JP2001354629A - NEW alpha,beta-UNSATURATED DICARBOXYLIC ACID ESTER AND METHOD FOR PRODUCING THE SAME - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a new α,β-unsaturated dicarboxylic acid ester containing an oxycarbonylmethyl ester group as an active ester group and to provide a method for producing the same. SOLUTION: This new α,β-unsaturated dicarboxylic acid ester contains an oxycarbonylmethyl ester group as an active ester group. This method for producing the α,β-unsaturated dicarboxylic acid ester comprises reacting one kind of an α,β-unsaturated carboxylate selected from the group consisting of a fumarate, a fumaric acid half ester salt, a maleate and a maleic acid half ester salt with an α-halocarboxylic acid ester.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to an α, β-unsaturated dicarboxylic acid ester and a method for producing the same. More specifically, the present invention relates to novel α, β-unsaturated dicarboxylic esters such as novel fumaric esters or maleic esters each having an oxycarbonylmethyl ester group and a method for producing the same. Α, β of the present invention
The unsaturated dicarboxylic acid ester is a compound having both an active ester group and a polymerizable unsaturated double bond, and can be effectively used for 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, α, β such as fumaric acid or maleic acid, each containing an oxycarbonylmethyl ester group,
-Derivatives of unsaturated dicarboxylic acids are not known.

[0003]

SUMMARY OF THE INVENTION However, the inventors of the present invention have eagerly started research to develop a novel α, β-unsaturated dicarboxylic acid ester having an oxycarbonylmethyl ester group as an active ester group. did.

An object of the present invention is to provide a novel α, β-unsaturated dicarboxylic acid ester having an oxycarbonylmethyl ester group as an active ester group and a method for producing the same.

[0005]

Means for Solving the Problems The present inventors have conducted intensive studies in order to solve the above-mentioned problems, and as a result, a novel α, β-unsaturated dicarboxylic acid having an oxycarbonylmethyl ester group as an active ester group. The inventors have found an acid ester and a method for producing the same, and have completed the present invention.

That is, the present invention provides a compound represented by the following general formula (I-
1) and (I-2) [Hereinafter, these two formulas may be collectively abbreviated as general formula (I). Α, β
-To provide unsaturated dicarboxylic esters.

[0007]

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[0008] (wherein, R _1, R ₄ is a hydrogen atom, a phenyl group or an alkyl group having a carbon number of 1 to 12, R _2,
R ₃ and R ₅ each independently represent a monovalent organic group. )

[0009] The present invention also relates to an α, β selected from the group consisting of fumaric acid salts, fumaric acid half ester salts, maleic acid salts and maleic acid half ester salts.
-A process for producing an α, β-unsaturated dicarboxylic acid ester, characterized by reacting an unsaturated carboxylate with an α-halocarboxylic acid ester;

Alternatively, fumaric acid half ester and maleic acid half ester are represented by the following general formula (II-1) or (II-2) [hereinafter, these two formulas are collectively represented by the general formula (I)
Sometimes abbreviated as I). And a method for producing the above-mentioned α, β-unsaturated dicarboxylic acid ester, wherein the α-halocarboxylic acid ester is a compound represented by the following general formula (III): .

[0011]

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(Wherein R ₃ and R ₅ are each independently 1
R ₄ represents a hydrogen atom, a phenyl group or an alkyl group having 1 to 12 carbon atoms. )

[0013]

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(In the formula, R ₁ represents a hydrogen atom, a phenyl group or an alkyl group having 1 to 12 carbon atoms, R ₂ represents a monovalent organic group, and X represents a halogen atom.)

[0015]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below in detail. The α, β-unsaturated dicarboxylic acid ester of the present invention refers to compounds represented by the following general formulas (I-1) and (I-2). Such a general formula (I-
The compounds represented by 1) and (I-2) include both a fumarate ester in which two ester groups are in the trans position and a maleate ester in which two ester groups are in the cis position. is there.

[0016]

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[0017] (wherein, R _1, R ₄ is a hydrogen atom, a phenyl group or an alkyl group having a carbon number of 1 to 12, R _2,
R ₃ and R ₅ each independently represent a monovalent organic group. )

In the general formulas (I-1) and (I-2), typical examples of the monovalent organic groups R ₂ , R ₃ and R ₅ include an alkyl group, a substituted alkyl group and a cycloalkyl group. Alkyl group, aryl group, substituted aryl group and the like,
Of these, an alkyl group having 1 to 6 carbon atoms and an alkoxy-substituted alkyl group having 3 to 6 carbon atoms including an alkoxy group are preferable.

Among such monovalent organic groups, typical examples of the alkyl group include a methyl group, an ethyl group, an n-propyl group, an iso-propyl group, an n-butyl group, and an iso group.
-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-n
-Propoxyethyl group, 2-n-butoxyethyl group, 3
An alkyl group substituted by an alkoxy group such as -methoxypropyl group; an alkyl group substituted by an aryloxy group such as 2-phenoxyethyl group or 2- (4-methylphenoxy) ethyl group; 2-benzyloxyethyl group; −
An alkyl group substituted by an aralkyloxy group such as (2-phenylethoxy) ethyl group; an alkyl group substituted by 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.

The α represented by the general formula having a monovalent organic group various described above as R _2, R ₃ (I-1), among the β- unsaturated dicarboxylic acid esters, alkyl as R ₂ and R ₃ A typical example of a fumarate having a group and having a hydrogen atom as R ₁ is monomethyl-
Mono (methoxycarbonylmethyl) fumarate, monomethyl-mono (ethoxycarbonylmethyl) fumarate,
Monoethyl-mono (ethoxycarbonylmethyl) fumarate, mono (n-propyl) -mono (n-propoxycarbonylmethyl) fumarate, mono (n-butyl) -mono (n-butoxycarbonylmethyl) fumarate, mono (n-butyl) Mono (methoxycarbonylmethyl) fumarate, mono (n-hexyl) -mono (n-hexyloxycarbonylmethyl) fumarate, monomethyl-mono (2-ethylhexyloxycarbonylmethyl) fumarate, monomethyl-mono (n-decyloxycarbonylmethyl) ) Fumarate and the like.

Among the α, β-unsaturated dicarboxylic esters represented by the general formula (I-1), R ₂ has an alkyl group and R ₃ has an alkoxy-substituted alkyl group;
Typical examples of the fumaric acid ester having a hydrogen atom as R ₁ include mono (2-methoxyethyl)-
Mono (methoxycarbonylmethyl) fumarate, mono (2-methoxyethyl) -mono (ethoxycarbonylmethyl) fumarate, mono (2-ethoxyethyl) -mono (ethoxycarbonylmethyl) fumarate, mono (2-
Ethoxyethyl) -mono (n-propoxycarbonylmethyl) fumarate, mono (2-ethoxyethyl) -mono (n-butoxycarbonylmethyl) fumarate, mono (2-n-butoxyethyl) -mono (n-hexyloxycarbonylmethyl) Fumarate, mono (4-ethoxybutyl) -mono (2-ethylhexyloxycarbonylmethyl) fumarate, mono (3-n-propoxypropyl) -mono (n-decyloxycarbonylmethyl) fumarate, and the like.

Among the α, β-unsaturated dicarboxylic esters represented by the general formula (I-1), R ₂ has an alkyl group substituted with an alkyl group as R ₂ , and R ₃ has an alkyl group substituted with an aryl group. Representative examples of the fumarate having a hydrogen atom as ₁ include monobenzyl-mono (methoxycarbonylmethyl) fumarate, monobenzyl-mono (ethoxycarbonylmethyl) fumarate, and mono (2
-Phenylethyl) -mono (ethoxycarbonylmethyl) fumarate, mono (1-phenylethyl) -mono (n-propoxycarbonylmethyl) fumarate, monobenzyl-mono (n-butoxycarbonylmethyl) fumarate, and the like.

The α represented by formula (I-1), among the β- unsaturated dicarboxylic acid ester, the alkyl group as R _2, a cycloalkyl group as R _3, and, R ₁
Representative examples of the fumarate having a hydrogen atom include monocyclopentyl-mono (methoxycarbonylmethyl) fumarate, monocyclopentyl-mono (ethoxycarbonylmethyl) fumarate, monocyclohexyl-mono (ethoxycarbonylmethyl) fumarate, mono And cyclohexyl-mono (n-propoxycarbonylmethyl) fumarate, monocyclohexyl-mono (n-butoxycarbonylmethyl) fumarate, and the like.

Among the α, β-unsaturated dicarboxylic esters represented by the general formula (I-1), R ₂ has an alkyl group, R ₃ has an aryl group, and R ₁ has a hydrogen atom. Typical examples of the fumaric acid ester include monophenyl-mono (methoxycarbonylmethyl) fumarate, monophenyl-mono (ethoxycarbonylmethyl) fumarate, mono (1-naphthyl) -mono (ethoxycarbonylmethyl) fumarate, Phenyl-mono (n-propoxycarbonylmethyl) fumarate, monophenyl-mono (n-butoxycarbonylmethyl) fumarate, and the like.

In the α, β-unsaturated dicarboxylic acid ester represented by the general formula (I-1), an alkyl group as R ₂ , a substituted aryl group as R ₃ , and a hydrogen atom as R ₁ Representative examples of the fumaric acid ester having the following are mono (4-methylphenyl) -mono (methoxycarbonylmethyl) fumarate, mono (4-methylphenyl) -mono (ethoxycarbonylmethyl) fumarate, mono (4-chlorophenyl) ) -Mono (ethoxycarbonylmethyl) fumarate, mono (4-nitrophenyl) -mono (n-propoxycarbonylmethyl) fumarate, and the like.

Among the α, β-unsaturated dicarboxylic acid esters represented by the general formula (I-1), R ₂ has an alkoxy-substituted alkyl group and R ₃ has an alkyl group;
Representative examples of the fumarate having a hydrogen atom as R ₁ include monomethyl-mono (2-methoxyethoxycarbonylmethyl) fumarate, monoethyl-mono (2-ethoxyethoxycarbonylmethyl) fumarate, and mono (n- Propyl) -mono (2-n-propoxyethoxycarbonylmethyl) fumarate, mono (n
-Butyl) -mono (2-n-butoxyethoxycarbonylmethyl) fumarate, mono (n-hexyl) -mono (3-methoxypropoxycarbonylmethyl) fumarate, and the like.

Among the α, β-unsaturated dicarboxylic esters represented by the general formula (I-1), R ₂ and R ₃ have an alkoxy-substituted alkyl group and R ₁ has a hydrogen atom. Representative examples of fumaric acid esters include mono (2-methoxyethyl) -mono (2-methoxyethoxycarbonylmethyl) fumarate and mono (2-methoxyethyl) fumarate.
Ethoxyethyl) -mono (2-ethoxyethoxycarbonylmethyl) fumarate, mono (2-n-propoxyethyl) fumarate, mono (2-n-butoxyethyl) fumarate
-Mono (2-n-butoxyethoxycarbonylmethyl)
Fumarate, mono (3-methoxypropyl) -mono (3
-Methoxypropoxycarbonylmethyl) fumarate,
Etc.

In the α, β-unsaturated dicarboxylic acid ester represented by the general formula (I-1), R ₂ has an alkoxy-substituted alkyl group and R ₃ has an alkyl group substituted with an aryl group; Representative examples of the fumarate having a hydrogen atom as R ₁ include monobenzyl-mono (2-methoxyethoxycarbonylmethyl).
Fumarate, monobenzyl-mono (2-ethoxyethoxycarbonylmethyl) fumarate, mono (2-phenylethyl) -mono (2-n-propoxyethoxycarbonylmethyl) fumarate, mono (1-phenylethyl)-
Mono (2-n-butoxyethoxycarbonylmethyl) fumarate, and the like.

Among the α, β-unsaturated dicarboxylic esters represented by the general formula (I-1), R ₂ has an alkoxy-substituted alkyl group, R ₃ has an aryl group,
Representative examples of the fumaric acid ester having a hydrogen atom as R ₁ include monophenyl-mono (2-methoxyethoxycarbonylmethyl) fumarate and monophenyl-mono (2-ethoxyethoxycarbonylmethyl).
Fumarate, mono (1-naphthyl) -mono (2-n-propoxyethoxycarbonylmethyl) fumarate, monophenyl-mono (2-n-butoxyethoxycarbonylmethyl) fumarate, and the like.

In the α, β-unsaturated dicarboxylic acid ester represented by the general formula (I-1), R ₂ has an alkoxy-substituted alkyl group, R ₃ has a substituted aryl group, and R ₁ As typical examples of the fumaric acid ester having a hydrogen atom, mono (4-methylphenyl) -mono (2-methoxyethoxycarbonylmethyl)
Fumarate, mono (4-methylphenyl) -mono (2-
Ethoxyethoxycarbonylmethyl) fumarate, mono (4-chlorophenyl) -mono (2-n-propoxyethoxycarbonylmethyl) fumarate, mono (4-nitrophenyl) -mono (2-n-butoxyethoxycarbonylmethyl) fumarate, and the like. No.

Among the α, β-unsaturated dicarboxylic esters represented by the general formula (I-1), R ₂ has an alkoxy-substituted alkyl group, R ₃ has a cycloalkyl group, and R ₁ Typical examples of the fumaric acid ester having a hydrogen atom include monocyclohexyl-mono (2-methoxyethoxycarbonylmethyl) fumarate, monocyclohexyl-mono (2-ethoxyethoxycarbonylmethyl) fumarate, monocyclopentyl-
Mono (2-n-propoxyethoxycarbonylmethyl)
Fumarate, monocyclohexyl-mono (2-n-butoxyethoxycarbonylmethyl) fumarate, and the like.

In the α, β-unsaturated dicarboxylic acid ester represented by the general formula (I-1), an alkyl group substituted by an aryl group as R ₂ , an alkyl group as R ₃ , Representative examples of fumarate having a hydrogen atom as ₁ include monomethyl-mono (benzyloxycarbonylmethyl) fumarate, monoethyl-
Mono (1-phenylethoxycarbonylmethyl) fumarate, mono (n-propyl) -mono (2-phenylethoxycarbonylmethyl) fumarate, mono (n-hexyl) -mono (benzyloxycarbonylmethyl) fumarate, and the like.

