Acetyl nitrate

The effect of aromatic substrates on the formation of N02" is shown in the considerably increased substrate selectivity over that obtained with NO2+ salts. On the basis of the experimental data it is suggested that in these nitrations a weaker nitrating species than NO2+ must be involved in the primary interaction with the aromatic substrates. This incipient nitronium ion then attaches itself to the aromatics in a step giving high substrate selectivity. Whether the incipient nitronium ion is the nitracidium ion (H2NO3+), protonated acetyl nitrate (CH3COO—HN02 ) or probably a transition state of any of those unstable species to N02, in which water is loosened, but not yet completely eliminated, is difficult to say and no direct physical evidence is available. 

Another reason for discussing the mechanism of nitration in these media separately from that in inert organic solvents is that, as indicated above, the nature of the electrophile is not established, and has been the subject of controversy. The cases for the involvement of acetyl nitrate, protonated acetyl nitrate, dinitrogen pentoxide and the nitronium ion have been advocated. 

Because of the chemical similarity between benzoyl nitrate and the acetyl nitrate which is formed in solutions of nitric acid in acetic anhydride, it is tempting to draw analogies between the mechanisms of nitration in such solutions and in solutions of benzoyl nitrate in carbon tetrachloride. Similarities do exist, such as the production by these reagents of higher proportions of o-substituted products from some substrates than are produced by nitronium ions, as already mentioned and further discussed below. Further, in solutions in carbon tetrachloride of acetyl nitrate or benzoyl nitrate, the addition of acetic anhydride and benzoic anhydride respectively reduces the rate of reaction, implying that dinitrogen pentoxide may also be involved in nitration in acetic anhydride. However, for solutions in which acetic anhydride is also the solvent, the analogy should be drawn with caution, for in many ways the conditions are not comparable. Thus, carbon tetrachloride is a non-polar solvent, in which, as has been shown above,... 

Vandoni and Viala examined the vapour pressures of mixtures of nitric acid in acetic anhydride, and concluded that from o to mole-fraction of nitric acid the solution consisted of acetyl nitrate, acetic acid and excess anhydride in equimolar proportions the solution consisted of acetyl nitrate and acetic acid, and on increasing the fraction of nitric acid, dinitrogen pentoxide is formed, with a concentration which increases with the concomitant decrease in the concentration of acetyl nitrate. 

When acetic anhydride was in excess over nitric acid, acetyl nitrate and acetic acid were the only products. When the concentration of nitric acid was greater than 90 moles %, dinitrogen pentoxide, present as (N02+)(N0a ), was the major product and there were only small traces of acetyl nitrate. With lower concentrations of nitric acid the products were acetic acid, acetyl nitrate and dinitrogen pentoxide, the latter species being present as covalent molecules in this organic medium. A mixture of z moles of nitric acid and i mole of acetic anhydride has the same Raman spectrum as a solution of i mole of dinitrogen pentoxide in 2 moles of acetic acid. 

Evidence from the viscosities, densities, refractive indices and measurements of the vapour pressure of these mixtures also supports the above conclusions. Acetyl nitrate has been prepared from a mixture of acetic anhydride and dinitrogen pentoxide, and characterised, showing that the equilibria discussed do lead to the formation of that compound. The initial reaction between nitric acid and acetic anhydride is rapid at room temperature nitric acid (0-05 mol 1 ) is reported to be converted into acetyl nitrate with a half-life of about i minute. This observation is consistent with the results of some preparative experiments, in which it was found that nitric acid could be precipitated quantitatively with urea from solutions of it in acetic anhydride at —10 °C, whereas similar solutions prepared at room temperature and cooled rapidly to — 10 °C yielded only a part of their nitric acid ( 5.3.2). The following equilibrium has been investigated in detail ... 

The equilibrium constant K, the rate constants and and the dependences of all these quantities on temperature were determined. In the absence of added acetic acid, the conversion of nitric acid into acetyl nitrate is almost quantitative. Therefore, to obtain at equilibrium a concentration of free nitric acid sufficiently high for accurate analysis, media were studied which contained appreciable concentrations (c. 4 mol 1 ) of acetic acid. 

The mixture was prepared and allowed to achieve equilibrium to it was added an excess of urea which caused the immediate precipitation as urea nitrate of the free nitric acid present. As a result of the sudden removal of the nitric acid from the mixture, the system underwent change to re-establish the equilibrium however, the use of an excess of urea removed the nitric acid as it was produced from acetyl nitrate and acetic acid, and the consumption of acetyl nitrate proceeded to completion. Thus, by following the production of urea nitrate with the time from the addition of urea, the rate of the back reaction could be determined, and by extrapolating the results to zero time the equilibrium... 

