238 Synthetic Routes toN-Nitro
+ 4 CH 2 O + H 2 N(CH 2 )nNH 2NNNNN2 )nN(CHNO 2NO 2 NO 2NO 2HNO 3 , Ac 2 O
50–60 °C205, n = 2
206, n = 32
NHNO 2
2NHNO 2AcO
NO 2NO 2 NO 2203, n = 2
204, n = 3(CH 2 )n
2N N NFigure 5.85(204) are formed when the amine components are ethylenediamine and 1,3-diaminopropane
respectively.^161 Nitrolysis of the bicycles (203) and (204) with nitric acid in acetic anhydride
yields the linear diacetates (205) and (206), respectively.^161 Note that only bicycle (193), where
the triazacycloheptane units are separated by a single methylene group, leads to 1,3,5-trinitro-
1,3,5-triazacycloheptane (194) on nitrolysis. 1,3,5-Trinitro-1,3,5-triazacycloheptane (194) has
never been isolated from the nitrolysis of extended bicycles like (203) and (204).
NO 22 N COO 2 NO 2 N
NO 2CH 2 OHNH 4 OAc (aq) NO^2
C
NO 2CH 2 NHCH 2 CNO 2
NO 2
NO 2NO 2
C
NO 2CH 2 NCH 2 CNO 2NO 2NO 2
NO 2HNO 320720820984 %Figure 5.86The use of primary nitramines in Mannich reactions is an important route to numerous
secondary nitramines. However, a far more common route to such nitramines involves the
Mannich condensation of a terminalgem-dinitroalkane, formaldehyde, and an amine, followed
byN-nitration of the resulting polynitroalkylamine.^162 The preformed methylol derivative of
thegem-dinitroalkane is often used in these reactions and so formaldehyde can be omitted.
This route has been used to synthesize explosives like (92)^163 and (209).^164
NH 4 OAc (aq)
40–50 °CN
HNO 2O 2 N NO 2O 2 NNNO 2O 2 N NO 2O 2 NNO 2HNO 3 , Ac 2 O47 %210C211
92CCH 2NO 2NO 2NO 2NO 2HOCH 2 CH 2 OH
54 %Figure 5.87