The deuterium isotope effect in the permanganate oxidation of aromatic trifluoromethyl alcohols

✍ Scribed by R. Stewart; R. Van der Linden

• Publisher: Elsevier Science
• Year: 1960
• Tongue: French
• Weight: 118 KB
• Volume: 1
• Category: Article
• ISSN: 0040-4039
• DOI: 10.1016/s0040-4039(01)99276-7

✦ Synopsis

PHENYL trifluoromethyl carbinols are oxidized by aqueous alkaline permsnganate to the corresponding ketones. We wish to report a kinetic isotope effect of unusual size for the reaction of the 1-deuterio analogs of these compounds. YC6H4CDOHCF3 + 2Mn04-+ 2OH-4 YC H COCF3 + 2Mn0 * + H20 + RDO 64 4 1-Phenyl-2,2,2-trifluoroethan-l-01 (I) and its p-methyl (II) and m-bromo (III) derivatives were prepared by LiAlH 4 reduction of the corresponding ketones. (II), b-p., 94*5 (12 mm) r-$4 s 1.4650. Found: C, 57.1~ H, 5.0. C9H9F30 requires C, 56.9; H, 4.7. Phenylurethan of (II), m-p., 104-105. Found: C, 62.1; H, 4.5; N, 5.1. C16H14F302N require8 C, 62.1; H, 4-5; N, 5-l* (III), b-p. 115 (12 mm), ng7= 1.5005. Found: C, 38.0! H, 2.5; Br, 31*6. C8H6F3Br0 requires C, 37.1; H, 2.4; Br, 31.4. p-Tolyl trifluoromethyl ketone' was prepared from p-tolyl magnesium bromide and trifluoroacetic acid. Bromination of phenyl trifluoromethyl