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Article: Picosecond radical kinetics. Rate constants for ring openings of 2-aryl-substituted cyclopropylcarbinyl radicals

TitlePicosecond radical kinetics. Rate constants for ring openings of 2-aryl-substituted cyclopropylcarbinyl radicals
Authors
KeywordsBenzeneselenol
Cyclopropylcarbinyl Radical
Kinetics
Ptoc Esters
Issue Date1999
PublisherNRC Research Press. The Journal's web site is located at http://pubs.nrc-cnrc.gc.ca/cgi-bin/rp/rp2_desc_e?cjc
Citation
Canadian Journal Of Chemistry, 1999, v. 77 n. 5-6, p. 1123-1135 How to Cite?
AbstractThe kinetics of ring openings of a series of eight (trans-2-arylcyclopropyl)methyl radicals (1) were studied by indirect kinetic methods using Barton's PTOC esters as radical precursors and reaction with PhSeH as the competition reaction. The substituents were CF3, F, Me, and OMe located on both the para and meta positions of the aromatic ring. Syntheses of the radical precursors and the products of the radical reactions are described. Kinetics were determined between -43 and 25°C in four cases (CF3 and OMe substituents) and at 0 and 25°C in the other four cases. The rate constants at 25°C ranged from 1.0 × 1011 s-1 (p-CH3) to 4.1 × 1011 s-1 (p-CF3). The relatively large acceleration of the p-CF3 group, ca. 2.5 times as fast as the parent system with Ar = Ph, correlates well with Adam's ΔD substituent parameters but not with other radical substituent parameters. These calibrated radical rearrangements provide a new set of ultrafast reactions that can be applied in mechanistic probe studies.
Persistent Identifierhttp://hdl.handle.net/10722/167618
ISSN
2015 Impact Factor: 1.003
2015 SCImago Journal Rankings: 0.364
References

 

DC FieldValueLanguage
dc.contributor.authorNewcomb, Men_US
dc.contributor.authorChoi, SYen_US
dc.contributor.authorToy, PHen_US
dc.date.accessioned2012-10-08T03:09:06Z-
dc.date.available2012-10-08T03:09:06Z-
dc.date.issued1999en_US
dc.identifier.citationCanadian Journal Of Chemistry, 1999, v. 77 n. 5-6, p. 1123-1135en_US
dc.identifier.issn0008-4042en_US
dc.identifier.urihttp://hdl.handle.net/10722/167618-
dc.description.abstractThe kinetics of ring openings of a series of eight (trans-2-arylcyclopropyl)methyl radicals (1) were studied by indirect kinetic methods using Barton's PTOC esters as radical precursors and reaction with PhSeH as the competition reaction. The substituents were CF3, F, Me, and OMe located on both the para and meta positions of the aromatic ring. Syntheses of the radical precursors and the products of the radical reactions are described. Kinetics were determined between -43 and 25°C in four cases (CF3 and OMe substituents) and at 0 and 25°C in the other four cases. The rate constants at 25°C ranged from 1.0 × 1011 s-1 (p-CH3) to 4.1 × 1011 s-1 (p-CF3). The relatively large acceleration of the p-CF3 group, ca. 2.5 times as fast as the parent system with Ar = Ph, correlates well with Adam's ΔD substituent parameters but not with other radical substituent parameters. These calibrated radical rearrangements provide a new set of ultrafast reactions that can be applied in mechanistic probe studies.en_US
dc.languageengen_US
dc.publisherNRC Research Press. The Journal's web site is located at http://pubs.nrc-cnrc.gc.ca/cgi-bin/rp/rp2_desc_e?cjcen_US
dc.relation.ispartofCanadian Journal of Chemistryen_US
dc.subjectBenzeneselenolen_US
dc.subjectCyclopropylcarbinyl Radicalen_US
dc.subjectKineticsen_US
dc.subjectPtoc Estersen_US
dc.titlePicosecond radical kinetics. Rate constants for ring openings of 2-aryl-substituted cyclopropylcarbinyl radicalsen_US
dc.typeArticleen_US
dc.identifier.emailToy, PH:phtoy@hkucc.hku.hken_US
dc.identifier.authorityToy, PH=rp00791en_US
dc.description.naturelink_to_subscribed_fulltexten_US
dc.identifier.doi10.1139/v99-094-
dc.identifier.scopuseid_2-s2.0-0033306404en_US
dc.relation.referenceshttp://www.scopus.com/mlt/select.url?eid=2-s2.0-0033306404&selection=ref&src=s&origin=recordpageen_US
dc.identifier.volume77en_US
dc.identifier.issue5-6en_US
dc.identifier.spage1123en_US
dc.identifier.epage1135en_US
dc.publisher.placeCanadaen_US
dc.identifier.scopusauthoridNewcomb, M=7101865783en_US
dc.identifier.scopusauthoridChoi, SY=7408121670en_US
dc.identifier.scopusauthoridToy, PH=7006579247en_US

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