Acetone Oxime Research Articles

Reaction of aryldiazonium salts with acetone oxime

The reaction of aryl diazonium salts containing electron-withdrawing substituents in the aromatic ring with acetone oxime leads to the formation of nitrogen-containing products instead of the expected functional derivatives of 1-alkyl-3-aryltriazene 1-oxides. The structure of these products is a function of the number and chemical nature of the substituents in the diazo component.

Synthesis of Alkyl Substituted p-Benzoquinones from the Corresponding Phenols Using Molecular Oxygen Catalyzed by Copper(II) Chloride–Amine Hydrochloride Systems

Abstract 2,4,6-Trimethylphenol was effectively oxidized to trimethyl-p-benzoquinone with molecular oxygen in the presence of a catalytic amount of copper(II) chloride–amines in alcohol at ambient temperature. Various amines could be used as a co-catalyst in the presence of acids, and especially hydroxylamine hydrochloride and acetone oxime coupled with hydrochloric acid showed high activity. 2,6-Dimethyl-p-benzoquinone was also obtained from 2,6-dimethylphenol in good yield in this catalytic oxidation system.

Katalytische Carbonylierung von Aceton‐oxim an Bisoximato‐diruthenium‐Komplexen: Ein einfacher Zugang zu wasserfreiem Acetonin. Isolierung und Molekülstruktur von [Ru2(CO)5(Me2CNO)2(Me2CNOH)

Catalytic Carbonylation of Acetone Oxime at Bisoximatodiruthenium Complexes: A Simple Access to Anhydrous Acetonine. Isolation and Molecular Structure of [Ru2(CO)5(Me2CNO)2(Me2CNOH)]In the presence of catalytic amounts of [Ru2(CO)4(Me2CNO)2(Me2CNOH)2] (1), acetone oxime reacts with carbon monoxide to give 2,3,4,5‐tetrahydro‐2,2,4,4,6‐pentamethylpyrimidine (‘acetonine’). CO2, and NH3. The reaction proceeds presumably via carbonylation of Me2CNOH to the unstable intermediate Me2CNOCHO which undergoes decarboxylation to give the corresponding imine Me2CNH. The final product is assumed to result from the cyclotrimerisation of Me2CNH with elimination of NH3. Evidence for the intermediacy of the imine comes from the analogous reaction of acetophenone oxime, PhMeCNOH, which gives the corresponding imine PhMeCNH as a stable product. The isolation of the complex [Ru2(CO)5(Me2CNO)2(Me2CNOH)] (2) suggests the carbonylation to take place at the bridging oximato ligand of 1.

Nitroreduction is not involved in the genotoxicity of 2-nitropropane in cultured mammalian cells

We have investigated the importance of nitroreduction for the genotoxicity of the carcinogen 2-nitropropane (2-NP) in primary cultures of rat hepatocytes and in V79 Chinese hamster cells. Induction of DNA repair synthesis was used as an indicator of genotoxic effects in hepatocytes. Genotoxicity in V79 cells was determined as induction of DNA repair, micronuclei and mutations to 6-thioguanine (TG) resistance. Both hepatocytes and V79 cells were found capable of reducing and oxidizing 2-NP. Reduction of 2-NP was indicated by the formation of acetone oxime, the tautomeric form of 2-nitrosopropane, the first reduction product of 2-NP. Oxidation of 2-NP was indicated by the production of acetone and nitrite. 2-NP strongly elicited repair in hepatocytes, but acetone oxime and the products of a possible further nitroreduction, isopropyl hydroxylamine (IPHA) and 2-aminopropane did not. None of the reduction products caused repair synthesis in V79 cells. However, in these cells IPHA and 2-NP increased the frequency of TG-resistant mutants. IPHA also markedly induced micronuclei. This was not seen with 2-NP. Acetone oxime was not genotoxic in V79 cells. The observations suggest that reduced metabolites are responsible neither for the induction of DNA repair synthesis by 2-NP in hepatocytes nor for the induction of gene mutations by 2-NP in V79 cells.

