4122-13-8

Usage

InChI:InChI=1/C2H4O/c1-2-3/h2H,1H3/i2D

Upstream product

• 13031-34-0 1-deuterio-1-nitro-ethane 
• 13031-33-9 [1,1-2H₂]nitroethane 
• 60-35-5 acetamide 
• 132434-74-3 methylsilyl cation 
• 77081-37-9 3-Cyclohexyl-1-(2,2-dideuterio-2-hydroxyethyl)-1-nitrosourea 
• 1859-09-2 ethanol-1,1-d2 
• 344328-71-8 1,2-propanediol (2-d1) 
• 71-55-6 1,1,1-trichloroethane 
• 1346603-41-5 N-nitrosodi-[1-d⁽²⁾]ethylamine 
• 16972-33-1 pentacarbonylhydridomanganese 

Downstream Products

• 24613-14-7 (-)-(S)-N-(Aethyliden-1-d)-α-phenylaethylamin 
• 74-88-4 methyl iodide 
• 1624-36-8 (+-)-1-deuterio-ethanol 
• 1859-09-2 ethanol-1,1-d2 
• 2229-07-4 methyl radical 
• 2597-44-6 formyl radical 
• 24286-05-3 deuterioformyl 
• 676-49-3 Monodeuteromethan 
• 10457-11-1 deuteromethyl radical 
• 201230-82-2 carbon monoxide 
• 181053-44-1 C₈H₇⁽²⁾HN₄O₄ 
• 758-12-3 deuteroacetic acid 
• 64-19-7 acetic acid 

Relevant academic research and scientific papers

Oxidation of N-nitrosoalkylamines by human cytochrome p450 2a6: Sequential oxidation to aldehydes and carboxylic acids and analysis of reaction steps

Cytochrome P450 (P450) 2A6 activates nitrosamines, including N,N-dimethylnitrosamine (DMN) and N,N-diethylnitrosamine (DEN), to alkyl diazohydroxides (which are DNA-alkylating agents) and also aldehydes (HCHO from DMN and CH3CHO from DEN). The N-dealkylation of DMN had a high intrinsic kinetic deuterium isotope effect (Dkapp ～ 10), which was highly expressed in a variety of competitive and non-competitive experiments. The Dkapp for DEN was ～3 and not expressed in non-competitive experiments. DMN and DEN were also oxidized to HCO2H and CH3CO2H, respectively. In neither case was a lag observed, which was unexpected considering the kcat and Km parameters measured for oxidation of DMN and DEN to the aldehydes and for oxidation of the aldehydes to the carboxylic acids. Spectral analysis did not indicate strong affinity of the aldehydes for P450 2A6, but pulse-chase experiments showed only limited exchange with added (unlabeled) aldehydes in the oxidations of DMN and DEN to carboxylic acids. Substoichiometric kinetic bursts were observed in the pre-steady-state oxidations of DMN and DEN to aldehydes. A minimal kinetic model was developed that was consistent with all of the observed phenomena and involves a conformational change of P450 2A6 following substrate binding, equilibrium of the P450-substrate complex with a non-productive form, and oxidation of the aldehydes to carboxylic acids in a process that avoids relaxation of the conformation following the first oxidation (i.e. of DMN or DEN to an aldehyde).

The influence of H/D kinetic isotope effect on radiation-induced transformations of hydroxyl-containing compounds in aqueous solutions

Vicinal diols and its derivatives can be exploited as model compounds for the investigation of radiation-induced free-radical transformations of hydroxyl-containing biomolecules such as carbohydrates, phospholipids, ribonucleotides, amino acids, and peptides. In this paper, for the first time, the prospects of isotope reinforcement approach in inhibiting free-radical transformations of hydroxyl-containing compounds in aqueous solutions are investigated on the example of radiolysis of 1,2-propanediol and 1,2-propanediol-2-d1 aqueous solutions. At an absorbed dose rate of 0.110 ± 0.003 Gy·s?1 a profound kinetic isotope effect (KIE) is observed for the non-branched chain formation of acetone, which is a final dehydration product of predominant carbon-centred radicals CH3·C(OH)CH2OH. In 0.1 and 1 M deaerated solutions at pH 7.00 ± 0.01, the values of KIE are 8.9 ± 1.7 and 15.3 ± 3.1, respectively. A rationale for the fact that a strong KIE takes place only in the case of chain processes, which may occur during free-radical transformations of vicinal diols, is also provided herein based on the results of 2-propanol and 2-propanol-2-d1 indirect radiolysis. Lastly, the lack of KIE is shown in the case of 2-butanone formation from 2,3-butanediol or 2,3-butanediol-2,3-d2. This indicates that the type (primary, secondary) of the β-carbonyl radicals formed as a result of CH3·C(OH)CH(OH)R (R = H, CH3) dehydration determines the manifestation of the effect.

