JPH045271A - Production of aromatic polysulfide - Google Patents

Abstract

PURPOSE:To obtain the title substance simply and in high yield, to regenerate hydrogen iodide from iodine prepared as a by-product and to reuse hydrogen iodide, by reacting an aromatic sulfonyl halide or aromatic sulfinic halide or aromatic sulfinic acid with hydrogen iodide in the presence of hydrogen sulfide. CONSTITUTION:1 mol of a compound shown by formula I (R is H, OH, alkyl, alkylthio, acetyl, halogen or phenyl; X is H or halogen) is reacted with 0.0005-1.0 mol hydrogen iodide in the presence of 1.5-10.0 mol HS to give a compound shown by formula II (n is 2-8). Or 1 mol of a compound shown by formula III(A is single bond, S or S-S; Y is H or halogen) is reacted with 0.001-2.0 mol hydrogen iodide in the presence of 3.0-20.0 mol HS to give a compound shown by formula IV (y is 2-8; z is >=1 integer). The reaction temperature is 10-150 deg.C in both the reactions. The prepared aromatic polysulfide is useful as an intermediate for producing an aromatic thiol.

Description

[Detailed description of the invention] [Industrial application field] The present invention relates to a method for producing aromatic polysulfide.

Aromatic polysulfide is a compound useful as an intermediate raw material in the production of aromatic thiols, and aromatic thiols are used in various applications as intermediates for medicines, agricultural chemicals, and dyes.

[Conventional technology]

Conventionally, the following methods are known as methods for producing aromatic polysulfides using aromatic sulfonyl halides or aromatic sulfinic acids as raw materials.

■ Method of reacting benzenesulfonyl chloride or benzenesulfinic acid with hydrogen sulfide (J, Prak
Tische Chemie, [2] 37,207 (
1888)).

■ A method for producing di(m-nitrophenyl) disulfide by reacting m-nitrobenzenesulfonyl chloride with aqueous hydrogen iodide (OrganicSynthesi
s, 40.80 (1960)).

(2) A method for producing di(m-nitrophenyl) disulfide by reacting m-nitrobenzenesulfonyl chloride with sulfur dioxide or a compound that generates sulfur dioxide using hydrogen iodide as a catalyst (IJsP 2571440).

[Problem to be solved by the invention]

However, each of the above-mentioned known methods has the following drawbacks.

In method (2), when benzenesulfinic acid is used as a raw material, the reaction time is long and the yield is low. Moreover, especially when toluenesulfonyl chloride is used as a raw material, the target product, di(methylphenyl)polysulfide, is not produced.

Method (2) requires a large amount of expensive hydrogen iodide, which is not only economically disadvantageous, but also produces iodine as a by-product, which is 2.5 times the mole of m-nitrobenzenesulfonyl chloride as a raw material. This makes post-processing difficult.

In method (2), when sulfur dioxide is used, water is required for the reaction as shown in the following equation, so the aromatic sulfonyl chloride as a raw material is hydrolyzed by water.
Aromatic sulfonic acid is produced as a by-product, resulting in a low yield.

12+ SD2+ 2 H2O→ 2 tll+H,s
O.

As mentioned above, all the known methods have various problems and cannot be said to be industrially advantageous. Therefore, various attempts have been made in the technical field to develop industrially advantageous manufacturing methods, but no satisfactory method has yet been found.

The object of the present invention is precisely in this respect, and is to provide a method for producing aromatic polysulfides with high yield and without by-products.

[Means to solve the problem]

In view of this situation, the present inventors have conducted extensive studies on a method for producing aromatic polysulfide industrially with simple operations and high yields by improving the drawbacks of the conventional methods.

As a result, they focused on the fact that hydrogen sulfide can easily reduce iodine to hydrogen iodide even in the absence of water, as shown in Reaction Formula (I), and obtained the beginnings of the present invention.

I2+LS → 2HI+S (I) top,
Aromatic polysulfide can be produced by reacting aromatic sulfonyl halide or aromatic sulfinic acid with hydrogen sulfide.

Regarding the synthetic route for the aromatic polysulfide according to the present invention, reaction formula (n) shows a reaction when a compound represented by general formula (2) is used as a raw material.

