JP2693225B2 - Sulfur-containing aliphatic carboxylic acid ester and method for producing the acid - Google Patents

Description

TECHNICAL FIELD The present invention relates to a sulfur-containing aliphatic carboxylic acid ester and a method for producing the acid. Further speaking, thioaliphatic carboxylic acid ester, thiodialiphatic carboxylic acid ester and / or
Further, the present invention relates to a dithiodialiphatic carboxylic acid ester or a method for producing those acids.

These compounds are used as useful compounds in many fields, such as hair growth agents, pharmaceutical intermediates, heavy metal removing agents, polymerization regulators, antioxidants, metal surface treating agents, and rubber additives.

[Prior Art] Among the methods for producing a sulfur-containing aliphatic carboxylic acid or its ester, the representative ones are the following methods for producing thioglycolic acid or its ester.

(1) It is produced by the reaction of monochloroacetic acid and an aqueous solution of sodium hydrosulfide, which is a typical production method currently practiced industrially (JP-A-61-118358 and JP-A-55-145663). JP, JP-A-53-147026, JP-A-51
-29440 and JP-A-49-75527).

(2) A method in which monochloroacetic acid is reacted with sodium thiosulfate and then hydrolyzed (US Pat. No. 2,594,030).
No. 2,413,361 and British Patent No. 624,568).

(3) A method in which monochloroacetic acid and an alkali polysulfide are reacted, and then reduction treatment is performed by using zinc and a mineral acid (West German Patent No. 180,875).

(4) A method in which xanthogenic acid and sodium hydrosulfide are reacted by heating (US Pat. No. 3,860,641).

Further, as a method for producing a thioglycolic acid ester,
Method for esterifying thioglycolic acid (JP-A-56-972)
39), a method by reaction of chloroacetic acid ester with alkali hydrosulfide (JP-A-48-86818 and JP-A-63-1).
0755 publication).

Further, as a method for synthesizing β-mercaptopropionic acid or its ester, for example, JP-A-59-29656, JP-A-61-151163 or JP-A-59-186955,
The method for producing 3,3'-thiodipropionic acid is disclosed, for example, in JP-A-58-21662.

Thus, in order to industrially produce a mercapto aliphatic carboxylic acid, a method of synthesizing the acid, then esterifying the acid, and esterifying a halogenated aliphatic carboxylic acid, and then the halogen atom and a mercapto group Or a method of adding hydrogen sulfide at high pressure to an unsaturated aliphatic carboxylic acid ester such as an acrylic acid ester.

[Problems to be Solved by the Invention] In the conventional method for producing a mercapto aliphatic carboxylic acid represented by thioglycolic acid, since this acid is water-soluble, a by-product and a salt produced as a by-product are used. It is difficult to separate and purify.

Moreover, since the thermal stability is also poor, separation and purification by distillation are not effective means due to decomposition of the target substance.

Further, in the method of introducing hydrogen sulfide gas in order to increase the reaction yield, high temperature and high pressure are required, so that there are major problems in terms of material and investment of the apparatus.

On the other hand, the method for producing a mercapto aliphatic carboxylic acid ester has the above-mentioned problems as it is when esterifying a mercapto aliphatic carboxylic acid, so that only a large amount of impurities can be obtained. When synthesizing from a halogenated aliphatic carboxylic acid ester, the reaction with the alkali hydrosulfide is not performed unless the solvent is water-soluble, and as a result,
The solvent dissolves in both the organic layer and the aqueous layer, which causes problems in the cyclic use of the solvent and wastewater treatment.

Further, the method for synthesizing an ester by the addition reaction of hydrogen sulfide has the same problems as described above, and each has its own drawbacks.

In view of the above-mentioned problems, the present inventors have diligently studied an industrially advantageous method for a method for synthesizing a mercapto aliphatic carboxylic acid or an ester thereof, and when the reaction is carried out using a phase transfer catalyst, Therefore, the present invention has been completed by finding that it is obtained with high purity and high yield, and that the solvent and the catalyst can be reused, and at the same time, the wastewater treatment is easy.

