WO2024053502A1

WO2024053502A1 - METHOD FOR PRODUCING α-CHLOROACRYLIC ACID ESTER

Info

Publication number: WO2024053502A1
Application number: PCT/JP2023/031400
Authority: WO
Inventors: 淳白井; 暁久平野; 明俊尾形; 克親黒木
Original assignee: ダイキン工業株式会社
Priority date: 2022-09-09
Filing date: 2023-08-30
Publication date: 2024-03-14
Also published as: JP2024039659A; TW202421609A

Abstract

The present invention provides: a method for producing an α-chloroacrylic acid ester with excellent productivity or the like; and the like. The present invention discloses a method for producing a compound that is represented by formula (2), the method comprising a step A in which a compound that is represented by formula (1) is reacted with chlorine in the presence of a polar solvent. (In the formulae, each of R1 and R2 independently represents a hydrogen atom or an organic group, or alternatively, the R1 and R2 moieties combine with each other to form a ring together with an adjacent carbon atom; and R3 represents an alkyl group which may have one or more substituents, an aryl group which may have one or more substituents, or an aralkyl group which may have one or more substituents.)

Description

Method for producing α-chloroacrylic acid esters

The present disclosure relates to a method for producing α-chloroacrylic acid esters, etc.

As a method for producing α-chloroacrylic esters, there are known production methods that involve (1) dichlorination of acrylic ester and (2) dehydrochlorination reaction.

Patent Document 1 discloses that 1,1,1,3,3,3-hexafluoro-2-phenylpropan-2-yl acrylate is dichlorinated by reacting with chlorine in chloroform, and then is dechlorinated by reacting with pyridine. It is described that 1,1,1,3,3,3-hexafluoro-2-phenylpropan-2-yl α-chloroacrylate was produced by hydrogen chloride.

Patent Document 2 discloses that while irradiating light, acrylic acid or its ester is supplied at a constant flow rate while carbon tetrachloride is stirred, and at the same time, chlorine gas is blown in at a constant flow rate to perform a chlorination reaction. It is described that dichloropropionic acid or its ester was produced.

Japanese Unexamined Patent Publication No. 64-26611 Japanese Unexamined Patent Publication No. 134343/1983

When chloroform is used as a solvent as in the dichlorination reaction of Patent Document 1, C ₂ Cl ₆ is produced as a by-product. Since C ₂ Cl ₆ has sublimation property, there is a problem in that it reduces operability during distillation purification. Further, in the dichlorination reaction of Patent Document 2, since the reaction proceeds by a radical mechanism, there is a problem that the polymerization (or dimerization) reaction of acrylic acid or its ester proceeds, reducing the yield. There is also the problem that the polychlorination reaction tends to proceed due to the radical mechanism.

One object of the present disclosure is to provide a method for producing α-chloroacrylic acid esters with excellent productivity and the like.

The present disclosure includes the following aspects.
Item 1.
The following formula (2):

(In the formula,
R ¹ and R ² are each independently a hydrogen atom or an organic group, or
R ¹ and R ² are bonded to each other to form a ring with adjacent carbon atoms,
R ³ is an alkyl group that may have one or more substituents, an aryl group that may have one or more substituents, or one or more substituents. It is an aralkyl group. ) A method for producing a compound represented by
In the presence of a polar solvent, the following formula (1):

(In the formula, R ¹ , R ² , and R ³ have the same meanings as above.)
Step A of reacting the compound represented by with chlorine
method including.
Item 2.
The following formula (3):

(In the formula, R ¹ , R ² , and R ³ have the same meanings as above.)
Step A of reacting the compound represented by with chlorine, and Step B of reacting the reaction product of step A with a base.
method including.
Item 3.
Item 3. The method according to item 1 or 2, wherein the polar solvent is at least one selected from the group consisting of nitrile solvents, ester solvents, carbonate solvents, and carboxylic acid solvents. Item 4.
4. The method according to any one of Items 1 to 3, wherein the polar solvent has a Rohrschneider polarity parameter P' of 4.3 or more (provided that the polar solvent is not an alcoholic solvent).
Item 5.
The method according to any one of Items 1 to 4, wherein the amount of the polar solvent used is within the range of 100 to 10,000 parts by mass based on 100 parts by mass of the compound represented by the formula (1).
Item 6.
6. The method according to any one of items 1 to 5, wherein the step A is performed under light shielding.
Section 7.
R ¹ and R ² are each independently a hydrogen atom, an alkyl group which may have one or more substituents, a cycloalkyl group which may have one or more substituents, one Item 7. The method according to any one of Items 1 to 6, wherein the method is an aryl group which may have the above substituents, or an aralkyl group which may have one or more substituents.
Section 8.
8. The method according to any one of Items 1 to 7, wherein R ³ is a haloalkyl group, a haloaryl group, or a haloaralkyl group.
Item 9.
The following formula (3A):

A compound represented by
Item 10.
The following formula (3):

(In the formula,
R ¹ and R ² are each independently a hydrogen atom or an organic group, or
R ¹ and R ² are bonded to each other to form a ring with adjacent carbon atoms,
R ³ is an alkyl group that may have one or more substituents, an aryl group that may have one or more substituents, or one or more substituents. It is an aralkyl group. ) and a composition comprising water,
A composition having a water content in the range of 0.001 to 0.1% by mass.
Item 11.
The following formula (3):

(In the formula,
R ¹ and R ² are each independently a hydrogen atom or an organic group, or
R ¹ and R ² are bonded to each other to form a ring with adjacent carbon atoms,
R ³ is an alkyl group that may have one or more substituents, an aryl group that may have one or more substituents, or one or more substituents. It is an aralkyl group. ) and the following formula (4A):
R ³¹ -OH (4A)
(In the formula, R ³¹ is an alkyl group that may have one or more substituents, an aryl group that may have one or more substituents, or a (It is an aralkyl group that may be
A compound represented by the following formula (4B):

(In the formula, R ³² is an alkyl group that may have one or more substituents, an aryl group that may have one or more substituents, or an alkyl group that may have one or more substituents. (It is an aralkyl group that may be
A compound represented by and the following formula (4C):

