Ethylenedinitramine reactions

Ethylenedinitramine [505-71 -5] an explosive compound, is made by reaction of two moles of nitric acid [7697-37-2] per mole of EDA, splitting out two moles of water from the salt at elevated temperatures (6). 

Feuer and Miller synthesized 3,5,8,10-tetranitro-5,8-diazadodecane (183) and 3,8-dimethyl-2,4,7,9-tetranitro-4,7-diazadecane (184) from the reactions of ethylenedinitramine with 2-nitrobutyl acetate and 3-nitro-2-butyl acetate respectively the latter reagents readily undergo elimination in the presence of sodium acetate base to give the corresponding a-nitroalkenes. 

Some interesting nitramine products are derived from the reaction of ethylenedinitramine (2) with formaldehyde in the presence of various linear aliphatic diamines the bicycles (203) and... 

Pagoria and co-workers " " also reported the synthesis of (113) (K-56, TNABN) and the trinitrated derivative, 2,5,7-trinitro-2,5,7,9-tetraazabicyclo[4.3.0]nonane-8-one (115) (HK-56). Their route to the bicycle (112) was via bromination of l,3-diacetyl-2-imidazolone, followed by reaction with ethylenedinitramine and nitrolysis of the acetyl groups. 

The earliest method used at PicArsn was in 1933 It consisted of treating ethylenediamine with diethyl carbon ate to obtain ethyleneurea, followed by nitration to obtain Dinitroediyleneurea, which on hydrolysis gave Ethylenedinitramine. This process suffered from two disadvantages the overall yield was only 42% of the theoretical amt and the initial step, the reaction between ethylenediamine and diethyl carbon a re, required the use of high pressures and temperatures over an extended period of time. However, the expl props of EDNA were of sufficient in-, terest ro justify further study (Ref 4). See also Aaronson (Ref 5)... 

The second approach to cyclic nitramines may be illustrated in the reaction of ethylenedinitramine (5) with formaldehyde to produce l,3-dinitro-l,3-diazacyclopentane (6) (Refe. 18-20). This approach has limitations when applied to more complex cyclic nitramines (Ref. 20). 

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