JPH08283235A - Production of sulfides - Google Patents

Abstract

PURPOSE: To selectively and simply obtain a sulfide which is industrially useful as a coating additive, solvent, surfactant, chelating agent, an intermediate for medicines and agrochemicals, metal surface finishing agent and a raw material for dyes in high yield and selectivity with high reactivity. CONSTITUTION: A mercapto-alkanol of the formula: HO-R<1> -SH (R<1> is a residue of 2-8C hydrocarbon), e.g. 2-mercaptoethanol is allowed to react with an unsaturated compound of formula I (R<2> is H, a 1-4C hydrocarbon residue, R<3> is H, a 1-18C hydrocarbon residue), e.g. acrylic acid in the presence of a solid base catalyst at 40-150 deg.C for 1-36 hours to give the objective compound of formula II. The catalyst is an anion-exchange resin, an alkaline earth metal oxide and/or hydroxide and its amount is preferably 0.1-10wt.% of the compound of formula I. The amount of the compound given by the formula (mercapto-alkanol) is preferably 0.8-1.2 mole per mole of the compound of formula I. The solid base catalyst can readily be separated from the reaction mixture and can be reused for a prolonged period of time because of its excellent durability.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention uses a mercaptoalkanol and an unsaturated compound as starting materials and has the following general formula (3):

[0002]

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(Wherein R ¹ represents a hydrocarbon residue having 2 to 8 carbon atoms, R ² represents hydrogen, or a hydrocarbon residue having 1 to 4 carbon atoms, R ³ represents hydrogen, or 1 to 1 carbon atoms
Represents 8 hydrocarbon residues. ) Relates to a method for producing a sulfide compound. The sulfide compound is a coating additive, a solvent, a surfactant, a chelating agent,
It is an industrially useful compound as a pharmaceutical / agrochemical intermediate, a metal surface treatment agent, a dye raw material, and the like.

[0004]

2. Description of the Related Art A method using a solid base as a catalyst for producing a sulfide compound represented by the general formula (3) from a mercaptoalkanol and an unsaturated compound has not been known at all.

As a method for producing the sulfide compound represented by the general formula (3), a method using halogenated propionic acids as a starting material is disclosed in JP-A-4-356510, European Patent Publication No. 558370, and Sulfer.
Lett. 15 (4), 169-74 (19
1992) and the like. However, in these methods, since a halide is used as a starting material, there is an environmental problem in that it requires careful handling and that the halide produced as a by-product is disposed of.

Further, unsaturated compounds are used as starting materials, and tertiary aliphatic amines such as triethylamine, alkali metal hydroxides such as sodium hydroxide, and quaternary ammonium hydroxides such as trimethylammonium hydroxide. The method of reacting in the presence is described in J. Am. Chem. So
c. Volume 69 (1947), page 2333, JP-A-53-
No. 59636, U.S. Pat. No. 4,704,470, etc., it is difficult to recover and reuse these bases because they are homogeneous catalysts in industrial production. Further, when removing the catalyst, it is necessary to neutralize it with an acid or the like, and the produced salt becomes a waste, which complicates the treatment process after the reaction and adversely affects the environment. Further, if a base or an acid remains in the reaction solution in the distillation step in which the target compound is obtained from the reaction solution after neutralization with an acid and separation of the catalyst, the product may be altered or decomposed, resulting in purification yield. There is a problem that the rate is lowered and it is difficult to industrially obtain a product having a sufficient purity. If the catalyst separation step is complicated, purification without removing the catalyst may be considered, but as described above, the target material is altered by the homogeneous catalyst in the purification step, and the recovery rate of the target object decreases.

[0007]

An object of the present invention is to solve the above-mentioned problems, and to produce a sulfide compound represented by the general formula (3) which is an industrially useful compound in high yield. To provide a method.

[0008]

Means for Solving the Problems The present inventors have found that the sulfide compound represented by the general formula (3) has the following general formula (1): HO-R ¹ -SH (wherein R ¹ is a carbon number. A mercaptoalkanol represented by 2 to 8 hydrocarbon residues) and the following general formula (2):

[0009]

[Chemical 4]

(In the formula, R ² represents hydrogen and a hydrocarbon residue having 1 to 4 carbon atoms, and R ³ represents hydrogen and a hydrocarbon residue having 1 to 18 carbon atoms). By reacting a saturated compound with a solid base catalyst in the presence of a solid base catalyst, it was found to be obtained in high yield and high selectivity and industrially manufacturable, and the solid base is hardly soluble in the reaction solution. Therefore, it can be easily separated from the reaction solution and has excellent durability so that it can be reused for a long period of time, and since the reaction solution after catalyst separation contains almost no catalyst component,
The inventors have found that the target compound can be separated and purified easily and efficiently without causing alteration or decomposition, thus completing the present invention.

