CS225073B1 - The alkyl-beta /methylalcoxysilyle / ethylbenzsulphonates and their production - Google Patents

Abstract

The invention relates to alkyl-beta (methylalkoxysilyl) ethylbenzene sulfonates and the method of manufacture thereof. It is known that alkyl-substituted alkoxysilyl-substituted organofunctional compounds they are suitable chromatographic modifiers phase, while anchoring the compound to the surface no · Whips are mediated by silyl groups while a suitable selection organic funkoe allows you to modify the properties of the phase in the desired direction. The compounds of the invention facilitate preparation the cation exchanger phase, after being anchored to the carrier, it can be hydrdlyeou ester groups under moderate conditions are easily released

Description

Alkylbata (aetylalkoxysllyl) ethylbenzene sulfonates and process for their preparation

The present invention relates to alkyl beta (methylalkoxysilyl) ethylbenzene sulfonates and to a process for the preparation thereof.

It is known that organofunctional compounds substituted with alkylsiloxysilyl groups are suitable phase-phase modifiers, whereby the anchoring of the compound to the whip surface is mediated by silyl groups, while the appropriate selection of organic functionality allows modification of the phase properties in the desired direction. The compounds of the present invention facilitate the preparation of cation-exchange phases, since they can easily be liberated by hydrolysis of the ester group under moderate conditions after their anchoring on the support.

225 073

That is, the acidic function of -SO4H. ₂₂₅

The present invention, alkyl-beta (metylalkoxysilyl) ethylbenzenesulfonate formula (Ε0) ₅ _ _η (σΗ _{5) η 8ΐ} (0Η _{2) 2} 0 ₆ 80 _{4 Η?} 8 wherein R is methyl or ethyl and n is 0, 1 or 2;

These novel compounds can be prepared by reacting methanol or ethanol with beta (methylohlorosilyl) substituted ethylbenzene chlorosulfone compounds in a molar ratio of 1: 1 to 1: 6 at 20 to 60 ° C without solvent or in a hydrocarbon solvent, preferably benzene. The esterification of the reaction mixture after preparation of the beta (methylchlorosilyl) -substituted ethylbenzene chlorosulfonic compounds by chlorosulfonation of beta (methylchlorosilyl) ethylbenzene with chlorosulfonic acid (US Patent 2,955,128) can be advantageously used for the preparation.

The reaction may be carried out without a solvent or in a non-polar solvent, preferably benzene, at normal or slightly elevated temperature, using an anhydrous alcohol in equimolar amount or in excess. All conventional bases used for this purpose, e.g., tertiary amines or preferably alkali metal alcoholates, can be used to remove the hydrogen chloride released in the reaction.

The following examples characterize the compounds of the invention without limiting or restricting it. The weights are given in parts by weight.

Example 1

In a reaction vessel equipped with a stirrer, a separating funnel, a gas inlet and outlet, 175 parts of chlorine-22S-073 sulfonic acid and 520 parts of anhydrous chloroform were introduced. An inert atmosphere was maintained throughout the reaction by introducing a stream of argon or nitrogen. Then the rinse was immersed in an ice bath, the mixture cooled to 6 ° C and a solution of 115 parts beta (phenyl) ethyltrichlorosilane in 8 8 parts anhydrous chloroform was added dropwise from the separatory funnel over 10 minutes with stirring. The temperature of the reaction mixture was maintained at 6-10 ° C. Hydrogen chloride was released during the reaction. After the addition of all the vigorous amount, stirring was stopped, the reaction mixture was allowed to react for an hour and then transferred to a separatory funnel.

248 parts of anhydrous carbon tetrachloride were added to the solution, the mixture was shaken vigorously and allowed to stand. Over time, a layer of sulfuric acid began to precipitate out of the mixture, which was separated after hours. The organic layer was freed of residual sulfuric acid by shaking and standing for 15 hours with 50 parts of sodium carbonate. After the salts were filtered off, the solvents were evaporated under reduced pressure. The concentrated partially solidified reaction mixture was dissolved in a minimum amount of benzene and from the separatory funnel was added dropwise J2 parts of absolute methanol at 25-30 ° C. During the esterification and for a further 1 hour, the solution was bubbled vigorously with a stream of argon to prevent the evolution of hydrogen chloride evolution in the reaction mixture. The reaction was completed by titrating the reaction mixture with saturated sodium methylate solution to neutral. The precipitated salts were filtered through a pad of silica gel, washed with benzene, the two filtrates were combined and the volatiles were removed by evaporation under reduced pressure. Vacuum distillation begins