(In the formula, R ³³ is an alkyl group that may have one or more substituents, an aryl group that may have one or more substituents, or an alkyl group that may have one or more substituents. (It is an aralkyl group that may be
A composition comprising at least one selected from the group consisting of compounds represented by
A composition that satisfies at least one of the following (a), (b), and (c):
(a) The content of the compound represented by the formula (4A) is within the range of 0.01 to 5% by mass,
(b) the content of the compound represented by formula (4B) is within the range of 0.01 to 1.5% by mass;
(c) The content of the compound represented by formula (4C) is within the range of 0.01 to 1.5% by mass.
Item 12.
The following formula (3):

(In the formula,
R ¹ and R ² are each independently a hydrogen atom or an organic group, or
R ¹ and R ² are bonded to each other to form a ring with adjacent carbon atoms,
R ³ is an alkyl group that may have one or more substituents, an aryl group that may have one or more substituents, or one or more substituents. It is an aralkyl group. ), and has a Hazen color number of 100 or less.
Item 13.
The following formula (3):

(In the formula,
R ¹ and R ² are each independently a hydrogen atom or an organic group, or
R ¹ and R ² are bonded to each other to form a ring with adjacent carbon atoms,
R ³ is an alkyl group that may have one or more substituents, an aryl group that may have one or more substituents, or one or more substituents. It is an aralkyl group. ), and has a chlorine ion content of 1000 ppm or less.

According to the present disclosure, a method for producing α-chloroacrylic acid with excellent productivity and the like is provided.

The above summary of the present disclosure is not intended to describe each disclosed embodiment or every implementation of the present disclosure.

The following description of the disclosure more specifically exemplifies example embodiments. In several places in this disclosure, guidance is provided through examples, and the examples can be used in various combinations. In each case, the exemplary group can function as a non-exclusive and representative group.

All publications, patents, and patent applications cited herein are incorporated by reference in their entirety.

1. Unless otherwise specified , symbols and abbreviations used herein can be understood to have the meanings commonly used in the technical field to which this disclosure pertains, in accordance with the context of this specification.

As used herein, the phrase "contains" is intended to include the phrase "consisting essentially of" and the phrase "consisting of."

Unless otherwise specified, the steps, treatments, or operations described herein may be performed at room temperature. As used herein, room temperature can mean a temperature within the range of 10-40°C.

In this specification, the expression "C _nm " (where n and m are each an integer of 1 or more, and n<m) refers to the number of carbon atoms, as commonly understood by those skilled in the art. is greater than or equal to n and less than or equal to m.

In this specification, examples of the "halogen atom" include fluorine, chlorine, bromine, and iodine.

As used herein, the term "organic group" refers to a group formed by removing one hydrogen atom from an organic compound.
The "organic group" includes, for example,
A hydrocarbon group that may have one or more substituents,
a non-aromatic heterocyclic group which may have one or more substituents; a heteroaryl group which may have one or more substituents;
cyano group,
aldehyde group,
carboxyl group,
RO-,
RS-,
RCO-,
_RSO2- ,
ROCO-, and ROSO _2-
(In these formulas, R is independently,
A hydrocarbon group that may have one or more substituents,
A non-aromatic heterocyclic group which may have one or more substituents, or a heteroaryl group which may have one or more substituents)
can be mentioned.

Examples of the "substituent" include a halogen atom, a cyano group, an amino group, an alkoxy group, and an alkylthio group. Note that two or more substituents may be the same or different.

In the present specification, examples of the "hydrocarbon group" include an alkyl group, an alkenyl group, an alkynyl group, a cycloalkyl group, a cycloalkenyl group, a cycloalkadienyl group, an aryl group, and an aralkyl group.

In this specification, "alkyl group" includes, for example, methyl, ethyl, propyl (n-propyl, isopropyl), butyl (n-butyl, isobutyl, sec-butyl, tert-butyl), pentyl, and hexyl. , a linear or branched C _1-20 alkyl group.

As used herein, the term "haloalkyl group" means an alkyl group having one or more halogen atoms as a substituent. In the case of an alkyl group having two or more halogen atoms as a substituent, each halogen atom may be the same or different from each other. The "haloalkyl group" can be, for example, a fluoroalkyl group (eg, a perfluoroalkyl group). Examples of the "haloalkyl group" include trifluoromethyl, pentafluoroethyl, heptafluoropropyl (e.g., n-heptafluoropropyl, heptafluoroisopropyl), and nonafluorobutyl (e.g., n-nonafluorobutyl, nonafluorot). -butyl), straight-chain or branched haloC _1-20 alkyl groups.

As used herein, examples of "alkoxy group" include methoxy, ethoxy, propoxy (n-propoxy, isopropoxy), butoxy (n-butoxy, isobutoxy, sec-butoxy, tert-butoxy), pentyloxy, and hexyl. Examples include straight-chain or branched C _1-20 alkoxy groups such as oxy.

As used herein, examples of "alkylthio group" include methylthio, ethylthio, propylthio (n-propylthio, isopropylthio), butylthio (n-butylthio, isobutylthio, sec-butylthio, tert-butylthio), pentylthio, and hexylthio. Examples include straight-chain or branched C _1-20 alkylthio groups.

In the present specification, examples of "alkenyl group" include vinyl, 1-propen-1-yl, 2-propen-1-yl, isopropenyl, 2-buten-1-yl, 4-penten-1-yl , and straight-chain or branched C _2-20 alkenyl groups such as 5-hexen-1-yl.

In this specification, examples of "alkynyl group" include ethynyl, 1-propyn-1-yl, 2-propyn-1-yl, 4-pentyn-1-yl, and 5-hexyn-1-yl. , a straight-chain or branched C _2-20 alkynyl group.

As used herein, the "cycloalkyl group" includes, for example, C _3-10 cycloalkyl groups such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, and cycloheptyl.

As used herein, the "cycloalkenyl group" includes, for example, C _3-10 cycloalkenyl groups such as cyclopropenyl, cyclobutenyl, cyclopentenyl, cyclohexenyl, and cycloheptenyl.

As used herein, examples of "cycloalkadienyl group" include cyclobutadienyl, cyclopentadienyl, cyclohexadienyl, cycloheptadienyl, cyclooctadienyl, cyclononadienyl, and cyclodecadienyl. Examples include C _4-20 cycloalkadienyl groups such as enyl.

