Novel resin supported gold catalysts were developed for the synthesis of carbamates by oxidative carbonylation of aniline and its derivatives. At 175 ℃ and 5.0 MPa, the oxidative carbonylation of aniline to the corre...Novel resin supported gold catalysts were developed for the synthesis of carbamates by oxidative carbonylation of aniline and its derivatives. At 175 ℃ and 5.0 MPa, the oxidative carbonylation of aniline to the corresponding carbamates over these catalysts could be proceeded with a high conversion(96%), selectivity(99%) and 532 for TOF was achieved. The resin supported gold castalyst would be reusable and the catalytic performance was much better than that of the resin supported Pd catalyst.展开更多
At 200 ℃ and 50 mPa, the oxidative carbonylation of amines catalyzed by organic gold complexes HAuCl 4, Au(PPh 3)Cl, Au(PPh 3) 2Cl, Au(PPh 3)NO 3 and [Au(PPh 3)] 2S afforded R(NHCO 2CH 3) n with a high conversion and...At 200 ℃ and 50 mPa, the oxidative carbonylation of amines catalyzed by organic gold complexes HAuCl 4, Au(PPh 3)Cl, Au(PPh 3) 2Cl, Au(PPh 3)NO 3 and [Au(PPh 3)] 2S afforded R(NHCO 2CH 3) n with a high conversion and selectivity. The best results were obtained when using the catalyst Au(PPh 3)Cl in the presence of PPh 3. The catalytic efficiency of catalytic Au(PPh 3)Cl was compared to Pd(PPh 3) 2Cl 2, e.g. the conversion was 97.2% and selectivity was 89% when using catalyst Au(PPh 3)Cl in the presence of PPh 3, while the conversion was 98.8% and selectivity was 86% when using catalyst Pd(PPh 3) 2Cl 2 in the presence of PPh 3. The experimental results suggested that Au complexes might be promising catalysts instead of Pd catalysts for the oxidative carbonylation of amines to carbamates.展开更多
Novel combined PdCl 2(RuCl 3) with ZrO 2 SO 3 catalysts were developed for the synthesis of carbamates by oxidative carbonylation of aliphatic and aromatic amines. At 170 ℃ and 4.0 MPa, oxidative carbonylation of aro...Novel combined PdCl 2(RuCl 3) with ZrO 2 SO 3 catalysts were developed for the synthesis of carbamates by oxidative carbonylation of aliphatic and aromatic amines. At 170 ℃ and 4.0 MPa, oxidative carbonylation of aromatic amines to the corresponding carbamates over this catalyst system could be proceeded with a high conversion and selectivity. Especially when β naphthylamine was used as the substrate, 100% conversion and 95% selectivity were obtained in only 15 min. The catalytic performance of PdCl 2/ZrO 2 SO 3 was better than that of RuCl 3/ZrO 2 SO 3 for such oxidative carbonylation reaction. Possible role of ZrO 2 SO 3 as co catalyst was also conjectured.展开更多
A bromine-containing copper-organic coordination compound was prepared by the reaction of tetrrpropylammonium bromide with copper bromide in ethyl acetate solution.The compound obtained was characterized with FTIR,XRD...A bromine-containing copper-organic coordination compound was prepared by the reaction of tetrrpropylammonium bromide with copper bromide in ethyl acetate solution.The compound obtained was characterized with FTIR,XRD,ICP-AES and EA.Meanwhile,its catalytic performance for the oxidative carbonylation of methanol was investigated.The results showed that the introduction of ligand could change the density of copper electron cloud,which improved the redox property for the oxidative carbonylation of methanol to prepare dimethyl carbonate.In the presence of strong base and weak acid salts,the per pass conversion of methanol could reach 57% under the reaction conditions of temperature 383 K,pressure 3.5 MPa,and the mass concentration of catalyst in methanol 0.20 g·ml-1.展开更多
文摘Novel resin supported gold catalysts were developed for the synthesis of carbamates by oxidative carbonylation of aniline and its derivatives. At 175 ℃ and 5.0 MPa, the oxidative carbonylation of aniline to the corresponding carbamates over these catalysts could be proceeded with a high conversion(96%), selectivity(99%) and 532 for TOF was achieved. The resin supported gold castalyst would be reusable and the catalytic performance was much better than that of the resin supported Pd catalyst.
文摘At 200 ℃ and 50 mPa, the oxidative carbonylation of amines catalyzed by organic gold complexes HAuCl 4, Au(PPh 3)Cl, Au(PPh 3) 2Cl, Au(PPh 3)NO 3 and [Au(PPh 3)] 2S afforded R(NHCO 2CH 3) n with a high conversion and selectivity. The best results were obtained when using the catalyst Au(PPh 3)Cl in the presence of PPh 3. The catalytic efficiency of catalytic Au(PPh 3)Cl was compared to Pd(PPh 3) 2Cl 2, e.g. the conversion was 97.2% and selectivity was 89% when using catalyst Au(PPh 3)Cl in the presence of PPh 3, while the conversion was 98.8% and selectivity was 86% when using catalyst Pd(PPh 3) 2Cl 2 in the presence of PPh 3. The experimental results suggested that Au complexes might be promising catalysts instead of Pd catalysts for the oxidative carbonylation of amines to carbamates.
文摘Novel combined PdCl 2(RuCl 3) with ZrO 2 SO 3 catalysts were developed for the synthesis of carbamates by oxidative carbonylation of aliphatic and aromatic amines. At 170 ℃ and 4.0 MPa, oxidative carbonylation of aromatic amines to the corresponding carbamates over this catalyst system could be proceeded with a high conversion and selectivity. Especially when β naphthylamine was used as the substrate, 100% conversion and 95% selectivity were obtained in only 15 min. The catalytic performance of PdCl 2/ZrO 2 SO 3 was better than that of RuCl 3/ZrO 2 SO 3 for such oxidative carbonylation reaction. Possible role of ZrO 2 SO 3 as co catalyst was also conjectured.
文摘A bromine-containing copper-organic coordination compound was prepared by the reaction of tetrrpropylammonium bromide with copper bromide in ethyl acetate solution.The compound obtained was characterized with FTIR,XRD,ICP-AES and EA.Meanwhile,its catalytic performance for the oxidative carbonylation of methanol was investigated.The results showed that the introduction of ligand could change the density of copper electron cloud,which improved the redox property for the oxidative carbonylation of methanol to prepare dimethyl carbonate.In the presence of strong base and weak acid salts,the per pass conversion of methanol could reach 57% under the reaction conditions of temperature 383 K,pressure 3.5 MPa,and the mass concentration of catalyst in methanol 0.20 g·ml-1.
