title: 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.
abstract: 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.
authors.affiliation: Department of Chemistry, Point Loma Nazarene University, San Diego, California 92106-2899, USA. vheasley@ptloma.edu
authors.forename: Victor L
authors.initials: VL
authors.lastname: Heasley
authors.forename: James D
authors.initials: JD
authors.lastname: Anderson
authors.forename: Zachery S
authors.initials: ZS
authors.lastname: Bowman
authors.forename: John C
authors.initials: JC
authors.lastname: Hanley
authors.forename: Geoffery A
authors.initials: GA
authors.lastname: Sigmund
authors.forename: David
authors.initials: D
authors.lastname: Van Horn
authors.forename: Dale F
authors.initials: DF
authors.lastname: Shellhamer
mesh_terms: 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
chemical_list: D017610:Calcium Compounds; D003408:Cresols; D007659:Ketones; D010636:Phenols; D011809:Quinones; C004488:calcium hypochlorite; D000432:Methanol