77440-95-0Relevant articles and documents
SUR LA REACTION ENTRE LE CHLORURE DE PYRIDINIUM ET LES NITROALCANES PRIMAIRES
Dauzonne, Daniel,Demerseman, Pierre,Royer, Rene
, p. 601 - 608 (2007/10/02)
The lack of homogeneity in the dealkylation of phenol ethers by pyridinium halides had been overcome in a few cases by the use of solvents such as quinoline.The high dissolving power of nitrohydrocarbons led us to study their behaviour in the presence of pyridinium chloride and of 2-methoxynaphthalene 1, taken as the reference ether.On one hand, nitrobenzene is a good solvent which homogenizes the reaction mixture but slows down the reaction; on the other hand, it is not so with nitroalkanes which quickly interact.Thus, a mixture of 2-methoxynaphthalene 1, nitroethane and pyridinium chloride yields, after refluxing, 1-chloro-2-methoxynaphthalene 2, 1-acetylpyridinium chloride oxime 3, acetic acid, acetohydroxamic acid 5, acetonitrile, acetamide and ammonium chloride, in various proportions according to the relative amounts of reagents or the heating duration.The unusual chlorination of 1 can be carried out with primary nitro-alkanes other than nitroethane.Methyl phenol ethers other than 1 can be halogenated if they have a sufficiently electrophilic position.With this method, we were able to synthesize a few mono- or dichlorinated compounds starting from 1,6- or 1,7-dimethoxynaphthalenes and 5-methoxybenzofuran.The study of the experiments run with varying proportions of reactants or with overaddition of one or the other of the resulting products suggests a few mechanisms.Pyridinium bromide induces the same type of reaction, but with lower yields.
