74880-46-9Relevant academic research and scientific papers
Electrophilic cleavage of cyclopropanes. II. Concerning the effect of increasing electron demand upon the product-determining transition state in the reaction of 4-substituted-2-nitrobenzenesulphenyl chlorides and benzenesulphenyl chlorides with tetracyclo2,7.04,6>heptane....
Beaulieu, Pierre L.,Kabo, Ann,Garratt, Dennis G.
, p. 1014 - 1020 (2007/10/02)
The effect of increasing electron demand upon the product-determining transition state in the reaction of arenesulphenyl chlorides with tetracyclo2,7.04,6>heptane has been investigated.As the electron donating ability of the remote substituents on the phenyl ring of the sulphenyl chloride is varied from nitro to methoxy the relative proportion of adducts derived from edge-on attack is found to increase relative to that of adducts derived from corner attack.An ortho-nitro group was found to lead to a stabilizing interaction only in the case of 2,4-dinitrobenzenesulphenyl chloride.A mechanism involving the competition between the two conceptual modes of approach is suggested.
Addition of arenesulphenyl chlorides to 2-methylenebicyclohept-5-ene: effect of increasing electron demand upon the rate and product determining transition states
Garratt, Dennis G.,Beaulieu, Pierre L.,Morisset, Veronique M.
, p. 1021 - 1029 (2007/10/02)
The rates and products of addition of a series of sixteen arenesulphenyl chlorides to 2-methylenebicyclohept-5-ene, 7, and the E,Z isomeric 2-ethylidenebicyclohept-5-enes, 8, and 9, have been determined in methylene chloride solution.The major species from attack on 7 is always endo-3-arylthio-1-chloromethyltricyclo2,6>heptane, the product of exo attack upon the endocyclic double bond with homoallylic participation of the exocyclic Π system.No evidence was found for initial electrophilic attack upon the exocyclic double bond.
