[1]王娟,刘大斌,周新利.1,4-二叠氮-2,3-二叠氮甲基-2,3-二硝基丁烷的合成[J].爆破器材,2012,41(04):1-4、8.
　WANG Juan,LIU Dabin,ZHOU Xinli.Synthesis of 1, 4-Diazido-2, 3-Bis-Azidomethyl-2, 3-Dinitro-Butane[J].EXPLOSIVE MATERIALS,2012,41(04):1-4、8.
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1,4-二叠氮-2,3-二叠氮甲基-2,3-二硝基丁烷的合成()
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《爆破器材》[ISSN:1001-8352/CN:32-1163/TJ]

卷:
41
期数:
2012年04
页码:
1-4、8
栏目:
基础理论
出版日期:
2012-08-20

文章信息/Info

Title:
Synthesis of 1, 4-Diazido-2, 3-Bis-Azidomethyl-2, 3-Dinitro-Butane
文章编号:
4473
作者:
王娟; 刘大斌; 周新利
南京理工大学化工学院（江苏南京，210094）
Author(s):
WANG Juan;  LIU Dabin;  ZHOU Xinli
School of Chemical Engineering; Nanjing University of Science and Technology (Jiangsu,Nanjing, 210094)
关键词:
1; 4-二叠氮-2; 3-二叠氮甲基-2; 3-二硝基丁烷; 合成; 表征; 含能增塑剂
Keywords:
1;  4-diazido-2;  3-bis-azidomethyl-2;  3-dinitro-butane;  synthesis;  characterization;  energy plasticizer
分类号:
TQ56 O62 TJ55
文献标志码:
A
摘要:
以硝基甲烷为原料合成了1,4-二叠氮-2,3-二叠氮甲基-2,3-二硝基丁烷，总收率为37.8%。采用1H NMR﹑IR和MS对目标产物及中间体的结构进行了表征。在三羟甲基硝基甲烷的合成中，结合反应机理确定了氢氧化钙的用量为：n(CH3NO2)∶n(Ca(OH)2)=100∶1；通过对催化剂浓硫酸﹑三氟化硼—乙醚络合物和对甲苯磺酸的比较，得出对甲苯磺酸为中间体2,2-二甲基-5-羟甲基-5-硝基-1,3-二氧杂环己烷合成的较优催化剂；分别采用2,3-二羟甲基-2,3-二硝基-1,4-丁二醇四硝酸酯和2,3-二羟甲基2,3-二硝基-1,4-丁二醇四对甲苯磺酸酯与NaN3反应，发现磺酸酯基易离去，叠氮化反应更易进行，收率较高；叠氮化反应的较优溶剂为DMSO。DSC分析表明，1,4-二叠氮-2,3-二叠氮甲基-2,3-二硝基丁烷的分解峰温为223.46℃。
Abstract:
The 1,4-diazido-2,3-bis-azidomethyl-2,3-dinitro-butane was synthesized from nitromethane. The overall yield is 37.8%. The characterization methods of 1H NMR, IR and MS were applied to confirm the structures of the intermediates and the product. Based on the reaction mechanism, the best process condition for synthesizing tris(hydroxymethyl)nitromethane was determined as n(CH3NO2): n(Ca(OH)2)=100∶1; Comparing three different catalysts including concentrated sulfuric acid, boron trifluoride etherate and p-toluenesulfonic acid, p-toluenesulfonic acid served the best catalyst for forming the intermediate, 2,2dimethyl-5-hydroxymethyl-5-nitro -1,3-dioxane; Both the reactants, 2, 3-bis(hydroxymethyl)-2,3-dinitro -1,4-butanediol tetranitrate and 2,3-bis(hydrox-ymethyl)2,3-dinitro-1,4-butanediol etrasulphonate, were used for the azide reaction with NaN3, and the phenomena is observed that it is easy for the leaving of sulphonate group and azide substitution with high yield in comparison with the methods using nitrate with sulphonate; A better solvent of azide reaction is DMSO. The results of DSC show that the temperature peak of decomposition of 1,4-diazido-2,3-bis-azidomethyl -2,3-dinitro-butane is 223.46℃.

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备注/Memo

备注/Memo:
收稿日期：2012-03-27
作者简介：王娟(1983~)，女，博士研究生，主要从事有机合成的研究。E-mail：wangjuan830508@163.com
通讯作者：周新利（1973~），男，副研究员，主要从事含能材料的研究。E-mail：xinlizhou@yahoo.com.cn
更新日期/Last Update: 2012-08-29