JP2001354625A - New itaconic acid ester and method for producing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain new itaconic acid esters containing oxycarbonylmethyl ester groups as active ester groups and to provide a method for producing the same. SOLUTION: The new itaconic acid esters containing oxycarbonylmethyl ester groups as active ester groups are represented by general formulas I-1 to I-3, (R1 and R3 are each independently hydrogen, a phenyl group or a 1-12C alkyl group; R2, R4 and R5 are each independently a monofunctional organic group). The methods for producing the itaconic acid esters comprise reacting an itaconate or an itaconic acid half ester salt with an α-halocarboxylic acid ester.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a novel itaconic ester and a method for producing the same. For more information,
The present invention relates to a novel itaconic acid ester having an oxycarbonylmethyl ester group and a production method thereof. The itaconic acid ester of the present invention 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, but derivatives of itaconic acid containing an oxycarbonylmethyl ester group are not known.

[0003]

SUMMARY OF THE INVENTION An object of the present invention is to provide a novel itaconic ester having an oxycarbonylmethyl ester group as an active ester group and a method for producing the same.

[0004]

Means for Solving the Problems As a result of intensive studies to solve the above problems, the present inventors have found a novel itaconic acid ester having an oxycarbonylmethyl ester group and a method for producing the same, and completed the present invention. I came to.

That is, the present invention provides the following general formula (I-1):
(I-2) and (I-3) [Hereinafter, these three formulas may be collectively abbreviated as general formula (I). ] Itaconic acid ester represented by the formula:

[0006]

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(Wherein R ₁ and R ₃ each independently represent a hydrogen atom, a phenyl group or an alkyl group having 1 to 12 carbon atoms, and R ₂ , R ₄ and R ₅ each independently represent Represents a monovalent organic group.)

The present invention also provides a method for producing an itaconic acid ester, which comprises reacting a salt of itaconic acid or a salt of an itaconic acid half ester with an α-halocarboxylic acid ester.

Further, the itaconic acid half ester is a compound represented by the following general formula (II), and
An object of the present invention is to provide a method for producing an itaconic ester in which the halocarboxylic acid ester is a compound represented by the following general formula (III).

[0010]

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(In the formula, one of R ₆ and R ₇ is a hydrogen atom, and the other is a monovalent organic group.)

[0012]

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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.)

[0014]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail. The itaconic acid ester of the present invention refers to compounds represented by the following formulas (I-1), (I-2) and (I-3).

[0015]

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(Wherein R ₁ and R ₃ each independently represent a hydrogen atom, a phenyl group or an alkyl group having 1 to 12 carbon atoms, and R ₂ , R ₄ and R ₅ each independently represent Represents a monovalent organic group.)

The above general formulas (I-1), (I-2),
R ₁ and R ₃ contained in (I-3) are each independently
It represents any of a hydrogen atom, a phenyl group and an alkyl group having 1 to 12 carbon atoms, and among these, a typical alkyl group having 1 to 12 carbon atoms includes:
Methyl group, ethyl group, n-propyl group, iso-propyl group, n-butyl group, iso-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.

The above general formulas (I-1), (I-2),
R ₂ , R ₄ , which are monovalent organic groups contained in (I-3),
Representative examples of R ₅ include, independently of each other, various groups such as an alkyl group, a substituted alkyl group, a cycloalkyl group, an aryl group, and a substituted aryl group. Alkoxy-substituted alkyl groups having 3 to 6 carbon atoms, including alkyl groups and alkoxy groups, are preferred.

Among such monovalent organic groups, typical examples of the alkyl group include various groups described above as specific examples of the alkyl group of R ₁ and R ₃ .

Representative examples of the substituted alkyl group include:
2-methoxyethyl group, 2-ethoxyethyl group, 2-
(N-propoxy) ethyl group, 2- (n-butoxy) ethyl group, 2- (n-hexyloxy) ethyl group, 3-methoxypropyl group, 4-methoxybutyl group, 4- (n-
Alkyl group substituted by an alkoxy group such as propoxy) butyl group; 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 -phenylethoxy) ethyl group; benzyl group, 1-phenylethyl group,
And an alkyl group substituted by an aryl group such as -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:
2-methylphenyl group, 4-methylphenyl group, 4-chlorophenyl group, 4-nitrophenyl group, 4-methyl-
And a 1-naphthyl group.

In the itaconic ester represented by the general formula (I-1), R ₂ and R ₄ have alkyl groups,
Representative compounds having a hydrogen atom as R ₁ and R ₃ include di (methoxycarbonylmethyl) itaconate, di (ethoxycarbonylmethyl) itaconate, di (n-propoxycarbonylmethyl) itaconate, and di (iso -Propoxycarbonylmethyl) itaconate, di (n-butoxycarbonylmethyl) itaconate, di (iso-butoxycarbonylmethyl) itaconate, di (n-hexyloxycarbonylmethyl)
Itaconate, di (2-ethylhexyloxycarbonylmethyl) itaconate, di (n-decyloxycarbonylmethyl) itaconate, and the like.

Representative of the itaconic esters represented by the general formula (I-1), compounds having an alkoxy-substituted alkyl group as R ₂ and R ₄ and a hydrogen atom as R ₁ and R _3. Typical examples are di (2-methoxyethoxycarbonylmethyl) itaconate, di (2-ethoxyethoxycarbonylmethyl) itaconate, di [2- (n-propoxy) ethoxycarbonylmethyl]
Itaconate, di [2- (n-butoxy) ethoxycarbonylmethyl] itaconate, di (3-methoxypropoxycarbonylmethyl) itaconate, and the like.

Among the itaconic esters represented by the general formula (I-1), R ₂ and R ₄ have an alkyl group substituted by an aryloxy group, and R ₁ and R ₃ have a hydrogen atom. Representative compounds include di (2
-Phenoxyethoxycarbonylmethyl) itaconate, di [2- (4-methylphenoxy) ethoxycarbonylmethyl] itaconate, and the like.

Among the itaconic esters represented by the general formula (I-1), R ₂ and R ₄ have an alkyl group substituted by an aralkyloxy group, and R ₁ and R ₃ have a hydrogen atom. Representative compounds include di (2-benzyloxyethoxycarbonylmethyl) itaconate, di [2- (2-phenylethoxy) ethoxycarbonylmethyl] itaconate, and the like.

Among the itaconic esters represented by the formula (I-1), compounds having an alkyl group substituted with an aryl group as R ₂ and R ₄ and having a hydrogen atom as R ₁ and R ₃ Representative examples of di (benzyloxycarbonylmethyl) itaconate, di (1-phenylethoxycarbonylmethyl) itaconate, di (2
-Phenylethoxycarbonylmethyl) itaconate,
And the like.

Among the itaconic esters represented by the general formula (I-1), representative of compounds having a cycloalkyl group as R ₂ and R ₄ and a hydrogen atom as R ₁ and R ₃ Examples thereof include di (cyclopentyloxycarbonylmethyl) itaconate, di (cyclohexyloxycarbonylmethyl) itaconate, di (4-methylcyclohexyloxycarbonylmethyl) itaconate, and the like.

In the itaconic acid ester represented by the general formula (I-1), R ₂ and R ₄ have aryl groups,
Representative compounds having a hydrogen atom as R ₁ and R ₃ include di (phenoxycarbonylmethyl)
Itaconate, di (1-naphthoxycarbonylmethyl)
Itaconate, di (2-naphthoxycarbonylmethyl)
Itaconate, and the like.

Among the itaconic esters represented by the general formula (I-1), typical examples of compounds having a substituted aryl group as R ₂ and R ₄ and a hydrogen atom as R ₁ and R ₃ Examples thereof include di (3-methylphenoxycarbonylmethyl) itaconate, di (4-methylphenoxycarbonylmethyl) itaconate, di (4-nitrophenoxycarbonylmethyl) itaconate, and the like.

In the itaconic ester represented by the general formula (I-1), R ₂ and R ₄ have an alkyl group,
Representative compounds having a methyl group as R ₁ and R ₃ include di (1-methoxycarbonylethyl) itaconate, di (1-ethoxycarbonylethyl) itaconate, and di [1- (n-propoxycarbonyl). ) Ethyl] itaconate, di [1- (iso-propoxycarbonyl) ethyl] itaconate, di [1- (n
-Butoxycarbonyl) ethyl] itaconate, di [1
-(Iso-butoxycarbonyl) ethyl] itaconate, di [1- (n-hexyloxycarbonyl) ethyl] itaconate, di [1- (2-ethylhexyloxycarbonyl) ethyl] itaconate, di [1- (n-
Decyloxycarbonyl) ethyl] itaconate, and the like.

Representative of the itaconic esters represented by the general formula (I-1), compounds having an alkoxy-substituted alkyl group as R ₂ and R ₄ and a methyl group as R ₁ and R _3. Typical examples include di [1- (2-methoxyethoxycarbonyl) ethyl] itaconate, di [1- (2-ethoxyethoxycarbonyl) ethyl] itaconate, and di {1- [2- (n-propoxy) ethoxycarbonyl]. ] Ethyl itaconate, di-1- [2-
(N-butoxy) ethoxycarbonyl] ethyl diitaconate, di [1- (3-methoxypropoxycarbonyl) ethyl] itaconate, and the like.

Among the itaconic esters represented by the general formula (I-1), R ₂ and R ₄ have an alkyl group substituted by an aryloxy group, and R ₁ and R ₃ have a methyl group. Representative compounds include di [1
-(2-phenoxyethoxycarbonyl) ethyl] itaconate, di {1- [2- (4-methylphenoxy) ethoxycarbonyl] ethyl} itaconate, and the like.

Among the itaconic esters represented by the general formula (I-1), R ₂ and R ₄ have an alkyl group substituted by an aralkyloxy group, and R ₁ and R ₃ have a methyl group. Representative examples of the compound include di [1- (2-benzyloxyethoxycarbonyl) ethyl] itaconate, di {1- [2- (2-phenylethoxy) ethoxycarbonyl] ethyl} itaconate, and the like.

Among the itaconic esters represented by the formula (I-1), compounds having an alkyl group substituted with an aryl group as R ₂ and R ₄ and a methyl group as R ₁ and R ₃ Representative examples include di (1-benzyloxycarbonylethyl) itaconate and di [1-
(1-phenylethoxycarbonyl) ethyl] itaconate, di [1- (2-phenylethoxycarbonyl) ethyl] itaconate, and the like.