Investigation of the chemical basis of nitroalkane toxicity: Tautomerism and decomposition of propane 1- and 2-nitronate under physiological conditions

Unlike primary nitroalkanes, such as 1-nitropropane, the secondary nitroalkane 2-nitropropane is geno- and hepatotoxic. Nitroalkanes exist in equilibrium with alkane nitronates. In order to investigate the relationship between nitroalkane toxicity and generation and stability of nitronates, propane 1- or 2-nitronate (4–6 mM) were incubated in buffer (pH 3.8–7.4) in the absence or presence of cysteine. Equilibrium formation and degradation were studied by 1H-NMR spectroscopy and ion pair HPLC chromatography. Propane 1-nitronate generated 1-nitropropane rapidly and almost quantitatively. In the case of propane 2-nitronate equilibrium at pH 7.4 was reached within 8 h, when 48% of initial nitronate had tautomerised to 2-nitropropane. The p K a of the reaction 2-nitropropane 〈- -〉 propane 2-nitronate measured by HPLC was 7.63. Equilibrium formation, hydrolysis and reduction of nitronates were pH-dependent and, in the case of propane 2-nitronate, yielded mainly acetone, nitrite and acetone oxime, apart from 2-nitropropane. Hydrolysis of propane 2-nitronate (4 mM) to nitrite was modulated by cysteine (4 mM) and p-methoxyphenol (0.4 mM). At pH 7.4 they increased nitrite generation by 300 and 28%, respectively, at pH 4.8 they decreased nitrite formation by 91 and 82%, respectively, probably by scavenging radical intermediates. Differences between nitroalkanes in terms of content of nitronate tautomer at equilibrium are probably an important chemical determinant of their toxic potential.

Oxygenhydrogen versus nitrogenoxygen bond cleavage in the oxidative addition of oximes to [Os 3(CO) 10(MeCN) 2]: crystal structures of the isomers [Os 3H(Me 2CNO)(CO) 10] and [Os 3(OH)(Me 2CN) (CO) 10

Acetone oxime (Me 2CNOH) reacts with [Os 3(CO) 10(MeCN) 2] to give the bridging oximato cluster [Os 3(μ-H)(μ-Me 2CNO)(CO) 10] ( 1) resulting from oxidative addition with OH bond cleavage. An X-ray crystal structure determination showed that the oximato ligand is bridging two osmium atoms by bonding to one Os atom through the N-atom and to another through the O-atom. A range of clusters with similarly bonded oximato ligands were synthesised from the oximes derived from benzophenone (Ph 2CNOH), cyclohexanone (C 6H 10NOH), acetaldehyde (MeCHNOH), benzaldehyde (PhCHNOH) (two isomers obtained), and formamide (NH 2CHNOH). Compound 1 isomerises at 125°C to the non-hydrido isomer [Os 3(μ-OH)(μ-Me 2CN)(CO) 10] ( 2) which was characterised spectroscopically and crystallographically and shown to contain the bridging hydroxy and the N-bonded Me 2CN ligands. Overall oxidative addition of the oxime with NO bond cleavage has been achieved by an initial oxidative addition with OH cleavage followed by isomerisation.

ChemInform Abstract: New Oximation Method for Aldehydes and Ketones.

AbstractThe trans‐oximation of oxo‐compounds such as (I) by acetone oxime (II) produces oximes (III) in high yields provided acetone (IV) is distilled off and the oxo group is not overcrowded by substituents R1,R2.

