JPH04182463A - Production of halogenothiophenols and derivatives thereof - Google Patents

Abstract

PURPOSE:To obtain the subject compound useful as an intermediate for dyes, pigments, electronic chemicals, agricultural chemicals, drugs, etc., in a high yield by a simple process under a mild condition by reacting a halogenobenzene compound with a sulfide in a polar organic solvent as a reaction solvent. CONSTITUTION:A compound of formula I (X is Cl, Br; m is 2, 3) is reacted with a sulfide (preferably sodium hydrosulfide) in a polar organic solvent, preferably N-methyl-2-pyrrolidone, N,N-dimethylformaldehyde, sulfolane, ethylene glycol, etc., as a reaction solvent at 50-220 deg.C, preferably 120-170 deg.C, to obtain a halogenothiophenol of formula II (M is H, alkali metal). The reaction of the compound of formula II with a halogenated compound of formula III (Y is Cl, Br; R is 1-12C alkylene, phenylene) can easily give a sulfide compound of formula IV.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a method for producing halogenothiophenols and derivatives thereof.

Halogenothiophenols and their derivatives are dyes,
It is a compound useful as an intermediate for pigments, electronic industry chemicals, medicines, agricultural chemicals, etc.

[Conventional technology]

Conventionally, the following methods are known as methods for producing halogenothiophenols.

■ Under pressure in a liquid ammonia solvent in the presence of copper acetate as a catalyst, 125% of chlorobenzenes and sodium hydrosulfide were added.
A method for producing halogenothiophenols by reacting at °C for 10 to 20 hours.

The yield when dichlorothiophenol is produced using this method is 17 to 34%, but if acetic acid steel is not added, dichlorothiophenol is not produced (Kogaku Journal
701384 (1967)).

■ Heat chlorobenzenes and hydrogen sulfide to 500-600°C.
A method for producing the corresponding halogenothiophenols by reacting with

Using this method, the reaction rate when trichlorobenzene was used as a raw material was 32%, and the selectivity for dichlorothiophenol was 56%; when dichlorobenzene was used as a raw material, the reaction rate was 75%, and the selectivity for dichlorothiophenol was 56%. The selection rate is 16
% (Zh, Kano G, Khim, Yu I 1132
(1975)).

[Problem to be solved by the invention]

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

Method (2) uses liquid ammonia, which is difficult to handle, and a copper compound, which is difficult to dispose of, and because the reaction is carried out under pressure, there are problems with operability, etc., and the yield is also low.

In method (2), the reaction is carried out at a high reaction temperature of 500 to 600°C, and hydrogen chloride is produced as a by-product, so there are problems with the reaction operation and the material of the reactor, and the yield is low.

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

[Failure to solve the problem]

The present inventors have conducted intensive studies on a method for obtaining halogenothiophenols and derivatives thereof under mild conditions in an industrially advantageous manner and in high yields.

As a result, using a polar organic solvent as a solvent, the general formula (
I) If a sulfide is reacted with a halogenobenzene represented by the formula (A), the reaction can be easily represented by the general formula (II) under normal pressure without the need for the addition of a catalyst. Halogenothiophenols are obtained, <Reaction formula (A)> (I) (n) [wherein, X represents a chlorine atom and/or a bromine atom]. m represents 2 or 3. M represents a hydrogen atom or an alkali metal. ] Furthermore, by subsequently reacting the generated halogenothiophenols represented by general formula (n) with a halogenated compound represented by general formula (I) as shown in reaction formula (B), The present invention has been achieved by discovering that sulfides represented by general formula (IV) can be obtained.