In this specification, the "aryl group" can be monocyclic, bicyclic, tricyclic, or tetracyclic, for example. Examples of the "aryl group" include C _6-20 aryl groups such as phenyl, 1-naphthyl, 2-naphthyl, 2-biphenyl, 3-biphenyl, 4-biphenyl, and 2-anthryl.

As used herein, the term "haloaryl group" means an aryl group having one or more halogen atoms as a substituent. In the case of an aryl group having two or more halogen atoms as substituents, each halogen atom may be the same or different from each other. The "haloaryl group" can be, for example, a fluoroaryl group. Examples of the "haloaryl group" include halo C _6-20 aryl groups such as fluorophenyl and fluoronaphthyl.

As used herein, examples of "aralkyl group" include benzyl, phenethyl, diphenylmethyl, 1-naphthylmethyl, 2-naphthylmethyl, 2,2-diphenylethyl, 3-phenylpropyl, 4-phenylbutyl, 5- C _7-19 aryl groups such as phenylpentyl, 2-biphenylmethyl, 3-biphenylmethyl, and 4-biphenylmethyl are mentioned.

As used herein, the term "haloaralkyl group" means an aralkyl group having one or more halogen atoms as a substituent. In the case of an aralkyl group having two or more halogen atoms as substituents, each halogen atom may be the same or different from each other. The "haloaralkyl group" can be, for example, a fluoroaralkyl group. Examples of the "haloaralkyl group" include haloC _7-19 aryl groups such as fluorobenzyl, 1,3-hexafluoro-2-phenylpropyl, and fluorophenethyl.

As used herein, the term "non-aromatic heterocyclic group" means a group formed by removing one hydrogen atom from a non-aromatic heterocyclic ring. The "non-aromatic heterocyclic group" can be, for example, monocyclic, bicyclic, tricyclic, or tetracyclic. The "non-aromatic heterocyclic group" can be saturated or unsaturated. The "non-aromatic heterocyclic group" can be, for example, a 5- to 18-membered non-aromatic heterocyclic group. The "non-aromatic heterocyclic group" is, for example, a non-aromatic heterocyclic ring containing, in addition to carbon atoms, 1 to 4 heteroatoms selected from oxygen atoms, sulfur atoms, and nitrogen atoms as ring constituent atoms. can be a base.

Examples of the "non-aromatic heterocyclic group" include tetrahydrofuryl, oxazolidinyl, imidazolinyl (e.g. 1-imidazolinyl, 2-imidazolinyl, 4-imidazolinyl), aziridinyl (e.g. 1-aziridinyl, 2-aziridinyl), pyrrolidinyl. (e.g. 1-pyrrolidinyl, 2-pyrrolidinyl, 3-pyrrolidinyl), piperidinyl (e.g. 1-piperidinyl, 2-piperidinyl, 3-piperidinyl), azepanyl (e.g. 1-azepanyl, 2-azepanyl, 3-azepanyl, 4 -Azepanyl), azocanyl (e.g. 1-azocanyl, 2-azocanyl, 3-azocanyl, 4-azocanyl), piperazinyl (e.g. 1,4-piperazin-1-yl, 1,4-piperazin-2-yl), Diazepinyl (e.g. 1,4-diazepin-1-yl, 1,4-diazepin-2-yl, 1,4-diazepin-5-yl, 1,4-diazepin-6-yl), diazocanyl (e.g. 1 ,4-diazocan-1-yl, 1,4-diazocan-2-yl, 1,4-diazocan-5-yl, 1,4-diazocan-6-yl, 1,5-diazocan-1-yl, 1 , 5-diazocan-2-yl, 1,5-diazocan-3-yl), tetrahydropyranyl (e.g. tetrahydrofuran-4-yl), morpholinyl (e.g. 4-morpholinyl), thiomorpholinyl (e.g. 4-thiomorpholinyl) , 2-oxazolidinyl, dihydrofuryl, dihydropyranyl, and dihydroquinolyl.

In the present specification, the "heteroaryl group" can be, for example, monocyclic, bicyclic, tricyclic, or tetracyclic. The "heteroaryl group" can be, for example, a 5- to 18-membered heteroaryl group. The "heteroaryl group" can be, for example, a heteroaryl group containing 1 to 4 heteroatoms selected from oxygen atoms, sulfur atoms, and nitrogen atoms in addition to carbon atoms as ring constituent atoms. . The "heteroaryl group" includes a "monocyclic heteroaryl group" and an "aromatic fused heterocyclic group."

Examples of the "monocyclic heteroaryl group" include pyrrolyl (e.g., 1-pyrrolyl, 2-pyrrolyl, 3-pyrrolyl), furyl (e.g., 2-furyl, 3-furyl), and thienyl (e.g., 2-pyrrolyl). thienyl, 3-thienyl), pyrazolyl (e.g. 1-pyrazolyl, 3-pyrazolyl, 4-pyrazolyl), imidazolyl (e.g. 1-imidazolyl, 2-imidazolyl, 4-imidazolyl), isoxazolyl (e.g. 3-isoxazolyl, 4) -isoxazolyl, 5-isoxazolyl), oxazolyl (e.g. 2-oxazolyl, 4-oxazolyl, 5-oxazolyl), isothiazolyl (e.g. 3-isothiazolyl, 4-isothiazolyl, 5-isothiazolyl), thiazolyl (e.g. 2-thiazolyl, 4-thiazolyl, 5-thiazolyl), triazolyl (e.g. 1,2,3-triazol-3-yl, 1,2,4-triazol-4-yl), oxadiazolyl (e.g. 1,2,4-oxadizolyl) azol-3-yl, 1,2,4-oxadiazol-5-yl), thiadiazolyl (e.g. 1,2,4-thiadiazol-3-yl, 1,2,4-5-yl), tetrazolyl, Pyridyl (e.g. 2-pyridyl, 3-pyridyl, 4-pyridyl), pyridazinyl (e.g. 3-pyridazinyl, 4-pyridazinyl), pyrimidinyl (e.g. 2-pyrimidinyl, 4-pyrimidinyl, 5-pyrimidinyl), pyrazinyl, etc. can be mentioned.

