Energetic nitrate esters 113
O
CH 2 N 3
CH 2 N 3 HOCH 2
CH 2 N 3
CH 2 N 3
O 2 NOCH 2 CCH 2 ONO 2
CH 2 N 3
CH 2 N 3
N 3 CH 2
CH 2 N 3
CH 2 N 3
100
(BAMO)
101 102
(PDADN)
70 % HNO 3 ,
CH 2 Cl 2
78 %
C
C
CH 2 ONO 2
CH 2 ONO 2
HNO 3 , Ac 2 O,
CH 2 Cl 2
84 %
103
Figure 3.45
The incorporation of nitrate ester functionality into molecules containing other ‘ex-
plosophores’ is a common strategy for increasing oxygen balance and improving explo-
sive performance. Pentaerythritol diazido dinitrate (102) (PDADN) has been synthesized by
the ring cleavage of 3,3-bis(azidomethyl)oxetane (100) [BAMO, an energetic monomer to
Poly(BAMO) energetic binder] with 70 % nitric acid, followed by nitration of the product
(101) with fuming nitric acid in acetic anhydride.^151 The thermal properties of PDADN have
been investigated.^152 Pentaerythritol triazide mononitrate (103) has also been synthesized by
O-nitration of the corresponding alcohol with acetyl nitrate.^151
O 2 NOCH 2
NO 2
NO 2
C CH 2 ONO 2
NO 2
NO 2
C
NO 2
NO 2
O 2 NO(CH 2 ) 3 CH 2 C
NO 2
NO 2
CH 2 C
NO 2
NO 2
CH 2 C
NO 2
NO 2
(CH 2 ) 3 ONO 2
H 3 C C CH 2 ONO 2
NO 2
NO 2
104 105 106
2 N CO CH 2 OCH 2 CH 2 ONO 2
107
Figure 3.46
The Henry condensation of nitroform and terminal dinitromethyl compounds with formalde-
hyde and other aldehydes, followed by nitration of the resulting alcohol functionality, has been
used to synthesize numerous explosives. The nitrate esters (104)^153 , (105)^153 , (106)^154 and
(107)^155 have been synthesized from the action of absolute nitric acid on the parent alcohols.
In a similar manner, NMHP (109) is synthesized from the condensation of TNHP (108) with
formaldehyde, followed byO-nitration with absolute nitric acid.^156
O 2 N NO 2
O 2 N ONO 2
NN NN
O 2 N NO 2
NO 2
109
(NMHP)
108
(TNHP)
- CH 2 O
- 100 % HNO 3
Figure 3.47