Among the itaconic esters represented by the general formula (I-1), typical examples of compounds having a cycloalkyl group as R ₂ and R ₄ and a methyl group as R ₁ and R ₃ Examples thereof include di (1-cyclopentyloxycarbonylethyl) itaconate, di (1-cyclohexyloxycarbonylethyl) itaconate, di [1
-(4-methylcyclohexyloxycarbonyl) ethyl] itaconate, and the like.

In the itaconic acid ester represented by the general formula (I-1), R ₂ and R ₄ have aryl groups,
Representative compounds having a methyl group as R ₁ and R ₃ include di (1-phenoxycarbonylethyl) itaconate, di [1- (1-naphthoxycarbonyl) ethyl] itaconate, di [1- (2-naphthoxycarbonyl) ethyl] itaconate, and the like.

Among the itaconic esters represented by the general formula (I-1), representative of itaconic esters having a substituted aryl group as R ₂ and R ₄ and a methyl group as R ₁ and R ₃ Typical examples are di [1- (3-methylphenoxycarbonyl) ethyl] itaconate, di [1- (4-methylphenoxycarbonyl) ethyl] itaconate and di [1- (4-nitrophenoxycarbonyl) ethyl] itaconate. And the like.

Further, among the itaconic esters of the present invention represented by the general formula (I-1), compounds having various alkyl groups having 2 to 12 carbon atoms or phenyl groups as R ₁ or R ₃ Is a typical example of R ₁
And various compounds having a structure in which a methyl group is substituted with various alkyl groups having 2 to 12 carbon atoms or a phenyl group in the various itaconate esters described above as examples of those containing a methyl group as R _3. Examples can be given.

Further, as the itaconic ester represented by the general formula (I-1), R ₁ and R ₃ are the same and R
Only compounds in which ₂ and R ₄ are the same are illustrated, but R ₁ and R ₃
Are the same and R ₂ and R ₄ are different, a compound is R ₁ and R ₃ are different and R ₂ and R ₄ are the same, or R ₁ and R ₃
And R ₂ and R ₄ are also included in such itaconic esters.

The general formula having a monovalent organic group various described above as _{R 2, R 5 (I-} 2), among the itaconic acid ester represented by (I-3), alkyl as R ₂ and R ₅ Representative compounds having a group and having a hydrogen atom as R ₁ include monomethyl-mono (methoxycarbonylmethyl) itaconate, monomethyl-mono (ethoxycarbonylmethyl) itaconate, monomethyl-
Mono (n-butoxycarbonylmethyl) itaconate,
Monoethyl-mono (ethoxycarbonylmethyl) itaconate, mono (n-propyl) -mono (n-propoxycarbonylmethyl) itaconate, mono (n-butyl)
-Mono (methoxycarbonylmethyl) itaconate, mono (n-butyl) -mono (n-butoxycarbonylmethyl) itaconate, mono (n-hexyl) -mono (n-
Hexyloxycarbonylmethyl) itaconate, monomethyl-mono (2-ethylhexyloxycarbonylmethyl) itaconate, monomethyl-mono (n-decyloxycarbonylmethyl) itaconate, and the like.

The formula (I-2), among the itaconic acid ester represented by (I-3), the alkyl group as R _2, having an alkoxy group-substituted alkyl group as R _5, and, as R ₁ Representative compounds having a hydrogen atom include mono (2-methoxyethyl) -mono (methoxycarbonylmethyl) itaconate, mono (2-methoxyethyl) -mono (ethoxycarbonylmethyl) itaconate, mono (2-ethoxy) Ethyl) -mono (ethoxycarbonylmethyl) itaconate, mono (2-ethoxyethyl) -mono (n-propoxycarbonylmethyl) itaconate, mono (2-ethoxyethyl) -mono (n-
Butoxycarbonylmethyl) itaconate, mono [2-
(N-butoxy) ethyl] -mono (n-hexyloxycarbonylmethyl) itaconate, mono (4-ethoxybutyl) -mono (2-ethylhexyloxycarbonylmethyl) itaconate, mono [3- (n-propoxy)
Propyl] -mono (n-decyloxycarbonylmethyl) itaconate, and the like.

Among the itaconic esters represented by formulas (I-2) and (I-3), R ₂ has an alkyl group substituted with an alkyl group as R ₂ and R ₅ has an alkyl group substituted with an aryl group; Representative compounds having a hydrogen atom as ₁ include monobenzyl-mono (methoxycarbonylmethyl) itaconate, monobenzyl-mono (ethoxycarbonylmethyl) itaconate, and mono (2-phenylethyl) -mono (ethoxycarbonylmethyl). ) Itaconate, mono (1-phenylethyl) -mono (n-propoxycarbonylmethyl) itaconate, monobenzyl-mono (n-butoxycarbonylmethyl) itaconate, and the like.

Among the itaconic esters represented by the general formulas (I-2) and (I-3), an alkyl group as R ₂ , a cycloalkyl group as R ₅ , and a hydrogen atom as R ₁ Representative compounds having the formula: monocyclopentyl-mono (methoxycarbonylmethyl)
Itaconate, monocyclopentyl-mono (ethoxycarbonylmethyl) itaconate, monocyclohexyl-
Mono (ethoxycarbonylmethyl) itaconate, monocyclohexyl-mono (n-propoxycarbonylmethyl) itaconate, monocyclohexyl-mono (n-butoxycarbonylmethyl) itaconate, and the like.

Among the itaconic esters represented by the general formulas (I-2) and (I-3), R ₂ has an alkyl group, R ₅ has an aryl group, and R ₁ has a hydrogen atom. Representative compounds having the compound include monophenyl-mono (methoxycarbonylmethyl) itaconate and monophenyl-mono (ethoxycarbonylmethyl).
Itaconate, mono (1-naphthyl) -mono (ethoxycarbonylmethyl) itaconate, monophenyl-mono (n-propoxycarbonylmethyl) itaconate, monophenyl-mono (n-butoxycarbonylmethyl) itaconate, and the like.

Among the itaconic esters represented by the general formulas (I-2) and (I-3), an alkyl group as R ₂ , a substituted aryl group as R ₅ , and a hydrogen atom as R ₁ Representative compounds having the following are mono (4-methylphenyl) -mono (methoxycarbonylmethyl) itaconate, mono (4-methylphenyl) -mono (ethoxycarbonylmethyl) itaconate, mono (4-chlorophenyl)- Mono (ethoxycarbonylmethyl) itaconate, mono (4-nitrophenyl) -mono (n-propoxycarbonylmethyl) itaconate,
And the like.

Among the itaconic esters represented by the general formulas (I-2) and (I-3), an alkoxy-substituted alkyl group as R ₂ , an alkyl group as R ₅ , and R ₁ as R ₁ Representative compounds having a hydrogen atom include monomethyl-mono (2-methoxyethoxycarbonylmethyl) itaconate and monoethyl-mono (2
-Ethoxyethoxycarbonylmethyl) itaconate,
Mono (n-propyl) -mono [2- (n-propoxy)
[Ethoxycarbonylmethyl] itaconate, mono (n-
Butyl) -mono [2- (n-butoxy) ethoxycarbonylmethyl] itaconate, mono (n-hexyl) -mono (3-methoxypropoxycarbonylmethyl) itaconate, and the like.

Among the itaconic esters represented by formulas (I-2) and (I-3), R ₂ and R ₅ have an alkoxy-substituted alkyl group and R ₁ has a hydrogen atom. As a typical example of the compound, mono (2-
Methoxyethyl) -mono (2-methoxyethoxycarbonylmethyl) itaconate, mono (2-ethoxyethyl) -mono (2-ethoxyethoxycarbonylmethyl)
Itaconate, mono [2- (n-propoxy) ethyl]
-Mono [2- (n-propoxy) ethoxycarbonylmethyl] itaconate, mono [2- (n-butoxy) ethyl] -mono [2- (n-butoxy) ethoxycarbonylmethyl] itaconate, mono (3-methoxypropyl)
-Mono (3-methoxypropoxycarbonylmethyl) itaconate;

Among the itaconic esters represented by formulas (I-2) and (I-3), R ₂ has an alkoxy-substituted alkyl group as R ₂ and R ₅ has an alkyl group substituted with an aryl group; Representative compounds having a hydrogen atom as R ₁ include monobenzyl-mono (2
-Methoxyethoxycarbonylmethyl) itaconate,
Monobenzyl-mono (2-ethoxyethoxycarbonylmethyl) itaconate, mono (2-phenylethyl)-
Mono [2- (n-propoxy) ethoxycarbonylmethyl] itaconate; mono (1-phenylethyl) -mono [2- (n-butoxy) ethoxycarbonylmethyl] itaconate;

Among the itaconic esters represented by formulas (I-2) and (I-3), an alkoxy-substituted alkyl group as R ₂ , an aryl group as R ₅ , and R ₁ as R ₁ Representative compounds having a hydrogen atom include monophenyl-mono (2-methoxyethoxycarbonylmethyl) itaconate, monophenyl-mono (2-ethoxyethoxycarbonylmethyl) itaconate, and mono (1-naphthyl) -mono [ 2- (n-propoxy) ethoxycarbonylmethyl] itaconate, monophenyl-mono [2- (n-butoxy) ethoxycarbonylmethyl] itaconate, and the like.

Among the itaconic esters represented by formulas (I-2) and (I-3), R ₂ has an alkoxy-substituted alkyl group as R ₂ and a substituted aryl group as R ₅ ;
A typical compound having a hydrogen atom as R ₁ is mono (4-methylphenyl) -mono (2-
Methoxyethoxycarbonylmethyl) itaconate, mono (4-methylphenyl) -mono (2-ethoxyethoxycarbonylmethyl) itaconate, mono (4-chlorophenyl) -mono [2- (n-propoxy) ethoxycarbonylmethyl] itaconate, mono ( 4-nitrophenyl) -mono [2- (n-butoxy) ethoxycarbonylmethyl] itaconate;

Among the itaconic esters represented by formulas (I-2) and (I-3), R ₂ has an alkoxy-substituted alkyl group, R ₅ has a cycloalkyl group, and R ₁ Representative examples of the compound having a hydrogen atom include monocyclohexyl-mono (2-methoxyethoxycarbonylmethyl) itaconate, monocyclohexyl-mono (2-ethoxyethoxycarbonylmethyl) itaconate, monocyclopentyl-mono [2
-(N-propoxy) ethoxycarbonylmethyl] itaconate, monocyclohexyl-mono [2- (n-butoxy) ethoxycarbonylmethyl] itaconate, and the like.