[Means for Solving the Problems] That is, the present invention comprises a substantially water-insoluble halogenated aliphatic carboxylic acid ester, Me (SH) _m , Me _{2 / m} S or Me _{2 / m}
S _p [in the formula, Me represents an alkali metal, NH ₄ or an alkaline earth metal, m represents a valence of a cation (Me), and p represents a number greater than 1] The present invention relates to a method for producing a sulfur-containing aliphatic carboxylic acid ester, which comprises reacting an aqueous sulfide selected from sulfide or polysulfide in a water-insoluble catalyst in the presence of a phase transfer catalyst.

Furthermore, the present invention relates to a method for producing a sulfur-containing aliphatic carboxylic acid, which comprises hydrolyzing the sulfur-containing aliphatic carboxylic acid ester obtained by the above method.

[Operation] Hereinafter, the present invention will be described in detail.

In the method according to the present invention, the starting halogenated aliphatic carboxylic acid ester must be substantially water-insoluble.

The reason for this is taken into consideration in terms of recovery and utilization of the solvent, separation and purification, etc., and those represented by the following general formula are preferred in the present invention: X (CH ₂ ) _n COOR ¹ (1) [In the formula, X represents Cl or Br, R ¹ represents an alkyl group having ³ to 18 carbon atoms, R ² and R ³ represent H or an alkyl group having 1 to 4 carbon atoms, and n is 1 to 3 Represents the integer].

In the present invention, the reaction product obtained by esterifying the ester precursor acid and alcohol by azeotropic dehydration using an acid catalyst and a water-insoluble solvent can be directly used as a starting material.

Therefore, the method by the mercapto reaction described below using such a reaction product can be mentioned as a preferred embodiment in which the method of the present invention can be more industrially advantageously carried out.

The esterification reaction is well known, and examples thereof include sulfuric acid, hydrochloric acid, phosphoric acid, p-trienesulfonic acid, methanesulfonic acid, sulfates and acidic sulfates, and one or two of them are used. The above are used.

The amount of catalyst is preferably in the range of 0.01 to 10 g per mol of distilled water. The water-insoluble solvent that also serves as a dehydrating azeotrope is not particularly limited as long as it is used in a usual esterification reaction, and for example, benzene, toluene, xylene, cyclohexane, n-hexane, n-heptane and the like. Hydrocarbons, carbon tetrachloride, chloroform, chlorine-based hydrocarbons such as 1,1,1-trichloroethane, ketones such as methyl isobutyl ketone, higher alcohols such as pentyl alcohol, 2-ethylhexanol and octanol. , They may be one kind or two or more kinds.
However, industrially, benzene, toluene, and xylene (BTX) are preferable. The amount used may be the minimum amount necessary for distilling off water in the reaction system, but in the present invention, it is preferably in the range of 50 to 500 g per mol of the halogenated aliphatic carboxylic acid.

Further, as the alcohol used for esterification,
Since the ester must be substantially water-insoluble as shown in the above general formula, any alcohol other than lower alcohols such as methanol and ethanol may be used, but carbon Alcohols of number 3-18 are suitable. The alkyl group in the alcohol may be a cycloalkyl group or an alkylcyclo group.

Further, dihydric or higher alcohols such as propyl glycol, trihydric alcohols such as 1,5-pentadiol, glycerol and trimethylolpropanol, or polyhydric alcohols such as pentaerysterol may be used.

Next, as another raw material, a water-soluble sulfide, the following formula: Me (SH) _m ... (a) Me _{2 / m} S ... (b) Me _{2 / m} S _p ... (c) Represents an alkali metal (Na, K) or ammonium ion or an alkaline earth metal (Ca, Ba, Sr), m represents a cation (Me) valence, and p represents a value greater than 1] Hydrosulfide or polysulfide, which may be a mixture.

However, conventionally, these two raw materials were reacted in a water-soluble solvent to obtain a mercapto-formed product. However, it is difficult to separate and collect an aqueous solution containing a by-product salt such as salt and the solvent, and to efficiently The desired product cannot be obtained. The present invention is based on the fact that the decomposition of an ester does not occur at atmospheric pressure by using a phase transfer catalyst even in a water-insoluble solvent for the two raw materials as described above, and the mercapto-forming reaction occurs efficiently. There is.

Here, as the phase transfer catalyst, quaternary ammonium salt, pyridinium salt, picolinium salt, quaternary phosphonium salt, crown ether and the like are known, but industrially, quaternary ammonium salt, pyridinium salt or Quaternary phosphonium salts are suitable.

