Method of producing dimethyl sulphoxide

IPC classes for russian patent Method of producing dimethyl sulphoxide (RU 2440336):

C07C317/04 - of an acyclic saturated carbon skeleton

C07C315/02 - by formation of sulfone or sulfoxide groups by oxidation of sulfides, or by formation of sulfone groups by oxidation of sulfoxides

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FIELD: chemistry.

SUBSTANCE: invention relates to production of dimethyl sulphoxide (DMSO) which is widely used in organic synthesis. According to the invention, dimethyl sulphide is oxidised with chlorine dioxide with molar ratio of sulphide to chlorine dioxide equal to 1:0.5 at temperature 7-10°C. The invention also describes preferable conditions for conducting the process.

EFFECT: improved method.

3 cl, 3 ex

The invention relates to the field of production of dimethyl sulfoxide oxidation of dimethyl sulfide. Dimethyl sulfoxide is used in organic synthesis, as a solvent of inorganic and organic compounds, pharmaceuticals, and medicine.

A known method of producing dimethyl sulfoxide, consisting in the oxidation of dimethyl sulfide with organic hydroperoxides [patent SU 474977]. The disadvantage of this method is the control of the acidity of the aqueous phase.

Known methods for producing dimethyl sulfoxide, consisting in the oxidation of pulp and paper industry containing sulfur-containing organic compounds, oxygen at 20-50°C by passing the reaction mixture through activated carbon, modified chloride or potassium iodide [patent SU 749830] and through the activated carbon, modified tetrachloroplatinate or acetylacetonates of metals of variable valence [patent SU 1054347]. The drawback of both methods is the difficulty in the selection of the target product.

A known method of producing dimethyl sulfoxide, taken as a prototype, which consists in the oxidation of dimethyl sulfide 30%hydrogen peroxide [patent SU 249375]. Dimethyl sulphide pre-treated with concentrated sulfuric acid. The disadvantage of this method is the use of a large Koli is estva of concentrated sulfuric acid.

The problem to which the invention is directed, is expanding the range of application of the original substances, the use of less toxic and available reagent chlorine dioxide produced by industry.

As the tonnage by product to be used for disinfection of drinking water and industry for pulp bleaching, chlorine dioxide is available and promising oxidant. Thanks to the good solubility of chlorine dioxide in water and in organic solvents it is possible to carry out reactions in different environments, and high reactivity allows you to get as a final product the dimethyl sulfoxide with the yield up to 92%.

The technical result is achieved in that in the method of producing dimethyl sulfoxide, including the oxidation of dimethyl sulfide and the selection of the target product by known methods, according to the invention, the oxidation is performed with chlorine dioxide in the environment of an organic solvent at a molar ratio of sulfide and chlorine dioxide equal to 1:0.5, respectively, at a temperature of 7-10°C. alternatively, the oxidation is carried out by adding to the dimethyl sulfide aqueous solution of chlorine dioxide; the oxidation is carried out by ozonation in organic solution of dimethyl sulfide chlorine dioxide.

Previously we have shown that chlorine dioxide is selectively oxidizes sulfides to sulfox the Dov [patent RU No. 2127258, patent RU No. 2139275, 1999].

For optimal reaction conditions for the oxidation of varied parameters such as reaction temperature and the method of supplying oxidant. Thus, the reaction temperature was changed from 7 to 25°C. it Was observed that at low temperatures increases the reaction time, reduces the loss of dimethyl sulfide, increases the yield of dimethyl sulfoxide.

The oxidant can be fed into the reaction mixture in various ways: method 1 - organic solution of chlorine dioxide is added dropwise in the organic sulfur compound; method 2 - aqueous solution of chlorine dioxide is added dropwise in the organic sulfur compound; method 3 - by ozonation in organic sulfur compound mixture of chlorine dioxide from the air.

The optimum temperature for the reaction between 7 and 10°C. the Advantage of the output of dimethylsulfoxide is carrying out reaction according to the method 3.

We used industrial chlorine dioxide in aqueous solution. In an organic solvent chlorine dioxide translated by extraction or by bubbling with air.

The reaction was carried out prior to the bleaching solution of chlorine dioxide. Monitoring the progress of reactions was carried out by gas chromatography.

The described method is demonstrated by the following examples.

Example 1. To dimethyl sulfide (7.64 g, 0.12 mol) dropwise (853 is l) was added an aqueous solution of chlorine dioxide (4.16 g, 0.06 mol) (method 1). The reaction was carried out in a three-neck flask, equipped with reflux condenser and thermometer, under constant stirring for 3 hours at 7°C. After the reaction water drove away. The reaction products were shared by vacuum distillation. Got 7.11 g of dimethyl sulfoxide (74% of theoretical). BP. 186 to 190°C, n_D²⁰=1.4750. [Beilst. E.V., n, 281, 139 I, II, 269]. IR-spectrum (CCl₄), ν/cm^-1: 1050 (S=O). Range¹H (300 MHz, CDCl₃, δ, ppm): 2.48 (s, 6N, 2CH₃). Range¹³(300 MHz, CDCl₃, δ, ppm): 40.62 (CH₃).

Example 2. To dimethyl sulfide (10.97 g, 0.18 mol) dropwise (746 ml) was added a solution of chlorine dioxide (5.97 g, 0.09 mol) in dichloromethane (method 2). The reaction was carried out in a three-neck flask, equipped with reflux condenser and thermometer, under constant stirring for 3 hours at 10°C. After the end of dichloromethane drove away. The reaction products were shared by vacuum distillation. Got 11.31 g of dimethyl sulfoxide (82% of theoretical).

Example 3. In dimethyldisulfide 10.99 g (0.18 mol) was barbotirovany chlorine dioxide (5.98 g, 0.09 mol) with air (method 3) for 2 hours at 7-10°C. Received 12,58 g (91% of theoretical) of dimethyl sulfoxide.

1. A method of producing dimethyl sulfoxide, characterized in that dimethyl sulfide are oxidized by chlorine dioxide in the environment of an organic solvent at a molar balance of the attachment sulphide to chlorine dioxide, equal to 1:0,5, respectively, at a temperature of 7-10°C.

2. The method according to claim 1, characterized in that the oxidation is carried out by adding to the dimethyl sulfide aqueous solution of chlorine dioxide.

3. The method according to claim 1, characterized in that the oxidation is carried out by ozonation in organic solution of dimethyl sulfide chlorine dioxide.