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The reaction of cyclopentadienylidine, fluorenylidene and tetrachlorocyclopentadienylidene with alcohols. A laser flash photolysis study
Author(s) -
Olson David R.,
Platz Matthew S.
Publication year - 1996
Publication title -
journal of physical organic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.325
H-Index - 66
eISSN - 1099-1395
pISSN - 0894-3230
DOI - 10.1002/(sici)1099-1395(199611)9:11<759::aid-poc834>3.0.co;2-o
Subject(s) - chemistry , tetrahydrofuran , flash photolysis , photochemistry , ylide , pyridine , methanol , alcohol , benzophenone , reaction rate constant , benzyl alcohol , organic chemistry , medicinal chemistry , kinetics , catalysis , physics , quantum mechanics , solvent
Rate constants of reaction of cyclopentadienylidene, fluorenylidene and tetrachlorocyclopentadienylidene with alcohols and other quenchers were determined by laser flash photolysis methods. The rate constants of reaction of cyclopentadienylidene and fluorenylidene with various alcohols were determined and found to increase with increasing alcohol acidity. Alcohols as a group reacted faster with cyclopentadienylidene and fluorenylidene than likely ylide formers such as pyridine, ethyl acetate and tetrahydrofuran. Brønsted plots of the reaction of cyclopentadienylidene and fluorenylidene with alcohols are linear with slopes of 0·061 and 0·082, respectively. In the case of tetrachlorocyclopentadienylidene, an ylide type of reaction mechanism with alcohols is indicated. Tetrachlorocyclopentadienylidene reacts most rapidly with the least acidic alcohol studied and this carbene reacts more rapidly with tetramethylurea, pyridine and tetrahydrofuran than with methanol.