?-Hydroxy carbocation intermediates in solvolyses of di- and tetra-hydronaphthalene substrates.

ABSTRACT: Solvolysis of trichloroacetate esters of 2-methoxy-1,2-dihydro-1-naphthols shows a remarkably large difference in rates between the cis and trans isomers, k(cis)/k(trans) = 1800 in aqueous acetonitrile. This mirrors the behaviour of the acid-catalysed dehydration of cis- and trans-naphthalene-1,2-dihydrodiols to form 2-naphthol, for which k(cis)/k(trans) = 440, but contrasts with that for solvolysis of tetrahydronaphthalene substrates, 1-chloro-2-hydroxy-1,2,3,4-tetrahydronaphthalenes, for which k(cis)/k(trans) = 0.5. Evidence is presented showing that the trans isomer of the dihydro substrates reacts unusually slowly rather than the cis isomer unusually rapidly. Comparison of rates of solvolysis of 1-chloro-1,2,3,4-tetrahydronaphthalene and the corresponding (cis) substrate with a 2-hydroxy group indicates that a ?-OH slows the reaction by nearly 2000-fold, which represents a typical inductive effect characteristic also of cis-dihydrodiol substrates. The slow reaction of the trans-dihydrodiol substrate is consistent with initial formation of a ?-hydroxynaphthalenium carbocation with a conformation in which a C-OH occupies an axial position ? to the carbocation centre preventing stabilisation of the carbocation by C-H hyperconjugation, which would occur in the conformation initially formed from the cis isomer. It is suggested that C-H hyperconjugation is particularly pronounced for a ?-hydroxynaphthalenium ion intermediate because the stability of its no-bond resonance structure reflects the presence of an aromatic naphthol structure.

SUBMITTER: Kudavalli JS 

PROVIDER: S-EPMC2981814 | biostudies-other | 2010

REPOSITORIES: biostudies-other