JP2002322124A - Method for producing unsaturated dicarboxylic ester - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method by which a high purity product can be obtained in short reaction time, for producing an unsaturated dicarboxylic ester having an oxycarbonyl methyl ester group and/or a carbonyl methyl ester group. SOLUTION: The method for producing the unsaturated dicarboxylic ester is characterized by reacting an α-chloro carboxylic ester and/or an α-chloro ketone with a salt of a kind of unsaturated carboxylic acid selected from a group consisting of itaconic acid, itaconic half ester, fumaric acid, fumaric half ester, maleic acid and maleic half ester in the presence a salt of which the counter ion is a bromide ion and/or a salt of which the counter ion is an iodide ion.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to an unsaturated dicarboxylic acid ester and a method for producing the same. More specifically, the present invention relates to a method for producing an unsaturated dicarboxylic acid ester having an oxycarbonylmethyl ester group and / or a carbonylmethyl ester group, such as itaconic acid ester, fumaric acid ester or maleic acid ester. The unsaturated dicarboxylic acid ester obtained by the present invention is a compound having both an active ester group and an unsaturated double bond,
It is a compound applicable to various uses such as paints and adhesives.

[0002]

2. Description of the Related Art Conventionally, as a compound having both an oxycarbonylmethyl ester group which is one of active ester groups and a polymerizable unsaturated double bond, German Patent No. 196071
No. 6 (meth) acrylic acid and α
Esters with hydroxycarboxylic acids are known.
However, a derivative of an unsaturated dicarboxylic acid ester having an oxycarbonylmethyl ester group and / or a carbonylmethyl ester group, such as an itaconic ester, a fumaric ester or a maleic ester, is not known.

[0003]

SUMMARY OF THE INVENTION However, the present inventors have conducted intensive studies to develop a novel unsaturated dicarboxylic acid ester having an oxycarbonylmethyl ester group and / or a carbonylmethyl ester group as an active ester group. Started. The object of the present invention is to achieve a short reaction time,
Provided is a method for producing an unsaturated dicarboxylic acid ester having an oxycarbonylmethyl ester group and / or a carbonylmethyl ester group from which a high-purity target product can be obtained in a high yield. It is an object of the present invention to provide a method for producing a target product having high purity by suppressing the production.

[0004]

Means for Solving the Problems The inventors of the present invention have conducted intensive studies to solve the above-mentioned problems, and as a result, itaconic ester and fumaric acid having an oxycarbonylmethyl ester group and / or a carbonylmethyl ester group. The present inventors have found a method for producing an unsaturated dicarboxylic acid ester such as an ester or a maleic acid ester in a short reaction time with high purity and high yield, and have completed the present invention.

That is, the present invention relates to a salt (A) of one kind of unsaturated carboxylic acid selected from the group consisting of itaconic acid, itaconic acid half ester, fumaric acid, fumaric acid half ester, maleic acid and maleic acid half ester To
Α-chlorocarboxylic acid ester (D) and / or α-chloroketone (E) in the presence of salt (B) in which the counter ion is bromide and / or salt (C) in which the counter ion is iodide
And a method for producing an unsaturated dicarboxylic acid ester.

[0006]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below in detail. The salt of itaconic acid half ester used in the present invention is prepared, for example, from the itaconic acid half ester represented by the following general formula (I). The fumaric acid half ester salt or maleic acid half ester salt is prepared from fumaric acid half ester or maleic acid half ester represented by the following general formula (II).

[0007]

Embedded image

In the formulas (I) and (II), R ^a and R
^b is a group in which one is a hydrogen atom and the other is —CH (R ₁ ) C
OOR ₂ , —CH (R ₃ ) COR ₄ or R ₅ . R ₁ and R ₃ contained therein each independently represent a hydrogen atom, a phenyl group or an alkyl group having 1 to 12 carbon atoms, and R ₂ , R ₄ and R ₅ each independently represent:
Represents a monovalent organic group. ]

The itaconic acid half ester represented by the general formula (I) includes the following general formulas (I-1), (I-2),
There are compounds represented by (I-3), (I-4), (I-5) and (I-6).

[0010]

Embedded image

[Wherein, R ₁ and R ₃ each independently represent a hydrogen atom, a phenyl group or a carbon atom number of 1 to 12;
R ₂ , R ₄ and R ₅ each independently represent a monovalent organic group. ]

The fumaric acid half ester or maleic acid half ester represented by the general formula (II) includes:
There are compounds represented by the following general formulas (II-1), (II-2) and (II-3).

[0013]

Embedded image

[Wherein, R ₁ and R ₃ each independently represent a hydrogen atom, a phenyl group or a carbon atom number of 1 to 12;
R ₂ , R ₄ and R ₅ each independently represent a monovalent organic group. ]

The above general formulas (I), (II) and (I-1)
In (I-6) and (II-1) to (II-3), typical examples of the monovalent organic group R ₂ , R ₄ and R ₅ include an alkyl group, a substituted alkyl group and a cycloalkyl group. Alkyl group,
And an aryl group and a substituted aryl group.

Among such monovalent organic groups, typical examples of the alkyl group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group and an iso-group.
-Butyl group, sec-butyl group, tert-butyl group,
n-pentyl group, n-hexyl group, 2-ethylhexyl group, n-octyl group, n-decyl group, n-dodecyl group,
And the like.

Representative examples of the substituted alkyl group include:
2-methoxyethyl group, 2-ethoxyethyl group, 2-
An alkyl group substituted by an alkoxy group such as a (n-propoxy) ethyl group, a 2- (n-butoxy) ethyl group, a 3-methoxypropyl group, or a 2- (n-hexyloxy) ethyl group; a 2-phenoxyethyl group; An alkyl group substituted by an aryloxy group such as a 2- (4-methylphenoxy) ethyl group; a 2-benzyloxyethyl group, a 2- (2-
An alkyl group substituted with an aralkyloxy group such as phenylethoxy) ethyl group; an alkyl group substituted with an aryl group such as benzyl group, 1-phenylethyl group and 2-phenylethyl group.

Representative examples of the cycloalkyl group include a cyclopentyl group, a cyclohexyl group, a 4-methylcyclohexyl group and a cyclooctyl group.

Representative examples of the aryl group include a phenyl group, a 1-naphthyl group and a 2-naphthyl group.

Representative examples of the substituted aryl group include:
Examples thereof include a 2-methylphenyl group, a 4-methylphenyl group, and a 4-nitrophenyl group.

In the above general formulas (I) and (II), R ₁ and R ₃ each independently represent a hydrogen atom, a phenyl group or an alkyl group having 1 to 12 carbon atoms. When R ₁ is an alkyl group having 1 to 12 carbon atoms, a typical example of the alkyl group is one of the above-described monovalent organic groups. And the like.

[0022] Among the itaconic acid half ester represented by the general formula containing monovalent organic group of various as mentioned above as R ₂ (I-1) and (I-2), have a alkyl group as R ₂ Representative compounds having a hydrogen atom as R ₁ include mono (methoxycarbonylmethyl) itaconate and mono (ethoxycarbonylmethyl)
Itaconate, mono (n-propoxycarbonylmethyl) itaconate, mono (iso-propoxycarbonylmethyl) itaconate, mono (n-butoxycarbonylmethyl) itaconate, mono (iso-butoxycarbonylmethyl) itaconate, mono (n-hexyloxycarbonylmethyl) ) Itaconate, mono (2-ethylhexyloxycarbonylmethyl) itaconate, mono (n-decyloxycarbonylmethyl) itaconate,
And the like.

Among the itaconic acid half esters represented by the general formulas (I-1) and (I-2), compounds having an alkoxy-substituted alkyl group as R ₂ and a hydrogen atom as R ₁ Representative examples include mono (2-methoxyethoxycarbonylmethyl) itaconate, mono (2-ethoxyethoxycarbonylmethyl) itaconate, mono [2- (n-propoxy) ethoxycarbonylmethyl] itaconate, and mono [2- (n -Butoxy) ethoxycarbonylmethyl] itaconate, mono (3-methoxypropoxycarbonylmethyl) itaconate, mono [2- (n-hexyloxy) ethoxycarbonylmethyl] itaconate, and the like.

In the itaconic acid half esters represented by the general formulas (I-1) and (I-2), R ₂ has an alkyl group substituted by an aryloxy group, and R ₁ has a hydrogen atom. Typical examples of the compound having the compound include mono (2-phenoxyethoxycarbonylmethyl) itaconate and mono [2- (4-methylphenoxy) ethoxycarbonylmethyl] itaconate.

In the itaconic acid half esters represented by formulas (I-1) and (I-2), R ₂ has an alkyl group substituted by an aralkyloxy group, and R ₁ has a hydrogen atom. Representative compounds having
Mono (2-benzyloxyethoxycarbonylmethyl)
Itaconate, mono [2- (2-phenylethoxy) ethoxycarbonylmethyl] itaconate, and the like.

In the itaconic acid half esters represented by formulas (I-1) and (I-2), R ₂ has an alkyl group substituted with an aryl group, and R ₁ has a hydrogen atom. Representative examples of the compound include mono (benzyloxycarbonylmethyl) itaconate, mono (1-phenylethoxycarbonylmethyl) itaconate, mono (2-phenylethoxycarbonylmethyl) itaconate, and the like.

Among the itaconic acid half esters represented by formulas (I-1) and (I-2), representative compounds having a cycloalkyl group as R ₂ and a hydrogen atom as R ₁ Examples include mono (cyclopentyloxycarbonylmethyl) itaconate, mono (cyclohexyloxycarbonylmethyl) itaconate, mono (4-methylcyclohexyloxycarbonylmethyl)
Itaconate, and the like.

Among the itaconic acid half esters represented by the general formulas (I-1) and (I-2), representative compounds having an aryl group as R ₂ and a hydrogen atom as R ₁ Examples thereof include mono (phenoxycarbonylmethyl) itaconate, mono (1-naphthoxycarbonylmethyl) itaconate, and mono (2-naphthoxycarbonylmethyl) itaconate.

Representative of the compounds having a substituted aryl group as R ₂ and a hydrogen atom as R ₁ among the itaconic acid half esters represented by the general formulas (I-1) and (I-2). Examples include mono (3-methylphenoxycarbonylmethyl) itaconate, mono (4-methylphenoxycarbonylmethyl) itaconate, mono (4
-Nitrophenoxycarbonylmethyl) itaconate,
And the like.

Among the itaconic acid half esters represented by the general formulas (I-1) and (I-2), typical examples of the compound having an alkyl group as R ₂ and a methyl group as R ₁ Examples thereof include mono (1-methoxycarbonylethyl) itaconate, mono (1-ethoxycarbonylethyl) itaconate, mono [1- (n-propoxycarbonyl) ethyl] itaconate, and mono [1- (iso)
-Propoxycarbonyl) ethyl] itaconate, mono [1- (n-butoxycarbonyl) ethyl] itaconate, mono [1- (iso-butoxycarbonyl) ethyl] itaconate, mono [1- (n-hexyloxycarbonyl) ethyl] itaconate And mono [1- (2-ethylhexyloxycarbonyl) ethyl] itaconate, mono [1- (n-decyloxycarbonyl) ethyl] itaconate, and the like.

Among the itaconic acid half esters represented by the general formulas (I-1) and (I-2), compounds having an alkoxy-substituted alkyl group as R ₂ and a methyl group as R ₁ As a typical example, a thing [1-
(2-methoxyethoxycarbonyl) ethyl] itaconate, mono [1- (2-ethoxyethoxycarbonyl)
Ethyl] itaconate, mono {1- [2- (n-propoxy) ethoxycarbonyl] ethyl} itaconate, mono {1- [2- (n-butoxy) ethoxycarbonyl]
Ethyl {itaconate, mono [1- (3-methoxypropoxycarbonyl) ethyl] itaconate, mono {1-
[2- (n-hexyloxy) ethoxycarbonyl] ethyl} itaconate, and the like.

In the itaconic acid half esters represented by the general formulas (I-1) and (I-2), R ₂ has an alkyl group substituted with an aryloxy group, and R ₁ has a methyl group. Representative compounds having the compound include mono [1- (2-phenoxyethoxycarbonyl) ethyl] itaconate, mono {1- [2- (4-methylphenoxy) ethoxycarbonyl] ethyl} itaconate,
And the like.