In the α, β-unsaturated dicarboxylic acid ester represented by the general formula (I-1), an alkyl group substituted with an aryl group as R ₂ and an alkoxy-substituted alkyl group as R ₃ ; Representative examples of the fumarate having a hydrogen atom as R ₁ include mono (2
-Methoxyethyl) -mono (benzyloxycarbonylmethyl) fumarate, mono (2-ethoxyethyl) -mono (1-phenylethoxycarbonylmethyl) fumarate, mono (2-n-butoxyethyl) -mono (2-phenylethoxycarbonyl) Methyl) fumarate, and the like.

In the α, β-unsaturated dicarboxylic acid ester represented by the general formula (I-1), an alkyl group substituted with an aryl group as R ₂ , a cycloalkyl group as R ₃ , and Representative examples of the fumaric acid ester having a hydrogen atom as R ₁ include monocyclopentyl-mono (benzyloxycarbonylmethyl) fumarate, monocyclopentyl-mono (1-phenylethoxycarbonylmethyl) fumarate, monocyclohexyl-
Mono (2-phenylethoxycarbonylmethyl) fumarate, and the like.

In the α, β-unsaturated dicarboxylic acid ester represented by the general formula (I-1), an alkyl group substituted with an aryl group as R ₂ , an aryl group as R ₃ , and R Representative examples of the fumarate having a hydrogen atom as ₁ include monophenyl-mono (benzyloxycarbonylmethyl) fumarate, monophenyl-mono (1-phenylethoxycarbonylmethyl) fumarate, and mono (1-naphthyl)- Mono (2-phenylethoxycarbonylmethyl) fumarate, and the like.

In the α, β-unsaturated dicarboxylic acid ester represented by the formula (I-1), an alkyl group substituted with an aryl group as R ₂ , a substituted aryl group as R ₃ , and Representative examples of the fumarate having a hydrogen atom as R ₁ include mono (4-methylphenyl) -mono (benzyloxycarbonylmethyl) fumarate and mono (4-methylphenyl) -mono (1-phenylethoxycarbonyl). Methyl) fumarate, mono (4
-Chlorophenyl) -mono (2-phenylethoxycarbonylmethyl) fumarate, and the like.

Among the α, β-unsaturated dicarboxylic acid esters represented by the general formula (I-1), a cycloalkyl group as R ₂ , an alkyl group as R ₃ , and R ₁
Representative examples of the fumarate having a hydrogen atom include monomethyl-mono (cyclopentyloxycarbonylmethyl) fumarate, monoethyl-mono (cyclohexyloxycarbonylmethyl) fumarate, and mono (n-butyl) -mono (cyclohexyloxycarbonyl) Methyl) fumarate, mono (n-hexyl) -mono (cyclohexyloxycarbonylmethyl) fumarate, and the like.

Among the α, β-unsaturated dicarboxylic esters represented by the general formula (I-1), a cycloalkyl group as R ₂ , an alkoxy-substituted alkyl group as R ₃ , and R ₁ As typical examples of the fumaric acid ester having a hydrogen atom, mono (2-methoxyethyl) -mono (cyclopentyloxycarbonylmethyl)
Fumarate, mono (2-ethoxyethyl) -mono (cyclohexyloxycarbonylmethyl) fumarate, and compounds such as mono (2-n-butoxyethyl) -mono (cyclohexyloxycarbonylmethyl) fumarate.

Among the α, β-unsaturated dicarboxylic esters represented by the formula (I-1), fumaric acid having a cycloalkyl group as R ₂ and R ₃ and a hydrogen atom as R ₁ Representative examples of the ester include monocyclopentyl-mono (cyclopentyloxycarbonylmethyl) fumarate, monocyclohexyl-mono (cyclohexyloxycarbonylmethyl) fumarate, monocyclopentyl-mono (cyclohexyloxycarbonylmethyl) fumarate, and the like.

In the α, β-unsaturated dicarboxylic acid ester represented by the general formula (I-1), a cycloalkyl group as R ₂ , an aryl group as R ₃ , and R ₁
Representative examples of the fumarate having a hydrogen atom include monophenyl-mono (cyclopentyloxycarbonylmethyl) fumarate and mono (1-naphthyl) -mono (cyclohexyloxycarbonylmethyl)
Fumarate, etc.

Among the α, β-unsaturated dicarboxylic esters represented by the general formula (I-1), a cycloalkyl group as R ₂ , a substituted aryl group as R ₃ , and
Representative examples of the fumarate having a hydrogen atom as R ₁ include mono (4-methylphenyl) -mono (cyclopentyloxycarbonylmethyl) fumarate and mono (4-chlorophenyl) -mono (cyclohexyloxycarbonylmethyl) fumarate , Mono (4-nitrophenyl) -mono (cyclohexyloxycarbonylmethyl) fumarate, and the like.

In the α, β-unsaturated dicarboxylic acid ester represented by the general formula (I-1), an aryl group as R ₂ , an alkyl group as R ₃ , and a hydrogen atom as R _1. Typical examples of the fumaric acid ester include monomethyl-mono (phenoxycarbonylmethyl) fumarate, monoethyl-mono (phenoxycarbonylmethyl) fumarate, mono (n-butyl) -mono (phenoxycarbonylmethyl) fumarate, and mono (n
-Hexyl) -mono (phenoxycarbonylmethyl) fumarate, monomethyl-mono (1-naphthoxycarbonylmethyl) fumarate, monomethyl-mono (2-naphthoxycarbonylmethyl) fumarate, and the like.

The α, β-unsaturated compound represented by the general formula (I-1)
Among the dicarboxylic acid esters, R_TwoAs aryl
A group represented by R_ThreeHas an alkoxy-substituted alkyl group as
One, R ₁ Of fumaric acid ester having hydrogen atom as
Representatively, mono (2-methoxyethyl) -mo
No (phenoxycarbonylmethyl) fumarate, mono
(2-ethoxyethyl) -mono (phenoxycarbonyl)
Methyl) fumarate, mono (2-n-butoxyethyl)
Mono (phenoxycarbonylmethyl) fumarate,
No (2-methoxyethyl) -mono (1-naphthoxycal
Bonylmethyl) fumarate, and the like.

In the α, β-unsaturated dicarboxylic acid ester represented by the general formula (I-1), an aryl group is substituted as R ₂ and an alkyl group substituted with an aryl group as R ₃ , and Representative examples of the fumarate having a hydrogen atom as ₁ include monobenzyl-mono (phenoxycarbonylmethyl) fumarate, monobenzyl-
Mono (1-naphthoxycarbonylmethyl) fumarate,
And the like.

In the α, β-unsaturated dicarboxylic acid ester represented by the general formula (I-1), an aryl group as R ₂ , a cycloalkyl group as R ₃ , and R ₁
Typical examples of the fumaric acid ester having a hydrogen atom include monocyclopentyl-mono (phenoxycarbonylmethyl) fumarate, monocyclohexyl-mono (phenoxycarbonylmethyl) fumarate, and monocyclohexyl-mono (1-naphthoxycarbonylmethyl) Fumarate and the like.

Among the α, β-unsaturated dicarboxylic esters represented by the formula (I-1), fumaric esters having an aryl group as R ₂ and R ₃ and a hydrogen atom as R ₁ Representative examples include monophenyl-mono (phenoxycarbonylmethyl) fumarate,
Mono (1-naphthyl) -mono (phenoxycarbonylmethyl) fumarate; monophenyl-mono (1-naphthoxycarbonylmethyl) fumarate;

In the α, β-unsaturated dicarboxylic acid ester represented by the general formula (I-1), an aryl group as R ₂ , a substituted aryl group as R ₃ , and a hydrogen atom as R ₁ Representative examples of the fumaric acid ester having the following are mono (4-methylphenyl) -mono (phenoxycarbonylmethyl) fumarate, mono (4-chlorophenyl) -mono (phenoxycarbonylmethyl) fumarate, mono (4-methylphenyl) ) -Mono (1-naphthoxycarbonylmethyl) fumarate, and the like.

Among the α, β-unsaturated dicarboxylic esters represented by the general formula (I-1), a substituted aryl group as R ₂ , an alkyl group as R ₃ , and a hydrogen atom as R ₁ Representative examples of the fumaric acid ester having the following are monomethyl-mono (3-methylphenoxycarbonylmethyl) fumarate and monomethyl-mono (4-
Methylphenoxycarbonylmethyl) fumarate, monoethyl-mono (4-methylphenoxycarbonylmethyl) fumarate, mono (n-butyl) -mono (4-methylphenoxycarbonylmethyl) fumarate, mono (n
-Hexyl) -mono (4-methylphenoxycarbonylmethyl) fumarate, monomethyl-mono (4-nitrophenoxycarbonylmethyl) fumarate, and the like.

Among the α, β-unsaturated dicarboxylic esters represented by the general formula (I-1), R ₁ has a substituted aryl group as R ₂ , an alkoxy-substituted alkyl group as R ₃ , and R ₁ Representative examples of the fumaric acid ester having a hydrogen atom include mono (2-methoxyethyl) -mono (3-methylphenoxycarbonylmethyl)
Fumarate, mono (2-methoxyethyl) -mono (4-
Methylphenoxycarbonylmethyl) fumarate, mono (2-ethoxyethyl) -mono (4-methylphenoxycarbonylmethyl) fumarate, mono (2-n-butoxyethyl) -mono (4-methylphenoxycarbonylmethyl) fumarate, mono (2 -Methoxyethyl) -mono (4-nitrophenoxycarbonylmethyl) fumarate, and the like.

In the α, β-unsaturated dicarboxylic acid ester represented by the formula (I-1), R ₂ has a substituted aryl group, R ₃ has an alkyl group substituted with an aryl group, and Representative examples of the fumarate having a hydrogen atom as R ₁ include monobenzyl-mono (3-methylphenoxycarbonylmethyl) fumarate, monobenzyl-mono (4-methylphenoxycarbonylmethyl) fumarate, monobenzyl-mono (4-nitrophenoxycarbonylmethyl) fumarate, and the like.

Among the α, β-unsaturated dicarboxylic acid esters represented by the general formula (I-1), a substituted aryl group as R ₂ , a cycloalkyl group as R ₃ , and
Representative examples of the fumaric acid ester having a hydrogen atom as R ₁ include monocyclopentyl-mono (3-methylphenoxycarbonylmethyl) fumarate, monocyclopentyl-mono (4-methylphenoxycarbonylmethyl) fumarate, monocyclohexyl-mono (4-methylphenoxycarbonylmethyl) fumarate, monocyclooctyl-mono (4-methylphenoxycarbonylmethyl) fumarate, monocyclohexyl-mono (4-
Nitrophenoxycarbonylmethyl) fumarate, and the like.

Among the α, β-unsaturated dicarboxylic esters represented by the general formula (I-1), a substituted aryl group as R ₂ , an aryl group as R ₃ , and a hydrogen atom as R ₁ Representative examples of the fumaric acid ester having the following are monophenyl-mono (3-methylphenoxycarbonylmethyl) fumarate, monophenyl-mono (4-methylphenoxycarbonylmethyl) fumarate, and mono (1-naphthyl) -mono ( 4-methylphenoxycarbonylmethyl) fumarate, monophenyl-mono (4-nitrophenoxycarbonylmethyl) fumarate, and the like.

Among the α, β-unsaturated dicarboxylic acid esters represented by the general formula (I-1), fumaric acid having a substituted aryl group as R ₂ and R ₃ and a hydrogen atom as R ₁ Representative examples of the ester include mono (3-methylphenyl) -mono (3-methylphenoxycarbonylmethyl) fumarate, mono (4-methylphenyl) -mono (4-methylphenoxycarbonylmethyl) fumarate, mono (4 -Chlorophenyl) -mono (4-methylphenoxycarbonylmethyl) fumarate, mono (4-methylphenyl) -mono (4-nitrophenoxycarbonylmethyl) fumarate, and the like.

Further, α, β represented by the general formula (I-1)
Among the unsaturated dicarboxylic acid esters, typical examples of fumaric acid esters having various alkyl groups having 1 to 12 carbon atoms or phenyl groups as R ₁ include those represented by formula (I-1): In the various fumarate esters listed above as examples of those containing a hydrogen atom as R ₁ , various kinds of compounds having a structure in which a hydrogen atom of R ₁ is replaced with various alkyl groups or phenyl groups having 1 to 12 carbon atoms. Can be mentioned.

Further, α, β- represented by the general formula (I-1) having various monovalent organic groups described above as R ₂ and R _3.
Among the unsaturated dicarboxylic esters, a typical maleic ester having an alkyl group as R ₂ and R ₃ and a hydrogen atom as R ₁ is monomethyl-mono (methoxycarbonylmethyl) malate. ,
Monomethyl-mono (ethoxycarbonylmethyl) malate, monoethyl-mono (ethoxycarbonylmethyl) malate, mono (n-propyl) -mono (n-propoxycarbonylmethyl) malate, mono (n-butyl) -mono (methoxycarbonylmethyl) Malate, mono (n-
Butyl) -mono (n-butoxycarbonylmethyl) malate, mono (n-hexyl) -mono (n-hexyloxycarbonylmethyl) malate, monomethyl-mono (2
-Ethylhexyloxycarbonylmethyl) malate,
Monomethyl-mono (n-decyloxycarbonylmethyl) malate, and the like.

Among the α, β-unsaturated dicarboxylic esters represented by the general formula (I-1), R ₂ has an alkyl group and R ₃ has an alkoxy-substituted alkyl group;
A typical maleic ester having a hydrogen atom as R ₁ is mono (2-methoxyethyl)
-Mono (methoxycarbonylmethyl) malate, mono (2-methoxyethyl) -mono (ethoxycarbonylmethyl) malate, mono (2-ethoxyethyl) -mono (ethoxycarbonylmethyl) malate, mono (2-ethoxyethyl) -mono (N-propoxycarbonylmethyl) malate, mono (2-ethoxyethyl) -mono (n
-Butoxycarbonylmethyl) malate, mono (2-n
-Butoxyethyl) -mono (n-hexyloxycarbonylmethyl) malate, mono (4-ethoxybutyl)-
Mono (2-ethylhexyloxycarbonylmethyl) malate, mono (3-n-propoxypropyl) -mono (n-decyloxycarbonylmethyl) malate, and the like.

