JPH01258656A - 2,3,5-trichloro-4-alkylbenzenesulfonic acid or its salt and production thereof - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION <Industrial Application Field> The present invention relates to 2.8.5-)dichloro-4-alkylbenzenesulfonic acids or salts thereof, and methods for producing them.

<Prior Art> 2,13.5-)lichloro-4-alkylbenzenesulfonic acid is a new compound that has not been described in the literature.

<Problems to be Solved by the Invention> The present invention provides an industrial advantage for 2,4-dichloro-0-8-alkyl-6-nitrophenols, which are intermediates of cyan coloring agents in the field of color photographic light-sensitive materials. jttth intermediate produced and useful r, r 2.8.5-)
It is an object of the present invention to provide dichloro-4-alkylbenzenesulfonic acids or salts thereof, and methods for producing them.

<Means for Solving the Problems> The present invention is based on the following formula (I) [wherein R represents a straight chain or branched alkyl group having 2 to 8 carbon atoms]. ] 2,8.5-trichloro-4-alkylbenzenesulfonic acid or a salt thereof, and 4 represented by the following formula (II) b (Jsl-1 [wherein R has the above meaning] - 2,8.5-trichloro-4-alkylbenzene represented by the formula CI] characterized in that the alkylbenzenesulfonic acid or its salt is reacted with a chlorinating agent in the presence or absence of a catalyst in a solvent. A method for producing sulfonic acid or a salt thereof is provided.

In formula (I) above, the alkyl group represented by I< is ethyl, n-propyl, i-propyl, n
-butyl, t-butyl, i-amyl, n-octyl and the like are exemplified, among which ethyl and i-propyl are particularly preferred.

The salts of the compounds represented by formulas (I) and (II) include alkali metal salts, alkaline earth metal salts, amine salts, and the like, such as sodium salts, potassium salts, and magnesium salts.

Examples of the solvent used for chlorination include non-acid, organic acid, polar organic solvent, halogenated hydrocarbon, and mixtures thereof.

As the inorganic acid, mineral acids such as sulfuric acid and hydrochloric acid are used, and if necessary, sulfuric anhydride and chlorosulfonic acid may be used in combination.

Examples of organic acids include acetic acid, trichloroacetic acid, monochloroacetic acid, dichloroacetic acid, and formic acid.

Examples of the polar organic solvent include nitrobenzene, 0-chloronitrobenzene, N,N-dimethylformamide, and the like.

Examples of halogenated hydrocarbons include methylene chloride, chloroform, carbon tetrachloride, and monochlorobenzene.

Among these solvents, inorganic acids and halogenated hydrocarbons are preferred, and inorganic acids such as sulfuric acid are particularly preferred.

Examples of the nutrient that may be used for chlorination include iron chloride, antimony chloride, aluminum chloride, and iodine. Although the amount used is not particularly limited, it is preferable that -
) is 1 to 1% by weight.

The chlorinating agent is not particularly limited, but chlorine gas, sulfuryl chloride, and the like are preferably used.

Chlorination is carried out until the content of the compound represented by formula (I) or its salt reaches the maximum value or its vicinity.More specifically, the content of the compound represented by formula [I] or its salt is Chlorine is added to the chlorination reaction mixture [the sum of the compound represented by formula (material) or its salt and the compound produced by chlorination] until it reaches preferably 60% by weight or more, more preferably 70 to 90% by weight. make a change. For this purpose, the chlorinating agent should be used in a molar ratio of 2 to 6, preferably 2
．． A molar ratio of 5 to 4.5, more preferably 2.7 to 4, is used. In addition, the reaction temperature is usually 0 to 150°C,
Preferably it is 20-80°C.

After completion of the reaction, the obtained 2,8.5-trichloro-4-furkylbenzenesulfonic acid or its salt can be isolated from the reaction mixture by a known method, if desired.

2,8.5-trichloro-4- thus obtained
Alkylbenzenesulfonic acids can be industrially advantageously derived into 2,4-dichloro-3-alkyl-6-nitrophenols, which are intermediates of cyan coloring agents, by desulfonation, nitration, and then hydrolysis. .

The present invention will be explained in more detail with reference to Examples below.
The present invention is not limited in any way by the following examples. In the examples, parts and % represent parts by weight and % by weight.

