Nitration m-xylene

Acetoxylation and nitration. It has already been mentioned that 0- and m-xylene are acetoxylated as well as nitrated by solutions of acetyl nitrate in acetic anhydride. This occurs with some other homologues of benzene, and with methyl phenethyl ether,ii but not with anisole, mesitylene or naphthalene. Results are given in table 5.4. 

Nitration of m xylene is directed ortho to one methyl group and para to the other... 

Tnflic acid is an excellent catalyst for the nitration of aromatic compounds [.S7]. In a mixture with nitnc acid, it forms the highly electrophilic nitronium inflate, which can be isolated as a white crystalline solid Nitronium inflate is a powerful nitrating reagent in inert organie solvents and in tnflic acid or sulfuric acid. It nitrates benzene, toluene, chlorobenzene, nitrobenzene, m-xylene, and benzotn-fluoride quantitatively in the temperature range of-110 to 30 °C with exeeptionally high positional selectivity [87],... 

Acetoxylation has been found to accompany the nitration of o- and m-xylene... 

Pertechnetate in neutral and alkaline media can be extracted into solutions of tetra-alkylammonium iodides in benzene or chloroform. With tetra-n-heptylammo-nium iodide (7.5 x 10 M) in benzene distribution coefficients up to 18 can be obtained . A solution of fV-benzoyl-iV-phenylhydroxylamine (10 M) in chloroform can be used to extract pertechnetate from perchloric acid solution with a distribution coefficient of more than 200, if the concentration of HCIO is higher than 6 M The distribution of TcO between solutions of trilauryl-ammonium nitrate in o-xylene and aqueous solutions of nitrate has been measured. In 1 M (H, Li) NOj and 0.015 M trilaurylammonium nitrate the overall equilibrium constant has been found to be log K = 2.20 at 25 °C. The experiments support an ion exchange reaction . Pertechnetate can also be extracted with rhodamine-B hydrochloride into organic solvents. The extraction coefficient of Tc (VII) between nitrobenzene containing 0.005 %of rhodamine-B hydrochloride and aqueous alcoholic " Tc solution containing 0.0025 % of the hydrochloride, amounts to more than 5x10 at pH 4.7 . 

Benzol hjthiophene, see Naphthalene 1,2,3-Benzotriazin-4 (3/J -one, see Azinnhos-methyl Benzotriazole, see Tetrachloroethylene Benzyl alcohol, see Benzo[a]anthracene, Benzyl butyl phthalate. Benzyl chloride, Permethrin. o-Xylene, m-Xylene, p-Xylene. Toluene 0-Benzyl alcohol, see o-Xylene m-Benzyl alcohol, see m-Xylene p-Benzyl alcohol, see p-Xylene 10-Benzyl-10-hydroanthracen-9-one, see Benzo [ a] anthracene Benzyl hydroperoxide, see Toluene Benzyl nitrate, see Toluene Benzylsuccinic acid, see Toluene... 

Methylbenzyl nitrate, see o-Xylene m-Methylbenzyl nitrate, see m-Xylene Methylbenzylsuccinic acid, see o-Xylene, m-Xylene, p-... 

The presence of two methyl groups in m-xylene makes it a more reactive substrate than toluene, but as a consequence, this substrate is more susceptible to oxidation. Therefore, the nitration of m-xylene requires lower temperatures and the use of less concentrated mixed acid. In fact, the nitration of either 2,4- or 2,6-dinitro-m-xylenes to 2,4,6-trinitroxylene (TNX) can be achieved with mixed acid containing up to 10 % water. TNX is a less powerful explosive than TNT and has a poor oxygen balance (—78.4 %). 

Trinitrobenzene is present in crude TNT manufactured by mixed acid nitration and results from methyl group oxidation followed by decarboxylation." In fact, a convenient method for the synthesis of 1,3,5-trinitrobenzene involves oxidation of 2,4,6-trinitrotoluene with a solution of sodium dichromate in sulfuric acid, followed by decarboxylation of the resulting 2,4,6-trinitrobenzoic acid in boiling water." 1,3,5-Trinitrobenzene is prepared from 2,4,6-trinitro-m-xylene by a similar route." 2,4,6-Trinitroanisole can be prepared from the... 

C12H15N3O6, Mr 291.21, mp 114°C, does not occur in nature. It forms yellow crystals with a persistent musk odor. Musk xylol is prepared by alkylation of m-xylene with isobutene and subsequent nitration with a sulfuric acid nitric acid... 

