Substituent effects on strained rings. part A ; The kinetics of hydrolysis of A quinuclidone using FTIR. part B

Author

Yeu-Yi Chiu, New Jersey Institute of Technology

Document Type

Thesis

Date of Award

5-31-1989

Degree Name

Master of Science in Chemistry - (M.S.)

Department

Chemical Engineering, Chemistry and Environmental Science

First Advisor

Arthur Greenberg

Second Advisor

Tamara M. Gund

Third Advisor

James M. Grow

Abstract

PART A: The energies of a series of monosubstitued propane, cyclopropane and cyclopropene compounds were calculated using ab initio molecular orbital calculations optimized at the 3-21G level using Gaussian 82 and Gaussian 86 programs. The effects of substituents on stabilization energies and geometries are rationalized with respect to the parent molecules. The result is presented which indicated that for substituted cyclopropyl and cyclopropenyl compounds, most of the substituents induce stabilization except the —NC substituent group is destabilizing in cyclopropyl and cyclopropenyl systems. Indications of relative electrostatic and resonance effects are also analyzed. A linear free energy relationship has been exam-ined by comparing the stabilization energies and appropriate Taft Dual Substituent Parameter equation substituent constants: σ_I (induction effect) and s_R (resonance effect).

PART B: The synthesis of 6,6,7,7-Tetramethy1-1-azabicyclo[2.2.2] octan-2-one (6,6,7,7-tetramethy1-2-quinuclidone) was done by Dr. Wu Guanli. Some kinetic data are obtained using conditions from a paper by Pracejus and co-workers. FTIR was em¬ployed to monitor the rate of decomposition which was then compared with others, less sterically-hindered, guinuclidone derivatives.

Recommended Citation

Chiu, Yeu-Yi, "Substituent effects on strained rings. part A ; The kinetics of hydrolysis of A quinuclidone using FTIR. part B" (1989). Theses. 1912.
https://digitalcommons.njit.edu/theses/1912