35188-27-3Relevant articles and documents
Reactions of Cyclohexane Derivatives in Superacids
Dean, Christopher,Whittaker, David
, p. 1541 - 1543 (2007/10/02)
The reactions of menthol with FSO3H-SO2 and neomenthyl chloride with SbF5-SO2ClF follow different routes.The first yields a substituted cyclopentyl cation and the second a substituted cyclohexyl cation.Experiments on substituted cyclohexyl chlorides show that replacement of all the hydrogen atoms on the next but one carbon atom to the reaction centre blocks formation of a carbocation.It is suggested that ionisation of an equatorial chlorine atom takes place with assistance from an intramolecular electronic interaction, forming the methyl cyclopentyl carbocation in a synchronous process, rather than stepwise via the cyclohexyl carbocation.Reasons for contrasting behaviour in solvolytic reactions are discussed.
Carbon-13 magnetic resonance: hydrogen involvement in γ-anti substituent effects
Forrest, T. P.,Thiel, J.
, p. 2870 - 2875 (2007/10/02)
Chemical shifts have been determined for the carbons in a series of 3,3-dimethylcyclohexyl derivatives, (substituent = H, CH3, NH2, OH, Cl, Br, I).Comparison of the γ-anti substituent effects at carbons 3 and 5 indicates that presence of axial protons on these carbons causes increased shielding by all of the above substituents.The shielding by γ-anti substituents is decreased by the replacement of either the α or γ protons by methyl groups; the extent of the decrease is dependent upon the substituent and upon the position of the hydrogen which is replaced.