These catalysts are, for example, "phase transfer catalysts" [(WPWebe
r, GW Gokel, co-authored by Kagaku Dojin], that is, tetramethylammonium chloride, benzyltrimethylammonium chloride, benzyltriethylammonium chloride (Makosza) can be used as the quaternary ammonium salt. Catalyst), benzyltributylammonium chloride, tetrabutylammonium bromide, tetrabutylammonium hydrogensulfate (Brandstorm's catalyst), trioctylmethylammonium chloride (Starks' catalyst), and the like. Include N-laurylpyridinium chloride, N-lauryl-4-picolinium chloride, N-laurylpicolinium chloride, N-benzylpicolinium chloride and the like. As the quaternary phosphonium salt, triethylbenzylphosphonium chloride, tetra-n-butylphosphonium chloride, tetra-n-butylphosphonium bromide, tetra-n-butylphosphonium iodide, tri-n-butylmethylphosphonium iodide. , Tri-n
-Butylallylphosphonium bromide, tri-n-butylbenzylphosphonium chloride, tetra-n-butylphosphonium 0,0-diethylphosphorodithioate, tri-n-butylhexadecylphosphonium bromide, tri-n-octylethylphosphonium bromide, Examples thereof include tris-2-cyanoethylallylphosphonium chloride, ethylenebistris (2-cyanoethyl) phosphonium bromide and tetrakis (hydroxymethyl) phosphonium sulfate. Examples of the crown ether include dibenzo-18-crown-6 and dicyclohexyl-18-. Mention may be made of Crown-6 and 18-Crown-6.

As can be seen from the above, the present invention produces a sulfur-containing aliphatic compound by reacting a substantially water-insoluble halogenated aliphatic carboxylic acid ester with an aqueous sulfide solution in the presence of a phase transfer catalyst in a water-insoluble solvent. As the ester, a reaction product containing a water-insoluble solvent may be directly used, or may be itself, and in many cases, it is represented by the general formula (1) or (2). It is what is done.

This reaction is liable to cause side reactions, and the sulfide aqueous solution is different depending on any of the compounds represented by the above formula (a), (b) or (c), and produces various sulfur-containing aliphatic compounds. Therefore, in order to obtain the desired compound,
It is necessary to fully consider the reaction conditions and the adjustment of the sulfide aqueous solution.

That is, the sulfur-containing aliphatic carboxylic acid ester produced by the method according to the present invention has the general formula (1) or (2)
When the ester represented by is used, it has the following general formula: HS (CH ₂ ) _n COOR ¹ (3) S-[(CH ₂ ) _n COOR ¹ ] ₂ (5) [S (CH ₂ ) _n COOR ¹ ] ₂ … (7) (In the formula, R ¹ , R ² , R ³ and n have the same meanings as described above.) The basic reaction is the formation reaction of the compound represented by the general formula (3) or (4). It is obtained by reacting an ester of the general formula (1) or (2) with an aqueous solution of hydrosulfide of the formula (a).

However, commercially available hydrosulfides such as sodium hydrosulfide are not pure, and in many cases (b)
Alternatively, it is difficult to synthesize NaSH purely even when the sulfide of (c) is contained and hydrogen sulfide is absorbed in caustic soda, and when these are contained, the general formula (7) or ( A dithiodicarboxylic acid ester represented by 8) is produced. Therefore, if the above reaction is shown, for example, it can be expressed by the following formula: NaSH + ClCH ₂ COOR ¹ → SHCH ₂ COOR ¹ + NaCl (a) NaSH + HSCH ₂ COOR ¹ NaSCH ₂ COOR ¹ + H ₂ S (b) NaSCH ₂ COOR ¹ ＋ ClCH ₂ COOR ¹ → S (CH ₂ COOR ¹ ) ₂ ＋ NaCl… (C) Na ₂ S + 2ClCH ₂ COOR ¹ → S (CH ₂ COOR ¹ ) ₂ ＋ 2NaCl ・ (D) Na ₂ S ₂ ＋ 2ClCH ₂ COOR ¹ → (SCH ₂ COOR ¹ ) ₂ + 2NaCl (e) The above reaction is exactly the same even when an ester of the general formula (2) type is used.

In the present invention, in the reaction of the formula (a), the side reactions of the formulas (b) and (c) are smaller than the reaction in the water catalyst of the conventional method, and other reactions can be easily controlled.

