Deuterium kinetic isotope effects in boat cope rearrangements

Thesis/Dissertation · Sun Jan 01 00:00:00 EST 1984

OSTI ID:6177242

Jimenez, J L

In order to examine the extent of bond making in the boat-like 3,3-sigmatropic shift transition states cis-1,2-divinyl cyclobutane (DVCB), trans-2,3-dimethyl-1,4-dimethylenecyclohexane (DMCH), and cis-1,2-divinylcyclopropane (DVCP) have been prepared with zero and two or four exomethylene deuteria. From pmr, the bond making kinetic isotope effect (KIE) for the DVCB 3,3-shift to cis,cis-1,5-cyclo-octadiene is 1/1.04 (0.04) for four deuteria in hexachlorobutadiene at 77.7/sup 0/C. Since the maximum value from equilibrium isotope effects is 1/1.58, there is very little bond making in this rearrangement. The 3,3-shift of DMCH results in interconversion of starting tetra-deuterium compound, and 4,4,5,5-tetradeuterio-trans-2,3-dimethyl-1,4-dimethylenecyclohexane (TND), and 2,2,3,3-tetradeuterio-anti-1,4-diethylidenecyclohexane (AD). A kinetic analysis of the first order rate equations for the three component system in both protio and deuterio species by numerical integration of the data and simplex minimization of the rate constants using symmetry and the assumption of no equilibrium or kinetic isotope effect on the TDN-AD reaction gives a bond making kinetic isotope effect of 1/1.01 (0.04).

• Research Organization: Indiana Univ., Bloomington (USA)
• OSTI ID: 6177242
• Resource Relation: Other Information: Thesis (Ph. D.)
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC
ORGANIC
PHYSICAL AND ANALYTICAL CHEMISTRY
HEXANE
CHEMICAL PREPARATION
CHEMICAL REACTION KINETICS
PROPANE
DEUTERIUM
EXPERIMENTAL DATA
ISOTOPE EFFECTS
ALKANES
DATA
HYDROCARBONS
HYDROGEN ISOTOPES
INFORMATION
ISOTOPES
KINETICS
LIGHT NUCLEI
NUCLEI
NUMERICAL DATA
ODD-ODD NUCLEI
ORGANIC COMPOUNDS
REACTION KINETICS
STABLE ISOTOPES
SYNTHESIS
400301* - Organic Chemistry- Chemical & Physicochemical Properties- (-1987)
400302 - Organic Chemistry- Isotope Effects- (-1987)