Examples of the "aromatic fused heterocyclic group" include isoindolyl (e.g. 1-isoindolyl, 2-isoindolyl, 3-isoindolyl, 4-isoindolyl, 5-isoindolyl, 6-isoindolyl, 7-isoindolyl), indolyl (e.g. : 1-indolyl, 2-indolyl, 3-indolyl, 4-indolyl, 5-indolyl, 6-indolyl, 7-indolyl), benzo[b]furanyl (e.g. 2-benzo[b]furanyl, 3-benzo[ b]furanyl, 4-benzo[b]furanyl, 5-benzo[b]furanyl, 6-benzo[b]furanyl, 7-benzo[b]furanyl), benzo[c]furanyl (e.g. 1-benzo[c] ] Furanyl, 4-benzo[c]furanyl, 5-benzo[c]furanyl), benzo[b]thienyl, (e.g. 2-benzo[b]thienyl, 3-benzo[b]thienyl, 4-benzo[b] ]thienyl, 5-benzo[b]thienyl, 6-benzo[b]thienyl, 7-benzo[b]thienyl), benzo[c]thienyl (e.g. 1-benzo[c]thienyl, 4-benzo[c] thienyl, 5-benzo[c]thienyl), indazolyl (e.g. 1-indazolyl, 2-indazolyl, 3-indazolyl, 4-indazolyl, 5-indazolyl, 6-indazolyl, 7-indazolyl), benzimidazolyl (e.g. 1- benzimidazolyl, 2-benzimidazolyl, 4-benzimidazolyl, 5-benzimidazolyl), 1,2-benzisoxazolyl (e.g. 1,2-benzisoxazol-3-yl, 1,2-benzisoxazol-4-yl) , 1,2-benzisoxazol-5-yl, 1,2-benzisoxazol-6-yl, 1,2-benzisoxazol-7-yl), benzoxazolyl (e.g. 2-benzoxazol-yl) 4-benzoxazolyl, 5-benzoxazolyl, 6-benzoxazolyl, 7-benzoxazolyl), 1,2-benzisothiazolyl (e.g. 1,2-benzoisothiazole 3-yl, 1,2-benzisothiazol-4-yl, 1,2-benzisothiazol-5-yl, 1,2-benzisothiazol-6-yl, 1,2-benzisothiazol-7-yl yl), benzothiazolyl (e.g. 2-benzothiazolyl, 4-benzothiazolyl, 5-benzothiazolyl, 6-benzothiazolyl, 7-benzothiazolyl), isoquinolyl (e.g. 1-isoquinolyl, 3-isoquinolyl, 4-isoquinolyl, 5-isoquinolyl), quinolyl (e.g. 2-quinolyl, 3-quinolyl, 4-quinolyl, 5-quinolyl, 8-quinolyl), cinnolinyl (e.g. 3-cinnolinyl, 4-cinnolinyl, 5-cinnolinyl, 6-cinnolinyl, 7-cinnolinyl, 8- cinnolinyl), phthalazinyl (e.g. 1-phthalazinyl, 4-phthalazinyl, 5-phthalazinyl, 6-phthalazinyl, 7-phthalazinyl, 8-phthalazinyl), quinazolinyl (e.g. 2-quinazolinyl, 4-quinazolinyl, 5-quinazolinyl, 6-phthalazinyl) Quinazolinyl, 7-quinazolinyl, 8-quinazolinyl), quinoxalinyl (e.g. 2-quinoxalinyl, 3-quinoxalinyl, 5-quinoxalinyl, 6-quinoxalinyl, 7-quinoxalinyl, 8-quinoxalinyl), pyrazolo[1,5-a]pyridyl ( Examples: pyrazolo[1,5-a]pyridin-2-yl, pyrazolo[1,5-a]pyridin-3-yl, pyrazolo[1,5-a]pyridin-4-yl, pyrazolo[1,5- a] pyridin-5-yl, pyrazolo[1,5-a]pyridin-6-yl, pyrazolo[1,5-a]pyridin-7-yl), imidazo[1,2-a]pyridyl (e.g. imidazo [1,2-a]pyridin-2-yl, imidazo[1,2-a]pyridin-3-yl, imidazo[1,2-a]pyridin-5-yl, imidazo[1,2-a]pyridine -6-yl, imidazo[1,2-a]pyridin-7-yl, and imidazo[1,2-a]pyridin-8-yl).

2. In one embodiment of the method for producing a compound represented by formula (2) , the following formula (2):

(In the formula, R ¹ , R ² , and R ³ have the same meanings as above.)
A method for producing the compound represented by the following formula (1) in the presence of a polar solvent:

(In the formula, R ¹ , R ² , and R ³ have the same meanings as above.)
This method includes step A of reacting the compound represented by chlorine with chlorine.

(Compound represented by formula (1))
R ¹ and R ² are not particularly limited as long as the reaction proceeds. R ¹ and R ² are each independently preferably a hydrogen atom or a hydrocarbon group which may have one or more substituents; an alkyl group which may have one or more substituents, a cycloalkyl group which may have one or more substituents, an aryl group which may have one or more substituents, or an alkyl group which may have one or more substituents. More preferably, it is an aralkyl group which may have a hydrogen atom, a C _1-20 alkyl group which may have one or more substituents, a C aralkyl group which may have one or more substituents. It is _{a 5-20} cycloalkyl group, a C _6-20 aryl group which may have one or more substituents, or a C _7-20 aralkyl group which may have one or more substituents. is even more preferable. Examples of the substituent include, but are not limited to, a halogen atom, a cyano group, an amino group, an alkoxy group, and an alkylthio group.

In one embodiment, at least one of R ¹ and R ² is preferably a hydrogen atom, and more preferably both R ¹ and R ² are hydrogen atoms.

When R ¹ and R ² are bonded to each other to form a ring with adjacent carbon atoms, examples of the ring include cyclopentane, cyclohexane, cycloheptane, cyclooctane, cyclopentene, cyclohexene, cycloheptene, cyclo Examples include octene, benzene, and naphthalene.

R ³ is an alkyl group that may have one or more substituents, an aryl group that may have one or more substituents, or one or more substituents. An aralkyl group, a C _1-20 alkyl group which may have one or more substituents, a C 6-20 aryl group which may have one or more substituents, or a C _6-20 aryl group which may have one or more substituents. More preferably, it is a C _7-20 aralkyl group which may have a substituent. Examples of the substituent include, but are not limited to, a halogen atom, a cyano group, an amino group, an alkoxy group, and an alkylthio group. Preferably, the one or more substituents are at least a halogen atom (eg, fluorine).

