JP2000128857A - Production of aliphatic polythiol compound - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject compound useful as a raw material and an intermediate material of a drug, an agrochemical and a rubber chemical, and a raw material of an inhibitor and a metal surface-treating agent, etc., by reacting a polyhalogenated alkyl with ammonium hydrogen sulfide in a non- aqueous aprotic polar solvent. SOLUTION: This method for producing an aliphatic polythiol compound is provided by reacting a polyhalogenated alkyl of the formula: R(X)n [R is a 2-10C alkyl; X is a halogen except for F; (n) is 2-4], preferably 1,2,3- trichloropropane, 1,3-dichloro-2-(chloromethyl)-2-methylpropane, etc., with ammonium hydrogen sulfide in a non-aqueous aprotic polar solvent, preferably in a solvent such as N,N-dimethylformamide, N-methyl-2-pyrrolidone, etc.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a novel method for producing an aliphatic polythiol compound at a high yield and at a low cost. Aliphatic polythiol compounds are useful as raw materials and intermediates for pharmaceuticals, agricultural chemicals and rubber chemicals, inhibitors, metal surface treatment agents, lubricating oil additive raw materials, high refractive index plastic raw material monomers, and lithium battery electrode materials. is there.

[0002]

2. Description of the Related Art Conventionally, a process for producing an aliphatic polythiol compound is generally known by a reaction between a polyalkyl halide and sodium hydrogen sulfide or thiourea.

For example, when 1,2,3-trimercaptopropane is obtained from 1,2,3-trichloropropane,
Since a commercially available 70% sodium hydrogen sulfide is used as a thiolating agent, a side reaction such as the reaction formula (3) occurs due to about 30% of water contained in the sodium hydrogen sulfide. The yield of is significantly reduced (Reference: ORGANIC SYNTHESES)
２０, 209 (1941)).

[0004]

Embedded image (3) The above reaction formula (3) is easily generated when an alcoholic hydroxyl group is present.

Therefore, as a method for obtaining anhydrous sodium hydrogen sulfide, there is a method in which hydrogen sulfide is allowed to act on sodium methylate to concentrate and remove methanol. However, the operation is complicated and the above reaction formula is used. It is difficult to prevent a side reaction as in (3).

In order to prevent the side reaction as in the above reaction formula (3), it is necessary to select a method that does not use water or alcohols. For example, according to the reaction formula (4), 1,2,3-
A method of obtaining a thioacetyl compound by the reaction of trichloropropane and potassium thioacetate, and hydrolyzing the obtained thioacetyl compound (J. Chem. Soc., (196)
9), 16, 2087). However, in this method, the post-processing step is complicated, and it cannot be said that this method is industrially easy and inexpensive.

Embedded image (4)

[0007] Further, since sodium polysulfide is contained as an impurity in sodium hydrogen sulfide, a reaction as shown in the reaction formula (5) may be considered as a cause of a decrease in yield. RX + Na ₂ S → RSNa + NaX RSNa + RX → RSR + NaX (5) (wherein, R and X have the same meanings as in the general formula (1).)

The present invention solves the above problems and provides a method for producing a high-quality polythiol compound easily, inexpensively, and with a high yield.

[0009]

Means for Solving the Problems The present inventors have made intensive studies to achieve the above object, and as a result, have accomplished the present invention. The present invention relates to a method for producing a polythiol compound which is easy, inexpensive and has a high yield.

That is, the present invention provides a reaction in which a polyalkyl halide represented by the general formula (1) is used as a starting material, ammonium hydrogen sulfide is used as a thiolating agent, and the reaction is carried out in a system free of water and alcohol. A method for producing a polythiol compound represented by the general formula (2). R (X) n (1) (wherein, R represents an alkyl group having 2 to 10 carbon atoms;
Represents a halogen atom other than F, and n represents an integer of 2 to 4. R (SH) n (2) (wherein, R, X and n have the same meaning as in the general formula (1))

The present inventors believe that the use of ammonium hydrogen sulfide has the following synergistic effects. By blowing hydrogen sulfide and ammonia into the reaction solvent, an anhydride can be easily obtained, and the reaction as shown in the reaction formula (3) does not occur.

Embedded image (3) In the case of sodium hydrogen sulfide, sodium polysulfide is included as an impurity. In the case of ammonium hydrogen sulfide, (NH ₄ ) ₂ S is present by adding hydrogen sulfide in an equivalent amount or more to ammonia. Without doing
Ammonium hydrogen sulfide can be prepared. Since the basicity is low, the reaction such as the reaction formula (6) that occurs in the case of sodium hydrogen sulfide does not occur.

Embedded image (6) The solubility in an organic solvent is improved. Due to the above synergistic effect, polythiol compounds have high quality,
It is thought that it can be obtained at low cost and high yield.

In particular, when a secondary or tertiary polyalkyl halide is thiolated, a side reaction as shown in the reaction formula (3) is liable to occur, and it is necessary to react in a system free of water and alcoholic hydroxyl groups. is there.

