1,3,4,5,7,8-六硝基八氢化二咪唑[4,5-b∶4',5'-e]吡嗪-2,6-(1H,3H)-N,N'-二亚硝胺反应中间体的量子化学研究

doi:10.7503/cjcu20140661

摘要/Abstract

摘要：

应用密度泛函理论, 在B3PW91/6-31G++(d,p)水平下, 分析了合成1,3,4,5,7,8-六硝基八氢化二咪唑[4,5-b∶4',5'-e]吡嗪-2,6-(1H,3H)-N,N'-二亚硝胺(ONIP)时可能产生的不同数量硝基取代的中间产物, 并分析了在相同数量的硝基取代时, 中间产物可能具有的同分异构体的热力学选择性, 确认了热力学选择下的反应历程. 比较了4~8个硝基取代中间产物的结构性能数据, 计算结果表明, 超过四硝基取代后, 特别是六硝基中间产物, 具有良好的爆轰性能, 同时稳定性远超ONIP, 并且更易于合成.

关键词: 1, 3, 4, 5, 7, 8-六硝基八氢化二咪唑[4, 5-b∶4', 5'-e]吡嗪-2, 6-(1H, 3H)-N, N'-二亚硝胺, 硝基取代的中间产物, 密度泛函理论, 爆轰性能

Abstract:

The intermediate products of N,N'-(1,3,4,5,7,8-hexanitrooctahydro-diimidazo[4,5-b∶4',5'-e]pyrazine-2,6(1H,3H)-diylidene)dinitramide(ONIP) were studied via quantum chemistry method. When the ONIP is not nitrified completely, several intermediate products under different degree of nitrification are obtained. And what’s more, each intermediate has several isomers. We used the Gaussian 03 software to research these isomers. The thermodynamic selective products could be identified. Then the structures, density and some other important properties were calculated under B3PW91 level and 6-31G++(d,p)basis set with density functional theory. The results showed that the intermediate with six nitro groups owns very good detonation performance. It may be easier to be synthetized than ONIP, and more inactive than ONIP.

Key words: N, N'-(1, 3, 4, 5, 7, 8-hexanitrooctahydro-diimidazo[4, 5-b∶4', 5'-e]pyrazine-2, 6(1H, 3H)-diylidene)dinitramide, Intermediate with nitro group, Density functional theory, Detonation property

中图分类号:

O641

TrendMD:

申程, 王鹏程, 赵国政, 陆明. 1,3,4,5,7,8-六硝基八氢化二咪唑[4,5-b∶4',5'-e]吡嗪-2,6-(1H,3H)-N,N'-二亚硝胺反应中间体的量子化学研究. 高等学校化学学报, 2015, 36(1): 142.

SHEN Cheng, WANG Pengcheng, ZHAO Guozheng, LU Ming. Calculation Study on the Derivatives of N,N'-(1,3,4,5,7,8-Hexanitrooctahydro-diimidazo[4,5-b∶4',5'-e]-pyrazine-2,6(1H,3H)-diylidene)dinitramide^†. Chem. J. Chinese Universities, 2015, 36(1): 142.

图/表 12

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Number of nitro group, n	Substituents at different positions	ΔG/a.u.	Number of nitro group, n	Substituents at different positions	ΔG/a.u.
1	3or 6	-877.8980	3	12,13,15	-1286.7079
	10	-877.8815	4	3,6,13,15	-1491.1448^*
	12	-877.8911		6,7,13,15	-1491.1201
	13or 15	-877.9045^*		6,9,13,15	-1491.1170
2	3,15	-1082.3214		6,12,13,15	-1491.1078
	6,15	-1082.3182		6,10,13,15	-1491.1274
	13,15	-1082.3274^*	6	3,6,7,10,13,15	-1899.9057^*
	12,15	-1082.2860		3,6,7,9,10,12	-1899.7873
	10,15	-1082.2977		3,6,9,12,13,15	-1899.8811
	7,15	-1082.3037		3,6,7,9,13,15	-1899.8923
	9,15	-1082.3147		3,6,7,9,10,13	-1899.8655
3	7,13,15	-1286.7178		3,6,7,9,12,13	-1899.8731
	6,13,15	-1286.7390^*		3,6,9,12,13,15	-1899.8471

