DE1806993A1 - Aromatic di-and tri-sulphones - Google Patents

Abstract

Aromatic di- and tri-sulphones are prepared by reacting alkali metal salts of benzene sulphinic acids or their alkyl, halogen and carboxyl derivs. with aromatic NO2 gp. containing sulphones which contain at least one NO2 gp. in p-posn. to sulphonyl gp. in strongly polar solvents at 80 degrees-160 degrees C, pref. 120 degrees-160 degrees C. Reactn. pref. carried out in dimethylformamide or dimethylsulphoxide. The di- and tri-sulphones are starting substances for high polymers.

Description

Process for the preparation of aromatic di- and trisulfones Subject of the invention is a process for the preparation of aromatic di- and trisulfones from nitro-containing aromatic monosulfones and alkali metal salts of aromatic Sulfinic acids.

It is known that the nitro groups in aromatic nitro compounds can replace by alkoxy groups.

For example, 4,4'-dinitrobenzophenone and sodium methylate are obtained from 4,4'-dinitrobenzophenone 4,41-dimethoxybenzophenone (Chem. And Ind.

1967, vol. 36, 152). But you have to use very dilute solutions work to achieve high yields. It is also known that by implementation of sodium benzenesulfinate with 2,4-dinitrodiphenylsulfone in aqueous dioxane a single nitro group is exchanged for a phenyl sulfone group, although a molar ratio of benzenesulfinate to 2,4-dinitrodiphenylsulfone how 4: 1 was waved (J. D. Loudon, J. chem. Soc., London 1936, 2185.

Reworking the specified synthesis resulted in despite the excess Sodium Benzolsulfinsaurem that the desired product only in'6 show yield was obtained.

The present invention relates to a method of production of aromatic di- and trisulfones, which is characterized in that alkali salts of benzenesulfinic acids or their alkyl, halogen and carboxy derivatives with aroma tables containing sulfones containing nitro groups, which have at least one nitro group in the para position to the sulfonyl group, in strongly polar solvents at temperatures between 80-16GO \ J, preferably 120-160 ° C, are implemented.

The procedure can be illustrated using the following equation as an example: The alkali metal sulfinates are preferably used in approximately stoichiometric amounts.

It was now surprising that when 4,4'-dinitrodiphenylsulfone was reacted with the alkali metal salts of aromatic sulfinic acids, both nitro groups were exchanged, although no excess of sulfinate was used. Compounds of the following structure are preferably used as aromatic sulfones containing nitro groups where X - denotes H, NO 2 or halogen.

These compounds can also carry further substituents, provided that they are inert to the reaction.

The following compounds, for example, can therefore be used: 4-nitrodiphenyl sulfone, 4,4'-dinitrodiphenyl sulfone, 4-nitro-4'-chloro-diphenyl sulfone and their alkyl and halogen derivatives. The alkali metal salts can be used as the sulfinic acid component the following sulfinic acids can be used: benzenesulfinic acid or with alkyl (e.g. C1 - C6) halogen (e.g.

Chlorine) and carboxyl groups substituted benzenesulfinic acid, such as. B. p-toluenesulfinic acid, 4-chloro-benzenesulfinic acid and 4-carboxy-behzenesulfinic acid. The sodium salts are preferred, but potassium salts can also be used.

The reaction can be carried out by heating the above Components in the appropriate molar ratio in the solvents already mentioned. A slight excess of one of the components can of course be used will. The reaction temperature is between 80-1600C, preferably 120- 1400 ° C. The reaction is complete after 1 to 12 hours, preferably 4 to 6 hours. The isolation of the reaction products can, for. B. by filtering off the accumulated Reaction products after cooling the Solution or failure of the reaction product e.g. B.

with water or by concentrating the solution in vacuo.

The aromatic di- and trisulfones obtained in this way are important starting substances for high polymers.

Example 200 parts by weight of sodium benzene sulfinate are used in 1000 parts by volume Dimethyl sulfoxide is admixed with 265 parts by weight of 4-nitrodiphenyl sulfone while stirring and heated to 1300C for 4 hours.

It is allowed to cool, the reaction mixture is poured into ice water and suctioned the resulting precipitate. Then it is recrystallized from 2000 parts by volume of acetone. The corresponding disulfonyl compound was obtained in 63% yield. matted needles of mp 235-2380C.

If one uses dimethylformamide as a solvent among other things the same Conditions then a 90% yield is obtained.

The following products were reacted analogously to this: 4-Nitrodiphenylsulfon 1 4,4'-Dinitrodiphenylsul £ on II 4-Nitro-4'-Chloro-diphenylsulfon III Appendix for entry of 12/9/68 P 18 06 993.7 No. Sulfin @ .Na Sul final product Lsgm. Asb. Fp. phone (%) 1 Ph-SO2-Na I Ph-SO2-Ph-SO2-Ph DMSO 63 235/8 2 Ph-SO2-Na II Ph-SO2-Ph-SO2-Ph-SO2-Ph DMSO 62 305/8 3 Cl-Ph-SO2Na I Cl-Ph-SO2-Ph-SO2-Ph DMSO 67 171 4 CH3-Ph-SO2Na I CH3-Ph-SO2-Ph-SO2-Ph DMSO 70 198 5 Cl-Ph-SO2Na II Cl-Ph-SO2-Ph-SO2-Ph-NO2 DMSO 60 300 6 CH3-Ph-SO2Na II CH3-Ph-SO2-Ph-SO2-Ph-NO2 DMSO 69 300 7 HOOC-Ph-SO2Na I HOOC-Ph-SO2-Ph-SO2-Ph DMSO 63 300 8 Ph-SO2-Na III Ph-SO2-Ph-SO2-Ph-SO2-Ph DMF 68 305/8 No. Calculated analytical values, found analytical values c HN s 0 Cl CHX 5 0 Cl 1 60.34 3.94 - 17.86 17.86 - 59.1 4.0 - 18.0 18.8 - 58.8 4.0 - 17.8 18.4 2 57.84 3.64 - 19.26 19.26 - 57.5 3.9 - 18.9 19.9 - 57.4 3.5 18.9 19.3 3 55.02 3.33 - 16.32 - 9.02 56.0 3.6 - 15.9 - 5.0 56.5 3.0 15.3 5.0 4 61.29 4.33 - 17.19 17.10 - 61.2 4.3 - 16.2 17.6 - 61.0 16.2 17.6 5 49.39 2.76 - - 21.90 8.13 49.6 3.0 - - 19.8 8.3 49.5 2.9 20.0 8.2 6 54.68 3.62 - 15.34 23.00 - 54.7 4.1 - 16.8 20.7 - 54.7 16.8 20.6 7 @ 55.52 3.67 - 15.57 25.30 - 55.9 3.4 - 15.4 24.8 - 55.9 15.3 24.8 7 * calculated with 0.5 mol of water of crystallization

Claims (1)

Claims 1) Process for the production of aromatic di- and trisulfones, characterized in that alkali salts of benzenesulfinic acids or their alkyl, halogen and carboxy derivatives with aromatic nitro-containing groups Sulfones which have at least one nitro group in the para position to the sulfonyl group, in strongly polar solvents at temperatures between 80-160 ° C, preferably 120 - 16000, are implemented 2) Process for the production of aromatic di- and trisulfones according to claim 1), characterized in that the reaction takes place in dimethylformamide or dimethyl sulfoxide is carried out.