Nitromethane reactions

Since many nitrogen-containing organic compounds are explosive, some mention is appropriate here of possible hazards in working with nitromethane. Occasionally, some evidence of decomposition, in the form of mild evolution of heat and gases, has been observed by the author in concentrated, acidified aldose-nitromethane reaction residues from which the bulk of the nitroalcohols had been separated. Such residues usually have been either discarded at once or stored at —20° when further crystallization was anticipated. Generally, it may be stated that the aldose-nitromethane condensation reaction does not involve serious explosion hazards. 

In contrast with the addition of OH and many other radicals to the acz-form of nitromethane [reaction (34)], it has been found that... 

An intriguing and important adaptation of the aldose-nitromethane reaction was also studied in Toronto by Fischer and Jean Grosheintz. By addition of nitromethane to 1,2-0-isopropylidene-n-a 2/fo-pentodialdose and subsequent hydrolysis of the acetone group, they obtained a mixture of 6-deoxy-6-nitro-D-glucose and 6-deoxy-6-nitro-L-idose. A second, intramolecular reaction of these substances led to a mixture of deoxynitro-inositols and, by reduction, to the related aminodeoxyinositols. One of the latter was successfully deaminated a few years later, by T. Posternak, to the B-vitamin, mt/o-inositol (12), thus completing a synthesis of the latter that started from n-glucose. 

The TTX complexes, tmro-[CoCl2(TTX)] (CIO4) and traw-[CoBr2(TTX)] CIO4, are prepared by allowing [Co(TTX)] ( 104)2 to react with an appropriate lithium halide in nitromethane. Reaction of [Co(TTX)] ( 104)2 with lithium iodide produces the cobalt(II) complex, [ ol2(TTX)]. 

Many of the reactions involving a nitroalkane will proceed through the aci structure. Nitroalkanes react slowly with strong bases to form the nitronate salt. Nitromethane reaction with strong bases (e.g., sodium hydroxide) proceeds rapidly to form the sodium salt of methazonic aci. 

RXZONE.MVE PISTON - Piston Driven Nitromethane Reaction Zones RXZONE.MVE INIT - Nitromethane Shock Initiation RXZONE.MVE RXPIST - Stable and Unstable Nitromethane Detonations RXZONE.MVE 9404 - Stable PBX-9404 Detonation... 

Studies of the nieehanism of the formaldehyde-nitromethane reaction by Gorski and Alakaro ha ce shown that methydolation is reversible and proceeds in a step-wise manner ... 

Nitromethane, CH3NO2, the first member of the homologous series, can, however, be readily prepared by a special reaction. When equimolecular amounts of sodium nitrite and sodium monochloroacetate are heated together in aqueous solution, the chlorine in the monochloroacetate is replaced by the nitro group, and the sodium nitroacetate thus formed undergoes hydrolysis follow ed by decarboxylation ... 

Reactions of Nitromethane. (1) Nitromethane, although only slightly soluble in cold water, is freely soluble in sodium hydroxide solution, the alkaline solution slowly becoming yellow in colour. 

Nitromethane is more easily prepared by heating together equimolecular amounts of sodium monochloroacetate and sodium nitrite in aqueous solution sodium nitroacetate is intermediately formed and is decomposed to nitromethane and sodium bicarbonate. The latter yields sodium carbonate and carbon dioxide at the temperature of the reaction. 

The simpler nitrop>arafIins (nitromethane, nitroethane, 1- and 2-nitroproj)ane) are now cheap commercial products. They are obtained by the vapour phase nitration of the hydrocarbons a gaseous mixture of two mols of hydrocarbon and 1 mol of nitric acid vapour is passed through a narrow reaction tube at 420-476°. Thus with methane at 476° a 13 per cent, conversion into nitro methane is obtained ethane at 420° gives a 9 1 mixture of nitroethane (b.p. 114°) and nitromethane (b.p. 102°) propane at 420° afifords a 21 per cent, yield of a complex mixture of 1- (b.p. 130-6°) and 2-nitropropane (b.p. 120°), nitroethane and nitromethane, which are separated by fractional distillation. 

