230 Synthetic Routes toN-Nitro
CH 3 NH 2
+
ClCO 2 EtCH 3 NHCO 2 Et
162SOOClCl SOONHCH 3NHCH 3
54SOONCH 3NCH 3NO 2NO 2NO 2
9NO 2
10CO 2 EtCO 2 EtCH 3 NCO 2 EtNO 2
163OONHCH 3NHCH 3
53OONCH 3NCH 3CH 3 NHNO 2
1100 % HNO 32 CH 3 NH 298 % HNO 3- NH 4 OH
- H+
- NH 4 OH
- H+
+
2 CH 3 NH 2100 % HNO 3+Figure 5.68Methylnitramine (1) can be prepared from the hydrolysis of an appropriate secondary
nitramide. One route involves the nitration ofN, N′-dimethylsulfamide (54) toN, N′-dinitro-
N, N′-dimethylsulfamide (10) with absolute nitric acid, followed by ammonolysis and subse-
quent acidification.^132
H 3 CCH 3OHN
HNH 3 C
NNCH 3ONO 2 NO 2CH 3 NHNO 2
1H 2 SO 4 , HNO 3 H 2 O, refux(^164165)
Figure 5.69
Methylnitramine (1) has also been synthesized from the hydrolysis of ethylN-methyl-
N-nitrocarbamate (163),^133 N, N′-dinitro-N, N′-dimethyloxamide (9)^69 andN, N′-dinitro-N, N′-
dimethylurea (165);^134 the latter, synthesized from the mixed acid nitration of N, N′-
dimethylurea (164), has been suggested as a possible industrial route to methylnitramine.^134
2 CH 3 CONH 2
- CH 2 O
H 2 C
NHCOCH 3
NHCOCH 3
166
H 2 C
NHNO 2
NHNO 2
168
H 2 C
NCOCH 3
NCOCH 3
NO 2
NO 2
167
100 % HNO 3 1. Ba(OH) 2
- H+
Figure 5.70