65861-87-2Relevant articles and documents
3α-Acetoxy-6,6-dimethylbicyclo[3.1.1]heptane-2-spiro-1′- cyclopropane from nopylamine deamination
Abraham, Raymond J.,Jones-Parry, Richard,Giddings, Rodney M.,Guy, Jonathan,Whittaker, David
, p. 643 - 646 (2007/10/03)
Deamination of nopylamine hydrochloride with sodium nitrite in acetic acid yields nopyl chloride 8, nopyl acetate 1 (R = OAc), 2-(1-acetoxyethyl)-6,6-dimethylbicyclo[3.1.1]hept-2-ene 9 and 3α-acetoxy-6,6-dimethylbicyclo[3.1.1]heptane-2-spiro-1′-cyclopropane 12. The products are consistent with initial formation of a diazonium ion which reacts by nucleophilic attack, hydride shift or by shift of electrons of the double bond. The reaction is contrasted with the acetolysis of nopyl toluene-p-sulfonate, which yields 8,8-dimethyltricyclo[4.2.1.03,7]nonan-6-ol as the main product. The difference is suggested to result from the transition state being reached early (deamination) or late (toluene-p-sulfonate acetolysis) on the reaction coordinate.