Studies on a strain-driven retro-aldol ring expansion reaction

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

OSTI ID:5528884

Adams, B R

A series of bicyclic sulfone alcohols showing varying amounts of strain energy was examined with regard to reactivity in a retro-aldol reaction. It was found that the activation energy for the reaction generally decreased with increasing strain energy release upon reaction. The correlation coefficient (for activation energy with strain energy) was 0.94. The slope of the regression line (0.37) shows that about one-third of the strain energy released contributes to a lowered activation energy, indicating a moderately early transition state for this reaction. A zero-strain activation energy of 17.9 kcal/mol was found. The kinetics measurements used to obtain these results were performed by quenching reactions run to partial completion, then integrating proton nmr spectra of the reaction mixtures to determine the degree of completion. In favorable cases this allows determination of rate constants to within 5%.

• OSTI ID: 5528884
• Resource Relation: Other Information: Thesis (Ph. D.)
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC
ORGANIC
PHYSICAL AND ANALYTICAL CHEMISTRY
ALCOHOLS
CHEMICAL REACTION KINETICS
SULFONES
ACTIVATION ENERGY
EXPERIMENTAL DATA
NUCLEAR MAGNETIC RESONANCE
STRAINS
DATA
ENERGY
HYDROXY COMPOUNDS
INFORMATION
KINETICS
MAGNETIC RESONANCE
NUMERICAL DATA
ORGANIC COMPOUNDS
ORGANIC SULFUR COMPOUNDS
REACTION KINETICS
RESONANCE
400301* - Organic Chemistry- Chemical & Physicochemical Properties- (-1987)