Among the α, β-unsaturated dicarboxylic esters represented by the general formula (I-1), R ₂ has an alkyl group substituted with an alkyl group as R ₂ , and R ₃ has an alkyl group substituted with an aryl group. Representative examples of the maleic ester having a hydrogen atom as ₁ include monobenzyl-mono (methoxycarbonylmethyl) malate, monobenzyl-mono (ethoxycarbonylmethyl) malate, and mono (2-
Phenylethyl) -mono (ethoxycarbonylmethyl)
Malate, mono (1-phenylethyl) -mono (n-propoxycarbonylmethyl) malate, monobenzyl-
Mono (n-butoxycarbonylmethyl) malate and the like.

[0062] α represented by formula (I-1), among the β- unsaturated dicarboxylic acid ester, the alkyl group as R _2, a cycloalkyl group as R _3, and, R ₁
Representative examples of the maleic ester having a hydrogen atom include monocyclopentyl-mono (methoxycarbonylmethyl) malate, monocyclopentyl-mono (ethoxycarbonylmethyl) malate, monocyclohexyl-mono (ethoxycarbonylmethyl) malate,
Monocyclohexyl-mono (n-propoxycarbonylmethyl) malate, monocyclohexyl-mono (n-butoxycarbonylmethyl) malate and the like can be mentioned.

In the α, β-unsaturated dicarboxylic acid ester represented by the general formula (I-1), an alkyl group as R ₂ , an aryl group as R ₃ , and a hydrogen atom as R ₁ Representative maleic acid esters include monophenyl-mono (methoxycarbonylmethyl) malate, monophenyl-mono (ethoxycarbonylmethyl) malate, mono (1-naphthyl) -mono (ethoxycarbonylmethyl) malate, Phenyl-mono (n-propoxycarbonylmethyl) malate, monophenyl-mono (n-butoxycarbonylmethyl) malate, and the like.

In the α, β-unsaturated dicarboxylic acid ester represented by the general formula (I-1), an alkyl group as R ₂ , a substituted aryl group as R ₃ , and a hydrogen atom as R ₁ Representative examples of the maleic acid ester having the following are mono (4-methylphenyl) -mono (methoxycarbonylmethyl) malate, mono (4-methylphenyl) -mono (ethoxycarbonylmethyl) malate, mono (4-chlorophenyl) ) -Mono (ethoxycarbonylmethyl) malate, mono (4-nitrophenyl)
Mono (n-propoxycarbonylmethyl) malate,
And the like.

In the α, β-unsaturated dicarboxylic acid ester represented by the general formula (I-1), R ₂ has an alkoxy-substituted alkyl group and R ₃ has an alkyl group;
Representative examples of the maleic ester having a hydrogen atom as R ₁ include monomethyl-mono (2-methoxyethoxycarbonylmethyl) malate, monoethyl-mono (2-ethoxyethoxycarbonylmethyl) malate, and mono (n- Propyl) -mono (2-n-propoxyethoxycarbonylmethyl) malate, mono (n-butyl) -mono (2-n-butoxyethoxycarbonylmethyl) malate, mono (n-hexyl) -mono (3-methoxypropoxycarbonyl) Methyl) fumarate, and the like.

Among the α, β-unsaturated dicarboxylic esters represented by the formula (I-1), R ₂ and R ₃ have an alkoxy-substituted alkyl group and R ₁ has a hydrogen atom. Representative examples of maleic acid esters include mono (2-methoxyethyl) -mono (2-methoxyethoxycarbonylmethyl) malate and mono (2-methoxyethoxycarbonylmethyl) malate.
(Ethoxyethyl) -mono (2-ethoxyethoxycarbonylmethyl) malate, mono (2-n-propoxyethyl) -mono (2-n-propoxyethoxycarbonylmethyl) malate, mono (2-n-butoxyethyl) -mono ( 2-n-butoxyethoxycarbonylmethyl) malate, mono (3-methoxypropyl) -mono (3-methoxypropoxycarbonylmethyl) malate, and the like.

In the α, β-unsaturated dicarboxylic acid ester represented by the general formula (I-1), R ₂ has an alkoxy-substituted alkyl group and R ₃ has an alkyl group substituted with an aryl group; Representative examples of maleic esters having a hydrogen atom as R ₁ include monobenzyl-mono (2-methoxyethoxycarbonylmethyl) malate, monobenzyl-mono (2-ethoxyethoxycarbonylmethyl) malate, mono ( 2-phenylethyl) -mono (2-n-propoxyethoxycarbonylmethyl) malate, mono (1-phenylethyl) -mono (2-n-butoxyethoxycarbonylmethyl) malate, and the like.

Among the α, β-unsaturated dicarboxylic esters represented by the general formula (I-1), R ₂ has an alkoxy-substituted alkyl group, R ₃ has an aryl group,
Representative examples of the maleic ester having a hydrogen atom as R ₁ include monophenyl-mono (2-methoxyethoxycarbonylmethyl) malate and monophenyl-mono (2-ethoxyethoxycarbonylmethyl).
Maleate, mono (1-naphthyl) -mono (2-n-propoxyethoxycarbonylmethyl) malate, monophenyl-mono (2-n-butoxyethoxycarbonylmethyl) malate, and the like.

Among the α, β-unsaturated dicarboxylic acid esters represented by the general formula (I-1), R ₂ has an alkoxy-substituted alkyl group, R ₃ has a substituted aryl group, and R ₁ Representative examples of a maleic ester having a hydrogen atom include mono (4-methylphenyl) -mono (2-methoxyethoxycarbonylmethyl).
Malate, mono (4-methylphenyl) -mono (2-ethoxyethoxycarbonylmethyl) malate, mono (4
-Chlorophenyl) -mono (2-n-propoxyethoxycarbonylmethyl) malate, mono (4-nitrophenyl) -mono (2-n-butoxyethoxycarbonylmethyl) malate, and the like.

In the α, β-unsaturated dicarboxylic acid ester represented by the general formula (I-1), an alkoxy-substituted alkyl group as R ₂ , a cycloalkyl group as R ₃ , and R ₁ Representative examples of the maleic ester having a hydrogen atom include monocyclohexyl-
Mono (2-methoxyethoxycarbonylmethyl) malate, monocyclohexyl-mono (2-ethoxyethoxycarbonylmethyl) malate, monocyclopentyl-mono (2-n-propoxyethoxycarbonylmethyl) malate, monocyclohexyl-mono (2-n- Butoxyethoxycarbonylmethyl) malate.

In the α, β-unsaturated dicarboxylic acid ester represented by the general formula (I-1), an alkyl group substituted with an aryl group as R ₂ , an alkyl group as R ₃ , Representative examples of the maleic ester having a hydrogen atom as ₁ include monomethyl-mono (benzyloxycarbonylmethyl) malate and monoethyl-
Mono (1-phenylethoxycarbonylmethyl) malate, mono (n-propyl) -mono (2-phenylethoxycarbonylmethyl) malate, mono (n-hexyl)
Mono (benzyloxycarbonylmethyl) malate,
And the like.

Among the α, β-unsaturated dicarboxylic esters represented by the general formula (I-1), R ₂ has an alkyl group substituted with an aryl group, and R ₃ has an alkoxy-substituted alkyl group; Representative examples of maleic acid esters having a hydrogen atom as R ₁ include mono (2-methoxyethyl) -mono (benzyloxycarbonylmethyl) malate and mono (2-ethoxyethyl)-
Mono (1-phenylethoxycarbonylmethyl) malate, mono (2-n-butoxyethyl) -mono (2-phenylethoxycarbonylmethyl) malate, and the like.

In the α, β-unsaturated dicarboxylic acid ester represented by the general formula (I-1), an alkyl group substituted with an aryl group as R ₂ , a cycloalkyl group as R ₃ , and Representative maleic acid esters having a hydrogen atom as R ₁ include monocyclopentyl-mono (benzyloxycarbonylmethyl) malate, monocyclopentyl-mono (1-phenylethoxycarbonylmethyl) malate, monocyclohexyl-mono (2 -Phenylethoxycarbonylmethyl) malate.

In the α, β-unsaturated dicarboxylic acid ester represented by the general formula (I-1), an alkyl group substituted with an aryl group as R ₂ , an aryl group as R ₃ , and R Representative examples of the maleic ester having a hydrogen atom as ₁ include monophenyl-mono (benzyloxycarbonylmethyl) malate, monophenyl-mono (1-phenylethoxycarbonylmethyl) malate, and mono (1-naphthyl)- Mono (2-phenylethoxycarbonylmethyl) malate, and the like.

In the α, β-unsaturated dicarboxylic acid ester represented by the general formula (I-1), an alkyl group substituted with an aryl group as R ₂ , a substituted aryl group as R ₃ , and Representative examples of the maleic ester having a hydrogen atom as R ₁ include mono (4-methylphenyl) -mono (benzyloxycarbonylmethyl) fumarate and mono (4-methylphenyl) -mono (1-phenylethoxycarbonyl) Methyl) malate, mono (4
-Chlorophenyl) -mono (2-phenylethoxycarbonylmethyl) malate, and the like.

Among the α, β-unsaturated dicarboxylic esters represented by the general formula (I-1), a cycloalkyl group as R ₂ , an alkyl group as R ₃ , and R ₁
Representative examples of maleic acid esters having a hydrogen atom include monomethyl-mono (cyclopentyloxycarbonylmethyl) malate, monoethyl-mono (cyclohexyloxycarbonylmethyl) malate, and mono (n-butyl) -mono (cyclohexyloxycarbonyl). Methyl) malate, mono (n-hexyl) -mono (cyclohexyloxycarbonylmethyl) malate, and the like.

In the α, β-unsaturated dicarboxylic acid ester represented by the formula (I-1), a cycloalkyl group as R ₂ , an alkoxy-substituted alkyl group as R ₃ , and R ₁ Representative examples of a maleic ester having a hydrogen atom include mono (2-methoxyethyl) -mono (cyclopentyloxycarbonylmethyl) malate, mono (2-ethoxyethyl) -mono (cyclohexyloxycarbonylmethyl) malate, Mono (2-n-butoxyethyl) -mono (cyclohexyloxycarbonylmethyl) malate.

Among the α, β-unsaturated dicarboxylic esters represented by the general formula (I-1), maleic acid having a cycloalkyl group as R ₂ and R ₃ and a hydrogen atom as R ₁ Representative examples of the ester include monocyclopentyl-mono (cyclopentyloxycarbonylmethyl) malate, monocyclohexyl-mono (cyclohexyloxycarbonylmethyl) malate, monocyclopentyl-mono (cyclohexyloxycarbonylmethyl) malate, and the like.

In the α, β-unsaturated dicarboxylic acid ester represented by the formula (I-1), a cycloalkyl group as R ₂ , an aryl group as R ₃ , and R ₁
Representative examples of the maleic ester having a hydrogen atom include monophenyl-mono (cyclopentyloxycarbonylmethyl) malate and mono (1-naphthyl) -mono (cyclohexyloxycarbonylmethyl).
Malate, etc.

Among the α, β-unsaturated dicarboxylic acid esters represented by the general formula (I-1), a cycloalkyl group as R ₂ , a substituted aryl group as R ₃ , and
Representative maleic acid esters having a hydrogen atom as R ₁ include mono (4-methylphenyl) -mono (cyclopentyloxycarbonylmethyl) malate,
Mono (4-chlorophenyl) -mono (cyclohexyloxycarbonylmethyl) malate, mono (4-nitrophenyl) -mono (cyclohexyloxycarbonylmethyl) malate and the like can be mentioned.

Among the α, β-unsaturated dicarboxylic acid esters represented by the general formula (I-1), an aryl group as R ₂ , an alkyl group as R ₃ and a hydrogen atom as R _1. Representative maleic acid esters include monomethyl-mono (phenoxycarbonylmethyl) malate, monoethyl-mono (phenoxycarbonylmethyl) malate, mono (n-butyl) -mono (phenoxycarbonylmethyl) malate, mono (n -Hexyl) -mono (phenoxycarbonylmethyl) malate,
Monomethyl-mono (1-naphthoxycarbonylmethyl)
Malate, monomethyl-mono (2-naphthoxycarbonylmethyl) malate, and the like.

The α, β-unsaturated compound represented by the general formula (I-1)
Among the dicarboxylic acid esters, R_TwoAs aryl
A group represented by R_ThreeHas an alkoxy-substituted alkyl group as
One, R ₁ Of maleic acid ester having a hydrogen atom as
A typical example is mono (2-methoxyethyl)-
Mono (phenoxycarbonylmethyl) malate, mono
(2-ethoxyethyl) -mono (phenoxycarbonyl)
Methyl) malate, mono (2-n-butoxyethyl)-
Mono (phenoxycarbonylmethyl) malate, mono
(2-methoxyethyl) -mono (1-naphthoxycarbo
Nylmethyl) malate, and the like.

In the α, β-unsaturated dicarboxylic acid ester represented by the general formula (I-1), an aryl group is substituted as R ₂ , and an alkyl group substituted with an aryl group is substituted as R _3. Representative examples of the maleic ester having a hydrogen atom as ₁ include monobenzyl-mono (phenoxycarbonylmethyl) malate and monobenzyl-
Mono (1-naphthoxycarbonylmethyl) malate and the like.

[0084] α represented by formula (I-1), among the β- unsaturated dicarboxylic acid ester, the aryl group as R _2, a cycloalkyl group as R _3, and, R ₁
Representative examples of the maleic ester having a hydrogen atom include monocyclopentyl-mono (phenoxycarbonylmethyl) malate, monocyclohexyl-mono (phenoxycarbonylmethyl) malate, and monocyclohexyl-mono (1-naphthoxycarbonylmethyl).
Malate, and the like.