Sex and organ differences in oxidative DNA and RNA damage due to treatment of Sprague-Dawley rats with acetoxime or 2-nitropropane

The hepatocarcinogens 2-nitropropane and acetoxime have previously been found to induce a specific and qualitatively identical pattern of base damage in rat liver DNA and RNA, including the induction of increased levels of 8-hydroxyguanine. Because both 2-nitropropane and acetoxime are weaker carcinogens in female rats than male rats, we examined the ability of these chemicals to induce this pattern of damage in liver and kidney nucleic acids of male and female Sprague-Dawley rats 6 and 18 h after administration. Significantly lower levels of 8-hydroxydeoxyguanosine, 8-hydroxyguanosine and other presumed modified nucleosides discernible by high-performance liquid chromatography with electrochemical detection were found in liver nucleic acids of female rats at both time points. In addition, minimal alteration of nucleic acids was observed in the kidney, which is not a target organ for the carcinogenicity of either 2-nitropropane (2-NP) or acetoxime (ACO). These results support the hypothesis that the specific DNA alterations observed are relevant to the hepatocarcinogenicity of 2-NP and ACO.

Oxidative DNA and RNA damage in rat liver due to acetoxime: similarity to effects of 2-nitropropane

Acetoxime (ACO) and 2-nitropropane (2-NP), both industrially important chemicals and known hepatocarcinogens in rats, induced increased levels of 8-hydroxy-guanine in liver DNA and RNA of male Sprague-Dawley and F344 rats after either oral or i.p. administration. Both compounds also produced qualitatively the same patterns of other apparent modifications of liver DNA and RNA nucleosides, discernible by HPLC with electrochemical detection. Six hours after administration, the effects of 2-NP on liver nucleic acids were more pronounced in F344 rats than in Sprague-Dawley rats, suggesting that 2-NP may prove to be a stronger carcinogen in the F344 strain. The effects of ACO, a weaker carcinogen than 2-NP, were less than those of the nitroalkane in both rat strains. These results suggest that the hepatocarcinogenicity of ACO, like that of 2-NP, may depend on increased generation of reactive oxygen species capable of producing DNA and RNA base damage in rat liver. In addition, the data support the hypothesis that the hepatocarcinogenicity of ACO depends on its partial in vivo N-oxidation to 2-NP.

ChemInform Abstract: Claisen Rearrangement of O‐Perfluoroalkenyloximes.

AbstractDehydrofluorination of O‐fluoroalkenyloxime (III), obtained from acetone oxime (II) and perfluoroisobutene (I), gives the pyrrolinone (IV).

Effect of Copper (I) Iodide and Magnesium Chloride on Amination of Aryl Grignards with Ketoximes

Abstract Acetone oxime O-mesitylenesulphonate is shown to be a convenient reagent for amination of aryl Grignard reagents in ether-toluene in the presence of a catalytic amount of copper (I) iodide or magnesium chloride.

Gas phase chemistry of nitrogen containing negative ions: deprotonated nitromethane, acetone oxime, and acetone oxime o-methyl ether

The ion [CH 2NO 2] − is a weak base, a poor nucleophile and a weak oxidising agent. It is unable to oxidise COS but does react with CS 2 by the reaction [CH 2NO 2] − + CS 2 → CS 2O −· + [CH 2NO] ·. Deprotonated acetone oxime [Me 2CNO] − is a moderate gas phase oxidising agent reacting with COS, CS 2 and SO 2 to yield CO 2S −·, CS 2O −· and SO −· 3 respectively. Δ H ∘ acid of (CH 3) 2CNOMe is bracketted at 1560±15 kJ mol −1; the deprotonated species forms addition complexes with CO 2, CS 2, COS and SO 2.

Reversal of EPTC inhibition of aryl acylamidase activity by oximes

Aryl acylamidase (aryl-acylamine amidohydrolase, E.C.3.5.1.13) isolated from lettuce ( Lactuca sativa L.) leaf and stem tissue was assayed using propanil [ N-(3,4-dichlorophenyl)propanamide] as substrate. EPTC ( S-ethyl dipropyl carbamothioate) inhibited aryl acylamidase activity 20 to 65% at concentrations of 10 −4 to 10 −3 M. Kinetic studies indicated a K i of about 4.0 μ M for EPTC. When supplied simultaneously with and at concentrations equal to EPTC, acetone oxime, pyridine-2-aldoxime methiodide, and dimethylglyoxime each reduced the EPTC inhibition of aryl acylamidase activity by about 50%. These oximes alone had little or no effect on aryl acylamidase activity, but another oxime, benzoin-α-oxime, was inhibitory. These results indicate that molecular substituents near the oxime group can alter oxime function related to this class of herbicide safeners.