In other words, when hydrogen sulfide is introduced into the reaction system, the formula (b)
The reaction of the formula (d) due to the sulfide existing in the hydrosulfide can be suppressed, and a small amount of sulfur is added to the starting hydrosulfide to form the polysulfide, and the formula (d) is converted into the formula (d). ) To produce a dithiocarboxylic acid ester, and then the ester transferred to the organic layer is subjected to a reduction treatment to give a high yield of the mercaptocarboxylic acid ester of the general formula (3) or (4). Can be obtained at

In most cases, this reduction treatment is carried out with nascent hydrogen gas consisting of mineral acid and metal powder such as zinc, tin, or palladium.
Alternatively, electrolytic reduction is industrially advantageous, but is not particularly limited thereto.

In the present invention, the target product of the general formula (3) or (4) type is as described above, but the target product of the general formula (5) or (6) is a sulfurized water solution of the formula (b). It is obtained by using the thing.

However, since the sulfide of the formula (b) produces the hydrosulfide of the formula (a) by hydrolysis, it may be adjusted by adding hydrogen sulfide or sulfur so as to have the composition of the formula (b) in an aqueous solution. is necessary.

Alternatively, in the reaction between the aqueous hydrosulfide solution of the formula (a) as shown in the formula (a) and the halogenated aliphatic carboxylic acid ester, the reaction is performed at a temperature higher than the reaction temperature in the formula (a). Alternatively, by heating the reaction product of the formula (a), a mercaptodicarboxylic acid ester of the general formula (5) or (6) can be obtained.

Further, in order to obtain the target product of the general formula (7) or (8) type, the prepared polysulfide aqueous solution of the formula (c) is reacted. However, none of the compounds of the general formula (7) or (8) can be obtained, and a mixture with the compounds of the general formula (3) or (4) type is obtained. Therefore, if it is reduced, it becomes a compound of the general formula (3) or (4) type, but conversely, by subjecting the organic layer containing these products to an oxidation treatment with a desired oxidizing agent, The (7) or (8) type can be obtained in high yield.

In this reaction, the concentration of the sulfide aqueous solution is 5 to 50% by weight.
Although it is used in the range of, the higher concentration is industrially advantageous in consideration of wastewater. However, since salts such as common salt are precipitated, it is industrially preferable to be in the range of 20 to 40% by weight in consideration of reuse of wastewater as sulfide dissolution water.

Next, the reaction ratio of the raw material ester and the sulfide is not significantly different from the case of the conventional method, but in many cases the molar ratio of the ester and the cation in the sulfide is 1.0 to 2.0, preferably 1.2 to 1.7. Is in the range.

The sulfur added to the aqueous sulfide solution is, for example, in the case of sodium sulfide, an amount of 1-1.1 corresponding to Na ₂ S.
It is a 5-fold molar amount and is completely dissolved in 50 to 100 ° C. in 20 to 30 minutes.

The amount of the phase transfer catalyst used is in the range of 0.1 to 10 g / mol with respect to the halogenated aliphatic carboxylic acid ester,
It is preferably in the range of 1 to 3 g / mol.

The reaction temperature is in the range of 0 to 150 ° C., though it varies greatly depending on the type of the starting material ester and the desired product. For example, when a chloroacetic acid ester of the general formula (3) type is obtained, the temperature is 0 to 40 ° C., and similarly α-chloropropiolic acid ester is 40 to 70 ° C., β-chloropropiolic acid ester and 4-bromoacetic acid ester are used. 50 for Esters
Proceeds rapidly at ~ 80 ° C.

The reaction time varies for the same reason as above, but is in the range of 0.5 to 6 hours, and in most cases 1 to 2 hours is sufficient.

After the reaction is completed, a by-product salt such as sodium chloride is dispersed, and the aqueous layer is reused as much as possible.

On the other hand, the recovered organic layer can be recovered after dispersing the solvent depending on the intended product to be recovered, but the reduction treatment or the oxidation treatment was performed in the vicinity of the greenhouse for 1 to 6 hours as described above. After that, the reaction is terminated and the desired product is recovered after separating from the solvent by a conventional method.

Next, according to the present invention, the sulfur-containing aliphatic carboxylic acid ester obtained above is hydrolyzed by an ordinary method on the acidic side to obtain the corresponding sulfur-containing aliphatic carboxylic acid.

