Jinqiao Lu

Date of Award


Degree Type


Degree Name

Doctor of Philosophy


Part I. The halogenation of propiophenone has been reported to give rise to benzoic acid and acetic acid. It was discovered that under some conditions, the major product of the chlorination of propiophenone is 2-phenylglyceric acid, and that this appears to be a general reaction. 1-Phenyl-1,2-propanedione and 3-chloro-1-phenyl-1,2-propanedione have been proven to be the key intermediates on the chlorination path leading to 2-phenylglyceric acid. The migratory aptitudes of substituted methides ({dollar}\sp-{dollar}CH{dollar}\sb2{dollar}X) are also reported.;Part II. For the classical Michael reaction, the forward addition rate is second order overall, first order in the concentration of methyl cinnamate and first order in the concentration of the anion of dimethyl malonate. The pKa's of dimethyl malonate and the adduct have been measured in methanol by C-13 NMR. The rate constants and equilibrium constants in methanol and water are reported. The study of this single Michael addition reaction demonstrated that methods exist to study more Michael additions.;(CF{dollar}\sb3)\sb2{dollar}CHOH was found to be a good buffer reagent for measuring the pKa values of a series of {dollar}\beta{dollar}-diketones in methanol. The unsubstituted {dollar}\beta{dollar}-diketone decomposes with nearly the same rate constant, 10{dollar}\sp{lcub}-7{rcub}{dollar} s{dollar}\sp{lcub}-1{rcub}{dollar} when (NaOMe) is between 0.10 M and 1.00 M. This rate constant is 10,000 times smaller than that of 2,2-dimethyl-1,5-diphenyl-1,3-propanedione at (NaOMe) = 1.00 M.;Claisen condensations have an intrinsic barrier of 17.60 {dollar}\pm{dollar} 0.72 kcal/mol in methanol and an intrinsic barrier of 16.31 {dollar}\pm{dollar} 0.76 kcal/mol in water. Provided equilibrium constants can be obtained, it will be possible to make useful estimates of the rate constants for novel Claisen reactions by using the above intrinsic barriers. Since experimental measurement of these rate constants is often difficult, this should prove a useful method.;Part III. Several compounds are needed for an investigation of structural effects on free energies of transfer. Thus, CF{dollar}\rm\sb3CH\sb2{dollar}OPh, CF{dollar}\rm\sb3CH\sb2{dollar}NMePh, PhNMeCH{dollar}\rm\sb2CH\sb2{dollar}NMePh, and PhNMeCH{dollar}\rm\sb2CH\sb2{dollar}OMe were synthesized successfully. An alternative method for measuring the free energies of transfer was developed and proved valid for the standard compounds PhCOOEt and PhNMe{dollar}\sb2{dollar}.



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