JPH06306046A - Production of thio(meth)acrylate - Google Patents

Abstract

PURPOSE:To obtain the compound useful as a raw material for spectacle lenses having a high refractive index, etc., from inexpensive raw materials in a high yield, while avoiding side reactions, by reacting a thiol compound with (meth) acrylic acid in the presence of a base and a condensing agent. CONSTITUTION:A compound of formula I (R is organic residue; n is 1-10) is reacted with (meth)acrylic acid in the presence of a base (e.g. pyridine) and in the presence of a 1,3-dialkyl-2-halogeno-imidazolinium halogenide of formula II (R2, R3 are 1-5C alkyl; X is halogen) as a condensing agent in a solvent such as dichloromethane at -10 to 30 deg.C to produce a compound of formula III (R1 is H, methyl). The (meth)acrylic acid, the base, and the condensing agent are used in amounts of 1.0-1.5 times moles, 2.0-3.0 times moles, and 1.0-1.5 times moles, respectively, the sum of the mercapto groups.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a thio (meth) acrylate compound useful as a raw material for eyeglass lenses having a high refractive index.

[0002]

2. Description of the Related Art In general, a thio (meth) acrylate compound is produced by dehydrohalogenating a thiol compound and a (meth) acrylic acid halide (JP-A-64-26613). JP, 64-31759, JP, 63-1
88660 bulletin).

[0003]

However, these methods have problems that the yield is low and the purification is difficult because a side reaction occurs in which the thiol group is added to the double bond portion of the (meth) acrylic group. It was Further, there is a drawback that the cost of (meth) acrylic acid chloride is high. The present invention is intended to solve the drawbacks of the prior art, and an object thereof is to provide a method for producing a thio (meth) acrylate compound with high yield and easy purification.

[0004]

Means for Solving the Problems As a result of intensive studies to solve the above problems, the present inventors have found that the general formula (I)

[Chemical 4] (Wherein, R is an organic residue, R1 is a hydrogen atom or a methyl group, n
Is an integer of 1 to 10) in the method of the thio (meth) acrylate compound represented by the general formula (II)

[Chemical 5] (Wherein R represents an organic residue, n represents an integer of 1 to 10), and (meth) acrylic acid,
General formula (III) in the presence of a base

[Chemical 6] (In the formula, R2 and R3 are alkyl groups having 1 to 5 carbon atoms, X is a halogen atom), and 1,3-dialkyl-2-halogeno-imidazolinium halogenide is reacted as a condensing agent. It was found that a thio (meth) acrylate compound can be obtained in high yield, and the present invention has been completed.

The compound of the present invention represented by the general formula (I) is an acroyl or metacroyl compound of a thiol compound represented by the following general formula (II), but is not particularly limited. In the general formula (I), R represents an organic residue, for example, an alkyl group or alkylene group having 1 to 20 carbon atoms, an aryl group or arylene group having 6 to 30 carbon atoms, an aralkyl group or aralkylene having 7 to 30 carbon atoms. A group, which may contain a sulfur atom or an oxygen atom in the main chain or aromatic nucleus, and which has a halogen atom, a nitro group, an alkoxy group, an alkoxycarbonyl group, an alkanoyl group or the like in the main chain or side chain, or an aromatic nucleus. It may contain a group.

The thiol compound represented by the general formula (II) used in the present invention may contain other substituents in addition to the mercapto group.

