JPH08291125A - Production of cinnamic hydrazide derivative - Google Patents

Abstract

PURPOSE: To easily obtain in high yield a compound useful as an intermediate for photopolymerization initiators by reaction between a cinnamic ester derivative and a hydrazine hydrate in acetonitrile followed by taking the resultant deposit through filtration. CONSTITUTION: (A) A cinnamic ester derivative of formula I (R<1> -R<3> are each H, a halogen, 1-10C alkyl, 1-10C alkoxyl, 6-12C aryl, etc.; R<4> and R<5> are each H, 1-10C alkyl or 6-10C aryl; R<6> is a 6-12C aryl, 3-12C alkoxycarbonylmethyl or cyanomethyl)(e.g. 3-methoxy-4-methoxycarbonylmethoxycinnamic p-nitrophenyl ester) is reacted with (B) a hydrazine hydrate in acetonitrile (mixed solvent) followed by taking the crystal deposited in the resultant reaction mixture through filtration, and the deposit is washed with acetonitrile to obtain (C) the objective cinnamic hydrazide derivative of formula II (e.g. 3-methoxy-4- methoxycarbonylmethoxycinnamic hydrazide).

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a method for producing a hydrazide derivative useful as an intermediate for a halogen-substituted methyloxadiazole compound.

[0002]

2. Description of the Related Art Compounds (free-radical generators) that decompose to form free radicals when exposed to light are graphic arts,
It is well known in the field of photosensitive recording materials. They are widely used as photoradical polymerization initiators in photopolymerizable compositions, photoactivators in free radical photographic compositions and as photoinitiators of reactions catalyzed by photogenerated acids. Such free radical generators have been used to make a variety of photosensitive materials useful in printing, reproduction, reproduction and other recording material systems.

As such a compound, a halogen-substituted methyl oxadiazole compound has been proposed as a halogen free radical generating agent having a photosensitive wavelength in the near-ultraviolet to visible light region. For example, U.S. Pat. Nos. 4,212,970, 4,232,106, JP-A-55-24113, JP-A-60-177340 and JP-A-59-1487.
Detailed in No. 84 etc. These compounds are produced using a cinnamic acid hydrazide derivative as an intermediate. The method for producing the cinnamic acid hydrazide derivative described in the above patent is disclosed in W.
O. Godtfredsen, S.M. Vangedal
Written by Acta Chem. Scand. 9 1498
(1955) and S.S. Harada, H .; Kondo
By Bull. Chem. Soc. Jap. 41 (1
0) 2521 (1968). That is, an activated ester such as cyanomethyl ester of cinnamic acid or p-nitrophenyl ester is dissolved or dispersed in methanol, hydrazine hydrate is added, and the mixture is stirred at room temperature to solution reflux temperature to treat the reaction mixture with water. Is the way. However, this method has a drawback that there is an isolation loss due to the water solubility of the cinnamic acid hydrazide derivative.

[0004]

An object of the present invention is to provide a process for producing a cinnamic acid hydrazide derivative useful as an intermediate for a halogen-substituted methyloxadiazole compound.

[0005]

The object of the present invention is to react a cinnamic acid ester derivative represented by the following general formula (I) with hydrazine monohydrate in acetonitrile or a mixed solvent of acetonitrile, and This was achieved by a method for producing a cinnamic acid hydrazide derivative represented by the general formula (II), characterized in that the target substance precipitated in the mixture was collected by filtration. General formula (I)

[0006]

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In the formula, R ¹ , R ² and R ³ may be the same or different and each is a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms which may have a substituent, a substituent An alkoxy group having 1 to 10 carbon atoms which may have a group, an aryl group having 6 to 12 carbon atoms which may have a substituent, or a carbon which may have a substituent It represents an alkenyl group having 2 to 12 atoms, R ⁴ and R ⁵ may be the same or different, and may have a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or a substituent. Represents a good aryl group having 6 to 12 carbon atoms, R ⁶ represents an aryl group having 6 to 12 carbon atoms which may have a substituent, an alkoxycarbonylmethyl group having 3 to 12 carbon atoms, Or cyanomethyl Represents a group.