In the itaconic acid half esters represented by formulas (I-1) and (I-2), R ₂ has an alkyl group substituted by an aralkyloxy group, and R ₁ has a methyl group. Representative compounds having
Mono [1- (2-benzyloxyethoxycarbonyl)
Ethyl] itaconate, mono {1- [2- (2-phenylethoxy) ethoxycarbonyl] ethyl} itaconate, and the like.

Among the itaconic acid half esters represented by formulas (I-1) and (I-2), R ₂ has an alkyl group substituted with an aryl group, and R ₁ has a methyl group. As a typical example of the compound, mono (1
-Benzyloxycarbonylethyl) itaconate, mono [1- (1-phenylethoxycarbonyl) ethyl]
Itaconate, mono [1- (2-phenylethoxycarbonyl) ethyl] itaconate, and the like.

Among the itaconic acid half esters represented by the general formulas (I-1) and (I-2), representative compounds having a cycloalkyl group as R ₂ and a methyl group as R ₁ Examples include mono (1-cyclopentyloxycarbonylethyl) itaconate and mono (1-cyclopentyloxycarbonylethyl) itaconate.
Cyclohexyloxycarbonylethyl) itaconate, mono [1- (4-methylcyclohexyloxycarbonyl) ethyl] itaconate, and the like.

Among the itaconic acid half esters represented by the general formulas (I-1) and (I-2), typical examples of compounds having an aryl group as R ₂ and a methyl group as R ₁ Examples thereof include mono (1-phenoxycarbonylethyl) itaconate, mono [1- (1-naphthoxycarbonyl) ethyl] itaconate and mono [1- (2-
Naphthoxycarbonyl) ethyl] itaconate, and the like.

Representative of the itaconic acid half esters represented by formulas (I-1) and (I-2), compounds having a substituted aryl group as R ₂ and a methyl group as R ₁ Examples include mono [1- (3-methylphenoxycarbonyl) ethyl] itaconate and mono [1
-(4-methylphenoxycarbonyl) ethyl] itaconate, mono [1- (4-nitrophenoxycarbonyl) ethyl] itaconate, and the like.

Among the itaconic acid half esters represented by the general formulas (I-1) and (I-2), compounds having various alkyl groups having 2 to 12 carbon atoms or phenyl groups as R ₁ can be used. As a typical example, in the various itaconic acid half esters described above as examples of the compound containing a methyl group as R ₁ , the methyl group is replaced with various alkyl groups having 2 to 12 carbon atoms or a phenyl group. Compounds having the following structures:

Of the itaconic acid half esters represented by the above-mentioned general formulas (I-1) and (I-2), R ₂ is preferably an alkyl or alkoxy group having 1 to 8 carbon atoms. And a compound having an alkoxy-substituted alkyl group having 3 to 8 carbon atoms. Particularly preferred compounds among such preferred compounds are those represented by the general formula (I
It is a compound having a hydrogen atom or a methyl group as R _{1 in} -1) and (I-2).

[0040] containing monovalent organic group of various as mentioned above as R _4, in the itaconic acid half ester represented by Formula (I-3) and (I-4), the alkyl group as R ₄ A typical compound having a hydrogen atom as R ₃ is mono (2-oxopropyl)
Itaconate, mono (2-oxobutyl) itaconate, mono (3-methyl-2-oxobutyl) itaconate, mono (2-oxopentyl) itaconate, mono (4-methyl-2-oxopentyl) itaconate, mono (2-oxooctyl) ) Itaconate, mono (2-oxotridecyl) itaconate, mono (2-oxotetradecyl) itaconate, and the like.

Among the itaconic acid half-esters represented by the general formulas (I-3) and (I-4), compounds having an alkoxy-substituted alkyl group as R ₄ and a hydrogen atom as R ₃ Representative examples include mono (4-methoxy-2-oxobutyl) itaconate and mono (4-methoxy-2-oxobutyl) itaconate.
Ethoxy-2-oxobutyl) itaconate, mono [2
-Oxo-4- (n-propoxy) butyl] itaconate, mono [4- (n-butoxy) -2-oxobutyl]
Itaconate, mono (5-methoxy-2-oxopentyl) itaconate, and the like.

In the itaconic acid half esters represented by formulas (I-3) and (I-4), R ₄ has an alkyl group substituted with an aryloxy group, and R ₃ has a hydrogen atom. Typical examples of the compound having the compound include mono (2-oxo-4-phenoxybutyl) itaconate and mono [4- (4-methylphenoxy) -2-oxobutyl] itaconate.

In the itaconic acid half esters represented by formulas (I-3) and (I-4), R ₄ has an alkyl group substituted by an aralkyloxy group, and R ₃ has a hydrogen atom. Representative compounds having
Mono (4-benzyloxy-2-oxobutyl) itaconate, mono [2-oxo-4- (2-phenylethoxy) butyl] itaconate, and the like.

In the itaconic acid half esters represented by formulas (I-3) and (I-4), R ₄ has an alkyl group substituted with an aryl group, and R ₃ has a hydrogen atom. A typical example of the compound is mono (2
-Oxo-3-phenylpropyl) itaconate, mono (2-oxo-4-phenylbutyl) itaconate, and the like.

Among the itaconic acid half esters represented by the general formulas (I-3) and (I-4), representative compounds having a cycloalkyl group as R ₄ and a hydrogen atom as R ₃ Specific examples include mono (cyclopentylcarbonylmethyl) itaconate, mono (cyclohexylcarbonylmethyl) itaconate, and the like.

Among the itaconic acid half esters represented by the general formulas (I-3) and (I-4), representative examples of compounds having an aryl group as R ₄ and a hydrogen atom as R ₃ Examples thereof include mono (benzoylmethyl) itaconate, mono (1-naphthoylmethyl) itaconate, and the like.

Representative of the compounds having a substituted aryl group as R ₄ and a hydrogen atom as R ₃ among the itaconic acid half esters represented by formulas (I-3) and (I-4). Specific examples include mono (3-methylbenzoylmethyl) itaconate, mono (4-methylbenzoylmethyl) itaconate, and mono (4-nitrobenzoylmethyl) itaconate.

Among the itaconic acid half esters represented by the general formulas (I-3) and (I-4), typical examples of the compound having an alkyl group as R ₄ and a methyl group as R ₃ Examples thereof include mono (1-methyl-2-oxopropyl) itaconate, mono (1-methyl-2-oxobutyl) itaconate and mono (1,3-dimethyl-2) itaconate.
-Oxobutyl) itaconate, mono (1-methyl-2)
-Oxopentyl) itaconate, mono (1,4-dimethyl-2-oxopentyl) itaconate, mono (1-
Methyl-2-oxooctyl) itaconate, mono (1
-Methyl-2-oxotridecyl) itaconate, mono (1-methyl-2-oxotetradecyl) itaconate, and the like.

Among the itaconic acid half esters represented by the general formulas (I-3) and (I-4), compounds having an alkoxy-substituted alkyl group as R ₄ and a methyl group as R ₃ Representative examples include mono (4-methoxy-1-methyl-2-oxobutyl) itaconate, mono (4-ethoxy-1-methyl-2-oxobutyl) itaconate, and mono [1-methyl-2-oxo-4].
-(N-propoxy) butyl] itaconate, mono [4
-(N-butoxy) -2-oxobutyl] itaconate, mono (5-methoxy-1-methyl-2-oxopentyl) itaconate, and the like.

In the itaconic acid half esters represented by formulas (I-3) and (I-4), R ₄ has an alkyl group substituted by an aryloxy group, and R ₃ has a methyl group. As a typical example of the compound having, mono (1-methyl-2-oxo-4-phenoxybutyl)
Itaconate, mono [1-methyl-4- (4-methylphenoxy) -2-oxobutyl] itaconate, and the like.

In the itaconic acid half esters represented by formulas (I-3) and (I-4), R ₄ has an alkyl group substituted by an aralkyloxy group, and R ₃ has a methyl group. Representative compounds having
Mono (4-benzyloxy-1-methyl-2-oxobutyl) itaconate, mono [1-methyl-2-oxo-
4- (2-phenylethoxy) butyl] itaconate,
And the like.

Among the itaconic acid half esters represented by formulas (I-3) and (I-4), R ₄ has an alkyl group substituted with an aryl group, and R ₃ has a methyl group. As a typical example of the compound, mono (1
-Methyl-2-oxo-3-phenylpropyl) itaconate, mono (1-methyl-2-oxo-4-phenylbutyl) itaconate, and the like.

Among the itaconic acid half esters represented by the general formulas (I-3) and (I-4), representative of compounds having a cycloalkyl group as R ₄ and a methyl group as R ₃ Specific examples include mono (1-cyclopentylcarbonylethyl) itaconate, mono (1-cyclohexylcarbonylethyl) itaconate, and the like.

Among the itaconic acid half esters represented by the general formulas (I-3) and (I-4), typical examples of compounds having an aryl group as R ₄ and a methyl group as R ₃ Mono (1-benzoylethyl)
Itaconate, mono [1- (1-naphthoyl) ethyl]
Itaconate, and the like.

Representative of the itaconic acid half esters represented by formulas (I-3) and (I-4), compounds having a substituted aryl group as R ₄ and a methyl group as R ₃ Examples include mono [1- (3-methylbenzoyl) ethyl] itaconate, mono [1- (4-methylbenzoyl) ethyl] itaconate, mono [1-
(4-nitrobenzoyl) ethyl] itaconate, and the like.

Among the itaconic acid half-esters represented by formulas (I-3) and (I-4), representative examples of compounds containing an alkyl group having 2 to 12 carbon atoms or a phenyl group as R ₃ For example, in the various itaconic acid half-esters listed above as examples of compounds containing a methyl group as R ₃ , the methyl group has 2 carbon atoms.
And compounds having a structure substituted with various alkyl groups or phenyl groups represented by the following formulas:

Among the various compounds exemplified as the itaconic acid half ester represented by the general formulas (I-3) and (I-4), preferred are compounds having 1 carbon atom as the monovalent organic group R _4. Among them, compounds having a hydrogen atom as R ₃ are particularly preferable.

[0058] containing as mentioned above various monovalent organic group as R _5, in itaconic acid half ester represented by the general formula (I-5) and (I-6), as R _5, the alkyl group Representative examples of the compound containing: monomethyl itaconate, monoethyl itaconate, mono (n-propyl) itaconate, mono (iso-propyl) itaconate, mono (n-butyl) itaconate,
Mono (iso-butyl) itaconate, mono (n-hexyl) itaconate, mono (2-ethylhexyl) itaconate, mono (n-decyl) itaconate, and the like can be mentioned.

Among the itaconic acid half esters represented by the general formulas (I-5) and (I-6), a compound having an alkoxy-substituted alkyl group as R ₅ is represented by mono (2) -Methoxyethyl) itaconate, mono (2-ethoxyethyl) itaconate, mono [2-
(N-propoxy) ethyl] itaconate, mono [2-
(N-butoxy) ethyl] itaconate, mono (3-methoxypropyl) itaconate, mono [2- (n-hexyloxy) ethyl] itaconate, and the like.

Among the itaconic acid half esters represented by the general formulas (I-5) and (I-6), typical compounds having an alkyl group substituted by an aryloxy group as R ₅ include: Mono (2-phenoxyethyl) itaconate, mono [2- (4-methylphenoxy) ethyl] itaconate, and the like.

Among the itaconic acid half esters represented by the general formulas (I-5) and (I-6), typical compounds having an alkyl group substituted by an aralkyloxy group as R ₅ include: Mono (2-benzyloxyethyl) itaconate, mono [2- (2-phenylethoxy) ethyl] itaconate, and the like.

Among the itaconic acid half esters represented by the general formulas (I-5) and (I-6), a typical compound having an alkyl group substituted with an aryl group as R ₅ is mono Benzyl itaconate, mono (1-phenylethyl) itaconate, mono (2-phenylethyl) itaconate and the like can be mentioned.

Among the itaconic acid half esters represented by the general formulas (I-5) and (I-6), typical compounds having a cycloalkyl group as R ₅ include monocyclopentyl itaconate, Monocyclohexylitaconate, mono (4-methylcyclohexyl) itaconate, and the like.

