CS235425B1 - Process for the production and isolation of sodium alkensulfonates - Google Patents

Abstract

The invention relates to a method for the production and isolation of sodium alkene sulfonates of general formula 1 by the action of an aqueous solution of sodium aryl sulfate on 2-alken-1-yl chloride, the essence of which is that the reaction takes place at a ratio of reactants of 1.0 to 1.2:1.0 in the presence of a catalytic amount of 9.1 to 1.0 mol% of sodium iodide and 0.05 to 10 mol% of a quaternary phosphonium salt at a temperature of 25 to 70 °C, while after the reaction is completed, the bulk of the reaction volume is distilled under reduced pressure and the separated sodium chloride is filtered off with suction, washed with hot water and after repeating the reaction, a product of general formula I with a maximum content of 4% chloride ions is obtained.

Description

BACKGROUND OF THE INVENTION The present invention relates to a process for the preparation and isolation of 2-alkenyl-1-ylsulphenes of the seventh general formula I

R.

-C «C-CH _of S0, N"'and ³ RR'

CD where

R @ 1 denotes hydrogen or alkyl having 1 to 5 carbon atoms or phenyl, R @ 1 denotes hydrogen or methyl and R @ 1 denotes hydrogen or methyl.

The compounds have considerable practical applications in a number of industries. They are used in toothpastes (Japanese Pat. No. 81 10 285) as ingredients for the preparation of textile articles (U.S. Pat. No. 2,278,064). They also found wide application in preparations used in electroplating (Soviet patents 765,404 and 742,489, Romanian patents 72,377, French patents 2,472,621). They are also used to prepare copolymers with special properties (U.S. Pat. No. 2,501,256).

Several methods for the preparation of these compounds are described which utilize the reaction of the corresponding 1-halon-2-alene with sodium sulfite in an aqueous medium. This embodiment is generally carried out at elevated temperatures using pressure vessels (DRP Pat. No. 73,888, US Pat. No. 2,278,064, 2,243,332) or long reaction times (J. Amer. Chem. Soc 63,1954). (1941). Soviet Patent Specification 859 357 discloses a process for the preparation of sodium 2-propen-1-ylsulfonate (sodium allylsulfonate) starting from allyl chloride and sodium sulfite in the presence of surfactant and cuprous chloride. A similar process using methylcellulose as a solvating agent and elevated temperature protects another U.S. Patent No. 90,946. Another process (Ger. Offen 2,545,644) performs the reaction in aqueous alcoholic solutions in the presence of quaternary ammonium salts under mild reaction conditions.

In all these processes, the pure product is obtained by crystallization or extraction of lower alcohols, optionally mixed with alkyl acetates. This operation is very lengthy and the solvent consumption is relatively high, despite the fact that work with large volumes of boiling methanol, ethanol or propanol requires special precautions.

These known processes are followed in a positive way by the method according to the invention.

The process according to the invention is based on the reaction of a 2-alken-1-yleoride of the formula II

R

C = C-CH ₂ C 1 '(II)

R ¹ -? 1.2 where

2

R, R, R are as hereinbefore defined with an aqueous solution of sodium sulfite in the presence of a catalytic amount of sodium iodide and 0.05 to 10 mol%, phosphonium salt, preferably 0.3 to 5 mol%, at a temperature of 25 to 70 ° C, preferably 40 to 50 ° C, with vigorous stirring of the reaction mixture. The reaction used sodium sulfite to 2-alken-1-yl chloride in a ratio of 1.0 to 1.2: 1.0. Tetrabutyl phosphonium bromide, tributylhexadecylphosphonium bromide, methyltriphenylphosphonium bromide are preferably used as phosphonium salts. After completion of the reaction, 3/4 to 4/5 of the volume of water is evaporated from the reaction mixture on a vacuum evaporator, the precipitated sodium chloride is suctioned off hot and washed with a small amount of hot water. After re-concentration of the mother liquors, the remaining portion of sodium chloride is separated. This simple procedure yields the product of formula I in a yield of 92 to 98% containing a maximum of 4% chloride ions. The product of this purity is a preferred agent for preparations for electroplating and other industries. The process according to the invention is simple, easy to carry out on special-purpose devices and is harmless in terms of hygiene and safety. The high yields and purity of the product obtained make this process for the preparation of the compounds according to the invention economically advantageous.

The process according to the invention is described in several specific examples, which are illustrative only and in no way limit the scope and scope of the invention.

