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Volumn 70, Issue 13, 2005, Pages 5144-5149

Electron-transfer mechanism in the N-demethylation of N,N-dimethylanilines by the phthalimide-N-oxyl radical

Author keywords

[No Author keywords available]

Indexed keywords

AMINES; CARBON DIOXIDE; CHEMICAL BONDS; DEUTERIUM; HYDROLYSIS; POSITIVE IONS; REACTION KINETICS; SUBSTITUTION REACTIONS; SUBSTRATES;

EID: 20844463434     PISSN: 00223263     EISSN: None     Source Type: Journal    
DOI: 10.1021/jo0503916     Document Type: Article
Times cited : (68)

References (62)
  • 37
    • 20844454838 scopus 로고    scopus 로고
    • note
    • From the initial ΔOD we can estimate that the PINO concentration is about 0.03 mM.
  • 40
    • 20844435394 scopus 로고    scopus 로고
    • note
    • 2 = 0.997), that probably indicates that the partial positive charge in the transition state should be mainly localized on the nitrogen atom and not on the aromatic ring.
  • 41
    • 20844432618 scopus 로고    scopus 로고
    • note
    • Secondary isotope effects are likely obscured by the error limit.
  • 43
    • 20844437340 scopus 로고    scopus 로고
    • note
    • Of course, substituents also influence the rate of the second step. However, the effect on the electron-transfer step should be much more important, as also shown by the observed electronic effects of the substituents.
  • 44
    • 20844451657 scopus 로고    scopus 로고
    • note
    • Actually, for this reaction Watanabe et al. assumed that the radical cation undergoes a hydrogen atom transfer and not a proton-transfer reaction. At present, we cannot exclude that such a possibility occurs also in our case, the radical cation reacting with PINO to form an a-amino carbocation that can either be converted into the carbinolamine or react with the N-hydroxyphthalimide anion, produced in step a, to give the adduct (Scheme 1).
  • 47
    • 20844461753 scopus 로고    scopus 로고
    • note
    • ΔG°′ values and the details of their calculation are reported in the Supporting Information.


* 이 정보는 Elsevier사의 SCOPUS DB에서 KISTI가 분석하여 추출한 것입니다.