JPS61151162A - 2-or 4-chloro-3,4'-dinitrodiphenyl sulfone and production thereof - Google Patents

Abstract

NEW MATERIAL:2- Or 4-chloro-3,4'-dinitrodiphenyl sulfone shown by the formula I (substitution position of chlorine is in 2- or 4-position). USE:Useful as a raw material for producing 3,4'-diaminodiphenyl sulfone extremely useful for producing heat-resistant high polymer materials, agricultural chemicals, drugs, dye, etc. PREPARATION:2- Or 4-chloro-4'-nitrodiphenyl sulfide shown by the formula II is oxidized and nitrated with nitric acid and a mixed acid, to give a compound shown by the formula I. The reaction is carried out at 20-100 deg.C, preferably at 30-90 deg.C for about 2-12hr. This method has no problem of environmental pollution, an isolated product has high purity, requires no complicated purification process, so it is an extremely improved industrial method.

Description

DETAILED DESCRIPTION OF THE INVENTION (Industrial Application Field) The present invention relates to a new compound, 2- or 4-chlorodinitrodiphenyl sulfone, and a method for producing the same. More specifically, 2- or 4-chloro-4-nitrodiphenyl sulfide represented by the general formula (II)l (in which the chloro group is substituted at the 2- or 4-position) is treated with nitric acid and 2- or 4-chloro-3.4- represented by the general formula (I) (in the formula, the chloro group is substituted at the 2- or 4-position), which is characterized by being oxidized and nitrated with a mixed acid. Concerning the manufacturing capacity of dinitrodiphenyl sulfone.

2-Mataha 4-chloro o-3,4-dinitrodiphenylsulfone is an important compound that is an intermediate for 3,4-diaminodiphenylsulfone, which is useful as a monomer for heat-resistant polymers, and as a raw material for agricultural chemicals, dyes, etc. It is.

(Technical background) 3,41-diaminosyphenyl sulfone can be produced in high yield and purity by catalytic reduction and dechlorination of the compound of the present invention in an organic solvent in the presence of a reduction catalyst and a base.

Conventionally, 3,4-diaminodiphenylsulfone is 3,4-
It is manufactured by reducing dinitrodiphenyl sulfone. That is, a method of catalytic reduction using Raney nickel (Takubo, Pharmaceutical Journal, Gen.

518 (1942)), and C using stannous chloride and hydrochloric acid.
・Reduction method (B, R, Baker et al., J, Org
.

Chem, 15,400 (1950)) are known. However, in these methods, the intermediate 3.
When producing 41-dinitrosif nil sulfone,
, it is difficult to suppress the by-product of isomers during the nitration of 4-nitrodiphenylsulfone, and therefore high quality 3
, 4-dinitrodiphenylsulfone, it is necessary to repeat recrystallization several times for purification. Additionally, a method for producing 3,4-dinitrodiphenyl sulfone by oxidizing 3,4-dinitrodiphenyl sulfide with chromic acid is also known (Takubo, Pharmaceutical Journal, 63, 5).
18 (1942), because it was necessary to use a large amount of chromic acid, there was a problem in the treatment of heavy metals, and furthermore, it was necessary to use large amounts of chromic acid.
Another drawback is that ditrothiophenol is very expensive.

(Problems to be Solved by the Invention) By the way, diamines used as raw materials for heat-resistant and durable polymer monomers, agricultural chemicals, dyes, and the like are required to be extremely pure in terms of quality. Therefore, in the method using 3,4-dinitrodiphenylsulfone as an intermediate as described above, there are problems with by-production of isomers or processing of a large amount of constant electric metal.

This cannot be said to be an industrially advantageous manufacturing method.

The present inventors have based on the production technology of 3,4-diaminodiphenylsulfone, without producing isomer by-products,
In addition, while intensively investigating the industrial production method of 3,4-diaminodiphenylsulfone, 3, It has been found that 41-diaminodiphenylsulfone can be advantageously produced (Japanese Patent Application No. 146,015/1986).

That is, the object of the present invention is to use 2-Mat, ::, Ha4 as a raw material for the production of 3,4-diaminodiphenylsulfone, which is extremely useful for the production of heat-resistant polymeric materials, agricultural chemicals, and dyes.
-Chloro-3,4-dinitrodiphenyl sulfone and a method for producing the same.