Example 1

Sodium 2-propen-1-yl-sulfonate (I, R> B ¹ * R ² sH)

To a solution of 201.6 g of crystalline sodium sulfite in 240 ml of water was added 0.5 g of sodium iodide and 1.2 g of tetrabutylphosphonium bromide. After homogenizing the reaction mixture at 40-45 ° C, 61.2 g of 2-propen-1-yl chloride was added to the reaction mixture and stirred at this temperature for 2 hours. After completion of the reaction, about 250 ml of water was distilled off from the reaction mixture in vacuo and the precipitated salt was filtered off with suction and washed with steam (about 2 ml); this operation was repeated once more. After evaporation of the mother liquors, 109.2 g of a product containing 2.7% of chloride ions were obtained.

Example 2

Sodium 2-methyl-2-propen-1-ylsulfonate (I, R = r '= H, Η ² · ΟΗ ^)

To a solution of 20.2 g of crystalline sodium sulfite in 20 ml of water was added 0.04 g of sodium iodide and 0.15 g of tetrabutylphosphonium bromide. After homogenizing the mixture at 35-45 ° C, 7.36 g of 2-methyl-2-propenyl-yl chloride was added and after 1.5 hours of heating and stirring, the reaction mixture was worked up as in Example 1. 12.2 g of product were obtained. containing 3.1% chloride ions.

Example 3

3-phenyl-2-propen-1-ylsulfonét ate sodium (I, R ^ C ^ H ^, R * R ² = H) £ solution of 10.1 g of anhydrous sodium sulfite in 35 mL water was added 0.06 g of iodide sodium and 1.5 g of tributylhexadecylphosphonium bromide. To this reaction mixture, after homogenization, 12.4 g of 3-phenyl-2-propen-1-yl chloride was added and stirred at 25-35 ° C for 1 hour. Thereafter, the reaction mixture was worked up as in Example 1 to obtain 16.9 g of a product containing 2.1% chloride ions.

Example

2-buten-ylsulfonét carbonate (I, R = R ² = H, R '= GH ^)

To a mixture of 40.4 g of crystalline sodium sulfite, 0.1 g of sodium iodide, 2 g of tributylhexadecylphosphonium bromide in 35 ml of water at 40-50 ° C was added 15.1 g of 2-buten-1-yl chloride. After stirring at this temperature for 3 hours, the reaction mixture was worked up as in Example 1. 23.2 g of product containing 3.2% chloride ions were obtained.

Example 5

Sodium 2-hexen-1-ylsulfonate (1, R ⁵ CH ² G 1 H 8 CH 8, r '= R ² = H)

To a solution of 20.2 g of crystalline sodium sulfite, 0.05 g of sodium iodide and 0.9. g of methyltriphenylphosphonium bromide in 22 ml of defect was added 9.7 g of 2-hexen-1-yl chloride and stirred at 50-60 ° C for 4 hours. After working up the reaction mixture as in Example 1, 13.6 g of product with 2.6% chloride ions were obtained.

Claims (3)

SUBJECT OF THE INVENTION 1 2 R, R and R are as defined above, characterized in that the reaction proceeds at a reactant ratio of 1.0 to 1.2: 1.0 in the presence of a catalytic amount of 0.1 to 1.0 mol%. sodium iodide and 0.05-10 moles of quaternary phosphonium salt at 25-70 [deg.] C., after which the bulk of the volume of water is distilled off under reduced pressure and the precipitated sodium chloride is filtered off with suction, washed with hot water and repeated. of the formula I with a maximum content of 4% chloride ions. 1. A process for the production and isolation of sodium alkene sulfonates of the general formula 1 C> C-CU ₂ SO ₃ Na (I), where S is hydrogen or alkyl of 1 to 5 carbon atoms or phenyl, R * denotes hydrogen or methyl; and 2 R is hydrogen or methyl by treating an 2-alken-1-yl chloride of formula 11 with an aqueous solution of sodium metabisulphite C-CH ₂ Cl (IX) wherein Process according to claim 1, characterized in that tributylhexadecylphosphonium bromide, tetrabutylphosphonium bromide, triphenylmethylphosphonium bromide is used as quaternary phosphonium salt, preferably in an amount of 0.3 to 5 mol%. 3. The process according to claim 1, wherein 3/4 to 4/5 of the original volume of water is evaporated after the reaction is complete.