Nitroethyl nitrate

If ethylene is treated with nitrating acid, nitroethyl nitrate, N02.CH2.CH20N02 is produced, as has already been mentioned. The nitroethyl alcohol which is first formed by addition of nitric acid is fixed by esterification, whereas the addition compound with HNOs which is first formed at the double bond of benzene is decomposed with elimination of H20 for reasons which have been mentioned repeatedly. This case is therefore analogous to the reactions of bromine with ethylene and with benzene (p. 106). 

In a quite analogous way ethylene reacts with nitric-sulphuric acid, nitroethyl nitrate (p. 164) being produced. How are alkyl sulphonic... 

Kekule Oil. A liq expl (d=l ATglee) prepd in 1869 by passing ethylene gas into mixed nitric-sulfuric acid. The oil consisted of a mixt (about 50/50) of Nitroglycol, CH2(0N02)-CH2(0N02), and beta-Nitroethyl Nitrate, CH2(0N02)CH2N02... 

EthanoJ,2-Nitronitrate 2-Nitroethanol Nitrate l-Nitroxy-2-nitroethane or 9-Nitroethyl Nitrate,... 

On distilling Kekule oil in steam and in vacuum were obtd Nitroglycol, bp 105° at 19mm and / -Nitroethyl Nitrate, bp 120—122° at 17mm... 

This 2nd reaction, in which a 3rd mole of nitric acid drives out the nitrous acid, explains the rather high content of nitrogen oxides in the spent acid. This mixture of 40—50% Nitroethyl Nitrate 40—50% Nitro-glycol is known as Kekule Oil . As its N content is up to 19 5% which is even higher... 

A simple method of separating NGc from Kekule Oil was described in GerP 384107 of 1923. Here the oil was slowly distilled with steam or better digested with w at 80—90°, until the Nitroethyl Nitrate it contained was almost completely converted into products sol in w. 

The undissolved portion was separated and neutralized. It consisted of almost pure NGc. From 100 parts of crude oil about 40 parts of NGc were obtd. The economy of the process depended upon a cheap source of ethylene and upon the possibility of recovering valuable by-products from the destroyed Nitroethyl Nitrate (Ref 7, pp 220—22)... 

Fifty to sixty per cent of ethylene reacts in accordance with eqn. (4), and 40-50% in accordance with eqn. (5). Numerous attempts to use an oil comprising a mixture of (I) and (II) in the manufacture of explosives have been unsuccessful, because jS-nitroethyl alcohol nitrate is insufficiently stable. Experiments have been made to partially hydrolyse the oil with hot water at 80-90°C. Under these conditions nitroethyl nitrate undergoes decomposition, whereas nitroglycol remains unchanged (Oehme [25]). However, the method was not adopted in practice because the yield of nitroglycol is relatively low, i.e. about 40% by weight of the oily product. 

A considerable amount of nitrous acid is present in the spent acid. /J-Nitroethyl nitrate is feebly acidic and dissolves in dilute alkali solutions with a yellow color. It is not sufficiently stable for use in commercial explosives. On digestion with warm water or on slow distillation with steam it undergoes a decomposition or sort of hydrolysis whereby nitrous acid and other materials are produced. Numerous patents have been issued for processes of procuring pure nitroglycol from the Kekule oil. One hundred parts of the last-named material yield about 40 parts of nitroglycol, and the economic success of the Process depends upon the recovery of valuable by-products from the 0-nitroethyl nitrate which is destroyed. ... 

Nitrogen dioxide and oxirane in chloroform at 0-20° give an almost quantitative yield of 2-nitroethyl nitrate, which can be hydrolysed to 2-nitroethanol by 10% sodium carbonate solution at 35-45°.1115 The latter product can also be obtained in 85% yield directly by allowing oxirane and carbon dioxide to react with aqueous sodium nitrite solution at 25-300.1116... 

---