Metal ions do not play a direct role in the formation of carbon-carbon triple bonds during reduction of trihaloalkyls by CrII or V II

Carbyne radicals: Reactions of trihaloalkyl compounds with Cr2+ or V2+ in aqueous solutions yield alkynes and other products. Stepwise halogen abstractions from the trihaloalkyls form alkyl carbyne triradicals in solution. These radicals undergo coupling reactions, producing triply bonded alkyne molecules (see scheme). This process is not metal-assisted and does not occur in the coordination sphere of the metal ions.

Kinetics and mechanism of the oxidation of aliphatic primary alcohols by imidazolium fluorochromate

The oxidation of nine aliphatic primary alcohols by imidazolium fluorochromate (IFC) in dimethylsulphoxide leads to the formation of corresponding aldehydes. The reaction is first order with respect to IFC. A Michaelis-Menten type kinetics is observed with respect to alcohols. The reaction is promoted 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 (kH/kD = 5.87 at 298 K). The reaction has been studied in nineteen different organic solvents. The solvent effect was analysed using Taft's and Swain's multiparametric equations. The rate of oxidation is susceptible to both polar and steric effects of the substituents. A suitable mechanism has been proposed.

Preparation of human drug metabolites using fungal peroxygenases

The synthesis of hydroxylated and O- or N-dealkylated human drug metabolites (HDMs) via selective monooxygenation remains a challenging task for synthetic organic chemists. Here we report that aromatic peroxygenases (APOs; EC 1.11.2.1) secreted by the agaric fungi Agrocybe aegerita and Coprinellus radians catalyzed the H2O2-dependent selective monooxygenation of diverse drugs, including acetanilide, dextrorphan, ibuprofen, naproxen, phenacetin, sildenafil and tolbutamide. Reactions included the hydroxylation of aromatic rings and aliphatic side chains, as well as O- and N-dealkylations and exhibited different regioselectivities depending on the particular APO used. At best, desired HDMs were obtained in yields greater than 80% and with isomeric purities up to 99%. Oxidations of tolbutamide, acetanilide and carbamazepine in the presence of H218O2 resulted in almost complete incorporation of 18O into the corresponding products, thus establishing that these reactions are peroxygenations. The deethylation of phenacetin-d1 showed an observed intramolecular deuterium isotope effect [(kH/kD) obs] of 3.1 ± 0.2, which is consistent with the existence of a cytochrome P450-like intermediate in the reaction cycle of APOs. Our results indicate that fungal peroxygenases may be useful biocatalytic tools to prepare pharmacologically relevant drug metabolites.

Oxidation of aliphatic primary alcohols by morpholinium chlorochromate: A kinetic and mechanistic approach

The oxidation of nine aliphatic primary alcohols by morpholinium chlorochromate (MCC) in dimethylsulfoxide leads to the transformation of alcohols to the corresponding aldehydes. The reaction is first order with respect to both MCC and the alcohol both. The reaction is catalysed by hydrogen ions. The hydrogen-ion dependence has the form: kobs = a + A[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 analysed using Taft's and Swain's multiparametric equations. The rate of oxidation is susceptible to both polar and steric effects of the substituents. A suitable mechanism has been proposed.

Kinetics and mechanism of oxidation of aliphatic alcohols by [bis(trifluoroacetoxy)iodo]benzene

The oxidation of some aliphatic alcohols by [bis(trifluoroacetoxy)iodo] benzene (TFAIB) in aqueous acetic acid solution leads to the formation of the corresponding carbonyl compounds. The reaction is first order in TFAIB and a Michaelis-Menten kinetics is obtained with respect to the alcohols. The reaction shows a first order dependence on hydrogen ions. The oxidation of [1,1- 2H2]ethanol and [2-2H]propan-2-ol exhibits the presence of a substantial primary kinetic isotope effect at 298 K (k H/kD = 3.64 and 3.89 respectively). The rate of disproportionation of the intermediate is susceptible to both polar and steric effects of the substituents. A suitable mechanism has also been proposed.