Among the itaconic acid half esters represented by the general formulas (I-5) and (I-6), typical compounds having an aryl group as R ₅ include monophenylitaconate and monophenylitaconate. (1-naphthyl) itaconate, mono (2-naphthyl) itaconate, and the like.

Among the itaconic acid half esters represented by the general formulas (I-5) and (I-6), a typical compound having a substituted aryl group as R ₅ is mono (3-methyl). Phenyl) itaconate, mono (4-methylphenyl) itaconate, mono (4-nitrophenyl) itaconate, and the like.

Among the various compounds exemplified as the itaconic acid half ester represented by the general formulas (I-5) and (I-6), preferred are those having 1 carbon atom as the monovalent organic group R _5. It is a compound having an alkoxy-substituted alkyl group having 3 to 8 carbon atoms, including an alkyl group or an alkoxy group.

[0067] Among the unsaturated dicarboxylic acid half ester represented by containing monovalent organic group of various as mentioned above as R _2, the general formula (II-1), having an alkyl group as R _2, and Representative examples of fumaric acid half esters having a hydrogen atom as R ₁ include mono (methoxycarbonylmethyl) fumarate, mono (ethoxycarbonylmethyl) fumarate, mono (n-propoxycarbonylmethyl) fumarate, and mono (iso- Propoxycarbonylmethyl) fumarate, mono (n-butoxycarbonylmethyl) fumarate, mono (iso-butoxycarbonylmethyl) fumarate, mono (n-hexyloxycarbonylmethyl) fumarate, mono (2-ethylhexyloxycarbonylmethyl) fumarate, mono ( n
-Decyloxycarbonylmethyl) fumarate, and the like.

Among the unsaturated dicarboxylic acid half esters represented by the general formula (II-1), representative of fumaric acid half ester having an alkoxy-substituted alkyl group as R ₂ and a hydrogen atom as R ₁ Typically,
Mono (2-methoxyethoxycarbonylmethyl) fumarate, mono (2-ethoxyethoxycarbonylmethyl)
Fumarate, mono [2- (n-propoxy) ethoxycarbonylmethyl] fumarate, mono [2- (n-butoxy) ethoxycarbonylmethyl] fumarate, mono (3
-Methoxypropoxycarbonylmethyl) fumarate,
Mono [2- (n-hexyloxy) ethoxycarbonylmethyl] fumarate, and the like.

Among the unsaturated dicarboxylic acid half esters represented by the general formula (II-1), fumaric acid half having an alkyl group substituted with an aryloxy group as R ₂ and a hydrogen atom as R ₁ Representative examples of the ester include mono (2-phenoxyethoxycarbonylmethyl) fumarate, mono [2- (4-methylphenoxy) ethoxycarbonylmethyl] fumarate, and the like.

Among the unsaturated dicarboxylic acid half esters represented by the general formula (II-1), fumaric acid half having an alkyl group substituted by an aralkyloxy group as R ₂ and a hydrogen atom as R ₁ Representative examples of the ester include mono (2-benzyloxyethoxycarbonylmethyl) fumarate, mono [2- (2-phenylethoxy) ethoxycarbonylmethyl] fumarate, and the like.

Among the unsaturated dicarboxylic acid half esters represented by the general formula (II-1), fumaric acid half ester having an alkyl group substituted with an aryl group as R ₂ and a hydrogen atom as R ₁ Representative examples include mono (benzyloxycarbonylmethyl) fumarate, mono (1-phenylethoxycarbonylmethyl) fumarate, mono (2-phenylethoxycarbonylmethyl) fumarate, and the like.

Among the unsaturated dicarboxylic acid half esters represented by the general formula (II-1), typical examples of a fumaric acid half ester having a cycloalkyl group as R ₂ and a hydrogen atom as R ₁ Examples thereof include mono (cyclopentyloxycarbonylmethyl) fumarate, mono (cyclohexyloxycarbonylmethyl) fumarate, mono (4-methylcyclohexyloxycarbonylmethyl) fumarate, and the like.

Among the unsaturated dicarboxylic acid half esters represented by the general formula (II-1), representative of fumaric acid half ester having an aryl group as R ₂ and a hydrogen atom as R ₁ Examples thereof include mono (phenoxycarbonylmethyl) fumarate, mono (1-naphthoxycarbonylmethyl) fumarate, and mono (2-naphthoxycarbonylmethyl) fumarate.

Among the unsaturated dicarboxylic acid half esters represented by the general formula (II-1), typical examples of the fumaric acid half ester having a substituted aryl group as R ₂ and a hydrogen atom as R ₁ Examples thereof include mono (3-methylphenoxycarbonylmethyl) fumarate, mono (4-methylphenoxycarbonylmethyl) fumarate, and mono (4-nitrophenoxycarbonylmethyl) fumarate.

Among the unsaturated dicarboxylic acid half esters represented by the general formula (II-1), representative ones of fumaric acid half ester having an alkyl group as R ₂ and a methyl group as R ₁ Mono (1-methoxycarbonylethyl) fumarate, mono (1-ethoxycarbonylethyl) fumarate, mono [1- (n-propoxy) carbonylethyl] fumarate, mono [1-
(Iso-propoxy) carbonylethyl] fumarate, mono [1- (n-butoxy) carbonylethyl] fumarate, mono [1- (iso-butoxy) carbonylethyl] fumarate, mono [1- (n-hexyloxy) carbonylethyl ] Fumarate, mono [1- (2-
Ethylhexyloxycarbonyl) ethyl] fumarate, mono [1- (n-decyloxy) carbonylethyl] fumarate, and the like.

Among the unsaturated dicarboxylic acid half esters represented by the general formula (II-1), representative of fumaric acid half ester having an alkoxy-substituted alkyl group as R ₂ and a methyl group as R ₁ Typically,
Mono [1- (2-methoxyethoxycarbonyl) ethyl] fumarate, mono [1- (2-ethoxyethoxycarbonyl) ethyl] fumarate, mono {1- [2- (n
-Propoxy) ethoxycarbonyl] ethyl} fumarate, mono {1- [2- (n-butoxy) ethoxycarbonyl] ethyl} fumarate, mono [1- (3-methoxypropoxycarbonyl) ethyl] fumarate, mono {1
-[2- (n-hexyloxy) ethoxycarbonyl]
Ethyl difumarate and the like.

Among the unsaturated dicarboxylic acid half esters represented by the general formula (II-1), fumaric acid half having an alkyl group substituted with an aryloxy group as R ₂ and a methyl group as R ₁ Representative examples of the ester include mono [1- (2-phenoxyethoxycarbonyl) ethyl] fumarate and mono {1- [2- (4-methylphenoxy) ethoxycarbonyl] ethyl} fumarate.

Among the unsaturated dicarboxylic acid half esters represented by the general formula (II-1), fumaric acid half having an alkyl group substituted by an aralkyloxy group as R ₂ and a methyl group as R ₁ Representative examples of the ester include mono [1- (2-benzyloxyethoxycarbonyl) ethyl] fumarate and mono {1- [2-
(2-phenylethoxy) ethoxycarbonyl] ethyl difumarate, and the like.

Among the unsaturated dicarboxylic acid half esters represented by the general formula (II-1), fumaric acid half ester having an alkyl group substituted with an aryl group as R ₂ and a methyl group as R ₁ Representative examples include mono (1-benzyloxycarbonylethyl) fumarate, mono [1- (1-phenylethoxycarbonyl) ethyl] fumarate, mono [1- (2-phenylethoxycarbonyl) ethyl] fumarate, and the like. Is mentioned.

Among the unsaturated dicarboxylic acid half esters represented by the general formula (II-1), typical examples of fumaric acid half ester having a cycloalkyl group as R ₂ and a methyl group as R ₁ Things are things (1-
Cyclopentyloxycarbonylethyl) fumarate,
Mono (1-cyclohexyloxycarbonylethyl) fumarate, mono [1- (4-methylcyclohexyloxycarbonyl) ethyl] fumarate, and the like can be mentioned.

Among the unsaturated dicarboxylic acid half esters represented by the general formula (II-1), representative ones of fumaric acid half ester having an aryl group as R ₂ and a methyl group as R ₁ As mono (1-phenoxycarbonylethyl) fumarate, mono [1- (1-
Naphthoxycarbonyl) ethyl] fumarate, mono [1
-(2-naphthoxycarbonyl) ethyl] fumarate,
And the like.

Among the unsaturated dicarboxylic acid half esters represented by the general formula (II-1), representative of fumaric acid half ester having a substituted aryl group as R ₂ and a methyl group as R ₁ As a thing, a thing [1-
(3-methylphenoxycarbonyl) ethyl] fumarate, mono [1- (4-methylphenoxycarbonyl) ethyl] fumarate, mono [1- (4-nitrophenoxycarbonyl) ethyl] fumarate, and the like.

Among the fumaric acid half esters represented by the general formula (II-1), typical compounds having various alkyl groups or phenyl groups having 2 to 12 carbon atoms as R ₁ include: In the various compounds listed above as examples of fumaric acid half esters containing a methyl group as R ₁ , various compounds having a structure in which the methyl group is replaced with various alkyl groups having 2 to 12 carbon atoms or a phenyl group. Compounds can be exemplified.

[0084] Among the unsaturated dicarboxylic acid half ester represented by containing monovalent organic group of various as mentioned above as R _2, the general formula (II-1), having an alkyl group as R _2, and Representative examples of maleic acid half esters having a hydrogen atom as R ₁ include mono (methoxycarbonylmethyl) malate, mono (ethoxycarbonylmethyl) malate, mono (n-propoxycarbonylmethyl) malate, mono (iso- Propoxycarbonylmethyl) malate, mono (n-butoxycarbonylmethyl) malate, mono (iso-butoxycarbonylmethyl) malate, mono (n-hexyloxycarbonylmethyl) malate, mono (2-ethylhexyloxycarbonylmethyl) malate, mono ( n-decyloxycarbonylmethyl) Rate, and the like.

Among the unsaturated dicarboxylic acid half esters represented by the general formula (II-1), representative of maleic acid half ester having an alkoxy-substituted alkyl group as R ₂ and a hydrogen atom as R ₁ Typical examples include mono (2-methoxyethoxycarbonylmethyl) malate, mono (2-ethoxyethoxycarbonylmethyl) malate, mono [2- (n-propoxy) ethoxycarbonylmethyl] malate, mono [2- (n- Butoxy) ethoxycarbonylmethyl] malate, mono (3-
Methoxypropoxycarbonylmethyl) malate, mono [2- (n-hexyloxy) ethoxycarbonylmethyl] malate, and the like.

Among the unsaturated dicarboxylic acid half esters represented by the general formula (II-1), maleic acid half having an alkyl group substituted with an aryloxy group as R ₂ and a hydrogen atom as R ₁ Representative examples of the ester include mono (2-phenoxyethoxycarbonylmethyl) malate and mono [2- (4-methylphenoxy) ethoxycarbonylmethyl] malate.

Among the unsaturated dicarboxylic acid half esters represented by the general formula (II-1), maleic acid half having an alkyl group substituted by an aralkyloxy group as R ₂ and a hydrogen atom as R ₁ Representative examples of the ester include mono (2-benzyloxyethoxycarbonylmethyl) malate and mono [2- (2-phenylethoxy) ethoxycarbonylmethyl] malate.

Among the unsaturated dicarboxylic acid half esters represented by the general formula (II-1), maleic acid half ester having an alkyl group substituted with an aryl group as R ₂ and a hydrogen atom as R ₁ Representative examples include mono (benzyloxycarbonylmethyl) malate, mono (1-phenylethoxycarbonylmethyl) malate, mono (2-phenylethoxycarbonylmethyl) malate, and the like.

Among the unsaturated dicarboxylic acid half esters represented by the general formula (II-1), a typical maleic acid half ester having a cycloalkyl group as R ₂ and a hydrogen atom as R ₁ Examples include mono (cyclopentyloxycarbonylmethyl) malate, mono (cyclohexyloxycarbonylmethyl) malate,
Mono (4-methylcyclohexyloxycarbonylmethyl) malate, and the like.

