Solutions of nitric acid in organic solvents

This reaction showed certain characteristics which distinguish it from nitrations in solutions of nitric acid in organic solvents. Thus, in changing the solvent from carbon tetrachloride to nitromethane, the rate increased by a factor of only 6, whereas nitration involving the nitronium ion was accelerated by a factor of about 30 when the solvent was changed from acetic acid to nitromethane. It was held that the... 

Olah and his co-workers compared the behaviour of nitronium salts in competitive nitrations with the behaviour of other nitrating systems. The results are given in table 4.1, columns (a)-(j), and also in table 4.2. The results obtained from competitive nitrations using solutions of nitric acid in organic solvents (table 4.1, columns (6)-(e)) are in line with those obtained by earlier workers. The evidence that in nitromethane,... 

Application of kinetic studies to elucidate the structure of nitrating mixtures Nitric acid and sulphuric dioxide Nitric acid and fluorine compounds Nitric acid and perchloric acid Nitric acid and acetic acid or anhydride Nitric acid and acetic acid Nitric acid and acetic anhydride Solutions of nitric acid in organic solvents Nitric acid salts in mixture with other acids Metal nitrates in the presence of Fricdcl-Crafts catalysts Literature... 

Recent experiments have shown that the concentration of aromatic compound needed to maintain zeroth-order kinetics (see below) was much greater than for nitrations with solutions of nitric acid in some inert organic solvents reactions which were first order in the concentration of the aromatic were obtained when [ArH] < c. 2 x io mol 1 . ... 

Nitrations of the zeroth order are maintained with much greater difficulty in solutions of acetyl nitrate in acetic anhydride than in solutions of nitric acid in inert organic solvents, as has already been mentioned. Thus, in the former solutions, the rates of nitration of mesi-tylene deviated towards a dependence on the first power of its concentration when this was < c. o-05-o-i mol 1 , whereas in nitration with nitric acid in sulpholan, zeroth-order kinetics could be observed in solutions containing as little as 10 mol 1 of mesitylene ( 3.2.1). 

The observation of nitration at a rate independent of the concentration and nature of the aromatic excludes AcONOa as the reactive species. The fact that zeroth-order rates in these solutions are so much faster than in solutions of nitric acid in inert organic solvents, and the fact that HNO3 and H2NO3+ are ineffective in nitration even when they are present in fairly lai e concentrations, excludes the operation of either of these species in solutions of acetyl nitrate in acetic anhydride. 

The existence of the nitronium ion in sulfuric-nitric acid mixtures was demonstrated both by cryoscopic measurements and by spectroscopy. An increase in the strong acid concentration increases the rate of reaction by shifting the equilibrium of step 1 to the right. Addition of a nitrate salt has the opposite effect by suppressing the preequilibrium dissociation of nitric acid. It is possible to prepare crystalline salts of nitronium ions, such as nitronium tetrafluoroborate. Solutions of these salts in organic solvents rapidly nitrate aromatic compounds. ... 

The question of what other species can be the active electrophile in nitration arises in the case of nitration using solutions of nitric acid in acetic anhydride. The solutions are very potent nitrating mixtures and effect nitrations at higher rates than solutions of nitric acid in inert organic solvents. Acetyl nitrate is formed in such solutions, and mty be the actual nitrating agent. 

The above statement concerning the effectiveness of the nitronium ion over a wide range of conditions has not always been accepted and, until recently, some workers held that the nitronium ion was not the effective electrophile in solutions of nitric acid in aqueous acids and organic solvents. It is unnecessary now to go into these arguments since the subject has been covered in a number of recent reviews (Ridd, 1971a Hoggett et al., 1971 Stock, 1976), and the... 

As outlined above (p. 3), a reaction can be subject to microscopic diffusion control only if one of the reactive intermediates is formed from an inactive precursor in the reaction mixture. There are two sets of conditions which have provided evidence for microscopic diffusion control in nitration. One concerns solutions of nitric acid in aqueous mineral acids or organic solvents for, in most of these solutions, the stoicheiometric nitric acid is mainly present as the molecular species in equilibrium with a very small concentration of nitronium ions. A reaction between a substrate and a nitronium ion from this equilibrium concentration can, in principle, be subject to microscopic diffusion control. The other set of conditions is when the substrate is mainly present as the protonated form SH+ but when reaction occurs through a very small concentration of the neutral base S. A reaction between the neutral base and a nitronium ion can then, in principle, be subject to microscopic diffusion control even if the nitronium ions are the bulk component of the HN03/N0 equilibrium. In considering the evidence for microscopic diffusion control it is convenient to consider separately the reactions of those species involved in prototopic equilibria. 

For laboratory experiments and sometimes in industry more expensive nitrating agents may be used, as for example solutions of nitric acid in inert organic solvents (chloroform, carbon tetrachloride, ether, nitromethane, etc.), or a solution of nitric acid in phosphoric or acetic acids or in acetic anhydride. The use of these nitrating agents may be of some practical value and will be discussed later on in detail. 

Nitric acid in organic solvents does not produce the 1050 and 1400 cm 1 lines. On examination of absorption spectra in the infra-red, the conclusion has been drawn that nitric acid in chloroform or carbon tetrachloride solutions is less associated than when in a sulphuric acid solution (Dalmon [8,9,49]). 

Until the 1960s, the nitration of aromatic compounds by solutions of nitric acid in sulfuric acid or other mineral acids, as well as in organic solvents, was confidently discussed in terms of the attack by the nitro-nium ion, N02+. Support for this hypothesis came from spectroscopy, cryoscopic measurements, and the comparison between the rate of nitration and the rate of lsO exchange between nitric acid and the media. Accordingly the generally accepted mechanism of aromatic nitration involved the steps outlined in Equations (3.1)—(3.4). Depending on the conditions and the aromatic substrate, either of... 

The solutions are very potent nitrating mixtures and effect nitrations at higher rates than solutions of nitric acid in inert organic solvents. 

THE STATE OF NITRIC ACID IN INERT ORGANIC SOLVENTS The absence of ions in mixtures of acetic acid and nitric acid is shown by their poor electrical conductivity and the Raman spectra of solutions in acetic acid, nitromethane, and chloroform show only the absorptions of the solvent and molecular nitric acid the bands corresponding to the nitronium and nitrate ions cannot be detected. -... 

The more strongly acidic a solution of nitric acid at a given concentration is in a particular organic solvent, the more readily should that solvent support zeroth-order nitration. The values of for solutions of sulphuric acid in nitromethane, sulpholan, and acetic acid show clearly the superiority of nitromethane in this respect. ... 

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