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Volumn 70, Issue 10, 2005, Pages 3884-3891

The effect of ring substitution on the O-neophyl rearrangement of 1,1-diarylalkoxyl radicals. A product and time-resolved kinetic study

Author keywords

[No Author keywords available]

Indexed keywords

ABSORPTION; ELECTRON TRANSITIONS; ELECTRONIC PROPERTIES; FREE RADICALS; ISOMERS; KETONES; MOLECULAR STRUCTURE; REACTION KINETICS; SUBSTITUTION REACTIONS;

EID: 18744377711     PISSN: 00223263     EISSN: None     Source Type: Journal    
DOI: 10.1021/jo0502448     Document Type: Article
Times cited : (65)

References (38)
  • 1
    • 0035955789 scopus 로고    scopus 로고
    • For an excellent review on radical aryl migration reactions, see: Studer, A.; Bossart, M. Tetrahedron 2001, 57, 9649-9667.
    • (2001) Tetrahedron , vol.57 , pp. 9649-9667
    • Studer, A.1    Bossart, M.2
  • 3
    • 18744390152 scopus 로고    scopus 로고
    • note
    • For alkoxyl radicals bearing a single phenyl substituent such as the benzyloxyl and cumyloxyl radicals, aryl migration would lead to carbon-centered radicals that are significantly less stable than those formed from both the 1,1-diphenylethoxyl and triphenylmethoxyl radicals. Accordingly, with the former radicals the 1,2-phenyl shift does not compete with hydrogen atom abstraction, and β-fragmentation reactions.
  • 6
    • 18744400636 scopus 로고    scopus 로고
    • note
    • 2-saturated MeCN solution at 230 K, the peroxyl radical is described to be formed by oxygen quenching of either the bridged radical or the rearranged 1-phenoxy-1- phenylethyl radical. However, due to the very short lifetime suggested for the former radical (see ref 5), quenching of this radical by traces of oxygen is expected to be slower than the formation of the 1-phenoxy-1-phenylethyl radical. As a consequence, the peroxyl radical (if formed) is likely to derive from the reaction of this radical with oxygen.
  • 16
    • 0000213430 scopus 로고    scopus 로고
    • Renaud, P., Sibi, M. P., Eds.; Wiley-VCH: Weinheim, Germany
    • Suárez, E.; Rodriguez, M. S. In Radicals in Organic Synthesis; Renaud, P., Sibi, M. P., Eds.; Wiley-VCH: Weinheim, Germany, 2001; Vol. 2, pp 440-454.
    • (2001) Radicals in Organic Synthesis , vol.2 , pp. 440-454
    • Suárez, E.1    Rodriguez, M.S.2
  • 20
    • 18744397364 scopus 로고    scopus 로고
    • note
    • No evidence for the formation of phenols was obtained in the product analysis experiments.
  • 35
    • 18744399121 scopus 로고    scopus 로고
    • note
    • According to this picture, the observation that the rate constants for β-scission of ring-substituted cumyloxyl radicals are essentially independent from the nature of the substituent (see ref 22) may indicate that substituent effects operate in the same direction on both the cumyloxyl radical and the product acetophenone.
  • 38
    • 18744381414 scopus 로고    scopus 로고
    • note
    • Ar BDE in the 1,1-diaryalkoxyl radicals determined by the presence of ring substituents should not be important.


* 이 정보는 Elsevier사의 SCOPUS DB에서 KISTI가 분석하여 추출한 것입니다.