Deamination of endo-and exo-2-aminobicyclo[3.1 .O] hexanes (7) and (8) and solvolysis of the corresponding 2-chloro-compounds (1) and (2) yield very similar ratios of products showing the intervention of a common 2-cation. Rate studies of solvolysis of 2-substituted bicyclohexyl derivatives and some 5-methyl-substituted compounds indicate that the normal rate-enhancing effect of the cyclopropyl group is due to delocalisation of the symmetrical homoallyl type for endo-and exo-leaving groups. Deuterium scrambling from the 5-position was not observed in solvolysis of chlorides (1) and (2). Leeds LS2 9JT 1 Preliminary communication, P. R. Brook, R. M. Ellam, and A. S. Bloss, Chem. Cornm., 1968, 425. p. 1295; (d) see also M. Hanack and H. J. Schneider, Angew. Chem. Internat. Edn., 1967, 6, 666; (e) B. Capon, Quart. Rev., 1964, 18, 45. charge and the neighbouring cyclopropyl group. Z-Substituted bicyclo[3.1 .O]hexanes were readily accessible compounds for study.A recent report prompts publication now. Tosyl esters of the epimeric bicyclo[3.1 .O]hexan-2-01s (4) and (5) were found too reactive for convenient isolation.g The corresponding endo-(1) and exo-Z-chlorobicyclohexanes (Z), were then chosen, as g.1.c. techniques could be used for analysis and purification (although not without difficulty).Reduction of bicyclohexan-%one (3) with sodium borohydride gave a mixture of the epimeric 2-alcohols containing 93% eutdo-derivative (4) .7 This mixture on of work closely related to our own
Some stilbene ozonides react mith dimethyl THE recent report1 that ozonides are readily solvolysed by sulphoxide, dimethyfformamide, and primary, secondary alcohols prompts us to report our observations on the and tertiary amines to give a single aldehyde and a reactions of some stilbene ozonides with dimethyl sulphsingle acid in quantitative yield oxide, dimethylformamide, and amines The ozonides
cis and trans-4-t-Butylcyclohexanol and 1-menthol have been converted to the phosphorodichloridates with phosphorus oxychloride. Similar reaction with thiophosphoryl chloride afforded the phosphorodichloridothioates. By using 2 mol equivs. of 4-r-butylcyclohexanol, analogous condensations gave the corresponding phosphochloridates and chloridothioates, but with 1-menthol the reaction was unsuccessful. The various chloridates were characterized by preparation of a wide range of derivatives, e.g. amidates, azides, hydrazides, and hydrazones. These compounds are of interest as potential pesticides and their spectral features are discussed.
a-Alkoxybenzyl hydroperoxides are converted rapidly and quantitatively a t room temperature into the corresponding alkyl benzoates by primary, secondary, and tertiary amines and by dimethyl sulphoxide.
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