Abstract
The solvolysis of 9-methyl-9-(2-X-2-propyl)fluorene (X = Cl, Br, or OOCCF3) (1-X) in aqueous acetonitrile or aqueous 1,1,1-trifluoroethanol (TFE) yields the alkene, 9-methyl-9-(propen-2-yl)fluorene (2), and the alcohol, 9-methyl-9-(2-hydroxy-2-propyl)fluorene (1-OH), accompanied by a small amount of substitution product from the reaction with the organic component of the solvent mixture. The fraction of elimination product increases with decreasing fraction of water in the solvent mixture as well as by addition of general bases, which can be expressed by a Bronsted parameter of β = 0.07 for the reaction of 1-Cl, measured with substituted acetate anions. Also, the addition of chloride ions increases the fraction of alkene. The kinetic deuterium isotope effects on the reactions of the hexadeuterated substrates vary with solvent composition in a way which is not consistent with a common carbocation intermediate which has time to choose between dehydronation and addition of a solvent water molecule. A stepwise preassociation mechanism is proposed for the elimination reaction.
Talk to us
Join us for a 30 min session where you can share your feedback and ask us any queries you have
More From: Journal of the Chemical Society, Perkin Transactions 2
Disclaimer: All third-party content on this website/platform is and will remain the property of their respective owners and is provided on "as is" basis without any warranties, express or implied. Use of third-party content does not indicate any affiliation, sponsorship with or endorsement by them. Any references to third-party content is to identify the corresponding services and shall be considered fair use under The CopyrightLaw.