225 073

Uště of the densified fraction was obtained 62 parts fraction with bv at 150-8 ° C / 8.10 mm ² Pa * for ^{C 12 H} 20 ° 6 ^S 1 ^Si 2 → ^{20 4} calculated: 10.0 f S, 45.0% C H, 6.3%. Found: 10.1% S, 44.9% C, 6.2%. The yield of methyl beta (trimethoxysilyl) ethylbenzenesulfonate (calculated on the starting beta (phenyl) ethyl triclorosilane) was 39 mol%.

Example 2

Example 1 was repeated except that calcium chloride was used to remove sulfuric acid residues from the reaction mixture after chlorosulfonation of the (phenyl) ethyltrichlorosilane by a procedure analogous to Example 1, and esterification of the concentrated reaction mixture and vacuum distillation yielded 33.4 mol% methyl. -beta (trimethoxysilyl) ethylbenzenesulfoaate.

Example 3

Example 1 was repeated except that absolute ethanol and saturated sodium ethylate solution were used to esterify beta (chlorosulfonylphenyl) ethyl trichlorosilane. Vacuum distillation of the concentrated reaction mixture after filtration of the salts yielded 34 mol% ethylbeta (triethoxysilyl) ethylbenzenesulfonate. For ^C 16 ^H 28 ° 6 ^S 1 ^Si (376.5) calculated: 8.5% S, 51.0% C, 5 H; found: 8.7% S »50.6% G, 7.4% Η»

Example 4

To a solution of 175 parts of chlorosulfonic acid in 520 parts of anhydrous chlorine, 110 parts of beta (phenyl) ethylmethylene-228 073 chlorosilane in 178 parts of anhydrous chloroform were added dropwise in the arrangement and conditions of Analogous Example 1. Further work-up of the reaction mixture after chlorosulfonation and esterification with methanol and sodium methylate was analogous to Example 1. 28 mol% of methyl beta (methyldimethoxysilyl) ethylbenzenesulfonate was obtained by vacuum distillation. For ^C 20 ^H I2 O5 ^S l ^a l vypočtenol 10.5% S, 47.3% C, 6.6% H; found: 10.3% S, 47.5% C, 6.6% H.

Example 5

To a solution of 175 parts of chlorosulfonic acid in 520 parts of anhydrous chloroform, 100 parts of beta (phenyl) ethyldimethylchlorosilane in 178 parts of anhydrous chloroform were added dropwise in an arrangement and under conditions analogous to Example 1. The procedure was the same as in Example 1 except (Chlorosulfonylphenyl) ethyldimethylchlorosilane was used with absolute ethanol to complete the reaction and bind the liberated hydrogen chloride saturated sodium ethylate solution. After filtration and concentration, 37.7 mol% of ethyl beta (dimethylethoxysilyl) efcylbenzenesulfonate was isolated from the reaction mixture by vacuum distillation.

Pfo C 14 ^H 24 ° 4 ^S 1 ^Si 1 (316.5) calculated: 10.1% S, 53.1% C,

7.6 H; Found: 10.1% S, 52.8% C, 7.5% H.

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Claims (2)

Object of the invention 225 073 Alkyl-beta (methylalkoxysilyl) ethylbenzenesulfonates of the general formula ^CR0) 3-n ^CCH 3 ⁾ n ^{Si (CH} 2 ⁾ 2 ^C 6 ^H 4 ^S ° 3 ^R * where represents R is methyl or ethyl and n is 0, 1 or 2. 2. A process according to claim 1, wherein the alcohol is reacted with beta (methylchlorosilyl) substituted ethylbenzene chlorosulfone compounds in a molar ratio of 1: 1 to 1: 6 at a temperature of 20 to 60 ° C without solvent or in a solvent. a hydrocarbon solvent, preferably in benzene. J. A method according to claim 1, wherein the reaction is carried out by reacting an alcohol with a mixture obtained by chlorosulfonation of beta (methylchlorosilyl) ethylbenzene in a molar ratio of 1: 1 to 1: 6 at 20 to 60 ° C without solvent or in a solvent. a hydrocarbon solvent, preferably in benzene.