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The use of azodicarboxylic acid esters as dealkylating agents has been studied. The isolation and structure proof of the intermediate adducts obtained from the reaction of the azo esters with secondary and tertiary amines is reported. Dealkylation of compounds other than amines by this method is also discussed.The diesters of azodicarboxylic acid (1, 2) react with aliphatic primary amines to give amides,2-4 while primary aromatic amines yield either triazan addition compounds4-6 or ring-substituted systems.6'7 It was (1) Taken in part irom the dissertation presented by A, Makriyannis, March 1967, to the Graduate School of the University of Kansas in partial fulfillment of the requirements for the Doctor of Philosophy degree.

HYDROGEN BONDIPI'G IN 3-PIPERIDINOLS 1207were vacuum distilled from the residue. The remaining material was dissolved in 3 ml. of benzene and treated with 520 mg. (0.002 mole) of stannic chloride. After 1 hour a t ordinary temperature, the mixture was diluted with ether and extracted successively with 2 N aqueous hydrochloric acid, 2 N aqueous potassium hydroxide and water. The remainder from the dried (MgSOa) ether solution was recrystallized from a mixture of ethanol and water: vield 34 mg. (107'); infrared spectrum: 6.10 p (carbonyl associated with NH); m.p. 250-252°.32 Calcd. for CllHgSO (171.19): C, 77.17; H, 5.30. Found: C, 77.04; H, 5.66.Anal.Diethyl a,a-di-(4-cyanoskatyl)-malonate was isolated from the mother liquors remaining after the crystallization of ethyl a-carboethoxy-~-(4-cyano-3-indole)-propionate1 and was purified by recrystallization from acetone; m.p. 235-237".Anal. Calcd. for CnH24N204 (440.48): C, 69.22; H, 516; N, 11.96. Found: C, 69.10; H, 5.50: N, 11..97.Methyl (4-Carbomethoxy-3-indole)-acetate.-To a solution of 200 mg. (0.001 mole) of 4-cyanogramine and 326 mg. (0.005 mole) of potassium cyanide in 25 ml. of methanol was added, in 4 portions a t 15-minute intervals, 2.0 ml. (0.02 mole) of dimethyl sulfate. After 3 hours a t ordinary tem-(32) Cf. the preparation of this substance by the Fischer procedure from 1,2-cyclopentadione monophenylhydrazone: R . H. F. hlanske, Can.