Specifically, methyl mercaptan, ethyl mercaptan, propyl mercaptan, butyl mercaptan, amyl mercaptan, hexyl mercaptan, heptyl mercaptan, octyl mercaptan, nonyl mercaptan, decyl mercaptan, undecyl mercaptan, dodecyl mercaptan, tridecyl mercaptan. Decyl mercaptan, cetyl mercaptan,
Octadecyl mercaptan, 2-butene-1-thiol, 1-
Butene-4-thiol, 1-pentenyl mercaptan, 2-i-
Pentenyl mercaptan, oleyl mercaptan, cyclopentyl mercaptan, cyclohexyl mercaptan, cyclopentylmethyl mercaptan, 3-methylcyclohexyl mercaptan, 2-methylcyclohexyl mercaptan, 3-methylcyclohexylmethyl mercaptan, β-tetrahydronaphthyl mercaptan, β-decahydronaphthyl mercaptan, β- Cyclohexylethyl mercaptan, δ- (β-tetrahydronaphthyl) butyl mercaptan, δ- (β-decahydronaphthyl) butyl mercaptan, furfuryl mercaptan, methylfurfuryl mercaptan, 2-mercaptothiophene, 3-mercaptothiophene, 2-ethyl- 3-mercaptothiophene, thiophenol, thiocresol, o-ethylthiophenol, m-ethylthiophenol, p- Tylthiophenol, 2,4-thioxylenol, 2,5-thioxylenol, o-propylthiophenol, m-propylthiophenol, p-propylthiophenol, o-phenylthiophenol, m-phenylthiophenol, p- Phenylthiophenol, o-chlorothiophenol, m-chlorothiophenol, p-chlorothiophenol, o-bromothiophenol, m-bromothiophenol, p-bromothiophenol, o-iodothiophenol, m-iodothio Phenol, p-iodothiophenol, o-nitrothiophenol, m-nitrothiophenol, p-nitrothiophenol, nitrobromothiophenol, nitrochlorothiophenol, methylsulfonylthiophenol, benzylmercaptan, o-nitrobenzylmercaptan, m-nitrobenzyl mercaptan , P-nitrobenzyl mercaptan, α-phenylethyl mercaptan, β-phenylethyl mercaptan, α-phenylpropyl mercaptan, γ-phenylpropyl mercaptan, β-phenylpropyl mercaptan, β-phenyl-i-propyl mercaptan, α, β- Diphenylethyl mercaptan, o-
Methylbenzyl mercaptan, m-methylbenzyl mercaptan, p-methylbenzyl mercaptan, o-nitro-p-
Trilyl mercaptan, S-benzylethanedithiol, α
-(O-Tolyl) benzyl mercaptan, α- (p-tolyl) benzyl mercaptan, chlorobenzyl mercaptan, o, p-dichlorobenzyl mercaptan, o-bromobenzyl mercaptan, p-bromobenzyl mercaptan, α
-Phenyl-p-chlorobenzyl mercaptan, cinnamyl mercaptan, β-γ-diphenylallyl mercaptan, 4,4'-dichlorobenzhydryl mercaptan,
Triphenylmethyl mercaptan, 1-thionaphthol,
2-thionaphthol, 4-chloro-1-thionaphthol, 4-bromo-1-thionaphthol, 1-nitro-2-thionaphthol, 4-nitro-1-thionaphthol, and as a polythiol compound, methanedithiol, 1 , 2-ethanedithiol, 1,2-propanedithiol, 1,3-propanedithiol, 1,4-butanedithiol, 1,6-hexanedithiol, 1,2,3-propanetrithiol, 1,2-cyclohexanedithiol , 2,2-Dimethylpropane-1,3-
Dithiol, 3,4-dimethoxybutane-1,2-dithiol, 2-methylcyclohexane-2,3-dithiol, bicyclo [2.2.1] hepta-exo-cis-2,3-dithiol, 1,1-
Bis (mercaptomethyl) cyclohexane, o-benzenedithiol, m-benzenedithiol, p-benzenedithiol, o-xylene-α, α'-dithiol, m-xylene-
α, α'-dithiol, p-xylene-α, α'-dithiol, o-bis (β-mercaptoethyl) benzene, m-bis (β-mercaptoethyl) benzene, p-bis (β-mercaptoethyl) benzene , O-bis (β-mercaptoethyloxy) benzene, m-bis (β-mercaptoethyloxy) benzene, p-bis (β-mercaptoethyloxy) benzene, o-bis (mercaptoethylthio) benzene, m-bis (Β-mercaptoethylthio) benzene, p-
Bis (mercaptoethylthio) benzene, α, α'-bis (β-mercaptoethyloxy) -o-xylene, α,
α'-bis (β-mercaptoethyloxy) -m-xylene, α, α'-bis (β-mercaptoethyloxy) -p-
Xylene, α, α'-bis (β-mercaptoethylthio)
-o-xylene, α, α'-bis (β-mercaptoethylthio) -m-xylene, α, α'-bis (β-mercaptoethylthio) -p-xylene, 1,2,3-benzenetrithiol 1,2,4-benzenetrithiol, 1,3,5-benzenetrithiol, 1,2,3-tris (mercaptomethyl) benzene, 1,2,4-tris (mercaptomethyl)
