The acid-catalyzed rearrangement of cinenic acid. V. evidence for a decarbonylation-rearbonylation mechanism

Journal Article · Wed Jan 20 04:00:00 EST 1960 · Journal of the American Chemical Society (U.S.)

DOI:https://doi.org/10.1021/ja01487a060· OSTI ID:4176465

Meinwald, J; Hwang, Ho Chien; Christman, D; Wolf, A P

A series of steps involving the loss and subsequent recapture of carbon monowde is suggested to account for the carboxyl group transfer characteristic of the cinenic acid rearrangement (I yields II). This reaction sequence is compatible with earlier observations. and can be supported by analogies at every stage. The participation of carbon monoxide is indicated by an experiment in which the rearrangement, carried out in the presence of excess carbon monoxide, gave a significantly increased yield of geronic acid (II). Rearrangement in the presence of C¹⁴-labeled carbon monoxide yielded labeled geronic acid. The possibillty that this incorperation is due to exchange of the carboxylic carbon of either the starting material I or the product II with the externally supplied carbon monoxide is excluded by appropriate c ontrol experiments.

• Research Organization: Cornell Univ., Ithaca, N.Y.; and Brookhaven National Lab., Upton, N.Y.
• Sponsoring Organization: USDOE
• NSA Number: NSA-14-007349
• OSTI ID: 4176465
• Journal Information: Journal of the American Chemical Society (U.S.), Journal Name: Journal of the American Chemical Society (U.S.) Vol. Vol: 82; ISSN JACSA
• Country of Publication: Country unknown/Code not available
• Language: English

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
ACIDS
CARBON 14
CARBON MONOXIDE
CATALYSIS
LABELLED COMPOUNDS
ORGANIC ACIDS
REACTION KINETICS