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Rearrangements in the Solvolysis of 2-Butyl-1-C14 p-Toluenesulfonate1,2

Journal Article · · Journal of the American Chemical Society
DOI:https://doi.org/10.1021/ja01137a013· OSTI ID:4383799

Solvolysis of 2-butyl-l-C14 p-toluenesulfonate in acetic acid in the presence of acetate ion under conditions where the reaction rate is essentially independent of the acetate ion concentration leads to a mixture of 91 ± 1% of 2-butyl-l-C14 acetate and 9 ± 1% of the rearranged product, 2-butyl-4-C14 acetate. It has been shown that the rearrangement is not due to re-arrangement of the starting material or to elimination to yield butenes followed by addition of acetic acid. Much less rearrangement occurs in the hydrolysis of 2-butyl-l-C14 p-toluenesulfonate in 75% acetone-25% water (by volume). It is concluded that a non-classical cation of the type CH3CH~CHCH3 is not an important intermediate in the unimolecular hydrolysis or acetolysis of 2-butyl p-toluenesulfonate.

Research Organization:
Massachusetts Inst. of Technology (MIT), Cambridge, MA (United States). Laboratory for Nuclear Science and Engineering
Sponsoring Organization:
US Atomic Energy Commission (AEC); US Department of the Navy, Office of Naval Research (ONR)
NSA Number:
NSA-06-004471
OSTI ID:
4383799
Report Number(s):
NYO--774
Journal Information:
Journal of the American Chemical Society, Journal Name: Journal of the American Chemical Society Journal Issue: 17 Vol. 74; ISSN 0002-7863
Publisher:
American Chemical Society (ACS)Copyright Statement
Country of Publication:
Country unknown/Code not available
Language:
English

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