That is, in the method of the present invention, aromatic sulfonyl halide or aromatic sulfinic acid is reacted with hydrogen iodide to reduce it to the corresponding aromatic polysulfide. On the other hand, hydrogen iodide is oxidized to iodine, which is regenerated by reacting with hydrogen sulfide according to the reaction formula (I) described above, and is used to reduce aromatic sulfonyl halides or aromatic sulfinic acids. Reused.

As mentioned above, in the present invention, aromatic sulfonyl halide or aromatic sulfinic acid is reacted with hydrogen iodide in the presence of hydrogen sulfide. All you have to do is add the amount required for the reaction, and in the apparent formula 6, R is hydrogen, hydroxy group,
It represents an alkylthio group having 1 to 12 carbon atoms, an acetyl group, an alkyl group having 1 to 12 carbon atoms, a halogen atom, or a phenyl group. n is an integer of 2 to 8, and X represents hydrogen or a halogen atom. ] Further, reaction formula (III) shows a case where the compound represented by general formula (4) is used as a raw material.

When producing an aromatic polysulfide represented by the general formula (2), [wherein, Y represents hydrogen or a halogen atom]. A represents a single bond, -S- or -5-8-. y represents an integer of 2 to 8, and 2 represents an integer of 1 or more. ] The present invention has been made based on the above findings, and the gist thereof is as follows: General formula (1) [In the formula, R has the same meaning as above, and X represents hydrogen or a halogen atom. ] A method for producing an aromatic polysulfide of the general formula (1), which is characterized by reacting a compound represented by the formula with hydrogen iodide in the presence of hydrogen sulfide, and a method for producing an aromatic polysulfide of the general formula (3) [wherein R represents hydrogen, a hydroxy group, an alkylthio group having 1 to 12 carbon atoms, an acetyl group, an alkyl group having 1 to 12 carbon atoms, a halogen atom, or a phenyl group. n is 2 to 8
represents an integer. ] [In the formula, A represents a single bond, -8- or -5-S-,
l and y represent integers of 2 to 8, and 2 represents an integer of 1 or more. ] When producing an aromatic polysulfide represented by the general formula (4) [wherein, Y represents hydrogen or a halogen atom]. A represents a single bond, -8- or -5-8-. The present invention relates to a method for producing an aromatic polysulfide of general formula (3), which comprises reacting a compound represented by the formula (3) with hydrogen iodide in the presence of hydrogen sulfide.

General formulas (2) and (4) which are raw material compounds in the present invention
The compound represented by is either a known compound per se or a compound that can be synthesized by a known synthesis method.

In the compound of general formula (2), R represents hydrogen, a hydroxy group, an alkylthio group having 1 to 12 carbon atoms, an acetyl group, an alkyl group having 1 to 12 carbon atoms, a halogen atom, or a phenyl group. Here, when R is an alkylthio group having 1 to 12 carbon atoms, the alkyl portion thereof may be straight or branched, and may be methylthio, ethylthio, n-propylthio, isopropylthio, n-butylthio, 1so-
Examples include propylthio, 5ec-butylthio, tert-butylthio, and n-dodecylthio.

The alkyl group in which R has 1 to 12 carbon atoms may be straight or branched, and includes methyl, ethyl, n-propyl, isopropyl, n-butyl, 1so-propyl,
Examples include 5eC-butyl, tert-butyl, n-dodecyl, and the like.

Examples of the halogen atom for R include fluorine, chlorine, bromine, and iodine.

Further, X represents hydrogen or a halogen atom, and examples of the halogen atom include fluorine, chlorine, bromine, and iodine as in the case of R above.

In the compound of general formula (4), Y represents hydrogen or a halogen atom, and the halogen atom is the same as in the case of X above.

When the compound of general formula (4) is used, since the raw material is difunctional, a polymerization reaction occurs and a low polymer in which 2 is 1 or more is often produced. However, when these are reduced, they easily become the corresponding aromatic polysulfides, so they can be used without problems as raw materials for producing the aromatic thiols mentioned above.

In the present invention, the reaction temperature is preferably 10 to 150°C, more preferably 40 to 100°C.

At temperatures lower than 10°C, the reaction rate is slow;
Temperatures higher than °C may cause side reactions and should be avoided.

