Primary deuterium kinetic isotope effects for the thermal (1,7) sigmatropic rearrangement of 7-methylocta-1,3(Z),5(Z)-triene

Journal Article · Tue Nov 22 23:00:00 EST 1988 · Journal of the American Chemical Society; (USA)

DOI:https://doi.org/10.1021/ja00232a040· OSTI ID:5043425

Baldwin, J E; Reddy, V P ^[1]

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1. Syracuse Univ., NY (USA)

7-Methylocta-1,3(Z),5(Z)-triene isomerizes to 2-methylocta-2,4(Z),6(Z)-triene over the temperature range 60-115{degree}C through a first-order process characterized kinetically by the activation parameters log A{sup H} = 9.8 and E{sub a}{sup H} = 21.5 kcal/mol. Parallel kinetic work with the 7-deuterio-7-methyloctatriene establishes the Arrhenius parameters log A{sup D} = 10.3 and E{sub a}{sup D} = 23.5 kcal/mol. Thus A{sup D}/A{sup H} = 3.2 and (E{sub a}{sup D} - E{sub a}{sup H}) = 2.0 kcal/mol, and a substantial tunneling component for the (1,7) sigmatropic hydrogen migration is evident. 25 refs., 3 figs., 1 tab.

• OSTI ID: 5043425
• Journal Information: Journal of the American Chemical Society; (USA), Journal Name: Journal of the American Chemical Society; (USA) Vol. 110:24; ISSN 0002-7863; ISSN JACSA
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400201* -- Chemical & Physicochemical Properties
400202 -- Isotope Effects
Isotope Exchange
& Isotope Separation
ALKENES
CYCLOALKENES
DATA
DEUTERIUM
ELEMENTS
EXPERIMENTAL DATA
HYDROCARBONS
HYDROGEN
HYDROGEN ISOTOPES
INFORMATION
ISOTOPE EFFECTS
ISOTOPES
LIGHT NUCLEI
MIGRATION
MOLECULAR STRUCTURE
NONMETALS
NUCLEI
NUMERICAL DATA
ODD-ODD NUCLEI
ORGANIC COMPOUNDS
STABLE ISOTOPES
TEMPERATURE EFFECTS