Inorganic Reactions

Abstract

a monoester carboxylic acid (VI), m.p. 235-237°.7 Conversion of the carboxy group of VI to a hydroxy group was achieved by treatment of the acid chloride8 of VI with dimethylcadmium,9 followed by the Baeyer-Villeger reaction on the resulting methyl ketone (VII)10 (n.m.r. spectra: OMe (3) 6.29 r, CO-CH3 (3) 7.84, NCO-CH3 (3) 7.93, C-CH3 (3) 9.15) and finally mild alkaline hydrolysis of the acetate (VIII),10 ("»(5.81, 6.18, 8.05 µ). The resulting hydroxy compound (IX) melted at 205-206°. Oxidation of IX with chromic acid gave the corresponding ketone (X), m.p. 172-176°, which was carbomethoxylated with dimethyl carbonate and sodium methoxide11 to provide a ß-keto ester (XI) (amorphous, 5.82, 6.03, 6.20 µ: ^1 , 253 µ (e 9800)). Reduction of XI wth sodium borohydride and treatment of the resulting epimeric alcohols with tosyl chloride provided an un-saturated ester, m.p. 175-180°. This unsaturated ester was hydrogenated and the resulting mixture was treated with sodium methoxide. Chromatography of the saturated compounds separated a dimethyl ester (XII), m.p. 197-199°, and the alkaline hydrolysis of XII gave a monomethyl ester carboxylic acid (XIII), m.p. 248-250°. The identity of XII and XIII with those obtained from atisine612 was confirmed by means of mixture melting point and infrared spectra, respectively. Conversion of XIII to atisine has recently been reported.13 Thus, the first conversion of Garrya alka-loids, veatchine and garryine, to atisine has been achieved. Since garryine has been synthesized,1 we have now completed in a formal sense the synthesis of atisine also.14-16 Acknowledgment.-The author is grateful to Mr. N. T. Castellucci for his technical assistance throughout this work. (7) The direct alkaline hydrolysis of the dimethyl ester of IV at room temperature gave a cis ester carboxylic acid, m.p. 184-186°. See ref. 6. (8) The amide group was found to react with oxalyl chloride slowly. Therefore, addition of this reagent was carefully controlled.