Competing Reactions of Secondary Alcohols with Sodium Hypochlorite Promoted by Phase-Transfer Catalysis

• Published in: Journal of organic chemistry Vol. 70; no. 2; pp. 684 - 687
• Main Authors: Bright, Zack R, Luyeye, Cedric R, Morton, Angela Ste. Marie, Sedenko, Marina, Landolt, Robert G, Bronzi, Matthew J, Bohovic, Katherine M, Gonser, M. W. Alex, Lapainis, Theodore E, Hendrickson, William H
• Format: Journal Article
• Language: English
• Published: Washington, DC American Chemical Society 21-01-2005
• Subjects: Chemistry; Exact sciences and technology; Free radicals chemistry; Kinetics and mechanisms; Organic chemistry; Reactivity and mechanisms; Phase transfer catalysis; Solvent effect; Phase transfer reaction; Chlorination; Competitive reaction; Ketone; Free radical reaction; Scission; Sodium Hypochlorites; Cosolvent; Organic free radical; Hypochlorites; Benzenic compound; Secondary alcohol; Argon; Benzaldehyde derivatives
• ISSN: 0022-3263; 1520-6904
• DOI: 10.1021/jo0490651

With aqueous hypochlorite and a phase transfer catalyst, secondary alcohols undergo hitherto unreported free radical reactions that compete with and effectively limit traditional ketone syntheses. Product mixture profiles are determined by reactant ratios, organic cosolvent, and availability of oxygen to the system. Under argon, over half of substrate alcohols, PhCH(OH)R, are converted to benzaldehyde and free radical products through β-scission of intermediate alkyl hypochlorites. Secondary alcohols with R containing three or more carbons also may undergo δ chlorination.