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

  • Thomas Anderson Henry
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.

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    authors give m. p. 158°). Since no case is known in which a mercuri- residue enters the benzene ring meta to a hydroxyl group, it is highly probable that the dimercurated product is 4: 6-diacetoxymer- curicarvacrol (HO in 1), which also makes it analogous with the 2 : 4-diacetoxymercurithymol : the monomercurated carvacrol may have the mercuri-residue in either the 4- or the 6-position. Mercuration of Alkylphenolaldehydes. 2-Hydroxy-5-tert.-butylbenzaldehyde.—This substance has been prepared by the Reimer-Tiemann process (Dains and Rothrock, Amer. Chem. J., 1894,16, 635) but we were only able to obtain minute yields by this method. For these experiments, it was prepared by condensing _p-ter£.-butylphenol with formaldehyde (B.P. 161679/ 1920), a process which usually furnishes substances with the aldehyde group in the para-position to the hydroxyl group. In this case, the para-position is occupied and the aldehyde group enters the ortho-position. The yield of pure aldehyde, b. p. 138—140°/12 mm., was 46% of the theoretical. It gave a phenylhydrazone, bright yellow plates, m. p. 184° (Found : C, 76T9; H, 7-5; N, 10-4. Calc, for C17H20ON2 : C, 76-1; H, 7-5 ; N, 10-4%). 2-Hydroxy-5-£er£.-butylbenzaldehyde and mercuric acetate in molecular proportions, dissolved in alcohol containing acetic acid, were boiled under reflux for 15 minutes, a test portion then dis¬ solving completely in sodium hydroxide. On cooling, mercuric acetate separated and on reheating the mercury compound was again formed at once. The hot solution was therefore poured into a large volume of water and the resulting white precipitate was filtered ofi at once. After drying in a vacuum desiccator, the substance was crystallised from alcohol containing a very little acetic acid; white, needle-shaped crystals separated, m. p. 220°, but from the crystallisation of 3-8 g. only 1*93 g. of the mercury compound could be obtained (Found : C, 35-6; H, 3*8; Hg, 45*84, 45*96. C13H1604Hg requires C, 35*7; H, 3*7; Hg, 45*92%). This compound can only be 2-hydroxy-3-acetoxymercuri-5-teTt.-butyl- benzaldehyde. A yield of 73% of the theoretical can be obtained by heating together molecular proportions of the aldehyde and mercuric acetate on the water-bath for 2 hours without solvent. The liquid formed is then extracted with a hot mixture of benzene and ligroin containing acetic acid, filtered from mercurous acetate, and the filtrate set aside to cool, the mercuri-compound then separating. 2-Hydroxy-5-isoamylbenzaldehyde.—This substance has not been described previously. It was obtained by condensing p-isoamyl-