PART I. INVESTIGATIONS INTO THE REACTION OF BENZYLMAGNESIUM CHLORIDE WITH FORMALDEHYDE. PART II. THE REDUCTION OF IMINES TO AMINES BY THE ADDITION OF TRICHLOROSILANE
Abstract
I. The reaction of benzylmagnesium chloride in THF with monomeric formaldehyde was studied in detail. Time and concentration experiments, deuterium tracer studies, and trimethylchlorosilane trapping experiments provided adequate data to formulate a reasonable mechanism for the normal and abnormal products formed. It was determined that several steps of the reaction are reversible, a fact not previously considered. A stereospecific 1,3 hydrogen shift, possibly base-assisted, was documented and related to the formation of an anionic species which was trapped as the trimethylsilyl derivative. An ene reaction was also postulated as a probable route to the formation of an abnormal diol product. The various possible reaction pathways were compared and the relative importance of each discussed. II. The interaction of trichlorosilane with various imines was studied. It was found that trichlorosilane adds regiospecifically to the carbon-nitrogen double bond of imines without the necessity of a catalyst. The N-trichlorosilyl intermediates could be hydrolyzed in situ by alcoholic base to give the corresponding secondary amines in moderate to good yields. A mechanism was proposed, based on the formation of an initial complex between the silicon of the trichlorosilane and the nitrogen of the imine, followed by an intramolecular, four-centered hydride transfer to give the addition product.
Degree
Ph.D.
Subject Area
Organic chemistry
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