Research On Synthesis Of Tert-Butylsulfinyl Chloride

In recent years, tert-butylsulfinyl chloride has been widely used in research and production of various tert-butyl sulfinates. It has a certain market and the price is extremely expensive. The relevant domestic research and production of tert-butylsulfinyl chloride has been reported rarely. Therefore, there is a high academic value on synthesis of it, and there is a significant economic value on its mass production.In this paper, we used tert-butyl thiol as raw material, molybdenum oxide compound as catalyst, to synthesize di-tert-butyl disulfide which was followed by oxidation and chlorination reaction to obtain tert-butylsulfinyl chloride. The specific work carried out as follows:1. The catalyst of dimethyl sulfoxide complex trichloro oxomolybdenum (MoOCl3(DMSO)2) has been prepared with molybdenum trioxide, thionyl chloride and dimethyl sulfoxide as the raw material which reacted with thionyl chloride and then complexed with dimethyl sulfoxide. The structure of it was confirmed by m.p., IR and 1H NMR. The synthesis process of it has been optimized to obtain the optimum reaction conditions, namely thionyl chloride and molybdenum trioxide in the molar of 4:1, reflux time 3h, dimethyl sulfoxide and anhydrous ethanol in the molar ratio of 1.5:1.2. Di-tert-butyl disulfide has been prepared in high yield and high selectivity with tert-butylthiol as raw material, dimethyl sulfoxide complex trichloro oxomolybdenum as catalyst, dimethyl sulfoxide as oxidant for catalytic oxidation. The structure of it was confirmed by IR and 1H NMR. The synthesis process of it has been optimized to obtain the optimum reaction conditions, namely n(dimethyl sulfoxide):n(tert-butylthiol)=5.5:1, reaction temperature 65℃, reaction time 20h, the amount of catalyst for tert-butylthiol molar number of 4.7%. The reaction kinetics has been studied and the kinetic equation was derived as r=0.01914CA1.3CB1.2.3. A series of dialkyl disulfides have been prepared with different structures of thiols as raw material, namely RSSR, where R=s-C4H9,t-C4H9,n-C7H15,n-C8H17, i-C8H17, n-C12H25,n-C16H33,n-C18H37. The effect has been discussed for different alkyl structure on degree of difficulty, and the reaction mechanism has been also explored.4.tert-Butylsulfinyl chloride has been prepared with di-tert-butyl disulfide as raw material which was oxidized by 30% hydrogen peroxide and then was chloridized by chlorine or sulfonyl chloride. The structure of it was confirmed by gas chromatography and 1H NMR. The differences between two methods were discussed.5. The content of tert-butylsulfinyl chloride has been determined by gas chromatography and acid-base titration method. The differences were discussed between two methods.The method of synthesis of tert-butylsulfinyl chloride in this paper has advantage of stable condition, high yield and relatively simple operation. Among the process, dimethyl sulfoxide complex trichloro oxomolybdenum was prepared with molybdenum trioxide as raw material which is low coat. This method is simple and the yield is high. The catalyst has high catalytic activity, small amount, excellent selectivity and high yield when it was used to synthesize di-tert-butyl disulfide and dialkyl disulfides. The related patent has been in public.