Among the itaconic esters represented by the general formulas (I-2) and (I-3), R ₂ has an alkyl group substituted by an aryl group, R ₅ has an alkyl group,
Representative examples of the compound having a hydrogen atom as R ₁ include monomethyl-mono (benzyloxycarbonylmethyl) itaconate, monoethyl-mono (1-phenylethoxycarbonylmethyl) itaconate, and mono (n-propyl) -mono. (2-phenylethoxycarbonylmethyl) itaconate, mono (n-hexyl) -mono (benzyloxycarbonylmethyl) itaconate,
And the like.

Among the itaconic esters represented by formulas (I-2) and (I-3), R ₂ has an alkyl group substituted with an aryl group, and R ₅ has an alkoxy-substituted alkyl group; Representative examples of the compound having a hydrogen atom as R ₁ include mono (2-methoxyethyl) -mono (benzyloxycarbonylmethyl) itaconate and mono (2-ethoxyethyl) -mono (1-phenylethoxycarbonyl). Methyl) itaconate, mono [2- (n-butoxy) ethyl] -mono (2-phenylethoxycarbonylmethyl) itaconate, and the like.

Among the itaconic acid esters represented by formulas (I-2) and (I-3), R ₂ has an alkyl group substituted with an aryl group, R ₅ has a cycloalkyl group, and Representative compounds having a hydrogen atom as R ₁ include monocyclopentyl-mono (benzyloxycarbonylmethyl) itaconate, monocyclopentyl-mono (1-phenylethoxycarbonylmethyl) itaconate, monocyclohexyl-mono (2-phenyl) Ethoxycarbonylmethyl) itaconate, and the like.

Among the itaconic esters represented by formulas (I-2) and (I-3), R ₂ has an alkyl group substituted with an aryl group and R ₅ has an aryl group;
Representative compounds having a hydrogen atom as R ₁ include monophenyl-mono (benzyloxycarbonylmethyl) itaconate and monophenyl-mono (1
-Phenylethoxycarbonylmethyl) itaconate,
Mono (1-naphthyl) -mono (2-phenylethoxycarbonylmethyl) itaconate;

In the itaconic esters represented by formulas (I-2) and (I-3), an alkyl group substituted with an aryl group as R ₂ , a substituted aryl as R ₅ , Representative compounds having a hydrogen atom as ₁ include mono (4-methylphenyl) -mono (benzyloxycarbonylmethyl) itaconate and mono (4-methylphenyl) -mono (1-phenylethoxycarbonylmethyl) itaconate , Mono (4-chlorophenyl) -mono (2-phenylethoxycarbonylmethyl) itaconate, and the like.

Among the itaconic esters represented by formulas (I-2) and (I-3), a cycloalkyl group as R ₂ , an alkyl group as R ₅ , and a hydrogen atom as R ₁ Representative compounds having the following are monomethyl-mono (cyclopentyloxycarbonylmethyl) itaconate, monoethyl-mono (cyclohexyloxycarbonylmethyl) itaconate, mono (n-butyl) -mono (cyclohexyloxycarbonylmethyl) itaconate, (N-hexyl) -mono (cyclohexyloxycarbonylmethyl) itaconate, and the like.

Among the itaconic esters represented by the general formulas (I-2) and (I-3), a cycloalkyl group as R ₂ , an alkoxy-substituted alkyl group as R ₅ , and R ₁ Typical examples of the compound having a hydrogen atom include mono (2-methoxyethyl) -mono (cyclopentyloxycarbonylmethyl) itaconate, mono (2-ethoxyethyl) -mono (cyclohexyloxycarbonylmethyl) itaconate, mono [ 2-
(N-butoxy) ethyl] -mono (cyclohexyloxycarbonylmethyl) itaconate, and the like.

Among the itaconic esters represented by formulas (I-2) and (I-3), compounds having a cycloalkyl group as R ₂ and R ₅ and a hydrogen atom as R ₁ A typical example is monocyclopentyl-
Mono (cyclopentyloxycarbonylmethyl) itaconate, monocyclohexyl-mono (cyclohexyloxycarbonylmethyl) itaconate, monocyclopentyl-mono (cyclohexyloxycarbonylmethyl)
Itaconate, and the like.

Among the itaconic esters represented by formulas (I-2) and (I-3), a cycloalkyl group as R ₂ , an aryl group as R ₅ , and a hydrogen atom as R ₁ Representative compounds having the following are monophenyl-mono (cyclopentyloxycarbonylmethyl) itaconate, mono (1-naphthyl) -mono (cyclohexyloxycarbonylmethyl) itaconate, and the like.

Among the itaconic esters represented by formulas (I-2) and (I-3), R ₂ has a cycloalkyl group, R ₅ has a substituted aryl group, and R ₁ has hydrogen. Representative compounds having an atom include:
Mono (4-methylphenyl) -mono (cyclopentyloxycarbonylmethyl) itaconate, mono (4-chlorophenyl) -mono (cyclohexyloxycarbonylmethyl) itaconate, mono (4-nitrophenyl)-
Mono (cyclohexyloxycarbonylmethyl) itaconate; and the like.

Among the itaconic esters represented by formulas (I-2) and (I-3), an aryl group as R ₂ , an alkyl group as R ₅ , and a hydrogen atom as R _1. Typical examples of the compound having the compound include monomethyl-mono (phenoxycarbonylmethyl) itaconate and monoethyl-mono (phenoxycarbonylmethyl).
Itaconate, mono (n-butyl) -mono (phenoxycarbonylmethyl) itaconate, mono (n-hexyl) -mono (phenoxycarbonylmethyl) itaconate, monomethyl-mono (1-naphthoxycarbonylmethyl) itaconate, monomethyl-mono (2 -Naphthoxycarbonylmethyl) itaconate;

Among the itaconic esters represented by formulas (I-2) and (I-3), R ₂ has an aryl group, R ₅ has an alkoxy-substituted alkyl group, and R ₁ has hydrogen. Representative compounds having an atom include mono (2-methoxyethyl) -mono (phenoxycarbonylmethyl) itaconate, mono (2-ethoxyethyl) -mono (phenoxycarbonylmethyl) itaconate, mono [2- (n -Butoxy) ethyl] -mono (phenoxycarbonylmethyl) itaconate, mono- (2-methoxyethyl) -mono (1-naphthoxycarbonylmethyl) itaconate, and the like.

Among the itaconic esters represented by the general formulas (I-2) and (I-3), R ₂ has an aryl group substituted with an aryl group as R ₅ , and R ₅ has an alkyl group substituted with an aryl group. Representative compounds having a hydrogen atom as ₁ include monobenzyl-mono (phenoxycarbonylmethyl) itaconate and monobenzyl-mono (1
-Naphthoxycarbonylmethyl) itaconate;

Among the itaconic esters represented by the general formulas (I-2) and (I-3), R ₂ has an aryl group, R ₅ has a cycloalkyl group, and R ₁ has a hydrogen atom. Representative examples of the compound having the following are monocyclopentyl-mono (phenoxycarbonylmethyl) itaconate, monocyclohexyl-mono (phenoxycarbonylmethyl) itaconate, monocyclohexyl-mono (1-naphthoxycarbonylmethyl) itaconate, and the like. Can be

Representative of the itaconic esters represented by formulas (I-2) and (I-3), compounds having an aryl group as R ₂ and R ₅ and a hydrogen atom as R _1. Typical examples include monophenyl-mono (phenoxycarbonylmethyl) itaconate, mono (1-naphthyl) -mono (phenoxycarbonylmethyl) itaconate, monophenyl-mono (1-naphthoxycarbonylmethyl) itaconate, and the like. .

Among the itaconic acid esters represented by formulas (I-2) and (I-3), R ₂ has an aryl group, R ₅ has a substituted aryl group, and R ₁ is a hydrogen atom. Representative compounds having the following are mono (4-methylphenyl) -mono (phenoxycarbonylmethyl) itaconate and mono (4-chlorophenyl)-
Mono (phenoxycarbonylmethyl) itaconate, mono (4-methylphenyl) -mono (1-naphthoxycarbonylmethyl) itaconate, and the like.

Among the itaconic esters represented by formulas (I-2) and (I-3), R ₂ has a substituted aryl group, R ₅ has an alkyl group, and R ₁ has a hydrogen atom. As a typical example of the compound having the following formula, monomethyl-mono (3-methylphenoxycarbonylmethyl)
Itaconate, monomethyl-mono (4-methylphenoxycarbonylmethyl) itaconate, monoethyl-mono (4-methylphenoxycarbonylmethyl) itaconate, mono (n-butyl) -mono (4-methylphenoxycarbonylmethyl) itaconate, mono (n- Hexyl) -mono (4-methylphenoxycarbonylmethyl)
Itaconate, monomethyl-mono (4-nitrophenoxycarbonylmethyl) itaconate, and the like.

Among the itaconic esters represented by the general formulas (I-2) and (I-3), R ₂ has a substituted aryl group and R ₅ has an alkoxy-substituted alkyl group;
A typical compound having a hydrogen atom as R ₁ is mono (2-methoxyethyl) -mono (3-
Methylphenoxycarbonylmethyl) itaconate, mono (2-methoxyethyl) -mono (4-methylphenoxycarbonylmethyl) itaconate, mono (2-ethoxyethyl) -mono (4-methylphenoxycarbonylmethyl) itaconate, mono [2- ( n-butoxy) ethyl] -mono (4-methylphenoxycarbonylmethyl)
Itaconate, mono (2-methoxyethyl) -mono (4
-Nitrophenoxycarbonylmethyl) itaconate,
And the like.

In the itaconic esters represented by formulas (I-2) and (I-3), R ₂ has a substituted aryl group, R ₅ has an alkyl group substituted with an aryl group, and Representative compounds having a hydrogen atom as R ₁ include monobenzyl-mono (3-methylphenoxycarbonylmethyl) itaconate, monobenzyl-mono (4-methylphenoxycarbonylmethyl) itaconate, monobenzyl-mono (4 -Nitrophenoxycarbonylmethyl) itaconate;

Among the itaconic esters represented by the general formulas (I-2) and (I-3), a substituted aryl group as R ₂ , a cycloalkyl group as R ₅ , and a hydrogen atom as R ₁ Representative compounds having an atom include:
Monocyclopentyl-mono (3-methylphenoxycarbonylmethyl) itaconate, monocyclopentyl-mono (4-methylphenoxycarbonylmethyl) itaconate, monocyclohexyl-mono (4-methylphenoxycarbonylmethyl) itaconate, monocyclooctyl-mono (4- Methylphenoxycarbonylmethyl) itaconate, monocyclohexyl-mono (4-nitrophenoxycarbonylmethyl) itaconate, and the like.

