Catalytic hydrogenation of racemic 2-carbomethoxy-tropinone in acetic acid yields racemic alloecgonine methyl ester, which can be transformed to the racemates of alloecgonine, allococaine, allopseudoecgonine, allopseudoecgonine methyl ester, and allopseudococaine. Some limitations of a generalization concerning the course of the catalytic hydrogenation of cyclic ketones as it applies to certain keto derivatives of the tropane and morphine alkaloids are noted. The three-dimensional structures of the new cocaines are tentatively assigned. The possible utility of molecular rotation data in ascertaining the absolute configuration of transformation products of the 2-carbomethoxy derivatives of both tropinone and N-methylgranatonine is indicated. Some other possible methods of synthesizing the new cocaine isomers and the drawbacks thereof are mentioned. © 1959, American Chemical Society. All rights reserved.