SYNTHESIS AND REACTIONS OF TRIHALOMETHYL GROUP SUBSTITUTED ELECTRON-DEFICIENT OLEFINS.

Persistent Link:
http://hdl.handle.net/10150/187619
Title:
SYNTHESIS AND REACTIONS OF TRIHALOMETHYL GROUP SUBSTITUTED ELECTRON-DEFICIENT OLEFINS.
Author:
HEDRICK, STEVEN THOMAS.
Issue Date:
1983
Publisher:
The University of Arizona.
Rights:
Copyright © is held by the author. Digital access to this material is made possible by the University Libraries, University of Arizona. Further transmission, reproduction or presentation (such as public display or performance) of protected items is prohibited except with permission of the author.
Abstract:
The reactions of five trihalomethyl group substituted electron-deficient olefins with electron-rich olefins were studied in order to determine the effect of steric bulk upon the subsequent reactions of the tetramethylene intermediates initially formed. Reactions of β-trihalomethyl group substituted olefins yielded cyclobutane adducts, resulting from a gem dimethyl effect which accelerates the collapse of the tetramethylene intermediate. Reactions of α-trihalomethyl group substituted olefins gave both small molecule and polymeric products. Polymers were produced in reactions where steric interactions between the termini of the tetramethylene intermediates prevented ring formation. Ester substituted electron-deficient olefins reacted with electron-rich olefins to give both cyclobutane and 6-alkoxy-3,4-dihydro-2H-pyran derivatives. A transition from concerted to stepwise reaction was observed, resulting from steric hindrance in the transition state leading to [4+2] cycloaddition. Exploratory studies of ion-radical propagation and chain transfer in polymerization processes were also conducted. The acid catalyzed free radical polymerization of imines was attempted, along with chain transfer studies of zwitterion-radical intermediates.
Type:
text; Dissertation-Reproduction (electronic)
Keywords:
Alkenes.; Polymers.; Polymerization.; Electron donor-acceptor complexes.; Carbenes (Methylene compounds)
Degree Name:
Ph.D.
Degree Level:
doctoral
Degree Program:
Chemistry; Graduate College
Degree Grantor:
University of Arizona
Advisor:
Hall, H. K.

Full metadata record

DC FieldValue Language
dc.language.isoenen_US
dc.titleSYNTHESIS AND REACTIONS OF TRIHALOMETHYL GROUP SUBSTITUTED ELECTRON-DEFICIENT OLEFINS.en_US
dc.creatorHEDRICK, STEVEN THOMAS.en_US
dc.contributor.authorHEDRICK, STEVEN THOMAS.en_US
dc.date.issued1983en_US
dc.publisherThe University of Arizona.en_US
dc.rightsCopyright © is held by the author. Digital access to this material is made possible by the University Libraries, University of Arizona. Further transmission, reproduction or presentation (such as public display or performance) of protected items is prohibited except with permission of the author.en_US
dc.description.abstractThe reactions of five trihalomethyl group substituted electron-deficient olefins with electron-rich olefins were studied in order to determine the effect of steric bulk upon the subsequent reactions of the tetramethylene intermediates initially formed. Reactions of β-trihalomethyl group substituted olefins yielded cyclobutane adducts, resulting from a gem dimethyl effect which accelerates the collapse of the tetramethylene intermediate. Reactions of α-trihalomethyl group substituted olefins gave both small molecule and polymeric products. Polymers were produced in reactions where steric interactions between the termini of the tetramethylene intermediates prevented ring formation. Ester substituted electron-deficient olefins reacted with electron-rich olefins to give both cyclobutane and 6-alkoxy-3,4-dihydro-2H-pyran derivatives. A transition from concerted to stepwise reaction was observed, resulting from steric hindrance in the transition state leading to [4+2] cycloaddition. Exploratory studies of ion-radical propagation and chain transfer in polymerization processes were also conducted. The acid catalyzed free radical polymerization of imines was attempted, along with chain transfer studies of zwitterion-radical intermediates.en_US
dc.typetexten_US
dc.typeDissertation-Reproduction (electronic)en_US
dc.subjectAlkenes.en_US
dc.subjectPolymers.en_US
dc.subjectPolymerization.en_US
dc.subjectElectron donor-acceptor complexes.en_US
dc.subjectCarbenes (Methylene compounds)en_US
thesis.degree.namePh.D.en_US
thesis.degree.leveldoctoralen_US
thesis.degree.disciplineChemistryen_US
thesis.degree.disciplineGraduate Collegeen_US
thesis.degree.grantorUniversity of Arizonaen_US
dc.contributor.advisorHall, H. K.en_US
dc.identifier.proquest8405499en_US
dc.identifier.oclc690667105en_US
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