呋咱并[3,4-e]-4,6-二氧化-1,2,3,4-四嗪新法合成与表征
收稿日期: 2012-05-16
修回日期: 2012-06-05
网络出版日期: 2012-06-21
基金资助
国防基础科研计划(No. B0920110051)资助项目.
Novel Synthetic Route and Characterization of [1,2,5]oxadiazolo- [3,4-e][1,2,3,4]tetrazine 4,6-Di-N-oxide (FTDO)
Received date: 2012-05-16
Revised date: 2012-06-05
Online published: 2012-06-21
Supported by
Project supported by the National Defense Fundamental Scientific Research (No. B09201100051).
自行设计了呋咱并[3,4-e]-1,2,3,4-四嗪-4,6-二氧化(FTDO)新的合成路线, 采用3,4-二氨基呋咱(DAF)为起始原料, 经过氧化﹑缩合﹑硝化﹑成环4步反应合成了FTDO, 总收率为30.89%, 并采用核磁共振光谱﹑红外光谱﹑质谱及元素分析等进行了结构表征. 探讨了成环反应的机理, 并研究了硝化及成环反应条件, 确定硝化反应的最佳条件为: 硝化试剂为100% HNO3, 25 ℃下反应2 h, 收率为99.54%; 成环反应的最佳条件为: 55 ℃下反应5 h, n(化合物4)∶n(P2O5)为1∶16, 溶剂量为160 mL/g, 收率为46.37%.
关键词： 呋咱并[3,4-e]-1,2,3,4-四嗪-4,6-二氧化; 合成; 表征
李祥志 , 王伯周 , 李辉 , 李亚南 , 毕福强 , 霍欢 , 樊学忠 . 呋咱并[3,4-e]-4,6-二氧化-1,2,3,4-四嗪新法合成与表征[J]. 有机化学, 2012 , 32(10) : 1975 -1980 . DOI: 10.6023/cjoc201205019
A novel synthetic route of [1,2,5]oxadiazolo[3,4-e][1,2,3,4]tetrazine 4,6-di-N-oxide (FTDO) was designed and FTDO was synthesized from 3,4-diaminofurazan (DAF) via the reactions of oxidation, condensation, nitration and cyclization with a total yield of 30.89%. FTDO and its intermediates were characterized by NMR, IR, MS and elemental analysis etc. The mechanism of cyclization was proposed and the conditions for the reaction of nitration and cyclization were optimized. It was found that the optimal conditions for the reaction of nitration were followed as: nitration reagent was 100% HNO3, the reaction temperature was at 25 ℃ for 2 h with a yield of 99.54%. The optimal conditions for the reaction of cyclization were followed as: the reaction temperature was at 55 ℃, the molar ratio of compound 4 and P2O5 was 1∶16, and the volume of solvent was 160 mL/g with a yield of 46.37%.
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