(Means for Solving the Problems) As a result of intensive studies to achieve the above object, the present inventors found that 2 −
Alternatively, they discovered that 2- or 4-'chloro-3,4'-dinitrosif-nylsulfone can be produced by using 4-chloro-4"-nitrodiphenyl sulfide as a raw material and subjecting it to an oxidation-nitration reaction. This led to the invention.

That is, the present invention provides a novel 2-diaminodiphenylsulfone as an intermediate that can be advantageously and industrially produced.
or 4-chloro-3,4-dinitrodiphenylsulfone, ):H2-maf,:-HA4-RIO.

- A method for producing 2-Mataha 4-1'Roro 3,4-dinitrodiphenyl sulfone, which comprises oxidizing and converting 4-nitrodiphenyl sulfide with a mixed acid of nitric acid and dichloromethane.

The raw material used in the method of the present invention is 2- or 4-chloro-4-nitrodiphenyl sulfide represented by the general formula (n), and these may be used alone or as a mixture.

These raw materials are 2- or 4-chlorothiopheno-)v
can be easily prepared by condensation of and 4-trionitrobenzene (D,S, Tarbell et al., J, Am.

Chem, Soc, 70.1384 (1948); H
lBurton et al., J.Chem.Soc.
1945, 468; HlGi Iman et al.
J,Am,Chem,Soc,,69.2053(
1947); Culinane et al., Rec, fr.
av, Chim, 55, 881 (1936)).

As the oxidizing and nitrating agent, a mixed acid or nitric acid and a mixed acid are used.

The amount of nitric acid used is 2- or 4-chloro-4-nitrodiphenylsulfate (C3, 7 to 10.0
twice the molar amount, preferably 4.0 to 7.0 times the molar amount.

There is no particular restriction on the concentration used, but 1. Normal specific gravity is 1.
30 to 1.52, particularly preferably 1.42 to 1□52.

The amount of sulfuric acid used is 5.0 to 10.0 times the mole. There is no particular restriction on the concentration as long as it is 96% or more.

Although the method of the present invention can be carried out without the presence of a solvent, there is no harm in using a solvent.

The solvent used is preferably an aliphatic halogen hydrocarbon, specifically dichloromethane, chloroform, carbon tetrachloride, 1,1-dichloroethane, 1,2-dichloroethane, 1. ．． 1.1-1-IJ Chloroethane, 1
Examples include 1.2 metrichloroethane, 1,1,1,2-tetrachloroethane, 1,1,2,2-tetrachloroethane, 1,2-dichloroethylene, trichlorethylene, tetrachloroethylene, etc.The amount of solvent used is particularly Although there is no restriction, the amount is usually 0.2 to 20 times the weight of the raw material, preferably 0.5 to 5 times the weight of the raw material.

There are no particular limitations on the embodiments of the present invention.

The raw material 2- or 4-chloro-4-nitrodiphenyl sulfide is suspended or dissolved in a suitable solvent, or it is first oxidized to sulfoxide with nitric acid without using a solvent, and then nitric acid and sulfuric acid are added. A method of dropping and reacting,
A method is used in which the raw material is dissolved in nitric acid and oxidized to a sulfoxide, and then an organic solvent and a mixed acid are added to oxidize and nitrate, or a method in which the raw material is suspended or dissolved in an organic solvent and a mixed acid is added dropwise. Reaction temperature is 20-100°C
1 Preferably the temperature is 30 to 90°C, and the reaction time is 2 to 12
It takes about an hour.

As a post-treatment method for the reaction, when an organic solvent is used, the organic layer and mixed acid layer are separated under heat, the solvent is distilled off from the organic layer, and the desired crystals are obtained by filtration, washing with water, and drying. Another possible method is to separate the organic layer and the mixed acid layer under heat and then cool and crystallize the organic layer to obtain a highly pure target product. When an organic solvent is not used, the desired product can be obtained by directly discharging the reaction mixture into water, filtering and washing with water.

