Mononitrotoluenes

Mixtures of HNO, H2SO4, and SO also result in high concentrations of NO/, and toluene can be readily nitrated at —40 to — 10°C as a result (6). At these low temperatures, the formation of the meta-isomer of mononitrotoluene (MNT) is greatiy reduced. Such a reduction is highly desired in the production both of dinitrotoluenes (DNTs) employed to produce intermediates for polyurethane production and of trinitrotoluene (TNT), which is a high explosive. > -MNT results in the production of undesired DNT and TNT isomers (see Nitrobenzene and nitrotoluenes). 

Organic Reactions. Nitric acid is used extensively ia iadustry to nitrate aHphatic and aromatic compounds (21). In many iastances nitration requires the use of sulfuric acid as a dehydrating agent or catalyst the extent of nitration achieved depends on the concentration of nitric and sulfuric acids used. This is of iadustrial importance ia the manufacture of nitrobenzene and dinitrotoluene, which are iatermediates ia the manufacture of polyurethanes. Trinitrotoluene (TNT) is an explosive. Various isomers of mononitrotoluene are used to make optical brighteners, herbicides (qv), and iasecticides. Such nitrations are generally attributed to the presence of the nitronium ion, NO2, the concentration of which iacreases with acid strength (see Nitration). 

Manufacture and Processing. Mononitrotoluenes are produced by the nitration of toluene in a manner similar to that described for nitrobenzene. The presence of the methyl group on the aromatic ring faciUtates the nitration of toluene, as compared to that of benzene, and increases the ease of oxidation which results in undesirable by-products. Thus the nitration of toluene generally is carried out at lower temperatures than the nitration of benzene to minimize oxidative side reactions. Because toluene nitrates at a faster rate than benzene, the milder conditions also reduce the formation of dinitrotoluenes. Toluene is less soluble than benzene in the acid phase, thus vigorous agitation of the reaction mixture is necessary to maximize the interfacial area of the two phases and the mass transfer of the reactants. The rate of a typical industrial nitration can be modeled in terms of a fast reaction taking place in a zone in the aqueous phase adjacent to the interface where the reaction is diffusion controlled. 

Table 12. Isomer Ratio of Mononitrotoluenes with Different Catalysts...

Economic Aspects. Annual 1993 U.S. production of the mononitrotoluenes is 26,000 metric tons, with about 16,120 metric tons of the ortho isomer, 780 metric tons of the meta isomer, and 9,100 metric tons of the para isomer. The prices of (9-, m-., and -nitrotoluene in bulk fob are 1.15/kg, 2.54/kg, and 3.64/kg, respectively. The mononitrotoluenes are manufactured by Du Pont and First Chemical Corp. 

Analytical and Test Methods. o-Nitrotoluene can be analyzed for purity and isomer content by infrared spectroscopy with an accuracy of about 1%. -Nitrotoluene content can be estimated by the decomposition of the isomeric toluene diazonium chlorides because the ortho and meta isomers decompose more readily than the para isomer. A colorimetric method for determining the content of the various isomers is based on the color which forms when the mononitrotoluenes are dissolved in sulfuric acid (45). From the absorption of the sulfuric acid solution at 436 and 305 nm, the ortho and para isomer content can be deterrnined, and the meta isomer can be obtained by difference. However, this and other colorimetric methods are subject to possible interferences from other aromatic nitro compounds. A titrimetric method, based on the reduction of the nitro group with titanium(III) sulfate or chloride, can be used to determine mononitrotoluenes (32). Chromatographic methods, eg, gas chromatography or high pressure Hquid chromatography, are well suited for the deterrnination of mononitrotoluenes as well as its individual isomers. Freezing points are used commonly as indicators of purity of the various isomers. 

Health and Safety Factors. The toxic effects of the mononitrotoluenes are similar to but less pronounced than those described for nitrobenzene. The maximum allowable concentration for the mononitrotoluenes is 2 ppm (11 mg/m ) (6). Mononitrotoluenes are low grade methemoglobin formers (4) and may be absorbed through the skin and respiratory tract. The toxicity of alkyl nitrobenzenes decreases with an increasing... 

