Tetrafluoroborate, nitronium

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. 

This salt turned out to be remarkably stable and a powerful, convenient nitrating agent for a wide variety of aromatics (and later also aliphatics). Over the years, this chemistry was further developed, and nitronium tetrafluoroborate is still a widely used commercially available nitrating agent. 

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. 

Cryoscopic investigations suggest that in sulpholan nitronium tetrafluoroborate exists predominantly as ion pairs. - The specific conductivity of these solutions increases linearly with the concentration of the salt (up to 0-4 mol 1 ), and is attributed to the existence of ion-triplets rather than free ions. ... 

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 ... 

Quantitative eomparisons of aromatic reactivities were made by using the competitive method with solutions of nitronium tetrafluoroborate in sulpholan, and a concentration of aromatic compounds 10 times that of the salt. To achieve this condition considerable proportions of the aromatic compoimds were added to the medium, thus depriving the sulpholan of its role as true solvent thus, in the nitration of the alkyl- and halogeno-benzenes, the description of the experimental method shows that about 50-60 cm of mixed aromatic compounds were dissolved in a total of 130 cm of sulpholan. 

As a means of determining relative reactivities, the competition method using nitronium tetrafluoroborate in sulpholan has been criticised as giving results which arise from incomplete mixing of the reagents before reaction is complete. The difficulty of using the competition method when the rate of reaction is similar to, or greater than,... 

The data of table 4.1, column [a), do not suggest that nitration of the alkylbenzenes with nitronium tetrafluoroborate in sulpholan occurs upon encoimter mesitylene might be so reacting ( 3.3) but comparison with a more inherently reactive substance would be necessary before this possibility could be considered. 

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... 

Without further studies little weight can be given to these ideas. In particular there is the possibility that with acetanilide, as with anisole, nitrosation is of some importance, and further with nitrations in sulphuric acid the effect of protonation of the substrate needs quantitative evaluation. The possibility that the latter factor may be important has been recognised, and it may account for the difference between nitration in sulphuric acid and nitration with nitronium tetrafluoroborate. 

Pentamethylbenzene and anthracene react very rapidly with nitronium tetrafluoroborate in sulpholan to give cr-complexes, which decompose slowly (see below), and durene behaves similarly with nitronium hexafluorophosphate in acetonitrile. ... 

The cases of pentamethylbenzene and anthracene reacting with nitronium tetrafluoroborate in sulpholan were mentioned above. Each compound forms a stable intermediate very rapidly, and the intermediate then decomposes slowly. It seems that here we have cases where the first stage of the two-step process is very rapid (reaction may even be occurring upon encounter), but the second stages are slow either because of steric factors or because of the feeble basicity of the solvent. The course of the subsequent slow decomposition of the intermediate from pentamethylbenzene is not yet fully understood, but it gives only a poor yield of pentamethylnitrobenzene. The intermediate from anthracene decomposes at a measurable speed to 9-nitroanthracene and the observations are compatible with a two-step mechanism in which k i k E and i[N02" ] > / i. There is a kinetic isotope effect (table 6.1), its value for the reaction in acetonitrile being near to the... 

For nitration with nitronium tetrafluoroborate in sulpholan. " See table 4.1. 

Sodium P-chloroethanesulfonate [15484-44-3] can be obtained by reacting vinyl chloride with sodium bisulfite [7631-90-5] (66). Reaction with nitronium tetrafluoroborate [13826-86-3] yi ds l-chloro-l- uoro-2-nitroethane [461-70-1] (67). 

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. ... 

Fluorine and nitrogen may be added to olefins with the nitrogen in different oxidation states Fluorine and a nilro group are added by reaction of an olefin with nitryl fluoride [131], nitronium tetrafluoroborate [195] (equation 32), or a combination of nitric acid and hydrogen fluoride [131, 196] (equation 33)... 

An unusual transformation was observed on treatment of 3-amino-4-rerr-butylazoxyfurazan with an excess of nitronium tetrafluoroborate at -10°C in acetonitrile (Scheme 159). Furazano[3,4-e][l,2,3,4]tetrazine 4,6-dioxide 236 was obtained in 52% yield (95MC227). 

B. 3,5-Dinilro-o-tolunitrile. A 500-ml. four-necked flask is equipped with a mechanical stirrer, a dropping funnel, a thermometer, and an inlet for dry nitrogen (Note 13). It is baked thoroughly by means of a Bunsen flame and allowed to cool to room temperature with a slow stream of dry nitrogen passing through it. The flask is charged, preferably in a dry box, with 335 g. of tetramethylene sulfone (Note 14) and 73.1 g. (0.55 mole) of nitronium tetrafluoroborate. The thermometer is adjusted so... 

Nitronium tetrafluoroborate is commercially available from the Ozark-Mahoning Co., Tulsa, Oklahoma. 

An egg-shaped stirrer seems to work best. As the reaction proceeds, the precipitating nitronium tetrafluoroborate prevents the stirring bar from operating. This is not serious if the reaction mixture is shaken occasionally. 

Kel-F grease is recommended for ground-glass joints. Nitronium tetrafluoroborate slowly attacks silicone stopcock grease, causing air to enter the flask. 

Nitronium tetrafluoroborate is thermally stable up to 170°. Above this temperature it starts to dissociate into nitryl fluoride and boron trifluoride. 

Nitronium tetrafluoroborate is very hygroscopic. It is stable as long as it is anhydrous, but it is decomposed by moisture, and all transfers should be in a dry box. Its purity can be checked by conventional elemental analysis. However, because of the hygroscopic nature of the salt, the submitters have found it convenient to use neutron activation analysis (B, F, N, O) of samples... 

The last part of the procedure can be used to purify nitronium tetrafluoroborate that has picked up water on standing. The impure salt is washed twice with nitromethane, twice with methylene chloride, and is dried under reduced pressure. 

Nitronium tetrafluoroborate slowly attacks polyethylene and polypropylene, but apparatus made of these materials will last for several preparations of the salt. 

A saturated solution at 25° contains 7 g. of nitronium tetrafluoroborate per 100 g. of tetramethylene sulfone. 

Nitronium tetrafluoroborate has been prepared by interaction of nitric acid, hydrogen fluoride, and boron fluoride in nitromethane.5 However, mixtures of nitric acid and nitromethane are extremely explosive.6,7 The present modification of the procedure, in which the medium is methylene chloride instead of nitromethane, was developed to avoid this hazard. It has not been published before. 

Nitration of aromatic rings by nitronium tetrafluoroborate is a general method. Fifty-seven arenes, haloarenes, nitroarenes,... 

With ten 7i-electrons delocalized over seven atoms, trithiadiazepine is electron rich and should undergo electrophilic substitution, which indeed it does. Nitronium tetrafluoroborate at — 10 C or copper(II) nitrate gives the mononitro derivative 5, which can be converted into the dinitro compound 6 by the action of an excess of nitronium tetrafluoroborate at 10 C.388... 

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