I&any papers, including kinetical studies, have been published oonoerning N -c 0 aoyl migrations in 1,2-aminoalcohols /e.g. 1, 2/ and in alicyolic systems /e.g. 3/; details of the mechanism are still under investigation /4/. The similar reactions of 1,3_aninoalcohols /5-T/ and 1,4_nninoalcohols /8,9/, especially when the functional groups are attached to an alicyolic ring, have been studied in a few oases only.
Pe oompared the N + 0 aoyl migration and some other stereospecific reactions of alioyclic 1,2-, 1,3-and X,Ganinoalcohols.
Our aim was to obtain information ooncerning the conformational and energetical conditions of the starting alicyoliq skeletons and the bioyclio intermediates of the reactions. This paper deals with the N -+ 0 aoyl migration react.ions of B-benzoyl and p-substituted N-benzoyl derivatives of the compounds given in the title.
$&-and trans-2-aminomethyloyolohexanol and &-and trans--2-hydroxymethyzohexylamine were prepared by stereospecific synthesis, the last step being the reduction with LiA1H4 of cis_ and trans-2-hydroxyoyclohexanecarboxylic aride and c&s-and transethyl 2aminocyolohexaneoarboxylate, respectively. A kinetic study of the N -CO acyl migration reaotions in the Ibbenzoyl and p-substituted N-benzoyl derivatives of these compounds Vias mode in anhydrous dioxan, in presence of a 0,5 mole excess of El, between 80' and ll2', at 3-5 different temperatures for each compound. The reaction rate constants, calculated by seoond-orjer equation, the activation energies and activation entropie s are Given in Table I.
It is seen that N -0 aoyl migration takes place at a higher rate in the case of the trans isomers, v:hen the transitory formotion of a mono-aza-mono-oxa-trans-clecalin structure /I,II/ is more favoured than the ois-dcoalin-like intcrireciiate /IIi,IV/ arising from the corresponding cis-isoners. Since the reverso order of relative stabilities is expected for the intercedistes, it iS the forration of the cyclic internediztes :7l;ich lieo?lcs t!le reaction r:ltes.