The y -phenylenediamiaes are easily obtained by dinitrating, followed by catalyticaHy hydrogenating, an aromatic hydrocarbon. Thus, the toluenediamiaes are manufactured by nitrating toluene with a mixture of sulfuric acid, nitric acid, and 23% water at 330°C which first produces a mixture (60 40) of the ortho and para mononitrotoluenes. Further nitration produces the 80 20 mixture of 2,4- and 2,6-dinitrotoluene. Catalytic hydrogenation produces the commercial mixture of diamiaes which, when converted to diisocyanates, are widely used ia the production of polyurethanes (see Amines, aromatic, DIAMINOTOLUENES) (22). 

Because of Us high polarity and low nucleophilicity, a trifluoroacetic acid medium is usually used for the investigation of such carbocationic processes as solvolysis, protonation of alkenes, skeletal rearrangements, and hydride shifts [22-24] It also has been used for several synthetically useful reachons, such as electrophilic aromatic substitution [25], reductions [26, 27], and oxidations [28] Trifluoroacetic acid is a good medium for the nitration of aromatic compounds Nitration of benzene or toluene with sodium nitrate in trifluoroacetic acid is almost quantitative after 4 h at room temperature [25] Under these conditions, toluene gives the usual mixture of mononitrotoluenes in an o m p ratio of 61 6 2 6 35 8 A trifluoroacetic acid medium can be used for the reduction of acids, ketones, and alcohols with sodium borohydnde [26] or triethylsilane [27] Diary Iketones are smoothly reduced by sodium borohydnde in trifluoroacetic acid to diarylmethanes (equation 13)... 

Mononitrotoluenes are usually reduced to corresponding toluidines, which make dyes and ruhher chemicals ... 

Kostevich and Sapozhnikov have carried out extensive studies on the nitration of toluene to mononitrotoluene, using nitrating mixts of various compns and determining the compn of mixts leading to dinitrotoluene. Their results are shown in the ternary diagram of Fig 3... 

Toluene is continuously nitrated to mononitrotoluene in a cast-iron vessel, 1 m diameter, fitted with a propeller agitator 0.3 m diameter rotating at 2.5 Hz. The temperature is maintained at 310 K by circulating 0.5 kg/s cooling water through a stainless steel coil 25 mm o.d. and 22 mm i.d. wound in the form of a helix, 0.80 m in diameter. The conditions are such that the reacting material may be considered to have the same physical properties as 75 per cent sulphuric acid. If the mean water temperatute is 290 K, what is the overall coefficient of heat transfer ... 

HPA amount/g Regioselectivity ortho/% meta/% para/% para/ortho Total yield of mononitrotoluene/%... 

Smith and coworkers have screened the solid catalysts for aromatic nitration, and found that zeolite (3 gives the best result. Simple aromatic compounds such as benzene, alkylbenzenes, halogenobenzenes, and certain disubstituted benzenes are nitrated in excellent yields with high regioselectivity under mild conditions using zeolite (3 as a catalyst and a stoichiometric quantity of nitric acid and acetic anhydride.11 For example, nitration of toluene gives a quantitative yield of mononitrotoluenes, of which 79% is 4-nitrotoluene. Nitration of fluorobenzene under the same conditions gives p-fluoronitrobenzene exclusively (Eqs. 2.1 and 2.2)... 

Batch microwave reactors, reactions in, 16 554-555 Batch mixers, 16 721 Batch mononitrotoluene process, 17 265 Batch multipurpose plants, for fine chemical manufacture, 11 427 Batch nitrobenzene process, 17 252 Batch-operated settling tanks, 22 59 Batch pilot plants, 19 458 Batch plants, certified, 20 703 Batch polymerization, of vinyl acetate, 25 608... 

The 60 still base was a 45.5 m3 horizontal, cylindrical, mild steel tank 7.9 m long and 2.7 m diameter. The still was used to separate a mixture of the isomers of mononitrotoluene (MNT), two of which (o-nitrotoluene and m-nitrotoluene) are liquids at room temperature and third (p-nitrotoluene) a solid. Other byproducts were also present, principally dinitrotoluene and nitrocresols. It is well known in the industry that these nitro compounds can be explosive in the presence of strong alkali or strong acid, but in addition explosions can be triggered if they are heated to high temperatures or held at moderate temperatures for a long period. 

