Methylphenols, nitration

Photolytic. Sunlight irradiation of 2-methylphenol and nitrogen oxides in air yielded the following gas-phase products acetaldehyde, formaldehyde, pyruvic acid, peroxyacetyl nitrate, nitrocresols, and trace levels of nitric acid and methyl nitrate. Particulate phase products were also identified and these include 2-hydroxy-3-nitrotoluene, 2-hydroxy-5-nitrotoluene, 2-hydroxy-3,5-dinitrotoluene, and tentatively identified nitrocresol isomers (Grosjean, 1984). Absorbs UV light at a maximum wavelength of 270 nm (Dohnal and Fenclova, 1995). 

Methyl nitrate, see Acetaldehyde, 2-Butanone, 2-Methyl-1,3-butadiene, 2-Methylbutane, Methyl mercaptan. Methyl nitrite, 4-Methyl-2-pentanone, 2-Methylphenol, 2-Methylpropene, Methyl sulfide. Pentane, Toluene, o-Xylene, ro-Xylene... 

Methyl-l,3-bntadiene, 2-Methylbutane, 2-Methylpentane, 4-Methyl-2-pentanone, Pentane, Tolnene, o-Xylene, ro-Xylene Peroxyacetic acid, see Acetaldehyde Peroxyacetyl nitrate, see Acetone, Benzene, Butane, Dimethylamine, 2-Methylphenol, Triethylamine. o-Xylene... 

A strong base. Vigorous reaction with 1,2,4,5-tetrachlorobenzene has caused many industrial explosions and forms the extremely toxic 2,3,7,8-tetrachlorodibenzodioxin. Mixmres with aluminum + arsenic compounds form the poisonous gas arsine. Potentially explosive reaction with bromine, 4-chlorobutyronitrile, 4-chloro-2-methylphenol (in storage), nitrobenzene + heat, sodium tetrahydroborate, 2,2,2-trichloroethanol, zirconium + heat. Reacts to form explosive products with ammonia + silver nitrate (forms silver nitride), N,N -bis(trinitroethyl)urea (in storage), cyanogen... 

The direct nitration of m-cresol is unsatisfactory for obtaining 4-nitro-3-methylphenol (29%). A better procedure is to form the nitroso compound and oxidize it to the nitro compound (66% over-all). ... 

Methylphenol in ethanolic solution treated with ferric nitrate nonahydrate (1 equiv.) and heated briefly for 30 sec. afforded an 83% yield of 4-methyl-2-nitrophenol. Under similar conditions 4-chlorophenol gave 4-chloro-2-nitrophenol (88%), 4-bromophenol gave 4-bromo-2-nitrophenol (64%) and 2-chlorophenol, a mixture of 2-chloro-4-nitrophenol (56%) and 2-chk>ro-6-nitrophenol (35%). Aluminium, chromium and copper(ll) nitrates were also used (ref.63). 

For the formation of nitro derivatives mild conditions are essential to avoid replacement of the branched alkyl group (ref. 88). The nitration of 6-tert-butyl-3-methylphenol and methylation of the product 6-tert-butyl-2,4-dinitro-3-methylphenol in xylene containing potassium carbonate with dimethyl sulphate offers an alternative to the classical route for musk ambrette. Hazards can be involved in this more well-known procedure consisting of the nitration of 6-tert-butyl-3-methylanisole (ref. 89) in acetic anhydride. 

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