Among the unsaturated dicarboxylic acid half esters represented by the general formula (II-1), representative maleic acid half esters having an aryl group as R ₂ and a hydrogen atom as R ₁ Examples thereof include mono (phenoxycarbonylmethyl) malate, mono (1-naphthoxycarbonylmethyl) malate, and mono (2-naphthoxycarbonylmethyl) malate.

Among the unsaturated dicarboxylic acid half esters represented by the general formula (II-1), a typical maleic acid half ester having a substituted aryl group as R ₂ and a hydrogen atom as R ₁ Things are things (3-
Methylphenoxycarbonylmethyl) malate, mono (4-methylphenoxycarbonylmethyl) malate,
Mono (4-nitrophenoxycarbonylmethyl) malate, and the like.

Among the unsaturated dicarboxylic acid half esters represented by the general formula (II-1), representative maleic acid half esters having an alkyl group as R ₂ and a methyl group as R ₁ As mono (1-methoxycarbonylethyl) malate, mono (1-ethoxycarbonylethyl) malate, mono [1- (n-propoxy) carbonylethyl] malate, mono [1- (is
o-propoxy) carbonylethyl] malate, mono [1- (n-butoxy) carbonylethyl] malate,
Mono [1- (iso-butoxy) carbonylethyl] malate, mono [1- (n-hexyloxy) carbonylethyl] malate, mono [1- (2-ethylhexyloxycarbonyl) ethyl] malate, mono [1- (n −
Decyloxy) carbonylethyl] malate, and the like.

Among the unsaturated dicarboxylic acid half esters represented by the general formula (II-1), representative of maleic acid half ester having an alkoxy-substituted alkyl group as R ₂ and a methyl group as R ₁ Typical examples include mono [1- (2-methoxyethoxycarbonyl) ethyl] malate, mono [1- (2-ethoxyethoxycarbonyl) ethyl] malate, mono {1- [2- (n-
Propoxy) ethoxycarbonyl] ethyl dimalate,
Mono {1- [2- (n-butoxy) ethoxycarbonyl] ethyl} malate, mono [1- (3-methoxypropoxycarbonyl) ethyl] malate, mono {1- [2
-(N-hexyloxy) ethoxycarbonyl] ethyl dimalate, and the like.

Among the unsaturated dicarboxylic acid half esters represented by the formula (II-1), maleic acid half having an alkyl group substituted with an aryloxy group as R ₂ and a methyl group as R _1. Representative examples of the ester include mono [1- (2-phenoxyethoxycarbonyl) ethyl] malate and mono {1- [2- (4-methylphenoxy) ethoxycarbonyl] ethyl} malate.

Among the unsaturated dicarboxylic acid half esters represented by the general formula (II-1), maleic acid half having an alkyl group substituted by an aralkyloxy group as R ₂ and a methyl group as R ₁ Representative examples of the ester include mono [1- (2-benzyloxyethoxycarbonyl) ethyl] malate and mono {1- [2-
(2-phenylethoxy) ethoxycarbonyl] ethyl dimalate, and the like.

Among the unsaturated dicarboxylic acid half esters represented by the general formula (II-1), maleic acid half ester having an alkyl group substituted with an aryl group as R ₂ and a methyl group as R ₁ Representative examples include mono (1-benzyloxycarbonylethyl) malate, mono [1- (1-phenylethoxycarbonyl) ethyl] malate, mono [1- (2-phenylethoxycarbonyl) ethyl] malate, and the like. Is mentioned.

Among the unsaturated dicarboxylic acid half esters represented by the general formula (II-1), a typical maleic acid half ester having a cycloalkyl group as R ₂ and a methyl group as R ₁ Things are things (1
-Cyclopentyloxycarbonylethyl) malate,
Mono (1-cyclohexyloxycarbonylethyl) malate, mono [1- (4-methylcyclohexyloxycarbonyl) ethyl] malate, and the like.

Among the unsaturated dicarboxylic acid half esters represented by the general formula (II-1), representative maleic acid half esters having an aryl group as R ₂ and a methyl group as R ₁ As mono (1-phenoxycarbonylethyl) malate, mono [1- (1-
Naphthoxycarbonyl) ethyl] malate, mono [1-
(2-naphthoxycarbonyl) ethyl] malate, and the like.

Among the unsaturated dicarboxylic acid half esters represented by the general formula (II-1), a typical maleic acid half ester having a substituted aryl group as R ₂ and a methyl group as R ₁ As a thing, a thing [1-
(3-methylphenoxycarbonyl) ethyl] malate, mono [1- (4-methylphenoxycarbonyl) ethyl] malate, mono [1- (4-nitrophenoxycarbonyl) ethyl] malate, and the like.

In the maleic acid half ester represented by the general formula (II-1), R ₁ has 2 to 12 carbon atoms.
As typical examples of the compound having various alkyl groups or phenyl groups, in the various compounds described above as examples of maleic acid half ester containing a methyl group as R ₁ , the methyl group has a carbon atom number of 2-1
Various compounds having a structure substituted with two kinds of alkyl groups or phenyl groups can be exemplified.

Among the fumaric acid half-esters or maleic acid half-esters represented by the above general formula (II-1), R ₂ is preferably an alkyl or alkoxy group having 1 to 8 carbon atoms. Containing 3 to 8 carbon atoms
Is a compound having an alkoxy-substituted alkyl group. And especially preferable compound among such preferable compounds is a compound having a hydrogen atom or a methyl group as R ₁ in the general formula (II-1).

[0102] Among the unsaturated dicarboxylic acid half ester represented by containing monovalent organic group of various as mentioned above as R _4, formula (II-2), having an alkyl group as R _4, and Typical examples of fumaric acid half esters having a hydrogen atom as R ₃ include mono (2-oxopropyl) fumarate, mono (2-oxobutyl) fumarate, mono (3-methyl-2-oxobutyl) fumarate, (2-oxopentyl) fumarate, mono (4-methyl-2-oxopentyl) fumarate, mono (2-oxooctyl) fumarate, mono (2-oxotridecyl) fumarate, mono (2-oxotetradecyl) fumarate, And the like.

Among the unsaturated dicarboxylic acid half esters represented by the general formula (II-2), representative of fumaric acid half ester having an alkoxy-substituted alkyl group as R ₄ and a hydrogen atom as R ₃ Typically,
Mono (4-methoxy-2-oxobutyl) fumarate,
Mono (4-ethoxy-2-oxobutyl) fumarate,
Mono [2-oxo-4- (n-propoxy) butyl] fumarate, mono [4- (n-butoxy) -2-oxobutyl] fumarate, mono (5-methoxy-2-oxopentyl) fumarate, and the like. .

In the unsaturated dicarboxylic acid half ester represented by the general formula (II-2), fumaric acid half having an alkyl group substituted with an aryloxy group as R ₄ and a hydrogen atom as R _3. Representative examples of esters include mono (2-oxo-4-phenoxybutyl)
Fumarate, mono [4- (4-methylphenoxy) -2
-Oxobutyl] fumarate, and the like.

In the unsaturated dicarboxylic acid half ester represented by the general formula (II-2), fumaric acid half having an alkyl group substituted by an aralkyloxy group as R ₄ and a hydrogen atom as R _3. Representative examples of the ester include mono (4-benzyloxy-2-oxobutyl) fumarate, mono [2-oxo-4- (2-phenylethoxy) butyl] fumarate, and the like.

Among the unsaturated dicarboxylic acid half esters represented by formula (II-2), fumaric acid half ester having an alkyl group substituted with an aryl group as R ₄ and a hydrogen atom as R ₃ Representative examples include mono (2-oxo-3-phenylpropyl) fumarate, mono (2-oxo-4-phenylbutyl) fumarate, and the like.

Among the unsaturated dicarboxylic acid half esters represented by the general formula (II-2), representative of fumaric acid half ester having a cycloalkyl group as R ₄ and a hydrogen atom as R ₃ Examples thereof include mono (cyclopentylcarbonylmethyl) fumarate, mono (cyclohexylcarbonylmethyl) fumarate, and the like.

Among the unsaturated dicarboxylic acid half esters represented by the general formula (II-2), representative ones of fumaric acid half ester having an aryl group as R ₄ and a hydrogen atom as R ₃ Examples thereof include mono (benzoylmethyl) fumarate, mono (1-naphthoylmethyl) fumarate, and the like.

Among the unsaturated dicarboxylic acid half esters represented by the general formula (II-2), representative of fumaric acid half ester having a substituted aryl group as R ₄ and a hydrogen atom as R ₃ Examples thereof include mono (3-methylbenzoylmethyl) fumarate, mono (4-methylbenzoylmethyl) fumarate, mono (4-nitrobenzoylmethyl) fumarate, and the like.

Among the unsaturated dicarboxylic acid half esters represented by the general formula (II-2), representative ones of fumaric acid half ester having an alkyl group as R ₄ and a methyl group as R ₃ Mono (1-methyl-2-oxopropyl) fumarate, mono (1-methyl-2-oxobutyl) fumarate, mono (1,3-dimethyl-2-oxobutyl) fumarate, mono (1-methyl-2-fumarate) Oxopentyl) fumarate, mono (1,4-
Dimethyl-2-oxopentyl) fumarate, mono (1
-Methyl-2-oxooctyl) fumarate, mono (1
-Methyl-2-oxotridecyl) fumarate, mono (1-methyl-2-oxotetradecyl) fumarate,
And the like.

Among the unsaturated dicarboxylic acid half esters represented by the general formula (II-2), representative of fumaric acid half ester having an alkoxy-substituted alkyl group as R ₄ and a methyl group as R ₃ Typically,
Mono (4-methoxy-1-methyl-2-oxobutyl)
Fumarate, mono (4-ethoxy-1-methyl-2-oxobutyl) fumarate, mono [1-methyl-2-oxo-4- (n-propoxy) butyl] fumarate, mono [4- (n-butoxy) -1 -Methyl-2-oxobutyl] fumarate, mono (5-methoxy-1-methyl-2)
-Oxopentyl) fumarate and the like.

Among the unsaturated dicarboxylic acid half esters represented by the general formula (II-2), fumaric acid half having an alkyl group substituted with an aryloxy group as R ₄ and a methyl group as R _3. Representative examples of the ester include mono (1-methyl-2-oxo-4-phenoxybutyl) fumarate and mono [1-methyl-4- (4
-Methylphenoxy) -2-oxobutyl] fumarate, and the like.

Among the unsaturated dicarboxylic acid half esters represented by the general formula (II-2), fumaric acid half having an alkyl group substituted by an aralkyloxy group as R ₄ and a methyl group as R _3. Representative examples of the ester include mono (4-benzyloxy-1-methyl-
2-oxobutyl) fumarate, mono [1-methyl-2
-Oxo-4- (2-phenylethoxy) butyl] fumarate, and the like.

Among the unsaturated dicarboxylic acid half esters represented by the general formula (II-2), fumaric acid half ester having an alkyl group substituted with an aryl group as R ₄ and a methyl group as R ₃ Representative examples include mono (1-methyl-2-oxo-3-phenylpropyl) fumarate and mono (1-methyl-2-oxo-4).
-Phenylbutyl) fumarate, and the like.

Among the unsaturated dicarboxylic acid half esters represented by the general formula (II-2), representative of fumaric acid half ester having a cycloalkyl group as R ₄ and a methyl group as R ₃ Things are things (1-
Cyclopentylcarbonylethyl) fumarate, mono (1-cyclohexylcarbonylethyl) fumarate,
And the like.

Among the unsaturated dicarboxylic acid half esters represented by the general formula (II-2), representative of fumaric acid half ester having an aryl group as R ₄ and a methyl group as R ₃ Examples thereof include mono (1-benzoylethyl) fumarate, mono [1- (1-naphthoyl) ethyl] fumarate, and the like.

Among the unsaturated dicarboxylic acid half esters represented by the general formula (II-2), representative of fumaric acid half ester having a substituted aryl group as R ₄ and a methyl group as R ₃ As a thing, a thing [1-
(3-methylbenzoyl) ethyl] fumarate, mono [1- (4-methylbenzoyl) ethyl] fumarate,
Mono [1- (4-nitrobenzoyl) ethyl] fumarate; and the like.

