DMSO络合三氯一氧化钼催化合成二叔丁基二硫醚及其同系物的研究

Study on Catalytic Synthesis of Di-tert-butyl Disulfide and its Homologs by Using Molybdenum Trichloride Monoxide-DMSO Complex as Catalyst

二硫醚在生物和化学研究中有着重要的用途。由于多种硫醇价廉易得,因此,二硫醚的制备多采用硫醇氧化法制备。今采用以DMSO络合三氯一氧化钼(MoOCl3(DMSO)2)为催化剂,硫醇为原料,DMSO为氧化剂进行催化氧化,高收率制备系列二烃基二硫醚化合物的合成方法,研究表明,该催化剂具有催化活性高、用量小、反应选择性好等优点。其中重点研究了二叔丁基二硫醚的合成工艺,考察了原料配比、反应温度、反应时间和催化剂用量对反应收率的影响,得出最佳合成工艺条件,即n(DMSO):n(叔丁硫醇)=5.5:1,反应时间20 h,反应温度65℃,催化剂用量为叔丁硫醇摩尔数的4.7%,此时产物收率大于96%;此外,还对这一反应动力学进行了研究,得出动力学方程1.3 1.2r=0.01914C A CB。总之,以DMSO络合三氯一氧化钼(MoOCl3(DMSO)2)为催化剂氧化硫醇合成二硫醚是一个操作简单、选择性好、条件温和的二硫醚的制备方法。

Disulfides play important roles in biological and chemical studies.Oxidation of thiols is the method most in use for disulfide synthesis,it is because lots of thiols are commercially available and inexpensive.In this study,the thiols were oxidized to series of dialkyl disulfides by using the molybdenum trichloride monoxide-DMSO complex（MoOCl3（DMSO）2） as catalyst and dimethyl sulfoxide as oxidant,and the results show that the mentioned catalyst has the advantages of high catalytic activity,small using amount needed and excellent selectivity.Focusing on the synthesis of di-tert-butyl disulfide,the influences of material ratio,reaction temperature,reaction time and catalyst amount on the yield were investigated.The optimum reaction conditions found are as follows： n（dimethyl sulfoxide） ： n（tert-butyl thiol） = 5.5：1,reaction temperature 65℃,reaction time 20 h and catalyst amount 4.7% of tert-butyl thiol molar number,and under above conditions,the yield is greater than 96%.In addition,the reaction kinetics was studied and the kinetic equation was established.In conclusion,the study shows that the proposed method of oxidizing thiols with MoOCl3（DMSO）2 as catalyst is a simple,efficient and mild method for the conversion of thiols to disulfides.