JPS62249948A - Squarylium compound and production thereof - Google Patents

Abstract

NEW MATERIAL:A compound of formula I (R3 is H, F, methyl, hydroxyl; R1 is methyl, R2 is ethyl, benzyl, p-fluorobenzyl, p-chlorobenzyl or they are identical and represent ethyl, benzyl). USE:An organic photoconductive material such as an electrophotographic photoreceptor. It is used as a photoconductive substance for the electric charge- generating layer in the photosensitive material which is composed of the charge- generating layer and the charge-transferring layer. PREPARATION:For example, the Friedel-Craft reaction between 3,4-dichloro-3- cyclobutene-1,2-dione of formula II and an aniline derivative of formula III is carried out in the presence of a catalyst such as AlCl3 in a solvent. The product of formula IV is hydrolyzed in a water-acetic acid mixed solvent under reflux into a compound of formula V. The compound is heated together with an aniline derivative of formula VI under reflux in a solvent or under reduced pressure to remove the water formed whereby the compound of formula I of high purity is obtained.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to an asymmetric square IJ compound useful as a photoconductive material and a method for producing the same.

[Conventional technology]

Many inorganic and organic substances are known as photoconductive materials for electrophotographic photoreceptors and the like. Among these, conventionally known organic photoconductive materials include bisazo pigments, trisazo pigments, phthalocyanine pigments, cyanines, and pyrylium pigments. , representing a hydroxyl group or a methyl group) have been proposed.

These organic photoconductive materials generally have low sensitivity;
Furthermore, when used as a photoconductive material, it has drawbacks such as insufficient charging properties and low solubility in adhesive resins, and does not necessarily have satisfactory performance.

On the other hand, asymmetric squareylium compounds that have photoconductivity are also known, but in order to react simultaneously with square phosphoric acid and two types of aniline derivatives, it is necessary to combine an asymmetric compound and a symmetric square compound. A mixture of compounds is produced, which is difficult to separate, and no single product has been obtained.

[Problem that the invention seeks to solve]

An object of the present invention is to provide a novel asymmetric square aryllium compound and a method for producing the same.

[Failure to solve the problem]

As a result of extensive research, the present inventors reacted R4-dichloro-3-cyclobutene-L2-dione (square link acid chloride) with an aniline derivative to obtain a chlorocyclobutenedione derivative, and this derivative The present invention was completed based on the discovery that an asymmetric squarelylium compound can be easily obtained with high purity by hydrolyzing a hydroxycyclobutenedione derivative and then reacting the derivative with another aniline derivative.

That is, the present invention is based on the general formula (Il e [wherein R3 represents a hydrogen atom, a fluorine atom, a methyl group, or a hydroxyl group, and R1 and R2 are such that R1 is a methyl group and R2 is an ethyl group, an indyl group, a p-fluoro Does it represent a benzyl group or a p-chlorobenzyl group?

The present invention provides a squarelylium compound represented by (c), both of which represent an ethyl group or a benzyl group, and a method for producing the same.

The asymmetric type e represented by the general formula (I) of the present invention will be described below.The present invention is also directed to two methods for producing the squarelylium compound represented by the general formula (11).

The production method of the present invention is shown by reaction scheme A and reaction scheme B below.

Reaction scheme A <W> (V) (V)
(V[) Reaction formula B el (II) (Vl) (■(
■) (■) (I) [In reaction schemes A and B, R□, R2 and R
3 represents the same meaning as above. ] The difference between the reaction process scheme and B is that the aniline derivative to be reacted with the square acid chloride is an aniline derivative of formula (m) in the former, whereas it is an aniline derivative of formula (M) in the latter, Therefore, the subsequent steps (C1 and (C)'
Although the aniline derivatives reacted with are the reverse of this, the reaction operations are almost the same, so they will be explained together.

In the first reaction step (al and (已)'), the aniline derivative (III) or (■) is reacted at a molar ratio of 1 to 5 with respect to the square acid chloride (Ill. In this case, the raw material aniline If the derivative is a liquid, it also serves as a solvent, so it is not necessary to use a solvent, but it is possible to use ordinary free chemicals such as methylene chloride, carbon tetrachloride, halogenated hydrocarbons such as chloroform, nitrobenzene, ethyl ether, carbon disulfide, acetonitrile, etc. It is preferable to use a solvent for the Clach reaction.

The reaction proceeds even without the use of a catalyst, but for aniline derivatives with particularly low reactivity (where R3 is a fluorine atom), the catalyst used in the usual Friedel-Craflu reaction,
For example, aluminum chloride, antimony chloride, iron chloride (I
ll, iron chloride C']II), titanium chloride (■), boron trifluoride, tin chloride (■), bismuth chloride (■),
Zinc chloride (■), mercury chloride, etc. are added in an amount of 0.01 fi or more, preferably 0.1 to 1
Equivalent amounts are used.

The reaction is carried out at a temperature of 0 to 80°C, preferably 0 to 40°C, and the reaction time is 30 minutes to 20 hours.

