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
The oxidative carbonylation of phenol to diphenyl carbonate catalyzed by Pd Co, Pd Cu and Pd Mn catalyst systems has been studied with the addition of other components such as benzoquinone, Bu 2NBr and molecular sieve...The oxidative carbonylation of phenol to diphenyl carbonate catalyzed by Pd Co, Pd Cu and Pd Mn catalyst systems has been studied with the addition of other components such as benzoquinone, Bu 2NBr and molecular sieve. The results show that Bu 2NBr plays a very important role and Pd Mn catalyst has the highest activity among the three kinds of the catalysts studied. When the reaction is catalyzed by Pd Mn catalyst at n (PdCl 2)∶ n (Mn(OAc) 2)∶ n (Bu 4NBr)∶ n (benzoquinone)=1∶1∶ 10∶ 25, t =100 ℃, P =2 5 MPa( P CO / P O 2 =4∶1), reaction time 8 h, the yield of DPC is 7 23%. The yield of DPC is found to be increased with increase in total pressure of reactor and could be reached to 10 20% at total pressure of 3 5 MPa.展开更多
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
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The oxidative carbonylation of phenol to diphenyl carbonate catalyzed by Pd Co, Pd Cu and Pd Mn catalyst systems has been studied with the addition of other components such as benzoquinone, Bu 2NBr and molecular sieve. The results show that Bu 2NBr plays a very important role and Pd Mn catalyst has the highest activity among the three kinds of the catalysts studied. When the reaction is catalyzed by Pd Mn catalyst at n (PdCl 2)∶ n (Mn(OAc) 2)∶ n (Bu 4NBr)∶ n (benzoquinone)=1∶1∶ 10∶ 25, t =100 ℃, P =2 5 MPa( P CO / P O 2 =4∶1), reaction time 8 h, the yield of DPC is 7 23%. The yield of DPC is found to be increased with increase in total pressure of reactor and could be reached to 10 20% at total pressure of 3 5 MPa.
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.