Embedded image (3)

According to the present invention, the anhydride can be easily obtained, and for the above reasons, the polythiol can be easily obtained simply by distilling off the reaction solvent and removing the formed ammonium halide salt by washing with water or filtration. It has been found that a compound can be obtained.

[0014]

BEST MODE FOR CARRYING OUT THE INVENTION In the present invention, the compound represented by the general formula (1) is a polyhalogenated alkyl having a halogen atom other than fluorine at a secondary or tertiary position. Is used. Specifically, 1,2-dichloroethane, 1-bromo-2-chloroethane, 1,2-dibromoethane, 1,2-diiodoethane, 1,2-dichloroethylene, 1,2-dibromoethylene, 1,2-dichloroethane Chloropropane, 1,3-dichloropropane, 1-bromo-3-chloropropane, 1-chloro-3-iodopropane, 1,3-dibromopropane,
1,3-diiodopropane, 2,2-dichloropropane, 2-bromo-1-chloropropane, 1,2-dibromopropane, 2,2-dibromopropane, 1,3-dichlorobutane, 1,4-dichlorobutane , 1,4-dichloro-2-butene, 1-bromo-4-chlorobutane, 1,
4-dibromobutane, 2,3-dichlorobutane, 1,2
-Dibromobutane, 1,3-dibromobutane, 2,3-
Dibromobutane, 1,4-dibromo-2-butene, 1,
4-diiodobutane, 1,2-dichloro-2-methylpropane, 1,2-dibromo-2-methylpropane, 1-
Bromo-3-chloro-2-methylpropane, 1,5-dichloropentane, 1-bromo-5-chloropentane,
1,5-dibromopentane, 1,5-diiodopentane, 1,4-dibromopentane, 1,2-dibromocyclopentene, 1,6-dichlorohexane, 1-bromo-
6-chlorohexane, 1,6-dibromohexane, 1,
6-diiodohexane, 1,2-dibromohexane,
3,4-dibromohexane, 1,2-dichlorocyclohexane, 1,2-dibromocyclohexane, 1,7-dibromoheptane, 1,8-dichlorooctane, 1,8-
Dibromooctane, 1,8-diiodooctane, 1,9
-Dichlorononane, 1,9-dibromononane, 1,10
-Dichlorodecane, 1,10-dibromodecane, 1,1
Dihalides such as 0-diiododecane, 1,2-dibromo-1,2-diphenylethane, 1,2,3-trichloropropane, 1,2,3-tribromopropane,
Trihalides such as 3-dichloro-2- (chloromethyl) -2-methylpropane, 1,1,1-tris (chloromethyl) propane and tetrachloroethylene, tetraiodoethylene, pentaerythrityl tetrachloride, pentaerythrityl tetra And tetrahalides such as bromide.

Since ammonium hydrogen sulfide generally does not exist on the market, the one prepared by a conventional method described below is used. After blowing a predetermined amount of hydrogen sulfide gas into the following reaction solvent, ammonia gas was added at 0.80 to 1.
A molar amount of 00 times, preferably 0.90 to 0.95 times is added. The amount of ammonium hydrogen sulfide to be prepared is 0.9 to 1.5 equivalents, preferably 1.0 to 1.2 equivalents, to the halogen of the polyalkyl halide.

As described above, when a water and an alcoholic hydroxyl group are present in the reaction solvent, a elimination reaction of hydrogen halide as shown in the reaction formula (3) occurs. Therefore, it is desirable to avoid water and alcohols. In consideration of the solubility of hydrogen sulfide, for example, an aprotic polar solvent such as N, N-dimethylformamide (hereinafter, referred to as DMF), N-methyl-2-pyrrolidone, dimethylsulfoxide, and acetonitrile can be used. By blowing hydrogen sulfide and ammonia gas into these solvents, ammonium hydrogen sulfide anhydride can be easily obtained.

When the reaction temperature is increased, ammonium hydrogen sulfide is dissociated, so that the reaction at normal pressure becomes difficult and an apparatus such as an autoclave is required. Therefore, the reaction temperature is usually -20 to 80C, preferably 0 to 50C.

The reaction time is affected by stirring efficiency due to by-products of ammonium halide salt and the like, but is usually 1 to 30 hours, preferably 5 to 24 hours.

In the post-treatment step, the target polythiol compound can be easily obtained only by removing the by-product ammonium halide by filtration or washing with water, and concentrating and distilling off the reaction solvent and unreacted polyalkyl halide. be able to.

[0020]

The present invention will be described in more detail with reference to the following Examples and Comparative Examples, but the present invention is not limited to these Examples.

