Nitration Mixed acid

Berl et al. [22] established that the upper limit of cellulose nitration is reached when the composition of the nitrating mixed acid has the mole ratio... 

In an attempt to effect reaction on an unprotonated species thieno- 2,3-6 pyridine was treated with bromine in chloroform in the presence of a buffer,79 producing an improved yield (57%) of 52b. Nitration of 52a-c (mixed acid) gave rather poor yields (22-47%) of the 3-halogeno-2-nitrothieno 2,3-6]pyridine. Both of the quinoline isosteres73 and also 5-ethylthieno 2,3-6]pyridine ° were nitrated (mixed acid) at C-3 yields in all three cases were approximately 50%. 

Nitrations are usually carried out at comparatively low temperatures at higher temperatures there may be loss of material because of the oxidising action of the nitric acid. For substances which do not nitrate readily with a mixture of concentrated nitric and sulphuric acids ( mixed acid ), the intensity of the reaction may be increased inler alia by the use of fuming sulphuric acid (containing up to 60 per cent, of sulphur trioxide) or by fuming nitric acid. Thus nitrobenzene is converted by a mixture of fuming nitric acid and concentrated sulphuric acid into about 90 per cent, of wi-dinitrobenzene and small amounts of the o- and p-isomers the latter are eliminated in the process of recrystallisation ... 

Nitration of bromobenzene with mixed acid yields largely p-bromo nitrobenzene accompanied by a little of the o-isomeride ... 

During my Cleveland years, I also continued and extended my studies in nitration, which I started in the early 1950s in Hungary. Conventional nitration of aromatic compounds uses mixed acid (mixture of nitric acid and sulfuric acid). The water formed in the reaetion dilutes the acid, and spent aeid disposal is beeoming a serious environ-... 

To solve some of the environmental problems of mixed-acid nitration, we were able to replaee sulfuric acid with solid superacid catalysts. This allowed us to develop a novel, clean, azeotropic nitration of aromatics with nitric acid over solid perfluorinated sulfonic acid catalysts (Nafion-H). The water formed is continuously azeotroped off by an excess of aromatics, thus preventing dilution of acid. Because the disposal of spent acids of nitration represents a serious environmental problem, the use of solid aeid eatalysts is a significant improvement. 

The first nitration to be reported was that of beri2ene itself. Mitscher-lich in 1834 prepared nitrobenzene by treating benzene with fuming nitric acid. Not long afterwards the important method of effecting nitration with a mixture of nitric and sulphuric acids ( mixed acid ) was introduced, evidently in a patent by Mansfield the poor quality of early nitric acid was probably the reason why the method was developed. Since these beginnings, nitration has been the subject of continuous study. 

The relative abilities of nitromethane, sulpholan, and acetic acid to support the ionisation of nitric acid to nitronium ions are closely similar to their efficiencies as solvents in nitration. Raman spectroscopy showed that for a given concentration of mixed acid (i i nitric and sulphuric acids) the concentration of nitronium ions in these three solvents varied in the order nitromethane > sulpholan > acetic acid. The concentration of mixed acid needed to permit the spectroscopic detection of nitronimn ions was 25 %, 50 % and 60 % in the three solvents, respectively (see 4.4.3). 

Using sulpholan and acetic acid as solvents competitive nitrations were performed with solutions containing 75% and 30% of mixed acid (table 4.1, columns h, i and /, g, respectively). In the former the concentration of nitronium ions was substantial [c. 5-7 % by weight), whereas in the latter the concentration was below the level of spectroscopic detection. 

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... 

Evidence for the influence of protonation was convincingly adduced from the trend of the quantity m p (mixed acid)/ M p (acetyl nitrate) in the series Ph.CH2.OMe, Ph.(CH2)2 OMe, Ph.(CH2)3.0Me, hut it was argued that protonation in mixed acid cannot explain the change... 

Melander first sought for a kinetic isotope effect in aromatic nitration he nitrated tritiobenzene, and several other compounds, in mixed acid and found the tritium to be replaced at the same rate as protium (table 6.1). Whilst the result shows only that the hydrogen is not appreciably loosened in the transition state of the rate-determining step, it is most easily understood in terms of the S 2 mechanism with... 

That some modification to the position so far described might be necessary was indicated by some experiments of Nesmeyanov and his co-workers. Amongst other compounds they nitrated phenyl trimethyl ammonium and triphenyloxonium tetrafluoroborates with mixed acid the former gave 96 % of m- and 4 % of -nitro compound (88 % total yield), whilst the latter gave 80% of the tri-(p-nitrophenyl)oxonium salt. Ridd and his co-workers have made a quantitative study of the phenyl trimethyl ammonium ion. Their results, and those of other recent workers on the nitration of several cations, are collected in table 9.3. 