In one embodiment, R ³ is preferably a haloalkyl group, a haloaryl group, or a haloaralkyl group, and is a haloC _1-20 alkyl group, a haloC _6-20 aryl group, or a haloC _7-20 aralkyl group. It is even more preferable that there be. In this embodiment, R ³ is preferably a fluoroalkyl group, a fluoroaryl group, or a fluoroaralkyl group, and is a fluoroC _1-20 alkyl group, a fluoroC _6-20 aryl group, or a fluoroC _7-20 aralkyl group. More preferably, it is a group.

(chlorine)
The chlorine may be liquid chlorine or the like, but is usually chlorine gas. As a method of contacting the compound represented by formula (1) with chlorine, for example, chlorine gas is continuously or intermittently (intermittently) supplied to a reaction system containing the compound represented by formula (1). Examples include methods.

The amount of chlorine used is, for example, 1 mol or more, preferably 1.5 mol or more, and more preferably 2.5 mol or more, per 1 mol of the compound represented by formula (1). The amount of chlorine used is, for example, 5 mol or less, preferably 4 mol or less, more preferably 3 mol or less, per 1 mol of the compound represented by formula (1). The amount of chlorine used may be, for example, in the range of 1 to 5 mol, preferably in the range of 1.5 to 4 mol, per 1 mol of the compound represented by formula (1).

(polar solvent)
The reaction between the compound represented by formula (1) and chlorine is carried out in the presence of a polar solvent. Although not bound by any particular theory, it is believed that the use of a polar solvent facilitates the progress of the reaction based on the ionic mechanism.

The polar solvent is not particularly limited as long as it has polarity. The polar solvent may be a protic polar solvent or an aprotic polar solvent. Examples of the polar solvent include polar organic solvents such as ketone solvents, carboxylic acid solvents, ester solvents, carbonate solvents, nitrile solvents, amide solvents, and sulfoxide solvents.

Examples of ketone solvents include methyl ethyl ketone and acetone.

Examples of carboxylic acid solvents include formic acid and acetic acid.

Examples of ester solvents include ethyl acetate, butyl acetate, and the like.

Examples of carbonate-based solvents include ethylene carbonate, propylene carbonate, and butylene carbonate.

Examples of nitrile solvents include acetonitrile, propionitrile, and benzonitrile.

Examples of the amide solvent include formamide, N,N-dimethylformamide, and N-methylpyrrolidone.

Examples of the sulfoxide solvent include dimethyl sulfoxide.

In one embodiment, the polar solvent is preferably at least one selected from the group consisting of nitrile solvents, ester solvents, carbonate solvents, and carboxylic acid solvents.

In one embodiment, the polar solvent is preferably not an alcoholic solvent (eg, methanol, ethanol).

The Rohrschneider polarity parameter P' of the polar solvent is preferably 4.3 or more, more preferably 4.4 or more. The upper limit of the polarity parameter P' is not particularly limited, but may be, for example, 10 or less. The polarity parameter P' may be in the range of 4.3 to 10, for example.

The dielectric constant of the polar solvent at 25° C. is preferably 5.5 or more, more preferably 6 or more. The upper limit of the relative permittivity is not particularly limited, but is, for example, 50 or less. The dielectric constant may be in the range of 5.5 to 50, for example.

The amount of the polar solvent used may be, for example, 100 parts by mass or more, 150 parts by mass or more, 200 parts by mass or more, or 250 parts by mass or more with respect to 100 parts by mass of the compound represented by formula (1). . The amount of the polar solvent used is, for example, 10,000 parts by mass or less, 7,000 parts by mass or less, 5,000 parts by mass or less, 3,000 parts by mass or less, or 1,000 parts by mass or less, based on 100 parts by mass of the compound represented by formula (1). It may be. The amount of the polar solvent to be used may be, for example, in the range of 100 to 10,000 parts by mass based on 100 parts by mass of the compound represented by formula (1).

(other ingredients)
Step A may optionally be carried out in the presence of other components (eg a catalyst), but it is also preferably carried out in the absence of other components, particularly in the absence of a catalyst. The catalyst includes a catalyst that heterolyzes chlorine (eg, a chloride such as _I2 , ICl, _SbCl3 , _SbCl5 , _AlCl3 , _FeCl2, etc.).

(Reaction temperature and reaction time)
The reaction temperature and reaction time in Step A are not particularly limited as long as the reaction proceeds.
The reaction temperature is, for example, -80°C or higher, preferably -20°C or higher, more preferably 0°C or higher, and may be 10°C or higher. The reaction temperature is, for example, 100°C or lower, preferably 80°C or lower, more preferably 60°C or lower, and may be 40°C or lower. The reaction temperature may be, for example, in the range of -80 to 100°C, preferably in the range of -20 to 80°C, more preferably in the range of 0 to 60°C.
The reaction time can be, for example, 1 hour or more, 5 hours or more, or 10 hours or more. The reaction time may be, for example, 48 hours or less, preferably 24 hours or less, and more preferably 12 hours or less. The reaction time can be, for example, within the range of 1 to 48 hours, preferably within the range of 1 to 24 hours, more preferably within the range of 1 to 12 hours.

In one embodiment, step A is preferably performed under light shielding. In this embodiment, the polymerization (or dimerization) reaction can be suppressed and the yield can be further improved. Furthermore, this embodiment does not require a light irradiation device, and is excellent in terms of simplicity, economy, and the like.

The method for producing the compound represented by formula (2) may further include purification steps such as extraction, washing, drying, filtration, distillation, concentration, chromatography, and combinations thereof.

3. In one embodiment of the method for producing a compound represented by formula (3) , the following formula (3):

(In the formula, R ¹ , R ² , and R ³ have the same meanings as above.)
A method for producing a compound represented by: Step A, and Step B, in which the reaction product of Step A is reacted with a base.

(base)
The base is not particularly limited as long as it allows the dehydrochlorination reaction to proceed. The base may be an organic base or an inorganic base. Examples of the base include linear amines (e.g., tri-C _1-6 alkylamines such as trimethylamine, triethylamine, and N,N-diisopropylethylamine), cyclic amines (e.g., pyridine, morpholine, and N-methylmorpholine), ammonia, Ammonium hydroxide, metal hydroxides (e.g. alkali metal hydroxides such as sodium hydroxide, alkaline earth metal hydroxides such as calcium hydroxide), metal alkoxides (e.g. alkali metal alkoxides such as sodium alkoxide), etc. can be mentioned. One type of base can be used alone or two or more types can be used in combination.