In the present invention, a water-insoluble sulfur-containing aliphatic carboxylic acid ester is first obtained in a high yield using a water-insoluble organic solvent, and then the corresponding acid is produced by hydrolyzing this, which is different from the conventional method. Each is easy to separate and collect,
It does not decrease the yield of acid, and can be said to be a very industrially advantageous method.

[Example] Example 1 120.1 g of flake sodium hydrosulfide (70% by weight) was placed in a four-necked flask equipped with a stirrer, a gas inlet tube, and a thermometer.
Add 4.8g of sulfur and 120.1g of water and raise the temperature to 90 ° C to dissolve the sulfur. After dissolution, the mixture was cooled to room temperature, and 413.4 g of a 50% toluene solution of 2-ethylhexyl chloroacetate was added, and 4
Cool to ~ 6 ° C. Hydrogen sulfide is blown through the gas introduction pipe at a rate of 0.2 l / min for 5 to 10 minutes for replacement, and then 5.0 g of a 50% solution of tetra-n-butylphosphonium bromide is added. The temperature rises to near 30 ° C and the reaction is complete in about 1 hour.

After the reaction, the organic layer and the aqueous layer were separated, and 110 g of concentrated hydrochloric acid was added to the organic layer.
And 10.5 g of zinc powder are added, and the impurity 2-ethylhexyl dithiodiglycolate is reduced at room temperature for 3 hours, the aqueous layer is separated, and the organic layer is washed with water to obtain a toluene solution of 2-ethylhexyl thioglycolate.

Next, toluene was distilled off under reduced pressure, and the residue was removed at 2.0 mmH.
g, thioglycolic acid 2 by vacuum distillation at 110 ℃
202.3 g of ethylhexyl are obtained.

As a result of measuring pure content with a gas chromatograph, the purity is 9
It was 9.6%. The yield from 2-ethylhexyl chloroacetate was 98.6%.

Example 2 In a four-necked flask equipped with a stirrer and a thermometer, 120.1 g of flake sodium hydrosulfide (70% by weight), 4.8 g of sulfur, and water
120.1 g is added and the temperature is raised to 90 ° C. to dissolve the sulfur. After dissolution, 50% of 2-ethylhexyl β-chloropropionate
Toluene solution 441.5g was added, and the liquid temperature was adjusted to 80 ° C.
-Butylethylphosphonium bromide 2.5 g was added,
Incubate for 1 hour.

After the reaction, the organic layer and the aqueous layer were separated, and the organic layer was concentrated with hydrochloric acid 84.0
g of zinc powder and 8.0 g of zinc dust were added to reduce 2-ethylhexyl dithiodipropionate as an impurity.
A toluene solution of ethylhexyl is obtained.

Next, toluene was distilled off under reduced pressure, and the residue was removed at 2.0 mmH.
g, thiopropionic acid 2 by vacuum distillation at 118 ° C
216.2 g of ethylhexyl are obtained.

As a result of measuring the pure content with a gas chromatograph, the target product with a purity of 99.5% was obtained, and the yield from 2-ethylhexyl β-chloropropionate was 99.0%.

Example 3 In a four-necked flask equipped with a stirrer, a water separator and a thermometer, 130.2 g of 2-ethylhexanol and 9 of chloroacetic acid were added.
4.5g, 200g of toluene and 1g of p-toluenesulfonic acid were added, and the pressure was reduced to 400mmHg (gauge pressure) with an aspirator.
The temperature is raised to 0 to 90 ° C., and toluene is refluxed for 3 hours. The esterification reaction was carried out with the end point when 18 g of water was distilled into the water separator.

On the other hand, 120.1 g of flake sodium hydrosulfide (70% by weight), 4.8 g of sulfur and 120.1 g of water are added to the same four-necked flask as described above, and the temperature is raised to 60 ° C. to dissolve the sulfur. After dissolution, the mixture is cooled to room temperature, the 2-ethylhexyl chloroacetate product obtained above is added as it is, and the mixture is cooled to 4 to 6 ° C. Hydrogen sulfide is blown through the gas introduction pipe at a rate of 0.2 l / min for 5 to 10 minutes to replace the hydrogen sulfide, and 5.0 g of a 50% aqueous solution of tri-n-butylethylphosphonium bromide is added. The temperature rises to near 30 ° C and the reaction is complete in about 1 hour.