Benzene, 1,3,5-tris (mercaptomethyl) benzene, 1,2,3-tris (mercaptoethyl) benzene, 1,2,4-tris (mercaptoethyl) benzene,
1,3,5-Tris (mercaptoethyl) benzene, 1, 3,
2,3-Tris (mercaptoethyloxy) benzene, 1
, 2,4-Tris (mercaptoethyloxy) benzene, 1,3,5-Tris (mercaptoethyloxy) benzene, 1,2,3-Tris (mercaptoethylthio) benzene, 1,2,4-Tris (mercapto) Ethylthio) benzene, 1,3,5-tris (mercaptoethylthio) benzene, α, α ', α'',-tris (β-mercaptoethyloxy) -1,2,3-mesitylene, α, α' , Α '',-
Tris (β-mercaptoethyloxy) -1,2,4-mesitylene, α, α ', α'',-Tris (β-mercaptoethyloxy) -1,3,5-mesitylene, α, α', α '',
-Tris (β-mercaptoethylthio) -1,2,3-mesitylene, α, α ', α'',-tris (β-mercaptoethylthio) -1,2,4-mesitylene, α, α', α '',-
Tris (β-mercaptoethylthio) -1,3,5-mesitylene, 1,2,3,4-benzenetetrathiol, 1,2
, 3,5-benzenetetrathiol, 1,2,4,5-benzenetetrathiol, 1,2,3,4-tetrakis (mercaptomethyl) benzene, 1,2,3,5-tetrakis (mercaptomethyl) benzene , 1,2,4,5-tetrakis (mercaptomethyl) benzene, 1,2,3,4-tetrakis (mercaptoethyl) benzene, 1,2,3,3,
5-tetrakis (mercaptoethyl) benzene, 1, 2,
4,5-Tetrakis (mercaptoethyl) benzene, 1,
2,3,4-Tetrakis (mercaptoethyloxy) benzene, 1,2,3,5-tetrakis (mercaptoethyloxy) benzene, 1,2,4,5-tetrakis (mercaptoethyloxy) benzene, 1,2, 3,4-tetrakis (mercaptoethylthio) benzene, 1,2,3,5-tetrakis (mercaptoethylthio) benzene, 1,2,
4,5-tetrakis (mercaptoethylthio) benzene,
α, α ', α'',α'''-tetrakis (β-mercaptoethyloxy) -1,2,3,4-tetramethylbenzene,
α, α ', α'',α'''-tetrakis (β-mercaptoethyloxy) -1,2,3,5-tetramethylbenzene,
α, α ', α'',α'''-tetrakis (β-mercaptoethyloxy) -1,2,4,5-tetramethylbenzene,
α, α ', α ", α'"-tetrakis (β-mercaptoethylthio) -1,2,3,4-tetramethylbenzene, α,
α ', α'',α'''-Tetrakis (β-mercaptoethylthio) -1,2,3,5-tetramethylbenzene, α, α '
, Α '', α '''-tetrakis (β-mercaptoethylthio) -1,2,4,5-tetramethylbenzene, 4,4'-mercaptobiphenyl, 2,2'-mercaptobiphenyl,
2,5-Toluenedithiol, 3,4-Toluenedithiol, 1,4-Naphthalenedithiol, 1,5-Naphthalenedithiol, 2,6-Naphthalenedithiol, 2,7-Naphthalenedithiol, 1,4-Bis (mercaptomethyl) ) Naphthalene, 1,5-bis (mercaptomethyl) naphthalene,
Aromatic and nuclear alkylated polythiols such as 2,6-bis (mercaptomethyl) naphthalene and 2,7-bis (mercaptomethyl) naphthalene, and 2,5-dichlorobenzene-1,3-dithiol, 1, 3-di (p-chlorophenyl) propane-2,2-dithiol, 3,4,5-tribromo-
Chlorine-substituted aromatic polythiols such as 1,2-dimercaptobenzene and bromine-substituted aromatic polythiols, bis (mercaptoethyl) sulfide, bis (mercaptopropyl)
Sulfide, 4,4'-mercaptophenyl sulfide,
Aliphatic and aromatic sulfide compounds such as 2,2'-mercaptophenyl sulfide, bis (mercaptoethyl) disulfide, disulfide compounds such as bis (mercaptopropyl) disulfide, bis (2-mercaptoethylthio) methane, bis (3- Mercaptopropylthio) methane, 1,2-bis (2-mercaptoethylthio) ethane, 1
, 2-bis (3-mercaptopropyl) ethane, 1,3-bis (2-mercaptoethylthio) propane, 1,3-bis (3-mercaptopropyl) propane, 1,2,3-tris (2-mercapto) Aliphatic polythiols such as ethylthio) propane, 1,2,3-tris (3-mercaptopropylthio) propane, tetrakis (2-mercaptoethylthiomethyl) methane, tetrakis (2-mercaptopropylthiomethyl) methane, β- Examples thereof include ester compounds such as methyl mercaptopropionate, methyl thioglycolate, trimethylolpropane tris (β-thiopropionate), and 1,4-butanediol dithiopropionate.