That is, the present invention provides the mercaptoalkanols represented by the general formula (1) and the general formula (2).
The method for producing a sulfide compound represented by the general formula (3) is characterized in that the unsaturated compound represented by the formula (3) is reacted in the presence of a solid base catalyst.

The solid base catalyst is preferably an anion exchange resin.

The solid base catalyst is preferably an alkaline earth metal oxide and / or hydroxide.

[0014]

The present invention will be described in detail below.

The mercaptoalkanols represented by the general formula (1) used as a raw material in the present invention include compounds having a hydrocarbon residue having 2 to 8 carbon atoms, such as 2-mercaptoethanol and 3 -Mercaptopropanol, 1-methyl-2-mercaptoethanol, 2-methyl-2-mercaptoethanol, 1,1
-Dimethyl-2-mercaptoethanol, 1,2-dimethyl-2-mercaptoethanol, 2,2-dimethyl-
2-mercaptoethanol, 1-butyl-2-mercaptoethanol, 1-cyclohexyl-2-mercaptoethanol, 1-phenyl-2-mercaptoethanol and the like can be mentioned.

Examples of the unsaturated compound represented by the general formula (2) used as a raw material in the present invention include acrylic acid, methyl acrylate, butyl acrylate, acrylic acid (2-ethylhexyl), lauryl acrylate,
Stearyl acrylate, methacrylic acid, methyl methacrylate, butyl methacrylate, methacrylic acid (2-ethylhexyl) lauryl methacrylate, stearyl methacrylate and the like can be mentioned.

The amount of the mercaptoalkanols used is 0.5 to 3.0 mol, preferably 0.8 to 1.2 mol, per 1 mol of the unsaturated compound. If mercaptoalkanol is used in excess with respect to the unsaturated compound,
Unsaturated compounds can be converted to target compounds and the amount of residual unsaturated compounds can be reduced, but even if 3 mol or more is used, the above effect does not occur, and the amount of mercaptoalkanol recovered after the reaction increases, which is not economical. . Further, when the amount of mercaptoalkanol used is 0.5 mol or less per 1 mol of the unsaturated compound, unreacted unsaturated compound remains and side reactions such as polymerization occur, which is not preferable.

As the solid base used in the present invention, it is possible to use a base catalyst such as an anion exchange resin or an inorganic solid base. Until now, it was difficult to selectively obtain the desired sulfide compound when using an unsaturated carboxylic acid such as acrylic acid as a raw material, but especially when an anion exchange resin is used, it is highly active and highly selective. It is preferable to use this because the desired product can be obtained. Examples of the anion exchange resin used include various types such as a weakly basic anion exchange resin having a tertiary amine structure in the side chain and a strongly basic anion exchange resin having a quaternary ammonium salt structure. Things can be used. The synthetic resin as the base of the anion exchange resin is not particularly limited as long as it is insolubilized by crosslinking. Examples thereof include polystyrene, polyacrylamide, and epoxy resin. Specifically, Amberlyst A, Amberlite IRA (both manufactured by Rohm & Haas),
Examples include Dowex anion exchange resin (product of Dow Chemical Co., Ltd.), Duolite A (product of Sumitomo Chemical Co., Ltd.), and the like.

Examples of the inorganic solid base used include alkaline earth metal oxides such as magnesium oxide, calcium oxide, strontium oxide and barium oxide;
Alkaline earth metal hydroxides such as magnesium hydroxide and calcium hydroxide; oxides of rare earth metals such as yttrium oxide and lanthanum oxide; Y-type zeolite, mordenite-type zeolite, ZSM- ion-exchanged with alkali metals such as sodium Various types such as molecular sieves such as 5-like zeolite can be used, and one kind or two or more kinds of these compounds can be used.
Among these, oxides of alkaline earth metals, and /
Alternatively, hydroxides of alkaline earth metals are preferred.

The amount of the solid base catalyst used relative to the unsaturated compound is 0.01% by weight to 20% by weight, preferably 0.1% by weight.
% To 10% by weight. Further, when the solid base is not used in the production method of the present invention, the desired product can be obtained, but the activity is low, which is not industrial, and more by-products are formed, which is not preferable.

