THE REACTION OF ORGANIC ANIONS WITH CARBON MONOXIDE.
Abstract
The research described has been directed toward two objectives: first, elucidation of the mechanism of reaction of carbon monoxide with organolithium reagents; and second, exploration of the reactions of dialkyl-substituted acetylenes with triarylchromium(III) compounds. The broad outline of the former mechanism has been established. The initial step in the reaction involves formal insertion of carbon monoxide into an organolithium aggregate (illustrated by phenyllithium dimer) followed by partitioning of the resulting ketone dianion between two principal competing reaction paths leading ultimately after hydrolysis to benzhydryl phenyl ketone, benzhydrol, and benzophenone as the principal reaction products. The work is of interest as a potential entry into the chemistry of ketyls and ketone dianions, and for its elaboration of a unique mechanistic pathway for a reaction of an organolithium reagent. The cyclooligimerization of 2-butyne to 1,2,3,4-tetramethylnaphthalene on reaction with triphenyltris(tetrahydrofuran)chromium(III) has been shown to involve initial insertion of acetylene into a carbon-chromium sigma-bond, followed by elimination of benzene with formation of an intermediate metallocycle. The work also establishes a basis for rational application of organochromium reagents in certain types of organic synthesis, in addition to providing the most clearly established description available for cyclooligimerization of an acetylene using a transition metal catalyst. (Author)
Document Details
- Document Type
- Technical Report
- Publication Date
- Jan 01, 1969
- Accession Number
- AD0702990
Entities
People
- George M. Whitesides
Organizations
- Massachusetts Institute of Technology