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Stable Quinone Methides: Regioselective para ‐Oxidation of a 2,4‐bis[(alkylthio)methyl]phenol and addition reactions to quinonemethides
Author(s) -
Meier Hansrudolf,
Kuenzi Hanspeter,
Fuhrer Hermann,
Rist Günther
Publication year - 1994
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.19940770308
Subject(s) - chemistry , regioselectivity , benzaldehyde , potassium ferricyanide , phenol , dehydrogenation , hydrolysis , medicinal chemistry , organic chemistry , nuclear magnetic resonance spectroscopy , catalysis
The 2,4‐bis‐functionalized phenol 1 is dehydrogenated regioselectivity with potassium ferricyanide, affording the corresponding p ‐quinonemethide 2 . Hydrolysis of 2 affords a mixture of dithioacetal 5a and benzaldehyde 6 ; 1,6‐addition of thiols to 2 gives the dithioacetals 5 of benzaldehyde 6 ; reaction of 2 with 2,2′‐azobis(isobutyronitrile) (= 2,2′‐dimethyl‐2,2′‐azobis(propanenitrile)) leads to 9a, 9b , and 10 , addition products of the 1‐cyano‐1‐methylethyl radical. The structures of all products are confirmed mainly by 1 H‐ and 13 C‐NMR spectroscopy, and the mode of their formation is discussed.