2026-09-23T05:45:05Z https://www.ideals.illinois.edu/oai-pmh

oai:www.ideals.illinois.edu:2142/70215 2023-07-11 col_2142_5131 col_2142_14789 com_2142_5130 com_2142_14788 com_2142_8903

Embargo set by: Seth Robbins for item 70381 Lift date: Forever Reason: Restricted to the U of I community idenfinitely during batch ingest of legacy ETDs Restricted to the U of I community idenfinitely during batch ingest of legacy ETDs U of I Only 158 p. Thesis (Ph.D.)--University of Illinois at Urbana-Champaign, 1983. http://hdl.handle.net/2142/70215 Al-Aseer, Munther Adil 2014-12-15T23:17:53Z 2014-12-15T23:17:53Z 10000-01-01 1983 1983 The kinetics of the reactions of alkyllithium reagents with ketones and esters in cyclohexane and benzene have been investigated by stopped-flow infrared spectroscopy at 25.0(DEGREES)C. A series of substituted phenyl-sec-butyl ketones (10a-i) and substituted ethyl benzoates (13a-i) along with several aliphatic ketones (14-17) and esters (18,19) were utilized in the study. These compounds were found to form coordination complexes with alkyllithium aggregates. Evidence for this was demonstrated by the appearance of a new carbonyl band in the infrared spectrum of a reacting solution of ester or ketone and alkyllithium reagent immediately after mixing. The new band, which is shifted to lower wave-number relative to the carbonyl band of the carbonyl compound, has been attributed to the formation of a substrate-alkyllithium aggregate complex in rapid equilibrium with the free substrate. Equilibrium constants (K(,c)) for complexation with sec-butyllithium in cyclohexane were determined for several compounds. A trend in the K(,c) values for the substituted phenyl-sec-butyl ketones and ethyl benzoates was observed: the more electron donating the substituent the larger the equilibrium constant of complexation. Further, larger K(,c) values were obtained for the esters, in their reactions with sec-butyllithium, than for the corresponding ketones. The rate of disappearance of ketones 10a-i and esters 13a-i in the presence of excess sec-butyllithium exhibited good pseudo first order behavior. The dependence of the observed pseudo first order rate constant (k(,obs)) on sec-butyllithium concentration was complex indicating the lack of a simple order with respect to alkyllithium in these reactions. Within each class of carbonyl compounds a substituent effect on the rate data was noted. Electron-withdrawing substituents on the phenyl ring of the ketone or ester led to the common behavior of increasing k(,obs) with rising reagent concentration; whereas, electron-donating substituents brought about a maximum k(,obs) followed by a decrease in k(,obs) at higher lithium reagent concenrations. A mechanism (Scheme 5) that is consistent with the kinetic and equilibrium data has been proposed in which product is formed by two pathways: decomposition of the ketone/ester-alkyllithium complex and reaction of uncomplexed ketone/ester with monomeric alkyllithium. Made available in DSpace on 2014-12-15T23:17:53Z (GMT). No. of bitstreams: 1 8324499.pdf: 3598771 bytes, checksum: c63766d7e84a5810c6f479fd27339896 (MD5) Previous issue date: 1983 (UMI)AAI8324499 Chemistry, Organic Kinetics and Mechanism of the Reactions of Alkyllithium Reagents With Ketones and Esters in Hydrocarbon Solvents text Chemistry Chemistry University of Illinois at Urbana-Champaign Dissertation Ph.D.