The Research Of The Synthesis Of Sulfides, Disulfides And Sulfoxides

Sulfide is a kind of important basic organic compounds, which is used as a kind of intermediates for organic synthesis and drug synthesis, and it is widely used in the synthesis of medicine, polymer materials, pesticides, synthetic flavors. under the condition of no catalyst, We use two methods to study the synthesis of diaryldisulfides by aryl diazonium salts and sodium sulfide without any catalyst:①The reaction were performed with R-PhN2BF4 (0.2 mmol) and Na2S-9H2O (48.5 mg,0.2 mmol) in CH3CN (1.0 mL) at 0～25℃ (the temperature naturally back to room temperature during the reaction) for 24 h, and obtained 16 kinds of diarylsulfides with the highest yield of 67%; ②The reaction were performed with R-PhN2BF4 (0.2 mmol) and Na2S-9H2O (48.5 mg, 0.2 mmol) in water (1.0 mL) at 100℃ in the microwave with the power of 300 W for 5-20 mins, and obtained 10 kinds of diarylsulfides with the products yields of 36-92%.Disulfide is also a kind of important organic reagents and intermediates, which are widely used in organic synthesis, polymer, etc. Such as in the field of polymer, disulfides can be used as a curing agent, used in the production of synthetic rubber, natural rubber, and other high projectile, can make them have good tensile strength. In the study of synthesis of sulfide, an accidental opportunity, we found that PhN2BF4 and Na2S·9H2O in methanol generated in the main product of diphenyl disulfide, so we began to optimize and select the best reaction conditions to synthesis of diaryl disulfides, We also use two methods to synthesis diaryl disulfides by aryl diazonium salts and sodium sulfide.①The reaction were performed with R-PhN2BF4 (0.2 mmol) and Na2S-9H2O (72.8 mg,0.3 mmol) in CH3OH (1.0 mL) at 0～25℃ (the temperature naturally back to room temperature during the reaction) for 24 h, and obtained 10 kinds of diarylsulfides with poor to meddle yields (5-54%); ②The reaction were performed with R-PhN2BF4 (0.2 mmol) and Na2S·9H2O (72.8 mg,0.3 mmol) in CH3OH (1.0 mL) catalysted by FeCl3 at 0～25℃ (the temperature naturally back to room temperature during the reaction) for 24 h, and obtained 11 kinds of diaryl sulfides with poor to meddle yields (10～73%).On the basis of the synthesis of asymmetric diaryl disulfides, we studied the the cross-coupling reaction of diphenyl disulfide and aryl diazonium salts. Under the optimized conditions, we got the best method to synthesis the unsymmetric diaryl disulfides:All reactions were performed with R-PhN2BF4 (44.4mg,0.2 mmol), (PhS)2 (39.2 mg,0.18 mmol) and K2CO3 (27.6 mg,0.2 mmol) at 25℃ in CH3CN (1.0 mL) for 24 h under N2 atmosphere, and we obtained 13 kinds of unsymmetrical diaryl disulfides with poor to middle yields (17-77%).Sulfoxides have broad applications in pharmaceutical agents and pesticide due to their biologically activities and they are important synthetic intermediates in C—C bond formation and various molecular rearrangements. It’s one of the most common method to synthesis sulfoxide is direct oxidation of sulfide. On the basis of the synthesis of sulfides, we began to study the oxidation of sulfide catalyzed by Cat.l with H2O2. Under the optimized conditions, we got the best reaction condition of oxidation of sulfide:reactions were performed with sulfide (0.2 mmol), Cat.1 (7.1 mg,0.2 mol%) and H2O2 in MeOH (1.0 mL) at 60℃ for 16h, and we got 29 kinds of sulfoxide with middle to best yields (41～>99%).