Chemistry of tetraazapentalenes
Chemistry of tetraazapentalenes
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DOI：
10.1021/jo972252x
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发表时间：
1998-05-15
影响因子：
3.6
通讯作者：
Gilardi, R
中科院分区：
文献类型：
--
作者：
Altmann, KL;Chafin, AP;Gilardi, R
2，4，8，10-四硝基苯并三唑并[2，1-α]苯并三唑（TACOT）是一种热稳定性很好且不敏感的炸药，但易受亲核试剂的攻击。与叠氮离子的反应导致硝基在4，10-位上的置换，用甲醇根离子的处理影响1-位上的氢原子的置换和远程三唑环的断裂，而“替代亲核胺化”置换所有芳香族氢。3，5，7-三硝基-1，3，3-三唑并[2，1-α]苯并三唑和3，5，7-三硝基-1，2，3-三唑并[1，2-α]苯并三唑容易通过母体三唑苯并三唑的硝化制备。然而，它们的热稳定性不如TACOT，对冲击引发更敏感。此外，尝试进一步硝化和与亲核试剂如叠氮化物和甲醇根离子的反应都能使三唑环断裂，留下4，6-二硝基苯并三唑。
2,4,8, 10-Tetranitrobenzotriazolo[2, 1-alpha]benzotriazole (TACOT), although thermally very stable and insensitive as an explosive, is susceptible to attack by nucleophiles. Reaction with azide ion results in displacement of nitro groups at the 4,10-positions, treatment with methoxide ion effects displacement of the hydrogen atom at the 1-position and scission of the remote triazole ring, while "vicarious nucleophilic amination" displaces all the aromatic hydrogens. 3,5,7-Trinitro-1,3,3-triazolo[2, 1-alpha]benzotriazole and 3,5,7-trinitro-1,2,3-triazolo[1,2-alpha]benzotriazole are prepared readily by nitration of the parent triazolobenzotriazoles. However they are thermally less stable than TACOT and more sensitive to initiation by impact. Furthermore, attempted further nitration and reaction with nucleophiles such as azide and methoxide ions both effect scission of the triazole ring to leave 4,6-dinitrobenzotriazole.