Cross-linked poly（diallyldimethylammonium chloride） and its derivative copolymers were synthesized and used as phase transfer catalyst in the nucleophilic substitution reaction especially halogen exchange reactions....Cross-linked poly（diallyldimethylammonium chloride） and its derivative copolymers were synthesized and used as phase transfer catalyst in the nucleophilic substitution reaction especially halogen exchange reactions.In addition,the effect of hydrophilic-hydrophobic character of the polymers in the nucleophilic reactions was investigated.展开更多
As a critical component of alkaline fuel cells, anion exchange membranes determine the energy efficiency, output power density and the long term stability. Recently, the anion exchange membranes with gemini-cation sid...As a critical component of alkaline fuel cells, anion exchange membranes determine the energy efficiency, output power density and the long term stability. Recently, the anion exchange membranes with gemini-cation side chains exhibit superior ion conductivity due to their good nanophase separation. However, the costly and complicated synthesis limits their scaling up and commercialization. To address this problem, a convenient synthetic procedure under mild conditions is well developed. A tertiary amine precursor is introduced onto the polymer by the nucleophilic substitution reaction to avoid the conventional chloro/bromo-methylation. Followed by a simple Menshutkin reaction with 6- bromo-N,N,N-trimethylhexan-1-am inium bromide, the polym er electrolytes are obtained in a high yield. The resulting anion exchange membranes with high conductivity, good fuel cell performance and restricted swelling suggest the potential for the application in fuel cell devices.展开更多
Tandem asymmetric double Michael addition/internal nucleophilic substitution of the novel chiral source, 5-(l-menthyloxy)-3-bromo-2(5H)-furanone with nucleophilic alcohol compounds has been investigated. The tandem as...Tandem asymmetric double Michael addition/internal nucleophilic substitution of the novel chiral source, 5-(l-menthyloxy)-3-bromo-2(5H)-furanone with nucleophilic alcohol compounds has been investigated. The tandem asymmetric reaction can afford four new stereogenic centers with one reaction and give optically pure spiro-cyclopropane derivatives 5a--5d which are difficult to obtain by routine methods. The synthetic method for 5a--5d was studied in detail and the new compounds were identified on the basis of their analytical data and spectroscopic data, such as [α]^(20),IR,~1H NMR,^(13)C NMR, MS and elementary analysis. The absolute configuration of the sprio [5-l-menthyloxy-3-bromo butyrolactocyclopropane-3″, 3′(4′-methyloxy-5′-menthyloxybutyrolactone)] (5a) was established by X-ray crystallography. The work can provide important synthetic strategy in synthesis of some new optically active spiro-cyclopropane analogues and some biologically active molecules with complex structure.展开更多
文摘Cross-linked poly（diallyldimethylammonium chloride） and its derivative copolymers were synthesized and used as phase transfer catalyst in the nucleophilic substitution reaction especially halogen exchange reactions.In addition,the effect of hydrophilic-hydrophobic character of the polymers in the nucleophilic reactions was investigated.
基金supported by the National Natural Science Foundation of China (21720102003, 91534203 and 21522607)the Fundamental Research Funds for the Central Universities (WK2060190072 and WK2340000066)
文摘As a critical component of alkaline fuel cells, anion exchange membranes determine the energy efficiency, output power density and the long term stability. Recently, the anion exchange membranes with gemini-cation side chains exhibit superior ion conductivity due to their good nanophase separation. However, the costly and complicated synthesis limits their scaling up and commercialization. To address this problem, a convenient synthetic procedure under mild conditions is well developed. A tertiary amine precursor is introduced onto the polymer by the nucleophilic substitution reaction to avoid the conventional chloro/bromo-methylation. Followed by a simple Menshutkin reaction with 6- bromo-N,N,N-trimethylhexan-1-am inium bromide, the polym er electrolytes are obtained in a high yield. The resulting anion exchange membranes with high conductivity, good fuel cell performance and restricted swelling suggest the potential for the application in fuel cell devices.
基金Project supported by the National Natural Science Foundation of China (Grant No. 29672004)
文摘Tandem asymmetric double Michael addition/internal nucleophilic substitution of the novel chiral source, 5-(l-menthyloxy)-3-bromo-2(5H)-furanone with nucleophilic alcohol compounds has been investigated. The tandem asymmetric reaction can afford four new stereogenic centers with one reaction and give optically pure spiro-cyclopropane derivatives 5a--5d which are difficult to obtain by routine methods. The synthetic method for 5a--5d was studied in detail and the new compounds were identified on the basis of their analytical data and spectroscopic data, such as [α]^(20),IR,~1H NMR,^(13)C NMR, MS and elementary analysis. The absolute configuration of the sprio [5-l-menthyloxy-3-bromo butyrolactocyclopropane-3″, 3′(4′-methyloxy-5′-menthyloxybutyrolactone)] (5a) was established by X-ray crystallography. The work can provide important synthetic strategy in synthesis of some new optically active spiro-cyclopropane analogues and some biologically active molecules with complex structure.