Event 10 Explosion—Mononitrotoluene. First Chemical Corporation, Pascagoula, Mississippi (October 13, 2002). Three workers injured fires, projectiles, and other damage to the plant and plant equipment (HighBeam 2008). 

A mixture of ortho, meta, and para-mononitrotoluenes containing 60, 4, and 36 mole per cent respectively of the three isomers is to be continuously distilled to give a top product of 98 mole... 

The problem of selecting the most appropriate operation will be further complicated by such factors as the concentration of liquid solution at which crystals start to form. Thus, in the separation of a mixture of ortho-, meta-, and para-mononitrotoluenes, the decision must be made as to whether it is better to carry out the separation by distillation followed by crystallisation, or in the reverse order. The same kind of consideration will arise when concentrating a solution of a solid then it must be decided whether to stop the evaporation process when a certain concentration of solid has been reached and then to proceed with filtration followed by drying, or whether to continue to concentration by evaporation to such an extent that the filtration stage can be omitted before moving on to drying. 

To elevate p-selectivity in nitration of toluene is another important task. Commercial production of p-nitrotoluene up to now leads with twofold amount to the unwanted o-isomer. This stems from the statistical percentage of o m p nitration (63 3 34). Delaude et al. (1993) enumerate such a relative distribution of the unpaired electron densities in the toluene cation-radical—ipso 1/3, ortho 1/12, meta 1/12, and para 1/3. As seen, the para position is the one favored for nitration by the attack of NO (or NO2 ) radical. A procednre was described (Delande et al. 1993) that used montmorillonite clay supported copper (cupric) nitrate (claycop) in the presence of acetic anhydride (to remove excess humidity) and with carbon tetrachloride as a medinm, at room temperature. Nitrotoluene was isolated almost quantitatively with 23 1 76 ratio of ortho/meta/para mononitrotoluene. 

Rickert DE et al Hepatic macromolecular covalent binding of mononitrotoluenes in Fischer-344 rats. Chem Biol Interact 52 131-139, 1984... 

The next problem with this reaction is that the mononitro compound can add successive nitro groups to produce the di- and trinitro toluenes in the reactions. Fortunately, the rate coefficients for adding the second and especially the third nitro groups are much smaller than for adding the first so mononitrotoluene can be made with good efficiency by simply heating toluene in nitric acid (Figure 3-19). 

Dumdum Bullet. Damudamu dan Dummy Ammunition. Renshuyo danyaku Ennayaku. A light-yellow expl mixture of K chlorate 80, MNT (Mononitrotoluene) 15 castor oil 5% extremely sensitive to mechanical action. It was used by the Army. as Substitute... 

DNB — Dinitrobenzene DNCB — Dinitrochlorobenzene DNCr — Dinitiocresole DNPh — Dinitro-phenol DNT — 2,4, Dinitrotoluene EtN — Erythritol Tetranitrate HNDPhA — Hexanitio-diphenylamine MHeN — Mannitol Hexanitrace MNPh — Mononitrophenol MNT — Mononitrotoluene PA — Picric Acid PETN — Pentaerythritol Tetranitrate TNAn — Trinitroaniline TNAns — Tri-nitroanisole TNB — Trinitrobenzene TNCr — Trinitrocresole TNPh — Tri nitro phenol TNT —... 

Fluaro-mononitrotoluene, F.C6H.g(N02).CH.g mw 155.13, N 9.03%. The 3-Fluoro-2-nitro- 4-Fluoro-2-nitro- 5-Fluoro-2-nitro- 6-Fluoro-2-nitro- 4-Fluoro-3 nitro- 2, 4- and 6-Fluoro-3 nitro- and 2- 5r 3-FTuoro-4-nitrotoluenes are all described in Ref 1. Ref 2 also describes 2-Fluoro-4-ni tro toluene Refs 1) Beil 6, 326, (161), [250, 251] ... 

TABLE 1 Formation of MNT (mononitrotoluenes), DNT (dinitrotoluenes) and MDPM (methyldiphenylmethanes) from toluene by using nitric acid in conjunction with a commercial acidic clay of the montmorillonite type (toluene 1.45 mole 100 % HN03 21 mmole clay 90 g. Reaction time 3.5 hr). 

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