JPS61126066A - Novel method of polysulfide production - Google Patents

Abstract

PURPOSE:The reaction between a mercaptan and a metal halide enables easy and high-yield production of a polysulfide which is used in medicines, agricultural chemicals, high polymer additives or an synthetic intermediate for organic chemistry under mild conditions. CONSTITUTION:The reaction between a mercaptan of the formula: R<1>-SH (R<1> is alkyl, aryl, substituted aryl, aralkyl, heterocyclic ring which may be substituted) is allowed to react with a metal halide of formula: MXn (M is copper ion, iron ion; X is halogen; n is the number of the halogen atoms depending on the valency of M such as cuprous chloride is carried out in an alkyl cyanide solvent such as acetonitrile under heating, normal temperature or under cooling. To give the objective compound of the formula: (R1/2Sm (m is 2-4). Preferably, the halogen metal salt is a little excessive than the stiochiometric amount.

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 of such methods, and only a few methods are known, but they all involve reacting mercaptan or disulfide with sulfur at high temperature for a long time, reacting IMized sulfenyl with hydrogen sulfide, and is a method in which mercaptan and disulfuric dichloride fi (52CI2) are reacted.

In the course of research on the reactivity of organic thionitrides, the present inventors discovered that polysulfides can be easily produced by a method completely different from these conventional methods, and have completed the present invention.

That is, 1 the present invention has the following features: (1) General formula R'-5) [II (wherein R1 represents a furkyl group, an aryl group, a substituted aryl group, an aralkyl group, a heterocyclic group, or a substituted heterocyclic group) and a mercaptan represented by the general formula MXn[R1 (wherein represents a copper ion or iron ion, ) represents a halogen atom, n represents the number of halogen determined by the valence of metal X). It is characterized by reacting with a metal halide.

General formula R2S, [ml In the formula, R1 is the same as above, 1m represents the number of lil yellow atoms, and is 2.3 or 4. ) is a method for producing polysulfide shown in

R1 in formulas [1 and [3] is, for example, a methyl group, an ethyl group, an n-pcopyl group, an i-propyl group, an n-butyl group, an i-butyl group, a 5ec-butyl group, an L-butyl group, Alkyl groups such as amyl i&, hexyl crystal, 2-ethylhexyl group, t-octyl group, dodecyl group 1 Aryl groups such as phenyl group, naphthyl group, anthranyl group, biphenyl group, and substituents introduced into these rings Substituted aryl group 1 such as benzyl group, phenethyl group.

-7ralkyl groups such as phenylpropyl group and triphenylmethyl group 1 For example, furyl group, furfuryl group, benzofuryl group, chenyl group, pyrrolyl group.

Pyridyl group, piperidyl group, 1 morpholyl group, quinolyl group, thiazolyl group, benzothiazolyl group.

Examples include heterocyclic groups such as an imidazolyl group, a penicillin group, and a sebu-gamma rosporin group, and substituted heterocyclic groups in which a substituent is introduced into these rings. The substituent for the W-substituted aryl group and the ffi-substituted heterocyclic group is preferably a substituent that does not participate in the reaction.1 For example, a lower alkyl group such as a methyl group, an ethyl group, or a propyl group.1 For example, a methoxy group, an ethoxy group, Lower alkoxy groups such as propoxy groups 1 For example, fluorine,
chlorine.

Examples include halogens such as bromine and ios, a nitro group, a hydroxyl group, a carboxyl group, and a hexafluoride group.

The metal halide (MX,) according to the present invention includes 4
For example, copper halides such as cupric oxide and cupric oxide,
Examples include iron halides such as #2 chloride.

The polysulfides produced by the method of the present invention include disulfide CR-5-5-R'), trisulfide F
(R-5-S-S-R') also 1*+ t9 suruy
Il'(R'-5-S-9-5-R') alone or in combination
The production ratio of disulfide, trisulfide or tetrasulfide differs mainly depending on the type of metal halide, the type of mercaptan reacted with the metal halide, and the reaction temperature.