After the reaction is completed, it is post-treated in a conventional manner and separated and purified by column chromatography or the like to obtain the chlorocyclobutenedione derivative (IV) or (■).

In the second stage reaction steps (b) and (b)', the chlorocyclobutenedione derivative (IV) or (■) produced in the first stage is hydrolyzed to produce the corresponding hydroxycyclobutenedione derivative (V) or (■l) This is the stage of t[. This hydrolysis reaction can be carried out, for example, by refluxing in acetic acid containing a small amount of water. After the reaction is completed, the produced crystals are separated from the furnace and washed to obtain a highly pure target product almost quantitatively.

The third reaction step (cl and (C)') involves reacting the hydroxycyclobutenedione (V) or (■) obtained in the second step with the aniline derivative (■) or (Ill) to obtain the final target product. This is a step to obtain an asymmetric square lylium compound gold.Since this reaction is a dehydration condensation reaction, it is preferable to carry out the reaction while removing the water produced by refluxing in a solvent or heating under reduced pressure. As the solvent in this case, a primary or secondary alcohol having 2 to 10 carbon atoms, or an azeotropic mixture of hasolella alcohol and an aromatic hydrocarbon such as benzene, toluene, or xylene, etc. can be effectively used.

The reaction temperature is preferably 80-140°C, and the reaction time is 2-140°C.
It is 50 hours.

After the reaction is completed, the generated crystal eF is separated, washed with ethanol, ether, etc., and then dried to obtain a highly purified asymmetric square lylium compound in high yield.

〔Effect of the invention〕

The present invention provides a novel asymmetric square IJ+J compound and a method for producing the same. According to the present invention, it is possible to easily obtain an asymmetric square aryllium compound with high purity. The square IJ compound of the present invention can be effectively used as an organic photoconductor such as an electrophotographic photoreceptor. Various types of electrophotographic photoreceptors can be considered, but in particular, the square aryllium compound of the present invention is a functionally separated photoreceptor, that is, a photoreceptor composed of a charge generation layer and a charge transport layer. It is useful as a photoconductive material used as a photoconductive material.

〔Example〕

The present invention will be explained below with reference to Examples.

Example 1 3.009 of 3.4-dichloro-3-7clopten-1.2-dione and 2.659 of aluminum chloride were kept at 5° C. or below in 30 ml of methylene chloride and stirred until the aluminum chloride was dissolved. To this, 2.439 N,N-dimenalaniline was added dropwise for 30 minutes, and then 2.5
The reaction was maintained at 5° C. or lower for a period of time.

After the reaction was completed, IM-H (4) was washed with water and then separated by column chromatography to produce the product shown by the following formula (
1.649 (yield: 35%) of the compound in which R3=H in the formula (2) was obtained.

Next, add 1.569' of this compound to 30M of glacial acetic acid and 6d of water.
After refluxing for 2 hours in a mixed solvent of
9 (yield 96%) was obtained.

Next, 0.459 of this product and 0.579 of N,N-dibenzylaniline were refluxed in 41 t/phthanol for 20.5 hours and then separated to obtain blue crystals. This is methanol,
After washing with ether and drying, the product represented by the structural formula (6) was obtained. Yield: 0.729 (74% yield).

Decomposition point: 250.5℃; Elemental analysis CHN calculated value as C3A8N20□ (%l 81.33 5.97 5.9
3 Actual value (%l 81.40 5.98 5.
95 maximum absorption wavelength λmax: 628 nm (CH2
Cj+2 middle).

Example 2 44-dichloro-3-cyclosthene-L2-dione 3.
369 and aluminum chloride 3.299 were stirred in 20° C. of methylene chloride while keeping the temperature below 5° C. until the aluminum chloride was dissolved. To this, a solution of N-methyl-N-ethelaniline 3.0291iE dissolved in methylene 12-
The mixture was added dropwise over a period of time, and then the temperature was kept below 5° C. for 2.5 hours to react. After the reaction was completed, it was washed with IM-HCp and water. Next, it is separated by column chromatography to produce a product represented by the following formula (■Formula-t'' R,=CH3,R2=
1.78 g (yield 32%) of C2f (5tD compound) was obtained.

Next, this compound 1.509. Glacial acetic acid 30ml, water 4t
/'i After refluxing for 4 hours and cooling to room temperature, crystals were precipitated with a small amount of water to produce a product represented by the following formula (■Formula TE R1-CH3, R2=C2H
5(7) Compound) 1.189 (yield: 85%) was obtained.

Then this product 1.009. After refluxing 1.579 g of N,N-dimethylaniline in 10 g of butanol and 5 g of toluene for 5 hours, the mixture was separated from the furnace to obtain blue-green crystals.

After washing with gold methanol and drying, the structural formula (1) is obtained.
The product shown was obtained. Yield 1.049 (yield 72%
).

Decomposition point: 228℃; Elemental analysis: HN calculated value as C2□H2□N20□ (%+ 75.42 6,63 8.3
8 Actual value (%+ 75.41 6.65 8.
34 maximum absorption wavelength λmax: 62 g nm (O
H2 (in 42); IR spectrum: Figure 1.