In the present invention, it is possible to carry out the reaction without a solvent, but since this reaction is an exothermic reaction, it is necessary to remove heat from the reaction system during the reaction, and a solvent is used to enhance the effect of heat removal. It is also possible to use. The solvent that can be used is not particularly limited as long as it is inert to the reaction and can dissolve the raw materials, and examples thereof include polar aprotic compounds such as acetonitrile and N, N-dimethylformamide, dioxane and Ethers such as diethylene glycol dimethyl ether, ketones such as acetone and methyl ethyl ketone, aliphatic hydrocarbons such as hexane and cyclohexane, aromatic hydrocarbons such as toluene and xylene, halogens such as chloroform and carbon tetrachloride. Various types such as alkyl halides can be used. You may use these solvent individually or in mixture of 2 or more types. In particular, as a solvent, an N-substituted amide group, a hydrocarbon residue having a carbon number of 1 to 6 is N
It is preferable to carry out in a compound having one or more functional groups selected from the group consisting of a amide group, a ureylene group, and a sulfoxide group, which are substituted at positions, because the selectivity of the target product is good and the compound is relatively easy to obtain. It is preferable that the compound having an amide group is, for example, formamide, N-
Methylformamide, N, N-dimethylformamide,
Acetamide, N-methylacetamide, N, N-dimethylacetamide, pyrrolidone, N-methylpyrrolidone and the like, N, N-dimethylimidazolidinone and the like as compounds having a ureylene group, and dimethylsulfoxide and the like as compounds having a sulfoxide group. Is preferred.
It is also possible to use the sulfide compound represented by the general formula (3) as a solvent. For example, in the reaction of 2-mercaptoethanol and methyl acrylate, the desired product, 3-[(2-hydroxyethyl) thio], is obtained.
The use of methyl propionate as a solvent has the advantage of simplifying the separation process.

When a solvent is used, the amount of the solvent to be used is usually more than 0 and up to 10 times (weight ratio), preferably 1 to 5 times, the unsaturated compound.

In the present invention, the reaction temperature is not particularly limited, but is preferably 40 ° C to 150 ° C. Reaction temperature is 40 ℃
In the following cases, the reaction rate is reduced and it takes time for the reaction to proceed, which is not economical, and at 150 ° C. or higher, side reactions such as polymerization of unsaturated compounds occur and the yield of the target compound decreases. This is not desirable.

In the present invention, the reaction time is not particularly limited, but in the case of a batch or semi-batch format, for example, 1 hour to 3 hours.
The range of 6 hours is preferable from the viewpoint of productivity.

In the present invention, a polymerization inhibitor such as a radical trapping agent may be used to suppress the polymerization. As the compound used as the polymerization inhibitor, various types such as benzoquinone derivatives and nitro compounds can be used.

The reaction may be carried out in any of a batch system, a semi-batch system and a continuous system. When using a batch system or a semi-batch system, the method of supplying the mercaptoalkanols and the unsaturated compound is
Although not particularly limited, it is preferable to supply the unsaturated compound later in order to prevent polymerization of the unsaturated compound. For example, after charging the reaction tank with the mercaptoalkanols and the catalyst, the unsaturated compound may be supplied together with the solvent, or the catalyst, the solvent and the mercaptoalkanols may be charged in advance in the reactor, and the unsaturated compound may be gradually supplied. May be.
In addition, when performing in a continuous tank type reactor among the continuous type,
The catalyst can be separated from the reaction solution by a simple operation such as filtration. When a continuous tubular reactor filled with a catalyst is used, the catalyst separation step is unnecessary, so the target compound can be obtained by, for example, distilling, recrystallizing, or reprecipitating the reaction solution obtained from the outlet as it is. It is possible.

[0027]

EXAMPLES The present invention will be described in detail below with reference to examples, but the present invention is not limited thereto.

Example 1 100 equipped with a thermometer, a reflux condenser and a nitrogen inlet tube
In a cc three-necked flask, 10 g of water, 7.8 g (0.1 mol) of 2-mercaptoethanol, 0.5 g (2-mercaptoethanol) of a weakly basic anion exchange resin, IRA94S (manufactured by Rohm & Haas) as a solid base. 6.5% by weight), and while stirring with a magnetic stirrer at 100 ° C., 7.2 g of acrylic acid (0.1 mo
1) was added dropwise in 30 minutes. After completion of dropping, the reaction was carried out for 4 hours. After completion of the reaction, a part of the reaction solution was sampled and analyzed by high performance liquid chromatography. The conversion rate of acrylic acid was 9
8%, conversion rate of 2-mercaptoethanol 97%, yield of reaction product 3-[(2-hydroxyethyl) thio] propionic acid based on charged 2-mercaptoethanol is 97%, selectivity 97 %Met.

