Photopromoted carbonylation of alkyl bromides with carbon monoxide or carbon dioxide catalyzed by copper salts can be carried out under ambient conditions （atmospheric pressure and room temperature） and the correspo...Photopromoted carbonylation of alkyl bromides with carbon monoxide or carbon dioxide catalyzed by copper salts can be carried out under ambient conditions （atmospheric pressure and room temperature） and the corresponding ester was produced. The yield and the selectivity of the ester can be improved greatly by addition of sodium phosphate.展开更多
The photopromoted carbonylation of chloroalkanes with carbon monoxide catalyzed by cobalt compounds[Co（OAc）2,CoCl2] in the presence of KI was carried out under ambient conditions.The results revealed that the cataly...The photopromoted carbonylation of chloroalkanes with carbon monoxide catalyzed by cobalt compounds[Co（OAc）2,CoCl2] in the presence of KI was carried out under ambient conditions.The results revealed that the catalytic activity of Co（OAc）2 was higher than that of CoCl2.A basic additive NaOAc was beneficial to the reaction.Interestingly,with NaOAc as an additive, Co（OAc）2 and CoCl2 exhibited similar catalytic activity.Preliminary work showed that the role of iodide ion was initially to form active iodoalkanes via substituting chloride ion in chloroalkanes in situ,and then,the carbonylation of iodoalkanes proceeded under irradiation.展开更多
Photopromoted carbonylation of alkyl halides with carbon monoxide can be carried out under ambient conditions with non-precious transition metal complexes (such as cobalt complexes) catalysts. Our preliminary work sh...Photopromoted carbonylation of alkyl halides with carbon monoxide can be carried out under ambient conditions with non-precious transition metal complexes (such as cobalt complexes) catalysts. Our preliminary work showed that alkyl halides can be transformed into alkene and alkane directly under irradiation, but the esters can not be transformed. It is assumed that the carbonylation of alkyl halides may be proceeded in two ways.展开更多
The photopromoted carbonylation of bromobenzene with carbon monoxide catalyzed by inexpensive commercially available cobalt salts [Co（OAc）2, COCl2] was carried out under ambient conditions. The results revealed that...The photopromoted carbonylation of bromobenzene with carbon monoxide catalyzed by inexpensive commercially available cobalt salts [Co（OAc）2, COCl2] was carried out under ambient conditions. The results revealed that methyl benzoate was produced in the presence of basic additives （CH3ONa, NaOAc or （n-C4H9）3N）. The catalytic activity of Co（OAc）2 was higher than that of COCl2. Furthermore, the activity of the carbonylation was greatly improved by addition of acetophenone, e.g. both the yield and selectivity of the ester were increased from 47% to 91% with Co（OAc）2 as catalyst and CH3ONa as additive, while the yield of byproduct benzene from hydrodehalogenation of bromobenzene decreased from 32% to 8%.展开更多
Photopromoted carbonylation of 1-bromo-6-chlorohexane with CO catalyzed by CuBr2 and CdI2 has been carried out under ambient conditions. The results indicate that the carbonylation proceeds with the major product of c...Photopromoted carbonylation of 1-bromo-6-chlorohexane with CO catalyzed by CuBr2 and CdI2 has been carried out under ambient conditions. The results indicate that the carbonylation proceeds with the major product of chloroester ClCH2（CH2）5COOCH3 under catalysis of CuBr2. Furthermore, the activity of the carbonylation can be improved by addition of basic additives （NaOAc, Na3PO4 or （n-C4H9）3N）. Among these additives, （n-C4H9）3N is the most efficient in terms of the yield of ClCH2（CH2）5COOCH3. However, the methoxycarbonyl substituting chlorine product of BrCH2（CH2）5COOCH3 is not obtained in the presence of CdI2. This is quite different from the carbonylation of monochloroalkane.展开更多
基金the National Natural Science Foundation of China(No.20372012)for the generous financial support.
文摘Photopromoted carbonylation of alkyl bromides with carbon monoxide or carbon dioxide catalyzed by copper salts can be carried out under ambient conditions （atmospheric pressure and room temperature） and the corresponding ester was produced. The yield and the selectivity of the ester can be improved greatly by addition of sodium phosphate.
文摘The photopromoted carbonylation of chloroalkanes with carbon monoxide catalyzed by cobalt compounds[Co（OAc）2,CoCl2] in the presence of KI was carried out under ambient conditions.The results revealed that the catalytic activity of Co（OAc）2 was higher than that of CoCl2.A basic additive NaOAc was beneficial to the reaction.Interestingly,with NaOAc as an additive, Co（OAc）2 and CoCl2 exhibited similar catalytic activity.Preliminary work showed that the role of iodide ion was initially to form active iodoalkanes via substituting chloride ion in chloroalkanes in situ,and then,the carbonylation of iodoalkanes proceeded under irradiation.
基金We are indebted to the National Natural Science Foundations of China(No.20172010,20242004),for the generous financial support
文摘Photopromoted carbonylation of alkyl halides with carbon monoxide can be carried out under ambient conditions with non-precious transition metal complexes (such as cobalt complexes) catalysts. Our preliminary work showed that alkyl halides can be transformed into alkene and alkane directly under irradiation, but the esters can not be transformed. It is assumed that the carbonylation of alkyl halides may be proceeded in two ways.
基金the Science and Technology Research Project for University of Liaoning Province(No.20060038)for the generous financial support.
文摘The photopromoted carbonylation of bromobenzene with carbon monoxide catalyzed by inexpensive commercially available cobalt salts [Co（OAc）2, COCl2] was carried out under ambient conditions. The results revealed that methyl benzoate was produced in the presence of basic additives （CH3ONa, NaOAc or （n-C4H9）3N）. The catalytic activity of Co（OAc）2 was higher than that of COCl2. Furthermore, the activity of the carbonylation was greatly improved by addition of acetophenone, e.g. both the yield and selectivity of the ester were increased from 47% to 91% with Co（OAc）2 as catalyst and CH3ONa as additive, while the yield of byproduct benzene from hydrodehalogenation of bromobenzene decreased from 32% to 8%.
基金We appreciate the National Natural Science Foundations of China （No. 20372012） the Natural Science Foundations of Liaoning （No. 20032099） for the generous financial support.
文摘Photopromoted carbonylation of 1-bromo-6-chlorohexane with CO catalyzed by CuBr2 and CdI2 has been carried out under ambient conditions. The results indicate that the carbonylation proceeds with the major product of chloroester ClCH2（CH2）5COOCH3 under catalysis of CuBr2. Furthermore, the activity of the carbonylation can be improved by addition of basic additives （NaOAc, Na3PO4 or （n-C4H9）3N）. Among these additives, （n-C4H9）3N is the most efficient in terms of the yield of ClCH2（CH2）5COOCH3. However, the methoxycarbonyl substituting chlorine product of BrCH2（CH2）5COOCH3 is not obtained in the presence of CdI2. This is quite different from the carbonylation of monochloroalkane.