Example 3 34-dichloro-3-cyclobutene-A2-dione 30
09 and aluminum chloride 2.659 and total methylene chloride 3
The temperature was maintained at 5° C. or lower in 0 ml of water and stirred until the aluminum chloride was dissolved.

Add 3-dimethylaminephenol 2.739 to this
The mixture was added dropwise over a period of minutes, and then the temperature was maintained at 5° C. or lower for 2.5 hours to react. After the reaction is completed, the product is washed with 1 M -HCl and water, and then separated by column chromatography to obtain the product represented by the following formula (compound of R3-OH in formula ①).
1.509 (yield 30%) was obtained.

Next, this compound 1.509, 30 g of glacial acetic acid, and 6 ml of water were refluxed for 2 hours, cooled to room temperature, and then separated from the furnace to produce a product represented by the following formula (a compound of R3-OH in formula ①).
1.339 (yield: 96 cm) was obtained.

This product was then refluxed for 20 hours in 1.009 kg of N-methyl-N-ethelaniline and 1.749 kg of butanol, followed by furnace separation to give evening green crystals.

This was washed with methanol and diethyl ether and then dried to obtain a product represented by the structural formula (19).

Yield: 0.939 (62% yield).

Decomposition point = 243℃; Elemental analysis: CHN as C2□H2□NO3 Calculated value (%) 75.42 6.63 8.3
8 Actual value (%+ 75.22 6.51 8.
32 maximum absorption wavelength λmaX: 630 nm (CH2CA2
During).

Examples 4 to 24 Twenty-one types of squarelylium compounds were totally synthesized in the same manner as in Example 1, except that the raw material aniline derivatives used were changed. Synthesized square aryllium compound, its elemental analysis results, and maximum absorption wavelength λm in dichloromethane
ax k shown in Table 2.

Further, the R spectrum of the compound (A 22 ) obtained in Example 17 is shown in FIG.

[Brief explanation of drawings]

FIGS. 1 and 2 are IR spectral diagrams of examples of square lylium compounds of the present invention. Heaving r

Claims (1)

[Claims] 1) General formula (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (I) [In the formula, R_3 represents a hydrogen atom, a fluorine atom, a methyl group, or a hydroxyl group, and R_1 and R_2 are R_1 represents a methyl group and R_2 represents an ethyl group, benzyl group, p-fluorobenzyl group or p-chlorobenzyl group,
Both represent an ethyl group or a benzyl group. ] A squarerium compound represented by. 2) Formula (II) ▲There are mathematical formulas, chemical formulas, tables, etc.▼(II) 3,4-dichloro-3-cyclobutene-1,
2-dione and general formula (III) ▲Mathematical formulas, chemical formulas, tables, etc.▼(III) [In the formula, R_3 represents a hydrogen atom, a fluorine atom, a methyl group, or a hydroxyl group. [In the formula, R_3 represents the same meaning as above. ] is obtained, and then the compound of general formula (III) is hydrolyzed to form general formula (V) ▲There are mathematical formulas, chemical formulas, tables, etc.▼(V) [In the formula, R_3 is Same meaning as above. [In the formula, R_1 and R_2 are both ethyl groups or It represents a benzyl group, or R_1 is methyl and R_2 represents an ethyl group, benzyl group, p-fluorobenzyl group or p-chlorobenzyl group. ] General formula (I) characterized by reacting with the aniline derivative represented by ▲ Numerical formulas, chemical formulas, tables, etc.▼ (I) [In the formula, all symbols have the same meanings as above. ] A method for producing a squarerium compound. 3) Formula (II) ▲There are mathematical formulas, chemical formulas, tables, etc.▼(II) 3,4-dichloro-3-cyclobutene-1,
2-dione and general formula (VI) ▲Mathematical formulas, chemical formulas, tables, etc.▼(VI) [In the formula, R_1 and R_2 both represent an ethyl group or a benzyl group, or R_1 is methyl and R_2 is an ethyl group or benzyl group. p-fluorobenzyl group or p-chlorobenzyl group. ] By reacting with the aniline derivative represented by the general formula (VII)
▲There are mathematical formulas, chemical formulas, tables, etc.▼ (VII) [In the formula, R_1 and R_2 represent the same meanings as above. ] to obtain a chlorocyclobutenedione derivative,
Next, the compound of the general formula (VII) is hydrolyzed to form the general formula (VIII) ▲Mathematical formula, chemical formula, table, etc.▼(VIII) [In the formula, R_1 and R_2 represent the same meanings as above. [In the formula, R_3 is a hydrogen atom, a fluorine atom, Represents a methyl group or a hydroxyl group. ] General formula (I) characterized by reaction with the aniline derivative represented by ▲ Numerical formulas, chemical formulas, tables, etc.▼ (I) [In the formula, all symbols have the same meanings as above. ] A method for producing a squarerium compound.