40365-04-6Relevant articles and documents
Substrate inhibition in ruthenium(III) catalyzed oxidation of propane-1,3-diol by periodate in acidic medium: A kinetic study
Koteswara Rao,Nadh, R. Venkata,Ratnam, K. Venkata
, p. 1569 - 1575 (2020/07/30)
Ruthenium(III) catalyzed oxidation of propane-1,3-diol by potassium periodate was studied in aqueous perchloric acid medium. Orders of reaction with respect to concentrations of oxidant, substrate, acid and catalyst were determined. First order in oxidant and catalyst concentrations, and inverse fractional order in acid medium were observed. In addition, substrate inhibition (i.e. a decrease in reaction rate with an increase in substrate concentration) was observed. Effect of addition of salt and solvent was studied. Based on the studies of temperature variation, Arrhenius parameters were calculated. Plausible mechanism was also proposed based on observed kinetics.
Kinetics and mechanism of the oxidation of diols by butyltriphenylphosphonium dichromate
Panday, Dinesh,Kothari, Seema
experimental part, p. 918 - 925 (2011/09/19)
The oxidation of four vicinal, four non-vicinal diols and one of their monoethers by butyltriphenylphosphonium dichromate (BTPPD), in dimethylsulfoxide (DMSO), resulted in the formation of corresponding hydroxyaldehyde as a main product of the oxidation. The reactions are of first order with respect to BTPPD, however, second order dependence is obtained with respect to each the diol and hydrogen ion. The oxidation of [1,1,2,2-2H 4]ethanediol exhibited primary kinetic isotope effect (k H/kD = 6.61 at 298 K). The temperature dependence of the kinetic isotope effect suggested the symmetrical transition state in the rate-determining step. The rate constants of oxidation of four vicinal diols show excellent correlation with Taft's ∑ σ* values with negative reaction constant, ρz.ast;. The rate of oxidation of ethanediol has been determined in nineteen different solvents. An analysis of the solvent effect indicates the importance of the cation-solvating power of the solvents. A suitable mechanism has been postulated involving the formation of chromate ester in a pre-equilibrium.
Oxidation of some vicinal and non-vicinal diols by morpholinium chlorochromate: A kinetic and mechanistic study
Barthora,Baghmar,Agarwal,Sharma, Vinita
experimental part, p. 677 - 683 (2012/04/10)
The kinetics of oxidation of four vicinal, four non-vicinal diols and two of their monoethers by morpholinium chlorochromate (MCC) have been studied in dimethylsulphoxide (DMSO). The main product of oxidation is the corresponding hydroxycarbonyl compound. The reaction is first order in MCC and the diols. The reaction is catalysed by hydrogen ions. The hydrogen ion dependence is taking the form : kobs = a + b [H+]. The oxidation of [1,1,2,2-2H4]ethanediol exhibits a substantial primary kinetic isotope effect (kH/kD = 5.82 at 298 K). The reaction has been studied in nineteen different organic solvents and the solvent effect has been analysed using Taft's and Swain's multiparametric equations. The temperature dependence of the kinetic isotope effect indicates the presence of a symmetrical transition state in the rate-determining step. A suitable mechanism has been proposed.
Kinetics and Mechanism of Ruthenium(III) Chloride Catalyzed Oxidation of Propane-1,3-diol by Ceric Sulphate in Aqueous Sulphuric Acid Medium.
Agrawal, Anju,Sharma, Indu,Gupta, Divya,Khandelwal, C. L.,Sharma, P. D.
, p. 621 - 636 (2007/10/03)
The kinetics of ruthenium(III) chloride catalyzed oxidation of propane-1,3-diol by ceric sulphate have been studied. 3-Hydroxypropanal is spectrally confirmed to be the oxidation product of the diol. The kinetic rate law (1) is based on the proposed reaction mechanism. Kinetic rate parameters have been evaluated.
N-dealkylation of an N-cyclopropylamine by horseradish peroxidase. Fate of the cyclopropyl group
Shaffer,Morton,Hanzlik
, p. 8502 - 8508 (2007/10/03)
Cyclopropylamines inactivate cytochrome P450 enzymes which catalyze their oxidative N-dealkylation. A key intermediate in both processes is postulated to be a highly reactive aminium cation radical formed by single electron transfer (SET) oxidation of the nitrogen center, but direct evidence for this has remained elusive. To address this deficiency and identify the fate of the cyclopropyl group lost upon N-dealkylation, we have investigated the oxidation of N-cyclopropyl-N-methylaniline (3) by horseradish peroxidase, a well-known SET enzyme. For comparison, similar studies were carried out in parallel with N-isopropyl-N-methylaniline (9) and N,N-dimethylaniline (8). Under standard peroxidatic conditions (HRP, H2O2, air), HRP oxidizes 8 completely to N-methylaniline (4) plus formaldehyde within 15-30 min, whereas 9 is oxidized more slowly (14C]-3, [1′-13C]-3, and [2′,3′-13C]-3 as substrates, radiochemical and NMR analyses of incubation mixtures revealed that the complete oxidation of 3 by HRP yields 4 (0.2 mol), β-hydroxypropionic acid (17, 0.2 mol), and N-methylquinolinium (16, 0.8 mol). In buffer purged with pure O2, the complete oxidation of 3 yields 4 (0.7 mol), 17 (0.7 mol), and 16 (0.3 mol), while under anaerobic conditions, 16 is formed quantitatively from 3. These results indicate that the aminium ion formed by SET oxidation of 3 undergoes cyclopropyl ring fragmentation exclusively to generate a distonic cation radical (14+?) which then partitions between unimolecular cyclization (leading, after further oxidation, to 16) and bimolecular reaction with dissolved oxygen (leading to 4 and 17 in a 1:1 ratio). Neither β-hydroxypropionaldehyde, acrolein, nor cyclopropanone hydrate are formed as SET metabolites of 3. The synthetic and analytical methods developed in the course of these studies should facilitate the application of cyclopropylamine-containing probes to reactions catalyzed by cytochrome P450 enzymes.
