 5 to 6 carbon atoms, a benzyl group, a phenyl group or a halogen atom, and when the substituent is a lower alkyl group or a lower alkoxy group, a lower alkoxy group having 1 to 4 carbon atoms or a halogen atom. It may be further substituted with an atom, and when the substituent is a benzyl group or a phenyl group, it is further substituted with a lower alkyl group having 1 to 4 carbon atoms, a lower alkoxy group having 1 to 4 carbon atoms, or a halogen atom. May be. Examples of the aryl group of Ar ₁ include a phenyl group, a naphthyl group, a biphenylyl group, an anthryl group and a pyrenyl group.
Ar ₂ has a substituent, a phenylene group, a naphthylene group,
When it is a biphenylene group or an anthrylene group, as a substituent, a lower alkyl group having 1 to 4 carbon atoms and 1 carbon atom
To 4 lower alkoxy group or halogen atom, and when the substituent is a lower alkyl group or a lower alkoxy group, it may be further substituted with a lower alkoxy group having 1 to 4 carbon atoms or a halogen atom.

When X, Y or Z is an aryl group having a substituent, the substituent may be the same as the above-mentioned substituent which Ar ₁ may have. When X is an alkyl group having a substituent, the substituent is a lower alkoxy group having 1 to 4 carbon atoms and 5 to 5 carbon atoms.
6 cycloalkyl groups, halogen atoms and the like. Examples of the X, Y or Z aryl group include a phenyl group, a naphthyl group, a biphenylyl group, an anthryl group and a pyrenyl group.

Specific examples of the compound represented by the general formula (1) of the present invention include the following.

Compound No. (1)

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Compound No. (2)

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Compound No. (3)

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Compound No. (4)

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Compound No. (5)

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Compound No. (6)

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Compound No. (7)

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Compound No. (8)

[Chemical 21]

Compound No. (9)

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Compound No. (10)

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Compound No. (11)

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Compound No. (12)

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Compound No. (13)

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Compound No (14)

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Compound No. (15)

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The electrophotographic photoreceptor using the acenaphthene compound of the present invention has a photosensitive layer containing one or more of the above acenaphthene compounds. There are various types of photosensitive layers, and a sensitizing dye is used, a single layer type in which a charge generating substance is dispersed to generate charge carriers, or a laminated type in which a charge transport layer is laminated on a charge generating layer. Also, there are those in which the order of laminating the charge generation layer and the charge transport layer are reversed, and those in which a protective layer is provided on the surface of the photoreceptor. The photoreceptor as described above is manufactured by a conventional method. For example,
The above-mentioned acenaphthene compound represented by the general formula (1) is dissolved in a suitable solvent together with a binder resin, and if necessary, a charge generating substance, a sensitizing dye, an electron-withdrawing compound or a plasticizer, a pigment, and other additives. A coating solution prepared by adding an agent is coated on a conductive support and dried to be several μm to several tens μm.
It can be produced by forming a photosensitive layer of. In the case of a photosensitive layer composed of two layers of a charge generation layer and a charge transport layer, the above-mentioned coating solution is applied onto the charge generation layer, or the charge generation layer is applied onto the charge transport layer obtained by applying the above-mentioned coating solution. It can be manufactured by forming. Further, the photoreceptor thus manufactured may be provided with an adhesive layer, an intermediate layer, and a barrier layer, if necessary.

Solvents for preparing the coating solution include tetrahydrofuran, 1,4-dioxane, methyl ethyl ketone,
Examples thereof include polar organic solvents such as cyclohexanone, acetonitrile, N, N-dimethylformamide and ethyl acetate, aromatic organic solvents such as toluene and xylene, and chlorinated hydrocarbon solvents such as dichloromethane and dichloroethane. A solvent having a high solubility in the acenaphthene compound and the binder resin is preferably used.

Examples of the binder resin include polymers and copolymers of vinyl compounds such as styrene, vinyl acetate, vinyl chloride, acrylic acid ester, methacrylic acid ester and butadiene, polyvinyl acetal, polycarbonate, polyester, polyphenylene oxide, polyurethane, Examples thereof include various resins compatible with the acenaphthene compound, such as cellulose ester, phenoxy resin, silicon resin, and epoxy resin. The amount of the binder resin used is usually in the range of 0.4 to 10 times by weight, preferably 0.5 to 5 times by weight, with respect to the acenaphthene compound.

[0054]

DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, the present invention will be described specifically with reference to examples.

Example 1 (Synthesis of Compound No. 1) “Synthesis of 5- (N, N-diphenylamino) acenaphthene” 33.85 g (0.2 mo) of 5-aminoacenaphthene
l) was added to 102.1 g (0.5 mol) of iodobenzene,
Copper powder 1.3g (0.02mol), anhydrous potassium carbonate 3
4.5 g (0.25 mol), nitrobenzene 100 m
It was mixed with 1 and stirred at 200 ° C. for 26 hours. After confirming that 5-aminoacenaphthene and the intermediate 5- (N-phenylamino) acenaphthene had disappeared, the reaction was terminated. 300 ml of toluene was added to dissolve the product,
Filtration and concentration. The concentrate was subjected to column chromatography (carrier; silica gel, eluent; toluene / hexane = 1 /
Purification by 4) yielded 48.7 g of 5- (N, N-diphenylamino) acenaphthene (yield; 75.7%, melting point; 168.5-170.5 ° C).

"5- [N- (4-formylphenyl)-
Synthesis of N-phenylamino] acenaphthene ”5- (N, N-diphenylamino) acenaphthene 3 synthesized above
2.14 g (0.1 mol) was dissolved in 300 ml of N, N-dimethylformamide, and phosphorus oxychloride 2 was added at room temperature.
2.73 g (0.15 mol) was added dropwise over 30 minutes.
It heated up at 50 degreeC and stirred for 14 hours. After confirming the disappearance of 5- (N, N-diphenylamino) acenaphthene, the reaction was terminated. The reaction product was poured into an aqueous solution in which 45 g (1.05 mol) of 93% sodium hydroxide was dissolved in 1000 ml of water. The crystals precipitated upon cooling were filtered, washed with water and dried to give 5- [N- (4-formylphenyl) -N.
-Phenylamino] acenaphthene 30.27 g (yield;
86.6%, melting point; 138.0-141.0 ° C).

"Synthesis of 5- {N- [4- (2,2-diphenylvinyl) phenyl] -N-phenylamino} acenaphthene (Compound No. 1)" 5- [N synthesized above
2.80 g (0.008 mol) of-(4-formylphenyl) -N-phenylamino] acenaphthene and 3.04 g (0.01 mo of diethyl diphenylmethylphosphonate)
1) was dissolved in 50 ml of N, N-dimethylformamide and potassium tert-butoxide (1.35 g) was obtained at room temperature.
(0.012 mol) was added over 20 minutes. After the addition, stirring was continued for 2 hours. After confirming the disappearance of the formyl compound, the reaction was terminated. The reaction product was poured into 300 ml of methanol at 5 ° C. or lower, 30 ml of water was added dropwise, and the precipitated crystals were filtered, washed with methanol and dried to give 3.38 g of crystals (yield; 84.6%). Obtained. 3.0 g of this crystal was purified by column chromatography (carrier; silica gel, eluent; toluene / hexane = 1/4) to give 5- {N- [4- (2,2-diphenylvinyl).
Phenyl] -N-phenylamino} acenaphthene (Compound No. 1) 2.30 g (purification yield; 76.7%, melting point; 189.0-190.5 ° C) was obtained. The elemental analysis values were as shown below as C ₃₈ H ₂₉ N. Carbon: 91.
39% (91.35%), hydrogen: 5.73% (5.85)
%), Nitrogen: 2.91% (2.80%) (calculated values are shown in parentheses.) Characteristic fundamental frequency (c) of infrared absorption spectrum (KBr tablet method)
m ^-1 ) is 3024, 2914, 1584, 1487, ¹
It was 292, 695 mag.

Example 2 (Synthesis of Compound No. 4) "5- {N- [4- (4-methylstyryl) phenyl]
Synthesis of —N-phenylamino} acenaphthene ”Example 1
5- [N- (4-formylphenyl) -N- synthesized in
Phenylamino] acenaphthene 20.96 g (0.06
mol) and diethyl 4-methylbenzylphosphonate 1
7.44 g (0.072 mol) was dissolved in 300 ml of N, N-dimethylformamide and potassium-te was added at room temperature.
20 g of 10.1 g (0.09 mol) of rt-butoxide
Added over minutes. After the addition, stirring was continued for 2 hours. After confirming the disappearance of the formyl compound, the reaction was terminated. The reaction product was poured into 1500 ml of methanol at 5 ° C or lower, 150 ml of water was added dropwise, and the precipitated crystals were filtered, washed with methanol and dried to give crude crystals 22.18.
g (yield; 84.5%) was obtained. 21.0 g of this crystal was subjected to column chromatography (carrier; silica gel, eluent;
5- {N by purifying with toluene / hexane = 1/4)
-[4- (4-Methylstyryl) phenyl] -N-phenylamino} acenaphthene (Compound No. 4) 17.8
5 g (purification yield; 85.0%, melting point; 148.0-14
9.0 ° C.) was obtained. The elemental analysis values were as shown below as C ₃₃ H ₂₇ N. Carbon: 90.49% (90.58
%), Hydrogen: 6.30% (6.22%), nitrogen: 3.0
2% (3.20%) (calculated values are shown in parentheses.) Characteristic fundamental wave number (c) of infrared absorption spectrum (KBr tablet method)
m ⁻¹ ) is 3022, 2914, 1586, 1487, ¹
It was 304, 694 mag.

Example 3 (Synthesis of Compound No. 5) “Synthesis of 5- (N-acetylamino) acenaphthene” 5
-Aminoacenaphthene (6.77 g, 0.04 mol) was added with glacial acetic acid (50 ml), stirred and dissolved at 60 ° C, and acetic anhydride (8.16 g, 0.08 mol) was added dropwise over 15 minutes. After completion of the dropwise addition, the mixture was stirred at the same temperature for 2 hours. After confirming the disappearance of 5-aminoacenaphthene, the reaction was terminated. The reaction product was poured into 500 ml of ice water, and the precipitated crystals were filtered,
It was washed with water and dried. 5- (N-acetylamino) acenaphthene 8.15 g (yield; 96.4%, melting point; 180.
0-186.0 ° C) was obtained.

[Synthesis of 5- [N- (4-tolyl) amino] acenaphthene] 7.39 g (0.035 mol) of 5- (N-acetylamino) acenaphthene synthesized above was added to 10.91 g of P-iodotoluene. (0.05 mol),
Copper powder 0.32 g (0.005 mol), anhydrous potassium carbonate 5.52 g (0.04 mol), nitrobenzene 10
It was mixed with ml and stirred at 200 ° C. for 6 hours. 5- (N-
After confirming the disappearance of (acetylamino) acenaphthene, the reaction was terminated. Isoamyl alcohol 10
ml and 85% potassium hydroxide 9.8g (0.15mo
1) was added to an aqueous solution of 10 ml of water to add 130-1.
The hydrolysis reaction was carried out at 40 ° C. for 4 hours. After confirming the completion of the hydrolysis reaction, 100 ml of water was added, and isoamyl alcohol and nitrobenzene were distilled off by azeotropic distillation. 100 ml of toluene was added to the residue to dissolve the product, and the toluene layer was separated. The toluene layer was washed with 100 ml of water and then concentrated, and the obtained oily substance was subjected to column chromatography (carrier; silica gel, eluent; toluene / hexane = 1).
Purification was carried out according to / 4). 5- [N- (4-tolyl)
Amino] acenaphthene 6.56 g (yield; 72.3%,
Melting point; 96.2-96.8 ° C.).

