title: Oxidation of alcohol by lipopathic Cr(VI): a mechanistic study.
abstract: The oxidation kinetics of various aliphatic primary and secondary alcohols having varied hydrocarbon chain length were studied using cetyltrimethylammonium dichromate (CTADC) in dichloromethane (DCM) in the presence of acetic acid and in the presence of a cationic surfactant. The rate of the reaction is highly sensitive to the change in [CTADC], [alcohol], [acid], [surfactant], polarity of the solvents, and reaction temperature. A Michaelis-Menten type kinetics was observed with respect to substrate. The chemical nature of the intermediate and the reaction mechanism were proposed on the basis of (i) observed rate constant dependencies on the reactants, that is, fractional order with respect to alcohol and acid and a negative order with respect to oxidant, (ii) high negative entropy change, (iii) inverse solvent kinetic isotope effect, k(H2O)/k(D2O) = 0.76, (iv) low primary kinetic isotope effect, kH/kD = 2.81, and (v) the k(obs) dependencies on solvent polarity parameters. The observed experimental data suggested the self-aggregation of CTADC giving rise to a reverse micellar system akin to an enzymatic environment, and the proposed mechanism involves the following: (i) formation of a complex between alcohol and the protonated dichromate in a rapid equilibrium, equilibrium constant K = 5.13 (+/-0.07) dm(3) mol(-1), and (ii) rate determining decomposition (k(2) = (7.6 +/- 0.7) x 10(-3) s(-1)) of the ester intermediate to the corresponding carbonyl compound. The effect of [surfactant] on the rate constant and the correlation of solvent parameters with the rate constants support the contribution of hydrophobic environment to the reaction mechanism.
authors.affiliation: Center of Studies in Surface Science and Technology, Department of Chemistry, Sambalpur University, Jyoti Vihar-768019, Orissa, India.
authors.forename: Sabita
authors.initials: S
authors.lastname: Patel
authors.forename: B K
authors.initials: BK
authors.lastname: Mishra
mesh_terms: D000438:Alcohols / Q000737:chemistry*; D002593:Cetrimonium Compounds / Q000737:chemistry; D002857:Chromium / Q000737:chemistry*; D057927:Hydrophobic and Hydrophilic Interactions; D007700:Kinetics; D019563:Mechanics; D008752:Methylene Chloride / Q000737:chemistry; D009942:Organometallic Compounds / Q000737:chemistry; D010084:Oxidation-Reduction; D012997:Solvents / Q000737:chemistry; D055672:Static Electricity
chemical_list: D000438:Alcohols; D002593:Cetrimonium Compounds; D009942:Organometallic Compounds; D012997:Solvents; C520498:cetyltrimethylammonium dichromate; D002857:Chromium; D008752:Methylene Chloride