P-Nitroso-N-methylaniline

There is no reference to the formation of the ortho nitroso amine in the benzene series, indeed the formation and characterisation of ortho nitroso amines from any reaction has only been reported once or twice79. When the para position is blocked by a substituent, de-nitrosation so the secondary amine can occur80 a certain amount (which depends on the conditions) of denitrosation occurs also, concurrently with the rearrangement81, so that N-nitroso-N-methylaniline (XLVII) yields N-methylaniline (XLVIII) as well as the rearrangement product p-nitroso-N-methylaniline XLIX, viz. 

Methylphenylnitrosoamine E thylpheny Ln itrosoamine Nitrosobenzene o-Nitrosotoluene. m-Nitrosotoluene. p-Nitrosotoluene. a-Nitrosonaphthalene. p-Nitrosophenol. a-Nitroso-P-naphthol. 4-Nitroso- a-naphthol pNitrosoNNdimethylaniline p-Nitroso -NN diethylani line. p-Nitroso-N-methylaniline p-Nitroso-Nethylaniline p-Nitrosodiphenylamine... 

N,4-DinitrO N-methylaniline, bright yellow needles from benz, mp 142.5° (Ref 2) CA Registry No 16698-03-6. It is prepu by the alkylation of N,p-dinitroaniline with methyl iodide in alk soln (Refs 8 9). It is one compd isolated from aged NC propints stabilized with N-methyl-p-nitroaniline. Hollingsworth at ERDE examined the reaction of nitrogen dioxide with this stabilizer in order to elucidate the mechanism of the formation of the compds isolated. He found that after 7 days at 35°,. a good yield of N,4-dinitro-N-methylaniline was obtd and postulated that it arose from the oxidn of N-nitroso-4-nitroaniline (Ref 16)... 

Battegay and Kern [58] treated methylaniline with nitrogen dioxide and obtained p- nitro-N-nitrosomethylaniline or, with nitrogen dioxide in excess, 2,4-di-nitromethylaniline. From dimethylaniline p- nitroso- and p- nitrodimethylaniline have been obtained, and with an excess of nitrogen dioxide, 2,4-dinitrodimethyl-aniline. Similar results have been obtained by Schaarschmidt, Balcerkiewicz and Gante [39],... 

N-nitrosation and simultaneous C-nitration of secondary aromatic amines by aqueous solution of N204 has been studied by Stoermer [61] and Ruff and Stein [62], Thus N-methylaniline yielded N-methyl-n-nitroso-p-nitroaniline. 

Miller and Meyer, 1971). The gaseous products are the same as those derived from the reaction of nitrous acid with azide ion. The reaction is kinetically first order in each reactant, and it is likely that an intermediate complex is also formed in this case. Similarly a p-nitroso complex is formed from the same ruthenium nitrosyl and N-methylaniline, possibly by initial... 

Another side reaction which occurs is reduction in the reaction the —N2C1 or —N(NO)COCH3 group is replaced by hydrogen. wi-Bromo-toluene was isolated in 6% yield from the reaction between the sodium diazotate from 2-bromo-4-methylaniline and benzene, and in 10% yield in a similar reaction from 2-methyl-4-bromoaniline.4 Some nitrobenzene is obtained in the preparation of 3-nitrobiphenyl from nitroso-w-nitro-acetanilide (p. 250). The source of the hydrogen effecting the reduction has not been determined. f... 

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