<Reaction formula (B)> (I[) (III) [wherein,
X represents a chlorine atom and/or a bromine atom. m represents 2 or 3. M represents a hydrogen atom or an alkali metal. Y represents a chlorine atom or a bromine atom. R has 1 or more carbon atoms
12 alkylene group or phenylene group. ] That is, the gist of the present invention is as follows: (1) General formula (I) [In the formula, X represents a chlorine atom and/or a bromine atom.

m represents 2 or 3. ] A halogenobenzene represented by the following is reacted with a sulfide to form a compound of the general formula (In) [wherein, X represents a chlorine atom and/or a bromine atom].

m represents 2 or 3. M represents a hydrogen atom or an alkali metal. ] A method for producing a halogenothiophenol represented by the general formula (I [), characterized in that a polar organic solvent is used as a solvent for the reaction, ( 2) General formula (I) [wherein, X represents a chlorine atom and/or a bromine atom].

m represents 2 or 3. ] The halogenobenzenes represented by these and sulfides are reacted in a polar organic solvent to form a compound of the general formula (It) [wherein, X represents a chlorine atom and/or a bromine atom]. m represents 2 or 3. M represents a hydrogen atom or an alkali metal. ] To obtain the halogenothiophenols represented by formula (III) Y-RCO
OM (I[) [wherein Y represents a chlorine atom or a bromine atom]. R represents an alkylene group having 1 to 12 carbon atoms or a phenylene group. M represents a hydrogen atom or an alkali metal. ] General formula (IV) characterized by reacting a halogenated compound represented by [wherein, X represents a chlorine atom and/or a bromine atom].

m represents 2 or 3. R represents an alkylene group having 1 to 12 carbon atoms or a phenylene group. M represents a hydrogen atom or an alkali metal. ] The present invention relates to a method for producing sulfides represented by the following.

The compound represented by the general formula (I) which is a raw material compound in the present invention includes 1,2,4-trichlorobenzene,
l, 2.3-trichlorobenzene, 1, 3. Trichlorobenzene such as 5-trichlorobenzene, 1,2.4
-tribromobenzene, 1゜2.3-tribromobenzene, 1,3.5-1ribromobenzene, etc., 1-bromo-2,5-dichlorobenzene, 1-
Bromo-2, 4-dichlorobenzene, 1-bromo-3,
Monobromodichlorobenzene such as 4-dichlorobenzene, ■, dibromomonochlorobenzene such as 4-dibromo-2-chlorobenzene, 1,5-dibromo-2-chlorobenzene, ■, 2-dichlorobenzene, 1,3-dichlorobenzene, ], Dichlorobenzene such as 4-dichlorobenzene, bromochlorobenzene such as ■-bromo-2-'70-lobenzene, 1-7-bromo-3-di-tetra-lobenzene, 1-bromo-4-chlorobenzene, 1.2-dibromobenzene, 1. Examples include dibromobenzenes such as 3-dibromobenzene and 1,4-dibromobenzene.

The polar organic solvents used in the present invention include N-methyl-2-pyrrolidone, N,N-dimethylformamide, N
, N-dimethylacetamide, acetamide, formamide, caprolactam, 1゜1゛-ethylenedipyrrolidone, tetramethylurea, hexamethylphosphoramide, acetonitrile, quinoline, pyridine, lutidine, picoline, dimethylsulfoxide, sulfolane, sulfolene, ethylene glycol , diethylene glycol, etc., preferably N-methyl-2-pyrrolidone, N,
At least one selected from the group consisting of N-dimethylformamide, N,N-dimethylacetamide, sulfolane, dimethyl sulfoxide, and ethylene glycol
It is a kind. The amount used is usually 1 to 20 times the weight of the halogenobenzenes, preferably 1.5 to 10 times the weight. Furthermore, two or more of the solvents listed here may be used in combination.

Sulfides used in the present invention include sodium hydrosulfide,
Potassium hydrosulfide, sodium sulfide, potassium sulfide, etc. are mentioned, and sodium hydrosulfide is preferred. The amount used is usually 0.5 to 10 per halogenobenzene.
It is twice the mole amount, preferably 1.0 to 4.0 times the mole amount. 0.
If the amount is less than 5 moles, there will be a large amount of unreacted raw materials, and 1
If the amount is more than 0 moles, by-products will be produced, which is not preferable.

