Phenetole, nitration

Phenol ethers, like the parent phenols, are reactive substrates. Phenol ethers like anisole and phenetole are readily nitrated to their picryl ethers, 2,4,6-trinitroanisole and 2,4,6-trinitrophenetole respectively, on treatment with mixed acid composed of concentrated nitric and sulfuric acids at 0 °C. Such reactions are vigorous, prone to oxidative side-reactions, and pose a considerable safety risk. The direct nitration of 2,4-dinitrophenol ethers, obtained from the reaction of 2,4-dinitrochlorobenzene with alkoxides, provides a more practical route to picryl ethers on an industrial scale. ... 

N, N -Dimethyl-Nl,4,6-trinitro-m-pbenylene-diamine, H3C.NH.C6H2(N02)2.N(N02)-CM3 crysts, mp 181.5° was prepd by treating 4,6-dinitro-3 methylnitramino-phenetole with an alcoholic methylamine soln can be nitrated to form an expl pentanitro deriv (Refs... 

Trinitro-4-acetaminophenolethylether (called by Lorang 4-Ethoxy-2,3,6-trinitroacetanilide), crysts (from ale), mp ca 260° (dec) sol in acet AcOH, diff sol in hot ale or benz. Can be prepd by nitrating 2,3-dinitro-4-acetamino-phenetole with mixed nitric-sulfuric acid at RT. Its expl props were not examined... 

Slavinskaya [21] in 1957, found that phenol can be nitrated to o-, p- and 2,4-dinitrophenol using nitric acid dissolved in ethyl nitrate at a concentration as low as 0.5% HN03. Phenetole and naphthalene can also be nitrated with this solution to yield mononitro products. The presence of N02 was essential for successful nitration at such a low concentration of HN03. 

Similarly trinitrophenetole was first obtained by file direct nitration of phenetole, but at present this method is not used, chlorodinitrobenzene being a starting material. Trinitrophenetole is less important then trinitroanisole. Its manufacture never developed beyond the semi-commercial scale. Similarly other picric acid ethers, as for example nitro derivatives of phenyl ether, have not found any practical use. 

DinitrophenetQle. Colorl leaflets from dil ale needles from w or ale mp 86—7° subl, decomps at higher temps. Can be prepd by the nitration of phenetole with fuming nitric acid or by other methods given in Ref 1. Desvergnes (Ref 3) gives a detailed description of its lab scale prepn. The Japanese (Ref 4) prepd it on... 

Alkyl derivatives other than halides have been used to form pyridinium salts. Potassium ethyl sulphate gives the ethyl-pyridinium salt i and dimethyl sulphate is nd alkyl toluenesulphonates i quaternize pyridine. Primary and secondary alkyl nitrates and polymethylene dinitrates have also been used, but with t-butyl and cyclohexyl nitrate only elimination occurs320. 2,4,6-Trinitro-anisole and -phenetole convert pyridine into the alkylpyridinium picrates32i. 

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