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Rh‐Catalyzed Oxidation of Anthracenes with tert ‐Butyl Hydroperoxide. Kinetic Aspects
Author(s) -
Müller Paul,
Bobillier Christiane
Publication year - 1985
Publication title -
helvetica chimica acta
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.74
H-Index - 82
eISSN - 1522-2675
pISSN - 0018-019X
DOI - 10.1002/hlca.19850680218
Subject(s) - chemistry , anthracene , catalysis , electrophile , reactivity (psychology) , medicinal chemistry , tert butyl hydroperoxide , oxygen , chromic acid , photochemistry , organic chemistry , medicine , alternative medicine , pathology
The polar effects of substituents on reactivity in oxidation of 2‐substituted anthracenes with tert ‐butyl hydroperoxide (TBHP)/Rh(PPh 3 ) 3 Cl have been investigated and compared with those obtained with TBHP/VO(acac) 2 and chromic acid. The anthracene reactivities obtained from competition experiments are correlated with Hammett ' s σ p ‐constants. The P ‐values are ‐2.60 for chromic acid and 0.72 for TBHP/VO(acac) 2 . A poor correlation with p = −0.17 (r = 0.756) was obtained for TBHP/Rh (PPh 3 ) 3 Cl. It is concluded that the Rh‐catalyzed reaction does not consist in electrophilic oxygen transfer to the anthracene.