Formation of dimer-type ketals in the reaction of 2,4,6-trichlorophenol and 2,4,6-trichloro-m-cresol with calcium hypochlorite in methanol: conversion to quinones and other compounds.
2,4,6-Trichlorophenol (2) and 2,4,6-trichloro-m-cresol (5) react with calcium hypochlorite (Ca(OCl)(2)) in MeOH to give respectively dimer-type ketals 2-(2',4',6'-trichlorophenoxy)-4,4-dimethoxy-6-chlorocyclohexadien-2,5-one (6) and 2-(3'-methyl-2',4',6'-trichlorophenoxy)-4,4-dimethoxy-5-methyl-6-chlorocyclohexadien-2,5-one (7). Ketal 6, which was too unstable to be isolated, and 7 hydrolyzed in H(2)O/HCl to 2-(2',4',6'-trichlorophenoxy)-6-chloro-1,4-benzoquinone (8) and 2-(3'-methyl-2',4',6'-trichlorophenoxy)-5-methyl-6-chloro-1,4-benzoquinone (9), respectively. Ketal 6 and quinone 8 were also produced when 2 and Ca(OCl)(2) reacted in DMF, followed by addition of MeOH and H(2)O, respectively. The mechanisms of these reactions are examined. Conversion of the ketals and quinones to other products is described.
Heasley
Victor L
VL
Department of Chemistry, Point Loma Nazarene University, San Diego, California 92106-2899, USA. vheasley@ptloma.edu
Anderson
James D
JD
Bowman
Zachery S
ZS
Hanley
John C
JC
Sigmund
Geoffery A
GA
Van Horn
David
D
Shellhamer
Dale F
DF
D017610:Calcium Compounds / Q000737:chemistry; D002384:Catalysis; D002625:Chemistry, Organic / Q000379:methods*; D003408:Cresols / Q000737:chemistry*; D008401:Gas Chromatography-Mass Spectrometry; D007659:Ketones / Q000737:chemistry*; D000432:Methanol / Q000737:chemistry; D015394:Molecular Structure; D010084:Oxidation-Reduction; D010636:Phenols / Q000737:chemistry*; D011809:Quinones / Q000737:chemistry*; D017550:Spectroscopy, Fourier Transform Infrared
D017610:Calcium Compounds; D003408:Cresols; D007659:Ketones; D010636:Phenols; D011809:Quinones; C004488:calcium hypochlorite; D000432:Methanol