JPS6289770A - Preparation of novel trisazo compound - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a novel method for producing a trisazo compound.

[Prior Art] In recent years, many electrophotographic photoreceptors using organic photoconductive materials have been proposed. A photoreceptor provided with a photosensitive layer, a photoreceptor provided with a photosensitive layer made by sensitizing poly-N-vinylcarbazole with a pyrylium salt dye, a photoreceptor provided with a photosensitive layer containing an organic pigment as a main component,
There are photoreceptors having a photosensitive layer formed by stacking a charge generation layer and a charge transport layer, and a photoreceptor having a photosensitive layer whose main component is a eutectic complex consisting of a dye and a resin.

[Problems to be Solved by the Invention] Although the above-mentioned photoreceptors have some excellent properties, they generally have lower photosensitivity than inorganic photoreceptors such as selenium. This is one of the major drawbacks as a photographic photoreceptor.

An object of the present invention is to eliminate the above-mentioned drawbacks and to provide a method for producing a novel trisazo compound having excellent properties as a photoconductive material.

[Means for Solving the Problems] Namely, 1. The present invention provides a hexazonium salt represented by the general formula (I) (wherein, X is an anionic functional group and R2 is an alkyl group, a cycloalkyl group, or an aralkyl group) and Formula CII) (wherein R1 is an alkyl group, an alkoxy group, a nitro group, a dialkylamino group, or a halogen, n is an integer of 0.1.2 or 3, and n is 2
or 3, the same or different groups may be used. (However, R1 is an alkyl group, an alkoxy group, Nitro group, dialkylamino group or halogen, n is an integer of 0.1.2 or 3, and when n is an integer of 2 or 3, R1 may be the same or different groups, R2 The present invention provides a method for producing a novel trisazo compound represented by an alkyl group, a cycloalkyl group, or an aralkyl group.

In the present invention, the hexazonium salt has the general formula (r
V) (wherein, Y is bromine or iodine, and R2 represents an alkyl group, cycloalkyl group, or aralkyl group), for example, 9-substituted-3,6-cyhalo-1-nitrocarbazole is reacted with p-nitrostyrene. 8-substituted-3,8-bis(p-
Reduction of nitrostyryl)-1-nitrocarbazole to obtain 9-substituted-3,6-bis(p-7minostyryl)-1-7minocarbazole represented by general formula (Vl), and then diazotization. It can be obtained by

The reaction of 9-11-substituted-3,6-cyhalo-1-nitrocarbazole with p-nitrostyrene usually 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-
diiso-propylphenyl)phosphine, triα-naphthylphosphine, tris(2,3,4,5-tetramethyl)phenylphosphine, tris(2-methyl-5-
Mention may be made of phosphines such as t-butylphenyl)phosphine and tris(p-carbomethoxyphenyl)phosphine, in particular tri0-tolylphosphine,
It is preferable to use tris(2-methyl-5-t-butylphenyl)phosphine. The amount of triarylphosphine used in the present invention is 0.5 to 1 per mole of palladium acetate.
0 mol is suitable. Further, the appropriate amount of palladium acetate to be used is 0.25 to 2 mol% of the amount of styrene derivative used.

Suitable hydrogen halide scavengers include secondary amines, tertiary amines, and basic salts such as sodium bicarbonate and sodium carbonate. Such secondary amines and tertiary amines include 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 equivalent of hydrogen halide generated.

Common reaction solvents such as N,N-dimethylformamide, dimethylacetamide, toluene,
0 reaction using xylene, chlorobenzene, O-dichlorobenzene, trichlorobenzene, tomethyl-2-pyrrolidone, dimethyl sulfoxide is carried out at 75-150°C.
It is carried out over a temperature range of

In this way, the novel compound 8-substituted-3,6
-Bis(p-nitrostyryl)-1-nitrocarbazole (V) is reduced to give a 3-substituted-3,tobis(p-7minostyryl)-1-aminecarbazole, which is diazotized to give a hexazonium salt. is 3-substitution-3
, 8-bis(p-aminostyryl)-1-7minocarbazole in a dilute inorganic acid such as dilute hydrochloric acid or dilute sulfuric acid,
Furthermore, add sodium nitrite aqueous solution to this
This is done by adding while maintaining the temperature at ℃.

This diazotization is completed in 30 minutes to 2 hours. in this case,
The reaction mixture is precipitated as a hexazonium salt by adding, for example, borofluoric acid.

It is desirable to obtain crystals by doing several.

Then, the compound (n) is added to the hexazonium salt (1).
is added in a molar amount of 1 to 10 times, preferably 2 to 5 times, relative to the hexazonium group, to cause a coupling reaction. In practice, this reaction is carried out by dissolving the hexazonium salt and the coupling component in an organic solvent such as N,N-dimethylformamide or dimethyl sulfoxide.
This is carried out by dropping an alkaline aqueous solution such as an aqueous sodium acetate solution while maintaining the temperature at 0 to 10°C.

The novel trisazo compound of the present invention thus obtained is
It is particularly useful as a photoconductive material for electrophotographic photoreceptors. Therefore, for example, (1) a photosensitive layer made of a trisazo compound, (2) a photosensitive layer made of a trisazo compound dispersed in bangu, (3) a photosensitive layer made of a trisazo compound dispersed in a well-known charge transfer medium, and (4) the above (1). ) to (3) as a charge generation layer,
Examples of uses of the new trisazo compound include a photosensitive layer in which a charge transfer layer containing a well-known charge transfer medium is laminated thereon.

