JPH02275845A - Novel aldehyde compound and its production - Google Patents

Abstract

NEW MATERIAL:An aldehyde compound shown by formula I. USE:Useful as a synthetic intermediate for a hydrazone compound effective as a photoconductive material useful as a sensitized material for electrophotography. PREPARATION:A compound shown by formula I is obtained by so-called Vilsmeier-Haak reaction wherein a triphenylamine compound shown by formula II is treated with Vilsmeier reagent to form an ammonium salt, which is hydrolyzed. The Vilsmeier reagent can be prepared by treating an amide such as N-methylformanilide with an equimolar amount of an acid halide. The amount of the Vilsmeier reagent used is approximately theoretical ratio based on the compound shown by formula II, preferably >=1mol. The reaction temperature is 0 to 150 deg.C, preferably 20 to 100 deg.C. Hydrolysis, for example, is carried out in an aqueous solution of sodium hydroxide.

Description

[Detailed Description of the Invention] [Industrial Application Field] The present invention provides a novel aldehyde compound that is an important intermediate for hydrazone compounds that are effective as photoconductive materials used in electrophotographic photoreceptors, and a method for producing the same. This is what we provide.

[Conventional technology]

In the field of electrophotographic photoreceptors, various photoconductive materials to be used in the photosensitive layer have been studied, and certain hydrazone compounds have been found to be effective.
-52064, JP-A-57-58156, JP-A-5
It is reported in No. 758157, etc.

However, there are problems with decomposition due to ozone generated during corona charging, and stability against light and heat.
Electrophotographic photoreceptors using conventional hydrazone compounds do not fully satisfy the mechanical properties required of photoreceptors, and there has been a desire to develop even better photoreceptors.

The aldehyde compound of the present invention is a novel compound that can be used as an intermediate for the hydrazone compound. Of course, the manufacturing method is also unknown.

[Problem to be solved by the invention]

The object of the present invention is to provide novel aldehyde compounds derived from hydrazone compounds that can be used for the above-mentioned applications.

[Means to solve the problem]

As a result of intensive studies, the present inventors discovered a novel aldehyde compound represented by formula (I), and it became possible to synthesize a new type of hydrazone compound.

That is, one aspect of the present invention is an aldehyde compound represented by 2(I), and another aspect of the present invention is a method for producing the same.

The compound of the present invention is a so-called Vilsmeier-Haak compound in which a triphenylamine compound represented by formula (n) is reacted with a Vilsmeier reagent to produce an immonium salt intermediate, which is then hydrolyzed. ) reaction (^, Vil
sseier, A., Haak, Ber., 60,1
19 (I927)).

The Wilsmeier reagent used in the method of the present invention includes N,
Amides such as N-dimethylformamide and N-methylformanilide, phosphorus oxychloride, phosphorus oxybromide,
It can be prepared by known methods from acid halides such as phosgene and thionyl chloride. Preferably, it is Vilsmeier's reagent prepared from dimethylformamide and phosphorus oxychloride. In carrying out the method of the present invention, after preparing the Wilsmeier reagent in advance, the formula (
II) a method of reacting with a triphenylamine compound;
Alternatively, in a suitable solvent, in the presence of the triphenylamine compound of the formula ([1) and the above-mentioned amides, an acid halide is reacted to produce a Willsmeier reagent, and then the formula (
Either of the methods II) of reacting with a triphenylamine compound can be used. The Vilsmeyer reagent can be prepared by reacting equimolar amounts of the above-mentioned amides and acid halides. The amount of Wilsmeyer reagent used is:
A theoretical ratio may be used for the triphenylamine compound of formula (■), and is not particularly limited, but preferably 1 mol or more is used.