Among the itaconic esters represented by the general formulas (I-2) and (I-3), a substituted aryl group as R ₂ , an aryl group as R ₅ , and a hydrogen atom as R ₁ Representative compounds having the following formulas are monophenyl-mono (3-methylphenoxycarbonylmethyl) itaconate, monophenyl-mono (4-methylphenoxycarbonylmethyl) itaconate and mono (1-
Naphthyl) -mono (4-methylphenoxycarbonylmethyl) itaconate, monophenyl-mono (4-nitrophenoxycarbonylmethyl) itaconate, and the like.

Among the itaconic acid esters represented by formulas (I-2) and (I-3), compounds having a substituted aryl group as R ₂ and R ₅ and a hydrogen atom as R ₁ A typical example is mono (3-methylphenyl) -mono (3-methylphenoxycarbonylmethyl)
Itaconate, mono (4-methylphenyl) -mono (4
-Methylphenoxycarbonylmethyl) itaconate,
Mono (4-chlorophenyl) -mono (4-methylphenoxycarbonylmethyl) itaconate; mono (4-methylphenyl) -mono (4-nitrophenoxycarbonylmethyl) itaconate;

[0076] In general formula having a monovalent organic group various described above as _{R 2, R 5 (I-} 2), among the itaconic acid ester represented by (I-3), R ₂ and R ₅ A typical example of the compound having an alkyl group as R ₁ and a methyl group as R ₁ is monomethyl-mono (1-
Methoxycarbonylethyl) itaconate, monomethyl-mono (1-ethoxycarbonylethyl) itaconate, monoethyl-mono (1-ethoxycarbonylethyl) itaconate, mono (n-propyl) -mono [1-
(N-propoxycarbonyl) ethyl] itaconate,
Mono (n-butyl) -mono [1- (n-butoxycarbonyl) ethyl] itaconate, mono (n-hexyl)-
Mono [1- (n-hexyloxycarbonyl) ethyl]
Itaconate, monomethyl-mono [1- (2-ethylhexyloxycarbonyl) ethyl] itaconate, monomethyl-mono [1- (n-decyloxycarbonyl) ethyl] itaconate, and the like.

Among the itaconic acid esters represented by formulas (I-2) and (I-3), R ₂ has an alkyl group, R ₅ has an alkoxy-substituted alkyl group, and R ₁ has Representative compounds having a methyl group include mono (2-methoxyethyl) -mono (1-methoxycarbonylethyl) itaconate, mono (2-methoxyethyl) -mono (1-ethoxycarbonylethyl) itaconate, (2-ethoxyethyl) -mono (1-ethoxycarbonylethyl) itaconate, mono (2-ethoxyethyl) -mono [1- (n-propoxycarbonyl) ethyl] itaconate, mono (2-ethoxyethyl) -mono [1 -(N-butoxycarbonyl) ethyl] itaconate, mono [2- (n-butoxy) ethyl] -mono [1- (n- Xyloxycarbonyl) ethyl] itaconate, mono (4-ethoxybutyl) -mono [1- (2-ethylhexyloxycarbonyl) ethyl] itaconate, mono [3- (n-propoxy) propyl] -mono [1- (n- Decyloxycarbonyl) ethyl] itaconate, and the like.

Among the itaconic esters represented by formulas (I-2) and (I-3), R ₂ has an alkyl group substituted with an alkyl group as R ₂ and R ₅ has an alkyl group substituted with an aryl group; Representative compounds having a methyl group as ₁ include monobenzyl-mono (1-methoxycarbonylethyl) itaconate, monobenzyl-mono (1-ethoxycarbonylethyl) itaconate, and mono (2-phenylethyl) -mono (1-ethoxycarbonylethyl) itaconate, mono (1-phenylethyl)
-Mono [1- (n-propoxycarbonyl) ethyl] itaconate; monobenzyl-mono [1- (n-butoxycarbonyl) ethyl] itaconate;

Among the itaconic esters represented by formulas (I-2) and (I-3), R ₂ has an alkyl group, R ₅ has a cycloalkyl group, and R ₁ has a methyl group. Representative compounds having the following are monocyclopentyl-mono (1-methoxycarbonylethyl) itaconate, monocyclopentyl-mono (1-ethoxycarbonylethyl) itaconate, monocyclohexyl-mono (1-ethoxycarbonylethyl) itaconate, Monocyclohexyl-mono [1- (n-propoxycarbonyl) ethyl] itaconate; monocyclohexyl-mono [1- (n-butoxycarbonyl) ethyl] itaconate;

Among the itaconic esters represented by formulas (I-2) and (I-3), R ₂ has an alkyl group, R ₅ has an aryl group, and R ₁ has a methyl group. Representative compounds having the compound include monophenyl-mono (1-methoxycarbonylethyl) itaconate, monophenyl-mono (1-ethoxycarbonylethyl) itaconate, and mono (1-naphthyl) -mono (1
-Ethoxycarbonylethyl) itaconate, monophenyl-mono [1- (n-propoxycarbonyl) ethyl] itaconate, monophenyl-mono [1- (n-butoxycarbonyl) ethyl] itaconate, and the like.

[0081] formula (I-2), among the itaconic acid ester represented by (I-3), the alkyl group as R _2, having a substituted aryl group as R _5, and a methyl group as R ₁ Representative compounds having the following are mono (4-methylphenyl) -mono (1-methoxycarbonylethyl) itaconate, mono (4-methylphenyl)
Mono- (1-ethoxycarbonylethyl) itaconate, mono (4-chlorophenyl) -mono (1-ethoxycarbonylethyl) itaconate, mono (4-nitrophenyl) -mono [1- (n-propoxycarbonyl) ethyl] itaconate; And the like.

Among the itaconic esters represented by formulas (I-2) and (I-3), an alkoxy-substituted alkyl group as R ₂ , an alkyl group as R ₅ , and R ₁ as R ₁ Representative compounds having a methyl group include monomethyl-mono [1- (2-methoxyethoxycarbonyl) ethyl] itaconate and monoethyl-
Mono [1- (2-ethoxyethoxycarbonyl) ethyl] itaconate, mono (n-propyl) -mono {1-
[2- (n-propoxy) ethoxycarbonyl] ethyl {itaconate, mono (n-butyl) -mono} 1-
[2- (n-butoxy) ethoxycarbonyl] ethyl} itaconate, mono (n-hexyl) -mono [1- (3-
Methoxypropoxycarbonyl) ethyl] itaconate, and the like.

Among the itaconic esters represented by formulas (I-2) and (I-3), R ₂ and R ₅ have an alkoxy-substituted alkyl group and R ₁ has a methyl group. As a typical example of the compound, mono (2-
Methoxyethyl) -mono [1- (2-methoxyethoxycarbonyl) ethyl] itaconate, mono (2-ethoxyethyl) -mono [1- (2-ethoxyethoxycarbonyl) ethyl] itaconate, mono [2- (n-propoxy) ) Ethyl] -mono {1- [2- (n-propoxy)
Ethoxycarbonyl] ethyl diitaconate, mono [2
-(N-butoxy) ethyl] -mono {1- [2- (n-
Butoxy) ethoxycarbonyl] ethyl} itaconate, mono (3-methoxypropyl) -mono [1- (3-
Methoxypropoxycarbonyl) ethyl] itaconate, and the like.

Among the itaconic esters represented by formulas (I-2) and (I-3), R ₂ has an alkoxy-substituted alkyl group as R ₂ and R ₅ has an alkyl group substituted with an aryl group; Representative compounds having a methyl group as R ₁ include monobenzyl-mono [1
-(2-methoxyethoxycarbonyl) ethyl] itaconate, monobenzyl-mono [1- (2-ethoxyethoxycarbonyl) ethyl] itaconate, mono (2-phenylethyl) -mono {1- [2- (n-propoxy)
[Ethoxycarbonyl] ethyl} itaconate, mono (1
-Phenylethyl) -mono {1- [2- (n-butoxy) ethoxycarbonyl] ethyl} itaconate;

Among the itaconic esters represented by formulas (I-2) and (I-3), R ₂ has an alkoxy-substituted alkyl group, R ₅ has an aryl group, and R ₁ has Representative compounds having a methyl group include monophenyl-mono [1- (2-methoxyethoxycarbonyl) ethyl] itaconate, monophenyl-mono [1- (2-ethoxyethoxycarbonyl) ethyl] itaconate and monophenyl-mono [1- (2-ethoxyethoxycarbonyl) ethyl] itaconate. (1-naphthyl) -mono ｛1
-[2- (n-propoxy) ethoxycarbonyl] ethyl {itaconate, monophenyl-mono} 1- [2-
(N-butoxy) ethoxycarbonyl] ethyl diitaconate, and the like.

Among the itaconic esters represented by formulas (I-2) and (I-3), R ₂ has an alkoxy-substituted alkyl group and R ₅ has a substituted aryl group;
A typical example of the compound having a methyl group as R ₁ is mono (4-methylphenyl) -mono [1-
(2-methoxyethoxycarbonyl) ethyl] itaconate, mono (4-methylphenyl) -mono [1- (2-
Ethoxyethoxycarbonyl) ethyl] itaconate,
Mono (4-chlorophenyl) -mono {1- [2- (n-
Propoxy) ethoxycarbonyl] ethyl {itaconate, mono (4-nitrophenyl) -mono} 1- [2-
(N-butoxy) ethoxycarbonyl] ethyl diitaconate, and the like.

Among the itaconic esters represented by the general formulas (I-2) and (I-3), R ₂ has an alkoxy-substituted alkyl group, R ₅ has a cycloalkyl group, and R ₁ As a typical example of the compound having a methyl group, monocyclohexyl-mono [1- (2
-Methoxyethoxycarbonyl) ethyl] itaconate, monocyclohexyl-mono [1- (2-ethoxyethoxycarbonyl) ethyl] itaconate, monocyclopentyl-mono {1- [2- (n-propoxy) ethoxycarbonyl] ethyl} itaconate, mono And cyclohexyl-mono {1- [2- (n-butoxy) ethoxycarbonyl] ethyl} itaconate.

Among the itaconic acid esters represented by formulas (I-2) and (I-3), R ₂ has an alkyl group substituted by an aryl group and R ₅ has an alkyl group;
Representative compounds having a methyl group as R ₁ include monomethyl-mono (1-benzyloxycarbonylethyl) itaconate and monoethyl-mono [1
-(1-Phenylethoxycarbonyl) ethyl] itaconate, mono (n-propyl) -mono [1- (2-phenylethoxycarbonyl) ethyl] itaconate, mono (n-hexyl) -mono (1-benzyloxycarbonylethyl) Itaconate, and the like.