The hydrogen iodide used in the present invention is usually produced by the reaction of hydrogen sulfide and iodine, but hydrogen iodide obtained by reacting an iodine compound such as potassium iodide or sodium iodide with the acid described below, Alternatively, commercially available hydrogen iodide water may be used. The amount used is 0.0005 to 1.0 times the mole of aromatic sulfonyl halide or aromatic sulfinic acid represented by general formula (2), preferably 0.0
It is 1 to 0.1 times the mole. If the amount is less than 0.0005 times the mole, the reaction will not substantially proceed, and if it is added more than 1.0 times the mole, no commensurate effect will be obtained. Moreover, the amount is usually 0.001 to 2.0 times, preferably 0.02 to 0.2 times, by mole, relative to the aromatic sulfonyl halide or aromatic sulfinic acid represented by the general formula (4). 0.
If the amount is less than 0.001 times the mole, the reaction will not substantially proceed as described above, and if it is more than 2.0 times the mole, no commensurate effect will be obtained, so it is not a good idea.

The hydrogen sulfide used in the present invention is hydrogen sulfide produced from hydrogen sulfide gas or a sulfide described below that can produce hydrogen sulfide in the reaction solution.

Examples of sulfides that can generate hydrogen sulfide include sodium sulfide, sodium bisulfide, potassium sulfide, potassium bisulfide, iron sulfide, and zinc sulfide. The amount is usually 1.5 to 10.0 times, preferably 2.5 to 8.0 times, by mole, relative to the group sulfonyl halide or aromatic sulfinic acid. 1.5
If the amount is less than twice the mole, the reaction will not substantially proceed, and 10.0
Even if more than twice the molar amount is used, no commensurate effect will be obtained. Further, for aromatic sulfonyl halide or aromatic sulfinic acid represented by general formula (4), it is usually 3.0 to
It is 20.0 times the mole, preferably 5.0 to 16.0 times the mole.

If the amount is less than 3.0 times the mole, the reduction reaction will not substantially proceed, and if it is more than 20.0 times the mole, no commensurate effect will be obtained, so it is not a good idea.

In order to generate hydrogen iodide from an iodine compound or hydrogen sulfide from a sulfide, the above-mentioned iodine compound or sulfide can be added to a solvent, and then an acid such as sulfuric acid or hydrochloric acid can be added. .

Such solvents include dioxane, ethers such as tetrahydrofuran, acetone, ketones such as methyl ethyl ketone, esters such as ethyl formate, ethyl acetate, methyl acetate, butyl acetate, acetonitrile,
Examples include polar solvents such as N,N-dimethylformamide and dimethylsulfoxide, and alcohols such as methanol and ethanol. Furthermore, organic acids such as formic acid and acetic acid, which are themselves acidic, may be used as the solvent. In this case, addition of acid as described above becomes unnecessary. The amount of acid such as sulfuric acid or hydrochloric acid to be added may be such that the reaction is always maintained in an acidic state and the required amount of hydrogen iodide or hydrogen sulfide is produced.

Although the addition of water is not particularly necessary in the method of the present invention, the addition of water is usually 0 to the aromatic sulfonyl halide or aromatic sulfinic acid represented by general formula (2) or general formula (4).
．． When 0.001 to 10 times the mole, preferably 1 to 6 times the mole, is added, the reaction rate is often significantly improved. It is surprising that almost no aromatic sulfonic acid by-product is produced at this time.

The aromatic polysulfide thus obtained is produced into aromatic thiol by known means, and is used for pharmaceuticals, agricultural chemicals, etc.
Used as an intermediate raw material for dye intermediates.

[Effects of the Invention] According to the present invention, aromatic polysulfides can be produced industrially in high yield by an extremely simple operation of reacting aromatic sulfonyl halide or aromatic sulfinic acid with hydrogen iodide in the presence of hydrogen sulfide. can be advantageously obtained.

〔Example〕

The present invention will be explained below with reference to Examples and Comparative Examples.
The present invention is not limited to these examples.

Example 1 17.7 g (0.1 mol) of benzenesulfonyl chloride and 0.13 g of iodine (
0,0005 mol), tetrahydrofuran 70 g, water 1
12.7 g (7 moles of OJ) of hydrogen sulfide was blown into the reactor while maintaining the temperature between 40 and 60 tons. After stirring for 1 hour while maintaining the temperature, tetrahydrofuran was distilled off and a 20% aqueous sodium hydroxide solution
g and 50 g of toluene were added, the toluene solution was concentrated,
15 g of diphenyl polysulfide was obtained.

The obtained polysulfide was subjected to field desorption mass spectrometry (FD-
MS) As a result, m/e = 218.250.282
, 314.346.378.410 Obtained Ni vs. Hector.

