Nitronium salt

The second equilibrium is the more important, giving rise to the nitronium ion, NOj, already mentioned as a product of the dis sociation of dinitrogen tetroxide. Several nitronium salts have been identified, for example nitronium chlorate(VII), (N02) (C104) . If pure nitric acid is dissolved in concentrated sulphuric acid, the freezing point of the latter is depressed to an extent suggesting the formation of four ions, thus ... 

Another aspect of my early research in Budapest was in nitration chemistry, specifically the preparation of nitronium tetrafluoroborate, a stable nitronium salt. 1 was able to prepare the salt in a simple and efficient way from nitric acid, hydrogen fluoride, and boron trifluoride. 

Nitronium salts in solution in inert organie solvents have been used in reeent years to nitrate a wide range of aromatic compounds. Yields are generally good, but in preparative work the method is advantageous only in speeial cases, notably where the aromatie contains a hydrolysable substituent ( 4.4). 

The Raman spectrum of nitric acid shows two weak bands at 1050 and 1400 cm. By comparison with the spectra of isolated nitronium salts ( 2.3.1), these bonds were attributed to the nitrate and nitronium ion respectively. Solutions of dinitrogen pentoxide in nitric acid show these bands , but not those characteristic of the covalent anhydride , indicating that the self-dehydration of nitric acid does not lead to molecular dinitrogen pentoxide. Later work on the Raman spectrum indicates that at —15 °C the concentrations of nitrate and nitronium ion are 0-37 mol 1 and 0 34 mol 1 , respectively. The infra-red spectrum of nitric acid shows absorption bands characteristic of the nitronium ion. The equivalence of the concentrations of nitronium and nitrate ions argues against the importance of the following equilibrium ... 

Nitronium salts of many acids have been prepared, " and some are commercially available. They have been used as nitrating agents ( 4-4-2). 

When mixed with Lewis acids, dinitrogen pentoxide yields crystalline white solids, which were identified as the corresponding nitronium salts by their infra-red spectra. The reaction with boron trifluoride can be formulated in the following way... 

Nitration with pre-formed nitronium salts is discussed below ( 4.4). 

NITRATIONS WITH SOLUTIONS OF NITRONIUM SALTS IN ORGANIC SOLVENTS... 

Preparation and properties of nitronium salts The first preparation of a nitronium salt by Hantzsch, who isolated the perchlorate mixed with hydroxonium perchlorate, and some of the subsequent history of these salts has already been recounted ( 2.3.1). 

Nitronium tetrafluoroborate was first prepared by adding a mixture of anhydrous hydrofluoric acid and boron trifluoride to a solution of dinitrogen pentoxide in nitromethane. Nitric acid can be used in place of dinitrogen pentoxide, and by replacing boron trifluoride by other Lewis-acid fluorides Olah and his co-workers prepared an extensive series of stable nitronium salts. ... 

Nitronium salts are colourless, crystalline and very hygroscopic nitronium perchlorate and sulphate are unstable and liable to spontaneous decomposition, whereas nitronium tetrafluoroborate and other complex fluoro-salts are relatively stable. 

Olah s original preparative nitrations were carried out with mixtures of the aromatic compound and nitronium salt alone or in ether, and later with sulpholan as the solvent. High yields of nitro-compounds were obtained from a wide range of aromatic compounds, and the anhydrous conditions have obvious advantages when functional groups such as cyano, alkoxycarbonyl, or halogenocarbonyl are present. The presence of basic fimctions raises difficulties with pyridine no C-nitration occurs, i-nitropyridinium being formed. ... 

The selection of solvents for quantitative work is not easy. Nitro-alkanes are sufficiently inert, but nitronium tetrafluoroborate is poorly soluble in them c. 0-3 %). Nitronium salts react rapidly with acetic anhydride, and less rapidly with acetic acid, A, A -dimethylformamide and acetonitrile, although the latter solvent can be used for nitration at low temperatures. Sulpholan was selected as the most suitable solvent ... 