After the reaction, the organic layer and the aqueous layer were separated, and 110 g of concentrated hydrochloric acid was added to the organic layer.
And 10.5 g of zinc dust are added, and the impurity 2-ethylhexyl dithiodiglycolate is reduced at 30 ° C. to obtain a toluene solution of 2-ethylhexyl thioglycolate. Toluene was distilled off under reduced pressure, and the residue was distilled under reduced pressure at 2.0 mmHg and 110 ° C. to give 2-ethylhexyl thioglycolate 20.
Get 1.0g.

As a result of measuring pure content with a gas chromatograph, the purity was 99.6.
% Target product was obtained. The yield from chloroacetic acid is
98.0%.

Examples 4-16, Comparative Examples 1-2 Example 17 Into a four-necked flask equipped with a stirrer and a thermometer, 65.1 g of sodium sulfide (60% by weight) and 120.1 g of water were added and dissolved. After dissolution, 413.4 g of a 50% benzene solution of 2-ethylhexyl chloroacetate was added, 2 g of tetra-n-butylphosphonium chloride was added, and the mixture was reacted at room temperature for 3 hours.

After the reaction, the organic layer and the aqueous layer are separated, the organic layer is washed with water until neutral, and benzene is distilled off under reduced pressure to obtain 186.0 g of 2-ethylhexyl thiodiglycolate. When the pure content was measured by a gas chromatograph, the target product having a purity of 98.0% was obtained. The yield from 2-ethylhexyl chloroacetate was 97.3%.

Example 18 The reaction liquid after completion of the sulfurization step of Example 1 is separated and an aqueous iodine solution is added with stirring until the aqueous layer is colored brown, and after coloring, the organic layer and the aqueous layer are separated. After washing with water and distilling off the toluene under reduced pressure, 2-ethylhexyl dithioglycolate
Get 202.3g. As a result of measuring pure content with a gas chromatograph, a target product having a purity of 98.8% was obtained. The yield from chloroacetic acid is 98.6%.

Example 19 The reaction solution after the reduction step of Example 4 is separated and toluene is distilled off under reduced pressure. The same amount of 10% hydrochloric acid as the organic layer is added and stirred, the temperature is raised to 70 ° C., the pressure is adjusted and the mixture is refluxed. After decomposition for 3 hours, hydrochloric acid is recovered until n-butanol does not distill. The same amount of dichloromethane is added to the aqueous layer, thioglycolic acid is extracted 3 times, and washed with water. The thioglycolic acid from which dichloromethane was recovered was distilled under reduced pressure at 107 ° C and 16 mmHg.
1.2g Obtain the desired product. As a result of measuring pure content with a gas chromatograph, a target product having a purity of 98.8% was obtained. The yield based on chloroacetic acid was 87.0%.

[Effect of the Invention] According to the method of the present invention, a sulfur-containing aliphatic carboxylic acid ester such as thioaliphatic carboxylic acid ester, thiodialiphatic carboxylic acid ester or dithiodicarboxylic acid ester, or an acid thereof or an ester thereof is obtained. It can be manufactured industrially advantageously.

That is, since the two starting materials are reacted in a water-insoluble solvent in the presence of a phase transfer catalyst, the target compound can be obtained in high purity because the yield is high and the separation operation is easy.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification number Reference number within the agency FI Technical display location C07B 61/00 300 C07B 61/00 300 (72) Inventor Yumitsu Uno 9-15 Kameido, Koto-ku, Tokyo No. 1 in Nippon Kagaku Kogyo Co., Ltd. (72) Inventor Eiichi Watanabe Kosaka-machi, Kazuno-gun, Akita Prefecture Kosaka Plant, Barite Industry Co., Ltd. (56) Reference JP-A-59-51256 (JP, A)

Claims (12)

