A Pd（II）-catalyzed oxidative cyclization of olefinic tosylamides was developed for the preparation of aryl-fused and N-containing six-membered heterocycles. Under optimized conditions the reaction proceeded with hig...A Pd（II）-catalyzed oxidative cyclization of olefinic tosylamides was developed for the preparation of aryl-fused and N-containing six-membered heterocycles. Under optimized conditions the reaction proceeded with high activity and selectivity, with yields of up to 83% being obtained. This procedure provides a facile and efficient route to the aforementioned heterocycles with 2-acetoxy functionality.展开更多
2-（Dinitromethylene）-1,3-diazacycloheptane （DNDH） was prepared by the reaction of 1,1-diamino-2,2-dinitro- ethylene （FOX-7） with 1,4-diaminoethane in NMP. Thermal decomposition behavior of DNDH was studied under...2-（Dinitromethylene）-1,3-diazacycloheptane （DNDH） was prepared by the reaction of 1,1-diamino-2,2-dinitro- ethylene （FOX-7） with 1,4-diaminoethane in NMP. Thermal decomposition behavior of DNDH was studied under the non-isothermal conditions with DSC method, and presents only one intensely exothermic decomposition process The kinetic equation of the decomposition reaction is da/dT= 103388× 3a2/3exp（--3.353 ×10^5/RT）/fl. The critical temperature of thermal explosion is 215.97℃. Specific heat capacity of DNDH was studied with micro-DSC method and theoretical calculation method, and the molar heat capacity is 215.40 Jomol-1,K-1 at 298.15 K. Adiabatic time-to-explosion was calculated to be 92.07 s. DNDH has same thermal stability to FOX-7.展开更多
基金Acknowledgement This work was partly supported by the National Natural Science Foundation of China （Nos. 20972095, 21172143, 21232004）, Nippon Chemical Industrial Co., Ltd., the Nature Science Foundation of Ningbo （No. 2012A610086） and Shanghai Jiao Tong University. We thank Prof. Tsuneo Imamoto and Dr. Masashi Sugiya for helpful discussions and the Instrumental Analysis Center of Shanghai Jiao Tong University for HRMS determination.
文摘A Pd（II）-catalyzed oxidative cyclization of olefinic tosylamides was developed for the preparation of aryl-fused and N-containing six-membered heterocycles. Under optimized conditions the reaction proceeded with high activity and selectivity, with yields of up to 83% being obtained. This procedure provides a facile and efficient route to the aforementioned heterocycles with 2-acetoxy functionality.
基金Project supported by the National Natural Science Foundation of China （No. 20803058）, the Basal Science Foundation of National Defense （No. B 0920110005 ） and the Education Committee Foundation of S haanxi Province （Nos. 2010J K881, 09J K820）.
文摘2-（Dinitromethylene）-1,3-diazacycloheptane （DNDH） was prepared by the reaction of 1,1-diamino-2,2-dinitro- ethylene （FOX-7） with 1,4-diaminoethane in NMP. Thermal decomposition behavior of DNDH was studied under the non-isothermal conditions with DSC method, and presents only one intensely exothermic decomposition process The kinetic equation of the decomposition reaction is da/dT= 103388× 3a2/3exp（--3.353 ×10^5/RT）/fl. The critical temperature of thermal explosion is 215.97℃. Specific heat capacity of DNDH was studied with micro-DSC method and theoretical calculation method, and the molar heat capacity is 215.40 Jomol-1,K-1 at 298.15 K. Adiabatic time-to-explosion was calculated to be 92.07 s. DNDH has same thermal stability to FOX-7.