Further, examples thereof include halogen-substituted compounds such as chlorine-substituted compounds and bromine-substituted compounds, but the compounds are not limited thereto.

The general formula (III) used in the present invention
Examples of the condensing agent include 1,3-dimethyl-2-chloro-imidazolinium chloride, 1,3-dimethyl-2-bromo-imidazolinium bromide and 1,3-diethyl-2-chloro.
-Imidazolinium chloride, 1,3-diethyl-2-bromo-imidazolinium bromide, 1,3-dipropyl
-2-chloro-imidazolinium chloride, 1,3-dipropyl-2-bromo-imidazolinium bromide and the like can be mentioned, but easily available 1,3-dimethyl
-2-Chloro-imidazolinium chloride is used.

The production method of the present invention will be described in more detail. The above-mentioned thiol compound, (meth) acrylic acid and the condensing agent represented by the general formula (III) are mixed in a solvent, and a base is added to the mixture. The reaction may be performed at room temperature.

Examples of the base to be used include triethylamine, pyridine, imidazole and the like, and it is not particularly limited as long as it does not react with a thiol compound, (meth) acrylic acid and a condensing agent, but pyridine is preferably used. These bases have a ratio of 2.0 to the total of mercapto groups.
~ 3.0 times the molar amount is preferably used, and more preferably 2.3
It is preferably used in a molar amount of up to 2.5 times. When the amount is less than 2.0 times by mole, the reaction is not completed because the stoichiometry is insufficient, unreacted thiol groups remain, and the yield tends to decrease due to the above-mentioned side reaction. Quantitatively, 2 of the total mercapto groups
It is sufficient to make it slightly more than double, and it becomes difficult to remove even if it is too much.

The (meth) acrylic acid may be used in a slight excess with respect to the total of mercapto groups (1.0 to 1.5 times by mole), and preferably 1.1 to 1.3 times by mole. When the amount is 1.0 times or less, the reaction is not completed because the stoichiometry is insufficient, unreacted thiol groups remain, and the above-mentioned side reaction reduces the yield, which is not preferable. Even if a large amount is used, it can be removed by washing with water, so there is no particular problem, but it is disadvantageous in terms of cost.

Solvents include thiol compounds and (meth)
If it does not react with acrylic acid, condensing agent, base,
Although not particularly limited, dichloromethane, chloroform and the like are preferably used.