Among the α, β-unsaturated dicarboxylic esters represented by the general formula (I-1), maleic esters having an aryl group as R ₂ and R ₃ and a hydrogen atom as R ₁ Representatives of are monophenyl-mono (phenoxycarbonylmethyl) malate,
Mono (1-naphthyl) -mono (phenoxycarbonylmethyl) malate, monophenyl-mono (1-naphthoxycarbonylmethyl) malate, and the like.

Among the α, β-unsaturated dicarboxylic esters represented by the general formula (I-1), an aryl group as R ₂ , a substituted aryl group as R ₃ , and a hydrogen atom as R ₁ Representative examples of the maleic acid ester having the following are mono (4-methylphenyl) -mono (phenoxycarbonylmethyl) malate, mono (4-chlorophenyl) -mono (phenoxycarbonylmethyl) malate, mono (4-methylphenyl) ) -Mono (1-naphthoxycarbonylmethyl) malate, and the like.

Among the α, β-unsaturated dicarboxylic acid esters represented by the general formula (I-1), a substituted aryl group as R ₂ , an alkyl group as R ₃ , and a hydrogen atom as R ₁ Representative examples of the maleic acid ester having the following are monomethyl-mono (3-methylphenoxycarbonylmethyl) malate and monomethyl-mono (4-
Methylphenoxycarbonylmethyl) malate, monoethyl-mono (4-methylphenoxycarbonylmethyl)
Malate, mono (n-butyl) -mono (4-methylphenoxycarbonylmethyl) malate, mono (n-hexyl) -mono (4-methylphenoxycarbonylmethyl)
Malate, monomethyl-mono (4-nitrophenoxycarbonylmethyl) malate, and the like.

In the α, β-unsaturated dicarboxylic acid ester represented by the general formula (I-1), R ₂ has a substituted aryl group, R ₃ has an alkoxy-substituted alkyl group, and R ₁ Representative examples of a maleic ester having a hydrogen atom include mono (2-methoxyethyl) -mono (3-methylphenoxycarbonylmethyl).
Malate, mono (2-methoxyethyl) -mono (4-methylphenoxycarbonylmethyl) malate, mono (2
-Ethoxyethyl) -mono (4-methylphenoxycarbonylmethyl) malate, mono (2-n-butoxyethyl) -mono (4-methylphenoxycarbonylmethyl)
Malate, mono (2-methoxyethyl) -mono (4-nitrophenoxycarbonylmethyl) malate, and the like.

In the α, β-unsaturated dicarboxylic acid ester represented by the general formula (I-1), R ₂ has a substituted aryl group, R ₃ has an alkyl group substituted with an aryl group, and Representative maleic acid esters having a hydrogen atom as R ₁ include monobenzyl-mono (3-methylphenoxycarbonylmethyl) malate,
Monobenzyl-mono (4-methylphenoxycarbonylmethyl) malate, monobenzyl-mono (4-nitrophenoxycarbonylmethyl) malate, and the like.

Among the α, β-unsaturated dicarboxylic acid esters represented by the general formula (I-1), a substituted aryl group as R ₂ , a cycloalkyl group as R ₃ , and
Representative examples of the maleic ester having a hydrogen atom as R ₁ include monocyclopentyl-mono (3-methylphenoxycarbonylmethyl) malate, monocyclopentyl-mono (4-methylphenoxycarbonylmethyl) malate, and monocyclohexyl-mono. (4-methylphenoxycarbonylmethyl) malate, monocyclooctyl-mono (4-methylphenoxycarbonylmethyl) malate, monocyclohexyl-mono (4-nitrophenoxycarbonylmethyl) malate, and the like.

Among the α, β-unsaturated dicarboxylic acid esters represented by the formula (I-1), a substituted aryl group as R ₂ , an aryl group as R ₃ , and a hydrogen atom as R ₁ Representative examples of the maleic acid ester having the following are monophenyl-mono (3-methylphenoxycarbonylmethyl) malate, monophenyl-mono (4-methylphenoxycarbonylmethyl) malate,
Mono (1-naphthyl) -mono (4-methylphenoxycarbonylmethyl) malate, monophenyl-mono (4-
Nitrophenoxycarbonylmethyl) malate.

Among the α, β-unsaturated dicarboxylic esters represented by the formula (I-1), maleic acid having a substituted aryl group as R ₂ and R ₃ and a hydrogen atom as R ₁ Representative examples of the ester include mono (3-methylphenyl) -mono (3-methylphenoxycarbonylmethyl) malate, mono (4-methylphenyl) -mono (4-methylphenoxycarbonylmethyl)
Malate, mono (4-chlorophenyl) -mono (4-methylphenoxycarbonylmethyl) malate, mono (4
-Methylphenyl) -mono (4-nitrophenoxycarbonylmethyl) malate, and the like.

Further, α, β represented by the general formula (I-1)
Among the unsaturated dicarboxylic acid esters, a typical maleic ester having various alkyl groups or phenyl groups having 1 to 12 carbon atoms as R ₁ is represented by the general formula (I-1). In the various maleic esters described above as examples of those containing a hydrogen atom as R ₁ , the hydrogen atom represented by R ₁ has 1 to 1 carbon atoms.
And various kinds of compounds having a structure substituted by two kinds of alkyl groups or phenyl groups.

The α, represented by the above general formula (I-1)
Among the β-unsaturated dicarboxylic acid esters, preferred are R ₂ and R ₃ , each of which is independently an alkyl group having 1 to 6 carbon atoms or an alkoxy group having 3 to 6 carbon atoms including an alkoxy group. It is a compound having an alkyl group. And especially preferable compound among such preferable compounds is a compound having a hydrogen atom as R ₁ in the general formula (I-1).

Further, among the α, β-unsaturated dicarboxylic acid esters represented by the general formula (I-2) containing various monovalent organic groups as described above as R ₂ and R ₅ ,
Representative examples of the fumarate having an alkyl group as ₂ and R ₅ and a hydrogen atom as R ₁ and R ₄ include di (methoxycarbonylmethyl) fumarate, di (ethoxycarbonylmethyl) fumarate, Di (n-propoxycarbonylmethyl) fumarate, di (iso-propoxycarbonylmethyl) fumarate, di (n-butoxycarbonylmethyl) fumarate, di (iso-butoxycarbonylmethyl) fumarate, di (n-hexyloxycarbonylmethyl) fumarate And di (2-ethylhexyloxycarbonylmethyl) fumarate, di (n-decyloxycarbonylmethyl) fumarate, and the like.

Among the α, β-unsaturated dicarboxylic acid esters represented by the formula (I-2), R ₂ and R ₅ have an alkoxy-substituted alkyl group and R ₁ and R ₄ are hydrogen. Representative examples of the fumarate having an atom include di (2-methoxyethoxycarbonylmethyl) fumarate, di (2-ethoxyethoxycarbonylmethyl) fumarate, di (2-n-propoxyethoxycarbonylmethyl) fumarate, (2-n-butoxyethoxycarbonylmethyl) fumarate, di (3-
Methoxypropoxycarbonylmethyl) fumarate, and the like.

In the α, β-unsaturated dicarboxylic acid ester represented by the general formula (I-2), R ₂ and R ₅ each have an alkyl group substituted by an aryloxy group, and
Representative examples of the fumarate having a hydrogen atom as R ₁ and R ₄ include di (2-phenoxyethoxycarbonylmethyl) fumarate, di [2- (4-methylphenoxy) ethoxycarbonylmethyl] fumarate, and the like. No.

The α, β-unsaturated compound represented by the general formula (I-2)
Among the dicarboxylic acid esters, R_TwoAnd R_FiveAs
Having an alkyl group substituted by an aralkyloxy group, and
One, R ₁And R_FourFumaric acid having a hydrogen atom as
Representative examples of ter include di (2-benzyloxy).
Ethoxycarbonylmethyl) fumarate, di [2- (2
-Phenylethoxy) ethoxycarbonylmethyl] fuma
Rate, and the like.

Among the α, β-unsaturated dicarboxylic esters represented by the general formula (I-2), R ₂ and R ₅ each have an alkyl group substituted with an aryl group, and R ₁ and R ₄ Representative examples of the fumarate having a hydrogen atom include di (benzyloxycarbonylmethyl) fumarate, di (1-phenylethoxycarbonylmethyl) fumarate, di (2-phenylethoxycarbonylmethyl) fumarate, and the like. Can be

In the α, β-unsaturated dicarboxylic acid ester represented by the formula (I-2), R ₂ and R ₅ have cycloalkyl groups, and R ₁ and R _{4 have} hydrogen atoms. Representative examples of the fumaric acid ester having di (cyclopentyloxycarbonylmethyl) fumarate, di (cyclohexyloxycarbonylmethyl)
Fumarate, di (4-methylcyclohexyloxycarbonylmethyl) fumarate, and the like.

Among the α, β-unsaturated dicarboxylic acid esters represented by the formula (I-2), R ₂ and R ₅ have an aryl group and R ₁ and R ₄ have a hydrogen atom. Representative examples of fumarate esters include di (phenoxycarbonylmethyl) fumarate and di (1-
Naphthoxycarbonylmethyl) fumarate, di (2-naphthoxycarbonylmethyl) fumarate, and the like.

In the α, β-unsaturated dicarboxylic acid ester represented by the formula (I-2), R ₂ and R ₅ have a substituted aryl group, and R ₁ and R ₄ are hydrogen atoms. Representative examples of the fumaric acid ester include di (3-methylphenoxycarbonylmethyl) fumarate, di (4-methylphenoxycarbonylmethyl)
Fumarate, di (4-nitrophenoxycarbonylmethyl) fumarate, and the like.

Among the α, β-unsaturated dicarboxylic esters represented by the general formula (I-2), R ₂ and R ₅ have an alkyl group, and R ₁ and R ₄ have a methyl group. Representative examples of fumarate esters include di (1-methoxycarbonylethyl) fumarate and di (1
-Ethoxycarbonylethyl) fumarate, di (1-n
-Propoxycarbonylethyl) fumarate, di (1-
iso-propoxycarbonylethyl) fumarate, di (1-n-butoxycarbonylethyl) fumarate, di (1-iso-butoxycarbonylethyl) fumarate, di (1-n-hexyloxycarbonylethyl) fumarate, di [1- ( 2-ethylhexyloxycarbonyl) ethyl] fumarate, di (1-n-decyloxycarbonylethyl) fumarate, and the like.

Among the α, β-unsaturated dicarboxylic acid esters represented by the formula (I-2), R ₂ and R ₅ have an alkoxy-substituted alkyl group and R ₁ and R ₄ are methyl. Representative examples of the fumaric acid ester having a group include di [1- (2-methoxyethoxycarbonyl) ethyl] fumarate, di [1- (2-ethoxyethoxycarbonyl) ethyl] fumarate, di [1-
(2-n-propoxyethoxycarbonyl) ethyl] fumarate, di [1- (2-n-butoxyethoxycarbonyl) ethyl] fumarate, di [1- (3-methoxypropoxycarbonyl) ethyl] fumarate, and the like.

Among the α, β-unsaturated dicarboxylic acid esters represented by the general formula (I-2), R ₂ and R ₅ each have an alkyl group substituted by an aryloxy group, and
Representative examples of the fumaric acid ester having a methyl group as R ₁ and R ₄ include di [1- (2-phenoxyethoxycarbonyl) ethyl] fumarate and di {1-
[2- (4-methylphenoxy) ethoxycarbonyl]
Ethyl difumarate and the like.

The α, β-unsaturated compound represented by the general formula (I-2)
Among the dicarboxylic acid esters, R_TwoAnd R_FiveAs
Having an alkyl group substituted by an aralkyloxy group, and
One, R ₁And R_FourFumaric acid having a methyl group as a substituent
Representative examples of ter include di [1- (2-benzyl)
Oxyethoxycarbonyl) ethyl] fumarate, di
{1- [2- (2-phenylethoxy) ethoxycarbo
Nyl] ethyl difumarate and the like.

The α, β-unsaturated compound represented by the general formula (I-2)
Among the dicarboxylic acid esters, R _TwoAnd R_FiveAs
The aryl group has a substituted alkyl group, and R₁You
And R_FourOf fumaric acid ester having methyl group as
Representatively, di (1-benzyloxycarbonyl)
Ruethyl) fumarate, di [1- (1-phenylethoxy)
(Cyclocarbonyl) ethyl] fumarate, di [1- (2-f
Enylethoxycarbonyl) ethyl] fumarate, etc.
No.

Among the α, β-unsaturated dicarboxylic esters represented by the general formula (I-2), R ₂ and R ₅ have a cycloalkyl group, and R ₁ and R _{4 have} a methyl group. Representative examples of the fumaric acid ester having di (1-cyclopentyloxycarbonylethyl)
Fumarate, di (1-cyclohexyloxycarbonylethyl) fumarate, di [1- (4-methylcyclohexyloxycarbonyl) ethyl] fumarate, and the like.

Among the α, β-unsaturated dicarboxylic esters represented by the general formula (I-2), R ₂ and R ₅ have an aryl group and R ₁ and R ₄ have a methyl group. Representative examples of the fumaric acid ester include di (1-phenoxycarbonylethyl) fumarate, di [1- (1-naphthoxycarbonyl) ethyl] fumarate, and di [1- (2-naphthoxycarbonyl) ethyl] fumarate. And the like.

Among the α, β-unsaturated dicarboxylic esters represented by the general formula (I-2), R ₂ and R ₅ have a substituted aryl group, and R ₁ and R _{4 have} a methyl group. Representative examples of the fumaric acid ester include di [1- (3-methylphenoxycarbonyl) ethyl] fumarate, di [1- (4-methylphenoxycarbonyl) ethyl] fumarate, and di [1- (4-nitro) fumarate. Phenoxycarbonyl) ethyl] fumarate, and the like.

Among the α, β-unsaturated dicarboxylic esters represented by the formula (I-2), fumar having various alkyl groups having 2 to 12 carbon atoms or phenyl groups as R ₁ and R _4. Representative examples of the acid ester include, in the various compounds listed above as examples of fumaric acid esters containing a methyl group as R ₁ and R ₄ , the methyl group is replaced with various alkyl groups having 2 to 12 carbon atoms. Alternatively, various compounds having a structure substituted with a phenyl group can be exemplified.

