Oxidation of secondary alcohols in diethyl ether with aqueous chromic acid. Convenient procedure for the preparation of ketones in high epimeric purity

1971 ◽  
Vol 36 (3) ◽  
pp. 387-390 ◽  
Author(s):  
Herbert Charles Brown ◽  
Chandra P. Garg ◽  
Kwang-Ting Liu
Keyword(s):  
Diethyl Ether ◽  
Chromic Acid ◽  
Secondary Alcohols ◽  
Convenient Procedure

Oxidation rates of triterpenoid secondary alcohols with chromic acid

1976 ◽  
Vol 41 (3) ◽  
pp. 770-779 ◽  
Author(s):  
M. R. Nair ◽  
S. Hilgard ◽  
J. Klinot ◽  
K. Waisser ◽  
A. Vystrčil
Keyword(s):  
Chromic Acid ◽  
Secondary Alcohols ◽  
Oxidation Rates

Chromic acid oxidation of aromatic alcohols

1969 ◽  
Vol 47 (17) ◽  
pp. 3207-3212 ◽  
Author(s):  
Ross Stewart ◽  
Fariza Banoo
Keyword(s):  
Chromic Acid ◽  
Acid Oxidation ◽  
Secondary Alcohols ◽  
Tertiary Alcohols ◽  
Chromic Acid Oxidation ◽  
Hydride Shift ◽  
Rate Of Reaction ◽  
Aromatic Alcohols ◽  
Reaction Constant ◽  
Rate Controlling Step

The mechanism of the chromic acid oxidation of di- and tri-aryl carbinols has been studied in 80 wt% acetic acid containing sulfuric acid. The reactions are cleanly second-order and give benzophenones in the case of the secondary alcohols and benzophenones plus phenols in the case of the tertiary alcohols. Electron-donating substituents in the tertiary alcohol appear predominantly in the phenol component and the rate-controlling step is believed to be a 1,2-aryl shift. The reaction constant for the migration is ρ+ = −1.44 and that for the overall reaction is ρ+ = −0.879. The presence of manganous ions does not alter these values although it lowers the overall rate of reaction. Although an analogous 1,2-hydride shift mechanism can be written for the oxidation of the secondary alcohols, there are enough points of difference between the oxidations of the secondary and tertiary systems to make this appear unlikely.

Formation of iodides and esters from alcohols and tributyldiiodophosphorane and diiodotriphenylphosphorane

1982 ◽  
Vol 35 (3) ◽  
pp. 517 ◽  
Author(s):  
RK Haynes ◽  
M Holden
Keyword(s):  
Diethyl Ether ◽  
Room Temperature ◽  
Temperature Treatment ◽  
Butyl Alcohol ◽  
Secondary Alcohols ◽  
Benzoic Acids ◽  
Lithium Iodide ◽  
Hexamethylphosphoric Triamide ◽  
Tertiary Alcohols

Tributyldiiodophosphorane and diiodotriphenylphosphorane, prepared in situ from the corresponding phosphine and iodine, are generally able to convert primary and secondary alcohols into iodides at room temperature in diethyl ether or benzene containing two equivalents of hexamethylphosphoric triamide. Tertiary alcohols, as gauged by the lack of reactivity of t-butyl alcohol, are, however, inert to these iodinating agents. 6-Hydroxyhexanoic acid yields a mixture of 6-iodohexanoic acid and 7-heptanolide. The first reagent also promotes facile condensation of secondary and tertiary alcohols with carboxylic acids to form hindered esters in good yields. The phosphorane derived from tris-(dimethy1amino)phosphine and iodine, while less effective as an iodinating agent, rapidly converts 6-hydroxyhexanoic acid into 6-iodo-N,N-dimethylhexanamide, and hexanoic and benzoic acids into the corresponding N,N-dimethylamides in excellent yields at room temperature. Treatment of 3β- tosyloxycholest-5-ene with lithium iodide yields 3β-iodocholest-5-ene, and not 3α-iodocholest-5-ene, as previously reported.

Kinetic Isotope Effect in the Chromic Acid Oxidation of Secondary Alcohols

2000 ◽  
Vol 77 (8) ◽  
pp. 1042 ◽  
Author(s):  
Charles E. Harding ◽  
Christopher W. Mitchell ◽  
Jozsef Devenyi
Keyword(s):  
Isotope Effect ◽  
Kinetic Isotope Effect ◽  
Chromic Acid ◽  
Acid Oxidation ◽  
Secondary Alcohols ◽  
Chromic Acid Oxidation ◽  
Kinetic Isotope
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