From this result, this polysulfide was sulfurized to 16% to reduce the polysulfide obtained with the general formula) IJ
After adding 72 g of an aqueous solution of 100% phthalate, the mixture was stirred for 1 hour, acidified with hydrochloric acid, extracted with toluene, and concentrated to obtain 10.4 g of thiophenol. This result revealed that 95% of benzenesulfonyl chloride was used to produce polysulfide.

Example 2 Into a flask similar to that used in Example 1, 21.1 g (0°1
mol), potassium iodide 0.17g (0,001 mol), dioxane 70g 1 hydrochloric acid 5g, and the temperature was set to 50
12.5g of hydrogen sulfide (0,3
7 mol) was injected. After continuing stirring at the same temperature for 1 hour, the same treatment as in Example 1 was performed to obtain 14.8 g of 4,4°-dichlorodiphenyl polysulfide. Then, to reduce polysulfide, 100 g of 20% sodium hydroxide was added, and 10.2 g of hydrogen sulfide (0
After dioxane was distilled off, the mixture was acidified with hydrochloric acid, extracted with toluene, and concentrated to obtain 13.2 g of 4-chlorothiophenol. From this result, 4-
It was found that 91% of the chlorophenylsulfonyl chloride was used in the production of polysulfide.

Example 3 3.8 g (0,0
2 mol), iodine 0.13g (0,0005 mol)
, 20 g of tetrahydrofuran 1 7.0 g of sulfuric acid (0
,07 mol), and while maintaining the temperature at 50 to 60°C, 19.2 g (0.08 mol) of sodium sulfide nonahydrate was added, and stirring was continued at the same temperature for 30 minutes. Thereafter, the same operation as in Example 1 was performed to obtain 2.0 g of 4,4°-dimethyldiphenyl polysulfide. Furthermore, reduction was carried out in the same manner as in Example 1 to obtain 1.7 g of toluenethiol. This result revealed that 68% of toluenesulfonyl chloride was used to generate polysulfide.

Example 4 A flask similar to that used in Example 1 was placed at 4° 4° −
Thiobis(phenylsulfonyl chloride) 19.3
g (0.05 mol), iodine 0.13 g (0
,0005 mol), 70 g of tetrahydrofuran, 5 g of water
of hydrogen sulfide while keeping the temperature between 50 and 66℃.
1.7 g (0.34 mol) was blown into the solution, and stirring was continued for 1 hour at the same temperature. Thereafter, the same operation as in Example 1 was performed to obtain 8.5 g of aromatic polysulfide.

Furthermore, reduction was carried out in the same manner as in Example 1, and 4゜4゛-
8.1 g of thiobis(phenylthiol) was obtained. From this result, 4. It was found that 64% of 4'-thiobis(phenylsulfonyl chloride) was used in the production of polysulfide.

Example 5 In a flask similar to that used in Example 1, 14.2 g (0.1 mol) of benzenesulfinic acid and 0°1 of iodine were added.
3 g (0,0005 mol), methanol 100 g
of hydrogen sulfide while keeping the temperature at 50-60℃.
．． 2 g (0°24 mol) was blown into the solution.

After stirring for 1 hour at the same temperature, 12.1 g of diphenyl polysulfide was obtained in the same manner as in Example 1.

Thereafter, the same operation as in Example 1 was performed to obtain 10.7 g of thiophenol. This result revealed that 97% of benzenesulfinic acid was used to produce polysulfide.

Example 6 In a flask similar to that used in Example 1, a 4° 4”-
Thiobis(phenylsulfinic acid) 15.7g (0,
0.05 mol), iodine 0.13 g (0,0005 mol), methanol 100 g, and water 5 g, and the temperature was set to 50 mol.
Hydrogen sulfide 8.2 g (0,2
4 mol) and continued stirring at the same temperature for 1 hour.

After that, the same operation as in Example 1 was performed, and 4 and 4
8.0 g of ゛-thiobis(phenylthiol) was obtained.

The results revealed that 64% of 4,4'-thiobis(phenylsulfinic acid) was used to produce polysulfide.

Example 7-10 Using 4-chlorophenylsulfonyl chloride, an iodine compound, various sulfides, and various solvents shown in Table 1, the reaction was carried out in the same manner as in Example 1 to obtain an aromatic polysulfide. The results are shown in Table 1.