General formula (II)

[0009]

[Chemical 4]

In the formula, R ¹ , R ² , R ³ , R ⁴ and R ⁵ represent the same groups as in formula (I).

In the general formula (I), R ¹ , R ² and R ³
Examples of the substituted alkyl group, the substituted alkoxy group, the substituted aryl group and the substituted alkenyl group, which may be the same or different, are a hydroxyl group, an aryl group, a halogen atom, an alkoxy group, a carboxyl group, an alkoxycarbonyl group, An aryloxycarbonyl group, a cyano group, an acyl group and the like can be mentioned, and among them, particularly preferable are a hydroxyl group, an aryl group having 6 to 10 carbon atoms, a halogen atom, an alkoxycarbonyl group having 2 to 11 carbon atoms or a carbon atom. It is an acyl group of the number 2 to 10.

In the general formula (I), preferred R ¹ and R ^{2 are}
And R ³ may be the same or different, and are each a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or a substituent. A substituted alkoxy group which is a hydroxyl group, a halogen atom, an alkoxycarbonyl group having 2 to 11 carbon atoms or an acyl group having 2 to 10 carbon atoms, an alkenyl group having 2 to 8 carbon atoms, or a substituent having 6 carbon atoms. To 10 are aryl groups or substituted alkenyl groups which are alkoxycarbonyl groups having 2 to 11 carbon atoms, in particular hydrogen atoms, chlorine atoms, bromine atoms, alkoxy groups having 1 to 6 carbon atoms, and substituents are carbon atoms. Number 2
A substituted alkoxy group which is an alkoxycarbonyl group having 1 to 7 or an acyl group having 2 to 6 carbon atoms, or a substituted alkenyl group which has a phenyl group as a substituent.

In the general formula (I), R ¹ , R ² and R ³
Specific examples of the following include, but are not limited to, the following.

[0014]

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In the general formula (I), preferable R ⁴ and R ⁵ may be the same or different and each is a hydrogen atom,
It is an alkyl group having 1 to 5 carbon atoms or a phenyl group, and a hydrogen atom is particularly preferable.

In the general formula (I), preferred R ⁶ is a phenyl group, a substituent is a cyano group, a nitro group, a phenyl group having a halogen atom or an alkoxycarbonyl group having 2 to 5 carbon atoms, and 3 carbon atoms. Up to 6 alkoxycarbonylmethyl groups or cyanomethyl groups, particularly preferably phenyl group, p-nitrophenyl group, methoxycarbonylmethyl group, ethoxycarbonylmethyl group, or cyanomethyl group.

Specific examples of the general formula (I) include, but are not limited to, the followings.

4-methoxycinnamic acid phenyl ester, 4
-N-butoxycinnamic acid p-nitrophenyl ester, 4
-Acetoxyethoxycinnamic acid phenyl ester, 4-hydroxyethoxycinnamic acid phenyl ester, 4-hydroxyethoxycinnamic acid cyanomethyl ester, 4-styrylcinnamic acid p-nitrophenyl ester, 3-methoxy-
4-Methoxycarbonylmethoxycinnamic acid phenyl ester, 3-methoxy-4-methoxycarbonylmethoxycinnamic acid p-nitrophenyl ester, 3-methoxy-4-
Methoxycarbonylmethoxy cinnamic acid cyanomethyl ester, 4-acetoxyethoxy-3-methoxycinnamic acid phenyl ester, 4-chloroethoxy-3-methoxycinnamic acid phenyl ester, 3-ethoxy-4-ethoxycarbonylmethoxycinnamic acid phenyl ester, 3 -Methoxy-4-methoxycarbonylethoxy cinnamic acid phenyl ester, 4-ethoxycarbonylethoxy-3-methoxycinnamic acid phenyl ester, 3-methoxy-4-methoxycarbonylpropoxycinnamic acid phenyl ester, 3-chloro-4-ethoxycarbonylmethoxy Cinnamic acid phenyl ester, 4-methoxy-3-methoxycarbonylmethoxycinnamic acid phenyl ester, 4-methoxy-3-methoxycarbonylmethoxycinnamic acid p-nitrophenyl ester, 3,5-di Butoxy-4-methoxycarbonyl-methoxycinnamic acid phenyl ester.

