3.5- dimethylphenol production

The selectivity of the oxidation of 2,6-disubstituted phenols depends on the type of oxidizing agent. For example, with a series of cobalt-containing catalysts of the salcomine type, oxidation of 2,6-dimethylphenol produces three products the poly(phenylene oxide), the diphenoquinone, and... 

Alkylated phenol derivatives are used as raw materials for the production of resins, novolaks (alcohol-soluble resins of the phenol—formaldehyde type), herbicides, insecticides, antioxidants, and other chemicals. The synthesis of 2,6-xylenol [576-26-1] h.a.s become commercially important since PPO resin, poly(2,6-dimethyl phenylene oxide), an engineering thermoplastic, was developed (114,115). The demand for (9-cresol and 2,6-xylenol (2,6-dimethylphenol) increased further in the 1980s along with the growing use of epoxy cresol novolak (ECN) in the electronics industries and poly(phenylene ether) resin in the automobile industries. The ECN is derived from o-cresol, and poly(phenylene ether) resin is derived from 2,6-xylenol. 

Dimethjlphenol (2,6-xylenol) is produced by the gas phase alkylation of phenol with methanol using modified alumina catalysis. The cmde product contains 2-methylphenol, 2,6-dimethylphenol, a minor amount of 2,4-dimethylphenol, and a mixture of trimethylphenols. The 2,6-dimethylphenol is purified by fractional distillation. The mixture of di- and trimethylphenols is sold as cresyHc acid for use as a solvent. 2,6-Dimethylphenol [576-26-1] is available in 55-gal dmms (208-L) and in bulk shipments in tank wagons and railcars. 

With 3-methylphenol (meto-cresol), around 8 % of dibromo products result when one equivalent of brominating agent is used, and this rises to 23 % of dibromo products on attempted monobromination of 3,5-dimethylphenol with 1 molar equivalent of resin. Nevertheless, the good yields of products obtained from the mono-substituted phenols tried demonstrate that this is a powerful new synthetic method for the organic chemist. 

The literature on basic- and acid-catalyzed alkylation of phenol and of its derivatives is wide [1,2], since this class of reactions finds industrial application for the synthesis of several intermediates 2-methylphenol as a monomer for the synthesis of epoxy cresol novolac resin 2,5-dimethylphenol as an intermediate for the synthesis of antiseptics, dyes and antioxidants 2,6-dimethylphenol used for the manufacture of polyphenylenoxide resins, and 2,3,6-trimethylphenol as a starting material for the synthesis of vitamin E. The nature of the products obtained in phenol methylation is affected by the surface characteristics of the catalyst, since catalysts having acid features address the electrophilic substitution in the ortho and para positions with respect to the hydroxy group (steric effects in confined environments may however affect the ortho/para-C-alkylation ratio), while with basic catalysts the ortho positions become the... 

The catalytic activity of Mg/Al/O sample in m-cresol gas-phase methylation is summarized in Figure 1, where the conversion of m-cresol, and the selectivity to the products are reported as a function of the reaction temperature. Products were 3-methylanisole (3-MA, the product of O-methylation), 2,3-dimethylphenol and 2,5-dimethylphenol (2,3-DMP and 2,5-DMP, the products of ortho-C-methylation), 3,4-dimethylphenol (3,4-DMP, the product of para-C-methylation), and poly-C-methylated compounds. Other by-products which formed in minor amounts were dimethylanisoles, toluene, benzene and anisole (not reported in the Figure). 

Gainesville, FL with individual fractions of three individual petroleum products at 24-25 °C for 24 h. The aqueous phase was analyzed for organic compounds via U.S. EPA approved test method 625. Average 2,4-dimethylphenol concentrations reported in water-soluble fractions of unleaded gasoline, kerosene, and diesel fuel were 50, 99, and 108 pg/L, respectively. 2,4-Dichlorophenol may also enter groundwater by leaching from coal tar, asphalt runoff, plastics, and pesticides (quoted, Verschueren, 1983). 