The amount of the base to be used is, for example, 0.9 mol or more, 1 mol or more, 1.2 mol or more, or 1.5 mol or more with respect to 1 mol of the compound represented by formula (1) or (2). could be. The amount of the base to be used may be, for example, 5 mol or less, preferably 3 mol or less, and more preferably 2 mol or less, per 1 mol of the compound represented by formula (1). The amount of the base to be used is, for example, within the range of 0.9 to 5 mol, preferably within the range of 0.9 to 3 mol, more preferably 0.9 to 3 mol, per 1 mol of the compound represented by formula (1). It may be within the range of 9 to 2 moles.

(Reaction temperature and reaction time)
The reaction temperature and reaction time in Step B are not particularly limited as long as the reaction proceeds.
The reaction temperature may be, for example, -80°C or higher, preferably -20°C or higher, and more preferably 0°C or higher. The reaction temperature may be, for example, 100°C or lower, preferably 50°C or lower, and more preferably 20°C or lower. The reaction temperature may be, for example, in the range of -80 to 100°C, preferably in the range of -20 to 50°C, more preferably in the range of 0 to 20°C.
The reaction time can be, for example, 0.1 hours or more, 1 hour or more, or 3 hours or more. The reaction time can be, for example, 12 hours or less, preferably 7 hours or less, more preferably 5 hours or less. The reaction time can be, for example, within the range of 0.1 to 12 hours, preferably within the range of 0.1 to 7 hours, more preferably within the range of 0.1 to 5 hours.

The compound represented by formula (3) includes a compound in which R ¹ and R ² are hydrogen atoms. The compounds represented by formula (3) include compounds in which R ¹ and R ² are hydrogen atoms, and R ³ is a haloalkyl group, a haloaryl group, or a haloaralkyl group. The compound represented by formula (3) includes compounds in which R ¹ and R ² are hydrogen atoms, and R ³ is a fluoroalkyl group. The compound represented by formula (3) includes a compound in which R ¹ and R ² are hydrogen atoms and R ³ is -C(CF ₃ ) ₃ , that is, the following formula (3A):

This includes compounds represented by:

The method for producing the compound represented by formula (3) may further include purification steps such as extraction, washing, drying, filtration, distillation, concentration, chromatography, and combinations thereof.

4. In one embodiment of the composition , the composition is a composition containing a compound represented by formula (3) and water (hereinafter referred to as "composition α").

In the composition α, the water content is not particularly limited, and may be, for example, 0.001% by mass or more, 0.005% by mass or more, or 0.01% by mass or more. The content of water is preferably 0.1% by mass or less or 0.05% by mass or less from the viewpoint of suppressing the progress of hydrolysis. The water content can be, for example, in the range of 0.001 to 0.1% by weight. The content of water can be measured, for example, by the Karl Fischer method.

In composition α, the content of the compound represented by formula (3) is not particularly limited, but is, for example, 80% by mass or more, preferably 90% by mass or more, and more preferably 95% by mass or more. The content of the compound represented by formula (3) may be, for example, 99.9% by mass or less, 99.5% by mass or less, or 99% by mass or less. The content of the compound represented by formula (3) is, for example, in the range of 80 to 99.9% by mass, preferably in the range of 90 to 99.9% by mass, and more preferably in the range of 95 to 99.9% by mass. It may be within the range of %. The content of the compound represented by formula (3) can be measured, for example, by NMR, gas chromatography (GC), or gas chromatography-mass spectrometry (GC-MS).

Composition α may further contain other components. Examples of other components include by-products of step A and/or step B. In one embodiment, the other components are at least selected from a compound represented by formula (4A), a compound represented by formula (4B), a compound represented by formula (4C), and a chloride ion, which will be described later. It may be one type. Composition α may have the configuration of composition β, composition γ, and/or composition δ, which will be described later.

In other embodiments, the composition comprises:
A compound represented by formula (3), and
The following formula (4A):
R ³¹ -OH (4A)
(In the formula, R ³¹ is an alkyl group that may have one or more substituents, an aryl group that may have one or more substituents, or a (It is an aralkyl group that may be
A compound represented by
The following formula (4B):

(In the formula, R ³³ is an alkyl group that may have one or more substituents, an aryl group that may have one or more substituents, or an alkyl group that may have one or more substituents. (It is an aralkyl group that may be
This is a composition (hereinafter referred to as "composition β") containing at least one selected from the group consisting of the compounds represented by:

It is preferable that the composition β satisfies at least one of the following (a), (b), and (c).
(a) The content of the compound represented by formula (4A) may be, for example, 0.01% by mass or more, 0.03% by mass or more, or 0.05% by mass or more, for example, 5% by mass or more. % or less, 3% by mass or less, or 1% by mass or less, for example, within the range of 0.01 to 5% by mass.
(b) The content of the compound represented by formula (4B) may be, for example, 0.01% by mass or more, 0.03% by mass or more, or 0.05% by mass or more, for example, 1. It may be 5% by weight or less, 1% by weight or less, or 0.5% by weight or less, for example, within the range of 0.01 to 1.5% by weight.
(c) The content of the compound represented by formula (4C) may be, for example, 0.01% by mass or more, 0.03% by mass or more, or 0.05% by mass or more, for example, 1. It may be 5% by weight or less, 1% by weight or less, or 0.5% by weight or less, for example, within the range of 0.01 to 1.5% by weight.

The content of the compounds represented by formulas (4A), (4B), and (4C) can be measured, for example, by NMR, gas chromatography (GC), or gas chromatography-mass spectrometry (GC-MS). Can be done.

R ³¹ in formula (4A), R ³² in formula (4B), and R ³³ in formula (4C) are each independently a group selected from the groups exemplified for R ³ in formula (3). could be. In one embodiment, R ³¹ in formula (4A), R ³² in formula (4B), and R ³³ in formula (4C) are each preferably the same as R ³ in formula (3).

