Substituted benzodiazepines of the general formula 2,2’-di(R)-5,6,6’,7’,8,13-hexahydro-5’H-spiro-benzo[2,3][1,4]diazepino[6,5-h]quinoline-7,8’-quinoline[R=H(L1),Me(L2),and Cl(L3)]were synthesized by the condensat...Substituted benzodiazepines of the general formula 2,2’-di(R)-5,6,6’,7’,8,13-hexahydro-5’H-spiro-benzo[2,3][1,4]diazepino[6,5-h]quinoline-7,8’-quinoline[R=H(L1),Me(L2),and Cl(L3)]were synthesized by the condensation reactions between 1,2-phenylenediamine and(2R)-5,6,7-trihydroquin-8-ones.Treatment of these compounds with two equivalents of C_(2)H_(5)MgBr or AlMe_(3)afforded the corresponding yellow magnesium complexes[R=H(C1)and Me(C_(2))],and the red aluminum complexes[R=H(C3),Me(C4)and Cl(C5)],respectively.The molecular structures of L1 and L3 and of complexes C1,C3 and C4 were determined by the single crystal X-ray diffraction study.L1 and L3 contain two 2R-substituted-5,6,7-trihydroquin-8-one groups fused with benzodiazepine through one-carbon or two-carbon atoms,respectively.The magnesium complex C1 displays a dinuclear bromomagnesium bridged by the ligand as the“pas de deux”arrangement,while aluminum complexes(C3 and C4)show bis(dimethylaluminum)benzodiazepines.In the presence of BnOH,the magnesium complexes showed efficient activities toward the ring-opening polymerization(ROP)ofε-caprolactone(ε-CL)with TOF up to 8100 h^(-1)at 60℃;while the aluminum complexes also initiated high conversion ofε-CL by ROP.展开更多
基金supported by the National Natural Science Foundation of China(No.51273202 and U1362204)supported by the Chinese Academy of Sciences Fellowship for Young International Scientists(Grant No.2015PM047).
文摘Substituted benzodiazepines of the general formula 2,2’-di(R)-5,6,6’,7’,8,13-hexahydro-5’H-spiro-benzo[2,3][1,4]diazepino[6,5-h]quinoline-7,8’-quinoline[R=H(L1),Me(L2),and Cl(L3)]were synthesized by the condensation reactions between 1,2-phenylenediamine and(2R)-5,6,7-trihydroquin-8-ones.Treatment of these compounds with two equivalents of C_(2)H_(5)MgBr or AlMe_(3)afforded the corresponding yellow magnesium complexes[R=H(C1)and Me(C_(2))],and the red aluminum complexes[R=H(C3),Me(C4)and Cl(C5)],respectively.The molecular structures of L1 and L3 and of complexes C1,C3 and C4 were determined by the single crystal X-ray diffraction study.L1 and L3 contain two 2R-substituted-5,6,7-trihydroquin-8-one groups fused with benzodiazepine through one-carbon or two-carbon atoms,respectively.The magnesium complex C1 displays a dinuclear bromomagnesium bridged by the ligand as the“pas de deux”arrangement,while aluminum complexes(C3 and C4)show bis(dimethylaluminum)benzodiazepines.In the presence of BnOH,the magnesium complexes showed efficient activities toward the ring-opening polymerization(ROP)ofε-caprolactone(ε-CL)with TOF up to 8100 h^(-1)at 60℃;while the aluminum complexes also initiated high conversion ofε-CL by ROP.