It can be concluded, as already stated above, that the diminution in intermolecular selectivity observed in these nitrations with nitronium salts in organic solvents does not of itself require any special mechanistic considerations as regards the process of substitution. 

It has already been noted that, as well as alkylbenzenes, a wide range of other aromatic compounds has been nitrated with nitronium salts. In particular the case of nitrobenzene has been examined kinetically. Results are collected in table 4.4. The reaction was kinetically of the first order in the concentration of the aromatic and of the nitronium salt. There is agreement between the results for those cases in which the solvent induces the ionization of nitric acid to nitronium ion, and the corresponding results for solutions of preformed nitronium salts in the same solvent. 

In nitration with nitronium salts in sulpholan, nitrobenzene was substituted in the following proportions 8% ortho, 90% meta and 2% paraf under the same conditions benzylidyne trifluoride yielded 8%, 88% and 4% of 0-, m- and p-nitro compound respectively Both of these aromatic compounds were stated to be io -10 times less reactive than benzene. "... 

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,... 

Work on the nitration of durene also gives evidence for the importance of the speed of mixing in nitration with nitronium salts. ... 

Even so, the results were claimed to show a greater resemblance to nitrations with nitronium salts than to nitrations in organic solvents. However, reaetion at the eneounter rate ( 3.3) imposes a limit to the rate of reaetion in these media, whieh deereases from 40 times the rate for benzene in 68 % sulphuric acid to 6 times the rate in 80 % sulphurie acid. Therefore it is reasonable to expeet that in stronger solutions even under homogeneous eonditions, the rates of these eompounds would approximate to that of benzene. 

With the more concentrated solution the results, as regards loss of intermolecular selectivity, were similar to those obtained with nitronium salts (table 4.1, column a), whilst with the more dilute solution a more usual situation was revealed. The significance of the former observations is again open to doubt because of the likelihood that mixing was relatively slow, and also because reaction upon encounter is here a serious probability. 

It has been necessary to comment upon these various studies because Olah and his co-workers have suggested that whilst nitrations, like those with nitronium salts, which give a relative rate of reaction of toluene with respect to benzene not much greater than unity involve the nitronium ion as the electrophile, this is not so in other cases. It is important to consider these opinions closely. In the earlier of the two relevant papers it is agreed that since nitrations of toluene with nitronium tetrafluoroborate in sulpholan show no abnormal o -ratio there... 

The nitronium ion is the electrophile in nitrations with nitronium salts in organic solvents. 

In other systems electrophiles other than the nitronium ion are involved with activated substrates (in these cases intermolecular selectivity is high, whereas with nitronium salts it is low). 

The nitration of alkylbenzenes and benzene with nitronium salts... 

The possibility mentioned in (4) is of great importance, and centres on the persistenee in nitrations with nitronium salts of positional seleetivities in the nitration of alkylbenzenes. It is discussed in 6.2. 

The work of Olah et al. on nitration with nitronium salts in organic solvents has already been discussed in some of its aspects ( 4.4). It will... 

Nitrations can be performed in homogeneous media, using tetramethylene sulfone or nitromethane (nitroethane) as solvent. A large variety of aromatic compounds have been nitrated with nitronium salts in excellent yields in nonaqueous media. Sensitive compounds, otherwise easily hydroly2ed or oxidized by nitric acid, can be nitrated without secondary effects. Nitration of aromatic compounds is considered an irreversible reaction. However, the reversibihty of the reaction has been demonstrated in some cases, eg, 9-nitroanthracene, as well as pentamethylnitrobenzene transnitrate benzene, toluene, and mesitylene in the presence of superacids (158) (see Nitration). 

Aliphatic Nitration. Alkanes undergo electrophilic nitration with nitronium salts such as (N02) piotic solvent such as CH2CI2... 

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