practically unlimited quantities, the first
nitroparaffins are produced:nitromethane, nitroethane, l-nitropropane, and 2-nitropropane.The nitrationof any of the volatile higher or lower homologs of the paraffinic or naphthenicseries can be accomplished by the same general procedure. From our mostinexpensive organic raw materials it is thus possible to obtain nitro derivativesby the action of the acid which the researches of Haber and Ostwald have placedamong our most available and cheapest inorganic reagents.
is thereforean appropriate time to review’ the syntheses, properties, uses, and reactionsof the nitroparaffins and their immediate derivatives.
REACTIONIn 1872 Meyer and Stuber (271) reported that the reaction between amyliodide and silver nitrite had yielded nitropentane and amyl nitrite. At thattime the aromatic nitro derivatives were already of substantial importance,since Mauvein had been made by Perkin sixteen years before and the anilinedye industry was in active development.
is not surprising, therefore, thatthis first synthesis of
nitroparaffin2 should have aroused general interest andresulted in the publication
a considerable number of papers. The VictorMeyer reaction has been reviewed and extended by Reynolds and Adkins (329),
that no detailed discussion need be given here.
should be mentioned, how-ever, that it has been found suitable for producing not only nitroparaffins butalso polynitroparaffins
nitroethers,nitroketones, and many other aliphatic nitro compounds.Salts of a-halocarboxylic acids react similarly even with sodium nitrite andyield salts of a-nitrocarboxylic acids which readily decompose, producing nitro-paraffins and metallic bicarbonates. Kolbe (202) reported this reaction onlyfive months after hleyer and Stiiber’s first announcement of the nitroparaffins?The reasons for the wide differences between the ratios of organic nitrite andnitro derivative obtained from various organic halides and metallic nitrites arestill obscure. Reynolds and Adkins have postulated that an addition complexis formed between the two reagents and that every constituent of the complex
thus in a position to influence the further course of the reaction to yield eithernitrite
is probably of significance that nitrites readilyrearrange
nitro derivatives at elevated temperatures (287). The yield maytherefore fluctuate with the amount of local overheating.
Thusmethylamine, ethylamine, tert-butylamine, and benzylamine have been oxidized
the corresponding nitro compounds. Bamberger and Seligman (18) give thefollowing equations
the very extensive literature, the present article is by no means exhaustive.
Chloropicrin and bromopicrin had been made much earlier (365, 366).
a recommended laboratory procedure, see
A primary amine may be oxidized directly to a nitroparaffin.
Brief reviews of this general nature have recently appeared by Hurd
the limitations of time and space and