Organic Chemistry of Explosives

Direct nitration of amines 201

Table 5.2 N-Nitration of 2,5,7,9-tetraazabicyclo[4.3.0]nonan-8-one.

dihydrochloride (41) with various nitrating agents (ref. 29)

Nitrating agent Product Yield (%)

NO 2 BF 4 /CH 3 NO 2 42 86

HNO 3 /Ac 2 O (20◦C) 43/44 (7:93) 53

HNO 3 /Ac 2 O (60◦C) 44 78

100 % HNO 3 (60◦C) 43/44 (10:90) 40

HNO 3 /N 2 O 5 (20◦C) 44 82

Source: Reprinted with permission from H. R. Graindorge, P. A. Lescop, M. J.

Pouet and F. Terrier, inNitration: Recent Laboratory and Industrial Develop-

ments, ACS Symposium Series 623, Eds. L. F. Albright, R. V. C. Carr and R.

J. Schmitt, American Chemical Society, Washington, DC, 46 (1996); Copyright

1996 American Chemical Society.

Three products have been observed from theN-nitration of the dihydrochloride salt of

2,5,7,9-tetraazabicyclo[4.3.0]nonan-8-one (41) with various nitrating agents, and two prod-

ucts observed for theN-nitration of 2,4,6,8-tetraazabicyclo[3.3.0]octan-3-one dihydrochloride

(45). Table 5.2 and Table 5.3 give a comparative idea of the efficiency and nitrating power of

different nitrating agents.

N

H

H

N

H

N

N

H

O

. 2HCl N

NN

N

O

N

H

NN

N

O

NO 2

NO 2

O 2 N NO 2 O 2 N

O 2 N O 2 N 47

(K-55)

46

(HK-55)

45

Figure 5.18

Table 5.3 N-Nitration of 2,4,6,8-tetraazabicyclo[3.3.0]octan-3-one. dihydrochloride

(45) with various nitrating agents (ref. 30a)

Nitrating agent Product Yield (%)

90 % HNO 3 /Ac 2 O(0◦Cto40◦C) 46 72

100 % HNO 3 /Ac 2 O(< 15 ◦C) 46 53

100 % HNO 3 /Ac 2 O (20◦Cto50◦C) 47 49

100 % HNO 3 /TFAA (0◦Cto40◦C) 47 51

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

Pagoria and R. D. Schmidt, inNitration: Recent Laboratory and Industrial Developments,

ACS Symposium Series 623, Eds. L. F. Albright, R. V. C. Carr and R. J. Schmitt, American

Chemical Society, Washington, DC, 153 (1996); Copyright 1996 American Chemical

Society.