JPS62108857A - Production of 2-or 4-chloro-3,4'-dinitrodiphenylsulfone - Google Patents

Abstract

PURPOSE:2- or 4-Chloro-4'-nitrodiphenylsulfone is nitrated to produce a compound which is used as a starting substance of a diamine with inhibition of formation of isomers as by-products and readily purified in no need of complicated purification process in high yield. CONSTITUTION:2- or 4-Chloro-4'-nitrodiphenyl sulfone of the formula (Cl substitutent is in the 2- or 4-position) is nitrated with mixed acid or a nitrate- sulfuric acid mixture at 10-100 deg.C, preferably 0-85 deg.C to give the objective compound. Further, the product is subject to reductive dechlorination to give 3,4'-diaminodiphenyl sulfone, which is used as a synthetic intermediate of monomers of heat-resistant polymers such as polyimide or polyamide, of agricultural chemicals or dyes. The amount of the nitrating agent used here is 1-5mol per mol of the starting substance.

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention consists of 2. Or, it relates to a method for producing 4-chloro-3,4°-dinitrodiphenylsulfone.

More specifically, nitration of 2- or 4-chloro-4°-nitrodiphenyl sulfone represented by general formula (1) (in which the substitution position of CI is at the 2- or 4-position) is described. The present invention relates to a method for producing 2- or 4-chloro-3,4°-dinitrodiphenyl sulfone.

2- or 4-chloro-3,4°-dinitrodiphenyl sulfone can be converted to 3°4 by reductive dechlorination.
'-Diamino diphenyl sulfone can be produced.

This 3,4'-diaminodiphenylsulfone is useful as an intermediate for heat-resistant polymer monomers, agricultural chemicals, dyes, etc., and is particularly useful as a backbone monomer for heat-resistant polyimides and polyamides.

That is, 2- or 4-chloro-3,4°-dinitrodiphenylsulfone is a compound that is a raw material for 3,4'-diaminodiphenylsulfone, which has extremely useful uses.

(Prior art) Conventionally, 3,4'-diaminodiphenylsulfone was 334
A method for converting °-dinitrodiphenyl sulfone into one element (Yakugaku Zasshi, 62 (1942), Journal of Organic Chemistry, Dan 400 (1650)) is known.

(Problems to be Solved by the Invention) However, according to these methods, 3,4'-dinitrodiphenylsulfone is produced by nitrating 4-dinitrodiphenylsulfone. However, with this method, it is difficult to suppress the by-product of isomers. Therefore, the 3,4°-diaminodiphenylsulfone obtained by reducing the obtained 334′-dinitrodiphenylsulfone has a low purity, and recrystallization must be repeated to obtain the target product with high purity.

The object of the present invention is to produce high-purity 3.4'-dinitrodiphenyl sulfone, and to use this as a raw material to produce high-quality 3.4'-dinitrodiphenyl sulfone.
The object of the present invention is to provide 4[deg.]-diaminodiphenylsulfone, and more directly, to provide a method for producing highly pure 3,4'-dinitrodiphenylsulfone.

(Means for Solving the Problems) In order to solve the above-mentioned problems, the present inventors have made extensive studies and have found that the 2- or 4-chloro-
Nitration of 4'-nitrodiphenylsulfone yields 3-
It is possible to selectively introduce a nitro group into the 2- or 4-reactive 3,4- The inventors discovered that dinitrodiphenyl sulfone can be produced and completed the present invention.

That is, the present invention provides nitration of 2- or 4-chloro-4'-nitrodiphenyl sulfone represented by general formula (I) (in which the substitution position of CI is at the 2- or 4-position). This is a method for producing 2- or 4-chloro-3,4+-dinitrodiphenyl sulfone.

The 2- or 4-chloro-3,4°-dinitrodiphenyl sulfone of the present invention is a novel compound.

2- or 4-chloro- used as raw material of the present invention
4''-nitrodiphenylsulfone can be produced by a known method. For example, 4-chloro-4°-nitrodiphenylsulfide is produced by condensing 2- or 4-chlorothiophenol and 4-chloronitrohenzene. A known method is to oxidize this with hydrogen peroxide (Journal of the Chemical Society, Mark 2053 (1947)).

The atomizing agent used in the method of the present invention is a mixed acid or a nitrate and sulfuric acid. As a nitrate, li
Sodium l'l acid, potassium nitrate, etc. are commonly used. During the use of these nitrating agents, 2 or 4
-1 for chloro-4'-nitrodiphenylsulfone
-5 molar ratio, preferably 1.1-3 molar ratio.

There is no particular limit to the concentration of nitric acid, but one having a specific gravity of 1.30 to 1.50 is usually used. There is no particular problem with sulfuric acid as long as it has a concentration of 702 or higher, and fuming sulfuric acid may also be used if necessary. During the use of sulfuric acid, the raw material 2
or 1-10 molar ratio to 4-chloro-4'-nitrodiphenylsulfone.

In the method of the present invention, nitration usually does not require the use of a reaction solvent. However, there is no problem in using organic solvents. In this case, the organic solvent used is not particularly limited as long as it does not inhibit the nitration reaction, but aliphatic halogenated hydrocarbons are usually used.