The condensing agent is 1. with respect to the total of mercapto groups.
It is used in an amount of 0 to 1.5 times, preferably 1.1 to 1.3 times. If the amount is 1.0 times or less, the reaction is not completed because the stoichiometry is insufficient, and unreacted thiol groups remain, and the yield tends to decrease due to the above-mentioned side reaction. Even if a large amount is used, it can be removed by washing with water, so there is no particular problem, but it is disadvantageous in terms of cost.

The reaction temperature may be room temperature. However, since heat may be generated during the dropping of the base, it is preferable to cool with a water bath or an ice bath in that case. Particularly preferably -10 ~
Perform at 30 ° C. At -10 ° C or lower, the reaction rate tends to be slow. If it exceeds 40 ° C, it tends to be difficult to control heat generation.

For the reaction treatment, since a (meth) acrylate compound can be quantitatively obtained if a condensing agent and a base are used in an appropriate amount, it is sufficient to add water, extract with an organic solvent, and wash with water.

[0017]

EXAMPLES The present invention will be described in detail below with reference to examples.

EXAMPLE 1 1.84 g (0.01 mol) of S-benzyl-1,2-ethanedithiol, 1.0 g (0.012 mol) of methacrylic acid and 10 g of 1,3-dimethyl-2-chloro-imidazolinium in 10 g of dichloromethane
Chloride (1.86 g, 0.011 mol) was dissolved and stirred in a water bath under a nitrogen atmosphere. To this, 1.9 g (0.024 mol) of pyridine was slowly added dropwise. After dropping, the mixture was stirred as it was for 5 hours. 30 g of water was added and the mixture was extracted with dichloromethane. The organic layer was washed twice with 30 g of water and then dried over sodium sulfate.
When the solvent was distilled off, 1.7 g (0.01 mol) of thiomethacrylic acid S-benzyl-2-mercaptoethyl ester was obtained.

[0019]

[Table 1] ^{IR (neat) 1660cm -1 (C} = O), 1620cm -1 (C = C) Example 2 dichloromethane 10g to alpha,. Alpha .'- bis (beta-mercaptoethyl thio)-p-xylene 2.9 g (0.01 mol) , Methacrylic acid 2.0g (0.024mol), 1,3-dimethyl-2-chloro-
3.72 g (0.022 mol) of imidazolinium chloride was dissolved and stirred in a water bath under a nitrogen atmosphere. To this, 3.8 g (0.048 mol) of pyridine was slowly added dropwise. After dropping, the mixture was stirred as it was for 5 hours. 30 g of water was added and the mixture was extracted with dichloromethane. The organic layer was washed twice with 30 g of water and then dried over sodium sulfate. When the solvent was distilled off, 4.2 g (0.01 mol) of α, α'-bis (β-mercaptoethylthio) -p-xylenedithiomethacrylate was obtained.

[0020]

[Table 2] ^{IR (neat) 1660cm -1 (C} = O), 1620cm -1 (C = C)

[0021]

Industrial Applicability According to the present invention, inexpensive (meth) acrylic acid can be used as a raw material, and by carrying out the reaction under mild conditions, side reactions during thiol esterification can be avoided and thio (meth) can be obtained in good yield. ) It has become possible to produce acrylate compounds.

Claims (3)

[Claims] 1. A compound represented by the general formula (I): (Wherein, R is an organic residue, R1 is a hydrogen atom or a methyl group, n
Is an integer of 1 to 10) in the method for producing a thio (meth) acrylate compound represented by the general formula (II): (Wherein R represents an organic residue, n represents an integer of 1 to 10), and (meth) acrylic acid,
In the presence of a base, the compound represented by the general formula (III): (Wherein R2 and R3 are alkyl groups having 1 to 5 carbon atoms, X is a halogen atom), and 1,3-dialkyl-2-halogeno-imidazolinium halogenide is reacted as a condensing agent. A method for producing a thio (meth) acrylate compound, which is characterized. 2. The method for producing a thio (meth) acrylate compound according to claim 1, wherein the compound represented by the general formula (II) is a mercaptan compound having a β-mercaptoethyl sulfide structure. 3. A compound represented by the general formula (III) is
The method for producing a thio (meth) acrylate compound according to claim 1, which is 3-dimethyl-2-chloroimidazolinium chloride.