Organic Chemistry of Explosives

Nitrolysis 219

from this study were found to be powerful explosives. Adolph and Cichra^108 found that the

hydrochloride salt oftert-butyldimethylamine (99) undergoes nitrolysis to dimethylnitramine

(100) in good yield when treated with nitric acid in acetic anhydride (Table 5.5, Entry 5); the

free amine base gives a much lower yield of nitramine product.

In some related work, Lear and co-workers^109 prepared the powerful cyclic nitramine explo-

sive Keto-RDX (102) from the nitrolysis–nitration of 2-oxa-5-tert-butyltriazone (101). Pagoria

and co-workers30a,^110 conducted a full study on the effect of different nitrating agents on the

yield of Keto-RDX (Table 5.6).

HN

N

NH

O

t-Bu

101

N

N

N

O

NO 2

102

(Keto-RDX or K-6)

O 2 N NO 2

NO 2 BF 4

Nitrating agent Yield (%)

Source: Reprinted with permission from C. L. Coon, E. S. Jessop, A. R.

Mitchell, P. F. Pagoria and R. D. Schmidt, in Nitration: Recent Laboratory

and Industrial Developments, ACS Symposium Series 623, Ed. L. F.

Albright, R. V. C. Carr and R. J. Schmitt, American Chemical Society,

Washington, DC, 155 (1996); Copyright 1996 American Chemical Society.

Table 5.6

57

43

57

21

0

0

40

TFAA/N 2 O 5 /HNO 3

TFAA/100 % HNO 3

Ac 2 O/100 % HNO 3

Ac 2 O/90 % HNO 3

Ac 2 O/70 % HNO 3

H 2 SO 4 /HNO 3

Table 5.6

Effect of nitrolysis agent on the yield of Keto-RDX (ref. 30a)

N

O 2 N

tBu

103

HNO 3 , Ac 2 O, 35 %

or

NH 4 NO 3 , Ac 2 O, 90 %

NO 2

N

O 2 N

NO 2

6

(TNAZ)

NO 2

Figure 5.50

Nitrolysis of atert-butyl group is also a key step in the synthesis of the high performance

explosive known as TNAZ (6). The nitrolysis of theN-tert-butylazetidine (103) has been

achieved with acetic anhydride–nitric acid^111 and acetic anhydride–ammonium nitrate.^112