Among the fumaric acid half-esters represented by the general formula (II-2), as a typical example of a compound containing an alkyl group having 2 to 12 carbon atoms or a phenyl group as R ₃ , _In the various fumaric acid half-esters listed above as examples of the compound of the general formula (II-2) containing a methyl group as ₃ , the methyl group is replaced with various alkyl groups having 2 to 12 carbon atoms or phenyl groups. Compounds having the substituted structure are mentioned.

[0119] Among the unsaturated dicarboxylic acid half ester represented by containing monovalent organic group of various as mentioned above as R _4, formula (II-2), having an alkyl group as R _4, and Representative examples of maleic acid half esters having a hydrogen atom as R ₃ include mono (2-oxopropyl) malate, mono (2-oxobutyl) malate, mono (3-methyl-2-oxobutyl) malate, and mono (3-methyl-2-oxobutyl) malate. (2-oxopentyl) malate, mono (4-
Methyl-2-oxopentyl) malate, mono (2-oxooctyl) malate, mono (2-oxotridecyl) malate, mono (2-oxotetradecyl) malate, and the like.

Among the unsaturated dicarboxylic acid half esters represented by the general formula (II-2), representative of maleic acid half ester having an alkoxy-substituted alkyl group as R ₄ and a hydrogen atom as R ₃ Typical examples include mono (4-methoxy-2-oxobutyl) malate, mono (4-ethoxy-2-oxobutyl) malate, mono [2-oxo-4- (n-propoxy) butyl] malate, mono [4 -(N-butoxy) -2-oxobutyl] malate, mono (5-methoxy-2-oxopentyl) malate, and the like.

Among the unsaturated dicarboxylic acid half esters represented by the general formula (II-2), maleic acid half having an alkyl group substituted with an aryloxy group as R ₄ and a hydrogen atom as R _3. Representative examples of the ester include mono (2-oxo-4-phenoxybutyl) malate and mono [4- (4-methylphenoxy)-
2-oxobutyl] malate, and the like.

Among the unsaturated dicarboxylic acid half esters represented by the general formula (II-2), maleic acid half having an alkyl group substituted by an aralkyloxy group as R ₄ and a hydrogen atom as R _3. Representative examples of the ester include mono (4-benzyloxy-2-oxobutyl) malate and mono [2-oxo-4- (2-phenylethoxy) butyl] malate.

Among the unsaturated dicarboxylic acid half esters represented by the formula (II-2), maleic acid half ester having an alkyl group substituted with an aryl group as R ₄ and a hydrogen atom as R ₃ Representative examples include mono (2-oxo-3-phenylpropyl) malate, mono (2-oxo-4-phenylbutyl) malate, and the like.

Among the unsaturated dicarboxylic acid half esters represented by the general formula (II-2), a typical maleic acid half ester having a cycloalkyl group as R ₄ and a hydrogen atom as R _3. Examples thereof include mono (cyclopentylcarbonylmethyl) malate and mono (cyclohexylcarbonylmethyl) malate.

Among the unsaturated dicarboxylic acid half esters represented by the general formula (II-2), representative maleic acid half esters having an aryl group as R ₄ and a hydrogen atom as R ₃ Examples thereof include mono (benzoylmethyl) malate and mono (1-naphthoylmethyl) malate.

Among the unsaturated dicarboxylic acid half esters represented by the general formula (II-2), a typical maleic acid half ester having a substituted aryl group as R ₄ and a hydrogen atom as R ₃ is shown below. Things are things (3-
Methylbenzoylmethyl) malate, mono (4-methylbenzoylmethyl) malate, mono (4-nitrobenzoylmethyl) malate, and the like.

Among the unsaturated dicarboxylic acid half esters represented by the general formula (II-2), typical maleic acid half esters having an alkyl group as R ₄ and a methyl group as R ₃ Mono (1-methyl-2-oxopropyl) malate, mono (1-methyl-2-oxobutyl) malate, mono (1,3-dimethyl-2-oxobutyl) malate, mono (1-methyl-
2-oxopentyl) malate, mono (1,4-dimethyl-2-oxopentyl) malate, mono (1-methyl-2-oxooctyl) malate, mono (1-methyl-
2-oxotridecyl) malate, mono (1-methyl-
2-oxotetradecyl) malate, and the like.

Among the unsaturated dicarboxylic acid half esters represented by the general formula (II-2), representative of maleic acid half ester having an alkoxy-substituted alkyl group as R ₄ and a methyl group as R ₃ Typical examples are mono (4-methoxy-1-methyl-2-oxobutyl) malate, mono (4-ethoxy-1-methyl-2-methyl).
Oxobutyl) malate, mono [1-methyl-2-oxo-4- (n-propoxy) butyl] malate, mono [4- (n-butoxy) -1-methyl-2-oxobutyl] malate, mono (5-methoxy) -1-methyl-2-
Oxopentyl) malate, and the like.

Among the unsaturated dicarboxylic acid half esters represented by the general formula (II-2), maleic acid half having an alkyl group substituted with an aryloxy group as R ₄ and a methyl group as R _3. Representative examples of the ester include mono (1-methyl-2-oxo-4-phenoxybutyl) malate and mono [1-methyl-4- (4
-Methylphenoxy) -2-oxobutyl] malate,
And the like.

Among the unsaturated dicarboxylic acid half esters represented by the general formula (II-2), maleic acid half having an alkyl group substituted with an aralkyloxy group as R ₄ and a methyl group as R _3. Representative examples of the ester include mono (4-benzyloxy-1-methyl-2-oxobutyl) malate and mono [1-methyl-2
-Oxo-4- (2-phenylethoxy) butyl] malate, and the like.

Among the unsaturated dicarboxylic acid half esters represented by the general formula (II-2), maleic acid half ester having an alkyl group substituted with an aryl group as R ₄ and a methyl group as R ₃ Representative examples include mono (1-methyl-2-oxo-3-phenylpropyl) malate and mono (1-methyl-2-oxo-4).
-Phenylbutyl) malate, and the like.

Among the unsaturated dicarboxylic acid half esters represented by the general formula (II-2), a typical maleic acid half ester having a cycloalkyl group as R ₄ and a methyl group as R _3. Things are things (1
-Cyclopentylcarbonylethyl) malate, mono (1-cyclohexylcarbonylethyl) malate, and the like.

Among the unsaturated dicarboxylic acid half esters represented by the general formula (II-2), representative maleic acid half esters having an aryl group as R ₄ and a methyl group as R ₃ Examples thereof include mono (1-benzoylethyl) malate and mono [1- (1-naphthoyl) ethyl] malate.

Among the unsaturated dicarboxylic acid half esters represented by the general formula (II-2), a representative maleic acid half ester having a substituted aryl group as R ₄ and a methyl group as R _3. As a thing, a thing [1-
(3-methylbenzoyl) ethyl] malate, mono [1
-(4-methylbenzoyl) ethyl] malate, mono [1- (4-nitrobenzoyl) ethyl] malate, and the like.

In the maleic acid half ester represented by the formula (II-2), R ₃ has 2 to 12 carbon atoms.
Typical examples of the compound containing an alkyl group or a phenyl group include the maleic acid half esters described above as examples of the compound of the general formula (II-2) containing a methyl group as R _3. Examples include compounds having a structure in which a methyl group is replaced with various alkyl groups having 2 to 12 carbon atoms or a phenyl group.

Among the various fumaric acid half-esters and / or maleic acid half-esters exemplified as the unsaturated dicarboxylic acid half-ester represented by the formula (II-2), preferred is a monovalent organic group R ₄ . A compound having an alkyl group having 1 to 8 carbon atoms, among which a compound having a hydrogen atom as R ₃ is particularly preferable.

Among the unsaturated dicarboxylic acid half esters represented by the general formula (II-3), typical examples of fumaric acid half ester having an alkyl group as R ₅ include monomethyl fumarate and monoethyl fumarate. Rate, mono (n-propyl) fumarate, mono (iso-propyl) fumarate, mono (n-butyl) fumarate, mono (iso-butyl) fumarate, mono (n-hexyl)
Fumarate, mono (2-ethylhexyl) fumarate,
Mono (n-decyl) fumarate, and the like.

Among the unsaturated dicarboxylic acid half esters represented by the general formula (II-3), a typical example of the fumaric acid half ester having an alkoxy-substituted alkyl group as R ₅ is mono (2-methoxy). Ethyl) fumarate, mono (2-ethoxyethyl) fumarate, mono [2- (n-propoxy) ethyl] fumarate, mono [2- (n-butoxy) ethyl] fumarate, mono (3
-Methoxypropyl) fumarate, mono [2- (n-hexyloxy) ethyl] fumarate, and the like.

Among the unsaturated dicarboxylic acid half esters represented by the general formula (II-3), typical examples of fumaric acid half ester having an alkyl group substituted with an aryloxy group as R ₅ include mono ( 2-phenoxyethyl) fumarate, mono [2- (4-methylphenoxy) ethyl] fumarate, and the like.

Among the unsaturated dicarboxylic acid half esters represented by the general formula (II-3), a typical example of the fumaric acid half ester having an alkyl group substituted with an aralkyloxy group as R ₅ is mono ( 2-benzyloxyethyl) fumarate, mono [2- (2-phenylethoxy) ethyl] fumarate, and the like.

Among the unsaturated dicarboxylic acid half esters represented by the formula (II-3), a typical example of fumaric acid half ester having an alkyl group substituted with an aryl group as R ₅ is monobenzyl fumaric acid. Rate, mono (1-phenylethyl) fumarate, mono (2-phenylethyl) fumarate, and the like.

Among the unsaturated dicarboxylic acid half esters represented by formula (II-3), typical examples of fumaric acid half ester having a cycloalkyl group as R ₅ include monocyclopentyl fumarate and monocyclohexyl. Fumarate, mono (4-methylcyclohexyl)
Fumarate and the like.

Among the unsaturated dicarboxylic acid half esters represented by the general formula (II-3), representative examples of fumaric acid half ester having an aryl group as R ₅ include monophenyl fumarate and mono (1 -Naphthyl) fumarate, mono (2-naphthyl) fumarate, and the like.

Among the unsaturated dicarboxylic acid half esters represented by the general formula (II-3), a typical example of fumaric acid half ester having a substituted aryl group as R ₅ is mono (3-methylphenyl) Fumarate, mono (4-methylphenyl) fumarate, mono (4-nitrophenyl) fumarate and the like.

Among the unsaturated dicarboxylic acid half esters represented by the general formula (II-3), typical examples of the maleic acid half ester having an alkyl group as R ₅ include monomethyl maleate and monoethyl maleate. Rate, mono (n-propyl) malate, mono (iso-propyl)
Malate, mono (n-butyl) malate, mono (iso
-Butyl) malate, mono (n-hexyl) malate,
Mono (2-ethylhexyl) malate, mono (n-decyl) malate and the like can be mentioned.

Among the unsaturated dicarboxylic acid half esters represented by the general formula (II-3), a typical maleic acid half ester having an alkoxy-substituted alkyl group as R ₅ is mono (2-methoxy). Ethyl) malate, mono (2-ethoxyethyl) malate, mono [2
-(N-propoxy) ethyl] malate, mono [2-
(N-butoxy) ethyl] malate, mono (3-methoxypropyl) malate, mono [2- (n-hexyloxy) ethyl] malate, and the like.

Among the unsaturated dicarboxylic acid half esters represented by the general formula (II-3), a typical maleic acid half ester having an alkyl group substituted with an aryloxy group as R ₅ is mono ( 2-phenoxyethyl) malate, mono [2- (4-methylphenoxy) ethyl] malate, and the like.

Among the unsaturated dicarboxylic acid half esters represented by the general formula (II-3), a typical maleic acid half ester having an alkyl group substituted by an aralkyloxy group as R ₅ is mono ( 2-benzyloxyethyl) malate, mono [2- (2-phenylethoxy) ethyl] malate, and the like.

Among the unsaturated dicarboxylic acid half esters represented by the general formula (II-3), a typical maleic acid half ester having an alkyl group substituted with an aryl group as R ₅ is monobenzyl maleic acid. Rate, mono (1-phenylethyl) malate, mono (2-phenylethyl) malate, and the like.

Among the unsaturated dicarboxylic acid half esters represented by the general formula (II-3), typical examples of the maleic acid half ester having a cycloalkyl group as R ₅ include monocyclopentyl malate and monocyclohexyl. Malate, mono (4-methylcyclohexyl) malate, and the like.

