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†

doi:10.7503/cjcu20140661

Abstract

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

CLC Number:

O641

TrendMD:

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^†[J]. Chem. J. Chinese Universities, 2015, 36(1): 142.

Figures/Tables 12

References 25

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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