JPS6149302B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a method for producing polysulfide. Polysulfides are useful as medicines, agricultural chemicals, polymer additives, organic synthesis intermediates, and the like. Conventionally, regarding the production method of polysulfide,
There are few examples, and a few methods are known, but they are all a method of reacting mercaptan or disulfide with sulfur at high temperature for a long time, a method of reacting sulfenyl chloride with hydrogen sulfide, or a method of reacting mercaptan or disulfide with sulfur. This method involves reacting sulfur dichloride (S ₂ Cl ₂ ) with disulfur dichloride (S 2 Cl 2 ). In the course of research on the reactivity of organic naonitrites, the present inventors discovered that polysulfide can be easily produced by a method completely different from these conventional methods, and have completed the present invention. That is, the present invention provides a compound having the general formula R ¹ --SNO [] or R ² ₂ S ₂ [] [wherein R ¹ represents an alkyl group, a cycloalkyl group, an aryl group, an alkyl-substituted aryl group, or an aralkyl group]. Moreover, R ² represents an alkyl group or an aralkyl group. ) and a thionitrite or disulfide represented by the general formula MX _o [ ] (where M represents a copper ion or an iron ion,
X represents a halogen atom. n represents the number of halogens determined by the valence of metal M. ) with the general formula R ¹ ₂ S _n [] or R ² ₂ S _l [] (wherein R ¹ and R ² are the same as above. m, 1 represents the number of sulfur atoms, m is 2, 3 or 4, and 1 is 3 or 4). R ¹ in formulas [] and [] is, for example, a methyl group, an ethyl group, an n-propyl group, an i-
Propyl group, n-butyl group, i-butyl group, sec
-Alkyl groups such as butyl group, t-butyl group, amyl group, hexyl group, 2-ethylhexyl group, t-octyl group, dodecyl group, etc.; cycloalkyl group such as cyclopropyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, etc. groups, such as aryl groups such as phenyl, naphthyl, anthranyl, and biphenyl groups, and substituents such as methyl, ethyl, n-propyl, i-propyl, and n-butyl groups on these aryl groups; Examples of introduced alkyl-substituted aryl groups include aralkyl groups such as benzyl group, phenethyl group, phenylpropyl group, and triphenylmethyl group. In the formulas [] and [], R ² is an alkyl group such as a sec-butyl group, a t-butyl group, or a t-octyl group, such as a benzyl group, a phenethyl group, a phenylpropyl group, or a triphenylmethyl group. Examples include aralkyl groups such as. Examples of the metal halide (MX _o ) according to the present invention include copper halides such as cuprous chloride and cupric chloride, iron halides such as ferric chloride, and the like. The polysulfide produced by the method of the present invention may be disulfide (R-S-S-R), trisulfide (R-S-S-S-R) or tetrasulfide ((R-S-S-S-S- R) alone or as a mixture of two or more, and the production rate of these disulfides, trisulfides, or tetrasulfides mainly depends on the type of metal halide, the type of disulfide or thionitrite to be reacted with the metal halide, and the reaction temperature. Different. When the metal halide is cupric halide, when tertiary thionitrite and the metal halide are reacted, it is possible to react selectively by controlling the reaction time at a relatively low temperature, for example around room temperature. Trisulfide (R-S-S-S-R) can be produced at a relatively high temperature, for example around 80°C, when disulfide and cupric halide are reacted. The tertiary disulfide forms a mixture of trisulfide and tetrasulfide, the main component of which is tetrasulfide, at relatively low temperatures, for example around room temperature.When the metal halide is ferric halide, tertiary disulfide and When reacting with ferric halide, a mixture of trisulfide and tetrasulfide is produced at a relatively low temperature, for example, around room temperature.The present invention can be easily carried out, for example, as follows:Disulfide or halogenation As for the metal, known metals were used, including thiophytolite (R-
For SNO), for example, a product obtained by reacting the corresponding mercaptan (R-SH) with dinitrogen tetroxide (N ₂ O ₄ ) is used, and these disulfides or thionitrites are mixed with a metal halide. death,
If necessary, a solvent that dissolves the metal halide, such as an alkyl cyanide solvent, an ester solvent, an aprotic solvent such as dimethylformamide, preferably a general formula such as acetonitrile, propionitrile, butyronitrile, amylonitrile, etc.
The reaction is carried out in the presence of an alkyl cyanide solvent represented by R ³ CN (wherein R ³ represents an alkyl group having 1 to 10 carbon atoms), for example, by heating and cooling or at room temperature. The metal halide is usually preferably used in a stoichiometric amount or in a slightly excess amount relative to the disulfide or thionitrite, and the reaction system may be homogeneous or heterogeneous. After the reaction, it is optional to separate and purify according to conventional methods. According to the present invention, not only can polysulfide be easily produced under mild conditions and in high yield, but also the desired polysulfide can be selectively produced if necessary. Examples are given below to further explain the present invention. Examples 1 to 8 3.57 g (200 mmol) of t-butyl disulfide and 5.38 g (40 mmol) of cupric chloride were reacted in 50 ml of acetonitrile at 25°C for 5 hours to produce 1.52 g ( 6.28mmol. Yield 63%)
and t-butyl trisulfide 0.83g
(3.42 mmol. Yield 25%) is obtained. (Example 1) t-butylthionitrite 1.79g
(15 mmol) in 20 ml of acetonitrile is added to a solution of 2.02 g (15 mmol) of cupric chloride in 20 ml of acetonitrile at about 25°C. A small amount of the reaction solution was taken out over time, and the formation of t-butyl trisulfide and tetrasulfide was confirmed by GLPC. After 20 minutes, the starting material t-butylthionitrite completely disappeared, and t-butyl trisulfide was selectively obtained. (Yield 81%). Diagram 1 shows the amounts of trisulfide, tetrasulfide, and the starting material thionitrite plotted over reaction time. T-butyl trisulfide and tetrasulfide were separated by distillation and identified by elemental analysis and spectroscopic analysis. t-Butyl trisulfide: mp14-15℃.
MS, m/e210 (M ⁺ ). Elemental analysis ( _C8H18S3 ) _, calculated C, 45.66; H, 8.62; S, 45.71, found C, 45.75; _H , 8.69; S, 45.82. t-Butyltetrasulfide: bp80-90℃
(2mmHg). MG, m/e242 (M ⁺ ). (Example 2) Similarly, a metal halide and a disulfide or thionitrite were reacted in acetonitrile, and the results shown in Table 1 were obtained (Examples 3 to 8). still,

[Table] Table 1 also shows the results of Examples 1 and 2.

Claims (1)

[Claims] 1 General formula R ¹ —SNO [] or R ² ₂ S ₂ [] (wherein R ¹ represents an alkyl group, a cycloalkyl group, an aryl group, an alkyl-substituted aryl group, or an aralkyl group. In addition, R ² represents an alkyl group or an aralkyl group.) Thionitrite or disulfide represented by the general formula MX _o [] (wherein M represents a copper ion or an iron ion,
X represents a halogen atom. n represents the number of halogens determined by the valence of metal M. ) with the general formula R ¹ ₂ S _n [] or R ² ₂ S _l [] (wherein R ¹ and R ² are the same as above. m, 1 represents the number of sulfur atoms, m is 2, 3 or 4, and 1 is 3 or 4.) A method for producing polysulfide. 2. The reaction according to claim 1, wherein the reaction is carried out in the presence of an alkyl cyanide solvent represented by the general formula R ³ CN [ ] (wherein R ³ represents an alkyl group having 1 to 10 carbon atoms). Method for producing polysulfide.