Medium Effects on C,C‐Bond Cleavage in the Alcohol Oxidation with Chromic Acid

Abstract

Dedicated to Professor AndrP Dreiding on occasion of his 60th birthday (23.VII.79) SummaryThe C, C-bond cleavage which occurs during chromic acid oxidation of t-butylphenylmethanol (1) and 1,2-diphenylethanol (2) to the extent of up to 67% is reduced to 3% for 1 and 13% for 2 when the reaction is run in acetone, and totally suppressed upon co-oxidation of the alcohols 1 and 2 with oxalic acid. Similarly, the yield of 7-norbornanone obtained from 7-norbornanol (7) is raised in going from acetic acid (24%) to acetone (41%) and approaches 100% in the co-oxidation. With the co-oxidation 5-endo-bicyclo [2.1 .l]hexanol (3) is converted to the corresponding ketone in 54% yield. Mechanistic implications of these results are discussed.

Stereomutation of Conformational Enantiomers of 9-Isopropyl-9-formylfluorene and Related Acyl Derivatives

“…The crude was identified by GCMS to contain mainly the intermediate alcohol. Oxidation was carried on at room temperature by adding H 2 SO 4 (0.2 mL, 1 N solution) and aliquots of CrO 3 to an acetone solution of the crude alcohol,following the reaction by GC-MS. When the alcohol disappeared, acetone was removed at reduced pressure, than H 2 O and Et 2 O were added.…”