The ab initio method has been used to study the 1-3 H transfer reaction on formamidine substituted by halogen. The calculation results show that the substituted halogen has two effects on the 1-3 H transfer reaction...The ab initio method has been used to study the 1-3 H transfer reaction on formamidine substituted by halogen. The calculation results show that the substituted halogen has two effects on the 1-3 H transfer reaction: decreasing the activation energy and stabilizing the C=N double bond owing to the conjugative effect of p-π-p of products and transition states.展开更多
For the isomerization reaction of monofluoro-disilene,the geometrical structures of reac- tant,product and transition state have been optimized and energy constant,vibrational frequency calculated.By means of the stat...For the isomerization reaction of monofluoro-disilene,the geometrical structures of reac- tant,product and transition state have been optimized and energy constant,vibrational frequency calculated.By means of the statistical thermodynamics and Eyring's transition state theory,the equilibrium constant,rate constant and heat of isomerization have also been computed.Hence, this reaction has been analysed completely.展开更多
The structures of singlet stannylenoid H2SnLiF have been examined by ab initio MO theory. Four equilibrium states and three transition states of isomerization reaction are located. The calculation shows that the p-com...The structures of singlet stannylenoid H2SnLiF have been examined by ab initio MO theory. Four equilibrium states and three transition states of isomerization reaction are located. The calculation shows that the p-complex 1 is the most stable and experimentally detectable. The other three species, three-membered ring 2, o-complex 3 and tetrahedron 4, are also local minima on the potential energy surface, but are higher in energy.展开更多
An efficient method for the synthesis of benzo[b]benzofurano[2,3-e][1,6]naphthyridine-8-one derivatives has been developed via Pictet-Spengler reaction of 4-（3-aminobenzofuran-2-yl）quinoline-2-ones,which could be ob...An efficient method for the synthesis of benzo[b]benzofurano[2,3-e][1,6]naphthyridine-8-one derivatives has been developed via Pictet-Spengler reaction of 4-（3-aminobenzofuran-2-yl）quinoline-2-ones,which could be obtained from alkylation of 4-bromomethylquinoline-2-ones with salicylonitrile and subsequent Thorpe-Ziegier isomerization,with aromatic aldehydes under p-TsOH as catalyst in good yields.展开更多
An efficient method for the preparation of thieno[3＇,2＇：2,3]pyrido[4,5-d]thiazolo[3,2-a] pyrimidin-5-ones 5 is described. The key intermediate, 7-（3-amino-4-cyano-5-phenyl aminothieno-2-yl）-5H-thiazolo-[80_TD$IF]...An efficient method for the preparation of thieno[3＇,2＇：2,3]pyrido[4,5-d]thiazolo[3,2-a] pyrimidin-5-ones 5 is described. The key intermediate, 7-（3-amino-4-cyano-5-phenyl aminothieno-2-yl）-5H-thiazolo-[80_TD$IF]3,2-a]pyrimidin-5-one（3）, was synthesized from 7-chloromethyl-5H-thiazolo[3,2-a]pyrimidin-5-one（1）with potassium-（2,2-dicyano-1-phenylaminoethen-1-yl）thiolate（2） by Thorpe–Ziegler isomerization.Subsequent reaction of the intermediate amine with aromatic aldehydes via Pictet–Spengler reaction provided thieno-pyridine fused thiazolo[3,2-a]pyrimidines under p-Ts OH as catalyst in good yields.展开更多
基金Supported by the Yunnan Provincial Science and Technology Department (2003A0003M)
文摘The ab initio method has been used to study the 1-3 H transfer reaction on formamidine substituted by halogen. The calculation results show that the substituted halogen has two effects on the 1-3 H transfer reaction: decreasing the activation energy and stabilizing the C=N double bond owing to the conjugative effect of p-π-p of products and transition states.
基金This research was supported by the National Natural Science Foundation of China.
文摘For the isomerization reaction of monofluoro-disilene,the geometrical structures of reac- tant,product and transition state have been optimized and energy constant,vibrational frequency calculated.By means of the statistical thermodynamics and Eyring's transition state theory,the equilibrium constant,rate constant and heat of isomerization have also been computed.Hence, this reaction has been analysed completely.
文摘The structures of singlet stannylenoid H2SnLiF have been examined by ab initio MO theory. Four equilibrium states and three transition states of isomerization reaction are located. The calculation shows that the p-complex 1 is the most stable and experimentally detectable. The other three species, three-membered ring 2, o-complex 3 and tetrahedron 4, are also local minima on the potential energy surface, but are higher in energy.
基金financial support from the Science and Technology Department of Liaoning Province(No.2011220022)
文摘An efficient method for the synthesis of benzo[b]benzofurano[2,3-e][1,6]naphthyridine-8-one derivatives has been developed via Pictet-Spengler reaction of 4-（3-aminobenzofuran-2-yl）quinoline-2-ones,which could be obtained from alkylation of 4-bromomethylquinoline-2-ones with salicylonitrile and subsequent Thorpe-Ziegier isomerization,with aromatic aldehydes under p-TsOH as catalyst in good yields.
基金partially supported by innovation team project of Liaoning Province Education Department(No.2015001)
文摘An efficient method for the preparation of thieno[3＇,2＇：2,3]pyrido[4,5-d]thiazolo[3,2-a] pyrimidin-5-ones 5 is described. The key intermediate, 7-（3-amino-4-cyano-5-phenyl aminothieno-2-yl）-5H-thiazolo-[80_TD$IF]3,2-a]pyrimidin-5-one（3）, was synthesized from 7-chloromethyl-5H-thiazolo[3,2-a]pyrimidin-5-one（1）with potassium-（2,2-dicyano-1-phenylaminoethen-1-yl）thiolate（2） by Thorpe–Ziegler isomerization.Subsequent reaction of the intermediate amine with aromatic aldehydes via Pictet–Spengler reaction provided thieno-pyridine fused thiazolo[3,2-a]pyrimidines under p-Ts OH as catalyst in good yields.
