Organic Chemistry of Explosives

288 Nitramines and Their Derivatives

amines have no quaternary nitrogen and have the negative charge counterbalanced with a

positively charged species.

NN

N

NH 2

162

NN

N

NH 2

163

NH 2

NO 3

NN

N

N

N

NO 2

NO 2

164

K

N

N

N

N N

O 2 N NO 2

K

N

N N

O 2 N NO 2

K

1. picryl-ONH 2


2. HNO 3 (aq)
   
   
   1. NO 2 BF 4
   
   
   2. KOAc
   
   
   
   

165 166

N

Figure 6.53

The nitrogen atoms of heterocycles like imidazoles and triazoles have been converted into

N-nitroimide groups. TheN-nitroimide (164) is synthesized from 1-amino-1,3,4-triazole (162)

byN-amination of the tertiary nitrogen withO-picrylhydroxylamine, addition of nitric acid

to give the nitrate salt (163), followed byN-nitration with nitronium tetrafluoroborate in

acetonitrile.^90 The 1,2,3-triazole (165)^91 and the imidazole (166)^90 are synthesized in a similar

way. The synthesis ofN-nitroimides has been the subject of an excellent review.^92

References

1. V. P. Iushin, M. S. Komelin and V. A. Tartakovsky,Zh. Org. Khim., 1999, 35 , 489.


2. R. D. Chapman, J. W. Fischer, R. A. Hollins, C. K. Lowe-Ma and R. A. Nissan,J. Org. Chem., 1996,
   61 , 9340.


3. J. O. Doali, R. A. Fifer, D. I. Kruezynski and B. J. Nelson,Technical Report No. BRL-MR-378/5,
   US Ballistic Research Laboratory, MD (1989).


4. T. G. Archibald, K. Baum, C. George and R. Gilardi,J. Org. Chem., 1990, 55 , 2920.


5. T. G. Archibald, S. G. Bott, A. P. Marchand and D. Rajagopal,J. Org. Chem., 1995, 60 , 4943.


6. K. Hayashi, T. Kumagai and Y. Nagao,Heterocycles, 2000, 53 , 447.


7. T. Axenrod, P. R. Dave, C. Watnick and H. Yazdekhasti,J. Org. Chem., 1995, 60 , 1959.


8. T. Axenrod, P. R. Dave, C. Watnick and H. Yazdekhasti,Tetrahedron Lett., 1993, 34 , 6677.


9. T. G. Archibald, M. D. Coburn and M. A. Hiskey,Waste Management, 1997, 17 , 143.


10. P. E. Eaton, K. Pramod and R. Gilardi,J. Org. Chem., 1990, 55 , 5746.


11. G. T. Cunkle and R. L. Willer, ‘Cubanes as Solid Propellants Ingredients’,SPIE Proceedings, 1988,

872 , 24.

12. J. C. Bottaro, P. E. Penwell and R. J. Schmitt,‘Synthesis of Cubane Based Energetic Materials, Final

Report, December 1989’, SRI International, Menlo Park, CA [AD-A217 147/8/XAB].

13. H. G. Adolph and D. A. Cichra,Synthesis, 1983, 830.


14. K. Klager,J. Org. Chem., 1958, 23 , 1519.


15. R. D. Chapman, R. D. Gilardi, C. B. Kreutzberger and M. F. Welker,J. Org. Chem., 1999, 64 ,

960.

16. R. Aniszfeld, G. A. Olah, G. Rasul and G. K. Surya Prakash,J. Am. Chem. Soc., 1992, 114 , 5608.


17. T. Axenrod, R. D. Chapman, R. D. Gilardi, X. -P. Guan, L. Qi and J. Sun,Tetrahedron Lett., 2001,

42 , 2621.

18. H. G. Adolph, M. Chaykovsky, C. George, R. Gilardi and W. M. Koppes,J. Org. Chem., 1987, 52 ,

1113.