320 N-Heterocycles
7.8 6-Membered rings – 3N
NNNNNN
NO 2O 2 NOH 2 CH 2 C CH 2 CH 2 ONO 2O 2 NO 2 N189
(Tris-X)188N 2 O 5 , CHCl 3- 30 °C, 96 %
NNNNN NCH 2 CH 2 ONO 2Figure 7.69The 1,2-nitramine-nitrate Tris-X (189) (VOD∼8700 m/s, m.p. 69◦C) has been synthesized
from the reaction of 2,4,6-tris(aziridino)-1,3,5-triazine (188) with dinitrogen pentoxide in
chloroform or methylene chloride at subambient temperature (Section 5.8.1).^120
190
(TPM)NNNNHHNNHO 2 N NO 2NO 2NO 22 O 2 NNONO 2O 2 NNO 2Figure 7.70Coburn^121 synthesized 2,4,6-tris(picrylamino)-1,3,5-triazine (TPM) (190) from the reaction
of aniline with cyanuric chloride followed by nitration of the product with mixed acid.^121
Treatment of TPM (190) with acetic anhydride–nitric acid leads toN-nitration and the isolation
of the corresponding tris-nitramine. The high thermal stability of TPM (m.p. 316◦C) coupled
with its facile synthesis and low sensitivity to impact has led to its large scale manufacture in
the US by Hercules Inc. China has reported a low-cost synthetic route to TPM but this has a
limited production capacity.1d
NN NH 2NNHHNNHO 2 N NO 2NO 2NO 2NO 2 O 2 N NO 2NO 2O 2 NNH 2ClClNNNClClClNH 2H 2 NNH 2H 2 N NH 2+ 3- DMF, 90 °C, 90 %
- oleum, HNO 3 , 70 %
- NH 3 , acetone, 50 %
191 192193
(PL-1)Figure 7.71