ChemInform Abstract: Reaction of Acetone Oxime (II) with Dialkylmalonyl Chlorides (I). Synthesis of 2‐(2‐Propenyl)isoxazolidine‐3,5‐diones (III) and 2,2‐Bis(2‐(4,4‐dialkylisoxazolidine‐3,5‐dione))propanes (IV).

ChemInformVolume 19, Issue 29 Heterocyclic Compounds ChemInform Abstract: Reaction of Acetone Oxime (II) with Dialkylmalonyl Chlorides (I). Synthesis of 2-(2-Propenyl)isoxazolidine-3,5-diones (III) and 2,2-Bis(2-(4,4-dialkylisoxazolidine-3,5-dione))propanes (IV). R. A. IZYDORE, R. A. IZYDORE Dep. Chem., North Carolina Central Univ., Durham, NC 27707, USASearch for more papers by this authorR. G. DAVIS, R. G. DAVIS Dep. Chem., North Carolina Central Univ., Durham, NC 27707, USASearch for more papers by this authorN. W. CLEMENTS, N. W. CLEMENTS Dep. Chem., North Carolina Central Univ., Durham, NC 27707, USASearch for more papers by this author R. A. IZYDORE, R. A. IZYDORE Dep. Chem., North Carolina Central Univ., Durham, NC 27707, USASearch for more papers by this authorR. G. DAVIS, R. G. DAVIS Dep. Chem., North Carolina Central Univ., Durham, NC 27707, USASearch for more papers by this authorN. W. CLEMENTS, N. W. CLEMENTS Dep. Chem., North Carolina Central Univ., Durham, NC 27707, USASearch for more papers by this author First published: July 19, 1988 https://doi.org/10.1002/chin.198829170AboutPDF ToolsRequest permissionExport citationAdd to favoritesTrack citation ShareShare Give accessShare full text accessShare full-text accessPlease review our Terms and Conditions of Use and check box below to share full-text version of article.I have read and accept the Wiley Online Library Terms and Conditions of UseShareable LinkUse the link below to share a full-text version of this article with your friends and colleagues. Learn more.Copy URL Share a linkShare onFacebookTwitterLinkedInRedditWechat No abstract is available for this article. Volume19, Issue29July 19, 1988 RelatedInformation

Inhibition of copper-containing amine oxidase by oximes.

The inhibitory effects of twelve oxime compounds on the activity of bovine serum monoamine oxidase (copper-containing amine oxidase, E.C. 1.4.3.6) were assayed in vitro. The most potent inhibitor among the compounds examined was 2-butanone oxime, of which the 50% inhibiting concentration in the reaction mixture was 7×10-6 M. Acetone oxime, acetoaldehyde oxime, salicylaldehyde oxime and formamide oxime were less potent inhibitors, while 2, 3-butanedione monooxime, 2, 3-butanedione dioxime, D-camphor oxime, α-furil dioxime, pyridine-2-aldehyde oxime, pyridine-4-aldehyde oxime, syn-2-pyridialdehyde oxime and di-2-pyridiketone oxime exhibited virtually no inhibitory effect on the enzyme activity. The type ofinhibition by 2-butanone oxime was non-competitive, and the inhibitor constant and Km value with respect to allylamine as the substrate were estimated graphically to be 6.7×10-6 and 3.9×10-4 M, respectively.

