Ethylenedinitramine

Franchimont and Klobbie [17] prepared ethylenedinitramine (EDNA, Haleite) by the nitration of ethylene urea (2-imidazolidone) with a mixture of nitric and sulphuric acids. (According to Schweitzer [18], ethylene urea is obtainable either by the action of urea on ethylenediamine at 110°C (initially) to 240-250°C (finally) in quantitative yield or by the action of urea on ethylene glycol at 160-240°C in 55% yield. W. E. Bachmann et al. [19] prepared ethylene urea by the action of ethyl carbonate on ethylenediamine in approximately 60% yield.) Hydrolysis of the dinitroethy-lene urea so formed gives ethylenedinitramine. Bachmann recommends nitration with mixed nitric acid and acetic anhydride  

Dinitroethylene urea is highly unstable and readily hydrolysable by heating in water. 

Another method of preparing ethylenedinitramine (also by Franchimont and Klobbie [17]), involves the action of chloroformate on ethylenediamine and nitration with nitric acid alone (98%). Bis-urethan after nitration is hydrolysed with ammonia solution (approximately 14%) at about 90°C  

CH2NH2 Cicooc2Hs CH2NH-COOC2Hs CH2N COOC2Hs ux nh3 CH2NHN02 

According to W. E. Bachmann et al. [19] the second of these methods gives a better yield (87% calculated in relation to the ethylenediamine used). 

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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). 

Br.(02NN)CH2.CH2(NN02).CH3, mw 243.04, N 23.06%, OB to C02 —29.6%, pale yellow cryst, mp 118—19° (decompn) sol in acet. Prepn from N-methyl-ethylenedinitramine dissolved in aq KOH by adding liq bromine drop-wise with stirring. Yield of w-washed ppt is 90%. Explosion temp is above 360°. Power is 101.2% (TNT=100%). Sensitivity to initiation is 6.6cm... 

N-Methyl-N -f2-Nitroxy ethyl) Ethylene Dinitra-mine. See 1 -Methyl-N -(2-Nitroxyethyl)-ethylenedinitramine in Vol 5, D1377-R... 

Octyl. Brit designation for Bitetryl or Ditetryl, described as l,2-Bis(2 >4, 6 -trinitronitranilino)-ethane in Vol 2, B131-R and Vol 5, D1513-L. Urbanskl (ReO describes It as Hexanitrodiphenyl-ethylenedinitramine... 

Henkin, Stability of Ethylenedinitramine (Hale-ite) and Related Nitramines , OSRD 1743 (Aug 1943), 25 4) A.T. Bloomquist, Certain... 

The chemical properties of primary and secondary nitramines are important in relation to their use as explosives. Primary nitramines contain acidic hydrogen in the form of —N//NO2 and, consequently, in the presence of moisture, primary nitramines corrode metals and form metal salts, some of which are primary explosives. This is one reason why powerful explosives like methyinitramine (1) have not found practical use. Ethylenedinitramine (EDNA) (2) suffers from similar problems but its high brisance (VOD 8240 m/s, d = 1.66 g/cm ) and low sensitivity to impact have seen it used for some applications. 

Nitric acid-acetic anhydride reagent has been used to synthesize N,N -Amitro-N,N -ethylenebisacetamide (58) from A, A -ethylenebisacetamide (57) the former is a secondary high explosive and a precursor to the powerful explosive ethylenedinitramine (Section 5.10). It is interesting to note that (58) is not formed when (57) is treated with nitric acid alone or with strong mixed acid. 

A,A -Dinitro-2-imidazolidone (67), a precursor to ethylenedinitramine (EDNA), is synthe-... 

Figure 5.71 Synthetic routes to ethylenedinitramine (EDNA) via nitramide hydrolysis...

The facile hydrolysis of A, A -dinitro-2-imidazolidone to ethylenedinitramine (EDNA) shows that A, A -dinitroureas can be useful precursors to linear dinitramines. Cyclic N,N -dinitroureas can be prepared indirectly from nitroguanidine. Nitroguanidine is found to... 

McKay and co-workers " " prepared a number of cyclic iV, M-dinitroureas via the ni-troguanidine route hydrolysis to the parent linear dinitramines was effected with boiling water or aqueous sodium hydroxide. This route was used to synthesize ethylenedinitramine (2), l,2-dinitraminopropane(176), l,3-dinitraminopropane(174), l,3-dinitraminobutane(177) and 1,4-dinitraminobutane (175). 

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. 

Ethylenedinitramine (EDNA) (2) condenses with ammonia in the presence of formaldehyde to form the triazacycloheptane bicycle (193). ° The chemistry of the bicycle (193) is very diverse and is only partly summarized in this discussion. ... 

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... 

The condensation of ethylenedinitramine (2) with paraformaldehyde in the presence of sulfuric acid at subambient temperature yields lV,Al -dinitroimidazolidine (88). ... 

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. 

Haleite. See Ethylenedinitramine under Ethy-lenediamine and Derivatives in Vol 6 of Encycl, p E238-R... 

WWII. Ethylenedinitramine, EDNA or Haleite, first prepd in 1887 by Franchimont Klobbie and developed in 1935 as a military explosive by G.C. Hale, was standardized during WWII as a component of EDNATOL (EDNA+TNT) serving as bursting charge for bombs and shells (Ref 70, pp 131-R and 154). See also Vol 6 of Encycl, pp E238ff... 

Hydroxyalkyl Alkylene Dinitramines and Their Nitrate Esters. Nitrate esters such as N,N -bis-(2-nitroxyethyl) ethylenedinitramine. 

NO-C2 H4-N(N02 >C2H4-N(N02 >C2 H4 -ono2 (qv) were proposed as non-volatile plasticizers for NC in prepn of propellants. The method of prepn consists of the hydroxyalkylation of a nitramine (such as ethylenedinitramine) by means of an alkylene oxide (such as ethylene oxide), followed by nitration ... 

N-Ethanolnitrate-N -methyl-ethylenedinitramine, called in Canad paper 1-Nitroxy-3,6-dinitro-3,6-dioza heptane,... 

When lOg of dinitrocompd was stirred with 27ml of coned Amm hydroxide, the EDNA (Ethylenedinitramine)was obtd in 91% yield Refs 1) Beil, not found 2) W.E. Bachmann et al, JACS 72, 3133(1950) CA 44, 10656(1950)... 

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)... 

These inferences concerning the structure of nitramines, based on their chemical properties, are confirmed by the data obtained by X-ray analysis of the simple nitramines dimethylnitramine and ethylenedinitramine. In particular, Costain and Cox [1], and Llewellyn and Whitmore [2], established that the grouping... 

R. N. Jones and Thom [3] adduce the two following typical absorption curves for nitramines a primary — ethylenedinitramine — Fig. 2 and a secondary — 2,5-dinitro-2,5-diazahexane (according to R. N. Jones and Thom) — Fig. 3. They have also been investigated by Baly and Desch [4], Franchimont and Backer [5], Carmack and Leavitt [6] and Corey, Dekker, Malmberg, Le Rosen, and Schroeder [7]. 

Fig. 2. Spectrum of typical primary nitr-amine (ethylenedinitramine), according to R. N. Jones and Thom [3].

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