Journal of the American Chemical Society p. 8873 - 8878 (1990)
Update date:2022-08-02
Topics:
Allen, Annette D.
Kitamura, Tsugio
McClelland
Stang, Peter J.
Tidwell, Thomas T.
Reactions of l-ethynyl benzoates RC≡CO2CC6H4X in H2O and CH3OH have been studied. In neutral H2O, reaction rates for CH3C≡CO2CC6H4X depend on σp of X with p of 1.3. Reaction of CH3C≡CO2CPh (1) in 18O-labeled H2O gives CH3CH2CO2H and PhCO2H in 54% relative yield with 90 and 83%, respectively, incorporation of a single 18O in the acids and CH3COCH2O2CPh (2) in 46% relative yield with 100% incorporation of 18O in both carbonyl oxygens. These results arc explained by the hypothesis that at least 46% of 1 reacts by cyclization to an intermediate 2-hydroxy-1,3-dioxolene 18. Mcthanolysis of 1 and other alkynyl benzoates gives 2-methoxy-1,3-dioxolenes, confirming the cyclization pathway. Reaction in 44% H2SO4 of 2-methoxy-2-phenyl-4-tert-butyl-1,3-dioxol-4-ene (8), prepared in this way, gives the 2-phenyl-4-tert-butyl-1,3-dioxol-4-enylium cation (16), directly observable by UV, which hydrolyzes to t-BuCOCH2O2CPh (12).
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(1990)