Organic Chemistry of Explosives

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