N 16.34% col ndls, turning bm in the light, deflgr on heating or on impact sol in HNO3 almost insol in w was obtd by nitrating 6-f amino-m-xylene-4-sulfonic acid with cold HNO3... 

N 17.90% expl oil, impact sensitive was prepd by DuPont by condensing Trinitro-m-Xylene with HCHO and nitrating the product Ref Blatt, OSRD 2014(1944)... 

Dinitro-l, 3-dime tbylbenzene, col prisms (from ale), mp 92—94°, bp—explodes prepd by nitrating m-xylene with coned nitric acid at RT (Ref 1, P380 Ref 2, pl84 Ref 3, p295 Ref 4, p844)... 

M. Warman, Preparation of Trinitro-Meta-Xylene (TNX) , PATM 1728 (1966) [Reported is a procedure for the pilot plant prepn of TNX from m-xylene. The nitration of m-xylene is carried out in two stages 1) The conversion of m-xylene to 2-nitro-m-xylene using mixed add (sulfuric 59/nitric 25/w 16%) at 35 to 50°, and 2) The trinitration of 2-nitro-m-xylene to trinitro-m-xylene, again using mixed add (sulfuric 79/nitric 17.5/w 3.5%), at 95 to 102°. The author states that the overall yield of TNX from m-xylene is as high as 94%. One crystn of the crude product from acet is sufficient to raise the mp to the 182-83° value reported in the literature]... 

When aquifers were amended with nitrate in order to stimulate biodegradation, the results were generally consistent with those obtained in laboratory investigations. In a field injection experiment at Seal Beach, California, Ball et al. (1994) demonstrated complete removal of w-xylene and the m-,/-xylene fraction decreased significantly in parallel bioreactor experiments. A Canadian study showed a decrease in m- and /-xylene of 14% and 15%, respectively, over aim flowpath in the Borden aquifer (Barbara et al., 1992). Very little degradation was observed beyond that point, presumably due to the availability of preferred electron donors in the landfill leachate impacted aquifer. 

In m-xylene the two methyl groups agree in activating the same positions, and this is the only one of the three isomeric xylenes which can be nitrated satisfactorily to yield a trinitro derivative. Since the three isomers occur in the same fraction of coal tar and cannot readily be separated by distillation, it is necessary to separate them by chemical means. When the mixed xylenes are treated with about their own weight of 93 per cent sulfuric acid for 5 hours at 50°, the o-xylene (b.p. 144°) and the m-xylene (b.p. 138.8°) are converted into water-soluble sulfonic acids, while the p-xylene (b.p. 138.5°) is unaffected. The aqueous phase is removed, diluted with water to about 52 per cent acidity calculated as sulfuric acid, and then heated in an autoclave at 130° for 4 hours. The m-xylene sulfonic acid is converted to m-xylene, which is removed. The o-xylene sulfonic acid, which remains in solution, may be converted into o-xylene by autoclaving at a higher temperature. The nitration of m-xylene is conveniently carried out in three steps. The effect of the two methyl... 

Figure 8 Extraction of some divalent metals (0.05 M as nitrates) from 1.0 M sodium nitrate solutions by 0.50 M solutions of Versatic 10 acid in xylene at 20 °C...

Figure 10 Extraction of some divalent metals and iron(IH) (0.01 M as nitrates) from 0,2 M ammonium nitrate by 0.10 M solutions of anti-1 -(2-hydroxy-5-methylpher>yl)octan-1 -one oxime in xylene at 30 °C...

C10H9N4O12 mw 391.24 N 17.90% OB to C02 -51.12% oil. Prepn is by condensing trinitro-m-xylene with formaldehyde, and nitrating the product. The compd can be detond with a hammer blow... 

The nitrosation of phenol and cresols in buffer solutions involves a diffusion-controlled C-nitrosation followed by rate-limiting proton loss. /r-Crcsol is much less reactive than the other substrates.79 Nitrosation in trifluoroacetic acid or in acetic-sulfuric acid mixtures is regioselective (e.g. 4-nitroso-m-xylene is fonned from m-xylene) and possible non-selective nitrous acid-catalysed nitration can be eliminated by purging reaction solutions with nitric oxide.80... 

Relative rate coefficients from (25) are listed in Table 6, taking that for benzene as unity. The most interesting feature of these results is the apparent limiting reaction rate at about forty times the reactivity of benzene. This limit is quite inconsistent with the predictions of the additivity principle. Thus, from the additivity principle and the partial rate factors for the nitration of toluene, the reactivities of m-xylene and mesitylene would be expected to exceed that of benzene by factors of 400 and 16 000 respectively (Coombes et al., 1968). 

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