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Bridging versus Hydride Shift in Gaseous Cations: Hydroxy as a Vicinal Substituent

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Viet Nguyen, Jacqueline S. Bennett, and Thomas Hellman Morton*

Contribution from the Department of Chemistry, University of California, Riverside, California 92521-0403

J. Am. Chem. Soc., 1997, 119 (35), pp 8342–8349

DOI: 10.1021/ja964475v

Publication Date (Web): September 3, 1997

Section:

Physical Organic Chemistry

Abstract

Primary cations of the form XCH₂CH₂⁺ (1) are unstable with respect to the bridged isomer cyclo-(CH₂)₂X⁺ (2) or the hydride-shift isomer CH₃CHX⁺ (3).Two independent hydrogen isotope experiments for X = OH demonstrate that gaseous HOCH₂CH₂⁺ (1a) gives less of its bridged isomer, protonated oxirane (2a), than of its hydride-shift isomer, protonated acetaldehyde (3a).Metastable ion decompositions of ionized HOCH₂CH₂OPh show that the radical cation decomposes via an ion−neutral complex containing 3a and phenoxy radical. Deuterium labeling studies exhibit no detectable interconversion of the two sp³-carbons, implying that complexes containing 2a are not formed to a measurable extent. An independent neutral product study looks at the radioactive oxirane and acetaldehyde produced when tritium on the methyl group of gaseous CH₂TCHTOH undergoes radioactive decay. Loss of a beta-particle and a helium atom forms transient, tritiated 1a. Ions from isomerization of this radiolabeled primary cation were deprotonated by Me₃N and gave a >97% yield of acetaldehyde. Quantitative assessment of possible routes to acetaldehyde (including rearrangement of excited 2a) implies that 1 undergoes hydride shift at least 5 times faster than bridging by neighboring oxygen.

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