In addition to the initial reaction between nitric acid and acetic anhydride, subsequent changes lead to the quantitative formation of tetranitromethane in an equimolar mixture of nitric acid and acetic anhydride this reaction was half completed in 1-2 days. An investigation of the kinetics of this reaction showed it to have an induction period of 2-3 h for the solutions examined ([acetyl nitrate] = 0-7 mol 1 ), after which the rate adopted a form approximately of the first order with a half-life of about a day, close to that observed in the preparative experiment mentioned. In confirmation of this, recent workers have found the half-life of a solution at 25 °C of 0-05 mol 1 of nitric acid to be about 2 days. ... 

TABLE 5.2 Nitrations of mono-substituted derivatives of benzene in solutions of acetyl nitrate in acetic anhydride ... 

Certain features of the addition of acetyl nitrate to olefins in acetic anhydride may be relevant to the mechanism of aromatic nitration by this reagent. The rapid reaction results in predominantly cw-addition to yield a mixture of the y -nitro-acetate and y5-nitro-nitrate. The reaction was facilitated by the addition of sulphuric acid, in which case the 3rield of / -nitro-nitrate was reduced, whereas the addition of sodium nitrate favoured the formation of this compound over that of the acetate. As already mentioned ( 5.3. i), a solution of nitric acid (c. i 6 mol 1 ) in acetic anhydride prepared at — 10 °C would yield 95-97 % of the nitric acid by precipitation with urea, whereas from a similar solution prepared at 20-25 °C and cooled rapidly to —10 °C only 30% of the acid could be recovered. The difference between these values was attributed to the formation of acetyl nitrate. A solution prepared at room... 

Protonated acetyl nitrate and, to a smaller extent, acetyl nitrate were... 

The authors of this work were concerned chiefly with additions to alkenes, and evidence about the mechanism of aromatic nitration arises by analogy. Certain aspects of their work have been repeated to investigate whether the nitration of aromatic compounds shows the same phenomena ( 5-3-6). It was shown that solutions of acetyl nitrate in acetic anhydride were more powerful nitrating media for anisole and biphenyl than the corresponding solutions of nitric acid in which acetyl nitrate had not been formed furthermore, it appeared that the formation of acetyl nitrate was faster when 95-98% nitric acid was used than when 70 % nitric acid was used. 

First-order nitrations. The kinetics of nitrations in solutions of acetyl nitrate in acetic anhydride were first investigated by Wibaut. He obtained evidence for a second-order rate law, but this was subsequently disproved. A more detailed study was made using benzene, toluene, chloro- and bromo-benzene. The rate of nitration of benzene was found to be of the first order in the concentration of aromatic and third order in the concentration of acetyl nitrate the latter conclusion disagrees with later work (see below). Nitration in solutions containing similar concentrations of acetyl nitrate in acetic acid was too slow to measure, but was accelerated slightly by the addition of more acetic anhydride. Similar solutions in carbon tetrachloride nitrated benzene too quickly, and the concentration of acetyl nitrate had to be reduced from 0-7 to o-i mol 1 to permit the observation of a rate similar to that which the more concentrated solution yields in acetic anhydride. 

The rates of nitration of benzene in solutions at 25 °C containing 0-4-2-0 mol 1 of acetyl nitrate in acetic anhydride have been deter-mined.2 The rates accord with the following kinetic law ... 

The nitric acid used in this work contained 10% of water, which introduced a considerable proportion of acetic acid into the medium. Further dilution of the solvent wnth acetic acid up to a concentration of 50 moles % had no effect on the rate, but the addition of yet more acetic acid decreased the rate, and in the absence of acetic anhydride there was no observed reaction. It was supposed from these results that the adventitious acetic acid would have no effect. The rate coefficients of the nitration diminished rapidly with time in one experiment the value of k was reduced by a factor of 2 in i h. Corrected values were obtained by extrapolation to zero time. The author ascribed the decrease to the conversion of acetyl nitrate into tetranitromethane, but this conversion cannot be the explanation because independent studies agree in concluding that it is too slow ( 5.3.1). 

Under these first-order conditions the rates of nitration of a number of compounds with acetyl nitrate in acetic anhydride have been determined. The data show that the rates of nitration of compounds bearing activating substituents reach a limit by analogy with the similar phenomenon shown in nitration in aqueous sulphuric and perchloric acids ( 2.5) and in solutions of nitric acid in sulpholan and nitro-methane ( 3.3), this limit has been taken to be the rate of encounter of the nitrating entity with the aromatic molecule. 

Zeroth-order nitrations. The rates of nitration at 25 °C in solutions of acetyl nitrate (6xio —0-22 mol 1 ) in acetic anhydride of 0- and jw-xylene, and anisole and mesitylene were independent of the concentration and nature of the aromatic compound provided that... 

The dependence of the zeroth-order rate constants on the concentration of acetyl nitrate is shown in fig. 5.1 in the absence of added acetic acid the rate increases according to the third power of the concentration of acetyl nitrate, but when acetic acid is added the dependence becomes... 

