310 N-Heterocycles
ANTA (114) readily forms a stable anion on reaction with bases like sodium ethoxide and this
anion has been used as a nucleophile for the synthesis of many ANTA derivatives. Laval and co-
workers^71 synthesized DANTNP (116) (calculated VOD∼8120 m/s,d= 1 .84 g/cm^3 , m.p.>
330 ◦C) from the reaction of 4,6-dichloro-5-nitropyrimidine (115) with two equivalents of
ANTA (114) in the presence of sodium ethoxide. Agrawal and co-workers^72 studied the thermal
and explosive properties of both ANTA and DANTNP and suggested their use for applications
in propellant/explosive formulations where insensitivity coupled with thermal stability is of
prime importance. The activation energies of ANTA and DANTNP indicate that DANTNP is
more thermally stable than ANTA.
O 2 NO 2 NO 2 NO 2 NH 2 N NNNNO 2NO 2NO 2NO 2NN
NNNH 2H 2 NH 2 NNH 2NH 2NO 2NO 2NO 2NO 2NO 2
NO 2117118
(PRAN) NN
NNNN
N
N119
(IHNX)NNNNNN120Figure 7.44NNNO 2
NNN
N NNH 2 NO 2 N NO
2NNNNNNNNNNO 2O 2 NNH 2H 2 NN
NNH 2 NNO 2N
NNNNNNNN
NH 2 NNH 2NO 2O 2 N
123122121Figure 7.45Pagoria and co-workers^2 synthesized a number of thermally stable explosives from the
reaction of the sodium salt of ANTA with chloro-substituted arylenes andN-heterocycles.
These include the synthesis of (117) from picryl chloride, PRAN (118) from 2-chloro-3,5-
dinitropyridine, IHNX (119) from 2,4-dichloro-5-nitropyrimidine, (120) from 1,5-dichloro-
2,4-dinitrobenzene, and (121) from 4-chloro-6-(3-nitro-1,2,4-triazolyl)-5-nitropyrimidine.
Coburn and co-workers^68 reported the synthesis of the tetrazine (122) and the triazine (123)
from the reaction of the sodium salt of ANTA with 3,6-dichlorotetrazine and cyanuric chloride
respectively.
NN NHNO 2
NH 2
124O 2 NH 2 NNO 2NO 2Figure 7.46