Mercuration of some alkylphenols and alkylphenolaldehydes / by T.A. Henry and T.M. Sharp.

  • Henry, Thomas Anderson, 1873-1958
Date:
[1926.]
Catalogue details

Licence: Public Domain Mark

Credit: Mercuration of some alkylphenols and alkylphenolaldehydes / by T.A. Henry and T.M. Sharp. Source: Wellcome Collection.

    4/16 (page 2433)
    It seemed desirable to ascertain whether the bactericidal action could be increased by the introduction of alkyl groups, since it is known that up to a certain point the O-alkylphenols show increasing bactericidal action with increasing weight of the substituent alkyl group. We selected for investigation p-tert.-butyl- and p-isoamyl- phenols, carvacrol, and thymol, and one aldehyde derived from each of these. Little has been done previously on the mercuration of alkyl- phenols and nothing on the mercuration of alkylphenolaldehydes. Dimroth has shown that p-cresol (Ber., 1902, 35, 2856) and thymol (ibid., 2864) both yield mono- and di-mercurated derivatives, and other workers have investigated the same substances. p4ert.- Butyl- and ^'soamyl-phenols are now found to behave similarly, yielding both mono- and di-substituted mercury derivatives. The positions of the two mercuri-groups in the latter are shown to be in both cases ortho to the hydroxyl groups, since on treatment with cold nitric acid o-dinitro-compounds are formed. The constitution of the monomercuri-compounds of these two phenols follows from those of the disubstituted derivatives, and similarly the mono- mercuri-derivatives of the corresponding aldehydes are shown to be 2-hydroxy-3-acetoxymercuri-54er£.-butylbenzaldehyde and 2-hydroxy-3-acetoxymercuri-5-^oamylbenzaldehyde, respectively. Carvacrol would be expected to yield three products, viz., the 4 : 6-diacetoxymercuri-, 4-acetoxymercuri-, and 6-acetoxymercuri- derivatives, since thymol yields the three analogous substances (Mameli and Mameli-Manessier, Gazzetta, 1922, 52, 1), but we have only succeeded in obtaining a dimercuri- and one monomercuri- compound from carvacrol. The former is, no doubt, the expected 4 : 6-diacetoxymercuri-derivative, but the position of the mercury in the latter is difficult to determine, since coupling with benzenedi- azonium chloride yields a dibenzeneazocarvacrol, and treatment with bromine gives rise to polybrominated products which furnish no clue to the constitution, whilst nitric and nitrous acids give only tarry products from which no crystalline substance could be obtained. In thymol- and carvacrol-aldehydes there are only two positions available for the entry of the acetoxymercuri-residue, one meta and one ortho to the hydroxyl group. It is almost certain, therefore, that the mercury in these substances occupies the ortho-position, since meta-substituted mercuri-compounds are rarely formed, even when the directing group is one which normally causes meta¬ substitution (compare, however, Dimroth, Annalen, 1925, 446, 148; Coffey, J., 1925, 127, 1029; this vol., p. 637). In the preparation of the four aldehydes used in the course of