Kinetics and deuterium kinetic isotope effects for the thermal (1,7) sigmatropic rearrangements of cis,cis-1,3,5-octatriene

Journal Article · Tue Dec 22 23:00:00 EST 1987 · J. Am. Chem. Soc.; (United States)

DOI:https://doi.org/10.1021/ja00260a017· OSTI ID:7004786

Baldwin, J E; Reddy, V P

Thermal isomerization of cis,cis-1,3,5-octatriene at 60-111/sup 0/C occur with activation parameters log A = 9.1 and E/sub a/ = 21.3 (to cis,cis,cis-2,4,6-octatriene) and E/sub a/ = 20.2 kcal mol/sup -1/ (to cis,cis,trans-2,4,6-octatriene). Primary deuterium kinetic isotope effects for these (1,7) sigmatropic shifts are found to be 6.4-7.7 and not markedly temperature dependent, indicative of a linear or nearly linear C7-H-C1 geometry in the transition-state structure.

• Research Organization: Syracuse Univ., NY (USA)
• OSTI ID: 7004786
• Journal Information: J. Am. Chem. Soc.; (United States), Journal Name: J. Am. Chem. Soc.; (United States) Vol. 109:26; 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
ACTIVATION ENERGY
CHEMICAL REACTION KINETICS
CHEMICAL REACTIONS
DATA
DEUTERIUM
DEUTERIUM COMPOUNDS
ENERGY
EXPERIMENTAL DATA
HYDROCARBONS
HYDROGEN COMPOUNDS
HYDROGEN ISOTOPES
INFORMATION
ISOMERIZATION
ISOTOPE EFFECTS
ISOTOPES
KINETICS
LIGHT NUCLEI
MAGNETIC RESONANCE
MEDIUM TEMPERATURE
NMR SPECTRA
NUCLEAR MAGNETIC RESONANCE
NUCLEI
NUMERICAL DATA
ODD-ODD NUCLEI
ORGANIC COMPOUNDS
POLYENES
REACTION KINETICS
RESONANCE
SPECTRA
STABLE ISOTOPES
TEMPERATURE DEPENDENCE