Biphenylene is nitrated with nitric acid in acetic acid at C(2), and further nitration with mixed acid gives 2,6-dinitrobiphenylene. The relative rate was not determined. 

The preparative nitration of quinoline in mixed acid has been described several times, and has usually been carried out under unnecessarily severe conditions good yields of 5- and 8-nitroquinoline in roughly... 

Phenylbenzimidazole is nitrated first at the 5-position with mixed acid, and subsequent reaction produces 5-nitro-2-(4-nitrophenyl)-and 5-nitro-2-(3-nitrophenyl)-benzimidazole. 2-Phenyl-, 2-(4-nitro-phenyl)- and 5-nitro-2-phenyl-benzimidazole are nitrated as their conjugate acids. ... 

Nitration of aromatic rings is possible by use of Pd(N03)2[356], Pd(OAc)2-NaN02[357], Pd(0Ac)2-N02[358], and Pd(0)-NO2[359], The nitration can be carried out fully catalytically by Pd(0Ac)2-N02 and oxygen. This reaction offers a promising new method of nitration without using mixed acids of HNO3 and H2SO4. 

Other Glycol Nitrates. Other Hquid nitrates have been used as explosive plasticizers for nitroceUulose (Table 8). These may be made by mixed-acid nitration using procedures similar to those used for nitroglycerin. 

Nitroglycol maybe made by nitration of ethylene glycol [107-21-1] with mixed acid with a yield of ca 93%. The demand for both NG and nitroglycol has been gready decreased (115,116). 

Cotton linters or wood pulp are nitrated using mixed acid followed by treatment with hot acidified water, pulping, neutralization, and washing. The finished product is blended for uniformity to a required nitrogen content. The controlling factors in the nitration process are the rates of diffusion of the acid into the fibers and of water out of the fibers, the composition of mixed acid, and the temperature (see Cellulose esters, inorganic esters). 

Quantitative estimation of cyclohexane in the presence of benzene and aUphatic hydrocarbons may be accompHshed by a nitration-dehydrogenation method described in Reference 61. The mixture is nitrated with mixed acid and under conditions that induce formation of the soluble mononitroaromatic derivative. The original mixture of hydrocarbons then is dehydrogenated over a platinum catalyst and is nitrated again. The mononitro compounds of the original benzene and the benzene formed by dehydrogenation of the cyclohexane dissolve in the mixed acid. The aUphatic compound remains unattacked and undissolved. This reaction may be carried out on a micro scale. 

Nitration. Naphthalene is easily nitrated with mixed acids, eg, nitric and sulfuric, at moderate temperatures to give mostly 1-nitronaphthalene and small quantities, 3—5%, of 2-nitronaphthalene. 2-Nitronaphthalene [581-89-5] is not made in substantial amounts by direct nitration and must be produced by indirect methods, eg, the Bucherer reaction starting with 2-naphthalenol (2-naphthol [135-19-3]). However, the 2-naphthylamine [91-59-8] made using this route is a carcinogen thus the Bucherer method is seldom used in the United States. 

Mechanism. The NO2 mechanism has been accepted since about 1950 for the nitration of most aromatic hydrocarbons, glycerol, glycols, and numerous other hydrocarbons in which mixed acids or highly concentrated nitric acid are used. The mechanism has been discussed in detail and critically analy2ed (1). NO2 attacks an aromatic compound (ArH) as follows ... 

In addition to the conventional mixed acids commonly used to produce DNT, a mixture of NO2 and H2SO4 (8), a mixture of NO2 and oxygen (9), and just HNO (10) can also be used. TerephthaUc acid and certain substituted aromatics are more amenable to nitrations using HNO, as compared to those using mixed acids. For compounds that are easily nitratable, acetic acid and acetic anhydride are sometimes added to nitric acid (qv). Acetyl nitrate, which is a nitrating agent, is produced as an intermediate as follows ... 

A significant concern in all nitration plants using mixed acids centers on the disposal method or use for the waste acids. They are sometimes employed for production of superphosphate ferti1i2ers. Processes have also been developed to reconcentrate and recycle the acid. The waste acid is frequently first stripped with steam to remove unreacted HNO and NO. Water is then removed by low pressure evapori2ation or vacuum distillation. 

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