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.

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    phenol with formaldehyde and is a liquid boiling at 165—168°/ 17 mm. The yield of pure aldehyde was 35% of the theoretical (Found : C, 74-6; H, 8-4. C12H1602 requires C, 74-96; H, 8-4%) : semicar bazone, white needles from alcohol, m. p. 222° (Found : C, 62-3; H, 7-55; N, 17-1. C13H1902N3 requires C, 62-55; H, 7-69; N, 16-89%). The phenylhydrazone crystallises from alcohol in white plates, which soon turn yellow, m. p. 177—178° (Found : C, 76-6; H, 8-0; N, 10-3. C18H22ON2 requires C, 76-52; H, 7-85; N, 9-97%). The mercuration of this aldehyde in alcoholic solution gave only a small yield of mercury compound, and the same phenomenon of demercuration was observed on cooling the alcoholic solution (see above). A much better yield was obtained by heating together equimolecular proportions of 2-hydroxy-5-isoamylbenzaldehyde and mercuric acetate on a water-bath in the absence of any solvent. After heating for 4 hours, a dark liquid was obtained which contained a trace of mercurous acetate but was otherwise completely soluble in sodium hydroxide. The liquid was extracted with ligroin, filtered from mercurous acetate, and the solution left to cool; bundles of white needles, m. p. 134—135°, were then obtained (yield 85% of theoretical) (Found : C, 37-27; H, 3-94; Hg, 44-6. Ci4Hi804Hg requires C, 37-27 ; H,4-0; Hg, 44-5%). This compound must be 2-hydroxy-Z-acetoxymercuri-5-isoamylbenzaldehyde. 4:-Hydroxy-3-methyl-Q-\sopropylbenzaldehyde (p-carvacrolaldehyde). —Molecular proportions of p-carvacrolaldehyde, prepared by Adams and Montgomery’s form of the Gattermann process (J. Amer. Chem. Soc., 1924, 46, 1519), and mercuric acetate, dissolved in alcohol containing acetic acid, were boiled under reflux for 1J hours; a test portion well diluted with water then dissolved com¬ pletely in sodium hydroxide solution. The solution was filtered from a trace of mercurous acetate into excess of a 10% solution of sodium chloride. A pale cream-coloured precipitate formed (m. p. about 260°, decomp.); it was filtered, dried in a desiccator, crystallised from acetone containing one drop of hydrochloric acid, and thus obtained in small, four-sided plates, which soften and darken at about 209° and decompose indefinitely at about 260° (Found : C, 31-92; H, 3-17; Hg, 48-67. CnH1302ClHg requires C, 31-95; H, 3-17; Hg, 48-54%). This substance is no doubt 4-hydroxy- 5-chbromercuri-3-methyl-ft-isopropylbenzaldehyde, since the only other possible position for the mercury is meta to the hydroxyl group. This compound is curiously unstable in solution; from 5-3 g. dis¬ solved in acetone only 2-7 g. of the mercury compound could be recovered and the mother-liquors yielded unmercurated p-carvacrol-