10312-83-1Relevant academic research and scientific papers
Kinetics and Mechanism of the Oxidation of Primary Alcohols by N-bromoacetamide in Alkaline Solution
Shah, Bindu,Banerji, Kalyan K.
, p. 33 - 36 (1983)
The kinetics of the oxidation of seven primary alcohols by N-bromoacetamide has been studied in alkaline solution.The main product of the oxidation is the corresponding aldehyde.The reaction first order with respect to the oxidant and alcohol.The oxidation of ethanol indicates an absence of a primary kinetic isotope effect.The rate decreases with the increase in the concentration of hydroxide ion.Addition of acetamide decreases the reaction rate.The rates were determined at five different temperatures and the activation parameters were evaluated.The activation enthalpies and entropies of the oxidation of seven alcohols are linearly related.Hypobromite ion has been postulated as the reactive oxidizing species.A mechanism involving rate-determining nucleophilic attack of hypobromite ion on the alcohol molecule has been proposed.
Oxidation of ethers with dimethyldioxirane
Grabovskiy,Timerghazin,Kabal'nova
, p. 2384 - 2393 (2005)
Oxidation of a series of tert-butyl ethers ButOR (R = Me, Et, CH2CH2Cl, Pri, Bui), diethyl ether, diisopropyl ether, 1,2-dimethoxyethane, diisobutoxymethane, 1,4-dioxane, and tetrahydrofuran with dimethyldioxirane (DMDO) was studied. The reaction kinetics obeys the second-order equation w = k[DMDO][ether]. The rate constants in a range of 5-50°C and the activation parameters of the reaction were determined. The solvent effect on the oxidation rate was studied. The oxidation products are the corresponding alcohols and carbonyl compounds. The competition between the nonradical (oxygen insertion) and radical mechanisms of the reaction is discussed. The reactions of the parent dioxirane and DMDO with a series of methyl ethers MeOR′ (R′ = Me, Et, CH2CH2F, Pri) were studied by the density functional theory (DFT). The (U)B3LYP-6-311G(d,p) method was employed to calculate the geometry and energies of the reactants and transition states. The data obtained indicate a possible increase in the probability of oxidation via the radical route and an increase in the activation barrier for the substrates containing electron-withdrawing substituents.
Kinetics and Mechanism of the Oxidation of Primary Alcohols by N-Bromoacetamide in Acid Medium
Mukherjee, Jogeshwar,Banerji, Kalyan K.
, p. 2323 - 2326 (1981)
The kinetics of the oxidation of ten primary alcohols by N-bromoacetamide (NBA) has been studied in acid medium.The main product of the oxidation is the corresponding aldehyde.The reaction is first order in alcohol, NBA, and H(+).The oxidation of ethanol-1,1-d2 indicates no primary kinetic isotope effect.A solvent isotope effect, k(D2O)/k(H2O)= 1.16, was observed at 308 K.The rates were determined at four different temperatures and the activation parameters were evaluated.Addition of acetamide decreases the rate. (H2OBr)(+) has been postulated as the oxidizing species.A mechanism involving formation of a hypobromite ester in the rate-determining step has been proposed.The reaction constant, ρ*, has a value of -1.53 at 303 K.
Kinetics and mechanism of the oxidation of aliphatic alcohols by quinolinium fluorochromate
Choudhary,Sharma,Banerji
, p. 469 - 475 (1999)
The oxidation of some aliphatic alcohols by quinolinium fluorochromate (QFC) in dimethyl sulfoxide leads to the formation of corresponding carbonyl compounds. The reaction is first order with respect to QFC. The reaction exhibited Michaelis-Menten type kinetics with respect to the alcohol. The reaction is catalyzed by hydrogen ions. The hydrogen-ion dependence has the form: kobs = a+b[H+]. The oxidation of [1,1-2H2]ethanol (MeCD2OH) exhibits a substantial primary kinetic isotope effect. The reaction has been studied in nineteen different organic solvents. The solvent effect was analyzed using Taft's and Swain's multiparametric equations. The rate of disproportionation of the complex is susceptible to both polar and steric effects of the substituents. A suitable mechanism has been proposed.
STUDY OF THE KINETICS AND MECHANISM OF THE ACID-BASE CATALYZED ENOLIZATION OF HYDROXYACETALDEHYDE AND METHOXYACETALDEHYDE
Fedoronko, Michal,Temkovic, Peter,Koenigstein, Jozef,Kovacik, Vladimir,Tvaroska, Igor
, p. 35 - 50 (1980)
In acid and alkaline media, glycolaldehyde (hydroxyacetaldehyde) exists in equilibrium with its enediol form, which is quantitatively oxidized to glyoxal by an excess of Methylene Blue.In acid and alkaline media, the enol form of methoxyacetaldehyde is formed.In alkaline medium, this enol is stable; in acid, it undergoes hydrolysis to glycolaldehyde.The kinetics of enolization of glycolaldehyde and methoxyacetaldehyde were studied polarographically.The mechanisms of enolization of glycolaldehyde and acid hydrolysis of methoxyacetaldehyde were established both from kinetic data and from deuterium-incorporation data.The proposed mechanisms were confirmed by quantum-mechanical calculation of the charge distribution in the two compounds studied and their reaction intermediates.The glyoxal obtained in the oxidation was isolated as quinoxaline and analyzed by mass spectrometry.
