Primary nitramines as nucleophiles 237NNNNNCH 2 NNO 2NO 2 NO 2NO 2N
N
NCH 2 OAcNO 2NO 2
197NNN NNN NO 2NO 2NO 2
194NNNNO 2NO 2
199NO 2CH 2 CH 2 NHNO 2NNNNNNO 2NO 2NNNNO 2NO NO^2
2 NO 2NNNNO 2NO 2
196NNNNO 2NO 2
198NHNO 2
2NHNO 2AcO OAcNO 2 NO 2NO 2NHNO 2NHNO 2200, n = 1, 75 %
201, n = 2, 50 %
202, n = 3, 39 %193AcOH, Ac 2 O
Heat, 27 %H 2 SO 4 , NaNO 263 %0.5 eq of
O 2 NHN(CH 2 )nNHNO 2
n = 1, 2 or 3
72 %NaN 3 , DMF87 %CH 2 O, NH 3 ,
acetoneH 2 SO 4 ,
NaNO 2 , 69 %
19599 % HNO 3
48 %HNO 3 , Ac 2 O
98 %77 %n1 eqNO CH 2 N 3CH 2 NFigure 5.84Nitrolysis of the bicycle (193) with absolute nitric acid, followed by quenching with water,
yields 1,3,5-trinitro-1,3,5-triazacycloheptane (194), whereas the same reaction with fuming
nitric acid in acetic anhydride leads to the formation of the linear diacetate (195), a feature
which is consistent with the nitrolysis of hexamine (Section 5.15). Reaction of (193) with a
solution of nitrous acid leads to CāN bond cleavage and yields the nitrosamine (196). Cleavage
of (193) is also seen on treatment with hot acetic anhydride in acetic acid; the product of this
reaction, the acetate (197), readily undergoes displacement of the acetate group with a range of
nucleophiles, of which products the azide (198) is probably the most interesting as a potential
explosive. The acetate (197) reacts with one equivalent of ethylenedinitramine in DMF to
form the tetranitramine (199). The reaction of two equivalents of the acetate (197) with one
equivalent of methylenedinitramine, ethylenedinitramine or 1,3-dinitraminopropane leads to
the formation of the bicycles (200), (201), or (202) respectively.
Some interesting nitramine products are derived from the reaction of ethylenedinitramine (2)
with formaldehyde in the presence of various linear aliphatic diamines; the bicycles (203) and