In the present invention, the reaction temperature between the compound of general formula (I) and the sulfide is usually 50 to 220°C, preferably 120 to 220°C.
The temperature is 170°C. A temperature lower than 50°C is undesirable because the reaction rate is low, and a temperature higher than 220°C may result in a decrease in yield due to side reactions.

The product obtained in this way is a salt of a halogenothiophenol represented by the general formula (II) in which M is an alkali metal such as sodium, and this salt is prepared by a conventional method, for example, by acidification. It can be a halogenothiophenol. Acids for acidification include hydrochloric acid, sulfuric acid,
Examples include nitric acid or phosphoric acid, and the amount used is usually 1.0 to 5.0 times the mole of the sulfide, preferably 1.0 to 5.0 times the mole of the sulfide.
It is 3.0 times the mole.

Another embodiment of the present invention is to continue to react halogenothiophenols obtained by reacting halogenobenzenes and sulfides in a polar organic solvent as described above with the general formula (II
The method is to react with a halogenated compound represented by I) to obtain sulfides.

In the halogenated compound represented by the general formula (I[I), Y is a chlorine atom or a bromine atom, and R has 1 to 1 carbon atoms.
Examples include halogenated compounds which are 12 alkylene groups or phenylene groups. Specific examples thereof include halogenated aliphatic carboxylic acids in which a linear or branched alkyl group is halogenated, such as acetic acid, propionic acid, n-valeric acid, 1so-valeric acid, lauric acid, p-chlorobenzoic acid, 0-
Nuclear halogenated benzoic acids such as bromobenzoic acid.

- The amount of the halogenated compound of formula (I) to be used is the amount of the halogenated compound of formula (1)
) for halogenobenzenes, i usually 1.0 to 3.0
The appropriate amount is double the mole.

In the present invention, the reaction temperature when the halogenated compound represented by the general formula (I) is reacted with the halogenated compound represented by the general formula (III) is usually 10 to 2°C, preferably 50 to 120'C. be. Through this reaction, sulfides represented by general formula (IV) can be obtained.

The sulfides obtained by the above reaction are acidified and extracted if necessary. Hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, etc. are used as the acid for acidification, and the amount used is usually 1.0% per sulfide. ~5.0 mole times, preferably 1.0
~3.0 times the mole.

In this way, by using the method of the present invention, sulfides can be consistently produced from halogenobenzenes in a simple manner and in a high yield, which is industrially advantageous.

Further, the halogenothiophenols represented by the general formula (■) obtained by the method of the present invention can be used as the halogenothiophenols represented by the general formula (IV
) In the same manner as in the case of obtaining the sulfides represented by the general formula (■'), the reaction is continued with the halogenated hydrocarbon represented by the general formula (■'), and as shown in the reaction formula (C), the general formula (■
It is possible to obtain a halogenothiophenol derivative represented by

<Reaction formula (C)> [In the formula, X, m, M, and Y are the same as above. R' represents an alkyl group having 1 to 12 carbon atoms, a phenyl group or a benzyl group. ] Examples of the compound represented by the general formula (■') include p-
Bromophenylmethyl sulfide, p-chlorophenylphenyl sulfide, p-chlorophenylmethyl sulfide, 0-bromophenyl-1so-propylsulfide, p-bromophenylbenzyl sulfide, dichlorophenyl-tert-butyl sulfide, dichlorophenylmethyl sulfide, dibromophenyl-n- Examples include dodecyl sulfide.

General formula (II) thus obtained by the method of the present invention
The halogenothiophenols represented by can be reacted with various halogenated compounds to give various corresponding derivatives of halogenothiophenols.

〔Effect of the invention〕

According to the present invention, halogenothiophenols can be industrially advantageously obtained in high yield by an extremely simple operation of reacting halogenobenzenes with sulfides in a polar organic solvent under normal pressure. Furthermore, various derivatives of halogenothiophenols can be easily produced by subsequently reacting them with various halogenated compounds such as halogenated hydrocarbons without isolating the resulting halogenothiophenols.

