Synthesis And Characterization Of Unsymmetrical Aryl Sulfides

Aryl sulfide is a common functionality found in numerous pharmaceuticallyactive compounds,biological and founctional materials.Based on the discussionof methods for preparation of aromatic thioethers, this paper synthesized some unsymmetrical aryl thioethers such as:(4-nitrophenyl)(phenyl)sulfane,4-(phenylthio)benzenamine,4-(phenylthio)phenol.(4-Nitrophenyl)(phenyl)sulfane was synthesized by nucleophilic substitutionreaction, ratio of raw materials,catalyst,temperature were particularly studied, theyield (purity) was94.2%(99.8%);4-(Phenylthio)benzenamine was reduced by hydrazine hydrate, temperature,amount of hydrazine hydrate and catalyst were studied, the optimal yield was92%(99.5%)；For diazotization and hydrolysis reactions,the conditions of hydrolysis including temperature, concentration of CuSO4and H2SO4influencing the reaction were particularly studied. The optimized hydrolysis conditions of diazonium salt were as follows:diazonium solution prepared from20.1g4-(phenylthio)benzenamine,8gCuSO4,70mLH2O and30gH2SO4,100gxylene,hydrolysis temperature90℃.The yield of4-(phenylthio)phenol was74%(99.5%).The second route was achieved by chlorination and electrophilic substitutionused phenol and thiophenol as raw materials. Ratio of raw materials, temperature and dropping speed were particularly studied. The optimized yield was80%(99%).The purity of all products and Intermediates were determined by GC or HPLC, structures confirmed by IR,1H NMR and GC-MS.