A Comparison of Reactivities and Properties of 3,3-Dimethylacrylic Acid, Isovaleric Acid and Their Derivatives

The effect of conjugated unsaturation on reactivity has been investigated by comparing properties and reactivities of isovaleric acid, 3,3-Dimethylacrylic acid and their derivatives; esters and amides. The electronic and resonance properties of these compounds were investigated by analyzing their carbon-13 chemical shifts and carbonyl infrared absorption frequencies. The carbonyl infrared absorption frequencies for saturated and unsaturated esters and amides were correlated with the corresponding rate constants. In each case a linear relationship was obtained. A Similar attempt with carbon-13 chemical shifts gave a poor correlation. In all cases, there was a lowering of carbonyl infrared absorption frequency in esters derived from 3,3- Dimethylacrylic acid (herein after referred to as a,f-unsaturated esters) when compared to their saturated analogs. The same trend applied to α, β-unsaturated amides. As regards the carbon-13 chemical shifts, it was found that all the nuclei of carbonyl carbon atoms in α, β-unsaturated compounds studied in this research resonated at higher applied magnetic fields as compared to those of the corresponding saturated compounds. The relative reactivities of esters and amides were determined from their respective rate constants. From the relative reactivity values, it was found that all the saturated compounds studied were more reactive than their unsaturated analogs. The size of the substituent groups in both amides and esters was varied in order to determine steric effects on reactivity of the systems.

Name thesis:degree_name

Master of Science

Level thesis:degree_level

Master's

Discipline thesis:degree_discipline

Chemistry

Grantor

Southwest Texas State University

Year dc:date.issued

1993

Author dc:creator

• Obhare, Joseph O.

Advisor dc:contributor.advisor

• Yager, Billy J.

Committee members dc:contributor.committeemember

• Willms, Charles R.
• Rudzinski, Walter E.

• acids
• reactivity
• esters
• amides
• isovaleric acid

Language dc:language.iso

en

Handle dc:identifier.uri

https://hdl.handle.net/10877/20861

OAI identifier oai:identifier

oai:digital.library.txst.edu:10877/20861