The Synthesis of Three Monodeuterionorbornanes, and the

ALEXNICKOSA I ~ DJAMES H . HAMMONS

3322 [CONTRIBUTION FROhl

THE

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DEPARTMEST O F CHEMISTRV O F THEJOHNSHOPKISSUSIVERSITY, BALTIMORE 18, MD.]

The Synthesis of Three Monodeuterionorbornanes, and the Stereochemistry of Acid-Catalyzed Cleavage of Nortricyclene' BY ALEXNICKONAND

JAMES

H HAMMOWS

RECEIVED MARCH28, 1964 This paper describes the synthesis and characterization of 1-deuterionorbornane (4), exo-deuterionorbornane

(7), and endo-deuterionorbornane (14), and their use in a stereochemical study of ring cleavage of nortricyclene (1). Reduction of 1-chloronorbornane (3)with sodium and methanol-d gave 4. Treatment of the p-bromobenzenesulfonate of endo-norborneol with lithium aluminum deuteride gave 7, which also was the principal product on similar reduction of either endo- or exo-chloronorbornane. Reaction of norbornan-2-one with lithium aluminum deuteride gave 2-exo-d-2-endo-norborneol ( 1Z), which was converted t o its p-bromobenzeuesulfonate and reduced with lithium aluminum hydride t o endo-d-norbornane ( 14), believed t o contain a small proportion (vided h y Pi-ofesior K J C', l i c , x e r i h r f i 84. l O i l 7 , l Q ( i 2 j ] ,

XIislow [ K h l i s l o w a n d

H. HAMMONS

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with no detectable amount (