Among the itaconic esters represented by formulas (I-2) and (I-3), R ₂ has an alkyl group substituted by an aryl group, and R ₅ has an alkoxy-substituted alkyl group; Representative examples of the compound having a methyl group as R ₁ include mono (2-methoxyethyl) -mono (1-benzyloxycarbonylethyl) itaconate and mono (2-ethoxyethyl) -mono [1-
(1-Phenylethoxycarbonyl) ethyl] itaconate, mono [2- (n-butoxy) ethyl] -mono [1
-(2-phenylethoxycarbonyl) ethyl] itaconate, and the like.

Among the itaconic esters represented by formulas (I-2) and (I-3), R ₂ has an alkyl group substituted with an aryl group, R ₅ has a cycloalkyl group, and Representative compounds having a methyl group as R ₁ include monocyclopentyl-mono (1-benzyloxycarbonylethyl) itaconate, monocyclopentyl-mono [1- (1-phenylethoxycarbonyl) ethyl] itaconate, monocyclohexyl −
Mono [1- (2-phenylethoxycarbonyl) ethyl] itaconate;

Among the itaconic esters represented by formulas (I-2) and (I-3), R ₂ has an alkyl group substituted by an aryl group and R ₅ has an aryl group;
Representative compounds having a methyl group as R ₁ include monophenyl-mono (1-benzyloxycarbonylethyl) itaconate, monophenyl-mono [1- (1-phenylethoxycarbonyl) ethyl] itaconate, Mono (1-naphthyl) -mono [1- (2-
Phenylethoxycarbonyl) ethyl] itaconate,
And the like.

Among the itaconic esters represented by formulas (I-2) and (I-3), R ₂ has an alkyl group substituted with an aryl group, R ₅ has a substituted aryl group, and Representative compounds having a methyl group as R ₁ include mono (4-methylphenyl) -mono (1-benzyloxycarbonylethyl) itaconate and mono (4-methylphenyl) -mono [1- (1- Phenylethoxycarbonyl) ethyl] itaconate, mono (4-chlorophenyl) -mono [1- (2-phenylethoxycarbonyl) ethyl] itaconate, and the like.

Among the itaconic esters represented by formulas (I-2) and (I-3), a cycloalkyl group as R ₂ , an alkyl group as R ₅ , and a methyl group as R ₁ Representative compounds having the following formulas are monomethyl-mono (1-cyclopentyloxycarbonylethyl) itaconate, monoethyl-mono (1-cyclohexyloxycarbonylethyl) itaconate, and mono (n-butyl) -mono (1-cyclohexyloxy). Carbonylethyl) itaconate, mono (n-hexyl)-
Mono (1-cyclohexyloxycarbonylethyl) itaconate; and the like.

Among the itaconic esters represented by the general formulas (I-2) and (I-3), a cycloalkyl group as R ₂ , an alkoxy-substituted alkyl group as R ₅ , and R ₁ Typical examples of the compound having a methyl group include mono (2-methoxyethyl) -mono (1-cyclopentyloxycarbonylethyl) itaconate and mono (2-ethoxyethyl) -mono (1-cyclohexyloxycarbonylethyl). Itaconate, mono [2- (n-butoxy) ethyl] -mono (1-cyclohexyloxycarbonylethyl) itaconate, and the like.

Among the itaconic esters represented by formulas (I-2) and (I-3), compounds having a cycloalkyl group as R ₂ and R ₅ and a methyl group as R ₁ A typical example is monocyclopentyl-
Mono (1-cyclopentyloxycarbonylethyl) itaconate, monocyclohexyl-mono (1-cyclohexyloxycarbonylethyl) itaconate, monocyclopentyl-mono (1-cyclohexyloxycarbonylethyl) itaconate, and the like.

Among the itaconic esters represented by formulas (I-2) and (I-3), a cycloalkyl group as R ₂ , an aryl group as R ₅ , and a methyl group as R ₁ Representative examples of the compound having the formula: monophenyl-mono (1-cyclopentyloxycarbonylethyl) itaconate, mono (1-naphthyl) -mono (1-cyclohexyloxycarbonylethyl) itaconate, and the like.

[0097] formula (I-2), among the itaconic acid ester represented by (I-3), a cycloalkyl group as R _2, having a substituted aryl group as R _5, and methyl as R ₁ Representative compounds having a group include
Mono (4-methylphenyl) -mono (1-cyclopentyloxycarbonylethyl) itaconate, mono (4-
Chlorophenyl) -mono (1-cyclohexyloxycarbonylethyl) itaconate, mono (4-nitrophenyl) -mono (1-cyclohexyloxycarbonylethyl) itaconate and the like can be mentioned.

Among the itaconic esters represented by formulas (I-2) and (I-3), an aryl group as R ₂ , an alkyl group as R ₅ , and a methyl group as R _1. Representative examples of the compound having the compound include monomethyl-mono (1-phenoxycarbonylethyl) itaconate, monoethyl-mono (1-phenoxycarbonylethyl) itaconate, and mono (n-butyl) -mono (1-
Phenoxycarbonylethyl) itaconate, mono (n
-Hexyl) -mono (1-phenoxycarbonylethyl) itaconate, monomethyl-mono [1- (1-naphthoxycarbonyl) ethyl] itaconate, monomethyl-mono [1- (2-naphthoxycarbonyl) ethyl] itaconate, and the like. No.

Among the itaconic esters represented by formulas (I-2) and (I-3), an aryl group as R ₂ , an alkoxy-substituted alkyl group as R ₅ , and methyl as R _1. Representative compounds having a group include mono (2-methoxyethyl) -mono (1-phenoxycarbonylethyl) itaconate and mono (2-methoxyethyl) itaconate.
Ethoxyethyl) -mono (1-phenoxycarbonylethyl) itaconate, mono [2- (n-butoxy) ethyl] -mono (1-phenoxycarbonylethyl) itaconate, mono- (2-methoxyethyl) -mono [1-
(1-naphthoxycarbonyl) ethyl] itaconate,
And the like.

In the itaconic esters represented by formulas (I-2) and (I-3), R ₂ has an aryl group substituted with an aryl group as R ₅ , and R ₅ has an alkyl group substituted with an aryl group. Representative compounds having a methyl group as ₁ include monobenzyl-mono (1-phenoxycarbonylethyl) itaconate, monobenzyl-mono [1- (1-naphthoxycarbonyl) ethyl] itaconate, and the like. .

Among the itaconic esters represented by formulas (I-2) and (I-3), an aryl group as R ₂ , a cycloalkyl group as R ₅ , and a methyl group as R ₁ As a typical example of the compound having the following formula, monocyclopentyl-mono (1-phenoxycarbonyl)
Ethyl] itaconate, monocyclohexyl-mono (1
-Phenoxycarbonyl) ethyl] itaconate, monocyclohexyl-mono [1- (1-naphthoxycarbonyl) ethyl] itaconate, and the like.

Representative of the itaconic esters represented by formulas (I-2) and (I-3), compounds having an aryl group as R ₂ and R ₅ and a methyl group as R _1. Typical examples are monophenyl-mono (1-phenoxycarbonylethyl) itaconate and mono (1-phenoxycarbonylethyl) itaconate.
Naphthyl) -mono (1-phenoxycarbonylethyl)
Itaconate, monophenyl-mono [1- (1-naphthoxycarbonyl) ethyl] itaconate, and the like.

Among the itaconic acid esters represented by formulas (I-2) and (I-3), an aryl group as R ₂ , a substituted aryl group as R ₅ , and a methyl group as R ₁ Representative compounds having the following formulas are mono (4-methylphenyl) -mono (1-phenoxycarbonylethyl) itaconate, mono (4-chlorophenyl) -mono (1-phenoxycarbonylethyl) itaconate, Methylphenyl) -mono [1- (1
-Naphthoxycarbonyl) ethyl] itaconate, and the like.

Among the itaconic esters represented by the general formulas (I-2) and (I-3), a substituted aryl group as R ₂ , an alkyl group as R ₅ , and a methyl group as R ₁ As a typical example of the compound having the following formula, monomethyl-mono [1- (3-methylphenoxycarbonyl)
Ethyl] itaconate, monomethyl-mono [1- (4-
Methylphenoxycarbonyl) ethyl] itaconate,
Monoethyl-mono [1- (4-methylphenoxycarbonyl) ethyl] itaconate, mono (n-butyl) -mono [1- (4-methylphenoxycarbonyl) ethyl]
Itaconate, mono (n-hexyl) -mono [1- (4
-Methylphenoxycarbonyl) ethyl] itaconate, monomethyl-mono [1- (4-nitrophenoxycarbonyl) ethyl] itaconate, and the like.

Among the itaconic esters represented by formulas (I-2) and (I-3), R ₂ has a substituted aryl group as R ₂ and an alkoxy group-substituted alkyl group as R ₅ ;
A typical example of the compound having a methyl group as R ₁ is mono (2-methoxyethyl) -mono [1-
(3-methylphenoxycarbonyl) ethyl] itaconate, mono (2-methoxyethyl) -mono [1- (4-
Methylphenoxycarbonyl) ethyl] itaconate,
Mono (2-ethoxyethyl) -mono [1- (4-methylphenoxycarbonyl) ethyl] itaconate, mono [2- (n-butoxy) ethyl] -mono [1- (4-methylphenoxycarbonyl) ethyl] itaconate, Mono (2-methoxyethyl) -mono [1- (4-nitrophenoxycarbonyl) ethyl] itaconate;

In the itaconic esters represented by formulas (I-2) and (I-3), R ₂ has a substituted aryl group as R ₂ , R ₅ has an alkyl group substituted with an aryl group, and Representative compounds having a methyl group as R ₁ include monobenzyl-mono [1- (3-methylphenoxycarbonyl) ethyl] itaconate and monobenzyl-mono [1- (4-methylphenoxycarbonyl) ethyl]. Itaconate, monobenzyl-mono [1-
(4-nitrophenoxycarbonyl) ethyl] itaconate, and the like.

Among the itaconic esters represented by formulas (I-2) and (I-3), the substituted aryl group as R ₂ , the cycloalkyl group as R ₅ , and the methyl as R ₁ Representative compounds having a group include
Monocyclopentyl-mono [1- (3-methylphenoxycarbonyl) ethyl] itaconate, monocyclopentyl-mono [1- (4-methylphenoxycarbonyl)
Ethyl] itaconate, monocyclohexyl-mono [1
-(4-methylphenoxycarbonyl) ethyl] itaconate, monocyclooctyl-mono [1- (4-methylphenoxycarbonyl) ethyl] itaconate, monocyclohexyl-mono [1- (4-nitrophenoxycarbonyl) ethyl] itaconate, etc. Is mentioned.