[0112] Furthermore, alpha formula containing monovalent organic group as mentioned above as R ₂ and R ₅ Various (I-2), among β- unsaturated dicarboxylic acid ester, R ₂
And maleic esters having an alkyl group as R ₅ and a hydrogen atom as R ₁ and R ₄ include di (methoxycarbonylmethyl) malate, di (ethoxycarbonylmethyl) malate, and di (methoxycarbonylmethyl) malate. (N-propoxycarbonylmethyl) malate, di (i
so-propoxycarbonylmethyl) malate, di (n
-Butoxycarbonylmethyl) malate, di (iso-
Butoxycarbonylmethyl) malate, di (n-hexyloxycarbonylmethyl) malate, di (2-ethylhexyloxycarbonylmethyl) malate, di (n-
Decyloxycarbonylmethyl) malate.

Among the α, β-unsaturated dicarboxylic esters represented by the general formula (I-2), R ₂ and R ₅ have an alkoxy-substituted alkyl group, and R ₁ and R ₄ are hydrogen. Representative maleic acid esters having an atom include di (2-methoxyethoxycarbonylmethyl) malate, di (2-ethoxyethoxycarbonylmethyl) malate, di (2-n-propoxyethoxycarbonylmethyl) malate, (2-n-butoxyethoxycarbonylmethyl) malate, di (3-methoxypropoxycarbonylmethyl) malate, and the like.

In the α, β-unsaturated dicarboxylic acid ester represented by the general formula (I-2), R ₂ and R ₅ each have an alkyl group substituted by an aryloxy group, and
Representative maleic esters having a hydrogen atom as R ₁ and R ₄ include di (2-phenoxyethoxycarbonylmethyl) malate, di [2- (4-methylphenoxy) ethoxycarbonylmethyl] malate,
And the like.

The α, β-unsaturated compound represented by the general formula (I-2)
Among the dicarboxylic acid esters, R_TwoAnd R_FiveAs
Having an alkyl group substituted by an aralkyloxy group, and
One, R ₁And R_FourMaleic acid having a hydrogen atom as
Representative steles include di (2-benzyloxy).
Siethoxycarbonylmethyl) malate, di [2- (2
-Phenylethoxy) ethoxycarbonylmethyl] male
And the like.

Among the α, β-unsaturated dicarboxylic acid esters represented by the formula (I-2), R ₂ and R ₅ have an alkyl group substituted with an aryl group, and R ₁ and R ₄ Representative examples of a maleic ester having a hydrogen atom include di (benzyloxycarbonylmethyl) malate, di (1-phenylethoxycarbonylmethyl) malate, di (2-phenylethoxycarbonylmethyl) malate, and the like. Can be

Among the α, β-unsaturated dicarboxylic acid esters represented by the formula (I-2), R ₂ and R ₅ have cycloalkyl groups, and R ₁ and R _{4 have} hydrogen atoms. Representative maleic acid esters include di (cyclopentyloxycarbonylmethyl) malate, di (cyclohexyloxycarbonylmethyl)
Maleate, di (4-methylcyclohexyloxycarbonylmethyl) malate, and the like.

Among the α, β-unsaturated dicarboxylic acid esters represented by the general formula (I-2), R ₂ and R ₅ have an aryl group and R ₁ and R ₄ have a hydrogen atom. Typical maleate esters include:
Di (phenoxycarbonylmethyl) malate, di (1-
Naphthoxycarbonylmethyl) malate, di (2-naphthoxycarbonylmethyl) malate, and the like.

Among the α, β-unsaturated dicarboxylic acid esters represented by the general formula (I-2), R ₂ and R ₅ have a substituted aryl group, and R ₁ and R ₄ are hydrogen atoms. Representative maleic acid esters include di (3-methylphenoxycarbonylmethyl) malate, di (4-methylphenoxycarbonylmethyl) malate, and di (4-nitrophenoxycarbonylmethyl) maleate.
Malate, and the like.

Among the α, β-unsaturated dicarboxylic esters represented by the general formula (I-2), R ₂ and R ₅ have an alkyl group and R ₁ and R ₄ have a methyl group. Typical maleate esters include:
Di (1-methoxycarbonylethyl) malate, di (1
-Ethoxycarbonylethyl) malate, di (1-n-
Propoxycarbonylethyl) malate, di (1-is
o-propoxycarbonylethyl) malate, di (1-
n-butoxycarbonylethyl) malate, di (1-i
so-butoxycarbonylethyl) malate, di (1-
n-hexyloxycarbonylethyl) malate, di [1- (2-ethylhexyloxycarbonyl) ethyl] malate, di (1-n-decyloxycarbonylethyl) malate, and the like.

Among the α, β-unsaturated dicarboxylic esters represented by the general formula (I-2), R ₂ and R ₅ have an alkoxy-substituted alkyl group, and R ₁ and R ₄ are methyl. Representative examples of the maleic ester having a group include di [1- (2-methoxyethoxycarbonyl) ethyl] malate, di [1- (2-ethoxyethoxycarbonyl) ethyl] malate, di [1- (2
-N-propoxyethoxycarbonyl) ethyl] malate, di [1- (2-n-butoxyethoxycarbonyl)
Ethyl] malate, di [1- (3-methoxypropoxycarbonyl) ethyl] malate, and the like.

In the α, β-unsaturated dicarboxylic acid ester represented by the general formula (I-2), R ₂ and R ₅ have an alkyl group substituted with an aryloxy group, and
Representative examples of maleic esters having a methyl group as R ₁ and R ₄ include di [1- (2-phenoxyethoxycarbonyl) ethyl] malate and di {1-
[2- (4-methylphenoxy) ethoxycarbonyl]
Ethyl dimalate, and the like.

The α, β-unsaturated compound represented by the general formula (I-2)
Among the dicarboxylic acid esters, R_TwoAnd R_FiveAs
Having an alkyl group substituted by an aralkyloxy group, and
One, R ₁And R_FourMaleic acid having a methyl group as
A typical example of the stell is di [1- (2-benzyl)
Ruoxyethoxycarbonyl) ethyl] malate, di
{1- [2- (2-phenylethoxy) ethoxycarbo
Nyl] ethyl dimalate.

In the α, β-unsaturated dicarboxylic acid ester represented by the general formula (I-2), R ₂ and R ₅ have an alkyl group substituted with an aryl group, and R ₁ and R ₄ Representative examples of a maleic ester having a methyl group include di (1-benzyloxycarbonylethyl) malate, di [1- (1-phenylethoxycarbonyl) ethyl] malate, and di [1- (2-phenyl) maleate. Ethoxycarbonyl) ethyl] malate.

Among the α, β-unsaturated dicarboxylic esters represented by the formula (I-2), R ₂ and R ₅ have a cycloalkyl group and R ₁ and R _{4 have} a methyl group. Representative maleic acid esters include di (1-cyclopentyloxycarbonylethyl) malate, di (1-cyclohexyloxycarbonylethyl) malate, di [1- (4-methylcyclohexyloxycarbonyl) ethyl] malate, And the like.

Among the α, β-unsaturated dicarboxylic esters represented by the general formula (I-2), R ₂ and R ₅ have an aryl group, and R ₁ and R ₄ have a methyl group. Typical maleate esters include:
Di (1-phenoxycarbonylethyl) malate, di [1- (1-naphthoxycarbonyl) ethyl] malate, di [1- (2-naphthoxycarbonyl) ethyl] malate, and the like.

Among the α, β-unsaturated dicarboxylic acid esters represented by the formula (I-2), R ₂ and R ₅ have a substituted aryl group, and R ₁ and R ₄ are methyl groups. Representative maleic acid esters include di [1- (3-methylphenoxycarbonyl) ethyl] malate, di [1- (4-methylphenoxycarbonyl) ethyl] malate and di [1- (4-nitro). Phenoxycarbonyl) ethyl] malate.

Among the α, β-unsaturated dicarboxylic esters represented by the general formula (I-2), maleic compounds having various alkyl groups having 2 to 12 carbon atoms or phenyl groups as R ₁ and R _4. As typical examples of the acid ester, in the various compounds listed above as examples of maleic acid esters containing a methyl group as R ₁ and R ₄ , the methyl group is replaced with various alkyl groups having 2 to 12 carbon atoms. Alternatively, various compounds having a structure substituted with a phenyl group can be exemplified.

Further, α, β represented by the general formula (I-2)
- unsaturated dicarboxylic acid ester, R ₁ and R ₄ are identical, and has been exemplified compound R ₂ and R ₅ are the same only, R ₁ and R ₄ are the same and R ₂ and R Compounds in which ₅ is different, compounds in which R ₁ and R ₄ are different and R ₂ and R ₅ are the same, or compounds in which R ₁ and R ₄ are different and R ₂ and R ₅ are different Included in α, β-unsaturated dicarboxylic esters.

The α, represented by the general formula (I-2) described above,
Among the β-unsaturated dicarboxylic acid esters, preferred are R ₂ and R ₅ , each of which is independently an alkoxy substituent having 3 to 6 carbon atoms including an alkyl group having 1 to 6 carbon atoms or an alkoxy group. It is a compound having an alkyl group. Particularly preferred compounds among the preferred compounds are R ₁ and R _{4 in the} general formula (I-2).
Is a compound having a hydrogen atom.

The present invention also relates to a salt of fumaric acid, a salt of fumaric acid half ester, a salt of maleic acid and a salt of α, selected from the group consisting of maleic acid half ester salt.
The present invention also provides a method for producing an α, β-unsaturated dicarboxylic acid ester, which comprises reacting a β-unsaturated carboxylic acid salt with an α-halocarboxylic acid ester. As the α, β-unsaturated dicarboxylic acid ester to be used, the above-mentioned general formula (I-
It includes various compounds represented by 1) and (I-2).

Representative examples of fumaric acid or maleic acid salts used in the production method of the present invention include:
Alkali metal salts such as lithium salt, sodium salt, potassium salt and cesium salt; alkaline earth metal salts such as magnesium salt, calcium salt and barium salt; various salts such as triethylamine, tributylamine and N, N-dimethylbenzylamine And salts of organic bases such as secondary amines with fumaric acid or maleic acid. Of these, alkali metal salts are particularly preferred.

The fumaric acid half-ester salt or maleic acid half-ester salt includes fumaric acid or maleic acid half-esters represented by the following formulas (II-1) and (II-2). , Half esters).) And the like.

[0134]

Embedded image

(Wherein R ₃ and R ₅ are each independently 1
R ₄ represents a hydrogen atom, a phenyl group or an alkyl group having 1 to 12 carbon atoms. )

The above general formulas (II-1) and (II-
Representative examples of the monovalent organic groups R ₃ and R ₅ contained in the half ester represented by 2) include the monovalent organic groups R ₃ and R ₅ contained in the aforementioned general formulas (I-1) and (I-2). Various examples of the organic groups represented by R ₃ and R ₅ are given as examples, and R ₄ has 1 to 12 carbon atoms.
As a typical example of the alkyl group represented by the general formula (I-
Those exemplified as typical examples of R ₄ contained in the compound represented by 2) can be mentioned.

Among the half esters represented by the general formula (II-1), typical examples of the fumaric acid half ester containing an alkyl group as R ₃ include monomethyl fumarate, monoethyl fumarate and 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 can be mentioned.

Among the half esters represented by the general formula (II-1), typical examples of the fumaric acid half ester having an alkoxy-substituted alkyl group as R ₃ include mono (2-methoxyethyl) fumarate, Things (2
-Ethoxyethyl) fumarate, mono (2-n-propoxyethyl) fumarate, mono (2-n-butoxyethyl) fumarate, mono (3-methoxypropyl) fumarate, and the like.

Among the half esters represented by the general formula (II-1), a typical example of fumaric acid half ester having an alkyl group substituted with an aryloxy group as R ₃ is mono (2-phenoxyethyl). ) Fumarate, mono [2- (4-methylphenoxy) ethyl] fumarate, and the like.

Among the half esters represented by the general formula (II-1), a typical example of fumaric acid half ester having an alkyl group substituted by an aralkyloxy group as R ₃ is mono (2-benzyloxy). Ethyl) fumarate, mono [2- (2-phenylethoxy) ethyl]
Fumarate and the like.

Among the half esters represented by the general formula (II-1), typical examples of fumaric acid half ester having an alkyl group substituted with an aryl group as R ₃ include monobenzyl fumarate and mono ( 1-phenylethyl) fumarate, mono (2-phenylethyl) fumarate, and the like.

Among the half esters represented by the general formula (II-1), typical examples of fumaric acid half ester having a cycloalkyl group as R ₃ include monocyclopentyl fumarate, monocyclohexyl fumarate, and monocyclopentyl fumarate. (4-methylcyclohexyl) fumarate, and the like.

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

Among the half esters represented by the general formula (II-1), a typical example of the fumaric acid half ester having a substituted aryl group as R ₃ is mono (3-
Methylphenyl) fumarate, mono (4-methylphenyl) fumarate, mono (4-nitrophenyl) fumarate, and the like.

Among the half esters represented by the general formula (II-1), typical examples of maleic acid half ester containing an alkyl group as R ₃ include monomethyl malate, monoethyl malate, 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.

Among the half esters represented by the general formula (II-1), typical examples of the maleic acid half ester having an alkoxy-substituted alkyl group as R ₃ include mono (2-methoxyethyl) malate, Things (2-
Ethoxyethyl) malate, mono (2-n-propoxyethyl) malate, mono (2-n-butoxyethyl) malate, mono (3-methoxypropyl) malate, and the like.

Among the half esters represented by the general formula (II-1), a typical maleic acid half ester having an alkyl group substituted with an aryloxy group as R ₃ is mono (2-phenoxyethyl). ) Malate, mono [2- (4-methylphenoxy) ethyl] malate, and the like.

Among the half esters represented by the general formula (II-1), a typical maleic half ester having an alkyl group substituted with an aralkyloxy group as R ₃ is mono (2-benzyloxy). Ethyl) malate, mono [2- (2-phenylethoxy) ethyl]
Malate, and the like.