Number of nitro group, n	Substituents at different positions	ΔG/a.u.	Number of nitro group, n	Substituents at different positions	ΔG/a.u.
1	3or 6	-877.8980	3	12,13,15	-1286.7079
	10	-877.8815	4	3,6,13,15	-1491.1448^*
	12	-877.8911		6,7,13,15	-1491.1201
	13or 15	-877.9045^*		6,9,13,15	-1491.1170
2	3,15	-1082.3214		6,12,13,15	-1491.1078
	6,15	-1082.3182		6,10,13,15	-1491.1274
	13,15	-1082.3274^*	6	3,6,7,10,13,15	-1899.9057^*
	12,15	-1082.2860		3,6,7,9,10,12	-1899.7873
	10,15	-1082.2977		3,6,9,12,13,15	-1899.8811
	7,15	-1082.3037		3,6,7,9,13,15	-1899.8923
	9,15	-1082.3147		3,6,7,9,10,13	-1899.8655
3	7,13,15	-1286.7178		3,6,7,9,12,13	-1899.8731
	6,13,15	-1286.7390^*		3,6,9,12,13,15	-1899.8471

n	Substituents at different positions	ΔG/a.u.	n	Substituents at different positions	ΔG/a.u.
1	3 or 6	-878.453902	3	12,13,15	-1287.440223
	10	-878.502922	4	3,6,13,15	-1491.905341
	12	-878.503118		6,7,13,15	-1491.908054
	13 or 15	-878.553303^*		6,9,13,15	-1491.906215
2	3,15	-1082.970770		6,12,13,15	-1491.905037
	6,15	-1082.988675		6,10,13,15	-1491.908688^*
	13,15	-1083.033147^*	5	6,10,12,13,15	-1696.349390
	12,15	-1082.959903		6,7,10,13,15	-1696.358696
	10,15	-1082.966772		6,9,10,13,15	-1696.357203
	7,15	-1082.979181		3,6,10,13,15	-1696.358877^*
	9,15	-1082.975842	6	3,6,10,12,13,15	-1900.808901
3	7,13,15	-1287.442363		3,6,7,10,13,15	-1900.817404^*
	6,13,15	-1287.443045^*		3,6,9,10,13,15	-1900.816813

n	Substituents at different positions	ΔG/a.u.	n	Substituents at different positions	ΔG/a.u.
1	3 or 6	-878.453902	3	12,13,15	-1287.440223
	10	-878.502922	4	3,6,13,15	-1491.905341
	12	-878.503118		6,7,13,15	-1491.908054
	13 or 15	-878.553303^*		6,9,13,15	-1491.906215
2	3,15	-1082.970770		6,12,13,15	-1491.905037
	6,15	-1082.988675		6,10,13,15	-1491.908688^*
	13,15	-1083.033147^*	5	6,10,12,13,15	-1696.349390
	12,15	-1082.959903		6,7,10,13,15	-1696.358696
	10,15	-1082.966772		6,9,10,13,15	-1696.357203
	7,15	-1082.979181		3,6,10,13,15	-1696.358877^*
	9,15	-1082.975842	6	3,6,10,12,13,15	-1900.808901
3	7,13,15	-1287.442363		3,6,7,10,13,15	-1900.817404^*
	6,13,15	-1287.443045^*		3,6,9,10,13,15	-1900.816813

Compound	Bond	Bond order	Bond	Bond order	Bond	Bond order
R4	C2—N3	0.9251	C1—H17	0.8525	N3—N24	1.0177
R5	C4—N10	0.9173	C4—H19	0.8348	N7—N25	0.9395
R6	C1—N7	0.9204	C4—H19	0.8336	N7—N22	0.9330
R7	C4—N10	0.9187	C5—H18	0.8247	N7—N25	0.8992