Among the itaconic esters represented by the general formulas (I-2) and (I-3), a substituted aryl group as R ₂ , an aryl group as R ₅ , and a methyl group as R ₁ Representative examples of the compound having the following are monophenyl-mono [1- (3-methylphenoxycarbonyl) ethyl] itaconate and monophenyl-mono [1-
(4-methylphenoxycarbonyl) ethyl] itaconate, mono (1-naphthyl) -mono [1- (4-methylphenoxycarbonyl) ethyl] itaconate, monophenyl-mono [1- (4-nitrophenoxycarbonyl) ethyl] itaconate And the like.

Among the itaconic acid esters represented by formulas (I-2) and (I-3), compounds having a substituted aryl group as R ₂ and R ₅ and a methyl group as R ₁ A typical example is mono (3-methylphenyl) -mono [1- (3-methylphenoxycarbonyl).
Ethyl] itaconate, mono (4-methylphenyl)-
Mono [1- (4-methylphenoxycarbonyl) ethyl] itaconate, mono (4-chlorophenyl) -mono [1- (4-methylphenoxycarbonyl) ethyl] itaconate, mono (4-methylphenyl) -mono [1-
(4-nitrophenoxycarbonyl) ethyl] itaconate, and the like.

Also, among the itaconic esters represented by the general formulas (I-2) and (I-3), representatives of those having various alkyl groups having 2 to 12 carbon atoms or phenyl groups as R _1. Typical examples are those represented by the general formula (I-
2) and (I-3), in various itaconic esters described above as examples of those containing a methyl group as R ₁ , the methyl group represented by R ₁ has 2 to 1 carbon atoms.
And various kinds of compounds having a structure substituted by two kinds of alkyl groups or phenyl groups.

Among the itaconic esters represented by the general formula (I-1), preferred are the monovalent organic groups R ₂
And R ₄ each independently have 1 to 6 carbon atoms.
Having 3 carbon atoms including an alkyl group or an alkoxy group
And compounds having an alkoxy-substituted alkyl group of from 6 to 6, particularly preferred among these are compounds having a hydrogen atom or a methyl group as R ₁ and R ₃ .

Among the itaconic esters represented by the general formulas (I-2) and (I-3), those which are preferable are each independently a monovalent organic group, R ₂ and R ₅ , each independently having a carbon atom. It is a compound having an alkoxy-substituted alkyl group having 3 to 6 carbon atoms, including an alkyl group or an alkoxy group having 1 to 6 carbon atoms. Particularly preferred among these are those having a hydrogen atom or a methyl group as R ₁ .

The present invention also provides a process for producing itaconic acid ester, characterized by reacting a salt of itaconic acid or a salt of itaconic acid half ester with an α-halocarboxylic acid ester. The itaconic acid ester produced by the method of the present invention includes various compounds represented by the aforementioned general formulas (I-1), (I-2) and (I-3).

Representative examples of the salt of itaconic acid used in the production method of the present invention include alkali metal salts such as lithium salt, sodium salt, potassium salt and cesium salt of itaconic acid; magnesium salt of itaconic acid; Alkaline earth metal salts such as calcium salts and barium salts; salts of itaconic acid with various organic bases such as tertiary amines such as triethylamine, tri-n-butylamine and N, N-dimethylbenzylamine. . Of these, alkali metal salts are particularly preferred.

Examples of the salt of itaconic acid half ester include salts of itaconic acid half ester represented by the following general formula (II).

[0116]

Embedded image

(In the formula, one of R ₆ and R ₇ is a hydrogen atom and the other is a monovalent organic group.)

A monovalent organic group R ₆ or R ₇ contained in the itaconic acid half ester represented by the general formula (II)
Representative examples of the compounds represented by formulas (I-2) and (I
Exemplified various kinds of can be given as specific ones of R ₅ is a monovalent organic group contained in the -3).

Among the itaconic acid half-esters represented by the general formula (II), typical compounds containing an alkyl group as R ₆ or R ₇ include monomethyl itaconate, monoethyl itaconate and monoethyl itaconate. (N-propyl) itaconate, mono (iso-propyl) itaconate, mono (n-butyl) itaconate, mono (is
o-butyl) itaconate, mono (n-hexyl) itaconate, mono (2-ethylhexyl) itaconate,
Mono (n-decyl) itaconate;

Among the itaconic acid half esters represented by the general formula (II), typical compounds having an alkoxy-substituted alkyl group as R ₆ or R ₇ include:
Mono (2-methoxyethyl) itaconate, mono (2-
Ethoxyethyl) itaconate, mono [2- (n-propoxy) ethyl] itaconate, mono [2- (n-butoxy) ethyl] itaconate, mono (3-methoxypropyl) itaconate, and the like.

Among the itaconic acid half esters represented by the general formula (II), a typical compound having an alkyl group substituted with an aryloxy group as R ₆ or R ₇ is mono (2-phenoxyethyl). ) Itaconate, mono [2- (4-methylphenoxy) ethyl] itaconate, and the like.

Among the itaconic acid half esters represented by the general formula (II), a typical compound having an alkyl group substituted by an aralkyloxy group as R ₆ or R ₇ is mono (2-benzyloxy). Ethyl) itaconate, mono [2- (2-phenylethoxy) ethyl]
Itaconate, and the like.

Among the itaconic acid half esters represented by the general formula (II), typical compounds having an alkyl group substituted with an aryl group as R ₆ or R ₇ include monobenzyl itaconate and mono ( 1-phenylethyl) itaconate, mono (2-phenylethyl) itaconate, and the like.

Among the itaconic acid half esters represented by the general formula (II), typical compounds having a cycloalkyl group as R ₆ or R ₇ include monocyclopentyl itaconate, monocyclohexyl itaconate and monocyclopentyl itaconate. (4-methylcyclohexyl) itaconate,
And the like.

Among the itaconic acid half esters represented by the general formula (II), typical compounds having an aryl group as R ₆ or R ₇ include monophenyl itaconate and mono (1-naphthyl) itaconate. And mono (2-naphthyl) itaconate.

Among the itaconic acid half esters represented by the general formula (II), typical compounds having a substituted aryl group as R ₆ or R ₇ include mono (3-methylphenyl) itaconate and mono ( 4-methylphenyl) itaconate, mono (4-nitrophenyl) itaconate, and the like.

Among the various itaconic acid half-esters described above, particularly preferred are those having 3 to 6 carbon atoms containing an alkyl group or an alkoxy group having 1 to 6 carbon atoms as R ₆ and R _7. It is a compound having a group-substituted alkyl group.

Representative examples of the above-mentioned salts of itaconic acid half ester include alkali metal salts such as lithium salt, sodium salt, potassium salt and cesium salt of itaconic acid half ester; magnesium salt and calcium salt of itaconic acid half ester. Salts, alkaline earth metal salts such as barium salts; triethylamine, tri-n-butylamine,
Salts of organic bases such as various tertiary amines such as N, N-dimethylbenzylamine and itaconic acid half ester,
And the like. Of these, particularly preferred are:
These are alkali metal salts.

As the salts of itaconic acid or the salts of itaconic acid half-ester, those prepared in advance may be used, or various reactions containing alkali metals may be added to the reaction system containing itaconic acid or itaconic acid half-ester. Various bases or organic bases containing bases and alkaline earth metals may be formed continuously or sequentially and by adding them separately.

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

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 and the like. And carbonates such as magnesium carbonate, calcium carbonate and barium carbonate.

The α-halocarboxylic acid esters used in the method of the present invention include various commonly used carboxylic acid esters having various halogen atoms such as fluorine, chlorine, bromine and iodine at the α-position. Can be used. A typical example of such an α-halocarboxylic acid ester is a compound represented by the following general formula (III).

[0133]

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.)

[0135] Such as typical alkyl groups of R ₁ are the α- halocarboxylic acid ester having represented by the general formula (III), R ₁ contained in the compounds of general formula (I-1) Among them, various ones exemplified as typical examples of the alkyl group can be mentioned. In addition, such α-
Representative examples of the monovalent organic group R ₂ contained in the halocarboxylic acid ester include those exemplified as typical examples of R ₂ contained in the aforementioned general formula (I-1).

Representative α-chlorocarboxylic acid esters among the α-halocarboxylic acid esters containing various R ₁ and R ₂ as described above include α-chlorophenyl acetates, chloroacetates, and the like. Examples of R ₁ include α-chlorocarboxylic acid esters having an alkyl group having 1 to 12 carbon atoms.

Specific examples of the α-chlorophenyl acetates include methyl α-chlorophenyl acetate, 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-decyl, α-chlorophenylacetic acid n-dodecyl, etc .; α-chlorophenylacetic acid 2-methoxyethyl, α-chlorophenylacetic acid 2-ethoxyethyl, α-chlorophenyl Alkoxy-substituted alkyl esters such as 2- (n-propoxy) ethyl acetate, 2- (n-butoxy) ethyl α-chlorophenylacetate, and 4-ethoxybutyl α-chlorophenylacetate;

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

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

Alkyl esters substituted with an aryl group such as benzyl chloroacetate, 2-phenylethyl chloroacetate and 1-phenylethyl chloroacetate; cycloalkyl esters such as cyclopentyl chloroacetate and cyclohexyl chloroacetate; phenyl chloroacetate and chloroacetate Aryl esters such as 1-naphthyl acetate; substituted aryl esters such as 4-methylphenyl chloroacetate, 4-chlorophenyl chloroacetate, and 4-nitrophenyl chloroacetate;

Among the α-chlorocarboxylic 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-
Alkyl esters such as n-propyl chloropropionate, n-butyl α-chloropropionate, n-hexyl α-chloropropionate, n-decyl α-chloropropionate and n-dodecyl α-chloropropionate;
2-methoxyethyl chloropropionate, 2-ethoxyethyl α-chloropropionate, 2- (n-propoxy) ethyl α-chloropropionate, 2- (n-butoxy) ethyl α-chloropropionate, α-chloropropion Alkoxy-substituted alkyl esters such as 4-ethoxybutyl acid;

Alkyl esters substituted with an aryl group such as benzyl α-chloropropionate, 2-phenylethyl α-chloropropionate and 1-phenylethyl α-chloropropionate; cyclopentyl α-chloropropionate, α-chloro Cycloalkyl esters such as cyclohexyl propionate; α-chloropropionic acid 4-
And substituted aryl esters such as methylphenyl, 4-chlorophenyl α-chloropropionate, and 4-nitrophenyl α-chloropropionate.

