FLOWING AFTERGLOW STUDIES OF ORGANIC ANIONS
Abstract
This thesis deals with the construction and use of the Purdue flowing afterglow (FA). The Purdue FA has been used primarily to study the properties and reactivities of anions and to investigate systematically the intrinsic behavior of ion-molecule reactions. Chapters One, Two, and Three give an overview of the thesis, a historical review of the applications of gas phase ion techniques, and details about the construction and use of the Purdue FA, respectively. Chapter Four describes the collision induced dissociations and rearrangements of ester enolates with a specific emphasis on the rearrangement of allylic ester enolates to the corresponding carboxylates. Chapter Five deals with the investigation of potential reference acids with acidities between those of water and methanol. Measurement of the acidities of several 1(DEGREES) and 2(DEGREES) amines with large or electronegative substituents indicates their acidities are within this range. The experimental acidity measurements presented in Chapter Six indicates that anionic homoaromaticity is responsible for the major portion of the 9.5 kcal/mol measured acidity difference between bicyclo 3.2.1 octa-2,6-diene and bicyclo 3.2.1 oct-2-ene. Model systems indicate that up to 3 kcal/mol of this difference may be contributed to inductive/field effects. Finally, Chapter Seven describes a gas phase investigation of the reactivity and rearrangements of several C(,6)H(,9)O('-) isomers and selected model compounds with 10 ion-molecule reactions. A new understanding of these ion-molecule reactions has been derived. Allyl ether undergoes proton abstraction with amide to produce an anion that incorporates up to 9 deuteriums when allowed to react with D(,2)O. However, allyl ether also undergoes proton abstraction with methoxide to produce an anion that does not incorporate deuterium when allowed to react with D(,2)O. Model studies indicate that the latter anion may be the result of a skeletal rearrangement.
Degree
Ph.D.
Subject Area
Organic chemistry
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