[Margin below]

Table 1 Examples 11-15 The aromatic sulfonyl halides shown in Table 2, iodine, and hydrogen sulfide were reacted in the same manner as in Example 1 to obtain corresponding aromatic polysulfides.

The results are shown in Table 2.

[Margin below]

Snake 1> The aromatic ring balance was determined by reducing polysulfide and using the corresponding aromatic thiol using the following formula.

Aromatic ring balance = [ffl thiol mono L@/C2 aromatic sulfonyl halide mono/La) Formula (calculate here t2.

Aromatic ring balance = [Monol illusion of C1 group thiol/Number of moles of aromatic sulfonyl nodide)] The reaction was carried out in the same manner.

Hydrogen sulfide 34.0 while keeping the reaction temperature at 50-65℃
(1.0 mol) was blown into the solution, and stirring was continued for 1 hour at the same temperature, but 33.1 g of the hydrogen sulfide blown in was blown through.

Thereafter, reduction was performed with 20% sodium hydroxide and hydrogen sulfide in the same manner as in Example 2, but 4-chlorothiophenol could not be obtained. The above results revealed that 4,4'-dichlorodiphenyl polysulfide was not produced.

Comparative Example 2 21.1 g (0.1 mol) of 4-chlorophenylsulfonyl chloride and 111.2 g (111.2 g) of 57% aqueous hydrogen iodide ( 0.5 mol) and stirred at 78°C for 2 hours. A large amount of by-product iodine was attached to the flask wall. After cooling, add 745 g of 5% sodium sulfite water and 100 g of chloroform to reduce iodine, separate the aqueous layer and organic layer, concentrate the organic layer,
10.0 g of '-dichlorodiphenyl polysulfide was obtained.

This was reduced by adding 50 g of 16% sodium sulfide to obtain 9.5 g of 4-chlorothiophenol.

From this result, 6 of 4-chlorophenylfonyl chloride
It was found that 5% was used in the production of 4,4°-dichlorodiphenyl polysulfide.

Procedural amendment (voluntary) June 8, 1990 1. Display of incident

Claims (7)

[Claims] (1) General formula (1) ▲ Numerical formulas, chemical formulas, tables, etc. ▼ (1) [In the formula, R is hydrogen, hydroxy group, alkylthio group having 1 to 12 carbon atoms, acetyl group, or Represents an alkyl group, a halogen atom, or a phenyl group. n is 2 to 8
represents an integer. ] When producing the aromatic polysulfide represented by the general formula (2) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (2) [In the formula, R has the same meaning as above, and X is hydrogen or halogen. represents an atom. ] A method for producing an aromatic polysulfide of general formula (1), which comprises reacting a compound represented by the following with hydrogen iodide in the presence of hydrogen sulfide. (2) General formula (3) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (3) [In the formula, A represents a single bond, -S- or -S-S-. y represents an integer of 2 to 8, and z represents an integer of 1 or more. ] When producing aromatic polysulfide represented by the general formula (4) ▲ There are numerical formulas, chemical formulas, tables, etc. ▼ (4) [In the formula, Y represents hydrogen or a halogen atom. A represents a single bond, -S- or -S-S-. ] A method for producing an aromatic polysulfide of general formula (3), which comprises reacting a compound represented by formula (3) with hydrogen iodide in the presence of hydrogen sulfide as a catalyst. (3) The manufacturing method according to claim (1) or (2), wherein the reaction temperature is in the temperature range of 10 to 150°C. (4) Claim (1) wherein the amount of hydrogen iodide used is 0.0005 to 1.0 times the mole of the aromatic sulfonyl halide or aromatic sulfinic acid of general formula (2) described in claim (1). ) manufacturing method described. (5) The amount of hydrogen iodide used is 0.001 to 2.0 times the mole of the aromatic sulfonyl halide or aromatic sulfinic acid of the general formula (4) described in claim (2). ) manufacturing method described. (6) The amount of hydrogen sulfide used is determined by the general formula (
Claim (1) in which the mole amount is 1.5 to 10.0 times that of the aromatic sulfonyl halide or aromatic sulfinic acid in 2).
) manufacturing method described. (7) The amount of hydrogen sulfide used is determined by the general formula (
Claim (2) wherein the molar amount is 3.0 to 20.0 times that of the aromatic sulfonyl halide or aromatic sulfinic acid in 4).
Manufacturing method described.