Among the half esters represented by the general formula (II-1), typical examples of the maleic acid half ester having an alkyl group substituted with an aryl group as R ₃ include monobenzyl maleate and mono ( 1-phenylethyl) malate, mono (2-phenylethyl) malate, and the like.

Among the half esters represented by the general formula (II-1), typical examples of maleic acid half ester having a cycloalkyl group as R ₃ include monocyclopentyl malate, monocyclohexyl malate,
Mono (4-methylcyclohexyl) malate, and the like.

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

Among the half esters represented by the general formula (II-1), a typical maleic acid half ester having a substituted aryl group as R ₃ is mono (3).
-Methylphenyl) malate, mono (4-methylphenyl) malate, mono (4-nitrophenyl) malate,
And the like.

[0153] Among the formula (II-1) various half ester represented by, especially preferred are carbon atoms as R ₃ is 3 carbon atoms containing an alkyl group or an alkoxy group having from 1 to 6 It is a compound having 6 alkoxy-substituted alkyl groups.

In the half ester represented by the general formula (II-2), an alkyl group is contained as R ₅ ,
Representative examples of fumaric acid half ester having a hydrogen atom as ₄ include mono (methoxycarbonylmethyl) fumarate, mono (ethoxycarbonylmethyl) fumarate, mono (n-propoxycarbonylmethyl) fumarate, mono (iso-propoxycarbonyl) Methyl) 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 half esters represented by the general formula (II-2), typical examples of the fumaric acid half ester having an alkoxy-substituted alkyl group as R ₅ and a hydrogen atom as R ₄ are given below. Is mono (2-methoxyethoxycarbonylmethyl) fumarate, mono (2-
Ethoxyethoxycarbonylmethyl) fumarate, mono (2-n-propoxyethoxycarbonylmethyl) fumarate, mono (2-n-butoxyethoxycarbonylmethyl) fumarate, mono (3-methoxypropoxycarbonylmethyl) fumarate, and the like.

Among the half esters represented by the general formula (II-2), representative of fumaric acid half ester having an alkyl group substituted by an aryloxy group as R ₅ and a hydrogen atom as R ₄ Specific examples include mono (2-phenoxyethoxycarbonylmethyl) fumarate, mono [2- (4-methylphenoxy) ethoxycarbonylmethyl] fumarate, and the like.

Among the half esters represented by the general formula (II-2), representative of fumaric acid half ester having an alkyl group substituted with an aralkyloxy group as R ₅ and a hydrogen atom as R ₄ Specific examples include mono (2-benzyloxyethoxycarbonylmethyl) fumarate, mono [2- (2-phenylethoxy) ethoxycarbonylmethyl] fumarate, and the like.

Among the half esters represented by the general formula (II-2), representative of fumaric acid half ester having an alkyl group substituted with an aryl group as R ₅ and a hydrogen atom as R ₄ Examples thereof include mono (benzyloxycarbonylmethyl) fumarate, mono (1-phenylethoxycarbonylmethyl) fumarate, mono (2-phenylethoxycarbonylmethyl) fumarate, and the like.

Among the half esters represented by the general formula (II-2), typical examples of the fumaric acid half ester having a cycloalkyl group as R ₅ and a hydrogen atom as R ₄ include: Mono (cyclopentyloxycarbonylmethyl) fumarate, mono (cyclohexyloxycarbonylmethyl) fumarate, mono (4-methylcyclohexyloxycarbonylmethyl) fumarate, and the like.

In the half ester represented by formula (II-2), R ₅ has an aryl group and R ₄
Typical examples of the fumaric acid half ester having a hydrogen atom include mono (phenoxycarbonylmethyl) fumarate, mono (1-naphthoxycarbonylmethyl) fumarate, mono (2-naphthoxycarbonylmethyl) fumarate, and the like. Can be

In the half ester represented by formula (II-2), R ₅ has a substituted aryl group, and
Representative examples of fumaric acid half esters having a hydrogen atom as R ₄ include mono (3-methylphenoxycarbonylmethyl) fumarate, mono (4-methylphenoxycarbonylmethyl) fumarate and mono (4-nitrophenoxycarbonylmethyl) Fumarate and the like.

In the half ester represented by the general formula (II-2), an alkyl group is contained as R ₅ ,
Representative examples of maleic acid half ester having a hydrogen atom as ₄ include mono (methoxycarbonylmethyl) malate, mono (ethoxycarbonylmethyl) malate, mono (n-propoxycarbonylmethyl) malate, and mono (iso-propoxycarbonyl). Methyl) malate, mono (n-butoxycarbonylmethyl) malate, mono (iso-butoxycarbonylmethyl) malate, mono (n-hexyloxycarbonylmethyl) malate, mono (2-ethylhexyloxycarbonylmethyl) malate, mono (n- Decyloxycarbonylmethyl) malate.

Among the half esters represented by the general formula (II-2), maleic acid half esters having an alkoxy-substituted alkyl group as R ₅ and a hydrogen atom as R ₄ are typical. Is mono (2-methoxyethoxycarbonylmethyl) malate, mono (2-
Ethoxyethoxycarbonylmethyl) malate, mono (2-n-propoxyethoxycarbonylmethyl) malate, mono (2-n-butoxyethoxycarbonylmethyl) malate, mono (3-methoxypropoxycarbonylmethyl) malate, and the like.

Among the half esters represented by the general formula (II-2), representative of maleic acid half ester having an alkyl group substituted with an aryloxy group as R ₅ and a hydrogen atom as R ₄ Specific examples include mono (2-phenoxyethoxycarbonylmethyl) malate, mono [2- (4-methylphenoxy) ethoxycarbonylmethyl] malate, and the like.

Among the half esters represented by the general formula (II-2), representative of maleic acid half ester having an alkyl group substituted by an aralkyloxy group as R ₅ and a hydrogen atom as R ₄ Specific examples include mono (2-benzyloxyethoxycarbonylmethyl) malate and mono [2- (2-phenylethoxy) ethoxycarbonylmethyl] malate.

Among the half esters represented by the general formula (II-2), representative of maleic acid half ester having an alkyl group substituted with an aryl group as R ₅ and a hydrogen atom as R ₄ Examples include mono (benzyloxycarbonylmethyl) malate, mono (1-phenylethoxycarbonylmethyl) malate, mono (2
-Phenylethoxycarbonylmethyl) malate.

Among the half esters represented by the general formula (II-2), typical maleic acid half esters having a cycloalkyl group as R ₅ and a hydrogen atom as R ₄ include: Mono (cyclopentyloxycarbonylmethyl) malate, mono (cyclohexyloxycarbonylmethyl) malate, mono (4-methylcyclohexyloxycarbonylmethyl) malate,
And the like.

In the half ester represented by the formula (II-2), R ₅ has an aryl group and R ₄
Representative examples of maleic acid half ester having a hydrogen atom include mono (phenoxycarbonylmethyl) malate, mono (1-naphthoxycarbonylmethyl) malate, mono (2-naphthoxycarbonylmethyl) malate, and the like. Can be

In the half ester represented by formula (II-2), R ₅ has a substituted aryl group, and
Representative maleic acid half esters having a hydrogen atom as R ₄ include mono (3-methylphenoxycarbonylmethyl) malate, mono (4-methylphenoxycarbonylmethyl) malate, and mono (4-nitrophenoxycarbonylmethyl) Malate, and the like.

Among the half esters represented by the general formula (II-2), typical maleic acid half esters having a phenyl group or an alkyl group having 1 to 12 carbon atoms as R ₄ include: in various of the compounds listed above as having a hydrogen atom as R _4,
The hydrogen atom is a phenyl group or a carbon atom having 1 to 12 carbon atoms.
And a compound having a structure replaced with an alkyl group.

Of the half esters represented by the general formula (II-2), particularly preferred are those having 3 to 6 carbon atoms including an alkyl or alkoxy group having 1 to 6 carbon atoms as R _5. And a compound having a hydrogen atom or a methyl group as R ₄ .

Representative examples of the above half ester salts include lithium salts, sodium salts, potassium salts,
Alkali metal salts such as cesium salts; alkaline earth metal salts such as magnesium salts, calcium salts, barium salts and the like; triethylamine, tributylamine, N, N-
And salts with organic bases such as various tertiary amines such as dimethylbenzylamine. Of these, alkali metal salts are particularly preferred.

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

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

The α-halocarboxylic acid ester used in the method of the present invention includes various known carboxylic acids having various halogen atoms such as fluorine, chlorine, bromine and iodine at the α-position. Esters can be used. Representative examples of such α-halocarboxylic acid esters include compounds represented by the following general formula (III).

[0177]

Embedded image

(In the formula, R ₁ represents a hydrogen atom, a phenyl group or an alkyl group having 1 to 12 carbon atoms, R ₂ represents a monovalent organic group, and X represents a halogen atom.)

[0179] Such, as being representative of R ₁ are the α- halocarboxylic acid ester having represented by formula (III), illustrated as typical in R ₁ in the above-mentioned formula (I-2) And various types of R.
Representative examples of ₂ include the above-mentioned general formula (I-2)
Various examples are exemplified as representative examples of R ₂ in the above.

Representative α-chlorocarboxylic esters among the α-halocarboxylic esters having R ₁ and R ₂ as described above include α-chlorophenylacetic esters, chloroacetic esters, and R ₁ Α-chlorocarboxylic acid esters having an alkyl group having 1 to 12 carbon atoms, 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; α-chlorophenylacetic acid 2-methoxyethyl, α-chlorophenylacetic acid 2-ethoxyethyl,
α-chlorophenylacetic acid 2-n-propoxyethyl, α
Alkoxy-substituted alkyl esters such as 2-n-butoxyethyl-chlorophenylacetate and 4-ethoxybutyl α-chlorophenylacetate; benzyl α-chlorophenylacetate, 2-phenylethyl α-chlorophenylacetate, α
-Alkyl esters substituted with an aryl group such as 1-phenylethyl chlorophenylacetate; cycloalkyl esters such as cyclopentyl α-chlorophenylacetate and cyclohexyl α-chlorophenylacetate; phenyl α-chlorophenylacetate and α-chlorophenylacetic acid 1- Aryl esters such as naphthyl and the like; α-chlorophenylacetic acid 4-methylphenyl, α-chlorophenylacetic acid 4-
And substituted aryl esters such as chlorophenyl and α-chlorophenylacetic acid 4-nitrophenyl.

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-
Ethoxyethyl, 2-n-propoxyethyl chloroacetate, 2-n-butoxyethyl chloroacetate, chloroacetic acid 4
Alkoxy-substituted alkyl esters such as -ethoxybutyl, etc .; alkyl esters substituted with aryl groups such as benzyl chloroacetate, 2-phenylethyl chloroacetate, 1-phenylethyl chloroacetate; cyclopentyl chloroacetate, cyclohexyl chloroacetate, etc. Aryl esters such as phenyl chloroacetate and 1-naphthyl chloroacetate; substituted aryl esters such as 4-methylphenyl chloroacetate, 4-chlorophenyl chloroacetate and 4-nitrophenyl chloroacetate; Is mentioned.

Among the α-chlorocarboxylic acid esters having an alkyl group having 1 to 12 carbon atoms as R ₁ , specific examples of the α-chloropropionates having a methyl group as R ₁ include: , Methyl α-chloropropionate, ethyl α-chloropropionate, α-
N-propyl chloropropionate, n-butyl α-chloropropionate, n-hexyl α-chloropropionate, n-octyl α-chloropropionate, n-decyl α-chloropropionate, n-chloroα-chloropropionate
Alkyl esters such as dodecyl; 2-methoxyethyl α-chloropropionate, α-chloropropionic acid 2
Alkoxy-substituted alkyl esters such as -ethoxyethyl, 2-n-propoxyethyl α-chloropropionate, 2-n-butoxyethyl α-chloropropionate, 4-ethoxybutyl α-chloropropionate; α-chloropropion Acid benzyl, α-chloropropionic acid 2-
Alkyl esters substituted with an aryl group such as phenylethyl and 1-phenylethyl α-chloropropionate; cycloalkyl esters such as cyclopentyl α-chloropropionate and cyclohexyl α-chloropropionate; α-chloropropionic acid Aryl esters such as phenyl 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 α-chlorocarboxylic acid esters having an alkyl group having 2 to 12 carbon atoms as R ₁ include the above-mentioned specific examples of α-chloropropionate esters. Among the various esters as described above, various compounds having a structure in which methyl as the substituent R ₁ is replaced by an alkyl group having 2 to 12 carbon atoms are exemplified.

Among the α-halocarboxylic acid esters containing R ₁ and R ₂ as described above, typical examples of α-fluorocarboxylic acid esters, α-bromolocarboxylic acid esters, and α-iodocarboxylic acid esters include: Examples of the various compounds listed above as specific examples of α-chlorocarboxylic acid esters include various compounds having a structure in which a chlorine atom is replaced with a fluorine atom, a bromine atom or an iodine atom, respectively.

Among the various compounds represented by the general formula (III), the monovalent organic group R ₂ has 1 carbon atom.
It is an alkoxy-substituted alkyl group having 3 to 6 carbon atoms including an alkyl group or an alkoxy group of 6 to 6, and a compound having a chlorine atom or a bromine atom as a halogen atom is preferable. Further, according Among preferred compounds, alpha-halopropionic acid esters having a methyl group as alpha-haloacetate compound or R ₁ to hydrogen atoms useful as R ₁ is particularly preferred.

The α, β-unsaturated carboxylate described above is
In order to prepare an α, β-unsaturated carboxylic acid ester by reacting with an α-halocarboxylic acid ester, (a) the salts described above and the α-halocarboxylic acid ester are collectively charged and reacted, and (b) as described above. A salt and an α-halocarboxylic acid ester are simultaneously added to the reaction system; (c) an α-halocarboxylic acid ester is divided and added with the above-mentioned salts to react; (d) fumaric acid, maleic acid or half ester and α-halocarboxylic acid Various reaction methods such as dividing the above-mentioned various basic compounds into a mixture of acid esters or adding them successively to react while forming the corresponding carboxylic acid salt, etc., are applied. I can do it.

