Construction Of S-X(P,S)Bond Based On Thiophenols(Thiols)

As an important compound,organic sulfur compounds have found wide industrial applications both in organic chemistry,pesticide chemistry and biochemistry.Consequently,it is of great significance to develop a simple and efficient methods to synthesis organic sulfides.Thiols usually used as the substrates due to its relatively inexpensive and readily available.Thus,the efficient methods have been developed to construct S-X?S,P?bond from thiols.A convenient one-pot prouduce synthetic method of construction of S-P bond through the coupling of thiols with phosphites promoted by trichloroisocyanuric acid?TCCA?.p-Toluenethiol and triethyl phosphite was chosen as a model substrate to identify and optimize the reaction conditions.The solvent and the amount of TCCA and so on were screened.On the basis of these experimental,we concluded that the optimal reaction conditions for the coupling of p-toluenethiol with triethyl phosphite was a one-pot two-step procedure with 1 mmol of p-toluenethiol,0.35 equiv.of TCCA and 1.2 equiv.of triethyl phosphite in 2 m L Me CN at ambient temperature,after reacted for 20 min,94%isolated yield of O,O-diethyl-S-p-tolyl phosphorothioate could be obtained.A wide substrate scope was exhibited,both aryl and alkyl thiols could react with phosphites to give the corresponding products successfully.On the other hand,phosphonite and phosphine were also tolerated in this reaction.The I₂/DMSO catalytic system was developed for the coupling of thiols and benzenesulfonyl hydrazine.p-Toluenethiol and benzenesulfonyl hydrazine was chosen as a model substrate to identify and optimize the reaction conditions.The solvent,temperature,the amount of catalyst were screened.The optimized conditions were 10 mol%I₂,3 equiv.DMSO,1,2-dichloroethane as the solvent,reaction for 2 h at 80 ^oC.A variety of aryl alkyl thiols could be converted with good yields to products.In summary,our group has developed two highly efficient systems for the construction of S-X?P,S?bond with wide range of substrates.