In composition β, the content of the compound represented by formula (3) is not particularly limited, but is, for example, 80% by mass or more, preferably 90% by mass or more, and more preferably 95% by mass or more. The content of the compound represented by the formula (3) may be, for example, 99.9% by mass or less, 99% by mass or less, or 98% by mass or less. The content of the compound represented by formula (3) is, for example, in the range of 80 to 99.9% by mass, preferably in the range of 90 to 99.9% by mass, and more preferably in the range of 95 to 99.9% by mass. It may be within the range of %. The content of the compound represented by formula (3) can be measured, for example, by NMR, gas chromatography (GC), or gas chromatography-mass spectrometry (GC-MS).

Composition β may further contain other components. Examples of other components include by-products of step A and/or step B. In one embodiment, the other component may be at least one selected from water and chloride ions. Composition β may have the composition of composition α, composition γ, and/or composition δ described below.

In yet another embodiment, the composition is a composition containing the compound represented by formula (3) and having a Hazen color number of 100 or less (hereinafter referred to as "composition γ"). The Hazen color number refers to the numerical value of the degree of coloring of a sample solution. The Hazen color number of the composition γ can be measured, for example, at room temperature using a spectral color/haze meter COH7700 manufactured by Nippon Denshoku Industries, Ltd. The Hazen color number of the composition γ may be, for example, 1 or more, 3 or more, or 5 or more, for example, 80 or less or 50 or less, for example, within the range of 1 to 100. Good too.

In the composition γ, the content of the compound represented by formula (3) is not particularly limited, but is, for example, 80% by mass or more, preferably 90% by mass or more, and more preferably 95% by mass or more. The content of the compound represented by formula (3) may be, for example, 99.9% by mass or less, 99.5% by mass or less, or 99% by mass or less. The content of the compound represented by formula (3) is, for example, in the range of 80 to 99.9% by mass, preferably in the range of 90 to 99.9% by mass, and more preferably in the range of 95 to 99.9% by mass. It may be within the range of %. The content of the compound represented by formula (3) can be measured, for example, by NMR, gas chromatography (GC), or gas chromatography-mass spectrometry (GC-MS).

Composition γ may further contain other components. Examples of other components include by-products of step A and/or step B. In one embodiment, the other component is at least selected from water, a compound represented by formula (4A), a compound represented by formula (4B), a compound represented by formula (4C), and a chloride ion. It may be one type. Composition γ may have the composition of composition α, composition β, and/or composition δ described below.

In another embodiment, the composition is a composition (hereinafter referred to as "composition δ") containing the compound represented by formula (3) and containing 1000 ppm or less of chlorine ions.

In the composition δ, the content of chlorine ions may be, for example, 0.1 ppm or more, 0.5 ppm or more, or 1 ppm or more, and may be, for example, 100 ppm or less or 10 ppm or less, for example, 0.1 ppm or more, or 1 ppm or more. It may be within the range of 1 to 1000 ppm or within the range of 0.1 to 100 ppm. The content of chlorine ions can be measured, for example, by ion chromatography. Specifically, 0.1% by mass sodium bicarbonate solution was added so that the content of the chlorine ions was about 10 times the amount of the compound represented by formula (3), and the mixture was stirred at room temperature for 3 minutes. After that, the aqueous layer is analyzed for chlorine ions using ion chromatography, and the concentration can be determined by using the obtained quantitative value as the amount of chlorine ions in the compound represented by formula (3). .

In the composition δ, the content of the compound represented by formula (3) is not particularly limited, but is, for example, 80% by mass or more, preferably 90% by mass or more, and more preferably 95% by mass or more. The content of the compound represented by formula (3) may be, for example, 99.9% by mass or less, 99.5% by mass or less, or 99% by mass or less. The content of the compound represented by formula (3) is, for example, in the range of 80 to 99.9% by mass, preferably in the range of 90 to 99.9% by mass, and more preferably in the range of 95 to 99.9% by mass. It may be within the range of %. The content of the compound represented by formula (3) can be measured, for example, by NMR, gas chromatography (GC), or gas chromatography-mass spectrometry (GC-MS).

The composition δ may further contain other components. Examples of other components include by-products of step A and/or step B. In one embodiment, the other component is at least one selected from water, a compound represented by formula (4A), a compound represented by formula (4B), and a compound represented by formula (4C). It's okay. Composition δ may have the composition of composition α, composition β, and/or composition γ.

Hereinafter, one embodiment of the present disclosure will be described in more detail with reference to Examples, but the present disclosure is not limited thereto. In addition, in the examples, Ph means phenyl.

Example 1: Chlorination reaction

The raw material acrylic ester (10 g, 33.6 mmol) and acetonitrile (30 g) were added to the reaction vessel.
Chlorine gas was bubbled intermittently while stirring at room temperature under light shielding (2.57 equivalents in total, 6 hours in total). After that, nitrogen gas was bubbled to replace the atmosphere with nitrogen, and then a crude liquid was obtained. The yield of the target dichloroform was measured by F-NMR and was 81%.

Example 2: Dehydrochlorination (HCl) reaction

The crude liquid obtained in Example 1 was cooled to 10° C. with stirring. Triethylamine (4.12 g, 40.8 mmol) was added dropwise to the crude liquid. Thirty minutes after the completion of the dropwise addition, 0.1 mol/L HCl water (17.4 g) and chloroform (50 g) were added while stirring.
After separation, the organic layer was washed with water and saturated saline to obtain an organic layer. The yield of the target product was measured by F-NMR and was 91%. After adding phenothiazine (50 mg) to the obtained organic layer, the target α-chloroacrylic acid ester (7.9 g, 23.8 mmol) was isolated by distillation purification.

Example 3: Composition The α-chloroacrylic acid ester obtained in Example 2 was analyzed, and the following results were obtained.
Purity (content of the compound obtained in Example 2): 97.3% by mass
Moisture: 157ppm
Content of the compound represented by the following formula (4A-1): 0.81% by mass
Content of the compound represented by the following formula (4B-1): 0.08% by mass
Content of the compound represented by the following formula (4C-1): 0.08% by mass

Hazen color number: 7
Chlorine ion: 0.9ppm
In addition, the content of the compound obtained in Example 2, the compound represented by formula (4A-1), the compound represented by formula (4B-1), and the compound represented by formula (4C-1) was measured by GC.
The water content was measured by Karl Fischer method.
The Hazen color number was measured using the compound (liquid sample) obtained in Example 2 at room temperature with a spectroscopic color/haze meter COH7700 manufactured by Nippon Denshoku Industries, Ltd.
The content of chlorine ions was determined by adding 0.1% by mass of sodium bicarbonate solution to the compound obtained in Example 2, and stirring for 3 minutes at room temperature. Chlorine ions were analyzed using chromatography, and the obtained quantitative value was determined as the amount of chlorine ions in the compound obtained in Example 2 by calculating the concentration.