"Synthesis of 5- [N- (4-tolyl) -N-phenylamino] acenaphthene" 5-synthesized above
[N- (4-Tolyl) amino] acenaphthene 4.66 g
(0.018 mol) of iodobenzene 4.99 g
(0.022 mol), 0.13 g of copper powder (0.002 m)
ol), 2.76 g of anhydrous potassium carbonate (0.02 mo
l), mixed with 5 ml of nitrobenzene and heated at 200 ° C for 25
Stirred for hours. After confirming that 5- [N- (4-tolyl) amino] acenaphthene had disappeared, the reaction was terminated.
100 ml of toluene was added to dissolve the product, which was filtered and concentrated. The concentrate was purified by column chromatography (carrier; silica gel, eluent; toluene / hexane = 1/4) and 5.06 g of 5- [N- (4-tolyl) -N-phenylamino] acenaphthene (yield; 83.8%,
Melting point; 147.0-148.0 ° C.).

"5- [N- (4-formylphenyl)-
Synthesis of N- (4-tolyl) amino] acenaphthene ”4.7 g (0.014 mol) of 5- [N- (4-tolyl) -N-phenylamino] acenaphthene synthesized above was added to 30 ml of N, N-dimethylformamide. Dissolved in 3.2 g (0.021 mol) of phosphorus oxychloride at room temperature
It was dropped in 0 minutes. It heated up at 50 degreeC and stirred for 14 hours. 5- [N- (4-tolyl) -N-phenylamino]
The reaction was terminated when it was confirmed that acenaphthene had disappeared. The reaction product was treated with 10% of 93% sodium hydroxide (0.23
(mol) was added to an aqueous solution of 250 ml of water.
The crystals precipitated by cooling were filtered, washed with water and dried to give 5- [N
4.94 g (yield; 97.1%) of-(4-formylphenyl) -N- (4-tolyl) amino] acenaphthene were obtained.

"Synthesis of 5- {N- [4- (4-methylstyryl) phenyl] -N- (4-tolyl) amino} acenaphthene (Compound No. 5)" 5-synthesized above
[N- (4-formylphenyl) -N- (4-tolyl)
Amino] acenaphthene 4.36 g (0.012 mol)
And diethyl 4-methylbenzylphosphonate 3.88 g
(0.016 mol) was dissolved in 40 ml of N, N-dimethylformamide, and 2.02 g (0.018 mol) of potassium tert-butoxide was added over 10 minutes at room temperature. After the addition, stirring was continued for 2 hours. After confirming the disappearance of the formyl compound, the reaction was terminated. The reaction product was poured into 200 ml of methanol at 5 ° C or lower, and the water was added to 5 ml.
Crystals precipitated by dropping 0 ml were filtered, washed with methanol and dried to obtain 4.44 g of crystals (yield: 81.9%).
I got 4.0 g of this crystal was subjected to column chromatography (carrier; silica gel, eluent; toluene / hexane = 1.
/ 4) to give 5- {N- [4- (4-methylstyryl) phenyl] -N- (4-tolyl) amino} acenaphthene (Compound No. 5) 3.63 g (purification yield; 9
0.8%, melting onset temperature; 87.5 ° C) was obtained. The elemental analysis values were as shown below as C ₃₄ H ₂₉ N. carbon:
90.51% (90.42%), hydrogen: 6.51%
(6.47%), nitrogen: 2.98% (3.10%) (calculated values are shown in parentheses.) Characteristic fundamental wave number (c) of infrared absorption spectrum (KBr tablet method)
m ^-1 ) is 3020, 2916, 1594, 1503, ¹
It was 310, 818 and so on.

Example 4 (Synthesis of Compound No. 14) "5- {N- [4- (4-methylstyryl) phenyl]
Synthesis of —N- (4-formylphenyl) amino} acenaphthene ”5- {N- [4- (4-methylstyryl) phenyl] -N-phenylamino} acenaphthene synthesized in Example 2 17.5 g (0. (04 mol) was dissolved in 150 ml of N, N-dimethylformamide, and 9.09 g (0.06 mol) of phosphorus oxychloride was added dropwise at room temperature over 40 minutes. It heated up at 50 degreeC and stirred for 22 hours. 5- {N-
After confirming that [4- (4-methylstyryl) phenyl] -N-phenylamino} acenaphthene had disappeared, the reaction was terminated. The reaction product is 93% sodium hydroxide 23 g
(0.53 mol) was added to an aqueous solution prepared by dissolving 1000 ml of water. The crystals precipitated by cooling were filtered, washed with water, washed with methanol and dried to give 17.66 g of crystals (yield; 94.
8%). 16.0 g of this crystal was purified by column chromatography (carrier; silica gel, eluent; toluene / hexane = 1/1) to give 5- {N- [4- (4-methylstyryl) phenyl] -N- (4- Formylphenyl) amino} acenaphthene 12.05 g (yield; 75.
3%, melting point; 105.0-108.0 ° C).

"5- {N- [4- (4-methylstyryl) phenyl] -N- [4- (2,2-diphenylvinyl) phenyl] amino} acenaphthene (Compound No. 1
Synthesis of 4) "5- {N- [4- (4-methylstyryl) phenyl] -N- (4-formylphenyl) amino} acenaphthene synthesized above 4.66 g (0.01 mo)
l) and diethyl diphenylmethylphosphonate 4.56 g
(0.015 mol) was dissolved in 40 ml of N, N-dimethylformamide, and 2.02 g (0.018 mol) of potassium tert-butoxide was added over 10 minutes at room temperature. After the addition, stirring was continued for 2 hours. After confirming the disappearance of the formyl compound, the reaction was terminated. The reaction product was poured into 400 ml of methanol at 5 ° C or lower, and water 4
Crystals precipitated by dropping 0 ml of the crystals were filtered, washed with methanol and dried to obtain 4.9 g of crystals (yield: 79.7%). 4.5 g of this crystal was subjected to column chromatography (carrier; silica gel, eluent; toluene / hexane = 1 /
4- {N- [4- (4-methylstyryl) phenyl] -N- [4- (2,2-diphenylvinyl) phenyl] amino} acenaphthene (Compound No.
14) 3.83 g (purification yield; 85.2%, melting start point: 102.0 ° C.) was obtained. The elemental analysis values were as shown below as C ₄₇ H ₃₇ N. Carbon: 91.49% (9
1.67%), hydrogen: 6.18% (6.06%), nitrogen: 2.33% (2.28%) (calculated values are shown in parentheses) Infrared absorption spectrum (KBr tablet method) Characteristic fundamental frequency of (c
m ⁻¹ ) is 3020, 2916, 1590, 1500, ¹
It was 306, 698 and so on.

Example 5 (Synthesis of Compound No. 15) "Synthesis of 5- [4,4'-bis (4-methylstyryl) diphenylamino] acenaphthene" 5- {N- [4 synthesized in Example 4 -(4-Methylstyryl) phenyl]-
4.66 g (0.01 mol) of N- (4-formylphenyl) amino} acenaphthene and 2.91 g (0.012 mol) of diethyl 4-methylbenzylphosphonate were dissolved in 40 ml of N, N-dimethylformamide and potassium was added at room temperature. -Tert-butoxide 1.68 g (0.0
15 mol) was added over 10 minutes. 2 more after addition
Stirred for hours. After confirming the disappearance of the formyl compound, the reaction was terminated. Methanol 4 at 5 ° C or below
It was poured into 00 ml and 40 ml of water was further added dropwise to precipitate crystals, which were filtered, washed with methanol and dried to obtain 5.1 g of crystals (yield: 92.3%). This crystal 5.0
g was purified by column chromatography (carrier; silica gel, eluent; toluene / hexane = 1/4) to give 5-
4.19 g of [4,4'-bis (4-methylstyryl) diphenylamino] acenaphthene (Compound No. 15)
(Purification yield; 83.8%, melting point: 101.5 ° C)
I got The elemental analysis values were as shown below as C ₄₂ H ₃₅ N. Carbon: 91.35% (91.10%), hydrogen:
6.25% (6.37%), nitrogen: 2.40% (2.5
3%) (calculated value is shown in parentheses.) Infrared absorption spectrum (KBr tablet method) characteristic fundamental wave number (c
m ⁻¹ ) is 3020, 2916, 1591, 1504, ¹
It was 306, 821 and so on.

