Methylbenzenes oxidation

Substitution of methyl groups on the oxirane ring tilts the stability of the tautomers in favor of oxepin. Thus 1-methylbenzene oxide (154) exists as 2-methyloxepin (155), in rapid equilibrium with the benzene oxide tautomer 154.74 The AH has been calculated as 0.4 0.02 kcal/mol, i.e., 1.3 kcal/mol... 

Support comes from the work on l-D-4-methylbenzene oxide (208),132 which rearranged to p-cresol (209) with up to 75% retention of deuterium. Moreover, 4-D-toluene was hydroxylated to p-cresol, also with comparable retention. Variation in the extent of retention of deuterium has been observed, depending on the conditions (Table VIII). 

In the case of methylbenzenes, oxidation of the side chain can be interrupted by trapping the aldehyde in the form of a non-oxidizable derivative, the gem-diacetate (Latin Gemini, twins), which is isolated and then hydrolyzed. 

The earliest reported demonstration of enzymatic activity in a supercritical fluid was for the reaction of disodium p-nitrophenyl phosphate to p-nitro-phenol, catalysed by alkaline phosphatase. Randolph et aL [26] detected the product in yields of up to 71% in carbon dioxide at 35°C and 100 atm, in the presence of 0.1% v/v water. Hammond et al. [33] found tyrosinase, a polyphenol oxidase, to be catalytically active for the oxidation of 4-methyl phenol in both supercritical carbon dioxide at (36 2)°C and supercritical trifluoro-methane at (34 2)°C, with oxygen, at a total pressure of 345 bar. Use of a flow reactor permitted isolation of greater quantities of the catecholic product (1,2-dihydroxy, 4-methylbenzene). Oxidative activity for 4-chlorophenol substrate was appreciably lower. 

Neither benzenepentacarboxylic acid nor mellitic acid are manufactured commercially, but synthetic mellitic acid can be purchased as a laboratory chemical (99). Both can be synthesized by oxidizing the corresponding methylbenzenes or other substituted benzenes, and both are present in trace amounts after oxidation of coal or coal-like substances. 

Toluene (methylbenzene) is similar to benzene as a mononuclear aromatic, but it is more active due to presence of tbe electron-donating metbyl group. However, toluene is much less useful than benzene because it produces more polysubstituted products. Most of tbe toluene extracted for cbemical use is converted to benzene via dealkylation or disproportionation. Tbe rest is used to produce a limited number of petro-cbemicals. Tbe main reactions related to tbe cbemical use of toluene (other than conversion to benzene) are the oxidation of the methyl substituent and the hydrogenation of the phenyl group. Electrophilic substitution is limited to the nitration of toluene for producing mono-nitrotoluene and dinitrotoluenes. These compounds are important synthetic intermediates. 

All of the reactions discussed up till now involve the autoxidation of methylbenzenes to the corresponding carboxylic acids. From a practical viewpoint it would also be interesting to devise a process for the production of the corresponding aldehyde. Unfortunately, as noted earlier, the oxidizability of ArCHO is about four orders of magnitude higher than ArCH3 which essentially precludes the selective production of the aldehyde when O2 is the oxidant. With all other oxidants, on the other hand, the rate of oxidation of ArCHO is lower than that of ArCH3 (ref. 24) (Fig. 21). 

Methylbenzenes were oxidized, and substituted benzaldehydes were... 

Amoco Amoco Chemicals Company, a subsidiary of Amoco Corporation, formerly Standard Oil Company (IN), is best known in the chemicals industry for its modification of the Mid-Century process for making pure terephthalic acid. /7-Xylene in acetic acid solution is oxidized with air at high temperature and pressure. Small amounts of manganese, cobalt, and bromide are used as catalysts. The modification allows the use of terephthalic acid, rather than dimethyl terephthalate, for making fiber. The process can also be used for oxidizing other methylbenzenes and methylnaphthalenes to aromatic carboxylic acids. See also Maruzen. 

Methylbenzenes are oxidized to the corresponding benzoic acids in very high yield under phase-transfer catalytic conditions by sodium hypochlorite in the presence of ruthenium trichloride, which is initially oxidized to ruthenium tetroxide [5]. Absence of either the ruthenium or the quaternary ammonium salt totally inhibits the reaction. 

In the presence of ruthenium trichloride, alkaline sodium hypochlorite is able to oxidize methylbenzenes to benzoic acids under phase-transfer conditions at room temperature. In a recent development, selective oxidation of xylenes to toluic acids has... 

Methylbenzenes lose a proton from a methyl group to form a benzyl radical. In aqueous M-percbloric acid this reaction is fast with a rate constant in the range 10 lO s and the process is not reversible [24]. The process becomes slower as the number of methyl substituents increases, Hexaethylbenzene radical cation is relatively stable. When the benzyl radical is formed, further reactions lead to the development of a complex esr spectrum. Anodic oxidation of hexamethylbenzene in trifluoroacetic acid at concentrations greater than 1 O M yields the radical-cation I by the process shown in Scheme 6.1 [14], Preparative scale, anodic oxidation of methylbenzenes leads to the benzyl carbonium ion by oxidation of the benzyl radicals formed from the substrate radical-cation. Products isolated result from further reactions of this carbonium ion. 

The a-substitution product from oxidation of methylbenzenes in acetic acid can be eliminated by electrochemical hydrogenolysis at the cathode. An undivided cell is used and a palladium on carbon catalyst is suspended in the medium. The necessary hydrogen is generated by reduction of protons at the cathode. In this way, the... 

Side chain oxidation of methylbenzenes has been developed into a route for the... 

Bromophenylazo)-2/-toluene, 309 (2-BromophenyI)-iVM7-azoxy (2-hydroxy-5-methylbenzene), 358 p-Bromophenylurea, 138-139 Bromopropadiene, 17 2,3-Butadienoic add, 16 iV-l-Butenylpiperazine, 92 Butter yellow, hazard of, 291 f-Butylamine, oxidation of, 323 -Butyl azide, 269 f-Butyl-OlW-azoxymethane, 349 t-Butyl p-Bromophenylazoformate, 328 t-Butyl 2-(p-bromophenyl)carbazate, 328 H-Butyl carbamate, 238-239 t-Butyl carbamate, 241-243... 

Modern polyimides are most likely an outgrowth of trying to find increased utilization of aromatic polycarboxylic acids as prepared by oxidation of poly-methylbenzenes, a major component in petroleum feedstocks. Therefore, it is not too surprising that the first commercial application of these materials appeared... 

A new reagent, AMiydroxyphthalimide combined with Co(acac)n (n = 2,3), transforms alkylbenzenes to ketones, whereas methylbenzenes give the corresponding carboxylic acids.1121 Phthalimide N-oxyl was found to be the key intermediate. Novel oxoperoxo Mo(VI) complexes mediate the cost-effective and environmentally benign oxidation of methylbenzenes to carboxylic acids.1384 Similar green oxidation of p-xylene to terephthalic acid was reported by using a Ru-substituted heteropolyanion.1385... 

M is shown in Table I. The effect of bromide ion on the cobalt-catalyzed oxidation of methylbenzenes is quite large. 

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