Example 2 Using the same apparatus as in Example 1, 10 g of toluene, 7.8 g (0.1 mol) of 2-mercaptoethanol, and IRA94S which is a weakly basic anion exchange resin as a solid base.
(Rohm & Haas Company) 0.5 g (6.5% by weight relative to 2-mercaptoethanol) was charged, and methyl acrylate was stirred at 50 ° C. with a magnetic stirrer.
6 g (0.1 mol) was added dropwise in 30 minutes. After the dropping was completed, the reaction was performed for 1 hour. After completion of the reaction, a part of the reaction solution was sampled and analyzed by gas chromatography. The conversion rate of methyl acrylate was 99%, the conversion rate of 2-mercaptoethanol was 99%, and the charged 2-mercaptoethanol was used as a reference. Reaction product 3-[(2-hydroxyethyl)
The yield of methyl [thio] propionate is 98%, selectivity 98.
%Met.

Example 3 Using the same apparatus as in Example 1, the reaction product 3-
Methyl [(2-hydroxyethyl) thio] propionate 10 g, 2-mercaptoethanol 7.8 g (0.1 m
ol), 0.5 g (6.5% by weight based on 2-mercaptoethanol) of IRA94S (made by Rohm & Haas Co., Ltd.) which is a weakly basic anion exchange resin as a solid base,
While stirring with a magnetic stirrer at 50 ° C., 8.6 g (0.1 mol) of methyl acrylate was added dropwise over 30 minutes. After the dropping was completed, the reaction was performed for 1 hour. After completion of the reaction, a part of the reaction solution was sampled and analyzed by gas chromatography. The conversion rate of methyl acrylate was 99%, the conversion rate of 2-mercaptoethanol was 100%, and the charged 2-mercaptoethanol was used as a reference. The yield of the reaction product methyl 3-[(2-hydroxyethyl) thio] propionate is 99.
%, The selectivity was 100%. Further, the solid catalyst was separated by filtration from the obtained reaction solution, and then simple distillation was carried out. As a result, the recovery rate of the target product was 95%.

Example 4 Using the same apparatus as in Example 1, 10 g of toluene, 7.8 g (0.1 mol) of 2-mercaptoethanol, and IRA94S which is a weakly basic anion exchange resin as a solid base.
(Rohm & Haas Company) 0.5 g (6.5% by weight based on 2-mercaptoethanol) was charged, and methyl methacrylate 1 was stirred at 50 ° C. with a magnetic stirrer.
0 g (0.1 mol) was added dropwise in 30 minutes. After the dropping was completed, the reaction was performed for 1 hour. After completion of the reaction, a part of the reaction solution was sampled and analyzed by gas chromatography. The conversion rate of methyl methacrylate was 95%, the conversion rate of 2-mercaptoethanol was 97%, and the charged 2-mercaptoethanol was used as a reference. The yield of the reaction product methyl 3-[(2-hydroxyethyl) thio] -2-methyl-propionate was 95%, and the selectivity was 97%.

Example 5 Using the same apparatus as in Example 1, 10 g of diethylene glycol dimethyl ether, 2-mercaptoethanol 7.
8 g (0.1 mol), IRA400T (manufactured by Rohm & Haas Co.) which is a strongly basic anion exchange resin as a solid base, 0.5 g (6.5 to 2-mercaptoethanol).
% Of butyl acrylate and stirred with a magnetic stirrer at 80 ° C. 10.2 g (0.08 m) of butyl acrylate
ol) was added dropwise in 30 minutes. After the dropping was completed, the reaction was performed for 2 hours. After completion of the reaction, a part of the reaction solution was sampled and analyzed by gas chromatography. The conversion of butyl acrylate was 96%, the conversion of 2-mercaptoethanol was 95%, and the reaction was based on the charged butyl acrylate. Product 3-
The yield of butyl [(2-hydroxyethyl) thio] propionate was 96% and the selectivity was 99%.