Chemical/Physical. Under atmospheric conditions, the gas-phase reaction of o-xylene with OH radicals and nitrogen oxides resulted in the formation of o-tolualdehyde, o-methylbenzyl nitrate, nitro-o-xylenes, 2,3-and 3,4-dimethylphenol (Atkinson, 1990). Kanno et al. (1982) studied the aqueous reaction of o-xylene and other aromatic hydrocarbons (benzene, toluene, w and p-xylene, and naphthalene) with hypochlorous acid in the presence of ammonium ion. They reported that the aromatic ring was not chlorinated as expected but was cleaved by chloramine forming cyanogen chloride. The amount of cyanogen chloride formed increased at lower pHs (Kanno et al., 1982). In the gas phase, o-xylene reacted with nitrate radicals in purified air forming the following products 5-nitro-2-methyltoluene and 6-nitro-2-methyltoluene, o-methylbenzaldehyde, and an aryl nitrate (Chiodini et ah, 1993). 

The phenol, the cresol isomers, and the dimethylphenols, major pyrolysis products in e Moscow wood sample, are probably also derived frt>m lignin precursors that have been altered through coalification reactions. Hatcher [fr] have shown that an increase is observed in the relative proportion of phenols and cresols as rank of coaHfred wood samples increases to subbituminous coal. Comparing the distribution of pyrolysis products from the Moscow wood to that of other coalified wood samples of Hatcher allows us to deduce that the... 

Waters (39) has described the oxidation of 2.6-dimethylphenol with alkaline ferricyanide. The products he obtained were the diphenoquinone (VIII R=R,=CH3) and an amorphous material (M.W. 800) which he did not further characterize. In retrospect, it would appear that this product was a low molecular weight polyphenylene ether (VII R=R1=CH3). 

Oxidation procedure. The reagent is freed from residual water by azeotropic distillation with benzene (CAUTION). The compound to be oxidised is then added and refluxed in benzene (c. 200ml for 0.5-2.0g of compound). At the end of the reaction (determined by t.l.c. monitoring), the solid phase is filtered off and the solvent evaporated. The product is usually highly pure and recrystallisation is unnecessary. With 2,6-dimethylphenol the molar ratio of phenol to silver carbonate is 1 4.4, and the reaction time is half an hour in this case 3,3, 5,5 -tetramethyldiphenoquinone is obtained in 98 per cent yield and has m.p. 217-218 °C. With 2,4,6-trimethylphenol, using the same molar ratio of phenol to oxidant, and a reaction time of 2 hours, 3,3, 5,5 -tetramethylstilbenequinone is obtained in 93 per cent yield and having m.p. 227-228 °C. 

Polyphenylenoxide (PPO) Substituted phenols are used as monomers for the production of polyphenylenoxides, (PPOs) so they as well as phenolic degradation products can be found as emitted odor active compounds. In one case the odor of a PPO was predominantly caused by 2,6-dimethylphenol and trimethylanisol as well as by a tentatively identified substituted methoxypyrazine (Mayer and Breuer, 2004a). Another potent odorant derived from higher molecular phenolic compounds, antioxidants for example, by the influence of heat (>200 °C) and pressure is guaiacol (2-methoxyphenol) (Mayer and Breuer, 2006). 

PdCl2(PhCN)2-catalysed Claisen rearrangement of the allyl vinyl ether 474 derived from cyclic ketone at room temperature affords the syn product 475 with high diastereoselectivity [203]. In contrast to thermal Claisen rearrangement, the Pd(II)-catalysed Claisen rearrangement is always stereoselective, irrespective of the geometry of allylic alkenes. The anti product is obtained by the thermal rearrangement in the presence of 2,6-dimethylphenol at 100 °C for lOh. 

Oxidation and polymerization of catechol, pyrogallol and 2,6-dimethylphenol (FTIR spectra) SEM coupled with energy dispersive X-ray spectrometry investigation of reaction products on surface of clay minerals, 13C NMR, MALDI MS study of reaction products... 

If the 2-naphthol derivative was replaced by 2,6-dimethylphenol, the main unexpected product is the [3]rotaxane (12%) among [2]rotaxane (9%) and the unencapsulated dye 5 (Figure 11) [35], The reaction mixture was separated by ultranitration. In [3]rotaxane there are three possible relative orientations of the CD units, but the compound is produced as a single stereoisomer. In DMSO [2]rotaxane exists preferentially in the conformation shown in Figure 11. 

---