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

[Example] Example 1 3.8-Dibromocarbazole 6.5 parts (by weight, same hereinafter) dissolved in 80 parts of acetic acid, and fuming nitric acid (d-1,52) dissolved in 10 parts of acetic acid with stirring. 1.33 parts were added dropwise at room temperature, and after the addition was completed, the mixture was heated to 70°C and reacted for 2 hours. The precipitate that precipitates out after cooling is heated in a furnace and recrystallized from chlorobenzene to produce 3,8-dibrol.
5.17 parts (yield 70%) of -nitrorubazole were obtained as yellow crystals.

Melting point 2B 7.8°C.

After dispersing 5.0 parts of 3.6-dipromo-1-nitrocarbazole in 45 parts of dimethylformamide (hereinafter abbreviated as DMF), 8 parts of powdered KOHo was added. DM
2.15 parts of isoamyl bromide dissolved in the FS part was dropped at room temperature, poured during the dropping, the precipitate that precipitated was filtered, washed thoroughly with water, and recrystallized from ethanol to obtain 9. 4.00 parts of -inamyl-3,6-dipromo-1-nitrocarbazole (yield 67%) was obtained as yellow crystals.

8-isoamyl-3,6-dipromo-1-nitrorubazole 4.00 parts, p-nitrostyrene 3.12 parts, tri-n-butylamine 3.88 parts, tri-tolylphosphine 0.111 parts, palladium acetate 0.041 parts,
N-methyl-2-pyrrolidone (hereinafter abbreviated as NMP) 1
A mixture of 5 parts was mixed with 10 parts while stirring under a nitrogen atmosphere.
By pouring the 0 reactant reacted at 0° C. for 10 hours into a large amount of methanol, the precipitate that had precipitated was removed from the furnace plate. After thorough washing with methanol and recrystallization from NMP, 3,87 parts of 8-isoamyl-3,8-bis(p-nitrostyryl)-1-nitrorubazole, (
(yield 74%) was obtained as orange crystals.

9-isoamyl-3,8-bis(p-nitrostyryl)
-1-nitrorubazole - 3,87 parts, iron powder 7.3
8 parts, concentrated hydrochloric acid 2.58 parts (volume), water 1.23 parts, N
A mixture consisting of 150 parts of MP was heated at 80° C. with stirring.
A 20% aqueous sodium carbonate solution was added to the 0 reaction mixture that had been reacted for 3 hours, and the pH of the 0 reaction mixture was adjusted to 8. By heating, washing with water, and drying, 8-ynamyl-3,6-bis(p-aminostyryl)-1-
3.13 parts of 7minocarbazole (yield 98%) were obtained as yellow crystals. 9-ynamyl-3,6-bis(P-
7 minostyril)-1-7 minocarbazole was added to dilute hydrochloric acid consisting of 7.7 parts of concentrated hydrochloric acid and 7.7 parts of water,
The mixture was stirred at 80°C for 30 minutes.Then, the mixture was cooled to 0°C, and a solution of 0.85 parts of sodium nitrite dissolved in 2.8 parts of water was added dropwise.After the dropwise addition, the mixture was stirred at the same temperature for 30 minutes. , insoluble matter was separated in a furnace, 8.2 parts of a 42% borohydrofluoric acid aqueous solution was added to the furnace solution, the precipitated crystals were filtered, washed with water and dried, and the hexazonium trifluoroporate was concentrated. Obtained as brown crystals.

The hexazonium salt thus obtained and 2.88 parts of 2-hydroxy-3-naphthoic acid anilide (naphthol As) as a coupling component were cooled in DMF2.
00 parts, and add an aqueous solution consisting of 7.58 parts of sodium acetate and 50 parts of water to this at a temperature of 4 to 8°C.
After 1 drop, the mixture was stirred at room temperature for 3 hours. The generated precipitate was plated in a furnace, washed three times with 200 parts of water, and then
It was washed three times with 300 parts of MF and once with A7Tone. This was dried to obtain 1.58 parts (yield: 38%) of a trisazo compound having the following structural formula.

Structural formula elemental analysis value HN Actual value (%) 7B, 78 5.01 10.8
4 Calculated value (%)? ? , 05 4.93 10.
70 Examples 2 to 4 A trisazo compound having the structural formula shown in Table 1 was produced in the same manner as in Example 1, except that the compound shown in Table 1 was used as a coupling component in the production of the trisazo compound of Example 1. . The results are shown in Table 1.

Example 5 In the production of the trisazo compound of Example 1, 9-ethyl-3,6-bis(p-7minostyryl)-1-amino Carbazole was synthesized, and then a trisazo compound having the following structural formula was produced.

Elemental analysis value HN Actual value (%) 78.23 3.72 12.2
1 Calculated value (%)? 7.19 4.08 11.
11 Yield: 39% [Effects of the Invention] According to the production method of the present invention, a novel trisazo compound can be easily produced. Moreover, the produced trisazo compound is recognized to have superior properties as a photoconductive material compared to conventional electrophotographic photoreceptors.

Claims (1)

[Claims] General formula (I) ▲Mathematical formulas, chemical formulas, tables, etc.▼(I) (However, X is an anionic functional group, R^2 is an alkyl group,
cycloalkyl group or aralkyl group) and the general formula (II) ▲There are mathematical formulas, chemical formulas, tables, etc.▼(II) (However, R^1 is an alkyl group, an alkoxy group, a nitro group, a dialkylamino group) group or halogen, n is an integer of 0, 1, 2, or 3, and when n is an integer of 2 or 3, they may be the same or different groups). General formula (III) ▲There are mathematical formulas, chemical formulas, tables, etc.▼(III) (However, R^1 is an alkyl group, an alkoxy group, a nitro group, a dialkylamino group, or a halogen, and n is 0 or 1 , 2 or 3, and when n is an integer of 2 or 3, R^1 may be the same or different groups.R^
2 is an alkyl group, a cycloalkyl group, or an aralkyl group. ) A method for producing a novel trisazo compound.