3655b. WENDER, I., GREENFIELD, H., METLIN, S., AND ORCHIN, M. Chemistry of the Oxo and Related Reactions. VI. Experiments With Meta- and Para-Substituted Benzyl Alcohols. Jour. Am. Chem. Soc., vol. 74, 1952, pp. 4079-4083.
Nuclear-substituted benzyl alcohols react with synthesis gas (2H2:1CO) in the present of a Co catalyst (dicobalt octacarbonyl) to give a mixture containing a substituted toluene derived from the hydrogenolysis of the hydroxyl group (reduction) in addition to a substituted 2-phenylethanol (homologation). The effect of the substituent on the overall rate of the reaction and on the product distribution was studied in a series of semiquantitative experiments. The rate of reaction decreased in the following order: p-OCH3>>p-CH3>m-CH3, p-t-butyl>H>p-Cl>m-OCH3>>m-CF3. The proportion of homologation product as compared to reduction product also increased in the order in which the substituent is capable of releasing electrons but this effect was not nearly as pronounced as the effect on the reaction rate.
WENDER, I., LEVINE, R., AND ORCHIN, M. Chemistry of the Oxo and Related Reactions. II. Hydrogenation. See abs. 3653.
WENDER, I., METLIN, S., AND ORCHIN, M. Chemistry of the Oxo and Related Reactions. V. Acid Catalysis With Pinacol. See abs. 3655a.