Example 6 Using the same apparatus as in Example 1, 10 g of acetonitrile,
2-mercaptoethanol 7.8 g (0.1 mol),
As a solid base, 0.5 g of Deuolite A-104 (Sumitomo Chemical Co., Ltd.) which is a strongly basic anion exchange resin (6.5% by weight with respect to 2-mercaptoethanol) was charged, and the temperature was 80 ° C.
Acrylic acid 2 while stirring with a magnetic stirrer
-Ethylhexyl 22.1 g (0.12 mol) 30
Dropped in minutes. After the dropping was completed, the reaction was performed for 2 hours. After completion of the reaction, a part of the reaction solution was sampled and analyzed by gas chromatography. The conversion rate of 2-ethylhexyl acrylate was 95%, the conversion rate of 2-mercaptoethanol was 96%, and the charged 2-mercaptoethanol was the standard. The yield of 2-ethylhexyl 3-[(2-hydroxyethyl) thio] propionate, a reaction product, was 95%, and the selectivity was 99%.

Example 7 Using the same apparatus as in Example 1, 30 g of chloroform and 2 g of chloroform were used.
-7.8 g (0.1 mol) of mercaptoethanol, 0.5 g of Diaion WA-10 (manufactured by Mitsubishi Kasei) which is a weakly basic anion exchange resin as a solid base (6.5% by weight based on 2-mercaptoethanol). Was charged, and 24.0 g (0.1 mol) of lauryl acrylate was added dropwise over 30 minutes while stirring with a magnetic stirrer at 80 ° C.
After completion of dropping, the reaction was carried out for 5 hours. After the completion of the reaction, a part of the reaction solution was sampled and analyzed by gas chromatography, the conversion rate of lauryl acrylate was 90%, the conversion rate of 2-mercaptoethanol was 92%, and the charged 2-mercaptoethanol was used as a reference. The yield of the reaction product, 3-[(2-hydroxyethyl) thio] lauryl propionate, was 91.
%, And the selectivity was 95%.

Example 8 Using the same apparatus as in Example 1, 50 g of xylene, 32.4 g (0.1 mol) of stearyl acrylate, and IRA94S which is a weakly basic anion exchange resin as a solid base.
(Rohm & Haas Co., Ltd.) 0.5 g (6.5% by weight with respect to 2-mercaptoethanol) was charged, and 30 g of 2-mercaptoethanol 7.8 g (0.1 mol) was stirred at 110 ° C. with a magnetic stirrer. Dropped in minutes.
After completion of dropping, the reaction was performed for 6 hours. After completion of the reaction, a part of the reaction solution was sampled and analyzed by gas chromatography. Stearyl acrylate conversion 90%, 2-mercaptoethanol conversion 85%, based on the charged 2-mercaptoethanol. The yield of the reaction product, stearyl 3-[(2-hydroxyethyl) thio] propionate, is 8
It was 6% and the selectivity was 85%.

Example 9 Using the same apparatus as in Example 1, 10 g of dioxane, 1-
Methyl-2-mercaptoethanol 9.2g (0.1m
ol), 0.5 g of Dowex SBR (manufactured by Dow Chemical Co.) which is a strongly basic anion exchange resin as a solid base.
(6.5% by weight based on 2-mercaptoethanol) was charged, and 8.6 g (0.1 mol) of methyl acrylate was added dropwise over 30 minutes while stirring with a magnetic stirrer at 50 ° C. After the dropping was completed, the reaction was performed for 1 hour. After the reaction,
A part of the reaction solution was sampled and analyzed by gas chromatography. The conversion rate of methyl acrylate was 98%, the conversion rate of 1-methyl-2-mercaptoethanol was 97%, and the charged 1-methyl-2-mercaptoethanol was The yield of the reaction product methyl 3-[(2-hydroxypropyl) thio] propionate, which is the standard, is 96% and the selectivity is 98%.
Met.

Example 10 Using the same apparatus as in Example 1, 10 g of cyclohexane,
1-phenyl-2-mercaptoethanol 15.4g
(0.1 mol), 0.5 g of magnesium oxide which is an inorganic base as a solid base (6.5% by weight with respect to 2-mercaptoethanol) were charged, and 8.6 g of methyl acrylate was stirred at 60 ° C. with a magnetic stirrer. (0.
1 mol) was added dropwise in 30 minutes. After the dropping was completed, the reaction was performed for 1 hour. After completion of the reaction, a part of the reaction solution was sampled and analyzed by gas chromatography. The conversion rate of methyl acrylate was 95%, the conversion rate of 1-phenyl-2-mercaptoethanol was 96%, and the charged 1-phenyl-2 was used. -The yield of the reaction product methyl 3-[(2-hydroxy-2-phenyl-ethyl) thio] propionate, based on mercaptoethanol, was 95%, the selectivity 98%.