Reaction of acetone oxime with dialkylmalonyl chlorides. Synthesis of 2‐(2‐propenyl)isoxazolidine‐3,5‐diones and 2,2‐bis‐(2‐(4,4‐dialkylisoxazolidine‐3,5‐dione))propanes

AbstractReaction of acetone oxime with dialkylmalonyl chlorides in the presence of triethylamine gave as products 2‐(2‐propenyl)‐4,4‐dialkylisoxazolidine‐3,5‐diones 4 and 2,2‐bis‐(2‐(4,4‐dialkylisoxazolidine‐3,5‐dione))propanes 5. The 4,4‐dialkylisoxazolidine‐3,5‐diones 6 and dimethylketoximyl 4,4‐dialkylmalonates 7 were formed as minor products. Compounds 4 are stable in refluxing ethanol and in aqueous solution. Compounds 5 are stable when heated in refluxing toluene in the presence of either pyridine or monochloroacetic acid.

Derivatization procedure for gas chromatographic determination of hydroxylamine

Hydroxylamine has been of special interest recently because of the possibilities of manufacturing it by using electrochemical methods in which ammonia might also be formed. Its general chemistry and applications have been described elsewhere. Presently, there are two gas chromatographic methods reported for the determination of hydroxylamine in aqueous media. The first involves reacting the hydroxylamine to form acetone oxime and subsequently injecting the aqueous solution directly into a gas chromatograph equipped with nitrogen and flame ionization detectors. The second involves oxidizing hydroxylamine to nitrous oxide and trapping the gas for determination in an electron capture equipped gas chromatograph. Limits of detection are in the micromolar range for the former and the nanomolar range for the latter. Here, an alternate gas chromatographic procedure for determining hydroxylamine as the acetone oxime is described. Neither direct aqueous injection nor elaborate instrumentation is required. Extraction of the oxime into an ether phase allows for concentrating the analyte ad facilitates the use of an internal standard. The limitations and inconveniences of direct aqueous injection are avoided included column degradation and filament burnout in mass spectrometry detectors.

Substrate diversity of an active heterotrophic nitrifier, an Alcaligenes sp.

Several oximes, acetohydroxamic acid, and 3-nitropropionic acid were examined to determine if they could serve as substrates for heterotrophic nitrification by an Alcaligenes sp., previously isolated from soil and shown to actively nitrify pyruvic oxime. Neither acetohydroxamic acid, the aldoximes of acetaldehyde or butyraldehyde, or the alkyl oxime, acetone oxime, were used as nitrification substrates or as sole sources of carbon or nitrogen. α-Ketobutyric oxime, α-ketoglutaric oxime, and 3-nitropropionic acid, however, were nitrified and growth occurred when these compounds served as sole sources of carbon and nitrogen. Experiments with resting cells and cell-free extracts of the Alcaligenes sp. grown on α-ketobutyric oxime and α-ketoglutaric oxime indicate that these substrates are nitrified via an organic pathway as the rates of hydroxylamine (the nitrogen hydrolysis product) conversion are kinetically insufficient. 3-Nitropropionic acid metabolism by resting cells of the Alcaligenes sp. grown in 3-nitropropionic medium is restricted to nitrite production. The substrate specificities of the Alcaligenes sp. for heterotrophic nitrification and the relevance of the mineralization of 3-nitropropionic acid by the bacterium are discussed.

Aromatic nucleophilic substitution on Cr(CO)3-complexed halogenoarenes: a new synthesis of O-aryloximes and their cyclization to benzofurans

O-Aryloximes are synthesized by reaction of acetone oxime with Cr(CO)3-complexed halogenoarenes and then cyclized to give benzofurans.

Solution NMR study of the post‐polymerization crosslinking agent N,N′‐(2‐propyloximino)‐4,4′‐methylenebis(phenylcarbamate). I

AbstractBecause of its possible use as a blocked “post‐polymerization crosslinking agent” for polymers containing labile hydrogen, the structure of the acetone oxime adduct of 4,4′‐methylenebis‐(phenylisocyanate) has been determined. 13C and 1H nuclear magnetic resonance (NMR) spectroscopy has identified this product to be N,N′‐(2‐propyloximino)‐4,4′‐methylenebis(phenylcarbamate). Chemical shift assignments were based on information obtained by proton decoupled, off‐resonance decoupled, and gated decoupled 13C‐NMR, proton‐NMR, and semiemperical substituent chemical shift (SCS) parameters.