The manufacturing method according to the present invention is represented by the following reaction formula.

[0020]

[Chemical 6]

The production method of the present invention is carried out by mixing the cinnamic acid ester derivative and hydrazine monohydrate in acetonitrile or a mixed solvent of acetonitrile and stirring. The method of dropping hydrazine monohydrate is preferred.

The hydrazine monohydrate is preferably an aqueous solution of 70% to 100%, and the amount of the hydrazine monohydrate used is 1.0 mol to 1.0 mol of the cinnamic acid ester derivative.
2.0 mol is preferable, and 1.0 mol to 1.2 mol is particularly preferable.

The amount of acetonitrile used is preferably 0.5 l to 5.0 l, particularly preferably 0.5 l to 3.0 l, based on 1.0 mol of the cinnamic acid ester derivative.

An auxiliary solvent may be used in the reaction, and as the solvent, methanol, ethanol isopropanol,
Ethyl acetate, tetrahydrofuran, acetone, water and the like are preferable. The amount of the auxiliary solvent used is preferably 0.5 l or less, and particularly preferably 0.3 l or less, relative to 1 l of acetonitrile.

The dropping temperature of hydrazine monohydrate is from 0 ° C to
40 ° C. is preferable, and 10 ° C. to 30 ° C. is particularly preferable,
The reaction temperature is preferably 0 ° C to 90 ° C, particularly 10 ° C.
~ 65 ° C is preferred.

In the production method of the present invention, the cinnamic acid hydrazide derivative is obtained by filtering the crystals of the target substance precipitated in the reaction mixture. The reaction mixture may be filtered as it is after the reaction, or may be cooled to some extent and then filtered. In addition, the reaction mixture may be diluted with a solvent compatible with acetonitrile or a poor solvent for the product, if necessary, and then filtered. Of these solvents, methanol, ethanol, isopropanol, ethyl acetate and the like are preferable.

After the above filtration, the obtained target substance may be washed with acetonitrile or a mixed solvent containing acetonitrile.

Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples.

[0029]

【Example】

Example 1 (Synthesis of 3-methoxy-4-methoxycarbonylmethoxycinnamic acid hydrazide) 3-methoxy-4-methoxycarbonylmethoxycinnamic acid p-nitrophenyl ester 7
In a 380 ml solution of 4.1 g of acetonitrile, 80%
11.6 ml of hydrazine monohydrate was added dropwise, and the mixture was mixed at 18 ° C for 3 hours.
Stirred for hours. The reaction mixture was cooled to 7 ° C., the precipitated crystals were filtered, washed with 22 ml of acetonitrile, and 3-
47.4 g of methoxy-4-methoxycarbonylmethoxycinnamic acid hydrazide was obtained (yield 87%, melting point 143-1).
44 ° C).

Example 2 (Synthesis of 4-methoxy-3-methoxycarbonylmethoxycinnamic acid hydrazide) 4-methoxy-3-methoxycarbonylmethoxycinnamic acid p-nitrophenyl ester 7
99% in a solution of 4.1 g of acetonitrile in 380 ml
9.6 ml of hydrazine monohydrate was added dropwise, and the mixture was stirred at 18 ° C for 3 hours. The reaction mixture was cooled to 7 ° C., and the precipitated crystals were filtered and washed with 22 ml of acetonitrile to obtain 46.3 g of 4-methoxy-3-methoxycarbonylmethoxycinnamic acid hydrazide (yield 85%, melting point 146-14.
7 ° C).

