Ethyl nitrate, reaction

Kakesu, M., H. Bandow, N. Takenaka, Y. Maeda, and N. Washida, Kinetic Measurements of Methyl and Ethyl Nitrate Reactions with OH Radicals, Int. J. Chem. Kinet., 29, 933-941 (1997). 

Furan-2-carbonyl chloride, 5-alkyl-3,4-dichloro-synthesis, 4, 690 Furancarboxamides rotational isomerism, 4, 543 Furan-2-carboxylic acid, 5-acetylamino-ethyl ester reactions, 4, 647 Furan-2-carboxylic acid, amino-properties, 4, 708 Furan-2-carboxylic acid, 5-bromo-nitration, 4, 603, 711 Furan-2-carboxylic acid, 3-methyl-methyl ester bromination, 4, 604 Furan-2-carboxylic acid, 5-methyl-nitration, 4, 602... 

A number of other gases can undergo reactions that produce decomposition flames—for instance, ethylene, ethylene oxide, methyl nitrate, ethyl nitrate, and hydrazine (CCPS 1993). 

The reaction of ethyl nitrate with the indole Grignard reagent is discussed... 

Step (2) is supported by the observed slowing down of the initial decompn stages when N02 is added. It is also supported by Levy s studies of the decompn of ethyl nitrate (Ref 15b). At the higher temps, steps (3) and (4) remove both RCH20 and N02 so rapidly that there is essentially no back reaction (step 2). Thus the reaction is first order (step 1) over its entire course. It would appear steps (3) and (4) are heterogenous reactions (at least at lower temps) that are favored by the combination of added surface and increased pressure (upper dashed line in Fig 13). The reacceleration... 

Alcohols form esters from inorganic acids as shown above. Like all esterifications, these reactions are reversible that is, in the presence of water and the right conditions, they revert to the original alcohol and acid. Nitrate esters are mainly used as explosives, but some have found use as diesel fuel additives. Note the difference between a nitrate ester such as ethyl nitrate (C2H5ONO2) and an organic nitro compound such as nitroethane (C2H5NO2). 

When alkyl nitrates and in particular methyl and ethyl nitrates are added to acids (H2SO4, SnCl4, BF3) they give rise to a very violent reaction with the formation of large quantities of gas. The presence of impurities, nitrogen oxid, transition metal oxides increases the sensitivity of these mixtures to detonation. 

Ethyl formate34,52 or orthoformate5 3,54 reacts with two equivalents of phenylhydrazine to yield 1,5-diphenylformazan (11) the reaction takes place under acidic conditions and involves an oxidation. Under basic conditions, ethyl nitrate reacts at the methylene position to yield 3-methyl-1,5-diphenylformazan (37) which can also be obtained from the reaction of phenyl-azoethane (38) with isoamyl nitrite (Scheme 4).8,68 Aryl hydrazines react with a variety of s-triazines (39) to yield 1,5-diaryl formazans with hydrogen, methyl, or phenyl groups in the 3-position as in 40 (Eq. 6).56 Hydrazines have also been reported to react with benzotrichloride55,658 and sym-diamino tetrazine659 to yield formazans. 

Houser and Lee [J. Phys. Chem., 71 (3422), 1967] have studied the pyrolysis of ethyl nitrate using a stirred flow reactor. They iiave proposed the following mechanism for the reaction. 

Table 11 Reaction of ethyl nitrate with 4-amino-1,2,4-triazole derivatives (Equation 31)...

A chain reaction was proposed for the pyrolysis of ethyl nitrate Houser Lee ( J Phys Chem 1 3422, 1967) ... 

In a round-bottomed flask (capacity 0-5 1.) 8 g. of sodium are dissolved in 120 c.c. of absolute alcohol. Into the solution, which is kept cool in water (precipitation of ethoxide is not detrimental) a mixture of 36 g. of benzyl cyanide (p. 137) and 32 g. of ethyl nitrate (p. 148) is poured in small portions. The salt formulated above separates gradually in the shape of almost colourless crystals. In order to allow the reaction to proceed to completion, the flask is left for one hour without cooling, but with exclusion of moisture the precipitate is then collected at the pump and subsequently washed first with alcohol-ether (1 1) and then with ether alone. Yield 40-45 g. 

Condensations with alkyl nitrites and nitrates, however, are not so generally applicable as the true ethyl acetoacetate reaction, and the possibility is not excluded that they proceed in another way compounds with mobile hydrogen might first he added to the inorganic part of the ester by means of an aldol condensation. The fact that fluorene, which contains no active double bond at all, combines with ethyl nitrate (as well as with ethyl oxalate) and sodium ethoxide in the same way, yielding oci-nitrofluorene, seems to support this second theory (W. Wislicenus). 