Specific examples of various α-chlorocarboxylic acid esters having an alkyl group having 2 to 12 carbon atoms as R ₁ include specific examples of α-chloropropionic acid esters. Among the various esters 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 can be mentioned.

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

Among the various compounds represented by the general formula (III) described above, when the monovalent organic group R ₂ has 3 carbon atoms including an alkyl group or an alkoxy group having 1 to 6 carbon atoms. Preferred are those having from 6 to 6 alkoxy-substituted alkyl groups and having a chlorine atom or a bromine atom as a halogen atom. Among such preferred compounds, α-haloacetic acid esters having a hydrogen atom or α-halopropionic acid esters having a methyl group are particularly preferred as R ₁ .

In order to prepare an itaconic ester by reacting a salt of itaconic acid or a salt of itaconic acid half ester with an α-halocarboxylic acid ester, it is necessary to prepare (a) a salt of itaconic acid or a salt of itaconic acid half ester. α-halocarboxylic acid ester is charged and reacted at once,
(B) a salt of itaconic acid or a salt of itaconic acid half ester and an α-halocarboxylic acid ester are simultaneously added to the reaction system; (c) a salt of itaconic acid or a salt of itaconic acid half ester is divided into α-halocarboxylic acid ester (D) a salt of itaconic acid by adding the above-mentioned various basic compounds to the mixture of itaconic acid or a mixture of half-esters of itaconic acid and α-halocarboxylate in a divided manner or continuously; Or reacting while forming a salt of itaconic acid half ester,
And other various reaction methods can be applied.

In the reaction, it is possible to carry out the reaction without using a solvent, depending on the type of the salt of itaconic acid or the salt of the half ester of itaconic acid or the type of the α-halocarboxylic acid ester. The reaction is preferably performed using a solvent.

Typical solvents used in this case include ketone compounds such as acetone, methyl ethyl ketone and methyl isobutyl ketone; glycol ethers such as ethylene glycol dimethyl ether, ethylene glycol diethyl ether, diethylene glycol dimethyl ether and diethylene glycol diethyl ether. Amide compounds such as N, N-dimethylformamide, N, N-dimethylacetamide and N-methylpyrrolidone; and sulfur-containing compounds such as dimethylsulfoxide and dimethylsulfolane. Among these, N, N are particularly preferable from the viewpoint of the solubility of the salt of itaconic acid or the salt of itaconic acid half ester.
-Dimethylformamide and N, N-dimethylacetamide.

In reacting an itaconic acid salt or a salt of itaconic acid half ester with an α-halocarboxylic acid ester, the latter α-halocarboxylic acid ester is used in an amount of 0.5 mol per 1 mol of the carboxylic acid base contained in the former. ~
The two may be reacted at a ratio of 4.0 mol, preferably 0.8 to 2.0 mol.

The reaction conditions must be appropriately set according to the type of the salt of itaconic acid or the salt of the itaconic acid half ester and the type of the α-halocarboxylic acid ester.
The reaction temperature may be about 50 to 130 ° C, and the reaction time may be about 0.5 to 150 hours.

[0151]

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 measurement device: JASCO FT / IR-610 manufactured by JASCO Corporation Sample preparation: Measured as a liquid film using a KBr cell

¹ H-NMR spectrum: Measuring device: JEOL JNM-EX270 (2, manufactured by JEOL Ltd.)
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

¹³ C-NMR spectrum: Measuring device: JEOL JNM-EX270 (6) manufactured by JEOL Ltd.
7.5 MHz) Solvent: deuterated chloroform Internal standard: tetramethylsilane

Example 1 In a four-necked flask equipped with a stirrer, a reflux condenser and a thermometer, 32.5 g (0.25 mol) of itaconic acid, 59.7 g (0.55 mol) of methyl chloroacetate, dimethylformamide 250 g (hereinafter abbreviated as DMF) were charged, 39.0 g (0.28 mol) of potassium carbonate was added, the temperature was raised to 70 ° C. with stirring, and the reaction was carried out at the same temperature for 15 hours.
After the obtained reaction mixture was cooled to room temperature, the formed potassium chloride salt was separated by filtration, and the filtrate was heated to 70 ° C. while evaporating DMF, unreacted methyl chloroacetate and the like under reduced pressure of 0.1 to 3 KPa. The minute was distilled off. Residue in toluene 30
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 magnesium sulfate 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 a thin-film distillation apparatus manufactured by Leybold of Germany to conduct colorless liquid di (methoxycarbonylmethyl) itaconate represented by the following formula (IV).
8 g were obtained. The yield of the target compound was 55.2% based on the raw material itaconic acid.

[0157]

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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 and
^{The 13} C-NMR spectrum, the respective data and the results of elemental analysis were as follows. ¹ H-NMR spectrum (δ ppm) 3.48 (2H, s), 3.74 (3H, s), 3.75 (3H, s), 4.64 (2H,
s), 4.71 (2H, s), 5.89 (1H, s), 6.47 (1H, s) ^13C -NMR spectrum (δ ppm) 37.1, 52.2, 61.0, 61.0, 130.3, 132.5, 165.3, 168.
0, 168.1, 169.9 ・ IR spectrum (cm ^-1 ) 3010 (CH), 2960 (CH), 2860 (CH), 1750 (C = O), 1642 (C
= C)-Elemental analysis results (numerical values in parentheses indicate calculated values) C: 48.26% (48.18%) H: 4.99% (5.15%)

Example 2 In place of 59.7 g of methyl chloroacetate, 67.4 g (0.55 mol) of ethyl chloroacetate was used.
The reaction was carried out in the same manner as in Example 1 except that the stirring was carried out for 20 hours. Subsequently, post-treatment and molecular distillation were carried out in the same manner as in Example 1 to obtain 39.4 of colorless liquid di (ethoxycarbonylmethyl) itaconate represented by the following formula (V).
g was obtained. The yield of the target compound is 5 based on the raw material of itaconic acid.
2.1%.

[0160]

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The IR spectrum of the obtained compound, ¹ H-
The NMR spectrum and ¹³ C-NMR spectrum, the respective data and the results of elemental analysis were as follows. ¹ H-NMR spectrum (δ ppm) 1.28 (6H, t, J = 7.8 Hz), 3.49 (2H, s), 4.25 (2H, q, J =
7.8Hz), 4.27 (2H, q, J = 7.8Hz), 4.65 (2H, s), 4.70 (2
H, s), 5.89 (1H, s), 6.47 (1H, s) ^13C -NMR spectrum (δ ppm) 14.1, 37.1, 61.1, 61.3, 61.4, 130.2, 132.5, 165.
3, 167.5, 167.6, 169.9 ・ IR spectrum (cm ^-1 ) 2984 (CH), 2960 (CH), 1750 (C = O), 1642 (C = C) ・ Elemental analysis results (Values in parentheses are calculated values. C: 51.70% (51.65%), H: 6.19% (6.00%)

Example 3 Instead of 59.7 g of methyl chloroacetate, n-chloroacetic acid was used.
Using 82.8 g (0.55 mol) of butyl and 7
The reaction was carried out in the same manner as in Example 1 except that stirring was performed at 0 ° C. for 25 hours. Subsequently, post-treatment and molecular distillation were carried out in the same manner as in Example 1 to obtain a colorless liquid of di (n-butoxycarbonylmethyl) itaconate of the formula (VI) 4
4.5 g were obtained. The yield of the target compound was 49.7% based on the raw material itaconic acid.

[0163]

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IR spectrum of the obtained compound, ¹ H-
The NMR spectrum and ¹³ C-NMR spectrum, the respective data and the results of elemental analysis were as follows. ¹ H-NMR spectrum (δ ppm) 0.93 (6H, t, J = 7.4 Hz), 1.38 (4H, m), 1.63 (4H, m), 3.
50 (2H, s), 4.16 (2H, t, J = 7.4Hz), 4.17 (2H, t, J = 7.4
Hz), 4.63 (2H, s), 4.70 (2H, s), 5.90 (1H, s), 6.48 (1
H, s) ¹³ C-NMR spectrum (δ ppm) 13.6, 19.0, 30.6, 37.0, 61.1, 65.3, 130.1, 132.6,
165.3, 167.6, 167.6, 169.9 ・ IR spectrum (cm ^-1 ) 2960 (CH), 2875 (CH), 1751 (C = O), 1641 (C = C) Elemental analysis results (Values in parentheses indicate calculated values. C) 56.83% (56.97%), H: 7.54% (7.31%)

Example 4 Instead of 59.7 g of methyl chloroacetate, 2-chloroacetic acid 2-
Using 83.9 g (0.55 mol) of methoxyethyl,
Example 1 and stirring was performed at 60 ° C. for 60 hours.
The reaction was carried out in the same manner as described above. Then, post-treatment and molecular distillation were carried out in the same manner as in Example 1 to give a colorless liquid of the following formula (VII)
40.9 g of di (2-methoxyethoxycarbonylmethyl) itaconate represented by the formula was obtained. The yield of the target compound was 45.1% based on the raw material itaconic acid.

[0166]

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The IR spectrum of the obtained compound is shown in FIG.
FIG. 4 shows the ¹ H-NMR spectrum. IR spectrum, ¹ H-NMR spectrum and
^{The 13} C-NMR spectrum, the respective data and the results of elemental analysis were as follows. ¹ H-NMR spectrum (δ ppm) 3.38 (6H, s), 3.50 (2H, s), 3.60 (4H, m), 4.31 (4
H, m), 4.68 (2H, s), 4.75 (2H, s), 5.90 (1H, s),
6.49 (1H, s) ¹³ C-NMR spectrum (δ ppm) 37.0, 58.9, 61.0, 61.1, 64.3, 70.1, 130.2,
132.5, 165.3, 167.5, 167.6, 169.8 IR spectrum (cm ^-1 ) 2952 (CH), 2884 (CH), 1746 (C = O), 1728 (C = O), 16
41 (CH)-Elemental analysis results (the figures in parentheses indicate calculated values) C: 49.88% (49.72%), H: 6.40% (6.12%)

Example 5 In place of 59.7 g of methyl chloroacetate, 91.6 g (0.55 mol) of methyl 2-chloropropionate was used.
Example 1 and stirring was performed at 70 ° C. for 50 hours.
The reaction was carried out in the same manner as described above. Then, post-treatment and molecular distillation were carried out in the same manner as in Example 1 to give a colorless liquid of the following formula (VIII)
32.3 g of di (1-methoxycarbonylethyl) itaconate represented by the formula was obtained. The yield of the target compound was 42.8% based on the raw material itaconic acid.

