JPS5865275A - Novel hydrazone compound and its preparation - Google Patents

Abstract

NEW MATERIAL:The compound of formulaI(R1 is H, 1-4C alkyl, alkoxy, or dialkylamino; R2 is 1-16 C alkyl or aralkyl; R3 and R4 are phenyl, naphthyl, heterocyclic group, 1-10C alkyl, etc. provided that R3 and R4 are not alkyl at the same time). USE:Photosensitive material for electrophotography. Extremely useful as a charge transfer substance of a photoconductive material. PROCESS:The compound of formulaIcan be prepared by reacting the compound of formula II with equimolar amount of the compound of formula III in an organic solvent (e.g. alcohol, ether, etc.) for 1-5hr. The compound of formula II is also novel, and can be prepared by reacting the compound of formula IV (X is Br or I with the compound of formula V at 75-150 deg.C using a catalyst comprising a combination of a noble metal compound such as palladium acetate, etc. and a phosphorus compound such as triaryl phosphine, in the presence of a hydrogen halide acceptor (e.g. a secondary amine).

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a novel hydrazone compound and a method for producing the same.

In recent years, many electrophotographic photoreceptors using organic photoconductive materials have been proposed. For example, poly(+)-N-vinylcarbashield 2. /I, 7-) A photoreceptor provided with a photosensitive layer containing IJ nitrofluoren-9-one,
A photoreceptor with a photosensitive layer containing poly-N-vinylcarbazole sensitized with a pyrylium salt dye, a photoreceptor with a photosensitive layer containing an organic pigment as a main component, and a eutectic complex consisting of a dye and a resin. Examples include photoreceptors provided with a photosensitive layer as a main component. Although these photoreceptors have excellent properties and are of high practical value, one of their major drawbacks is that they have lower sensitivity than inorganic photoreceptors such as selenium. There is.

Therefore, the present inventors conducted various studies with the aim of eliminating the drawbacks of conventional organic photoconductive materials and finding a compound that has excellent photoconductive properties as a material. As a result, a new hydrazone compound was discovered.

The hydrazone compound of the present invention has the following general formula CI'12 (wherein R1 is hydrogen, an alkyl group having 1 to 4 carbon atoms, an alkoxy group, or a sialgylamino group; R2 is an alkyl group having 1 to 16 carbon atoms or an aralkyl group; R3,R
4 is a substituted or unsubstituted phenyl group, naphthyl group, heterocyclic group, or an alkyl group having 1 to 10 carbon atoms, and is not exclusive of the alkyl group at the same time. ).

This compound [■] has the following general formula [■] 2 (where R+ is hydrogen, an alkyl group having 1 to 4 carbon atoms, an alkoxy group, or a dialkylamino group; R2 is an alkyl group having 1 to 16 carbon atoms or an aralkyl group) N-substituted-3-formyl-6-styrylcarbazole represented by group or carbon number 1-1
0 alkyl group, and it is difficult to have an alkyl group at the same time. ) can be easily obtained by reacting with 1,1-disubstituted hydrazine represented by

N-substituted-3-formyl-6 which is a raw material compound of the present invention
-Styrylcarbazole N:, corresponding to the following general formula] B2 (where X is bromine or iodine; and 2 is carbon number 1 to 16
an alkyl group or an aralkyl group. ) denoted by N-
Substituted-3-formyl-6-balocarbazole and the following general formula (V) 1>XC! This is a new compound produced by reacting a styrene derivative represented by H=OH2[:v) (wherein R1 is hydrogen, an alkyl group having 1 to 4 carbon atoms, an alkoxy group, or a dialkylamino group). This reaction typically requires a catalyst and a hydrogen halide scavenger.

A suitable catalyst is a combination of a noble metal compound such as palladium acetate and a phosphorus compound such as triarylphosphine. Triarylphosphines include triphenylphosphine, tri-tolylphosphine, tris(
2,5-diisopropylphenyl)phosphine, triα-naphthylphosphine, tris(2,3,/I, 5
-tetramethylphenyl)phosphine, tris(2-methyl-5-t-butylphenyl)phosphine, tris(
Phosphines such as p-carbomethoxyphenyl)phosphine can be mentioned, and use of tri-)lylphosphine and tris(2-methyl-t-butylphenyl)phosphine is particularly preferred. The amount of triarylphosphine used in the present invention is 0 per mole of palladium acetate.
5 to 10 mol is suitable. The appropriate amount of palladium acetate to be used is 0.25 to 2 mole of the amount of styrene derivative used.

Suitable hydrogen halide extractants include secondary amines, tertiary amines, and active salts such as sodium bicarbonate and sodium carbonate. Such secondary amines and tertiary amines may be common amines such as diethylamine, di-n-butylamine, piperidine, morpholine, triethylamine, tri-n-butylamine, triamylamine, and tetramethylethylenediamine.
The amount used is slightly in excess of the molar amount of hydrogen generated.

2. As a reaction solvent. General ones, such as N.

N-dimethylformamide, dimethylacetamide, toluene, xylene, chlorobenzene, O-dichlorobenzene, trichlorobenzene, N-methyl-2-pyrrolidone, and dimethylsulfoxide are used.

The reaction temperature ranges from 75 to 150°C.

N-substituted-3-formyl-6- thus obtained
A hydrazone compound can be easily obtained by reacting styrylcarbazole and hydrazine represented by the general formula above in an equimolar ratio in a suitable organic solvent. As is generally known, this dehydration condensation reaction can be accelerated by adding an acid, and inorganic acids such as hydrochloric acid, dilute sulfuric acid, etc., and organic acids such as acetic acid can be used as acid catalysts. It will be done. As the reaction solvent, any organic solvent can be used as long as it dissolves the reaction system, including lower alcohols such as methanol and ethanol, cyclic ethers such as 1,4-dioxane, and tetrahydronerane. Methyl cellosolve, ethyl cellosolve, corner cellosolves, N,N-dimethylformamide, N-
Examples include methyl-2-pyrrolidone and acetic acid.

The reaction temperature varies depending on the reaction solvent used, but when using N,N-dimethylformamide, etc., which has good solubility in the reaction system, the reaction proceeds at room temperature, but the reaction system dissolutes at room temperature. When using ethanol, it is desirable to heat it under reflux. In either case, the reaction is completed in 1 to 5 hours. When the condensation product obtained as a result of the reaction precipitates as crystals, the -44? ? If the product does not precipitate, use a diluent to make it precipitate and then use it several times. A pure hydrazone compound can be obtained by further recrystallizing the separated product using a suitable solvent.

The compound obtained by the method of the present invention is used for electrophotographic photoreceptors like poly-IJ-N-vinylcarbazole, which is a typical conventional organic conductive material. It is extremely useful as a charge transfer substance in a photoconductive material that combines a generation substance and a charge transfer substance, and can be used as an excellent photoconductive material together with various charge generation substances. As the charge generating substance used in this case, for example, inorganic pigments such as selenium, selenium-tellurium, cadmium sulfide, zinc sulfide, organic pigments, charge transfer complexes, mixtures thereof, etc. can be used as appropriate in Selection 1.

EXAMPLES The present invention will be specifically explained below using Examples, but the present invention is not limited to these Examples.

Example I 22.33 parts of N-ethyl-3-formylcarbasol (manufactured by Aldrich) (1 part by weight, same hereinafter) was mixed with 100 parts of acetic acid.
16.5 parts of bromine was added dropwise while stirring. After reacting for 10 minutes, the reaction product was poured into ice water, the resulting precipitate was filtered out, thoroughly washed with water, and then recrystallized from ethanol to give 3-bromo-N-ethyl-
26.0 parts of 6-formylcarbazole (yield 86%)
) It is available as white needle-like crystals.

3-bromo-N-ethyl-6-formylcarbazole 6
．． 04 parts, 2.60 parts of styrene, 4.64 parts of tri-n-butylamine, 0.044 parts of vinegar rl'7 palladium, 0.1122 parts of tri-n-tolylphosphine, 6 parts of xylene
A mixture consisting of 100 parts of
The reaction was carried out at ~120°C for 9 hours. The reaction mixture was filtered while it was still hot to remove insoluble matter, and then cooled and the precipitate was collected. The obtained precipitate is recrystallized from a mixed solvent of benzene and hexane, and a yellow color is delivered.
3.65 parts of N-ethyl-3-formyl-6-styrylcarbazole were obtained. (Melting 1:3J1s℃)N-ethyl-
3-formyl-6-styrylcal/<7”-)Ly
3.25 parts of 1-methyl-1-phenylhydrazone and 1.34 parts of 1-methyl-1-phenylhydrazone were added to 70 parts of ethanol and heated until the ethanol refluxed to dissolve.

After adding 3 drops of acetic acid, refluxing was continued for 4 hours. The precipitate that precipitated out after cooling was collected and recrystallized from a mixed solvent of benzene and ethanol to obtain the desired product. The structural formula, yield, melting point, and elemental analysis values of the obtained hydrazone compound are shown in Table 1, its infrared absorption spectrum is shown in FIG. 1, and its nuclear magnetic resonance spectrum is shown in FIG. 3.

Example 2 N-ethyl-3-
(P-diethylaminostyryl)-6-formylcarbazole was obtained.

N-ethyl-3-(P-diethylaminostyryl) = 6
- Dissolve 3.97 parts of formylcarbazole in 15 parts of N,N-dimethylformamide, and add 1N hydrochloric acid to the solution.
．． 5 mt was added, and while stirring, a solution of 2.03 parts of 1,1-diphenyl-hydrazine in N,N-dimethylformamide was added dropwise. After further stirring at room temperature for 1 hour, the mixture was poured into ice water and the precipitate was collected.

The obtained precipitate was washed with water, dried, and recrystallized from a mixed solvent of benzene and hexane to obtain the desired product. The structural formula, yield, melting point, and elemental analysis values of the obtained hydrazone compound are shown in Table 1, and its infrared absorption spectrum is shown in FIG.

Table 1 Reference Examples Chlorinated Diane Blue and polyester resin (Vylon 200 manufactured by Toyobo Co., Ltd.) shown in the structural formula are mixed at a weight ratio of 1:2, and this is mixed with n-butylamine and ethylenediamine (1=1 (volume)). ratio) was dissolved in a mixed solvent to obtain an 8.4% by weight solution.

This solution was applied onto an aluminum substrate using an applicator and dried to form a charge generation layer with a thickness of about 1 μm.

Next, the hydrazone compound produced in Example 1 and polycarbonate resin (manufactured by Tijin: Panrai L) were added to 1
:1 weight ratio, dissolved in tetrahydrofuran,
A 188% by weight solution was prepared, and this solution was applied onto the charge generation layer using an applicator, and after drying, the thickness was approximately 10 μm.
A charge transfer layer was formed.

This photoreceptor was charged negatively by applying -6KV corona discharge for 15 seconds using an electrostatic copying paper tester (manufactured by Rodenki Seisakusho, Model 5F-428), and then placed in a dark place for 20 seconds. The surface potential Vo (v) at that time was measured, and then the surface was illuminated with an illumination intensity of 2 using a tungsten lamp.
Light is irradiated so that the mouth potential becomes V
Find the time (seconds) it takes to reach the o bar, and calculate the half-reduction exposure Ev
Obtained 2 (looks seconds).

The results were VO--750V, E≠-29 lux·sec, and both charge retention in the dark and photosensitivity were high.

[Brief explanation of drawings]

Figures 1 and 2 are Example 1 and Example 2, respectively.
FIG. 3 shows the nuclear magnetic resonance spectrum of the hydrazone derivative of the present invention produced in Example 1.

Claims (2)

[Claims] (1) General formula (where R1 is hydrogen, an alkyl group having 1 to 4 carbon atoms, an alkoxy group, or a dialkyl amino group; R2 is an alkyl group having 1 to 16 carbon atoms or an aralkyl group; R3
, R4 are each a substituted or unsubstituted phenyl group, naphthyl group, heterocyclic group, or an alkyl group having 1 to 1 o carbon atoms, and cannot be an alkyl group at the same time. ) A novel hydrazone compound. (2) N-substituted-3 represented by the general formula (wherein R1 is hydrogen, an alkyl group having 1 to 4 carbon atoms, an alkoxy group, or a dialkylamino group; R2 is an alkyl group having 1 to 16 carbon atoms or an aralkyl group) formyl-6-styrylcarbazole and the general formula % formula % (wherein R3 and R4 are each substituted or unsubstituted phenyl group, naphthyl group, heterocyclic group or ij [element i1 to
10 alkyl groups, which cannot be alkyl groups at the same time. ) (wherein R, R2, R3, R, and 4 are the above-mentioned groups.)