Study On The Carbon-sulfur And C(sp)-C(sp~3) Bond Formation Reactions Catalyzed By Mesoporous MCM-41 Supported Copper Complex

This thesis describes the application of the mesoporous material MCM-41 supported copper complex catalysts in the construction of carbon-sulfur and C(sp)-C(sp3)bonds.The main research work includes the following two parts:1.N-Methylimidazole was reacted with(3-chloropropyl)tri ethoxy silane at reflux in anhydrous toluene to provide a triethoxysilyl-functionalized imidazolium chloride[(EtO)3Si-MPIM·Cl].Then a mixture of(EtO)3Si-MPIM.Cl and mesoporous material MCM-41 was refluxed in anhydrous toluene for 24 h,followed by silylation with Me3SiCl at room temperature for 24 hours to give MCM-41-supported imidazolium chloride[MCM-41-MPIM·Cl].The latter was reacted with CuI in THF at room temperature in the presence of NaOtBu to afford an MCM-41-supported NHC-Cu(Ⅰ)complex[MCM-41-NHC-CuI].The structure of this new heterogeneous copper catalyst was characterized by various physico-chemical techniques.The catalytic behavior of[MCM-41-NHC-CuI]in the cyclization of 2-haloanilides with metal sulfides towards substituted benzothiazoles was investigated.The results indicated that MCM-41-NHC-CuI displays a similar catalytic activity to homogeneous CuI,and can be recycled up to eight cycles without significant loss of activity,providing a new,practical and green route to synthesize benzothiazole derivatives.2.(4-Chloromethylphenyl)trichlorosilane was reacted with mesoporous material MCM-41 in dry toluene,followed by treatment with EtOH to give chloromethylfunctionalized MCM-41(MCM-41-CH2Cl).The latter underment the condensation with the N-Boc-4-hydroxy-L-proline using NaH as base and subsequent deprotection to provide the L-proline ligand-functionalized mesoporous MCM-41[MCM-41L-Proline].Finally,CuI is coordinated with MCM-41-L-Proline in acetone to afford MCM-41-L-Proline-CuI.The catalytic properties of MCM-41-L-Proline-CuI in the C(sp)-C(sp3)bond formation via copper-catalyzed cross-coupling reaction between N-tosylhydrazones and trimethylsilylacetylene was studied.The results showed that this supported copper catalyst has good catalytic performance in the cross-coupling reaction,and can be recycled for at least 8 times with almost consistent catalytic activity.Therefore,our work provides an efficient and practical new method for the synthesis of alkyl(trimethylsilyl)acetylenes.