Among the unsaturated dicarboxylic acid half esters represented by the general formula (II-3), typical examples of the maleic acid half ester having an aryl group as R ₅ include monophenylmalate and mono (1 -Naphthyl) malate, mono (2-naphthyl) malate and the like.

Among the unsaturated dicarboxylic acid half esters represented by the general formula (II-3), a typical maleic acid half ester having a substituted aryl group as R ₅ is mono (3-methylphenyl) Malate, mono (4-methylphenyl) malate, mono (4-nitrophenyl) malate, and the like.

Among the various fumaric acid half-esters and maleic acid half-esters exemplified as the unsaturated dicarboxylic acid half-esters represented by the formula (II-3), preferred are monovalent organic groups R ₅ and carbon 1 atom
It is a compound having an alkoxy-substituted alkyl group having 3 to 8 carbon atoms, including an alkyl group or an alkoxy group.

As described above, unsaturated esters of various unsaturated dicarboxylic acids, unsaturated dicarboxylic acids such as itaconic acid, maleic acid and fumaric acid, and typical salts thereof are lithium salt, sodium salt and potassium salt. And alkaline earth metal salts such as magnesium salt, calcium salt and barium salt; and various tertiary amines such as triethylamine, tributylamine, N, N-dimethylbenzylamine and the like. Salts of bases with itaconic acid, itaconic acid half ester, fumaric acid, fumaric acid half ester, maleic acid or maleic acid half ester are exemplified.

As the above-mentioned salt of itaconic acid, salt of itaconic acid half ester, salt of fumaric acid, salt of fumaric acid half ester, salt of maleic acid or salt of maleic acid half ester, those prepared in advance are used. Or itaconic acid, itaconic acid half ester, fumaric acid, fumaric acid half ester, maleic acid or maleic acid half ester, a reaction system containing various bases containing alkali metals, alkaline earth metals. Various bases or organic bases may be continuously or dividedly added to be sequentially produced.

Representative examples of the above-mentioned various bases containing an alkali metal include hydroxides such as lithium hydroxide, sodium hydroxide, potassium hydroxide and cesium hydroxide; lithium hydrogen carbonate and sodium hydrogen carbonate. , Potassium bicarbonate, cesium bicarbonate and the like; and carbonates such as lithium carbonate, sodium carbonate, potassium carbonate, cesium carbonate and the like.

Representative examples of the above-mentioned various bases containing alkaline earth metals include hydroxides of magnesium hydroxide, calcium hydroxide, barium hydroxide, etc .; magnesium hydrogen carbonate, calcium hydrogen carbonate, carbonate Bicarbonates such as barium hydrogen; and carbonates such as magnesium carbonate, calcium carbonate and barium carbonate.

The α- used in the production method of the present invention.
As the chlorocarboxylic acid ester and α-chloroketone, various known and commonly used α-chlorocarboxylic acid esters and α-chloroketones can be used. As typical examples, α-chlorocarboxylic acid ester is represented by the following general formula (III), and α-chloroketone is represented by the following general formula (I)
V).

[0159]

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[Wherein R ₁ and R ₃ represent a hydrogen atom, a phenyl group or an alkyl group having 1 to 12 carbon atoms, and R ₂ and R ₄ represent a monovalent organic group. ]

Representative examples of R ₂ and R ₄ contained in the above general formulas (III) and (IV) include an alkyl group, a substituted alkyl group, a cycloalkyl group, an aryl group and a substituted aryl group. No. And R ₂ and R ₄
Representative examples of the above-mentioned general formulas (I) and (I)
Examples of the monovalent organic group contained in I), such as an alkyl group, a substituted alkyl group, a cycloalkyl group, an aryl group or a substituted aryl group, are given as typical examples.

R ₁ and R ₃ contained in the above general formulas (III) and (IV) represent a hydrogen atom, a phenyl group or a group having 1 carbon atom.
1 to 12 alkyl groups. When R ₁ and R ₃ are an alkyl group having 1 to 12 carbon atoms, a typical example thereof is represented by the general formula (I) described above.
Examples of the alkyl group as one of the monovalent organic groups in (II) and (II) include those as exemplified above.

Representative examples of the above-mentioned α-chlorocarboxylic acid esters containing R ₁ or R ₂ include α-chloroacetic acid esters, α-chlorophenylacetic acid esters, and R ₁ represents a number of carbon atoms. Α-chlorocarboxylic acid esters having an alkyl group of 1 to 12,
And the like.

Specific examples of the chloroacetates include methyl chloroacetate, ethyl chloroacetate, n-propyl chloroacetate, n-butyl chloroacetate, and n-chloroacetate.
-Hexyl, n-octyl chloroacetate, n-chloroacetate
Alkyl esters such as decyl and n-dodecyl chloroacetate; 2-methoxyethyl chloroacetate, 2-chloroacetic acid 2-
Alkoxy-substituted alkyl esters such as ethoxyethyl, 2- (n-propoxy) ethyl chloroacetate, 2- (n-butoxy) ethyl chloroacetate, 4-ethoxybutyl chloroacetate, 2- (n-hexyloxy) ethyl chloroacetate Kind;

Alkyl esters substituted with an aryl group such as benzyl chloroacetate, 2-phenylethyl chloroacetate and 1-phenylethyl chloroacetate; cyclopentyl chloroacetate, cyclohexyl chloroacetate, chloroacetic acid 4
Cycloalkyl esters such as -methylcyclohexyl; aryl esters such as phenyl chloroacetate and 1-naphthyl chloroacetate; substitution of 4-methylphenyl chloroacetate, 4-chlorophenyl chloroacetate and 4-nitrophenyl chloroacetate; Aryl esters and the like.

Specific examples of α-chlorophenyl acetates include methyl α-chlorophenyl acetate and α-chlorophenyl acetate.
-Ethyl chlorophenylacetate, n-propyl α-chlorophenylacetate, n-butyl α-chlorophenylacetate, α
Alkyl esters such as -chlorophenylacetic acid n-hexyl, α-chlorophenylacetic acid n-octyl, α-chlorophenylacetic acid n-decyl, α-chlorophenylacetic acid n-dodecyl, etc .; α-chlorophenylacetic acid 2-methoxyethyl, α-chlorophenylacetic acid 2-ethoxyethyl, α
-2- (n-propoxy) ethyl chlorophenylacetate,
2- (n-butoxy) ethyl α-chlorophenylacetate,
alkoxy-substituted alkyl esters such as α-chlorophenylacetic acid 4-ethoxybutyl and α-chlorophenylacetic acid 2- (n-hexyloxy) ethyl;

Alkyl esters substituted with an aryl group such as benzyl α-chlorophenylacetate, 2-phenylethyl α-chlorophenylacetate and 1-phenylethyl α-chlorophenylacetate; cyclopentyl α-chlorophenylacetate, cyclohexyl α-chlorophenylacetate, α
Cycloalkyl esters such as 4-methylcyclohexyl-chlorophenylacetate; aryl esters such as α-chlorophenylacetate and 1-naphthyl α-chlorophenylacetate; 4-methylphenyl α-chlorophenylacetate and α-chlorophenylacetic acid 4- And substituted aryl esters such as chlorophenyl and α-chlorophenylacetic acid 4-nitrophenyl.

Among the α-chlorocarboxylic acid esters having an alkyl group having 1 to 12 carbon atoms as R ₁ , specific examples of the α-chlorocarboxylic acid esters having a methyl group as R ₁ include: Methyl α-chloropropionate, ethyl α-chloropropionate, n-propyl α-chloropropionate, n-butyl α-chloropropionate, n-hexyl α-chloropropionate,
alkyl esters such as n-octyl α-chloropropionate, n-decyl α-chloropropionate, n-dodecyl α-chloropropionate; 2-methoxyethyl α-chloropropionate, 2-α-chloropropionate Ethoxyethyl, 2- (n-propoxy) ethyl α-chloropropionate, 2- (n-butoxy) ethyl α-chloropropionate, 4-ethoxybutyl α-chloropropionate, 2- (n-α-chloropropionate) Alkoxy-substituted alkyl esters such as -hexyloxy) ethyl;

Alkyl esters substituted with an aryl group such as benzyl α-chloropropionate, 2-phenylethyl α-chloropropionate, 1-phenylethyl α-chloropropionate; cyclopentyl α-chloropropionate, α- Cyclohexyl chloropropionate, α
Cycloalkyl esters such as 4-methylcyclohexyl chloropropionate; aryl esters such as phenyl α-chloropropionate and 1-naphthyl α-chloropropionate; 4-methylphenyl α-chloropropionate, α- And substituted aryl esters such as 4-chlorophenyl chloropropionate and 4-nitrophenyl α-chloropropionate.

Specific examples of the α-chlorocarboxylic acid esters having an alkyl group having 2 to 12 carbon atoms as R ₁ include those described above as specific examples of the α-chloropropionate esters. In various esters, a methyl group which is a substituent R ₁ has 2 to 1 carbon atoms.
Various compounds having a structure substituted by two alkyl groups are exemplified.

Among the various compounds represented by the general formula (III) described above, the monovalent organic group R ₂ has 1 to 1 carbon atoms.
Having 8 carbon atoms, including an alkyl group or an alkoxy group;
Preferred are compounds having from 8 to 8 alkoxy-substituted alkyl groups. Further, according Among the preferred compounds, alpha-chloroacetic acid ester having a hydrogen atom as R ₁ or R ₁
Are particularly preferably α-chloropropionic esters having a methyl group.

The α containing R ₃ or R ₄ as described above
- Typical examples of the chloroketone have chloromethyl ketones, the number of carbon atoms as R ₃ is an alkyl group chromatic of 1 to 12 alpha-chloroalkyl ketones, phenyl group as R ₃ with a hydrogen atom as R ₃ α-chlorobenzyl ketones and the like.

Among the α-chloroketones, representatives of chloromethylketone include chloromethyl-methylketone, chloromethyl-ethylketone, and chloromethyl-ketone.
(N-propyl) ketone, chloromethyl- (n-butyl) ketone, chloromethyl- (n-hexyl) ketone,
Chloromethyl-alkyl ketones such as chloromethyl- (n-octyl) ketone, chloromethyl- (n-decyl) ketone, chloromethyl- (n-dodecyl) ketone; chloromethyl- (2-methoxyethyl) ketone; Chloromethyl- (2-ethoxyethyl) ketone, chloromethyl-
Chloromethyl-alkoxy-substituted alkyl ketones such as [2- (n-propoxy) ethyl] ketone, chloromethyl- [2- (n-butoxy) ethyl] ketone and chloromethyl- (4-ethoxybutyl) ketone;

Chloromethyl-benzylketone, chloromethyl- (2-phenylethyl) ketone, chloromethyl-
Chloromethyl-aryl group-substituted alkyl ketones such as (1-phenylethyl) ketone; chloromethyl-cycloalkyl ketones such as chloromethyl-cyclopentyl ketone and chloromethyl-cyclohexyl ketone; chloromethyl-phenyl ketone and chloromethyl- Chloromethyl-aryl ketones such as (1-naphthyl) ketone; chloromethyl- (4-methylphenyl) ketone, chloromethyl- (4-chlorophenyl) ketone, chloromethyl-
And chloromethyl-substituted aryl ketones such as (4-nitrophenyl) ketone.

Representative α-chloroalkyl ketones having a methyl group as R ₃ among α-chloroketones include 1-chloroethyl-methyl ketone and 1-chloroethyl ketone.
Chloroethyl-ethylketone, 1-chloroethyl- (n
-Propyl) ketone, 1-chloroethyl- (n-butyl) ketone, 1-chloroethyl- (n-hexyl) ketone, 1-chloroethyl- (n-octyl) ketone, 1-
1-chloroethyl-alkyl ketones such as chloroethyl- (n-decyl) ketone and 1-chloroethyl- (n-dodecyl) ketone; 1-chloroethyl- (2-methoxyethyl) ketone, 1-chloroethyl- (2-ethoxyethyl) Ketone, 1-chloroethyl- [2- (n-propoxy) ethyl] ketone, 1-chloroethyl- [2- (n-
Butoxy) ethyl] ketone, 1-chloroethyl- (4-
1-chloroethyl-alkoxy-substituted alkyl ketones such as ethoxybutyl) ketone;

1-chloroethyl-benzyl ketone, 1-
1-chloroethyl-aryl-substituted alkyl ketones such as chloroethyl- (2-phenylethyl) ketone and 1-chloroethyl- (1-phenylethyl) ketone; 1 such as 1-chloroethyl-cyclopentyl ketone and 1-chloroethyl-cyclohexyl ketone -Chloroethyl-cycloalkyl ketones; 1-chloroethyl-phenylketone, 1-chloroethyl- (1-naphthyl) ketone and the like
-Chloroethyl-aryl ketones; 1-chloroethyl- (4-methylphenyl) ketone, 1-chloroethyl-
(4-chlorophenyl) ketone, 1-chloroethyl-
1-chloroethyl such as (4-nitrophenyl) ketone
And substituted aryl ketones.