Example 4: Chlorination reaction The same method as Example 1 was carried out except that acetonitrile was changed to ethyl acetate. The yield of the target dichloroform was measured by F-NMR and was 99%.

Example 5: Dehydrochlorination (HCl) reaction A solution of the dichloro compound obtained in Example 4 in ethyl acetate was cooled to 10° C. with stirring. Triethylamine (4.12 g, 40.8 mmol) was added dropwise to the solution. Thirty minutes after the completion of the dropwise addition, 0.1 mol/L HCl water (20 g) was added while stirring.
After separation, the organic layer was washed with water and saturated saline to obtain an organic layer. The yield of the target product was measured by F-NMR and was 82%. After adding phenothiazine (50 mg) to the obtained organic layer, the target α-chloroacrylic acid ester (9.2 g, 27.6 mmol) was isolated by distillation purification.

Claims

The following formula (2):

(In the formula,
R 1 and R 2 are each independently a hydrogen atom or an organic group, or
R 1 and R 2 are bonded to each other to form a ring with adjacent carbon atoms,
R 3 is an alkyl group that may have one or more substituents, an aryl group that may have one or more substituents, or one or more substituents. It is an aralkyl group. ) A method for producing a compound represented by
In the presence of a polar solvent, the following formula (1):

(In the formula, R 1 , R 2 , and R 3 have the same meanings as above.)
Step A of reacting the compound represented by with chlorine
method including.
The following formula (3):

(In the formula,
R 1 and R 2 are each independently a hydrogen atom or an organic group, or
R 1 and R 2 are bonded to each other to form a ring with adjacent carbon atoms,
R 3 is an alkyl group that may have one or more substituents, an aryl group that may have one or more substituents, or one or more substituents. It is an aralkyl group. ) A method for producing a compound represented by
In the presence of a polar solvent, the following formula (1):

(In the formula, R 1 , R 2 , and R 3 have the same meanings as above.)
Step A of reacting the compound represented by with chlorine, and Step B of reacting the reaction product of step A with a base.
method including.
The method according to claim 1 or 2, wherein the polar solvent is at least one selected from the group consisting of nitrile solvents, ester solvents, carbonate solvents, and carboxylic acid solvents.
The method according to any one of claims 1 to 3, wherein the polar solvent has a Rohrschneider polarity parameter P' of 4.3 or more (provided that the polar solvent is not an alcoholic solvent).
The method according to any one of claims 1 to 4, wherein the amount of the polar solvent used is within the range of 100 to 10,000 parts by mass based on 100 parts by mass of the compound represented by formula (1). .
The method according to any one of claims 1 to 5, wherein step A is carried out in the absence of light.
R 1 and R 2 are each independently a hydrogen atom, an alkyl group which may have one or more substituents, a cycloalkyl group which may have one or more substituents, one The method according to any one of claims 1 to 6, wherein the method is an aryl group which may have the above substituents, or an aralkyl group which may have one or more substituents.
The method according to any one of claims 1 to 7, wherein R 3 is a haloalkyl group, a haloaryl group, or a haloaralkyl group.
The following formula (3A):

A compound represented by
The following formula (3):

(In the formula,
R 1 and R 2 are each independently a hydrogen atom or an organic group, or
R 1 and R 2 are bonded to each other to form a ring with adjacent carbon atoms,
R 3 is an alkyl group that may have one or more substituents, an aryl group that may have one or more substituents, or an alkyl group that may have one or more substituents. It is an aralkyl group. ) and a composition comprising water,
A composition having a water content in the range of 0.001 to 0.1% by mass.
The following formula (3):

(In the formula,
R 1 and R 2 are each independently a hydrogen atom or an organic group, or
R 1 and R 2 are bonded to each other to form a ring with adjacent carbon atoms,
R 3 is an alkyl group that may have one or more substituents, an aryl group that may have one or more substituents, or one or more substituents. It is an aralkyl group. ) and the following formula (4A):
R 31 -OH (4A)
(In the formula, R 31 is an alkyl group that may have one or more substituents, an aryl group that may have one or more substituents, or a (It is an aralkyl group that may be
A compound represented by the following formula (4B):

(In the formula, R 32 is an alkyl group that may have one or more substituents, an aryl group that may have one or more substituents, or an alkyl group that may have one or more substituents. (It is an aralkyl group that may be
A compound represented by and the following formula (4C):

(In the formula, R 33 is an alkyl group that may have one or more substituents, an aryl group that may have one or more substituents, or an alkyl group that may have one or more substituents. (It is an aralkyl group that may be
A composition comprising at least one selected from the group consisting of compounds represented by
A composition that satisfies at least one of the following (a), (b), and (c):
(a) The content of the compound represented by the formula (4A) is within the range of 0.01 to 5% by mass,
(b) the content of the compound represented by formula (4B) is within the range of 0.01 to 1.5% by mass;
(c) The content of the compound represented by formula (4C) is within the range of 0.01 to 1.5% by mass.
The following formula (3):

(In the formula,
R 1 and R 2 are each independently a hydrogen atom or an organic group, or
R 1 and R 2 are bonded to each other to form a ring with adjacent carbon atoms,
R 3 is an alkyl group that may have one or more substituents, an aryl group that may have one or more substituents, or one or more substituents. It is an aralkyl group. ), and has a Hazen color number of 100 or less.
The following formula (3):

(In the formula,
R 1 and R 2 are each independently a hydrogen atom or an organic group, or
R 1 and R 2 are bonded to each other to form a ring with adjacent carbon atoms,
R 3 is an alkyl group that may have one or more substituents, an aryl group that may have one or more substituents, or one or more substituents. It is an aralkyl group. ), and has a chlorine ion content of 1000 ppm or less.