Photopromoted carbonylation of 1-bromo-6-chlorohexane under ambient conditions

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.     

光促进下溴代烃在CH3OH/DMF体系中的羰基化反应

羰基化反应是有机合成中最重要的反应之一,其合成产品分别为醛、酮、酯、羧酸和酰胺等一系列化合物,可用作溶剂、增塑剂、润滑剂以及天然产物的替代品。卤代烷烃种类繁多,价格低廉,以其为底物进行羰基化反应,可以得到多种多样的羰基化合物。但常规羰基化反应往往需要高温(150-2     

Photopromoted Methoxycarbonylation of Olefins Under Ambient Conditions in DMF

Photopromoted methoxycarbonylation of olefins with carbon monoxide can be carded out under ambient conditions with non-precious transition metal complexes (such as cobalt complexes) catalysts in DME The isotope experiments show that DMF is decomposed under irradiation and is conveniently used as a carbon monoxide source for the reaction.     

Photopromoted Carbonylation of Alkyl Bromides Catalyzed by Copper Salts under Ambient Conditions

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.     

Cobalt-catalyzed photopromoted carbonylation of chloroalkanes in the presence of KI

<正>The photopromoted carbonylation of chloroalkanes with carbon monoxide catalyzed by cobalt compounds[Co(OAc)_2,CoCl_2] 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 CoCl_2.A basic additive NaOAc was beneficial to the reaction.Interestingly,with NaOAc as an additive, Co(OAc)_2 and CoCl_2 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.     

Photopromoted carbonylation of bromobenzene under ambient conditions

The photopromoted carbonylation of bromobenzene with carbon monoxide catalyzed by inexpensive commercially available cobalt salts[Co(OAc)_2,CoCl_2]was carried out under ambient conditions.The results revealed that methyl benzoate was produced in the presence of basic additives(CH_3ONa,NaOAc or(n-C_4H_9)_3N).The catalytic activity of Co(OAc)_2was higher than that of CoCl_2.Furthermore,the activity of the carbonylation was greatly improved by addition of acetophenone,e.g.both the yield and selectivity of t...     

Photopromoted Carbonylation of Alkyl Halides Under Ambient Conditions

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 sowed 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.     

光促进温和条件下溴代烷烃与甲酸甲酯的羰基化反应

研究了光促进温和条件下,以甲酸甲酯为C1源,非贵金属钴盐、铜盐催化的溴代烷烃的羰基化反应.实验表明,在光促进下,钴盐、铜盐均可催化溴代烷烃与甲酸甲酯的羰基化反应,得到相应的羧酸甲酯.钴盐催化下,碱性添加物NaOAc对反应有很好的促进作用,直链溴代烷烃在反应中除了得到相应的正构酯外,还有少量异构酯生成;铜盐催化下,直链溴代烷烃在反应中主要生成相应的正构酯.机理研究表明,在光照下甲酸甲酯先分解为CO和CH3OH,再与溴代烷烃进行羰基化反应.     

Photopromoted methoxycarbonylation of olefin with methyl formate by Co（OAc）2

The photopromoted methoxycarbonylation of olefin with methyl formate catalyzed by Co(OAc)2 at ambient conditions has been carried out.The results indicated that the reaction activity increased with the increasing temperature.Methyl formate decomposed into CO and CH_3OH firstly under irradiation,and then the methoxycarbonylation of olefin proceeded under catalysis of Co(OAc)_2. The mechanism of methyl formate participating in the methoxycarbonylation is verified by the IR analysis and the labeling experiments of CD_3OD and CH_3~(18)OH.