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ZEROVALENT-NICKEL CATALYZED CARBON-CARBON AND CARBON-HYDROGEN BOND FORMATION

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dc.creator FERREIRA, TAMIS WEINGARTNER
dc.date.accessioned 2007-05-09T19:29:29Z
dc.date.available 2007-05-09T19:29:29Z
dc.date.issued 1982
dc.identifier.uri http://hdl.handle.net/1911/15678
dc.description.abstract The bis(triphenylphosphine) nickel dichloride-catalyzed reaction of thiophenols and aryl sulfides with phenyl-magnesium and methylmagnesium bromides produced biphenyls and toluenes, respectively. The coupling of p-t-butylthioanisole with ethylmagnesium bromide and cyclohexylmagnesium bromide in the presence of (1,3-diphenylphosphinopropane)nickel dichloride produced p-t-butylethylbenzene and p-t-butylcyclohexylbenzene, respectively, while the coupling with isopropylmagnesium bromide led to the formatin of n-propyl as well as isopropyl aryl derivatives. The same sulfide reacted with isopropylmagnesium and cyclohexylmagnesium bromides in the presence of anhydrous nickel dichloride and triphenylphosphine to produce t-butyl-benzene. With ethylmagnesium bromide t-butylbenzene and p-t-ethylbutylbenzene were produced. p-t-Butylthiophenol afforded t-butylbenzene as the sole product, when treated with isopropylmagnesium bromide, nickel dichloride and triphenylphosphine, and t-butylbenzene as the major product, when treated with isopropylmagnesium bromide and (1,3-diphenylphosphinopropane)nickel dichloride. Ketenethioacetal C(,6)H(,5)CH(,2)CH=C(SEt)(,2) underwent reaction with Grignard reagents in the presence of phosphine-nickel complexes to produce vinyl sulfides in which the alkyl group is oriented trans to the initial benzyl group. When exposed to an excess of methylmagnesium bromide and (1,3-diphenylphosphinopropane)nickel dichloride, the thioacetal produced 1-phenyl-3-methyl-2-butene. Reaction of enol sulfides of ketones with Grignard reagents in the presence of the aforementioned nickel catalyst produced di- and tri-substituted olefins with retention of configuration at the sulfur-bearing olefinic carbon site. The reaction between 1,1-diethylthioethylene and phenylmagnesium bromide in the presence of nickel dichloride and triphenylphosphine led to (alpha)-ethylthio styrene, 1,1-diphenylethene and unreacted ketenethioacetal.
dc.format.mimetype application/pdf
dc.language.iso eng
dc.subject Chemistry, Organic
dc.title ZEROVALENT-NICKEL CATALYZED CARBON-CARBON AND CARBON-HYDROGEN BOND FORMATION
dc.type.genre Thesis
dc.type.material Text
thesis.degree.discipline Chemistry
thesis.degree.grantor Rice University
thesis.degree.level Doctoral
thesis.degree.name Doctor of Philosophy
dc.identifier.citation FERREIRA, TAMIS WEINGARTNER. (1982) "ZEROVALENT-NICKEL CATALYZED CARBON-CARBON AND CARBON-HYDROGEN BOND FORMATION." Doctoral Thesis, Rice University. http://hdl.handle.net/1911/15678.

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