Example 3 (Synthesis of 4-acetoxyethoxy-3-methoxycinnamic acid hydrazide) 4-acetoxyethoxy-3-methoxycinnamic acid phenyl ester 35.6 g of acetonitrile 15
5.0 ml of 99% hydrazine monohydrate in 0 ml solution
Was added dropwise, and the mixture was stirred at 20 ° C. for 3 hours. Reaction mixture at 5 ° C
Cooled to room temperature, the precipitated crystals are filtered, and acetonitrile 1
After washing with 5 ml, 23.5 g of 4-acetoxyethoxy-3-methoxycinnamic acid hydrazide was obtained (yield 80%, melting point 191-193 ° C).

Example 4 (Synthesis of 4-β-hydroxyethoxycinnamic acid hydrazide) In a solution of 28.4 g of 4-β-hydroxyethoxycinnamic acid phenyl ester in 150 ml of acetonitrile, 9
5.0 ml of 9% hydrazine monohydrate was added dropwise, and the mixture was stirred at 20 ° C. for 3 hours. The reaction mixture was cooled to 5 ° C., the precipitated crystals were filtered, washed with 15 ml of acetonitrile and washed with 4
-Β-hydroxyethoxycinnamic acid hydrazide was added to 18.4
g (yield 83%, melting point 128-129 ° C.).

Comparative Example 1 (Comparison with Example 1) According to the method described in JP-A-55-24113, 3-methoxy-4-methoxycarbonylmethoxymethoxycinnamic acid p-nitrophenyl ester 7 was used.
To a solution of 4.1 g of methanol in 250 ml, 11.6 ml of 80% hydrazine monohydrate was added dropwise, and the mixture was heated under reflux for 30 minutes. According to the method described in this publication, the reaction mixture was allowed to cool, 21 g of triethylamine was added, and the mixture was poured into 1.3 l of water, crystals did not precipitate, and the product could not be isolated.

Comparative Example 2 (Comparison with Example 1) According to the method described in JP-A-55-24113, 3-methoxy-4-methoxycarbonylmethoxy cinnamic acid p-nitrophenyl ester 74.
11.6 ml of 80% hydrazine monohydrate was added dropwise to a 250 ml solution of 1 g of methanol, and the mixture was heated under reflux for 30 minutes. The reaction mixture was cooled to 7 ° C., the precipitated crystals were filtered, washed with 22 ml of methanol, and 3-methoxy-4-
Methoxycarbonyl methoxycinnamic acid hydrazide 5.2
Although g (yield 9.8%) was obtained, the yield was remarkably low as compared with the method of reacting with acetonitrile of the present invention.

[0035]

Industrial Applicability According to the production method of the present invention, a cinnamic acid hydrazide derivative, which is a useful intermediate of a halogen-substituted methyloxadiazole compound useful as a photopolymerization initiator, can be easily produced in high yield.

Claims (1)

[Claims] 1. A cinnamic acid ester derivative represented by the following general formula (I) and hydrazine monohydrate are reacted in acetonitrile or in a mixed solvent of acetonitrile, and the target substance precipitated in the reaction mixture is collected by filtration. A method for producing a cinnamic acid hydrazide derivative represented by the general formula (II), wherein General formula (I) In the formula, R ¹ , R ² and R ^{3, which} may be the same or different, each represent a hydrogen atom, a halogen atom, an optionally substituted alkyl group having 1 to 10 carbon atoms, or a substituent. Optionally substituted alkoxy group having 1 to 10 carbon atoms, optionally substituted 6 to 12 carbon atoms
Up to aryl groups or alkenyl groups having 2 to 12 carbon atoms which may have a substituent, R ⁴ and R ⁵ may be the same or different, and each of them may be a hydrogen atom or 1 carbon atom. To an alkyl group having from 10 to 10 or an aryl group having from 6 to 12 carbon atoms which may have a substituent, and R ⁶ has from 6 to 12 carbon atoms which may have a substituent. It represents an aryl group, an alkoxycarbonylmethyl group having 3 to 12 carbon atoms, or a cyanomethyl group. General formula (II): In the formula, R ¹ , R ² , R ³ , R ⁴ and R ⁵ represent the same groups as in formula (I).