I. SYNTHESIS AND POLYMERIZATION OF TWO NEW METHYLENECYCLOBUTENE ESTERS; II. MODEL COMPOUND SYNTHESIS FOR CARBON-13 NMR STRUCTURAL ELUCIDATION OF POLYBICYCLOBUTANE-1-CARBONITRILE.

Persistent Link:
http://hdl.handle.net/10150/186293
Title:
I. SYNTHESIS AND POLYMERIZATION OF TWO NEW METHYLENECYCLOBUTENE ESTERS; II. MODEL COMPOUND SYNTHESIS FOR CARBON-13 NMR STRUCTURAL ELUCIDATION OF POLYBICYCLOBUTANE-1-CARBONITRILE.
Author:
SNOW, LARRY GLEN.
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 two new compounds methyl 3-methylenecyclobutene-1- carboxylate and dimethyl 3-methylenecyclobute.ne-l,2- dicarboxylate were synthesized. The cycloadduct which forms between allene and acrylonitrile was used as the starting point for the synthesis of the former. This was chlorinated with phosphorus pentachloride, hydrolyzed with aqueous base, esterified with methanol and p-toluenesulfonic acid, and dehydrochlorinated with potassium hydride providing methyl 3-methylenecyclobutene-l-carboxylate. Chloromaleic anhydride was cycloadded to allene as the starting point for the synthesis of dimethyl 3-methylenecyclobutene-l,2-dicarboxylate. This cycloadduct was then hydrolyzed under basic conditions, esterified with diazomethane and dehydrochlorinated with 1,4-diazabicyclo[2.2.2]octane yielding dimethyl 3-methylenecyclobutene- l,2-dicarboxylate. Each of these new methylenecyclobutenes was then polymerized. Free radical homopolymerization proceeded in a 1,5 manner in each case yielding film forming polymers. Copolymers were also prepared from each using representative comonomers in free radical systems. Dimers of bicyclobutane-l-carbonitrile were prepared by the reaction of cyanocyclobutyl sodium with cyclobutane-l-carbonitrile and then chlorinated with phosphorus pentachloride. The ¹³C nmr spectra of the dimers and the chlorinated dimers were instrumental in showing that po1ybicyc1obutane-1-carbonitrile obtained either radically or anionically is formed primarily by trans 1,3 incorporation of the cyc10butane rings.
Type:
text; Dissertation-Reproduction (electronic)
Degree Name:
Ph.D.
Degree Level:
doctoral
Degree Program:
Philosophy; Graduate College
Degree Grantor:
University of Arizona

Full metadata record

DC FieldValue Language
dc.language.isoenen_US
dc.titleI. SYNTHESIS AND POLYMERIZATION OF TWO NEW METHYLENECYCLOBUTENE ESTERS; II. MODEL COMPOUND SYNTHESIS FOR CARBON-13 NMR STRUCTURAL ELUCIDATION OF POLYBICYCLOBUTANE-1-CARBONITRILE.en_US
dc.creatorSNOW, LARRY GLEN.en_US
dc.contributor.authorSNOW, LARRY GLEN.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 two new compounds methyl 3-methylenecyclobutene-1- carboxylate and dimethyl 3-methylenecyclobute.ne-l,2- dicarboxylate were synthesized. The cycloadduct which forms between allene and acrylonitrile was used as the starting point for the synthesis of the former. This was chlorinated with phosphorus pentachloride, hydrolyzed with aqueous base, esterified with methanol and p-toluenesulfonic acid, and dehydrochlorinated with potassium hydride providing methyl 3-methylenecyclobutene-l-carboxylate. Chloromaleic anhydride was cycloadded to allene as the starting point for the synthesis of dimethyl 3-methylenecyclobutene-l,2-dicarboxylate. This cycloadduct was then hydrolyzed under basic conditions, esterified with diazomethane and dehydrochlorinated with 1,4-diazabicyclo[2.2.2]octane yielding dimethyl 3-methylenecyclobutene- l,2-dicarboxylate. Each of these new methylenecyclobutenes was then polymerized. Free radical homopolymerization proceeded in a 1,5 manner in each case yielding film forming polymers. Copolymers were also prepared from each using representative comonomers in free radical systems. Dimers of bicyclobutane-l-carbonitrile were prepared by the reaction of cyanocyclobutyl sodium with cyclobutane-l-carbonitrile and then chlorinated with phosphorus pentachloride. The ¹³C nmr spectra of the dimers and the chlorinated dimers were instrumental in showing that po1ybicyc1obutane-1-carbonitrile obtained either radically or anionically is formed primarily by trans 1,3 incorporation of the cyc10butane rings.en_US
dc.typetexten_US
dc.typeDissertation-Reproduction (electronic)en_US
thesis.degree.namePh.D.en_US
thesis.degree.leveldoctoralen_US
thesis.degree.disciplinePhilosophyen_US
thesis.degree.disciplineGraduate Collegeen_US
thesis.degree.grantorUniversity of Arizonaen_US
dc.identifier.proquest8315308en_US
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