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The oxidation of N-methyl-N-5-hexenylhydroxylamine with mercuric oxide and the condensation between 5-hexenal and N-methylhydroxylamine afforded cis-S-methyl-3-oxa-2-azabicyclo[3.3.0~octane (2). Other bicyclic isoxazolidines have been synthesized by the condensation reaction employing unsaturated aldehydes and unsaturated ketones. The structures of these compounds were proved by hydrogenolysis and, in some cases, independent synthesis of the amino alcohols. The mechanism of the cyclization reactions are postulated as intramolecular 1,3-additions of an unsaturated nitrone intermediate. The scope of this preparative route t o fused bicyclic isoxazolidines is discussed in terms of reactivity, orientation, and stereochemistry.The pyrolysis of a mixture of the isomeric N-methyl- methyl-8-oxa-2-azabicyclo[3.3.Oloctane (Z), and wasa-pipecoline oxides produced, in addition to the pre-postulated as having arisen from an unsaturated dicted unsaturated hydroxylamine, an unexpected nitrone intermediate (1). The nitrone may have been bicyclic base. * This product was identified as Nproduced from N-inethyl-N-5-hexenylhydroxylan1ine( 1 ) A preliminary communication concerning a part of this work has ap-by an oxidation-reduction reaction. However, this peared-J A m Chem Sot, 81, 6334 (1959). This work was reported in unsaturated hydroxylamine was obtained in good p a r t : Abstracts, 137th National Meeting of the American Chemical Society.Cleveland, Ohio, April 1960, p. 8.5-0.( 2 ) A C Cope and N A LeRel, J A m Chrm S o c , 81, 4656 (I$lRO)

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because of the instability of 5 toward handling in the pure state, quantitative extinction coefficients were not obtained); nmr (CDCla) 1. 95-3.50 (m, 6, Ar H), 3.28 (s, 2, CH=CH), and 6.98 (s, 3, NCH3); mass spectrum (70 eV) m/e (rel intensity) 237 (100) and 208 (26).Anal. Caled for CisHnNS: mol wt, 237.061. Found:(high-resolution mass spectrum), 237.061. Thermal Decomposition of 5.-A solution of 8 mg of 5 in 0.5 ml of benzene was placed in a thick-walled tube, degassed, sealed, and heated in an oil bath maintained at 203 ± 0.5°for 20 hr. After the tube had been cooled, it was opened and the solution was concentrated. Analysis of the residue by tic over silica gel using benzene for elution showed five components. The major component, also the one of highest Rt value (0.8), had a characteristic bright blue fluorescence. This was separated and rerun in a tic comparison with an authentic sample of 19. Both showed the same blue fluorescence and both were identical in their tic behavior.