Toluene, nitration sulfonation

The transport of toluene-4-sulfonate into Comamonas testosteroni has been examined (Locher et al. 1993), and rapid uptake required growth of the cells with toluene-4-sulfonate or 4-methylbenzoate. From the results of experiments with various inhibitors, it was concluded that a toluenesulfonate anion/proton symport system operates rather than transport driven by a difference in electrical potential (A (/), and uptake could not take place under anaerobic conditions unless an electron acceptor such as nitrate was present. 

A given group causes the same general kind of orientation— predominantly ortho.para or predominantly /we/a—whatever the electrophilic reagent involved. The actual distribution of isomers may vary, however, from reaction to reaction. In Table 11.2, for example, compare the distribution of isomers obtained from toluene by sulfonation or bromination with that obtained by nitration. 

Nitrations can be performed in homogeneous media, using tetramethylene sulfone or nitromethane (nitroethane) as solvent. A large variety of aromatic compounds have been nitrated with nitronium salts in excellent yields in nonaqueous media. Sensitive compounds, otherwise easily hydroly2ed or oxidized by nitric acid, can be nitrated without secondary effects. Nitration of aromatic compounds is considered an irreversible reaction. However, the reversibihty of the reaction has been demonstrated in some cases, eg, 9-nitroanthracene, as well as pentamethylnitrobenzene transnitrate benzene, toluene, and mesitylene in the presence of superacids (158) (see Nitration). 

Red Water — which can be almost black at times - also contains dissolved TNT however, it is not an incidental stream like Pink Water it is a major by-product stream from TNT manuf. The mixed-acid nitration of toluene yields not only 2,4,6-trinitrotoluene, the desired product, but also a host of other isomers and by-products amounting to approx 4.5% of the total yield and it is necessary to remove them from the product. They are removed by extraction with a Na sulfite—Na carbonate soln which sulfonates and dissolves them the extract is called Red Water. Red Water is a very complex and somewhat variable mixt containing 15% or so of sulfonated or sellited nitrobodies and a number of inorganic salts. Typical components are w, NajSOj—NaS04, NaN02— NaNOj, sulfonated or... 

Feuer and co-workers also nitrated ring-substituted toluenes to the corresponding arylnitromethanes with potassium amide in liquid ammonia. Sulfonate esters and NJ -dialkylamides undergo similar nitration the latter isolated as their a-bromo derivatives. Alkaline nitration of ethyl and ferf-butyl carboxylic esters with potassium amide in liquid ammonia yields both the a-nitroester and the corresponding nitroalkane from decarboxylation. ... 

Batch nitrations and sulfonations, e.g., reactions of toluene or chlorobenzene with a mixture of sulfuric and nitric acids... 

The reaction between Mo(H20)63+, prepared and purified following the procedure of Bowen and Taube (18), and nitrate was followed spec-trophotometrically under strict anaerobic conditions with nitrate in excess. The absorption spectrum of nitrite in 1.0M HPTS (p-toluene sulfonic acid) exhibits a multicomponent band (vibrational fine structure) between 350 and 400 nm which is attributable to the xBi <— 1A1 electronic transition. Purified Mo(H20)63+ in 1.0M HPTS has a low absorption at 293 nm, indicating the purity of the preparation (18). When Mo(H20)63+ is mixed with nitrate (constant concentration in large excess) and the reaction is allowed to go to completion, the nitrite fine structure appears between 350 and 400, concomitant with an increase in absorbance at 293 nm. The molybdenum species resulting from the oxidation of... 

Other than those of the carboxylic type for example, a mixture of p-toluene-sulfonic acid and triduoroacetic anhydride forms sulfones by reaction with suitably activated aromatic compounds. By the same technique, the hexa-nitrate esters of o-mannitol and D-glucitol were obtained by use of solutions of fuming nitric acid in trifluoroacetic anhydride at 0°. The probable reaction mechanisms of these and other examples of the conversion of oxy acids into reactive entities have been briefly considered. ... 

Aryl amine intermediates for azo and triphenylmethane dyes, as well as a number of vat dye (anthraquinone) intermediates, are made from compounds such as benzene, alkyl benzenes (toluene and higher homologues), phenol and naphthalene. A limited number of reactions are used to produce the most important dye intermediates, including nitration, reduction, halogenation, sulfonation, /V-alkylation, /V-acylation and alkali fusion33,34. 

Several heterogeneous catalysts have been investigated for the liquid and vapor phase nitration processes. An early attempt by McKee and Wilhelm (3) used sihca gel as a solid catalyst for the nitration of benzene and toluene in the vapor phase. Various other heterogeneous catalysts systems have also been studied such as sulfonated polyorganosiloxanes (4), acidic resins (5), modified clays (6), zeolites (7,8), sulfated zirconia... 

PMC, USA, Laporte, UK, Konan Chemicals, Japan, and Atul Limited, India are the key manufacturers of para-cresol and all of them use nitration grade toluene as the critical feedstock and produce para-cresol via sulfonation, neutralization, caustic fusion, acidification, and distillation. Name plate capacities of these major producers are PMC 15,000-16,000 tpa, Laporte 15,000-16,000 tpa, Konan approx. 4000 tpa and Atul 5500-6000 tpa. 

The isoxazoline is also obtained from other reactions with pyridinium nitrate and pyrrolidine <89JHC1569>. Silyl nitronate (259) (R = H, Me, Et, Ph) with Ar-acrylyl-(2/ )-bornane-10,2-sultam (260) yielded a mixture of adducts. Further treatment with p-toluene sulfonic acid afforded the diastereomeric isoxazoline (261) (Equation (45)) <91PHC166>. 

Vassena et al. [34] showed that zeolite H-beta resulted in enhanced para selectivity in the vapor phase nitration of toluene at 158 °C with 65 % nitric acid. H-ZSM-5 and Deloxan, a sulfonic acid-bearing polysiloxane, were not selective. Dealumination of H-beta to increase its hydrophobicity was detrimental with regard to activity and para selectivity suggesting that catalytic activity was directly related to the acid site concentration. Characterization of the recovered catalyst showed that deactivation was not related to structural damage in the highly acidic reaction medium but rather to pore filling by strongly adsorbed products/by-prod-ucts. 

---