Synthetic Routes to A-Nitro Functionality

There are four important groups of A-nitro compounds which are relevant to energetic materials synthesis. These are primary nitramines, secondary nitramines, secondary nitramides (including A-nitroureas and A, A -dinitroureas) and nitrimines. The synthesis and incorporation of these A-nitro functionalities into organic compounds is the focus of this chapter. 

The replacement of amine and amide hydrogen with a nitro group via direct nitration is an important route to A-nitro functionality. However, the cleavage of other bonds is also important. In the case of C-N bond cleavage the process is known as nitrolysis and is an invaluable route to many energetic materials (Section 5.6). The nitrolysis of hexamine and the syntheses of the important explosives HMX and RDX are discussed in Section 5.15. This area of chemistry could easily demand a separate chapter of its own and is the most complex and diverse in the field of nitramine chemistry. 

Organic Chemistry of Explosives 2007 John Wiley Sons, Ltd. 

Nitrimines are a relatively minor group of At-nitro compound. The nitro derivatives of guanidine and related compounds are the most important examples of the nitrimine group. 

Primary nitramines have acidic protons and are able to undergo condensation reactions to form functionalized nitramines. These reactions are discussed in Section 5.13 because the products have potential application as energetic polymer precursors or find use for the synthesis of other explosives. 

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