Energetic nitrate esters 113OCH 2 N 3
CH 2 N 3 HOCH 2CH 2 N 3CH 2 N 3O 2 NOCH 2 CCH 2 ONO 2CH 2 N 3CH 2 N 3N 3 CH 2CH 2 N 3CH 2 N 3100
(BAMO)101 102
(PDADN)70 % HNO 3 ,
CH 2 Cl 278 %CCCH 2 ONO 2CH 2 ONO 2HNO 3 , Ac 2 O,
CH 2 Cl 284 %103Figure 3.45The 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 2NO 2NO 2C CH 2 ONO 2NO 2NO 2CNO 2NO 2O 2 NO(CH 2 ) 3 CH 2 CNO 2NO 2CH 2 CNO 2NO 2CH 2 CNO 2NO 2(CH 2 ) 3 ONO 2H 3 C C CH 2 ONO 2NO 2NO 2
104 105 1062 N CO CH 2 OCH 2 CH 2 ONO 2107Figure 3.46The 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 2O 2 N ONO 2NN NN
O 2 N NO 2NO 2109
(NMHP)108
(TNHP)- CH 2 O
- 100 % HNO 3
Figure 3.47