Kinetics and correlation analysis of reactivity in the oxidation of aliphatic primary alcohols by isoquinolinium dichromate in non-aqueous medium
Kalal, Reena,Panday, Dinesh
, (2021)
Mild oxidation in dimethyl sulfoxide (DMSO) medium by isoquinolinium dichromate (IQDC) of aliphatic primary alcohols produces corresponding carbonyl compounds. A Michaelis-Menten kind kinetics noticed as for alcohols while unit dependency on rate observed as for IQDC. At non-identical temperatures the formation constants and the rates of decomposition of alcohol-IQDC complexes have been evaluated. Thermodynamic parameters and activation parameters for formation of the complex and break down of the complexes have been determined respectively. The oxidation process accelerates with increase in proton concentration. An α-C-H bond fisson in the rate-controlling step suggested by the deuterium isotope effect. For oxidation of ethanol, kH/kD = 5.82 at 293 K, was observed. The oxidation rates have been evaluated in 19 organic solvents and greater role of solvating power of the cation is observed. Depended on the kinetic parameters, solvent effect analysis and the outcome of thermodynamic parameters, a mechanism in which rate-controlling break down of the complex is suggested, to give the resulting product through hydride-ion transfer with a cyclic transition state.
DEHYDROGENATION OF SUBSTITUTED ALCOHOLS TO ALDEHYDES ON ZINC OXIDE-CHROMIUM OXIDE CATALYSTS
Gulkova, Daniela,Kraus, Milos
, p. 2215 - 2226 (1992)
Sixteen primary alcohols of the structure RCH2OH (R = CH3, C2H5, (CH3)2CH, (CH3)3CCH2, HOCH2, CH3OCH2, C6H5, C6H5CH2, C6H5OCH2, ClCH2, BrCH2, F3C, CNCH2, (CH3)2NCH2, (C2H5)2NCH2 and tetrahydrofurfuryl) were explored for the possibility of obtaining the corresponding aldehydes by dehydrogenation on solid catalysts.Various catalysts were tested and two zinc oxide-chromium oxide catalysts were selected for further work because their activity and selectivity was satisfactory; moreover, the selectivity could be improved by addition of sodium into the catalysts and of water into the feed.The reaction was performed in the temperature range 250 - 450 deg C and at atmospheric pressure. 2-Chloroethanol, 2-bromoethanol, ethylene glycol, 2-cyanoethanol and 2-(N,N-diethylamino)ethanol decomposed and deactivated the catalyst.The other alcohols were studied from the point of kinetics of dehydrogenation, which was described by a Langmuir-Hinshelwood type rate equation (3), and of substituent effects on rate, which were correlated by Taft equation (1) with the slope ρ* = -1.46.The preparative value of catalytic dehydrogenation for obtaining substituted aldehydes was confirmed by prolonged runs and isolation of the aldehydic product by distillation using as the feeds 2-methoxyethanol and 2-(N,N-dimethylamino)ethanol, respectively.
USE OF PHYSIOLOGICAL COOLING ACTIVE INGREDIENTS, AND COMPOSITIONS COMPRISING SUCH ACTIVE INGREDIENTS
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Paragraph 0398, (2020/07/07)
The invention relates primarily to a method of modulation, preferably of in vitro and/or in vivo modulation, of the cold menthol receptor TRPM8, wherein the receptor is contacted with at least one modulator selected from the group consisting of the compounds of the structure type 1 described herein. The present invention further relates to corresponding uses and compositions comprising such compounds.
1,5,7-TRISUBSTITUTED ISOQUINOLINE DERIVATIVES, PREPARATION THEREOF, AND USE THEREOF IN MEDICINES
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Paragraph 0150; 0257-0258, (2020/08/30)
The present disclosure relates to 1,5,7-trisubstituted isoquinoline derivatives, their preparation and pharmaceutical use. In particular, the present disclosure discloses a compound of formula (I) or a pharmaceutically acceptable salt, stereoisomer, solvate or prodrug thereof, and a preparation method and use thereof. The definitions of the groups in the formula can be found in the specification and claims.
CANCER TREATMENTS TARGETING CANCER STEM CELLS
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Paragraph 0331; 0509-0511, (2019/11/19)
Disclosed are compounds, methods, compositions, and kits that allow for treating cancer by, e.g., targeting cancer stem cells. In some embodiments, the cancer is colorectal cancer, gastric cancer, gastrointestinal stromal tumor, ovarian cancer, lung cancer, breast cancer, pancreatic cancer, prostate cancer, testicular cancer, or lymphoma. In some embodiments, the cancer is liver cancer, endometrial cancer, leukemia, or multiple myeloma. The compounds utilized in the disclosure are of Formula (0), (O'), and (I):