Application Example 1 As a charge generating agent, the following disazo compound

[0068]

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1.5 parts of polyester resin (Byron 2
00, Toyobo Co., Ltd.) 8 wt% THF solution 18.5
In addition to the parts, the mixture was placed in an agate pot containing agate balls, and rotated by a planetary type fine pulverizer (made by Fritz Co.) for 1 hour to disperse. The resulting dispersion is deposited on an aluminum deposited P as a conductive support.
It was applied on an aluminum surface of the ET film using a wire bar and dried at 60 ° C. under normal pressure for 2 hours and further under reduced pressure for 2 hours to form a charge generation layer having a thickness of 0.3 μm. On the other hand, Compound No. 1 acenaphthene compound 1.
5 parts of polycarbonate resin (Panlite K-130
No. 0, Teijin Kasei Co., Ltd. 8 wt% dichloroethane solution (18.75 parts) was added and ultrasonic waves were applied to completely dissolve the acenaphthene compound. This solution was applied on the above-mentioned charge generating layer with a wire bar, and dried at 60 ° C. under normal pressure for 2 hours and further under reduced pressure for 2 hours to form a charge transport layer having a thickness of 20 μm, thereby producing a photoreceptor. . The sensitivity of this photoconductor was measured using an electrostatic copying paper test device (trade name "EPA-8100" manufactured by Kawaguchi Electric Co., Ltd.). First, the photoreceptor is charged by a corona discharge of −8 kV in the dark, and then exposed to 3.0 lux of white light, and the time (seconds) until the surface potential is reduced to half of the initial surface potential is measured. The half-exposure amount E1 / 2 (lux seconds) was determined. The initial surface potential of this photoconductor is -1060V, and E1 / 2 is 0.85.
Looks seconds.

Comparative Example 1 Compound No. 1 in Application Example 1 Instead of using the acenaphthene compound of No. 1, the following compound

[0071]

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A photoconductor was prepared in the same manner as in Application Example 1 except that When the sensitivity of this photoconductor was measured in the same manner as in Application Example 1, the initial surface potential was -930 V and E
1/2 was 1.15 lux · sec.

[0073]

INDUSTRIAL APPLICABILITY As described above, the novel acenaphthene compound of the present invention has an excellent charge transporting ability and can be widely used as a charge transporting material.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Chieko Inayoshi 45 Miyukigaoka, Tsukuba, Ibaraki Hodogaya Chemical Industry Co., Ltd. Tsukuba Research Institute

Claims (1)

[Claims] 1. The following general formula (1): [In the formula, Ar ₁ represents an aryl group which may have a substituent, Ar ₂ represents a phenylene group, a naphthylene group, a biphenylene group or an anthrylene group which may have a substituent, and R ₁ represents hydrogen. Represents an atom, a lower alkyl group or a lower alkoxy group, X represents a hydrogen atom, an alkyl group which may have a substituent or an aryl group which may have a substituent, and Y represents a substituent. A good aryl group or the following general formula (2): (In the formula, R ₂ represents a hydrogen atom, a lower alkyl group or a lower alkoxy group, R ₃ represents a hydrogen atom, a halogen atom or a lower alkyl group, Z represents a hydrogen atom or an aryl which may have a substituent. Represents a group, and m and n represent an integer of 0 to 4). ] The acenaphthene compound represented by these.