Nitrolysis 215
CH 3 CO
C 2 H 5 CO
n-C 3 H 7 CO
(CH 3 ) 2 CHCO
(CH 3 ) 3 CCO
CH 3 OCO
t-BuOCO
N
N
RR
R
N
N
O 2 N NO 2
NO 2
R (see above) HNO 3 –P 2 O 5 HNO 3 –TFAA
95 15 a 80 b
80 55 98
60 40 94
50 30 94
15
1 2 3 4 5 0
0 0
6 ---
8 p-CH 3 C 6 H 4 SO 2 0 --- ---
7 --- ---
97
97
97
97
97
97
97
a Crude product contains 25 % TAX (82). b Crude product contains 4 % TAX (82).
nitrolysis
Table 5.4
Nitrolysis of 1,3,5-trisubstituted-1,3,5-triazacyclohexanes
see Table 5.4
Entry
Yield (%) of RDX (3)
Ref.
30
N N
5
0
100 % HNO 3
N
NN
Ac Ac
Ac
81
(TRAT)
N
NN
O 2 N NO 2
Ac
82
(TAX)
Figure 5.43
similar substrates, where R=alkanoyl, yield RDX as the sole product (Table 5.4, Entries 2, 3
and 4).^97 Carbamate derivatives derived from simple straight chain aliphatic alcohols are found
to be inert to nitrolysis, even with the powerful TFAA–nitric acid and phosphorus pentoxide–
nitric acid mixtures (Table 5.4, Entry 6).^97 The nitrolysis of thetert-butoxycarbonyl (BOC)
derivative gives a 5 % yield of RDX (Table 5.4, Entry 7).^30 Sulfonamide derivatives like the
tosylate appear to be fairly inert to nitrolysis in this particular case (Table 5.4, Entry 8).
NN
N
N N
N
AcAc
AcAc
Bn 83 Bn
NN
N
N N
N
AcAc
AcAc
ON 84 NO
NN
N
N N
N
NO 2
NO 2
NO 2
O 2 N
O 2 N
O 2 N
5
(CL-20)
N 2 O 4 (excess)
92 %
or
NOBF 4 , 55 %
99 % HNO 3
96 % H 2 SO 4
93 %
Figure 5.44