Solvents used in the reaction include aromatic hydrocarbons such as benzene and toluene, methylene chloride, chloroform, 1.
1-dichloroethane, 1,2-dichloroethane, 1,1
．． Examples include halogenated aliphatic hydrocarbons such as 1-trichloroethane, 1.1.2-trichloroethane and perchlorethylene, halogenated aromatic hydrocarbons such as monochlorobenzene and dichlorobenzene, acetonitrile, and ether. Additionally, N,N-dimethylformamide, which is suitable for preparing the Wilsmeier reagent, can also be used as a reaction solvent. Among these exemplified solvents, N,N-dimethylformamide can be preferably used. The amount used is not particularly limited, and the reaction proceeds whether the triphenylamine compound of formula (n) as a raw material is in a completely dissolved state or in a suspended state.

Usually, the amount of solvent is sufficient to be 1 to 10 times the weight of the raw material.

There is no particular restriction on the reaction temperature, - for boat fishing it is O~150
'C range, especially 20-100°C is preferred. Further, the reaction proceeds under reduced pressure, normal pressure, and increased pressure.

In this way, an immonium salt, which is a reaction intermediate resulting from the condensation of the triphenylamine compound of formula (II) and the Willsmeier reagent, is produced. The formed immonium salt is easily hydrolyzed by the action of water or alkaline aqueous solution,
It is derived from the aldehyde compound of the present invention represented by formula (I). As the alkaline aqueous solution, preferably used is an aqueous sodium hydroxide solution, an aqueous potassium hydroxide solution, an aqueous potassium acetate solution, an aqueous sodium acetate solution, or the like.

Hydrolysis does not require particular heating (it proceeds easily at room temperature).

After the reaction is completed, the target product can be extracted by a conventional method such as filtration or solvent extraction, and if necessary, purified by recrystallization, column chromatography, etc.

In this way, the aldehyde compound of the present invention can be produced.

(Functions and Effects) By reacting the novel aldehyde compound of the present invention with various 1,1-disubstituted hydrazines, it becomes possible to produce a novel and wide range of hydrazone compounds useful as photoconductive materials.

Therefore, the role of providing the novel aldehyde compound and the method for producing the same of the present invention is significant and valuable.

〔Example〕

The present invention will be described in detail below with reference to Examples.

Example 1 A triphenylamine compound represented by formula (II) (melting point 149-15
1.5°C) was dispersed, and 3.2g of phosphorus oxychloride was added dropwise at 0 to 5°C.

After stirring at the same temperature for 1 hour, the temperature was raised to 70-75°C and stirred for 3 hours. After the reaction solution was cooled to room temperature, it was poured into 200 d of ice water, and an aqueous sodium hydroxide solution was added to make it alkaline. After stirring for an additional hour, the precipitate was collected by filtration. The filter cake was dissolved in 100 mff1 of benzene, washed successively with a dilute aqueous sodium hydroxide solution and water, and then dried over anhydrous magnesium sulfate. After removing the drying agent, separation was performed by column chromatography (silica gel-benzene) and the effluent was concentrated to obtain 3.5 g of brown oil. After standing, the oil solidified into a yellow solid.

(Sinter from 93°C; λmax (CHClt) 38
9na+). The purity determined by high performance liquid chromatography was 99.7%.

This product was confirmed to be a compound of formula (I) by elemental analysis, infrared absorption spectrum, and nuclear magnetic resonance spectrum.

Elemental analysis value (as C2311tJO) CHN Calculated value (%) 88.20 5.12 3.1
2 Measured value (%) 88.04 5.10 3.
The 14 infrared absorption spectrum (KBr method) is shown in FIG. 1, and the nuclear magnetic resonance spectrum is shown in FIG.

[Brief explanation of drawings]

Figure 1 shows the infrared absorption spectrum (K
Br method), FIG. 2 is a diagram showing the nuclear magnetic resonance spectrum (CDCI s solution) of the compound of formula (+).

Claims (1)

[Claims] 1) An aldehyde compound represented by the formula (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼(I). 2) Formula (II) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ Formula (I) characterized in that the triphenylamine compound represented by (II) is hydrolyzed after acting with Vilsmeier's reagent. ▲ Formula , chemical formula, table, etc.▼(I) Production method of aldehyde compound represented by.