Much of the early work was inconclusive confusion sprang from the production by the reaction of water, which generally reduced the rate, and in some cases by production of nitrous acid which led to autocatalysis in the reactions of activated compounds. The most extensive kinetic studies have used nitromethane,acetic acid, sulpholan,i and carbon tetrachloride as solvents. 

It was from studies of nitration with solutions of nitric acid in nitromethane, and later in acetic acid, that Ingold and his co-workers first established the fundamental features of these reactions, and also correctly interpreted them. The use in these experiments of a large excess of nitric acid removed the problem caused by the formation of water. 

The observation of nitration in nitromethane fully dependent on the first power of the concentration of aromatic was made later. The rate of reaction of /)-dichlorobenzene ([aromatic] = 0-2 mol [HNO3] = 8-5 mol 1 ) obeyed such a law. The fact that in a similar solution 1,2,4-trichlorobenzene underwent reaction according to the same kinetic law, but about ten times slower, shows that under first-order conditions the rate of reaction depends on the reactivity of the compound. 

Nitration in acetic acid, in sulpholan and in carbon tetrachloride showed kinetic phenomena similar to those shown in nitromethane this is significant for it denies nitromethane a chemical involvement in the slow step. (Originally the rate of isomerization of nitromethane to its aci-form was believed to be a factor in the reaction. )... 

More typically its reactions showed an intermediacy of kinetic order like that observed with fluorobenzene or iodobenzene in nitromethane. 

Here we have the formation of the activated complex from five molecules of nitric acid, previously free, with a high negative entropy change. The concentration of molecular aggregates needed might increase with a fall in temperature in agreement with the characteristics of the reaction already described. It should be noticed that nitration in nitromethane shows the more common type of temperature-dependence (fig. 3.1). 

Nitration in organic solvents is strongly catalysed by small concentrations of strong acids typically a concentration of io mol 1 of sulphuric acid doubles the rate of reaction. Reaction under zeroth-order conditions is accelerated without disturbing the kinetic form, even under the influence of very strong catalysis. The effect of sulphuric acid on the nitration of benzene in nitromethane is tabulated in table 3.3. The catalysis is linear in the concentration of sulphuric acid. 

First-order nitrations in nitromethane are also markedly accelerated by addition of sulphuric acid, the effect being very similar to that observed with zeroth-order reactions. 

Unlike the effect of sulphuric acid upon nitration in nitric acid ( 2.2.3 where zeroth-order reactions are unknown), the form of the catalysis of zeroth-order nitration in nitromethane by added sulphuric acid does not deviate from a first-order dependence with low concentrations of catalyst. ... 

The addition of water depresses zeroth-order rates of nitration, although the effect is very weak compared with that of nitrate ions concentrations of 6x io mol 1 of water, and 4X io mol 1 of potassium nitrate halve the rates of reaction under similar conditions. In moderate concentrations water anticatalyses nitration under zeroth-order conditions without changing the kinetic form. This effect is shown below (table 3.5) for the nitration of toluene in nitromethane. More strikingly, the addition of larger proportions of water modifies the kinetic... 

A similar circumstance is detectable for nitrations in organic solvents, and has been established for sulpholan, nitromethane, 7-5 % aqueous sulpholan, and 15 % aqueous nitromethane. Nitrations in the two organic solvents are, in some instances, zeroth order in the concentration of the aromatic compound (table 3.2). In these circumstances comparisons with benzene can only be made by the competitive method. In the aqueous organic solvents the reactions are first order in the concentration of the aromatic ( 3.2.3) and comparisons could be made either competitively or by directly measuring the second-order rate constants. Data are given in table 3.6, and compared there with data for nitration in perchloric and sulphuric acids (see table 2.6). Nitration at the encounter rate has been demonstrated in carbon tetrachloride, but less fully explored. ... 

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... 

Hughes, Ingold and Reed discussed the relative merits of the and e3 schemes as mechanisms for nitration by considering the properties of acetic acid, nitromethane, nitric acid and sulphuric acid as media for the reaction. The facts have already been discussed ( 2.2.3, 2.2.4, 2.3.2, 2.4.2, 2.4.3, 3-2). 

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