Representative examples of the α-chloroalkyl ketones having an alkyl group having 2 to 12 carbon atoms as R ₃ include the above-mentioned examples of chloroethyl ketones having a methyl group as R _3. In the various compounds described above, the methyl group as R ₃ is replaced with a carbon atom having 2 to 12 carbon atoms.
Various compounds having a structure replaced with an alkyl group represented by the formula: Further, among α-chloroketones, R ₃
As typical examples of the α-chlorobenzyl ketones having a phenyl group, the various compounds listed above as typical examples of the chloromethyl ketones having a hydrogen atom as R ₃ include a hydrogen atom represented by R ₃ Are substituted with a phenyl group.

Among the various compounds represented by the general formula (IV), the monovalent organic group R ₄ has 1 to 1 carbon atoms.
Those having 8 alkyl groups are preferred. Also, among the preferred compounds represented by the general formula (IV), R ₃
Are particularly preferably chloromethyl ketones having a hydrogen atom as R 1 or 1-chloroethyl ketones having a methyl group as R ₃ .

In the present invention, typical examples of the salt (B) in which the counter ion is bromide ion and / or the salt (C) in which the counter ion is iodine ion include alkali metal bromide, alkaline earth metal bromide, and the like. Examples include quaternary ammonium bromide, alkali metal iodide, alkaline earth metal iodide, and quaternary ammonium iodide.

Examples of the alkali metal bromide include lithium bromide, sodium bromide, potassium bromide, cesium bromide and the like. Examples of the alkaline earth metal bromide include magnesium bromide, calcium bromide, barium bromide and the like. Examples of the quaternary ammonium bromide include tetramethylammonium bromide, tetrabutylammonium bromide and the like. Examples of the alkali metal iodide include lithium iodide, sodium iodide, potassium iodide, and cesium iodide. Examples of alkaline earth metal iodides include magnesium iodide, calcium iodide, barium iodide and the like. Examples of the quaternary ammonium iodide include tetramethylammonium iodide, tetrabutylammonium iodide and the like. These can be used alone or in combination of two or more.
Of these, particularly preferred are alkali metal bromide and alkali metal iodide.

The unsaturated carboxylic acid salt (A) is converted into an α-chlorocarboxylic acid ester (A) in the presence of a salt (B) in which the counter ion is bromide and / or a salt (C) in which the counter ion is iodine. In order to prepare the corresponding unsaturated dicarboxylic acid ester by reacting with D) and / or α-chloroketone (E), (a) the above (A), (B) and / or (C), (D) ) And / or (E) are charged at once and allowed to react. (B) The above (A), (B) and / or (C), (D) and / or (E) are simultaneously added to the reaction system. , (C) (D) and / or (E), (B) and / or
Or (d) reacting the mixture of (C) by adding the above-mentioned (A) in a divided manner; (d) a mixture of itaconic acid, itaconic acid half ester, fumaric acid, fumaric acid half ester, maleic acid, maleic acid half ester; Saturated carboxylic acid, (B) and / or (C), (D) and / or (E)
The above-mentioned various basic compounds can be divided or added continuously to the mixture of the above to react while forming the corresponding carboxylic acid salt, and various other reaction methods can be applied. it can.

In the reaction, depending on the kind of unsaturated carboxylate and the kind of α-chlorocarboxylic acid ester and / or α-chloroketone, the reaction can be carried out without using a solvent. The reaction is preferably carried out using a solvent.

Typical solvents used in this case include ketone compounds such as acetone, methyl ethyl ketone and methyl isobutyl ketone; and ethylene glycol dimethyl ether, ethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether and the like. Glycol ether compound; N, N-dimethylformamide, N, N-
Amide compounds such as dimethylacetamide and N-methylpyrrolidone; and sulfur-containing compounds such as dimethylsulfoxide and dimethylsulfolane. And among these, from the viewpoint of the solubility of the unsaturated carboxylate,
Particularly preferred are N, N-dimethylformamide and N, N-dimethylacetamide.

In reacting the above-mentioned various salts of unsaturated carboxylic acids (A) with α-chlorocarboxylic acid esters (D) and / or α-chloroketones (E), one mole of the carboxylic acid base contained in the former is used. Are reacted in such a ratio that the latter (D) and / or (E) is in the range of about 0.5 to 4.0 mol, preferably about 0.8 to 2.0 mol. I just need.

In the reaction, the amount of the salt (B) in which the counter ion is bromide ion and / or the salt (C) in which the counter ion is iodine ion is 1 mol of the carboxylate group contained in the unsaturated carboxylate. To 0.01 to 0.4 mol,
Preferably, the ratio may be in the range of about 0.04 to 0.2 mol.

The reaction conditions are the kind of unsaturated carboxylate, α
-Chlorocarboxylic acid ester (D) and type of α-chloroketone (E), salt (B) whose counter ion is bromine ion
And the counter ion must be appropriately set according to the type of the salt (C) in which the iodine ion is an iodine ion.
0 to 130 ° C. and the reaction time may be about 0.5 to 100 hours.

The production method of the present invention is characterized in that the reaction is carried out in the presence of a salt (B) in which the counter ion is bromide and / or a salt (C) in which the counter ion is iodine. These salts include salts of unsaturated carboxylic acids (A) and α-
It has a catalytic function of accelerating the reaction with chlorocarboxylic acid ester (D) and / or α-chloroketone (E), and has a salt of itaconic acid or a salt of itaconic acid half ester with (D) and / or In the reaction with (E), it has a function of suppressing the isomerization reaction.

That is, a halogen exchange reaction occurs between the chlorine atom contained in (D) and (E) and the bromine ion or iodine ion contained in (B) and (C), and bromine is converted as a halogen atom. Α- containing an atom or iodine atom
Produces halocarboxylic esters or α-haloketones. The α-halocarboxylic acid ester or α-haloketone thus formed is a salt of an unsaturated carboxylic acid (A)
, The reaction time is shortened, the reaction yield is improved, and itaconic acid ester also leads to suppression of the isomerization reaction.

The unsaturated dicarboxylic acid ester produced by the method of the present invention is represented by the following formulas (V) and (VI). The isomer formed by rearrangement of the double bond during production of the itaconic acid ester is represented by the following general formula (VI
It is a citraconic acid ester and / or a mesaconic acid ester represented by I).

[0190]

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[However, in the formulas (V), (VI) and (VII),
R ^c and R ^d are each independently —CH (R ₁ ) COO
R ₂ represents —CH (R ₃ ) COR ₄ or R ₅ ;
^At least one of ^c and R ^d is —CH (R ₁ ) COOR ₂
Or —CH (R ₃ ) COR ₄ . R ₁ and R ₃ contained therein each independently represent a hydrogen atom, a phenyl group or an alkyl group having 1 to 12 carbon atoms;
₂ , R ₄ and R ₅ each independently represent a monovalent organic group. ]

[0192]

Next, the present invention will be described in more detail with reference to examples, but the present invention is by no means limited to these examples. In the following, all parts and percentages are by weight unless otherwise specified.

In the examples, the following gas chromatograph was used in order to analyze the production ratio of isomers. Measurement equipment GC-14A manufactured by Shimadzu Corporation

Example 1 [Production of bis (methoxycarbonylmethyl) itaconate using sodium iodide] Itaconic acid 13 was placed in a glass flask equipped with a thermometer, a reflux condenser, a stirrer and an inert gas inlet. 0.0 g (0.10 mol), 23.9 g (0.22 mol) of methyl chloroacetate, 0.66 g (4.4 mmol) of sodium iodide,
100 grams of N, N-dimethylformamide (DMF) were charged and 15.2 grams (0.11 grams) of potassium carbonate.
Mol), and the temperature was raised to 70 ° C. with stirring, and stirring was continued at the same temperature for 3 hours. After cooling the reaction mixture to room temperature, the generated potassium chloride was filtered off, and the filtrate was cooled to 80 ° C.
While heating under reduced pressure, volatile components such as DMF and unreacted methyl chloroacetate were distilled off under reduced pressure of 1 to 3 kPa. The solution obtained by dissolving the residue in 120 grams of toluene was washed with 50 grams of a 2% aqueous solution of potassium carbonate. Two grams of anhydrous magnesium sulfate was added to the toluene solution and dried. After filtering off the desiccant, toluene was distilled off under reduced pressure to obtain a pale yellow liquid product. The product was subjected to GC analysis, and the yield ratio of the target compound bis (methoxycarbonylmethyl) itaconate to the isomer in which the double bond moiety was rearranged was 97.5: 2.5, calculated from the peak area ratio. The yield of the target compound was 92.3% based on the raw material itaconic acid.

Example 2 [Production of bis (methoxycarbonylmethyl) itaconate using potassium iodide]
The reaction was carried out in the same manner as in Example 1 except that 0.73 g (4.4 mmol) of potassium iodide was used instead of 6 g (4.4 mmol) to obtain a pale yellow liquid product. . The production ratio of the target compound bis (methoxycarbonylmethyl) itaconate and the isomer in which the double bond part was rearranged, calculated in the same manner as in Example 1, was 97.7: 2.
It was 3. The yield of the target compound was 88.3% based on the raw material itaconic acid.

Example 3 [Production of bis (ethoxycarbonylmethyl) itaconate using sodium iodide] In a reaction vessel similar to that of Example 1, 13.0 g (0.10 mol) of itaconic acid was added.
27.0 grams (0.22 mole) of ethyl chloroacetate;
1.65 g (11.0 mmol) of sodium iodide and 100 g of DMF were charged, 15.2 g (0.11 mol) of potassium carbonate was added, and the temperature was raised to 70 ° C. with stirring. Stirring was continued at the same temperature for 4 hours.
After cooling the reaction mixture to room temperature, the generated potassium chloride was filtered off, and the filtrate was heated to 80 ° C. while heating to 1 to 3 kPa.
Volatile components such as DMF and unreacted ethyl chloroacetate were distilled off under reduced pressure. The solution obtained by dissolving the residue in 120 grams of toluene was washed with 50 grams of a 2% aqueous solution of potassium carbonate. Two grams of anhydrous magnesium sulfate was added to the toluene solution and dried. After filtering off the desiccant,
The toluene was distilled off under reduced pressure to obtain a pale yellow liquid product. The formation ratio of the target compound, bis (ethoxycarbonylmethyl) itaconate, to the isomer in which the double bond moiety was rearranged, calculated in the same manner as in Example 1, was 98.0: 2.0. The yield of the target compound was 93.4% based on the raw material itaconic acid.

Example 4 [Production of bis (2-oxopropyl) itaconate using sodium iodide] In a reaction vessel similar to that in Example 1, 13.0 g (0.10 mol) of itaconic acid and chloromethyl -20.8 grams of methyl ketone (0.22
Moles), 1.65 grams (11.0 grams) of sodium iodide
Mmol) and 50 g of DMF, 15.2 g (0.11 mol) of potassium carbonate was added, the temperature was raised to 70 ° C. with stirring, and stirring was continued at the same temperature for 1 hour. After the reaction mixture was cooled to room temperature, the generated potassium chloride was filtered off, and the filtrate was heated to 80 ° C. to 1 to 3 k.
Volatile components such as DMF and unreacted chloromethyl-methyl ketone were distilled off under reduced pressure of Pa. The residue was treated with ethyl acetate 5
The solution obtained by dissolving 0 g in 2 g of potassium carbonate
Washing was performed with 50 grams of the aqueous solution. 2 g of anhydrous magnesium sulfate was added to the ethyl acetate solution and dried.
After filtering off the drying agent, the ethyl acetate was distilled off under reduced pressure to obtain a pale yellow liquid product. The production ratio of the target compound bis (2-oxopropyl) itaconate and the isomer in which the double bond moiety was rearranged was calculated in the same manner as in Example 1.
7: 1.3. The yield of the target compound was 76.0% based on the raw material itaconic acid.