[0169]

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The IR spectrum of the obtained compound, ¹ H-
The NMR spectrum and ¹³ C-NMR spectrum, the respective data and the results of elemental analysis were as follows. ¹ H-NMR spectrum (δ ppm) 1.50 (6H, m), 3.48 (2H, s), 3.74 (3H, s), 3.75 (3
H, s), 4.68 (2H, m), 5.89 (1H, s), 6.47 (1H,
s) ¹³ C-NMR spectrum (δ ppm) 16.8, 37.1, 52.2, 68.7, 69.0, 130.3, 132.5, 165.
3, 168.0, 168.1, 169.9 ・ IR spectrum (cm ^-1 ) 3010 (CH), 2960 (CH), 2860 (CH), 1750 (C = O), 1642 (C
= C)-Elemental analysis results (the figures in parentheses indicate calculated values) C: 51.56% (51.65%), H: 5.88% (6.00%)

Example 6 Monomethyl itaconate 3 obtained by reacting itaconic anhydride with methyl alcohol was placed in the same reaction vessel as in Example 1.
To 6.0 g (0.25 mol) of methyl chloroacetate.
4 g (0.28 mol) and 250 g of DMF were charged, 38.7 g (0.28 mol) of potassium carbonate was added, the temperature was raised to 70 ° C. with stirring, and the reaction was carried out at the same temperature for 15 hours. After cooling the obtained reaction mixture to room temperature, the generated potassium chloride salt was separated by filtration. While heating the filtrate to 70 ° C., volatile components such as DMF and unreacted methyl chloroacetate were distilled off under reduced pressure of 0.1 to 3 KPa. The solution obtained by dissolving the residue in 300 g of toluene 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 magnesium sulfate was filtered off, toluene was distilled off under reduced pressure to obtain a yellow liquid crude product. This crude product was subjected to molecular distillation in the same manner as in Example 1 to obtain 31.9 g of a colorless liquid monomethyl-monomethoxycarbonylmethylitaconate represented by the following formulas (IX-1) and (IX-2).
I got The yield of the target compound was 59.1% based on the raw material monomethyl itaconate.

[0172]

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The IR spectrum of the obtained compound is shown in FIG.
FIG. 6 shows the ¹ H-NMR spectrum. IR spectrum, ¹ H-NMR spectrum and
^{The 13} C-NMR spectrum, the respective data and the results of elemental analysis were as follows. · ¹ H-NMR spectrum (δppm) 3.39 (2H, s ), 3.69 (3H, s), 3.76 (3H, s), 4.71 (2H,
s), 5.84 (1H, s), 6.43 (1H, s) ¹³ C-NMR spectrum (δ ppm) 37.4, 52.1, 52.2, 61.1, 129.9, 133.1, 165.5, 168.
1, 170.9 ・ IR spectrum (cm ^-1 ) 3010 (CH), 2958 (CH), 2850 (CH), 1762 (C = O), 1740 (C
= O), 1640 (C = C)-Elemental analysis results (numerical values in parentheses indicate calculated values) C: 50.12% (50.00%), H: 5.71% (5.59%)

Example 7 In place of 30.4 g of methyl chloroacetate, n-chloroacetic acid was used.
Using 42.2 g (0.28 mol) of butyl and 7
The reaction was carried out in the same manner as in Example 6, except that stirring was performed at 0 ° C. for 20 hours. Subsequently, post-treatment and molecular distillation were carried out in the same manner as in Example 6 to obtain 39% of colorless liquid monomethyl-mono (n-butoxycarbonylmethyl) itaconate represented by the following formulas (X-1) and (X-2). 0.5 g was obtained.
The yield of the target compound is 6 based on the starting material monomethyl itaconate.
1.2%.

[0175]

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The IR spectrum of the obtained compound, ¹ H-
The NMR spectrum and ¹³ C-NMR spectrum, the 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), 1.38 (2H, m), 1.64 (2H, m),
3.39 (2H, s), 3.70 (3H, s), 4.17 (2H, t, J = 7.3Hz), 4.
70 (2H, s), 5.83 (1H, s), 6.45 (1H, s) ^13C -NMR spectrum (δ ppm) 13.7, 19.0, 30.6, 37.4, 52.1, 61.2, 65.3, 129.8, 1
33.1, 165.5, 167.6, 170.9 ・ IR spectrum (cm ^-1 ) 2960 (CH), 2878 (CH), 1742 (C = O), 1640 (C = C) ・ Elemental analysis results (Values in parentheses are calculated values. C: 55.74% (55.81%), H: 6.88% (7.02%)

Example 8 Instead of 36.0 g of monomethyl itaconate, 46.5 g (0.25 mol) of mono (n-butyl) itaconate obtained by reacting itaconic anhydride with n-butyl alcohol was used. And stirring was performed at 70 ° C. for 20 hours.
The reaction was carried out in the same manner as in Example 6. Then, Example 6
Post-treatment and molecular distillation were carried out in the same manner as described above to obtain 35.6 g of colorless liquid mono (n-butyl) -mono (methoxycarbonylmethyl) itaconate represented by the following formulas (XI-1) and (XI-2). Was. The yield of the target compound was 55.2% based on the raw material itaconic anhydride.

[0178]

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The IR spectrum of the obtained compound is shown in FIG.
FIG. 8 shows the ¹ H-NMR spectrum. IR spectrum, ¹ H-NMR spectrum and
^{The 13} C-NMR spectrum, the 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.
40 (2H, s), 3.69 (3H, s), 4.17 (2H, t, J = 7.3Hz), 4.70
(2H, s), 5.81 (1H, s), 6.45 (1H, s) ¹³ C-NMR spectrum (δ ppm) 13.7, 19.0, 30.7, 37.5, 52.1, 60.9, 65.5, 129.9, 1
32.9, 165.2, 167.5, 171.0 ・ IR spectrum (cm ^-1 ) 2958 (CH), 2878 (CH), 1740 (C = O), 1640 (C = C) ・ Elemental analysis results (Values in parentheses are calculated values C: 55.73% (55.81%), H: 7.22% (7.02%)

Example 9 The procedure of Example 9 was repeated except that 34.3 g (0.28 mol) of methyl 2-chloropropionate was used in place of 30.4 g of methyl chloroacetate, and stirring was performed at 70 ° C. for 50 hours. The reaction was carried out in the same manner as in 6. Then, post-treatment and molecular distillation were carried out in the same manner as in Example 6 to give a colorless liquid of the following formula (XII-1)
And 29.4 g of monomethyl-mono (1-methoxycarbonylethyl) itaconate represented by (XII-2). The yield of the target compound was 51.0% based on the raw material monomethyl itaconate.

[0181]

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The IR spectrum of the obtained compound, ¹ H-
The data of NMR spectrum and ¹³ C-NMR spectrum and the result of elemental analysis were as follows. ¹ H-NMR spectrum (δ ppm) 1.52 (3H, d, J = 7.8 Hz), 3.40 (2H, s), 3.69 (3H, s), 3.
77 (3H, s), 5.12 (1H, q, J = 7.8Hz), 5.84 (1H, s), 6.4
2 (1H, s) ¹³ C-NMR spectrum (δ ppm) 17.0, 37.5, 52.1, 52.3, 68.8, 129.7, 133.2, 165.
5, 168.0, 170.9 ・ IR spectrum (cm ^-1 ) 3000 (CH), 2960 (CH), 2846 (CH), 1760 (C = O), 1740 (C
= O), 1640 (C = C)-Elemental analysis results (numerical values in parentheses indicate calculated values) C: 52.02% (52.17%), H: 5.98% (6.13%)

[0183]

The present invention is to provide a novel itaconic acid ester having an active ester group, and to react an itaconic acid salt or an itaconic acid half ester salt with an α-halocarboxylic acid ester. It is intended to provide a novel method for producing an itaconic ester having an active ester group.

[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 4.

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

FIG. 5 is an IR spectrum of the compound obtained in Example 6.

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

FIG. 7 is an IR spectrum of the compound obtained in Example 8.

FIG. 8 is a ¹ H-NMR spectrum of the compound obtained in Example 8.

 ──────────────────────────────────────────────────続 き Continued on front page (72) Inventor Hiroo Tanaka 2-10-10 Tenjinyamacho, Kishiwada-shi, Osaka F-term (reference) 4H006 AA01 AA02 AB46 AB99 AC48 KA05

Claims (8)

[Claims] 1. A compound represented by the following general formula (I-1), (I-2) or (I-3)
Abbreviated. ] Itaconic acid ester represented by the formula: Embedded image (Wherein R ₁ and R ₃ each independently represent a hydrogen atom, a phenyl group or an alkyl group having 1 to 12 carbon atoms,
₂ , R ₄ and R ₅ each independently represent a monovalent organic group. ) 2. The method according to claim 1, wherein R ₂ , R ₄ and R _{5 in} formula (I) are each independently an alkyl group, a substituted alkyl group, a cycloalkyl group, an aryl group or a substituted aryl group. The itaconic acid ester described in the above. 3. The compound of the formula (I) wherein R ₂ , R ₄ and R ₅ are each independently an alkoxy group having 3 to 6 carbon atoms including an alkyl group having 1 to 6 carbon atoms or an alkoxy group. The itaconic ester according to claim 1, which is a group-substituted alkyl group. 4. The itaconic ester according to claim 1, wherein R ₁ and R _{3 in} formula (I) are each independently a hydrogen atom or a methyl group. 5. A method for producing an itaconic ester, which comprises reacting a salt of itaconic acid or a salt of itaconic acid half ester with an α-halocarboxylic acid ester. 6. The method according to claim 5, wherein the itaconic acid half ester is a compound represented by the following general formula (II), and the α-halocarboxylic acid ester is a compound represented by the following general formula (III). A method for producing itaconic acid esters. Embedded image (In the formula, one of R ₆ and R ₇ is a hydrogen atom and the other is 1
Is a valence organic group. ) (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. One of R ₆ and R _{7 in} the general formula (II) and R ₂ in the general formula (III) each independently represent an alkyl group, a substituted alkyl group, a cycloalkyl group, or an aryl group. Or the method for producing an itaconic acid ester according to claim 6, which is a substituted aryl group. 8. One of R ₆ and R _{7 in} the general formula (II) and R ₂ in the general formula (III) each independently represent an alkyl group or an alkoxy group having 1 to 6 carbon atoms. The method for producing an itaconic acid ester according to claim 6, wherein the compound is an alkoxy-substituted alkyl group having 3 to 6 carbon atoms, including: