JPH056540B2 - - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a novel method for producing 3,3'-diaminodiphenyl sulfone, and provides a method that is particularly advantageous in industrial implementation. For more details, see the general formula () (In the formula, X represents a hydrogen atom or a chlorine atom, and Y
indicates a chlorine atom and is at the 4- or 6-position)
The present invention relates to a method for producing 3,3'-diaminodiphenylsulfone, which comprises reducing and dechlorinating the diphenylsulfone compound represented by formic acid or a formate salt in the presence of a palladium catalyst. 3,3'-diaminodiphenyl sulfone is useful as a heat-resistant polymer monomer, agricultural medicine, dye intermediate, etc., and is particularly an important substance serving as a raw material for heat-resistant polyamides and polyimide resins. 3,3'-diaminodiphenyl sulfone is conventionally
A method for producing 3,3'-dinitrodiphenyl sulfone by reducing it is known [NP Hatge et al.
Angew.makromol Chem., 4 9 (1) 133 (1976),
Tamaki et al., JP-A-56-25150, NRAyyangar et al.
Synthesis Communications, 640 (1981),
Koiistek et al., Czech.158469; Chem Abstr., 8 4
16955K (1976)]. In this method, the raw material 3,3'-dinitrodiphenyl sulfone is produced by nitrating diphenyl sulfone with a mixed acid [CABuekler
et al., J.Crg.Chem., 4 262 (1939), J.Lacroix.
Bull.Soc.Chim., 35 1436−50 (1924); Chem.
Abstr. 19 980] or a method for producing diphenylsulfide by oxidizing and simultaneously nitrating it with fuming nitric acid [Baldo Ciocca et al., Gazz Chim.Ita., 76
113-19 (1946); Chem.Abstr., 40 7153 (1946)]
There is. Additionally, a method in which benzene is isolated as a by-product when nitrated in the presence of sulfuric anhydride [W.
Alama et al., Biul.Wozskowez Akad.Tech., 13 57
−63 (1964); Ckem.Abstr., 73 34962n (1970)]
In addition, there is a method in which nitrobenzene is sulfonated to produce m-nitrobenzenesulfonic acid, which is isolated as a by-product [Nazvanova
et al. Tr. Khim. Khim. Tekhnol., 178-9 (1969);
Chom.Abstr., 733.496.2n (1970)] is known. However, in the method of producing 3,3'-dinitrodiphenyl sulfone from diphenyl sulfone and diphenyl sulfide, the reaction product obtained by nitration is a mixture containing isomers, etc. In order to isolate '-dinitrodiphenyl sulfone, a large amount of solvent must be used and recrystallization purification must be repeated repeatedly. For this reason, the yield is greatly reduced, and there are also disadvantages such as the need for complicated steps such as recovery of the solvent used in purification, treatment of the residue, and treatment of a large amount of waste acid used in nitration. be. On the other hand, when 3,3'-dinitrodiphenyl sulfone is obtained as a by-product by nitration of benzene and sulfonation of nitrobenzene in anhydrous sulfuric acid, the yield is low and it must be produced as the main purpose. However, there is a problem with supply, and there is also the disadvantage that it is not possible to secure the necessary amount to meet increasing demand. The present inventors have proposed 3.
A method for producing 3'-diaminodiphenyl sulfone was intensively investigated. As a result, we used chloro-substituted diaminodiphenylsulfone represented by the general formula (), which is already widely used industrially as a raw material for agricultural medicines and dye intermediates, as a raw material, and in the presence of a palladium catalyst,
The present inventors have discovered that 3,3'-diaminodiphenylsulfone can be produced in high yield by reduction with formic acid or a formate salt and dechlorination, thereby completing the process of the present invention. That is, the method of the present invention is based on the general formula () (In the formula, X represents a hydrogen atom or a chlorine atom, and Y
indicates a chlorine atom and is at the 4- or 6-position)
This is a method for producing 3,3'-diaminodiphenylsulfone, which comprises reducing and dechlorinating the diphenylsulfone compound represented by formic acid or a formate salt in the presence of a palladium catalyst. The raw material used in the method of the present invention is a chloro-substituted diaminodiphenylsulfone represented by the general formula (), and it is known that it can be produced by the reduction reaction of the corresponding dinitro compound [for example, Budnii et al., Zh. Prikl. (Leningrad)
45 2704−10 (1972); Chem.Abstr., 78 83962z
(1973), WFHart et al., JOrg.Chem., 27 338
(1962)]. Specifically, the chloro-substituted diaminodiphenylsulfone includes, for example, 3,3'-diamino-4-chlorodiphenylsulfone, 3,3'-diamino-6
-chlorodiphenylsulfone, 3,3'-diamino-4,4'-dichlorodiphenylsulfone, 3,
Examples include 3'-diamino-4,6'-dichlorodiphenyl sulfone. The palladium catalyst used in the method of the invention is
Although it can be used in the form of a metal, it is usually attached to the surface of a carrier. Examples include palladium-activated carbon, palladium-alumina, palladium black, and the like. The amount of catalyst used is based on the raw material chloro-substituted diaminodiphenylsulfone.
It ranges from 0.01 to 10% by weight. The formic acid or formate salt used in the method of the invention is used as an aqueous solution. Further, the formate is an alkali formate salt such as sodium formate or potassium formate, and ammonium formate. These formic acid or formate salts are used in a small excess of the theoretically necessary amount relative to the raw materials, but may be in the range of 1.5 to 10 times the amount. This reaction usually uses a reaction solvent. The reaction solvent is not particularly limited as long as it is inert to the reaction, and a solvent miscible with water is usually used. For example, alcohols such as methanol, ethanol, and isopropyl alcohol, glycols such as ethylene glycol and propylene glycol, ethers such as tetrahydrofuran, dioxane, and methylcellosolve, and N,N'M dimethylformamide, N-methylpyrrolidone, and dimethylformamide. Examples include aprotic polar solvents such as. The amount of solvent used is sufficient to suspend or completely dissolve the raw materials, and although there is no particular limitation, it is usually sufficient to use 0.5 to 10 times the weight of the raw materials. The reaction temperature is not particularly limited, but is usually 30 to 110℃.
It is carried out within the range of. In carrying out the present invention, in general, raw materials are dissolved or suspended in a solvent, an aqueous solution of formic acid or a formate salt and a catalyst are added, and then the reaction is carried out at a predetermined temperature with stirring. In either case, the reaction proceeds smoothly and the desired product, 3,3'-diaminodiphenyl sulfone, can be produced. The reaction progress can be monitored by thin layer chromatography and high performance liquid chromatography. The reaction solution obtained by the above method is heat filtered to remove the catalyst, and then cooled or discharged into water to precipitate 3,3'-diaminodiphenylsulfone as crystals. Hereinafter, the present invention will be explained in more detail with reference to Examples. Example 1 3,3'-diamino-4,4'-dichlorodiphenyl sulfone 9.5 g (0.03 mol), 5% palladium/
Activated carbon (Japan Engelhard Co., Ltd.) 0.8 g, 86% formic acid 4.3 g and N,N-dimethylformamide 20
ml was stirred at 50-60°C for 13 hours. Separate the catalyst at the same temperature, drain the liquid into 50 ml of water, and remove the light brown 3,
A precipitate of 3'-diaminodiphenyl sulfone was obtained.
Yield 6.8g (92% yield), melting point 170-171°C. Recrystallization from ethanol yielded pure slightly brown prismatic crystals. Melting point 172.5-173℃. Elemental analysis C H N S Calculated value (%) 58.0 4.9 11.3 12.9 Measured value (%) 58.3 4.4 11.0 12.1 Example 2 3,3'-diamino-4,6'-dichlorodiphenyl sulfone 9.5 g (0.03 mol), 5% palladium/
Activated carbon (Japan Engelhard Co., Ltd.) 0.4g, sodium formate 6.8g, water 2g and methylcellusolve
20ml was stirred at 80-90°C for 9 hours. After cooling to 70°C, the catalyst was separated and the liquid was allowed to cool to room temperature, and 3,3'-diaminodiphenylsulfone was precipitated as pale brown crystals. The crystals were separated, washed with water, and then dried. Yield 6.5g (yield 88%), melting point 170-172°C. Example 3 5.6 g (0.2 mol) of 3,3'-diamino-4-chlorodiphenylsulfone, 0.4 g of palladium black,
2.3 g of potassium formate, 1 g of water and 25 ml of ethylene glycol were stirred at 100-105°C for 8 hours. 70℃
After cooling to temperature, separate the catalyst. After the liquid was allowed to cool to room temperature, 60 ml of water was added to obtain crystals of 3,3'-diaminodiphenylsulfone. yield
4.7g (94% yield), melting point 170-172°C. Example 4 3,3'-diamino-6-chlorodiphenyl sulfone 8.5 g (0.03 mol), 5% palladium/activated carbon
0.4 g, 86% formic acid, 2.3 g, aqueous ammonia, and ethanol were stirred at 50 to 60° C. for 18 hours. At the same temperature, the catalyst was separated and cooled to precipitate light brown crystals of 3,3'-diaminodiphenylsulfone. yield
6.4g (yield 86%), melting point 171-172°C.

Claims (1)

[Claims] 1. General formula (In the formula, X represents a hydrogen atom or a chlorine atom, and Y
indicates a chlorine atom and is at the 4- or 6-position)
A method for producing 3,3'-diaminodiphenylsulfone, which comprises reducing and dechlorinating the diphenylsulfone compound represented by formic acid or a formate salt in the presence of a palladium catalyst.