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
A highly efficient Pd\|BMImCl/TiO\-\%y\%\|SiO\-\%x\% catalyst system synthesized through sol\|gel method from palladium complex, ionic liquid, titanate and silicate esters was found for the oxidative carbonylation of ...A highly efficient Pd\|BMImCl/TiO\-\%y\%\|SiO\-\%x\% catalyst system synthesized through sol\|gel method from palladium complex, ionic liquid, titanate and silicate esters was found for the oxidative carbonylation of amines. The catalyst efficiency was much higher than that reported in previous papers and the TOF number reached to 10 372 when catalyst 0.05%Pd\|4.6%BMImCl/TiO\-\%y\%\|SiO\-\%x\% was used. The usability of ionic liquid was the key point for preparation of this catalyst system because of its high dissolvability to palladium complex and affording appropriate micro\|environment for the reaction. The synergism among palladium complex, ionic liquid, titanate and silicate was the main reason for the high catalytic activity of the catalyst system. BET, AES and XRD were used to characterized the catalysts in detail.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
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A highly efficient Pd\|BMImCl/TiO\-\%y\%\|SiO\-\%x\% catalyst system synthesized through sol\|gel method from palladium complex, ionic liquid, titanate and silicate esters was found for the oxidative carbonylation of amines. The catalyst efficiency was much higher than that reported in previous papers and the TOF number reached to 10 372 when catalyst 0.05%Pd\|4.6%BMImCl/TiO\-\%y\%\|SiO\-\%x\% was used. The usability of ionic liquid was the key point for preparation of this catalyst system because of its high dissolvability to palladium complex and affording appropriate micro\|environment for the reaction. The synergism among palladium complex, ionic liquid, titanate and silicate was the main reason for the high catalytic activity of the catalyst system. BET, AES and XRD were used to characterized the catalysts in detail.
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.