Example 1 A reaction vessel was charged with 750.0 g of DMF and cooled to 10 ° C. After sealing the inside of the system under reduced pressure, hydrogen sulfide
After blowing 0 g (2.59 mol), 42.0 g (2.47 mol) of ammonia was blown while maintaining the temperature at 20 ° C. or lower to prepare a DMF solution of ammonium hydrogen sulfide.
1,2,3-Trichloropropane 110.
5 g (0.75 mol) was added dropwise over 1 hour while maintaining the temperature at 20 ° C or lower, and the reaction was carried out at 30 ° C or lower for 18 hours.
In the steps after the dropping step, the inside of the system was kept in a nitrogen pressurized state. After completion of the reaction, the by-product ammonium chloride is filtered off,
DMF was concentrated under reduced pressure. 100.0 g of water and 10 of toluene
After adding 0.0 g and washing with water, liquid separation was performed. After the resulting toluene layer was dehumidified with 5.0 g of magnesium sulfate, toluene was distilled off by concentration under reduced pressure to obtain 100.2 g of 1,2,3-trimercaptopropane as a pale yellow liquid (yield 9).
5.3%). As a result of analysis by gas chromatography, the purity was 98.5%. Furthermore, simple distillation (75 ° C /
1.4 Torr), a clear, colorless 1,2,2
90.9 g of 3-trimercaptopropane (yield 86.4)
%). When analyzed by gas chromatography, the purity was 99.6%.

Example 2 A reaction vessel was charged with 270.0 g of DMF and cooled to 10 ° C. After sealing the inside of the system under reduced pressure, hydrogen sulfide
After blowing 4 g (0.92 mol), 15.0 g (0.88 mol) of ammonia was blown while maintaining the temperature at 20 ° C. or lower to prepare a DMF solution of ammonium hydrogen sulfide.
To this solution was added pentaerythrityl tetrachloride.
After dissolving 0 g (0.20 mol) in 30.0 g of DMF, the solution was added dropwise while maintaining the temperature at 20 ° C. or lower, and the reaction was carried out at 30 ° C. or lower for 24 hours. In the steps after the dropping step, the inside of the system was kept in a nitrogen pressurized state. After completion of the reaction, by-product ammonium chloride was filtered off, and DMF was concentrated under reduced pressure. After 50.0 g of water and 50.0 g of toluene were charged and washed with water, liquid separation was performed.
After the obtained toluene layer was dehumidified with 5.0 g of magnesium sulfate, toluene was distilled off under reduced pressure to obtain 37.8 g of pentaerythrityl tetramercaptan as a pale yellow liquid (yield 94.3%). When analyzed by gas chromatography, a high quality product having a purity of 98.5% was obtained.

Comparative Example 1 A reaction vessel was charged with 100.0 g of DMF and 26.4 g (0.33 mol) of 70% sodium hydrogen sulfide, and the system was purged with nitrogen. After cooling to 10 ° C, 1,2,3 under nitrogen pressure
14.7 g (0.10 mol) of trichloropropane in 1
The solution was added dropwise at 0 ° C. After the completion of the dropwise addition, the reaction was carried out at 30 ° C. or lower for 18 hours. After completion of the reaction, by-product sodium chloride was filtered off, and DMF was concentrated under reduced pressure. 30.0 g of water
And 30.0 g of toluene, and the mixture was washed with water and separated. After the obtained toluene layer was dehumidified with 2.0 g of magnesium sulfate, toluene was distilled off by concentration under reduced pressure, and yellow liquid 1,2,2 was removed.
13.7 g of 3-trimercaptopropane were obtained. When analyzed by gas chromatography, the purity was as low as 65.3%, and the impurities were by-produced high-boiling components.

[0024]

INDUSTRIAL APPLICABILITY The present invention is useful as raw materials and intermediates of pharmaceuticals, agricultural chemicals and rubber chemicals, inhibitors, metal surface treatment agents, lubricating oil additive raw materials, high refractive index plastic raw material monomers, and electrode materials for lithium batteries. The present invention provides a novel method for producing an aliphatic polythiol compound.
By employing the present invention, a high-quality aliphatic polythiol compound can be produced at a low cost and easily at a high yield. Therefore, the economic and industrial value is extremely large.

 ────────────────────────────────────────────────── ─── Continuing on the front page (72) Inventor Susumu Ohno 2900 Sone-cho, Takasago-shi, Hyogo F-term (reference) 4H006 AA02 AC24 AC63 BB20 BB21 BB22 BB24 BB41 BB61 BC10 BC19 TA04 TB73

Claims (3)

[Claims] 1. A polyalkyl halide represented by the general formula (1) and ammonium hydrogen sulfide are reacted in a non-aqueous aprotic polar solvent, represented by the general formula (2): For producing an aliphatic polythiol compound. R (X) n (1) (wherein, R represents an alkyl group having 2 to 10 carbon atoms;
Represents a halogen atom other than a fluorine atom;
Represents an integer of 4. R (SH) n (2) (wherein, R, X and n have the same meaning as in the general formula (1)) 2. The method according to claim 1, wherein the polyalkyl halide is 1,2,3.
Trichloropropane, 1,2,3-tribromopropane, 1,3-dichloro-2- (chloromethyl) -2-methylpropane, trihalide of 1,1,1-tris (chloromethyl) propane and tetrachloroethylene The method according to claim 1, wherein the method is selected from the group consisting of tetrahalide, tetraiodoethylene, pentaerythrityl tetrachloride, and pentaerythrityl tetrabromide. 3. The aprotic polar solvent is selected from the group consisting of N, N-dimethylformamide, N-methyl-2-pyrrolidone, dimethylsulfoxide, and acetonitrile. the method of.