196 Synthetic Routes toN-Nitro
low basicity i.e. those containing one or more nitro groups on the aromatic ring (Table 5.1,
Entry 3).^9 ,^11
NO 22 N CO
NO 2NO 22 N CO
NO 2NNO 2
CH 2
Ac 2 ONO 2
F C
NO 2NO 2
C
NO 2NNO 2
CH 2 CH 2 ONO 2NO 2
C
NO 2CNO 2NO 2CNO 2NO 2(^22)
16 17
fuming HNO 3
HNO 3 , H 2 SO 4
0 °C to 5 °C
HNO 3 , H 2 SO 4
0 °C to 5 °C
(^1819)
(^22)
20 21
CH 2 NHCH 2 CH 2
NO 2
F C
NO 2
N
NO 2
CH 2 CH 2
CH 2 NHCH 2 CH 2 OH
F CH 2 NHCH 2
F CH 2
Figure 5.7
A large number of nitramine-based explosives have been synthesized via Mannich-type con-
densation reactions (Section 5.13.2).12–18The amines generated from these reactions often have
the powerful electron-withdrawing trinitromethyl or fluorodinitromethyl groups positioned on
the carbonαto the amino group. This reduces amine basicity to an extent thatN-nitration
becomes facile. The energetic nitramines (17)^12 , (19)^13 and (21)^14 have been synthesized from
the condensation of ethylenediamine with 2,2,2-trinitroethanol, 2-fluoro-2,2-dinitroethanol
with ethanolamine, and 2-fluoro-2,2-dinitroethylamine with 2,2-dinitro-1,3-propanediol re-
spectively, followed byN-nitration of the resulting amine bases (16), (18) and (20), respectively.
22 N
N
CH 2 C(NO 2 ) 2 F
F(NO 2 ) 2 CCH 2
NO 2
NO 2
Figure 5.8
The energetic cubane-based nitramine (22) is also synthesized from the directN-nitration
of the parent amine using a mixture of trifluoroacetic anhydride and nitric acid.^15
HN
N
H
23
N
N
NO 2
OH
O 2 N NO 2
N
N
N
N
NO 2
ONO 2
O 2 NNO 2
NO 2
24
HNO 3 , Ac 2 O O 2 N
Figure 5.9