Example 11 Using the same apparatus as in Example 1, a reuse experiment was conducted using the catalyst separated from the reaction solution by filtration in Example 2. After the completion of the reaction of the fifth reuse experiment, a part of the reaction solution was sampled and analyzed by gas chromatography. The conversion rate of methyl acrylate was 97%, the conversion rate of 2-mercaptoethanol was 97%, and the charged 2- The yield of the reaction product methyl 3-[(2-hydroxyethyl) thio] propionate based on mercaptoethanol was 96% and the selectivity was 98%.

Comparative Example 1 The reaction was carried out under the same conditions as in Example 1 except that the solid base was not used. After 6 hours from the end of the dropping, a part of the reaction solution was collected and analyzed by high performance liquid chromatography. The conversion rate of acrylic acid was 80%, the conversion rate of 2-mercaptoethanol was 50%, and the charged 2-mercaptoethanol was used as a standard. The yield of the reaction product 3-[(2-hydroxyethyl) thio] propionic acid was 51% and the selectivity was 55%.

Comparative Example 2 The reaction was carried out under the same conditions as in Example 2 except that the solid base was not used. 6 hours after the end of the dropping, a part of the reaction solution was collected and analyzed by gas chromatography. The conversion rate of methyl acrylate was 70%, the conversion rate of 2-mercaptoethanol was 65%, and the charged 2-mercaptoethanol was used as a standard. The yield of the reaction product methyl 3-[(2-hydroxyethyl) thio] propionate is 60.
%, And the selectivity was 58%.

Comparative Example 3 The reaction was carried out under the same conditions as in Example 7, except that the solid base was not used. After 24 hours from the end of the dropping, a part of the reaction solution was collected and analyzed by gas chromatography. The conversion rate of stearyl acrylate was 34%, the conversion rate of 2-mercaptoethanol was 30%, and the charged 2-mercaptoethanol was used as a standard. Reaction product 3-[(2-
The yield of hydroxyethyl) thio] stearyl stearyl was 31% and the selectivity was 58%.

Comparative Example 4 The same reaction conditions as in Example 4 were used except that triethylamine was used as a homogeneous catalyst. After 3 hours from the end of the dropping, a part of the reaction solution was sampled and analyzed by gas chromatography to find that the conversion of methyl acrylate was 90.
%, Conversion of 2-mercaptoethanol 89%, yield of reaction product methyl 3-[(2-hydroxyethyl) thio] propionate 85%, selectivity 98 based on the charged 2-mercaptoethanol. %Met. When this reaction solution was distilled in the same manner as in Example 3, the recovery of the target product was 75%. The residual triethylamine accelerates the decomposition of the target substance, so that the recovery rate is greatly reduced.

As is clear from these results, according to the method of the present invention using a solid catalyst, the sulfide compound represented by the general formula (3) can be obtained in high yield, but no catalyst is used. However, when a homogeneous catalyst is used, the yield of the target product decreases and recovery becomes difficult.

[0044]

According to the process of the present invention, a mercaptoalkanol and an unsaturated compound are reacted in the presence of a solid base to give an industrially useful sulfide compound represented by the general formula (3). Can be obtained with high yield and high selectivity.

Further, since the solid base used as a catalyst is hardly soluble in the reaction solution, it can be easily separated from the reaction solution and has excellent durability, so that it can be reused for a long time. Furthermore, since the reaction liquid after catalyst separation contains almost no catalyst component, the target compound can be separated and purified easily and efficiently without deterioration or decomposition.

Therefore, it can be said that the production method of the present invention is excellent as an industrially advantageous and highly productive production method of the sulfide compound represented by the general formula (3).

Claims (3)

[Claims] 1. A mercaptoalkanol represented by the following general formula (1): HO—R ¹ —SH (wherein R ¹ represents a hydrocarbon residue having 2 to 8 carbon atoms), and the following general formula: Formula (2): (In the formula, R ² represents hydrogen or a hydrocarbon residue having 1 to 4 carbon atoms, and R ³ represents hydrogen or a hydrocarbon residue having 1 to 18 carbon atoms.) A compound represented by the following general formula (3) characterized by reacting with a compound in the presence of a solid base catalyst: (In the formula, R ¹ , R ² and R ³ are each represented by the general formula (1),
Same as (2). The manufacturing method of the sulfide compound shown by these. 2. The method according to claim 1, wherein the solid base catalyst is an anion exchange resin. 3. The method according to claim 1, wherein the solid base catalyst is an oxide and / or hydroxide of an alkaline earth metal.