When carrying out the method of the present invention, 2 or 4 of the raw materials
There are no particular limitations on the method of adding -chloro-4'-nitrodiphenylsulfone, the method of adding mixed acid, the method of adding nitrate, and the mode of use when using an organic solvent. For example, there is a method of dropping sulfuric acid into a mixture of a raw material and nitric acid or a nitrate, or a method of dropping nitric acid or a nitrate into a mixture of a raw material and sulfuric acid. When using an organic solvent, the mixed acid is added to the mixture of the raw material and the solvent, or the mixed acid is added to the mixture of the raw material, the solvent, and nitric acid or nitrate; conversely, the mixed acid is added to the mixture of the raw material and the solvent. There is a method of adding nitric acid or nitrate to a mixture with sulfuric acid.

The reaction temperature is in the range of -10-100°C, preferably 0
-85°C.

The end point of the reaction can be determined by thin layer chromatography or high performance liquid chromatography.

After the reaction is completed, the product is usually discharged into water, filtered, and washed with water.

If a solvent is used, either separate the solvent layer and mixed acid layer and remove the mixed acid, or dilute with water without separating and remove the solvent azeotropically, then filter, wash, and remove the target product. A method of drying may also be used.

(Functions and Effects) In the method of the present invention, since 2- or 4-chloro-4°-nitrodiphenyl sulfone having a chloro group at the 2- or 4-position is used as a raw material, isomer by-products are not produced during nitration. High purity 2- or 4-chloro-3,
4'-dinitrodiphenyl sulfone can be obtained in high yield. Therefore, when this is subjected to catalytic reduction and dechlorination in the presence of a reduction catalyst and a base in an organic solvent, 3.
4'-diaminonophenyl sulfone can be obtained in extremely high purity.

That is, the method of the present invention only requires a nitration reaction of 2- or 4-chloro-3,4'-dinitrodiphenyl sulfone, which is a raw material for a secondary noamine compound. ! This is an industrially extremely significant manufacturing method that enables production without the need for complicated purification steps.

(Example) Hereinafter, the present invention will be explained in more detail with reference to Examples.

Example-1 2-chloro-4°-nitrodiphenyl sulfone 59.5
g (0.2 mol) and 16.1 g of fuming nitric acid with a specific gravity of 1.50.
(0.24 mol) was added dropwise to a glass reaction vessel containing 98x sulfuric acid (60 g, 0.6 mol) at a temperature of 10-30°C for 30 minutes, and then stirred at 30-40°C for 3 hours. After the reaction was completed, it was discharged into water, filtered, washed with water, and dried to obtain 2-chloro-3,4°-dinitrodiphenyl sulfone.

Yield 11 67.6g (yield 98.7) Melting point 185-
A pure product was obtained by recrystallization with 1,2-dichloroethane at 188°C.

Melting point 187-189℃ Elemental analysis value CII CINS Calculated value (χ) 42.04 2.04 10.36 B, 1
8 9.34 Analysis value (χ) 42.20 1.89 1
0.48 8.14.9.48 Example-2 4-chloro-4"-nitrodiphenylsulfone 59.5
g (0.2 mol) and 1,2-dichloroethane 180 ml
A glass reaction vessel containing nitric acid with a specific gravity of 1.42
, 2g (0,6 mol) and 120g (1,6 mol) of 98χ sulfuric acid
2 mol) was added dropwise at a temperature of 0-30°C over 30 minutes, and then stirred at 80-85°C for 3 hours and at 70-85°C for 10 hours. After the reaction, the mixed acid layer was separated, 200 ml of water was added, 1,2-dichloroethane was removed azeotropically, filtrated, washed with water, and dried to give 4-chloro-3,4''~dinitrodiphenylsulfone. Yield 6G, 9g (Yield 97.6χ) Melting point 185-18
A pure product was obtained by recrystallization with 1,2-dichloroethane at 8°C.

Melting point 158-186.5℃ Elemental analysis value CHCI N S Calculated value (χ) 42.04 2.04 10.36 8
．． 18 9.34 Analysis value (X) 42.13 2.18
10.28 8.16 9.49 Example-3-6 Same as Example-1 and Example-2 except changing the type of 2-ma or 4-chloro-4°-nitrodiphenylsulfone and the nitrating agent A nitration reaction was carried out.

Application Example 34.3 g (0.1 mol) of 4-chloro-3,4'-dinitrodiphenyl sulfone obtained in Example 2, 172 me of isopropyl alcohol and 5z palladium/carbon catalyst (manufactured by Nippon Engelhard Co., Ltd. containing 50χ). Place 1.4g of crystal) in a glass airtight container at 20-40°C.
Hydrogen was absorbed while stirring within the range of . 9.4 β
When absorbed, ammonia water (28χ?87&)
18.7 g (0.3 mol) was added and further hydrogen was absorbed at 20-90°C. 15.61! The reaction ends when it is absorbed, and il! The catalyst was removed. When the isopropyl alcohol in the filtrate was distilled off, crystals were precipitated. The crystals were filtered, washed with water, and then dried to obtain 3,4-diaminodiphenyl sulfone. Yield + fIL 23.88 (yield 96.1χ) Melting point 13
A pure product was obtained by recrystallization with 0-132°C ethanol. Melting point 130-132°C Elemental analysis value CII, N S

Claims (1)

[Claims] 1) General formula (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼(I) (In the formula, the substitution position of Cl is the 2- or 4-position) 2- Or, a method for producing 2- or 4-chloro-3,4'-dinitrodiphenyl sulfone, which comprises nitrating 4-chloro-4'-nitrodiphenyl sulfone.