Fig. 5.1. Zeroth-order rates of nitration with acetyl nitrate compared with those for other systems, (a) HNOa/ sulpholan, (i) HNO3/CCI4, (c) AcONOj/AcjO/O % AcOH, (d) AcONOj/AcaO/O % AcOH/[mesitylene] = o-8 mol l-i,n (e) AcONOj/AcaO/ [AcOH] = 2-2moll-i,ii >(/)AcONOa/AcaO/[AcOH] = 1-96 mol l-i and (g) AcONOa/ AcaO/[AcOH] 3 9i mol l-i/[mesitylene] = o-8 mol 1-i H.

The results in fig. 5.1 show that zeroth-order rates of nitration in solutions of acetyl nitrate in acetic anhydride are much greater than the corresponding rates in solutions in inert organic solvents of nitric acid of the same stoichiometric concentration as that of acetyl nitrate. Thus, for corresponding concentrations of nitric acid and acetyl nitrate, nitration in acetic anhydride is e. 5 x 10 and 10 times faster than nitration in sulpholan and nitromethane respectively. This fact, and the fact that the fraction of free nitric acid in solutions of acetyl nitrate in acetic... 

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 the nature of the aromatic means only that the effective nitrating species is formed slowly in a step which does not involve the aromatic. The fact that the rates of zeroth-order nitration under comparable conditions in solutions of nitric acid in acetic acid, sulpholan and nitromethane differed by at most a factor of 50 indicated that the slow step in these three cases was the same, and that the solvents had no chemical involvement in this step. The dissimilarity in the rate between these three cases and nitration with acetyl nitrate in acetic anhydride argues against a common mechanism, and indeed it is not required from evidence about zeroth-order rates alone that in the latter solutions the slow step should involve the formation of the nitronium ion. 

Acetoxylation and nitration. It has already been mentioned that 0- and m-xylene are acetoxylated as well as nitrated by solutions of acetyl nitrate in acetic anhydride. This occurs with some other homologues of benzene, and with methyl phenethyl ether,ii but not with anisole, mesitylene or naphthalene. Results are given in table 5.4. 

The addition of sulphuric acid increased the rate of nitration of benzene, and under the influence of this additive the rate became proportional to the first powers of the concentrations of aromatic, acetyl nitrate and sulphuric acid. Sulphuric acid markedly catalysed the zeroth-order nitration and acetoxylation of o-xylene without affecting the kinetic form of the reaction. ... 

At 4-0 °C using a freshly prepared solution of nitric acid (0-14 mol 1 ) in acetic anhydride for 20 min under these conditions the half-life for the conversion of nitric acid into acetyl nitrate was 7 min. 

Despite the fact that solutions of acetyl nitrate prepared from purified nitric acid contained no detectable nitrous acid, the sensitivity of the rates of nitration of very reactive compounds to nitrous acid demonstrated in this work is so great that concentrations of nitrous acid below the detectable level could produce considerable catalytic effects. However, because the concentration of nitrous acid in these solutions is unknown the possibility cannot absolutely be excluded that the special mechanism is nitration by a relatively unreactive electrophile. Whatever the nature of the supervenient reaction, it is clear that there is at least a dichotomy in the mechanism of nitration for very reactive compounds, and that, unless the contributions of the separate mechanisms can be distinguished, quantitative comparisons of reactivity are meaningless. 

At this temperature, and provided that the concentration of acetic acid in the acetic anhydride was small, the conversion of nitric acid into acetyl nitrate would have had a half-life of 7-10 min. The description of the experimental method makes it clear that the solutions used by Dewar in this work contained acetyl nitrate over the vast majority of the reaction. Therefore it must be supposed that in this... 

Later experiments do not allow a clear choice between these alternatives. The high proportion of o-isomer formed when nitration is effected with acetyl nitrate in acetic anhydride is confirmed by the results of expts. 10-14 (table 5.5). The use of fuming, rather than pure nitric acid, in the preparation of the reagent, which may lead to nitration... 

In solutions of acetyl nitrate in acetic anhydride, prepared from purified nitric acid, the 0 -ratio increases slightly with increasing concentrations of acetyl nitrate (table 5.7, expts. 11,13,16). The use of fuming nitric acid in the preparation of the acetyl nitrate considerably accelerates the rates of reaction and also increases the proportion of o-substitution (table 5.7, expts. 12, 15, 18). These effects resemble, but are much stronger than the corresponding effects in nitrations with solutions of nitric acid in acetic acid contaimng dinitrogen tetroxide. 

In a later paper Knowles and Norman compared more fully nitrations of benzylic compounds in acetyl nitrate and in mixed acid (table 5.9), and interpreted the results in terms of three factors nitronium ion nitration in both media some degree of protonation of the oxygen... 

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