Several silica-supported poly-γ-aminopropylsiloxane-monometal and bimetal complexes (Si-NH_2-M,M = Cu or Co ; Si-NH_2-Cu-M', M' =Co, Sn, Mn, Ni or Fe) have been prepared. Their catalytic properties for oxidat...Several silica-supported poly-γ-aminopropylsiloxane-monometal and bimetal complexes (Si-NH_2-M,M = Cu or Co ; Si-NH_2-Cu-M', M' =Co, Sn, Mn, Ni or Fe) have been prepared. Their catalytic properties for oxidative ethoxycarbonylation of aniline to ethyl phenylcarbamate have been investigated.The catalytic reaction was carried out under relatively mild conditions. The catalyst Si-NH_2-Cu-CO had high activity and selectivity, and the turn-over number (molar of aniline converted/molar of metal in Si-NH_2-Cu-CO added) could amount to 450 under the conditions: 150℃ , 4 MPa (CO/O_2 =3) and 40 hours.The results of XPS and IR indicated that the coordination bonds were formed between nitrogen and metals in Si-NH2-Cu, Si-NH_2-Co and Si-NH_2-Cu-Co, and the coordination pattern was not single. In the oxidative ethoxycarbonylation of aniline to ethyl phenylcarbamate, the catalytic property of Si-NH_2-Cu-CO bimetallic complex was better than Si-NH_2-Cu or Si-NH_2-Co monometatlic complex. This indicated that there as synergistic action between different metals in the bimetallic complex.展开更多
2,3-Dihydro-2-phenyl-4-(4-methoxyphenyl)-1, 5-benzothiazepine reacts with ethoxycarbonyl carbene to give an unexpected compound 2,3-disubstituted-4H-1,4-benzothiazine Ⅲ. It was found to be a new rearrangement reactio...2,3-Dihydro-2-phenyl-4-(4-methoxyphenyl)-1, 5-benzothiazepine reacts with ethoxycarbonyl carbene to give an unexpected compound 2,3-disubstituted-4H-1,4-benzothiazine Ⅲ. It was found to be a new rearrangement reaction and the structure of the product was confirmed by IR, NMR, MS.展开更多
A novel [2＋4＋2]-macrocyclic compound 3（C52H69N16O12, Mr = 1109.53） con- taining bis（ethoxycarbonyl）glycoluril groups was synthesized via the Mannich three-component reaction in one pot and its structure was char...A novel [2＋4＋2]-macrocyclic compound 3（C52H69N16O12, Mr = 1109.53） con- taining bis（ethoxycarbonyl）glycoluril groups was synthesized via the Mannich three-component reaction in one pot and its structure was characterized by single-crystal X-ray diffraction. It crystallizes in triclinic, space group P1 with a = 10.077（3）, b = 10.642（3）, c = 15.324（5） , α = 96.704（5）, β = 102.304（5）, γ = 104.546（5）°, Z = 2, V = 1528.7（8）3, Dc = 1.283 g/cm3, μ = 0.097 mm-1, F（000） = 628, R = 0.0818 and wR（I 〉 2σ（I）） = 0.2346 for 3034 observed reflections.展开更多
文摘Several silica-supported poly-γ-aminopropylsiloxane-monometal and bimetal complexes (Si-NH_2-M,M = Cu or Co ; Si-NH_2-Cu-M', M' =Co, Sn, Mn, Ni or Fe) have been prepared. Their catalytic properties for oxidative ethoxycarbonylation of aniline to ethyl phenylcarbamate have been investigated.The catalytic reaction was carried out under relatively mild conditions. The catalyst Si-NH_2-Cu-CO had high activity and selectivity, and the turn-over number (molar of aniline converted/molar of metal in Si-NH_2-Cu-CO added) could amount to 450 under the conditions: 150℃ , 4 MPa (CO/O_2 =3) and 40 hours.The results of XPS and IR indicated that the coordination bonds were formed between nitrogen and metals in Si-NH2-Cu, Si-NH_2-Co and Si-NH_2-Cu-Co, and the coordination pattern was not single. In the oxidative ethoxycarbonylation of aniline to ethyl phenylcarbamate, the catalytic property of Si-NH_2-Cu-CO bimetallic complex was better than Si-NH_2-Cu or Si-NH_2-Co monometatlic complex. This indicated that there as synergistic action between different metals in the bimetallic complex.
文摘2,3-Dihydro-2-phenyl-4-(4-methoxyphenyl)-1, 5-benzothiazepine reacts with ethoxycarbonyl carbene to give an unexpected compound 2,3-disubstituted-4H-1,4-benzothiazine Ⅲ. It was found to be a new rearrangement reaction and the structure of the product was confirmed by IR, NMR, MS.
基金supported by Central China Normal University and the National Science Foundation of China(No.21272085)
文摘A novel [2＋4＋2]-macrocyclic compound 3（C52H69N16O12, Mr = 1109.53） con- taining bis（ethoxycarbonyl）glycoluril groups was synthesized via the Mannich three-component reaction in one pot and its structure was characterized by single-crystal X-ray diffraction. It crystallizes in triclinic, space group P1 with a = 10.077（3）, b = 10.642（3）, c = 15.324（5） , α = 96.704（5）, β = 102.304（5）, γ = 104.546（5）°, Z = 2, V = 1528.7（8）3, Dc = 1.283 g/cm3, μ = 0.097 mm-1, F（000） = 628, R = 0.0818 and wR（I 〉 2σ（I）） = 0.2346 for 3034 observed reflections.