In the reaction, depending on the kind of the α, β-unsaturated carboxylate and the kind of the α-halocarboxylic acid ester, the reaction can be carried out without using a solvent.
Generally, it is preferable to carry out the reaction using a solvent.

Representative 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. Of these, N, N-dimethylformamide and N, N-dimethylacetamide are particularly preferred in view of the solubility of the α, β-unsaturated carboxylate.

In reacting the above-mentioned various α, β-unsaturated carboxylic acid salts with α-halocarboxylic acid esters, 1 mol of the carboxylic acid base contained in the former is used.
Both may be reacted in such a ratio that the latter α-halocarboxylic acid ester is in the range of about 0.5 to 4.0 mol, preferably about 0.8 to 2.0 mol.

The reaction conditions need to be appropriately set according to the type of the α, β-unsaturated carboxylate and the type of the α-halocarboxylic acid ester.
The reaction time may be approximately 0.5 to 150 hours.

[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 equipment and measurement conditions used for the analysis of the compounds are as follows.

IR spectrum: Measuring apparatus: Preparation of JASCO FT / IR-610 sample manufactured by JASCO Corporation: For solid compounds, the KBr tablet method is used. For liquid compounds, liquid films are formed using a KBr cell. Was measured.

¹ H-NMR spectrum measuring apparatus: JEOL JNM-EX270 (2
70 MHz) Solvent: deuterated chloroform Internal standard: tetramethylsilane Explanation of peak shape abbreviation described in Examples s: singlet d: doublet t: triplet q: quartet m: multiplet

[0196] · ¹³ C-NMR spectrum measurement device ...... JEOL JEOL Co., Ltd. JNM-EX270 (6
7.5MHz) Solvent: Deuterated chloroform Internal standard: Tetramethylsilane

Example 1 In a glass flask equipped with a thermometer, a reflux condenser, and a stirrer, 29.0 g (0.25 mol) of fumaric acid, 60.0 g (0.55 mol) of methyl chloroacetate, N, 250 g of N-dimethylformamide (DMF) was charged, 38.7 g (0.28 mol) of potassium carbonate was added, the temperature was raised to 90 ° C. while stirring, and the mixture was stirred at the same temperature for 16 hours.
After cooling the reaction mixture to room temperature, the generated potassium chloride was filtered off, and the filtrate was heated to 70 ° C. for 0.1 to 3 k.
Volatile components such as DMF and unreacted methyl chloroacetate were distilled off under reduced pressure of Pa. The solution obtained by dissolving the residue in 300 g of ethyl acetate was washed twice with 100 g of a 2% aqueous solution of potassium carbonate. 20 g of anhydrous magnesium sulfate was added to the ethyl acetate solution and dried. After magnesium sulfate was filtered off, ethyl acetate was distilled off under reduced pressure, and the obtained crude product was recrystallized from methanol to obtain the following formula ( The di (methoxycarbonylmethyl) represented by IV)
Colorless crystals of fumarate (melting point: 84.5-85.5 ° C) 3
0.0 g was obtained. The yield of the target compound obtained by purification was 46.2% based on the raw material fumaric acid.

[0198]

Embedded image

The IR spectrum of the compound obtained is shown in FIG.
FIG. 2 shows the ¹ H-NMR spectrum. IR spectrum, ¹ H-NMR spectrum, ¹³
The C-NMR spectrum, respective data and the results of elemental analysis were as follows. · ¹ H-NMR spectrum (δppm) 3.78 (6H, s ), 4.74 (4H, s), 7.01 (2H, s) · 13 C-NMR spectrum (δppm) 52.4,61.3,133.6,164.0,167.6 · IR spectrum (Cm ^-1 ) 3070 (CH), 3000 (CH), 2958 (CH), 1751 (C = O), 1731 (C
= O), 1670 (C = C)-Elemental analysis results (numerical values in parentheses indicate calculated values) C: 46.27% (46.16%) H: 4.43 (4.65%)

Example 2 A reaction vessel similar to that of Example 1 was charged with 58.0 g of fumaric acid.
(0.50 mol), 134.8 g of ethyl chloroacetate
(1.10 mol), 500 g of DMF were charged, 76.0 g (0.55 mol) of potassium carbonate was added, the temperature was raised to 70 ° C. with stirring, and the mixture was stirred at the same temperature for 47 hours.
After cooling the reaction mixture to room temperature, the generated potassium chloride was filtered off, and the filtrate was heated to 70 ° C. for 0.1 to 3 k.
Volatile components such as DMF and unreacted ethyl chloroacetate were distilled off under reduced pressure of Pa. The solution obtained by dissolving the residual liquid in 300 g of chloroform was added to 2% of potassium carbonate, respectively.
Washing was performed twice with 200 g of the aqueous solution. After adding 20 g of anhydrous magnesium sulfate to the chloroform solution and drying, the magnesium sulfate is separated by filtration, chloroform is distilled off under reduced pressure, and the crude product is recrystallized from methanol to obtain a diamine represented by the following formula (V). 81.0 g of colorless crystals of (ethoxycarbonylmethyl) fumarate (melting point: 82.0 to 83.0 ° C.)
I got The yield of the target compound obtained by purification was 56.2% based on the raw material fumaric acid.

[0201]

Embedded image

The IR spectrum of the obtained compound, ¹ H-
The NMR spectrum, ¹³ C-NMR spectrum, respective data and the results of elemental analysis were as follows. ¹ H-NMR spectrum (δ ppm) 1.29 (6H, t, J = 7.8 Hz), 4.24 (4H, q, J = 7.8 Hz), 4.74 (4
H, s), 7.01 (2H, s) ¹³ C-NMR spectrum (δ ppm) 14.1, 61.4, 61.7, 133.6, 164.0, 167.1 IR spectrum (cm ⁻¹ ) 3078 (CH), 2996 (CH), 2960 (CH), 1746 (C = O), 1728 (C
= O), 1660 (C = C)-Elemental analysis results (numerical values in parentheses indicate calculated values) C: 49.88% (50.00%) H: 5.73 (5.59%)

Example 3 In a reactor similar to that of Example 1, 29.0 g of fumaric acid (0.
25 mol), n-butyl chloroacetate 82.8 g (0.5
5 mol), 250 g of DMF and potassium carbonate 3
8.6 g (0.28 mol) was charged, and stirred while stirring.
The temperature was raised to 0 ° C., and the mixture was stirred at the same temperature for 110 hours. After cooling the reaction mixture to room temperature, the generated potassium chloride was filtered off, and the filtrate was heated to 70 ° C. while heating to 0.1 to 3 kPa.
Volatile components such as DMF and unreacted n-butyl chloroacetate were distilled off under reduced pressure. The solution obtained by dissolving the residual liquid in 300 g of chloroform was added to 2% of potassium carbonate, respectively.
Washing was performed twice with 100 g of the aqueous solution. After adding 20 g of anhydrous magnesium sulfate to the chloroform solution and drying, magnesium sulfate is filtered off, chloroform is distilled off under reduced pressure, the obtained crude product is dissolved in methanol, and crystals are precipitated under ice cooling. Di (n-butoxycarbonylmethyl) fumarate 40.0 represented by the following formula (VI)
g was obtained. The target product obtained by purification was liquid at 25 ° C. The yield of the target compound obtained by purification was 46.5% based on the raw material fumaric acid.

[0204]

Embedded image

The IR spectrum of the obtained compound, ¹ H-
The NMR spectrum, ¹³ C-NMR spectrum, respective data and the results of elemental analysis were as follows. ¹ H-NMR spectrum (δ ppm) 0.94 (6H, t, J = 7.3 Hz), 1.38 (4H, m), 1.64 (4H, m), 4.
19 (4H, t, 7.3 Hz), 4.74 (4H, s), 7.02 (2H, s) ¹³ C-NMR spectrum (δ ppm) 13.6, 19.1, 30.6, 61.5, 65.6, 133.6, 164.2, 167.4 IR spectrum (Cm ^-1 ) 3080 (CH), 2961 (CH), 2875 (CH), 1760 (C = O), 1731 (C
= O), 1647 (C = C) Elemental analysis results (numerical values in parentheses indicate calculated values) C: 55.61% (55.81%) H: 6.96 (7.02%)

Example 4 In the same reaction vessel as in Example 1, monomethyl fumarate 4 was added.
4.2 g (0.34 mol), methyl chloroacetate 41.2
g (0.38 mol) and 100 g of DMF were charged, and 24.9 g (0.18 mol) of potassium carbonate was added, the temperature was raised to 90 ° C. with stirring, and the mixture was stirred at the same temperature for 10 hours. After cooling the reaction mixture to room temperature, the generated potassium chloride was filtered off, and the filtrate was heated to 70 ° C. for 0.1 to 0.1 ° C.
Volatile components such as DMF and methyl chloroacetate were distilled off under reduced pressure of 3 kPa. The solution obtained by dissolving the residual liquid in 200 g of chloroform was washed twice with 100 g of a 2% aqueous solution of potassium carbonate. After adding 20 g of anhydrous magnesium sulfate to the toluene solution and drying, the magnesium sulfate was separated by filtration and chloroform was distilled off under reduced pressure to obtain a yellow liquid crude product. This crude product is
Perform molecular distillation using a thin film distillation apparatus manufactured by eybold,
36.5 g of a colorless liquid mono (methoxycarbonylmethyl) -monomethyl fumarate represented by the following formula (VII) was obtained. The yield of the target compound was 53.1% based on the raw material monomethyl fumarate.

[0207]

Embedded image

The IR spectrum of the obtained compound, ¹ H-
The NMR spectrum, ¹³ C-NMR spectrum, respective data and the results of elemental analysis were as follows. • ¹ H-NMR spectrum (δppm) 3.77 (3H, s), 3.82 (3H, s), 4.70 (2H, s), 7.01 (2H, s) • ¹³ C-NMR spectrum (δppm) 52.2, 52.3, 61.4 , 129.8, 133.5, 164.2, 165.2, 167.
4 IR spectrum (cm ^-1 ) 3074 (CH), 2959 (CH), 2875 (CH), 1748 (C = O), 1731 (C
= O), 1642 (C = C)-Elemental analysis results (numerical values in parentheses indicate calculated values) C: 47.33% (47.53%) H: 5.04 (4.99%)

Example 5 In the same reaction vessel as in Example 1, 58.5 g (0.34 mol) of mono (n-butyl) fumarate and methyl chloroacetate 4 were added.
1.2 g (0.38 mol) and 100 g of DMF were charged,
24.9 g (0.18 mol) of potassium carbonate was added,
The temperature was raised to 90 ° C. with stirring, and the mixture was stirred at the same temperature for 10 hours. After the reaction mixture was cooled to room temperature, the formed potassium chloride was filtered off, and the filtrate was heated to 70 ° C. under 0.1 ml.
Volatile components such as DMF and methyl chloroacetate were distilled off under reduced pressure of 1 to 3 kPa. The solution obtained by dissolving the residual liquid in 200 g of toluene was washed twice with 100 g of a 2% aqueous solution of potassium carbonate. After adding 20 g of anhydrous magnesium sulfate to the toluene solution and drying, the desiccant was separated by filtration, and then toluene was distilled off under reduced pressure to obtain a yellow liquid crude product. This composition was subjected to molecular distillation using the same thin-film distillation apparatus as in Example 4, and 39.5 g of a colorless liquid mono (n-butyl) -mono (methoxycarbonylmethyl) fumarate represented by the following formula (VIII) was obtained. I got The yield of the target compound is determined based on the raw material mono (n-butyl) fumarate
It was 47.6% on a standard basis.

[0210]

Embedded image

The IR spectrum of the obtained compound, ¹ H-
The NMR spectrum, ¹³ C-NMR spectrum, respective data and the results of elemental analysis were as follows. ¹ H-NMR spectrum (δ ppm) 93 (3H, t, J = 7.3 Hz), 1.39 (2H, m, J = 7.3 Hz), 1.65 (2
H, m, J = 7.3Hz), 3.76 (3H, s), 4.17 (2H, t, J = 7.3H)
z), 4.69 (2H, s), 7.01 (2H, s) ¹³ C-NMR spectrum (δ ppm) 13.5, 19.1, 31.1, 52.2, 61.6, 65.7, 129.4, 133.6,
164.2, 165.3, 167.4 ・ IR spectrum (cm ^-1 ) 3074 (CH), 2956 (CH), 2870 (CH), 1749 (C = O), 1730 (C
= O), 1645 (C = C)-Elemental analysis results (numerical values in parentheses indicate calculated values) C: 53.98% (54.09%) H: 6.74 (6.60%)

Example 6 A reaction vessel similar to that of Example 1 was charged with 58.0 g of maleic acid.
(0.50 mol), 119.4 g of methyl chloroacetate
(1.10 mol) and 1,000 g of DMF were charged, and 76.0 g (0.55 mol) of potassium carbonate was added, the temperature was raised to 70 ° C. with stirring, and the mixture was stirred at the same temperature for 18 hours. After cooling the reaction mixture to room temperature, the generated potassium chloride was filtered off, and the filtrate was heated to 70 ° C. for 0.1 to 0.1 ° C.
Volatile components such as DMF and unreacted methyl chloroacetate were distilled off under reduced pressure of 3 kPa. The solution obtained by dissolving the residual liquid in 300 g of toluene was added with 2% of potassium carbonate, respectively.
Washing was performed twice with 200 g of the aqueous solution. 20 g of anhydrous magnesium sulfate was added to the toluene solution and dried, and after magnesium sulfate was filtered off, toluene was distilled off under reduced pressure.
The obtained crude product was subjected to molecular distillation using the same thin-film distillation apparatus as in Example 4 to obtain 71.5 g of colorless liquid di (methoxycarbonylmethyl) malate represented by the following formula (IX). The yield of the target compound obtained by purification was 55.0% based on maleic acid as a raw material.