(Action and Effect of the Invention) As a raw material, 2 in which a chloro group was introduced at the 2- or 4-position
- or 4-chloro-4-dinitrodiphenyl sulfide, no isomer by-product is produced during nitration, and in either case, m-position (3-
2- or 4-chloro-3,4-dinitrodiphenyl sulfone can be produced with high purity.

2- or 4-chloro-3,4 produced by the method of the present invention
-Dinitrodiphenylsulfone can be easily converted into extremely pure 3,4-diaminodiphenylsulfone by reduction-dechlorination.

The method of the present invention has the following advantages: there is no problem of environmental pollution, the isolated product has high purity, and no complicated purification process is required.
This is an extremely excellent method industrially.

(Example) Hereinafter, the present invention will be explained in more detail using solid line examples.

Example 1 Fuming nitric acid with a specific gravity of 1.50 in a glass reaction vessel.
8 (1,4 mol) and to this 4-chloro-4
-nitrodiphenylsulfi)" 53.1 '7 (0
, 2 mol) gradually. After stirring at 30-40°C for 2 hours, 200 g (2.0 mol) of 98-thiosulfuric acid was added dropwise.

After stirring at 30-710°C for 2 hours and further at 80-90°C for 2 hours, the reaction mixture was discharged into 500ml of ice water, and the product was filtered, washed with water, and dried to give 4-chloro-3,4- Cinitrodiphenyl sulfone was obtained.

Yield i66.1 (yield 96.5%), mp, 180
~1838C A pure product was obtained by recrystallization from 1,2-dichloroethane.

mp, 185-186.5°C Elemental analysis HNCIS calculated value (%) 42,04 2,04 8,18 10,
36 9.34 Analysis value (%) 42,21 1°98
8,14 10.48 9.38 Example 2 2-chloro-4-nitrodiphenyl sulfide 53.1
fuming nitric acid 67.Og (1.0 mol) with a specific gravity of 1.50 was added dropwise into a glass reaction vessel containing 100 g (0.2 mol) and 1,2-dichloroethane, and the mixture was heated at 30-40'C.
After stirring for 4 hours, 100 sulfuric acid and 157 ! 7 (1.6 mol) was added dropwise. 3 hours at 30~40°C, then 80~
After stirring at 90°C for 5 hours, 100 g of water was added and 1,2-dichloroethane was removed by azeotropy.

The product was passed through, washed with water, and dried to obtain 2-chloro-3,4-dinitrodiphenylsulfone.

Yield 66.67 (yield 97.2%) 1mp, 18
A pure product was obtained by recrystallization from 2-dichloroethane at 3 to 186° CI.

mp, 187-189°C Elemental analysis CHN CI S Calculated value (CH) 42.04 2.04 8,18 10
,36 9.36 analysis box (chi) 42.05 2,18
8.25 10.34 9.28 Example 3 4-40 rho 4-nitrodiphenyl sulfide 53.1
'7 (0.2 mol) and 250 d of dichloromethane were placed in a glass reaction vessel containing nitric acid 12 with a specific gravity of 1.42.
A mixed acid prepared from 1.4 moles of 96-trisulfuric acid and 204 moles of 96-thiosulfuric acid (2.0 moles) was added dropwise, and the mixture was stirred at 30-40°C for 12 hours. After the reaction, 250 g of water was added and dichloromethane was distilled off by azeotropy, and the product was filtered, washed with water,
After drying, 4-chloro-3,4-dinitrodiphenyl sulfone was obtained.

Yield 66.3 li (yield 96.8 ti) Examples 4-6 The reaction was carried out under different reaction conditions as shown in Table 1.

The results are shown in Table-1.

Claims (1)

[Claims] 1) General formula (I) ▲ Includes mathematical formulas, chemical formulas, tables, etc. ▼
(I) 2- or 4-chloro-3,4-dinitrodiphenyl sulfone represented by (in the formula, the substitution position of the chloro group is the 2- or 4-position) 2) General formula (II) ▲ Numerical formula, chemical formula There are tables, etc.▼(
II) oxidizing and nitrating 2- or 4-chloro-4-nitrodiphenyl sulfide represented by (in the formula, the chloro group is substituted at the 2- or 4-position) with nitric acid and a mixed acid. 2- or 4-chloro-
Method for producing 3,4-dinitrodiphenyl sulfone