114 Synthetic Routes to Nitrate Esters
A number of secondary high explosives containing both nitramine and nitrate ester func-
tionality have been reported. Aliphatic examples include:N-nitrodiethanolamine dinitrate
(DINA) (110), prepared from the nitration of diethanolamine with nitric acid–acetic anhydride
in the presence of zinc chloride,^157 ,^158 andN,N′-dinitro-N,N′-bis(2-hydroxyethyl)oxamide
dinitrate (NENO) (111), prepared from the mixed acid nitration ofN,N′-bis(2-hydroxyethyl)
oxamide^157 ,^159.
N
CH 2 CH 2 ONO 2CH 2 CH 2 ONO 2 CCOONCH 2 CH 2 ONO 2NCH 2 CH 2 ONO 2
NO 2NO 2NO 2 NO 2O 2 NNNNNO 2 NCH 2 CH 2 ONO 2NCH 2 CH 2 ONO 2
NO 2 NOCH 2 CH 2
110
(DINA)
111
(NENO)112
(Tris-X)Figure 3.48A number of nitramine-nitrate explosives have been prepared by Millar and co-workers
from the action of dinitrogen pentoxide on aziridines and azetidines (Section 5.8).^77 ,^88 Millar
and co-workers used their aziridine ring-opening nitration methodology (Section 5.8.1) to
synthesize the high performance melt-castable nitramine-nitrate explosive known as Tris-X
(112).^160
NO 2NO 2O 2 NNHCH 2 CH 2 OHNO 2NO 2O 2 NO 2 NCHN 2 CH 2 ONO 2HNO 3 , H 2 SO 490 %(^113114)
(pentryl)
Figure 3.49
NO 2 NO 2
NO 2 NO 2 NO 2 NO 2 NO 2
O 2 N
N
O 2 N
O 2 N
CH 2 CH 2 ONO 2 O 2 N CH 2 CH 2 ONO 2
NCH^2 CH^2 ONO^2
CH 2 CH 2 ONO 2
N
N N
O 2 NOCH 2 CH 2
115 116
Figure 3.50
Agrawal and co-workers^161 prepared some energetic explosives containing nitrate es-
ter, nitramine and aromatic C-nitro functionality within the same molecule and stud-
ied their thermal and explosive properties; 1-(2-nitroxyethylnitramino)-2,4,6-trinitrobenzene