Ethyl nitrate, 2-nitro

Nitromethoxymethoxymethyl Nitrate (Nitro-nitroxymethylol). C N.CH O.CHj.O.CHj.O.NOi, mw 182.1, N 15.38%, OB to C02 -17.6%, oily liq, bp 88—89° at 9mm. Usually present in the products of nitration of symm-dichlorom ethyl ether in the prepn of nitromethoxymethyl nitrate (see below), from which it can be sepd by fractional distn in vac at about 90°. It is a powerful expl, Houben and Pfankuch (Ref 2) reported that when they attempted the vac distn at 110°, violent expln occurred Refs 1) Beil 1, [649] 2) J. Houben E. 

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). 

Mixtures of sodium (or its alloy with potassium) and nitromethane, trichloroni-tromethane, nitrobenzene, dinitrobenzene, dinitronaphthalene, ethyl nitrite, ethyl nitrate or glyceryl nitrate are shock-sensitive, the sensitivity increasing with the number of nitro groups. 

Olsen and co-workers used a solution of nitronium tetrafluoroborate in acetonitrile for the V-nitration of acetamides and urethanes at —30°C. The following nitramides were obtained by this method V-nitroacetamide (13 %), V-nitro-2-chloroacetamide (55 %), V-nitro-n-butylacetamide (40 %), V-nitrobenzamide (53 %), ethyl V-nitro-n-butylcarbamate (91 %) and V-nitrosuccinimide (43 %). The low yield of V-nitroacetamide, a primary nitramide, is attributed to competing hydrolysis due to the release of tetrafluoroboric acid as the reaction progresses. The scope of the reaction is improved by moving to more basic solvents like ethyl acetate, 1,4-dioxane and trimethyl phosphate. ... 

N-ethyl nitro qninolones 6 E328 N-ethyl-6-nitro-2-quinolonium nitrate 6 E328 N-ethyl-5 (-6 or -7)-trinitro-2-quinolone 6 E329... 

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). 

Waldkotter, Rec 57,1294-1310(1938) Prepn and props of some explosive nitramines. such as N-(2,4,6-trinitrophenyl)-N-nitro- 3-amino-ethyl nitrate N-[4-chloro(or bromo)-2,6-dini-trophenyl]-N-nitro-/9-aminoethyI nitrate N-[5-chloro(or bromo)-2,4-dinitrophenyl]-N-nitro-p-aminoei nyl nitrate-, etc j)P. P. Shorygin et al.ZhObshKhim 8,986-90(1938)... 

Nitroethylene readily polymerizes to yield a white powder, insoluble in water and in most organic solvents. It may be obtained by direct action of bases on nitro-ethyl nitrate or -acetate or on dinitroethane. 

Indole with benzoyl nitrate at low temperatures gives 3-nitroindole this can also be obtained by reaction of the indolyl anion with ethyl nitrate. More vigorous conditions can be used for the nitration of 2-methylindole because of its resistance to acid-catalyzed polymerization. In nitric acid alone it is converted into the 3-nitro derivative, but in a mixture of concentrated nitric and sulfuric acids 2-methyl-5-nitroindole is formed, by conjugate acid nitration (see Section 3.3.3.2.1). 

Aminothiazole is converted by the action of ethyl nitrate into the 5-nitro derivative [352], As already mentioned 2-phenyloxazole and 2-phenylthiazole are nitrated into benzene ring by the sulfuric-nitric acid mixture. At the same time their nitration under conditions excluding protonation of the azole ring (with the use of acetylnitrate or /V-nitropicolinium tetrafluoroborate as nitrating agent) leads to the 5-nitro derivatives [353] (Scheme 40). 

N-Nitro-N -ethylurea, C2Hs.NH.C0.NH.N02 mw 133-11, N 31.60% hygr ndls (eth), mp 133-34° sol in eth. Prepd by reacting die parent with.ethyl nitrate in coned sulfuric acid at —5°... 

For example, dropping a mixture of benzyl cyanide and methyl or ethyl nitrate into a cooled alkoxide solution leads to an 80% yield of 2- a-nitro-2-phenylacetonitrile, which gives phenylnitromethane on hydrolysis and decarboxylation.155,156 Ethyl phenylacetate also gives phenylnitromethane analogously and in the same yield.157 Further examples are described by Wislicenus and Wren.158 Wieland et al.159 have converted cyclohexane by this method into the potassium salt of 2-aa-nitrocyclohexanone in about 40% yield, and cyclo-pentanone almost quantitatively into the dipotassium salt of 2,5-di-fla-nitrocyclopentanone. 

Priamary aliphatic nitramines can also obtained by converting the amine by butyllithium into its lithium salt and nitrating this with ethyl nitrate. A-Nitro-methylamine and -teA-butylamine, for example, have been prepared by this method.230... 

In taking up a more detailed study of nitration, the general methods of preparing nitro compounds may first be mentioned. The usual methods involve the action of nitric acid alone, or in the presence of sulfuric acid, or of water, or of a non-ionizing medium such as ether. Other methods involve the use of ethyl nitrate or of nitrosulfates (NO2.OSO2.OII), nitroacetates (or acetyl nitrate), etc. For methods used in isolated cases reference must be made to the books of Weyl, Lassar-Cohn, and others. 

Nitro compounds may be obtained by the action of ethyl nitrate and aluminium chloride. Since many of the Friedel-Crafts reactions may be carried out with sulfuric acid in place of aluminium chloride, and since in nitration with nitric acid, sulfuric acid is very often used, the fact is brought out again that nitration belongs to the same general type of reaction as the Friedel-Crafts reaction. This similarity may be brought out in the following manner. The reaction... 

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