(57) [Claims] 1. A substantially water-insoluble halogenated aliphatic carboxylic acid ester and Me (SH) _m , Me _{2 / m} S or Me _{2 / m} S _p [wherein, Me is an alkali metal, NH ₄ or an alkali. Represents an earth metal, m represents a valence of a cation (Me), and p represents a value greater than 1.]
Of a sulfur-containing aliphatic carboxylic acid ester characterized by reacting a hydrosulfide represented by, with an aqueous sulfide selected from sulfide or polysulfide in a water-insoluble solvent in the presence of a phase transfer catalyst. Production method. 2. A substantially water-insoluble halogenated aliphatic carboxylic acid ester is obtained by azeotropic dehydration of a halogenated aliphatic carboxylic acid and an alcohol having 3 or more carbon atoms in a water-insoluble solvent in the presence of an acid catalyst. The method for producing a sulfur-containing aliphatic carboxylic acid ester according to claim 1, wherein the obtained esterification reaction product is used as it is. 3. A substantially water-insoluble halogenated aliphatic carboxylic acid ester has the following general formula (1) or (2) X (CH ₂ ) _n COOR ¹ ... (1) (In the formula, X represents Cl or Br, R ¹ represents an alkyl group having ³ to 18 carbon atoms, R ² and R ³ represent H or an alkyl group having 1 to 4 carbon atoms, and n is 1 to 3 Is represented by the following formula): The process for producing a sulfur-containing aliphatic carboxylic acid ester according to claim 1 or 2. 4. A sulfur-containing aliphatic carboxylic acid ester is represented by the following general formula (3), (4), (5), (6), (7) or (8) thioaliphatic carboxylic acid ester: HS (CH ₂ ) _n COOR ¹ (3) Thioaliphatic carboxylic acid ester: Thiodi aliphatic carboxylic acid _{ester: S - [(CH 2)} n COOR 1] 2 ... (5) thiodi aliphatic carboxylic acid esters: Dithiodialiphatic carboxylic acid ester: [S (CH ₂ ) _n COOR ¹ ] ₂ (7) Dithiodialiphatic carboxylic acid ester: (In the formula, R ¹ represents an alkyl group having 3 to 18 carbon atoms, R ² and
R ³ represents H or an alkyl group having 1 to 4 carbon atoms, and n is 1
Represents an integer of 3 to 3).
4. The method for producing a sulfur-containing aliphatic carboxylic acid ester according to any one of 1 to 3. 5. A mercapto reaction is carried out by adding a small amount of sulfur or / and introducing hydrogen sulfide, and then the organic layer is subjected to a reduction treatment to produce a thioaliphatic carboxylic acid ester of the general formula (3) or (4). The method for producing a sulfur-containing aliphatic carboxylic acid ester according to any one of claims 1 to 3. 6. The method for producing a sulfur-containing aliphatic carboxylic acid ester according to claim 5, wherein the reduction treatment is carried out with active hydrogen generated by the reaction between the metal powder and the mineral acid. 7. An aqueous sulfide solution represented by Me _{2 / m} S (wherein Me represents an alkali metal, NH ₄ or an alkaline earth metal, and m represents a valence of a cation) as an aqueous sulfide solution. The mercapto reaction is carried out using the general formula (5) or (6)
The method for producing a sulfur-containing aliphatic carboxylic acid ester according to any one of claims 1 to 3, wherein a thiodialiphatic carboxylic acid ester represented by 8. A sulfur-containing aliphatic compound, characterized in that a thiodialiphatic carboxylic acid ester represented by the general formula (5) or (6) is produced by heating the reaction product according to claim 5. Method for producing carboxylic acid ester. 9. After the mercapto reaction, the separated organic layer is subjected to an oxidation treatment to produce the dithiodialiphatic carboxylic acid ester represented by the general formula (7) or (8), according to any one of claims 1 to 3. A method for producing a sulfur-containing aliphatic carboxylic acid ester. 10. Me _{2 / m} S ₂ (in the formula, Me ₂
Represents an alkali metal, NH ₄ or an alkaline earth metal,
m represents the valence of the cation) and a mercapto reaction is carried out using an aqueous polysulfide solution represented by the formula (7) or (8) to produce a dithiodialiphatic carboxylic acid ester. A method for producing the sulfur-containing aliphatic carboxylic acid ester according to any one of claims 1. 11. The method for producing a sulfur-containing aliphatic carboxylic acid ester according to claim 1, wherein the phase transfer catalyst is a quaternary phosphonium salt, a quaternary ammonium salt or a pyridinium salt. 12. A method for separating an organic layer of a sulfur-containing aliphatic carboxylic acid ester obtained by the method according to claim 1 and then hydrolyzing the organic layer on an acidic side. A method for producing a sulfur-containing aliphatic carboxylic acid.