Organic Chemistry of Explosives

Primary nitramines as nucleophiles 235

an excess of the Michael acceptor is warmed in the presence of a catalytic amount of Triton-B

base.

MeO 2 C

N

N

CO 2 Me

NO 2

NO 2

OMe

O

O 2 NHN

NHNO 2

Triton B,

(^2) MeOH, 72 %
182
2
Figure 5.78
1,4-Michael addition reactions are particularly useful when linear aliphatic bis-nitramines
are used because the products contain two terminal functional groups like in the diester (182).^155
The terminal functionality of such products can be used, or modified by simple functional group
conversion, to provide oligomers for the synthesis of energetic polymers; such oligomers often
use terminal alcohol, isocyanate or carboxy functionality for this purpose.
H 3 CH 3 C
CH 3
NO 2 NO 2
N
N
NO 2 NO 2
N
N
NO 2
CH 3
NO 2
NO 2
CH 3
NO 2
CH 3
183 184
Figure 5.79
Feuer and Miller^156 synthesized 3,5,8,10-tetranitro-5,8-diazadodecane (183) and 3,8-
dimethyl-2,4,7,9-tetranitro-4,7-diazadecane (184) from the reactions of ethylenedinitramine
with 2-nitrobutyl acetate and 3-nitro-2-butyl acetate respectively; the latter reagents read-
ily undergo elimination in the presence of sodium acetate base to give the corresponding
α-nitroalkenes.

5.13.2 Mannich condensation reactions

Primary nitramines react with amines in the presence of an aldehyde to form 1,3-amino-

nitramines in a reaction analogous to the Mannich condensation. In these reactions the amine

and aldehyde component combine to form an intermediate imine which is then attacked by the

nitramine nucleophile.

O 2 N NO 2

O 2 N

RR^1

R^1

R^1

R

R

NN

NN

N

RNHNO 2 + CH 2 O + R^12 NH + H 2 O (Eq. 5.20)

2 RNHNO 2 + 2 CH 2 O + R^1 NH 2 + 2 H 2 O (Eq. 5.19)

Figure 5.80