〔Example〕

The present invention will be described below with reference to Examples, but the present invention is not limited to these Examples.

Example 1 36.3 g of 1,2,4-trichlorobenzene in a 500 ml flask equipped with a thermometer, condenser and stirrer
(0.2 mol), 70% sodium hydrogen sulfide 32.0 g (
0.4 mol) and 320 g of N-methyl-2-pyrrolidone were charged, the temperature was raised to 140'C over 1 hour, and stirring was continued at that temperature for another 1 hour. Then increase the temperature to 10
The temperature was lowered to 0°C, N-methyl-2-pyrrolidone was distilled off under reduced pressure, 200 g of water and 50 g of toluene were added, and the mixture was separated. Add 25g of concentrated hydrochloric acid to the aqueous phase to make it acidic, and add 50g of toluene.
g was added and extracted, and the toluene was distilled off from the obtained toluene solution, and further distilled under reduced pressure (boiling point 132-134°C/
26.9 g of dichlorothiophenol at 30 Torr)
I got it. Yield 75.0%. As a result of gas chromatography analysis, the obtained dichlorothiophenol contained 2.5
-dichlorothiophenol (98,0%) and 2,4-dichlorothiophenol (2,0%) are present, 3,4-
Dichlorothiophenol was almost absent.

Examples 2 to 8 Using 1,2,4-trichlorobenzene, sulfide, and various solvents shown in Table 1, reactions were carried out in the same manner as in Example 1 to obtain dichlorothiophenol. The results are shown in Table 1.

(The following is a blank space) Examples 9 to 13 Using the halogenobenzenes, sulfides, and various solvents shown in Table 2, reactions were carried out in the same manner as in Example 1 to obtain halogenothiophenols. The results are shown in Table 2.

(Left below) Example 14 In a flask similar to that used in Example 1, a 1°2.4-
Trichlorobenzene 36.3g (0.2 mol), 7
32.0 g (0.4 mol) of 0% sodium hydrosulfide and 320 g of N-methyl-2-pyrrolidone were charged, the temperature was raised to 140° C. over 1 hour, and stirring was continued at that temperature for another 1 hour. Thereafter, the temperature was lowered to 100°C, 23.3 g (0.2 mol) of sodium monochloroacetate was added, and stirring was continued at that temperature for 1 hour. N-methyl-2-pyrrolidone was distilled off under reduced pressure, 200 g of water and 50 g of toluene were added, and after separation, 25 g of concentrated hydrochloric acid was added to the aqueous solution.
After cooling to room temperature, a white solid was obtained by filtration. This white solid was recrystallized from ethanol water and dried to obtain 36.3 g of dichlorophenylthioglycolic acid. The melting point was 129-131°C and the yield was 76.5%. As a result of high performance liquid chromatography analysis, the obtained dichlorophenylthioglycolic acid contained 2,5-dichlorophenylthioglycolic acid (98.0%) and 2,4-dichlorophenylthioglycolic acid (2.0%). ) exists,
Almost no 3,4-dichlorophenylthioglycolic acid was present.

Example 15 Using the halogenobenzenes and halogenated compounds shown in Table 3, the reaction was carried out in the same manner as in Example 14 to obtain a halogenthiophenol derivative. The results are shown in Table 3.

Reference Example 1 In a flask similar to that used in Example 1, a 1°2.3-
1-lichlorobenzene 36.3g (0.2 mol), 7
32.0 g (0.4 mol) of 0% sodium hydrosulfide and 320 g of N-methyl-2-pyrrolidone were charged, the temperature was raised to 140° C. over 1 hour, and stirring was continued at that temperature for another 1 hour. Then lower the temperature to 80°C and
rt-butyl chloride 18.5g (0.2 mol)
was added and stirring was continued at that temperature for 1 hour. N- under reduced pressure
Methyl-2-pyrrolidone was distilled off, 200 g of water and 50 g of toluene were added, and after liquid separation, toluene was distilled off from the toluene solution, and then distilled under reduced pressure (boiling point 90-92°C 10°3
Torr) to obtain 30.5% dichlorophenyl-tert-butyl sulfide. Yield 65.0%. As a result of gas chromatography analysis, the obtained dichlorophenyl-tert-butyl sulfide contained 2,3-dichlorophenyl-tert-butyl sulfide (40.5%
) 2°6-cyclophenyl-tert-butyl sulfide (59.5%) was present.