Angeli pioneered the concept of nucleophilic amine nitration by A-nitrating aniline with ethyl nitrate in the presence of potassium or sodium metal. In this reaction a complex anion... 

Acetone cyanohydrin nitrate will not nitrate amines with branching on the carbon a to the nitrate group. For these substrates the use of ethyl nitrate and lithium bases is favoured. a-Aminonitriles are frequently observed as impurities under the reaction conditions because of the slow decomposition of acetone cyanohydrin nitrate to hydrogen cyanide and acetone. The need for an excess of amine during these reactions is wasteful and only practical if this component is cheap and widely available. Other cyanohydrin nitrates are less efficient N-nitrating agents. ... 

Ellis and coworkers studied the effect of lead oxide on the thermal decomposition of ethyl nitrate vapor.P l They proposed that the surface provided by the presence of a small amount of PbO particles could retard the burning rate due to the quenching of radicals. However, the presence of a copper surface accelerates the thermal decomposition of ethyl nitrate, and the rate of the decomposition process is controlled by a reaction step involving the NO2 molecule. Hoare and coworkers studied the inhibitory effect of lead oxide on hydrocarbon oxidation in a vessel coated with a thin fQm of PbO.P l They suggested that the process of aldehyde oxidation by the PbO played an important role. A similar result was found in that lead oxide acts as a powerful inhibitor in suppressing cool flames and low-temperature ignitions.P l... 

Reaction with ethanol produces ethyl nitrate ... 

It has been shown by many investigators that gas-phase reactions of nitrate esters are affected by the addition of lead compounds. Adams and coworkers studied the gaseous combustion zone of ethyl nitrate.ps] The flame temperature of the ethyl nitrate was found to be reduced by the addition of 0.1-1.0% by mass of lead tetram-ethyl. The results are shown in Table 6.7. 

This reaction gives the volatile by-products ethyl nitrate, ethyl nitrite and acetic acid, NO, N02 and C02. 

Tetranitro-l -dimetboxybipbenyl, exists in two forms lower-melting crysts (from acet or ale), mp 179° higher-melting crysts, mp 191°, which are mutually interconvertible was prepd by reaction of 2,2 -dimethoxybiphenyl ethyl nitrate in coned. H2SO4 below 0° or by reaction of 3,5,3 l,5 -tetranitro-2,2 -dihydroxybiphenyl diazomethane in eth acet (Ref 1, 4, 5, 6, 8j 10 11). Other methods of prepn props are given in the above Refs... 

As long ago as 1896 Walther [43] observed that as the result of chemical reaction between ethyl nitrate and phenylhydrazine at an elevated temperature, aniline, ammonium nitrate and nitrogen are formed. If the reaction takes place in the presence of sodium ethoxide then, according to Bamberger and Billeter [44] even at room temperature nitrite ions, nitrogen, benzene, phenyl azide, azobenzene, nitrobenzene, aniline, acetic acid and acetaldehyde are formed. 

Merrow and van Dolah also established that during the hydrolysis of / -chloro-ethyl nitrate, l,3-dichloro-2-propyl nitrate, glycerol trinitrate or glycol dinitrate the gaseous products are evolved more vigorously than during the reaction of unsubstituted aliphatic nitrates. 

The above reaction scheme between nitric esters and hydrazine or its derivatives is confirmed by the reaction of methylhydrazine and ethyl nitrate which yield methane (not ethane) and nitrogen. This indicates that the unstable monomethyl-di-imid should have been an intermediate product ... 

In the presence of nitrogen oxides, ethyl alcohol is readily oxidized to acetaldehyde and this chemical change can upset the nitration reaction, if the add contains appreciable amounts of nitrogen dioxide. 

Trinitrohydroxyethylbenzene nitrate or trinitrophenyl-/J-ethyl nitrate, melting at 83°C, is obtained from trinitrotoluene, that undergoes an addition reaction with formaldehyde in an alkaline medium to produce the corresponding alcohol (m.p. 112°C), which is then nitrated (Vender [87]) ... 

Carbazoles normally react with electrophiles to yield the 3-monosubstituted and 3,6-disubstituted derivatives. Further reaction may occur at the 1- and the 8-positions. There is evidence that the initial reaction occurs at the 9-position. Thus, nitrosation of carbazole with sodium nitrite in acetic acid yields 9-nitrosocarbazole which, when treated with nitric acid, is converted into 3-nitrocarbazole (09CB3797) and 3,6-dinitrocarbazoIe (46USP2392067). Direct nitration of carbazole with nitric acid (02GEP128853) or with ethyl nitrate also yields the 3-nitro and 3,6-dinitro derivatives, together with 1,3,6,8-tetranitrocarbazole (27CB738). 

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