Example 5 [Production of bis (2-methoxyethoxycarbonylmethyl) itaconate using sodium iodide] In a reaction vessel similar to that of Example 1, 13.0 g (0.1%) of itaconic acid was added.
10 mol), 33.6 of 2-methoxyethyl chloroacetate.
Grams (0.22 mol), 0.66 of sodium iodide
G (4.4 mmol), 100 g of DMF, and 15.2 g (0.11 mol) of potassium carbonate
Was added, and the temperature was raised to 70 ° C. with stirring, and stirring was continued at the same temperature for 3.5 hours. After cooling the reaction mixture to room temperature, the generated potassium chloride was filtered off, and the filtrate was cooled to 80 ° C.
The volatile components such as DMF and unreacted 2-methoxyethyl chloroacetate were distilled off under reduced pressure of 1 to 3 kPa while heating. The solution obtained by dissolving the residue in 50 grams of toluene was washed with 50 grams of a 2% aqueous solution of potassium carbonate. Two grams of anhydrous magnesium sulfate was added to the toluene solution and dried. After filtering off the desiccant, toluene was distilled off under reduced pressure to obtain a pale yellow liquid product. The production ratio of bis (2-methoxyethoxycarbonylmethyl) itaconate, the target compound, and the isomer in which the double bond moiety was rearranged, calculated in the same manner as in Example 1, was 94.5: 5.5. The yield of the target compound was 7 based on the raw material itaconic acid.
2.0%.

Example 6 [Production of bis (1-methoxycarbonylethyl) itaconate using sodium iodide] 13.0 g (0.10 mol) of itaconic acid was placed in a reaction vessel similar to that of Example 1. -Charge 30.0 grams (0.22 mole) of methyl chloropropionate, 1.65 grams (11 mmol) of sodium iodide, 100 grams of DMF, and 15.2 grams (0.11 mole) of potassium carbonate Was added, and the temperature was raised to 70 ° C. with stirring, and stirring was continued at the same temperature for 4.5 hours. After the reaction mixture was cooled to room temperature, the generated potassium chloride was filtered off, and while the filtrate was heated to 80 ° C, the volatile components such as DMF and unreacted methyl 2-chloropropionate were distilled off under reduced pressure of 1 to 3 kPa. I left. The solution obtained by dissolving the residue in 120 grams of toluene was washed with 50 grams of a 2% aqueous solution of potassium carbonate.
Two grams of anhydrous magnesium sulfate was added to the toluene solution and dried. After filtering off the desiccant, toluene was distilled off under reduced pressure to obtain a pale yellow liquid product. The formation ratio of the target compound bis (1-methoxycarbonylethyl) itaconate and the isomer in which the double bond moiety was rearranged, calculated in the same manner as in Example 1, was 95.2: 4.8. The yield of the target compound was 73.8% based on the raw material itaconic acid.

Example 7 [Production of bis (methoxycarbonylmethyl) fumarate using sodium iodide] In a reaction vessel similar to that in Example 1, 11.6 g (0.10 mol) of fumaric acid and methyl chloroacetate were added. 23.9 grams (0.22 mole) of sodium iodide, 1.65 grams (11.0 mmol) of sodium iodide,
Charge 100 grams of DMF and add 15 grams of potassium carbonate.
2 grams (0.11 mol) are charged, and 9
The temperature was raised to 0 ° C., and stirring was continued at the same temperature for 12 hours. After the reaction mixture was cooled to room temperature, the generated potassium chloride was separated by filtration, and volatile matters such as DMF and unreacted methyl chloroacetate were distilled off under reduced pressure of 1 to 3 kPa while heating the filtrate to 80 ° C. The residue was dissolved in 120 grams of ethyl acetate and the resulting solution was washed with 50 grams of a 2% aqueous solution of potassium carbonate. 3 g of anhydrous magnesium sulfate was added to the ethyl acetate solution and dried. After filtering off the desiccant,
Ethyl acetate was distilled off under reduced pressure, and the obtained product was recrystallized from methanol to obtain 19.2 g of bis (methoxycarbonylmethyl) fumarate. The yield of the target compound was 73.8% based on the raw material fumaric acid.

Example 8 [Preparation of bis (methoxycarbonylmethyl) fumarate using sodium bromide] Except for using 1.13 g (11.0 mmol) of sodium bromide instead of sodium iodide, The reaction was carried out in the same manner as in Example 8. The obtained product was recrystallized from methanol to obtain 19.8 g of bis (methoxycarbonylmethyl) fumarate. The yield of the target compound was 76.2% based on the raw material fumaric acid.

REFERENCE EXAMPLE 1 [Production of bis (methoxycarbonylmethyl) itaconate] 15% at 70 ° C. without using sodium iodide.
The reaction and post-treatment were carried out in the same manner as in Example 1 except that the stirring was carried out for an hour to obtain a pale yellow liquid product. The production ratio of bis (methoxycarbonylmethyl) itaconate, the target compound, and the isomer in which the double bond moiety was rearranged, calculated in the same manner as in Example 1, was 91.8: 8.2. 15.1 g (yield: 55.1%) of the desired product was obtained.

Reference Example 2 [Production of bis (ethoxycarbonylmethyl) itaconate] 20% at 70 ° C. without using sodium iodide
The reaction and post-treatment were carried out in the same manner as in Example 3 except that the stirring was carried out for an hour to obtain a pale yellow liquid product. The production ratio of the target compound, bis (ethoxycarbonylmethyl) itaconate, to the isomer in which the double bond moiety was rearranged, calculated in the same manner as in Example 1, was 92.0: 8.0. 15.7 g (yield 52.0%) of the desired product was obtained.

Reference Example 3 [Production of bis (2-oxopropyl) itaconate] The reaction and post-treatment were carried out in the same manner as in Example 4 except that sodium iodide was not used and stirring was carried out at 70 ° C. for 20 hours. To give a pale yellow liquid product. The formation ratio of the target compound bis (2-oxopropyl) itaconate and the isomer in which the double bond part was rearranged, calculated in the same manner as in Example 1, was 80.8: 19.2. 15.
2 grams (62.8% yield) were obtained.

Reference Example 4 [Production of bis (2-methoxyethoxycarbonylmethyl) itaconate] No sodium iodide was used and
The reaction and post-treatment were carried out in the same manner as in Example 5 except that stirring was performed at 70 ° C. for 60 hours, to obtain a pale yellow liquid product. The production ratio of the target compound bis (2-methoxyethoxycarbonylmethyl) itaconate and the isomer in which the double bond part was rearranged was calculated in the same manner as in Example 1.
7: 9.3. 16.3 grams of the desired product (yield 4
5.0%).

Reference Example 5 [Production of bis (1-methoxycarbonylethyl) itaconate] The reaction and reaction were carried out in the same manner as in Example 6 except that sodium iodide was not used and stirring was carried out at 70 ° C. for 15 hours. The treatment was performed to obtain a pale yellow liquid product. The production ratio of the target compound bis (1-methoxycarbonylethyl) itaconate and the isomer in which the double bond part was rearranged, calculated in the same manner as in Example 1, was 62.4: 37.6. 12.9 g (yield 42.7%) of the desired product was obtained.

Reference Example 6 [Production of bis (methoxycarbonylmethyl) fumarate] 16% at 90 ° C. without using sodium iodide
The reaction and post-treatment were carried out in the same manner as in Example 7 except that stirring was carried out for an hour, and after recrystallization from methanol, 12.0 g (yield: 46.2%) of bis (methoxycarbonylmethyl) fumarate was obtained.

[0208]

According to the present invention, itaconic acid, itaconic acid half ester, fumaric acid, fumaric acid half ester, maleic acid are used in the presence of a salt whose counter ion is bromide and / or a salt whose counter ion is iodide. And one salt of an unsaturated carboxylic acid selected from the group consisting of maleic acid half ester and α-chlorocarboxylic acid ester and / or α-chlorocarboxylic acid ester.
The present invention relates to a production method for reacting with chloroketone. By this method, an unsaturated dicarboxylic acid ester having an oxycarbonylmethyl ester group and / or a carbonylmethyl ester group, such as an itaconic acid ester, a fumaric acid ester or a maleic acid ester, can be prepared by a conventional method.
Production can be performed with high purity and high yield in a short reaction time, and an economical production method has been established.

 ────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Asako Oda 2115-6, Fukai Shimizu-cho, Sakai City, Osaka (72) Inventor Masataka Ooka 6-11-4 Tomigaoka, Nara City, Nara Prefecture F-term (reference) 4H006 AA02 AC48 BA02 BA37 BB20 BC10 KA01 KF00 4H039 CA66 CD20

Claims (10)

[Claims] 1. A compound selected from the group consisting of itaconic acid, itaconic acid half ester, fumaric acid, fumaric acid half ester, maleic acid and maleic acid half ester
The salts of unsaturated carboxylic acids (A) are converted to α-chlorocarboxylic acid esters (B) in the presence of salts (B) in which the counter ion is bromide and / or salts (C) in which the counter ion is iodine. A method for producing an unsaturated dicarboxylic acid ester, characterized by reacting with D) and / or α-chloroketone (E). 2. The itaconic acid half ester is represented by the following general formula (I), the fumaric acid half ester or the maleic acid half ester is represented by the following general formula (II), and the α-chlorocarboxylic acid ester is represented by the following general formula: In (III), α-
The method for producing an unsaturated dicarboxylic acid ester according to claim 1, wherein the chloroketone is represented by the following general formula (IV). Embedded image [However, in formulas (I) and (II), one of R ^a and R ^b is a hydrogen atom, and the other is —CH (R ₁ ) COOR ₂ ,
CH (R ₃ ) represents COR ₄ or R ₅ . R ₁ and R ₃ contained therein are each independently a hydrogen atom,
A phenyl group or an alkyl group having 1 to 12 carbon atoms,
R ₂ , R ₄ and R ₅ each independently represent a monovalent organic group. [Chemical formula 2] [In the formula, R ₁ and R ₃ represent a hydrogen atom, a phenyl group or an alkyl group having 1 to 12 carbon atoms, and R ₂ and R ₄ represent a monovalent organic group. ] 3. The aforementioned R ₂ and R ₄ each independently represent an alkyl group, a substituted alkyl group, a cycloalkyl group,
The method for producing an unsaturated dicarboxylic acid ester according to claim 2, which is an aryl group or a substituted aryl group. 4. The above-mentioned R ₂ has 3 to 8 carbon atoms including an alkyl group or an alkoxy group having 1 to 8 carbon atoms.
4. An alkoxy-substituted alkyl group represented by the formula:
5. The method for producing an unsaturated dicarboxylic acid ester according to the above. 5. The method for producing an unsaturated dicarboxylic acid ester according to claim 2, wherein R ₄ is an alkyl group having 1 to 8 carbon atoms. 6. The method for producing an unsaturated dicarboxylic acid ester according to claim 2, wherein R ₁ is a hydrogen atom or a methyl group. 7. The method for producing an unsaturated dicarboxylic acid ester according to claim 2, wherein said R ₃ is a hydrogen atom. 8. The method for producing an unsaturated dicarboxylic acid ester according to claim 2, wherein R ₅ is an alkyl group, a substituted alkyl group, a cycloalkyl group, an aryl group or a substituted aryl group. . 9. The aforementioned R ₅ has 3 to 8 carbon atoms including an alkyl group or an alkoxy group having 1 to 8 carbon atoms.
The method for producing an unsaturated dicarboxylic acid ester according to any one of claims 2 to 8, wherein the alkyl group is an alkoxy-substituted alkyl group. 10. A salt (B) wherein the counter ion is bromine ion.
The method for producing an unsaturated dicarboxylic acid ester according to any one of claims 1 to 9, wherein an alkali metal bromide and / or an alkali metal iodide is used as the salt (C) whose counter ion is an iodine ion.