Reference Examples 2 to 3 Using the halogenobenzenes and 10genated compounds shown in Table 3, the reaction was carried out in the same manner as in Example 14 to obtain halogenothiophenol derivatives. The results are shown in Table 3.

(Left below) Comparative Example In a flask similar to that used in Example 1, a 1°2.4-
Trichlorobenzene 36.3g (0.2 mol), 70
32.0 g (0.4 mol) of sodium hydrogen sulfide and 320 g of kerosene were heated to 140°C over 1 hour.
and continued stirring at that temperature for another 10 hours.

Then, 200 g of water was added, the temperature was lowered to room temperature, the aqueous layer was separated, and the resulting aqueous layer was mixed with 50 g of concentrated hydrochloric acid and 50 g of toluene.
g was added and separated, and toluene was distilled off from the obtained toluene solution, but there was no residue and no dichlorothiophenol was produced. In addition, when the previously separated kerosene solution was analyzed by GC chromatography, it was found that 1,2
．． 36g of 4-trichlorobenzene remained.

Claims (5)

[Claims] (1) General formula (I) ▲Mathematical formulas, chemical formulas, tables, etc.▼(I) [In the formula, X represents a chlorine atom and/or a bromine atom. m represents 2 or 3. [In the formula, X represents a chlorine atom and/or a bromine atom. m represents 2 or 3. M represents a hydrogen atom or an alkali metal. ] A method for producing halogenothiophenols represented by general formula (II), characterized in that a polar organic solvent is used as a solvent for the reaction. (2) General formula (I) ▲Mathematical formulas, chemical formulas, tables, etc.▼(I) [In the formula, X represents a chlorine atom and/or a bromine atom. m represents 2 or 3. ] Halogenobenzenes represented by the formula and sulfide are reacted in a polar organic solvent to form the general formula (II) ▲ Numerical formulas, chemical formulas, tables, etc. ▼ (II) [In the formula, X is a chlorine atom and/or Represents a bromine atom. m represents 2 or 3. M represents a hydrogen atom or an alkali metal. ] Obtain the halogenothiophenols represented by the formula (III) Y-RCOO.
M(III) [In the formula, Y represents a chlorine atom or a bromine atom. R represents an alkylene group having 1 to 12 carbon atoms or a phenylene group. M represents a hydrogen atom or an alkali metal. ] General formula (IV) characterized by reacting a halogenated compound represented by ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (IV) [In the formula, X represents a chlorine atom and/or a bromine atom. m represents 2 or 3. R represents an alkylene group having 1 to 12 carbon atoms or a phenylene group. M represents a hydrogen atom or an alkali metal. ] A method for producing sulfides represented by (3) The polar organic solvent according to claim (1) or (2) is selected from N-methyl-2-pyrrolidone, N,N-dimethylformamide, N,N-dimethylacetamide, sulfolane, dimethylsulfoxide, and ethylene glycol. At least one type selected from the group consisting of: (
The manufacturing method described in 1) or (2). (4) The manufacturing method according to claim (1), (2) or (3), wherein the sulfide according to claim (1) or (2) is sodium bisulfide, sodium sulfide or potassium sulfide. (5) The halogenobenzene according to claim (2) comprises 1,
The manufacturing method according to claim (2), (3) or (4), wherein the halogenated compound according to claim (2) is 2,4-trichlorobenzene and sodium monochloroacetate.