[0213]

Embedded image

FIG. 3 shows the IR spectrum of the compound obtained.
FIG. 4 shows the ¹ H-NMR spectrum. IR spectrum, ¹ H-NMR spectrum, ¹³
The C-NMR spectrum, respective data and the results of elemental analysis were as follows. ¹ H-NMR spectrum (δppm) 3.78 (6H, s), 4.74 (4H, s), 6.43 (2H, s) ¹³ C-NMR spectrum (δppm) 52.4, 61.2, 129.8, 164.1, 167.7 IR spectrum (Cm ^-1 ) 2958 (CH), 1730 (C = O), 1643 (C = C)-Elemental analysis results (numerical values in parentheses indicate calculated values) C: 46.28% (46.16%) H: 4.48 ( (4.65%)

Example 7 In place of 119.4 g of methyl chloroacetate, 134.8 g (1.10 mol) of ethyl chloroacetate was used.
The reaction was carried out in the same manner as in Example 6, except that stirring was performed at 0 ° C. for 25 hours. Subsequently, post-treatment and molecular distillation of the crude product were carried out in the same manner as in Example 6 to obtain 72.0 g of a colorless liquid di (ethoxycarbonylmethyl) malate represented by the following formula (X). The yield of the target compound obtained by purification was 50.0% based on maleic acid as a raw material.

[0216]

Embedded image

The IR spectrum of the obtained compound, ¹ H-
The NMR spectrum, ¹³ C-NMR spectrum, respective data and the results of elemental analysis were as follows. ¹ H-NMR spectrum (δ ppm) 1.27 (6H, t, J = 7.6 Hz), 4.23 (4H, q, J = 7.6 Hz), 4.74 (4
H, s), 6.33 (2H, s) ¹³ C-NMR spectrum (δ ppm) 14.1, 61.5, 61.7, 129.9, 164.0, 167.2 IR spectrum (cm ⁻¹ ) 3070 (CH), 2994 (CH), 2958 (CH), 1748 (C = O), 1729 (C
= O), 1660 (C = C)-Elemental analysis results (numerical values in parentheses indicate calculated values) C: 49.83% (50.00%) H: 5.68 (5.59%)

Example 8 Instead of 119.4 g of methyl chloroacetate, chloroacetic acid n
The reaction was carried out in the same manner as in Example 6, except that 165.7 g (1.10 mol) of -butyl was used and stirring was performed at 70 ° C. for 30 hours. Subsequently, post-treatment and molecular distillation of the crude product were carried out in the same manner as in Example 6 to obtain 87.0 g of colorless liquid di (n-butoxycarbonylmethyl) malate represented by the following formula (XI). The yield of the target compound was 50.5% based on maleic acid.

[0219]

Embedded image

The IR spectrum of the obtained compound, ¹ H-
The NMR spectrum, ¹³ C-NMR spectrum, respective data and the results of elemental analysis were as follows. ¹ H-NMR spectrum (δ ppm) 94 (6H, t, J = 7.4 Hz), 1.37 (4H, m, J = 7.4 Hz), 1.66 (4
H, m, J = 7.4Hz), 4.19 (4H, t, 7.4Hz), 4.74 (4H, s),
6.33 (2H, s) ¹³ C-NMR spectrum (δ ppm) 13.7, 19.1, 30.6, 61.8, 65.6, 129.8, 164.3, 167.7 IR spectrum (cm ⁻¹ ) 3076 (CH), 2960 (CH), 2877 ( CH), 1760 (C = O), 1731 (C
= O), 1658 (C = C)-Elemental analysis results (numerical values in parentheses indicate calculated values) C: 56.01% (55.81%) H: 7.26 (7.02%)

Example 9 Instead of 119.4 g of methyl chloroacetate, chloroacetic acid 2
The reaction was carried out in the same manner as in Example 6 except that 167.8 g (1.10 mol) of -methoxyethyl was used and stirring was performed at 70 ° C for 50 hours. Subsequently, post-treatment and molecular distillation of the crude product were carried out in the same manner as in Example 6 to obtain 88.0 g of colorless liquid di (2-methoxyethoxycarbonylmethyl) malate represented by the following formula (XII). The yield of the target compound was 50.5% based on the starting maleic acid.

[0222]

Embedded image

The IR spectrum of the obtained compound, ¹ H-
The NMR spectrum, ¹³ C-NMR spectrum, respective data and the results of elemental analysis were as follows. ¹ H-NMR spectrum (δ ppm) 3.35 (6H, s), 3.60 (4H, t, J = 7.3 Hz), 4.33 (4H, t, J =
7.3 Hz), 4.74 (4H, s), 6.32 (2H, s) ¹³ C-NMR spectrum (δ ppm) 58.7, 60.5, 61.5, 64.7, 129.9, 164.0, 167.4 IR spectrum (cm ⁻¹ ) 3070 (CH ⁻¹ ) ), 2963 (CH), 1760 (C = O), 1726 (C = O), 1640 (C
= C)-Elemental analysis results (numerical values in parentheses indicate calculated values) C: 48.40% (48.28%) H: 5.98 (5.79%)

Example 10 A reaction vessel similar to that of Example 1 was charged with 58.5 g (0.34 mol) of mono (n-butyl) maleate, 41.2 g (0.38 mol) of methyl chloroacetate, and 100 g of DMF. And 24.9 g (0.18 mol) of potassium carbonate, and the mixture was heated to 90 ° C. while stirring, and stirred at the same temperature for 1 hour. After the reaction mixture was cooled to room temperature, the generated potassium chloride was filtered off, and volatiles such as DMF and unreacted methyl chloroacetate were distilled off under reduced pressure of 0.1 to 3 kPa while heating the filtrate to 70 ° C. did. Residual solution is toluene 20
The solution obtained by dissolving in 0 g was washed twice with 100 g of a 2% aqueous solution of potassium carbonate. 10 g of anhydrous magnesium sulfate was added to the toluene solution and dried. After the desiccant was filtered off, toluene was distilled off under reduced pressure to obtain a yellow liquid crude product. The crude product was subjected to molecular distillation using the same thin-film distillation apparatus as in Example 4 to obtain a colorless liquid mono (n-butyl) -mono (methoxycarbonylmethyl) malate represented by the following formula (XIII). 0 g was obtained. The yield of the target compound is determined based on the raw material maleic acid mono (n-
(Butyl) based on 49.4%.

[0225]

Embedded image

FIG. 5 shows the IR spectrum of the obtained compound.
FIG. 6 shows the ¹ H-NMR spectrum. IR spectrum, ¹ H-NMR spectrum, ¹³
The C-NMR spectrum, respective data and the results of elemental analysis were as follows. ¹ H-NMR spectrum (δ ppm) 0.93 (3H, t, J = 7.3 Hz), 1.39 (2H, m), 1.65 (2H, m), 3.
77 (3H, s), 4.19 (2H, t, J = 7.3Hz), 4.70 (2H, s), 6.34
(2H, s) ¹³ C-NMR spectrum (δ ppm) 13.7, 19.1, 30.5, 52.3, 61.1, 65.3, 128.2, 131.7,
164.4, 165.1, 167.7 ・ IR spectrum (cm ^-1 ) 3060 (CH), 2959 (CH), 2875 (CH), 1740 (C = O), 1725 (C
= O), 1643 (C = C)-Elemental analysis results (numerical values in parentheses indicate calculated values) C: 54.20% (54.09%) H: 6.78 (6.60%)

Example 11 44.2 g (0.34 mol) of monomethyl maleate was used instead of 58.5 g of mono (n-butyl) maleate, and 2-methoxyethyl chloroacetate 58 was used instead of 41.2 g of methyl chloroacetate. 0.0 g (0.38 mol), and
The reaction was carried out in the same manner as in Example 10 except that stirring was performed at 70 ° C. for 20 hours. Next, a post-treatment and molecular distillation of the crude product were carried out in the same manner as in Example 10 to give a colorless liquid of the following formula (XIV)
38.7 g of mono (2-methoxyethoxycarbonylmethyl) -monomethylmalate represented by the following formula: was obtained. The yield of the target compound was 46. based on the starting material monomethyl maleate.
2%.

[0228]

Embedded image

The IR spectrum of the obtained compound, ¹ H-
The NMR spectrum, ¹³ C-NMR spectrum, respective data and the results of elemental analysis were as follows. ¹ H-NMR spectrum (δ ppm) 3.34 (3H, s), 3.60 (2H, t, J = 7.3 Hz), 3.82 (3H, s), 4.
33 (2H, t, J = 7.3 Hz), 4.74 (2H, s), 6.32 (2H, s) ^13C -NMR spectrum (δ ppm) 52.2, 58.6, 60.9, 61.3, 65.0, 128.3, 131.9, 164.
4, 165.1, 167.9 ・ IR spectrum (cm ^-1 ) 3058 (CH), 2956 (CH), 2870 (CH), 1740 (C = O), 1722 (C
= O), 1640 (C = C) Elemental analysis results (numerical values in parentheses indicate calculated values) C: 48.91% (48.78%) H: 5.88 (5.69%)

Example 12 The procedure was repeated except that 44.2 g (0.34 mol) of monomethyl maleate was used in place of 58.5 g of mono (n-butyl) maleate, and stirring was performed at 90 ° C. for 2 hours. Example 1
The reaction was carried out in the same manner as in Example 1. Subsequently, post-treatment and molecular distillation of the crude product were carried out in the same manner as in Example 10 to obtain a colorless liquid mono (methoxycarbonylmethyl)-represented by the following formula (XV).
35.5 g of monomethyl malate were obtained. The yield of the target compound was 51.7% based on the starting material monomethyl maleate.

[0231]

Embedded image

The IR spectrum of the obtained compound, ¹ H-
The NMR spectrum, ¹³ C-NMR spectrum, respective data and the results of elemental analysis were as follows. ¹ H-NMR spectrum (δppm) 3.76 (3H, s), 3.82 (3H, s), 4.75 (2H, s), 6.34 (2H, s) ¹³ C-NMR spectrum (δppm) 52.2, 52.3, 61.2 , 128.2, 131.7, 164.4, 165.1, 167.
7 IR spectrum (cm ^-1 ) 3060 (CH), 2950 (CH), 2875 (CH), 1741 (C = O), 1720 (C
= O), 1642 (C = C)-Elemental analysis results (numerical values in parentheses indicate calculated values) C: 47.77% (47.53%) H: 5.21 (4.99%)

[0233]

The present invention can provide a novel α, β-unsaturated dicarboxylic acid ester having an oxycarbonylmethyl ester group as an active ester group, and a method for producing the same.

[Brief description of the drawings]

FIG. 1 is an IR spectrum of the compound obtained in Example 1.

FIG. 2 is a ¹ H-NMR spectrum of the compound obtained in Example 1.

FIG. 3 is an IR spectrum of the compound obtained in Example 6.

FIG. 4 is a ¹ H-NMR spectrum of the compound obtained in Example 6.

FIG. 5 is an IR spectrum of the compound obtained in Example 10.

FIG. 6 shows ¹ H-NMR of the compound obtained in Example 10.
It is a spectrum.

 ──────────────────────────────────────────────────続 き Continued on the front page (72) Inventor Hiroo Tanaka 2-10-10 Tenjinyamacho, Kishiwada-shi, Osaka F-term (reference) 4H006 AA01 AA02 AC24 AC48 BJ20 BJ50 BT12

Claims (8)

[Claims] 1. The following general formulas (I-1) and (I-2)
[Hereinafter, these two formulas are collectively abbreviated as general formula (I). An α, β-unsaturated dicarboxylic acid ester represented by the formula: Embedded image (In the formula, R ₁ and R ₄ represent a hydrogen atom, a phenyl group or an alkyl group having 1 to 12 carbon atoms, and R ₂ , R ₃ and R ₅ each independently represent a monovalent organic group. ) 2. The method according to claim 1, wherein R ₂ , R ₃ and R _{5 in the} general formula (I) are each independently an alkyl group, a substituted alkyl group, a cycloalkyl group, an aryl group or a substituted aryl group. Α, β-unsaturated dicarboxylic acid esters of 3. The compound of the formula (I) wherein R ₂ , R ₃ and R ₅ each independently represent an alkoxy group having 3 to 6 carbon atoms containing an alkyl group having 1 to 6 carbon atoms or an alkoxy group. The α, β-unsaturated dicarboxylic acid ester according to claim 1, which is a group-substituted alkyl group. 4. The α, β-unsaturated dicarboxylic acid ester according to claim 1, wherein R ₁ and R ₄ in the general formula (I) are hydrogen atoms. 5. An α, β-unsaturated carboxylate selected from the group consisting of fumaric acid salts, fumaric acid half ester salts, maleic acid salts and maleic acid half ester salts, A method for producing an α, β-unsaturated dicarboxylic acid ester, characterized by reacting with a halocarboxylic acid ester. 6. The half ester of fumaric acid and the half ester of maleic acid are represented by the following general formula (II-1) or (II)
-2) [Hereinafter, these two formulas are collectively abbreviated as general formula (II). The method for producing an α, β-unsaturated dicarboxylic acid ester according to claim 5, wherein the α-halocarboxylic acid ester is a compound represented by the following general formula (III). Embedded image (Wherein, R ₃ and R ₅ each independently represent a monovalent organic group, and R ₄ represents a hydrogen atom, a phenyl group, or a group having 1 carbon atom.
Represents an alkyl group of 1 to 12. ) (Wherein, R ₁ represents a hydrogen atom, a phenyl group or an alkyl group having 1 to 12 carbon atoms, R ₂ represents a monovalent organic group, X
Represents a halogen atom. ) 7. R ₃ and R ₅ in the general formula (II) and R ₂ in the general formula (III) each independently represent an alkyl group,
The method for producing an α, β-unsaturated dicarboxylic acid ester according to claim 6, which is a substituted alkyl group, a cycloalkyl group, an aryl group, or a substituted aryl group. 8. R ₃ and R ₅ in the general formula (II) and R ₂ in the general formula (III) each independently include an alkyl group or an alkoxy group having 1 to 6 carbon atoms. The method for producing an α, β-unsaturated dicarboxylic acid ester according to claim 6, which is an alkoxy-substituted alkyl group having 3 to 6 carbon atoms.