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[1]张俊林,王伯周,毕福强,等.六氮杂[3,3,3]螺桨烷的多位点烷基化反应[J].火炸药学报,2017,40(4):33-37.[doi:10.14077/j.issn.1007-7812.2017.04.006]
 ZHANG Jun-lin,WANG Bo-zhou,BI Fu-qiang,et al.Multiple Site N-Alkylation Reactivity of Hexaaza[3,3,3] propellane[J].,2017,40(4):33-37.[doi:10.14077/j.issn.1007-7812.2017.04.006]
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六氮杂[3,3,3]螺桨烷的多位点烷基化反应()
     
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《火炸药学报》[ISSN:1007-7812/CN:61-1310/TJ]

卷:
40卷
期数:
2017年第4期
页码:
33-37
栏目:
出版日期:
2017-08-30

文章信息/Info

Title:
Multiple Site N-Alkylation Reactivity of Hexaaza[3,3,3] propellane
作者:
张俊林 王伯周 毕福强 王锡杰 周静 张家荣
1. 西安近代化学研究所, 陕西 西安 710065;
2. 氟氮化工资源高效开发与利用国家重点实验室, 陕西 西安 710065
Author(s):
ZHANG Jun-lin WANG Bo-zhou BI Fu-qiang WANG Xi-jie ZHOU Jing ZHANG Jia-rong
1. Xi’an Modern Chemistry Research Institute, Xi’an 710065, China;
2. State Key Laboratory of Fluorine & Nitrogen Chemicals, Xi’an 710065, China
关键词:
六氮杂[333]螺桨烷空间位阻多位点烷基化三维立体骨架
Keywords:
hexaaza[333] propellanesteric hindrancemultiple reactive sitesalkylationthree-dimensional skeleton
分类号:
TJ55;O621
DOI:
10.14077/j.issn.1007-7812.2017.04.006
文献标志码:
-
摘要:
以2,4,6,8,9,11-六氮[3,3,3]杂螺桨烷-3,7,10-三酮(PTO)为原料,通过与亲电试剂发生烷基化反应,获得了具有含能化衍生前景的六烯丙基六氮杂螺桨烷、六乙氧羰甲基六氮杂[3,3,3]螺桨烷和六羧甲基六氮杂螺桨烷;系统研究了不同亲电试剂与六氮杂[3,3,3]螺桨烷之间的反应活性,探讨了不同取代基六氮杂螺桨烷化合物的酸碱稳定性和热稳定性。结果表明,不同取代基结构对于六氮杂[3,3,3]螺桨烷的骨架修饰具有显著影响,亲电试剂活性的增加和溶剂极性的增大对反应有利,但过高活性的亲电试剂因副反应过多无法获得相应的烷基化产物;烷基化取代后的六氮杂[3,3,3]螺桨烷体系的水解稳定性大大增加,酸性条件下可保持稳定而碱性条件下多数烷基化产物发生降解;烷基化取代的产物其热稳定性较PTO有所增强。
Abstract:
Taking 2,4,6,8,9,11-hexaaza[3,3,3] propellane-3,7,10-trione (PTO) as raw material, the reactivity of the hexaaza[3,3,3] propellane with different electrophilic reagents was systematically investigated. N-hexallyl-hexaaza[3,3,3] propellanes, N-hexethylacetic -hexaaza propellanes and N-hexacetoxyl-hexaaza[3,3,3] propellanes with energetic derivative prospect were designed and synthesized for the first time. The acid-stability, base-stability and thermal stability of hexaaza[3,3,3] propellane with different substituent were discussed. The results show that different substituent structure has significant effect on the modification of the hexaaza[3,3,3] propellane skeleton.Increasing the activity of electrophilic reagent and solvent polarity enhanced the reaction process, but extremely high activity failed to obtain the corresponding alkylation products due to the adverse reactions. The hydrolytic stability of the N-alkylated hexaaza[3,3,3] propellane system is greatly increased. Most of them remained stable under acidic conditions while decomposed under alkaline conditions. The thermal stability of the products was enhanced by alkylation compared with PTO.

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备注/Memo

备注/Memo:
收稿日期:2016-09-16;改回日期:2017-04-29。
基金项目:国家自然科学基金(No.21503162)
作者简介:张俊林(1986-),男,博士,从事含能材料合成研究。E-mail:junlin-111@163.com
通讯作者:毕福强(1982-),男,博士,高级工程师,从事含能材料合成研究。E-mail:bifuqiang@msn.com
更新日期/Last Update: 2017-08-30