Kinetics and mechanism of the oxidation of aliphatic alcohols by benzyltrimethylammonium dichloroiodate

The oxidation of a series of aliphatic alcohols by benzyltrimethylammonium dichloroiodate (BTMACI), in glacial acetic acid in the presence of zinc chloride, leads to the formation of the corresponding carbonyl compounds. The reaction is first order each with respect to the alcohol, zinc chloride and BTMACI. Addition of the benzyltrimethylammonium chloride enhances the rate slightly. The oxidation of deuteriated ethanol indicates the presence of a substantial kinetic isotope effect. [PhCH2Me3N]+[IZn2Cl 6]- is postulated to be the reactive oxidizing species. The reaction is susceptible to both polar and steric effects of the substituents. A mechanism involving transfer of a hydride ion from the alcohol to the oxidant has been proposed.

Kinetic and Mechanism of the Oxidation of Aliphatic Alcohols by Benzyltrimethylammonium chlorobromate

Oxidation of fourteen aliphatic alcohols by benzyltrimethylammonium chlorobromate (BTMACB) in aqueous acetic acid leads to the formation of the corresponding carbonyl compounds. The reaction is first order each in BTMACB and the alcohol. The reaction failed to induce the polymerization of acrylonitrile. There is no effect of benzyltrimethylammonium chloride or potassium bromide on the reaction rate. The proposed reactive oxidizing species is chlorobromate ion. The oxidation of [1,1-2]ethanol and [2-]propan-2-ol exhibited a substantial kinetic isotope effect. The effect of solvent composition indicated that the rate increases with an increase in the polarity of the solvent. The reaction is subject to both the polar and steric effects of the substituents. A mechanism involving transfer of a hydride ion from the alcohol to the oxidant has been proposed.

Aerobic oxidation of primary alcohols (including methanol) by copper(II)- and zinc(II)-phenoxyl radical catalysts

The tetradentate ligand N,N′-bis(3,5-di-tert-butyl-2-hydroxyphenyl)-1,2-phenylenediamme, H4L1, has been prepared, and its square planar complexes [Cu11(L3)] and [Zn11(L3)] have been synthesized from the reaction of H4L1 with [Cu1(NCCH3)4](CIO4) or Zn(BF4)2·2H2O in methanol in the presence of air. The dianion (L3)2- represents the two-electron oxidized form of (L1)4-, namely N,N′-bis(3,5-di-ferf-butyl-2-hydroxyphenyl)-1,2-diiminoquinone. Complexes [Cu11(L3)]·CH3CN and [Zn(L3)]·CH3CN have been characterized by X-ray crystallography, EPR spectroscopy, and magnetochemistry; [Cu11(L3)] has an S = 1/2 ground state, and [Zn-(L3)] is diamagnetic. Cyclic voltammetry established that both complexes undergo two successive reversible one-electron oxidations and two successive reversible one-electron reductions. Thus, the coordinated ligand exists in five oxidation levels. The species [M11(L4)]PF6 (M = Cu11, Zn11) and [M11(L4)](ClO4)2 (M = Cu11, Zn11) have been isolated and characterized by UV/vis, EPR, and 1H NMR spectroscopy and by magnetic susceptibility measurements, where (L4)- represents the monoanion N-(3,5-di-tert-butyl-2-hydroxyphenyl)-N′-(3,5-di-tert-butyl-2-phenoxyl)-1, 2-diiminoquinone and (L5) is the neutral ligand N,N′-bis(3,5-di-tert-butyl-2-phenoxyl)-1,2-diiminoquinone. Similarly, two complexes of the type [M11(L1H2)] (M = Cu11, Zn11) have been isolated from the reaction of L1H4 with Cu11(ClO4)2·6H2O or Zn(ClO4)2·6H2O under anaerobic conditions in the presence of NEt3. Complexes [Cu11(L4)]PF6 and [Zn(L4)]PF6 selectively oxidize primary alcohols (including methanol and ethanol) in a stoichiometric fashion under anaerobic conditions, yielding the corresponding aldehydes and [M11(L2H2)]+ (M = Cu11, Zn11), where (L2)3- is the trianionic form of N,N′-bis(3,5-di-fert-butyl-2-hydroxyphenyl)-l,2-diiminosemiquinone. Since the latter reduced forms react rapidly with dioxygen with formation of [M11(L4)]+ (M = Cu, Zn) and 1 equiv of H2O2, these oxidized species are catalysts for the air oxidation of primary alcohols, including ethanol and methanol, with concomitant formation of H2O2 and aldehydes. The kinetics of the stoichiometric reactions and of the catalyses (initial rate method) have been measured. Large kinetic isotope effects show that H-abstraction from the α-carbon atom of a coordinated alcoholato ligand is the rate-determining step in all cases.