title: Selective and Efficient Generation of ortho-Brominated para-Substituted Phenols in ACS-Grade Methanol.
abstract: The mono ortho-bromination of phenolic building blocks by NBS has been achieved in short reaction times (15-20 min) using ACS-grade methanol as a solvent. The reactions can be conducted on phenol, naphthol and biphenol substrates, giving yields of >86% on gram scale. Excellent selectivity for the desired mono ortho-brominated products is achieved in the presence of 10 mol % para-TsOH, and the reaction is shown to be tolerant of a range of substituents, including CH3, F, and NHBoc.
authors.affiliation: EaStCHEM School of Chemistry, The University of Edinburgh, David Brewster Road, Edinburgh EH9 3FJ, UK. D.Georgiev@sms.ed.ac.uk.
authors.forename: David
authors.initials: D
authors.lastname: Georgiev
authors.affiliation: EaStCHEM School of Chemistry, The University of Edinburgh, David Brewster Road, Edinburgh EH9 3FJ, UK. bartsaes@live.nl.
authors.forename: Bartholomeus W H
authors.initials: BW
authors.lastname: Saes
authors.affiliation: EaStCHEM School of Chemistry, The University of Edinburgh, David Brewster Road, Edinburgh EH9 3FJ, UK. hjohnst2@exseed.ed.ac.uk.
authors.forename: Heather J
authors.initials: HJ
authors.lastname: Johnston
authors.affiliation: EaStCHEM School of Chemistry, The University of Edinburgh, David Brewster Road, Edinburgh EH9 3FJ, UK. boys.sarah@gmail.com.
authors.forename: Sarah K
authors.initials: SK
authors.lastname: Boys
authors.affiliation: EaStCHEM School of Chemistry, The University of Edinburgh, David Brewster Road, Edinburgh EH9 3FJ, UK. alan.healy@yale.edu.
authors.forename: Alan
authors.initials: A
authors.lastname: Healy
authors.affiliation: EaStCHEM School of Chemistry, The University of Edinburgh, David Brewster Road, Edinburgh EH9 3FJ, UK. Alison.Hulme@ed.ac.uk.
authors.forename: Alison N
authors.initials: AN
authors.lastname: Hulme
mesh_terms: D001557:Benzenesulfonates / Q000737:chemistry; D001713:Biphenyl Compounds / Q000737:chemistry*; D001974:Bromosuccinimide / Q000737:chemistry; D054879:Halogenation; D007700:Kinetics; D000432:Methanol / Q000737:chemistry*; D009284:Naphthols / Q000737:chemistry*; D019800:Phenol / Q000737:chemistry*; D012997:Solvents
chemical_list: D001557:Benzenesulfonates; D001713:Biphenyl Compounds; D009284:Naphthols; D012997:Solvents; D019800:Phenol; D001974:Bromosuccinimide; C029501:4-toluenesulfonic acid; D000432:Methanol
keywords: ACS-grade methanol; NBS; ortho-bromination