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Published August 1946 | public
Journal Article

Allylic Rearrangements. XXI. Further Studies Related to the Nature of the Butenyl Grignard Reagent

Abstract

Cleavage of the butenyl Grignard reagent by water gives a mixture of butenes, although the products from a variety of addition and coupling reactions are almost exclusively α-methylallyl derivatives. To gain further information regarding the butenyl Grignard reagent we have turned to the study of some reactions expected to cleave the reagent to butenes through the operation of mechanisms different from that involved with water. For the cleavage of butenylmagnesium bromide by an enolizable ketone, acetomesitylene was chosen since several investigators have shown that organometallic compounds such as ethylmagnesium bromide, n-butyllithium and phenylsodium do not add to the carbonyl group of this compound but give enolization products exclusively. Contrary to expectation, the reaction of butenylmagnesium bromide with acetomesitylene gave a negligible amount of enolization products (less than 3% of the calculated amount of butenes was detected). From the reaction mixture was recovered about 12% of the original ketone and the principal product was the tertiary alcohol, α-methylallylmesitylmethylcarbinol (I). The yield was 83%.

Additional Information

© 1946 American Chemical Society. Received October 16, 1945. Presented in part before the Division of Organic Chemistry of the American Chemical Society at New York City, September, 1944. [John D. Roberts] Abbott Laboratories Research Fellow, 1943-1944.

Additional details

Created:
August 19, 2023
Modified:
October 24, 2023