Example 1 After 5 parts of iodine was dissolved in 1000 parts of 96% sulfuric acid, 186 parts of 4-ethylbenzenesulfonic acid was added thereto, and about 285 parts of chlorine was introduced at 40 to 60°C with stirring. At this time, the proportion of 2,8.5-trichloro-5ethylbenzenesulfonic acid in the chlorinated mixture was 78.8%. Next, this was poured into 2,700 parts of water to dilute it, and then 400 parts of a 28% aqueous sodium hydroxide solution was added to precipitate crystals. This is separated in a furnace and dried to give white crystals of 2,8.5-t1,1
Sodium chloro-4-ethylbenzenesulfonate 80
I got 8 copies. (Yield 81.6%) HPLC analysis value, 2,
8.5-) Sodium dichloro-4-ethylbenzenesulfonate: 82.5%, 2.8.5.6-Sodium tetrachloro-4-ethylbenzenesulfonate: 18.0
%, 8.8% sodium 5-dichloro-4-ethylbenzenesulfonate.

Example 2 The same procedure as in Example 1 was conducted except that 200 parts of 4-isopropylbenzenesulfonic acid was used as the raw material. Coarse 2.3.5-
Yield of sodium trichloro-4-isopropylbenzenesulfonate: 314 parts.

(yield 75.5%), HPLC analysis value, sodium 2.8.5-trichloro-4-isopropylbenzenesulfonate 8.8%, 2.8.5.6-tetrachloro-4
- Sodium isopropylbenzenesulfonate: 16.
5%, sodium 8,5-dichloro-4-isobrobylbenzenesulfonate: 4.8%.

Example 8 Add 5 parts of iodine and 62 parts of sodium 4-ethylbenzenesulfonate to 250 parts of 96% sulfuric acid, and add 40 to 6 parts of sodium 4-ethylbenzenesulfonate while stirring.
Approximately 60 parts of chlorine were introduced at 0°C. Next, add 500 yen of water to this
The precipitated crystals were filtered and dried to give a crude 2.
．． 76.9 parts of sodium 8.5-trichloro-4-ethylbenzenesulfonate were obtained. (yield 80.5%), H
PLC'tNR value, 2.8.5-), sodium dichloro-4-ethylbenzenesulfonate: 82.5%, 2,
8,5゜6-tetrachloro-4-ethylbenzenesulfonate sodium: ia, o%, 8,5-dichloro-4-
Sodium ethylbenzenesulfonate: 8.8%.

Example 4 17g 5 parts of iodine was dissolved in 100 parts of carbon chloride and 150 parts of acetic acid, and 46.6 parts of 4-ethylbenzenesulfonic acid was dissolved therein.
About 60 parts of chlorine was introduced at 50 to 70°C while stirring. After the reaction was completed, chlorine was purged with nitrogen, and carbon tetrachloride was removed under reduced pressure. Dilute the reaction mixture with 150 parts of water,
After cooling, the crystals were filtered and dried to obtain 65 parts of a crude product of 2,8.5-trichloro-4-ethylbenzenesulfonic acid. (Yield 70%) HPLC analysis value, 2°8.5-trichloro-4-ethylbenzenesulfonic acid nia 8.8%
, 2.8.5.6-tetrachloro-4-ethylbenzenesulfonic acid: 16.6%, 8,5-dichloro-4-ethylbenzenesulfonic acid 1.8%.

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Claims (5)

[Claims] (1) General formula [I] ▲ Numerical formulas, chemical formulas, tables, etc. are available▼ [I] [In the formula, R represents a straight chain or branched alkyl group having 2 to 8 carbon atoms. ] 2,3,5-trichloro-4-alkylbenzenesulfonic acid or a salt thereof. (2) General formula [II] ▲ Numerical formulas, chemical formulas, tables, etc. are available▼ [II] [In the formula, R represents a straight chain or branched alkyl group having 2 to 8 carbon atoms. ] The 2,3, A method for producing 5-trichloro-4-alkylbenzenesulfonic acid or a salt thereof. (3) The method according to claim 2, wherein the solvent is at least one selected from inorganic acids, organic acids, polar organic solvents, and halogenated hydrocarbons. (4) The method according to claim 2, wherein the chlorinating agent is chlorine or sulfuryl chloride. (5) The method according to claim 2, wherein the reaction is carried out until the content of the compound represented by general formula (I) in the chlorination reaction mixture becomes 60% by weight or more.