When the metal halide is cupric halide,
When reacting mercaptan and cupric halide,
-class and secondary mercaptans and aryl mercaptans selectively form disulfides at relatively low temperatures, e.g. around room temperature, and secondary mercaptans selectively form disulfides at relatively high temperatures, e.g.
At temperatures around 0.degree. C., a mixture of disulfide and trisulfide, mainly consisting of trisulfide, is produced, and tertiary mercaptans produce a mixture of trisulfide and tetrasulfide at relatively low temperatures, for example, around room temperature.

When the metal halide is cupric halide =
When V class mercaptan is reacted with cupric halide, disulfide is selectively produced at a relatively low temperature, for example around room temperature.

The present invention can be easily implemented in a first order manner, for example.

A known mercaptan or metal halide is used, and the mercaptan and metal halide are mixed, and if necessary, a solvent such as an alkyl cyanide solvent, an ester solvent, or an aprotic solvent such as dimethylformamide is used. Solvents that dissolve metal halides such as, preferably, those having the general formula R2CN [ff] (wherein R2 represents an alkyl group having 1 to 10 carbon atoms) such as 7cetonitrile, propionitrile, butyronitrile, 7mylonitrile, etc. One reaction is carried out in the presence of the indicated alkyl cyanide solvent, for example with heating and cooling or at room temperature. The metal halide is usually preferably used in a theoretical amount or in a slightly excess amount relative to the mercaptan, and the reaction system may be a homogeneous system; t: A homogeneous system may be used. After the reaction, separation and purification by conventional methods are optional. be.

According to the present invention, polysulfides can not only be easily produced under mild conditions and in high yields, but also, if necessary, a target polysulfide can be selectively produced.

Examples are given below to further explain the present invention.

Example 1 When t-butyl mercap 7710 ml o 1 and cupric chloride 40 ml 01 are reacted in acetonitrile 30 Id at 25°C, a mixture of t-butyl trisulfide and t-butyl tetrasulfide is produced. do. After 60 minutes, as shown in FIG. 1, the amounts of t-butyl trisulfide and t-butyl tetrasulfide produced become constant.

The experimental results are shown in Table 1.

Example 2 When E-butyl mercaptan and cuprous chloride are reacted at about 25°C, t-butyl disulfide is selectively produced, and no trisulfide or tetrasulfide is produced.

t-BuSH+ Curl -1 → t-Bu-SS-
The t-Bu experimental results are shown in Table 1.

Examples 3 to 9゜Example 1. and Example 2. In the same manner as above, various mercaptans and metal halides were reacted in 7cetonitrile to obtain the results shown in Table 1.

5ec-butyl mercaptan and cupric chloride at 25°C.
When reacted with
c-Butyl trisulfide is selectively produced. Note that Table 1 shows Example 1. and Example 2. The results are also shown.

Table L

[Brief explanation of drawings]

FIG. 1 shows Example 1. The graph shows the product formation curve of the reaction in which the amount of each product produced (w fat ol) obtained at each reaction time (minutes) on the horizontal axis is plotted along the vertical axis, and the points are connected. However, -0-0- is (t-Bu
) 2S2, 1ζ represents the production amount of (t-[1u)2S3, and 2×- represents the production amount of (t-Bu)2S4, respectively.

Claims (2)

[Claims] (1) Mercaptan represented by the general formula R^1-SH[I] (wherein R^1 represents an alkyl group, an aryl group, a substituted aryl group, an aralkyl group, a heterocyclic group, or a substituted heterocyclic group) and a halogenated compound represented by the general formula MX_n[II] (where M represents a copper ion or iron ion, X represents a halogen atom, and n represents the number of halogens determined by the valence of the metal M). With the general formula R^1_2S_m[III] (wherein R^1 is the same as above, m represents the number of sulfur atoms, and is 2, 3 or 4), which is characterized by reacting with a metal. A method for producing the polysulfide shown. (2) The reaction is carried out in the presence of an alkyl cyanide solvent represented by the general formula R^2CN[IV] (wherein R^2 represents an alkyl group having 1 to 10 carbon atoms). A method for producing polysulfide according to item 1.