Acetone Oxime Research Articles

Synthesis, characterization, DFT and molecular docking studies of acetone O-((2,5-dichlorophenyl)sulfonyl) oxime

Abstract Acetone O-((2,5-dichlorophenyl)sulfonyl) oxime was prepared from 2,5-dichlorophenylsulfonyl chloride and acetone oxime using triethylamine. The compound was characterized using 1H NMR and 13C NMR spectra. Molecular docking was performed with the compound and cholinesterase enzymes. The average affinity of the compound with the acetylcholinesterase and butyrylcholinesterase was calculated at −7.46 ± 0.14 and −6.70 ± 0.00 kcal/mol, respectively. The density functional theory method was also used to complement the experimental study. The findings of this work might be useful towards the applications of the compound studied.

Hydrophobic polyurethane powder clear coatings with lower curing temperature: Study on the synthesis of new blocked polyisocyanates

The method of the synthesis of blocked polyisocyanates (bPIC) used as a crosslinking agent for hydrophobic and low temperature curing powder coatings was developed. In the synthesis of polyisocyanates (PIC) isophorone diisocyanate, glycerine, xylitol, polyethylene glycol and polysiloxane KF-6000 as well as two different blocking agents, i.e. acetone oxime and butanone oxime were used. The chemical structure of the obtained blocked polyisocyanates was confirmed by IR and NMR spectroscopy and the molecular mass distribution was investigated using gel permeation chromatography (GPC). The thermal behavior and the deblocking process were investigated by means of TG, DSC and DMA. The obtained coatings were evaluated by performing the following tests: roughness, gloss, scratch resistance, hardness, adhesion to the steel and water contact angle. As part of this research, the hydrophobic and high scratch resistance coatings cured at 150 °C were developed.

Theoretical assessment of ketone ammoximation production using thermodynamic, techno-economic, and life cycle environmental analyses

An assessment method that combines thermodynamic, techno-economic, and life cycle environmental analyses was applied to estimate the theoretical production of ketone ammoximation. Based on the reaction kinetics of ketone ammoximation, the effects of operating conditions on the conversion and selectivity were explored. The maximum acetone conversion and acetone oxime selectivity were 95% and 98%, respectively. The total annual cost was 1.29 × 107 $/year. The exergy efficiency was found to be more than 19.9%. The product-refining unit was considered as the unit with the largest exergy loss contribution, and the exergy loss rate was 68.5%. The thermodynamic analysis of the acetone oxime production process showed that its exergy loss could be reduced. The environmental performance of the acetone ammoximation process was determined by life cycle analysis. The results of environmental indicators showed that the GWP, AP, and ODP of the ketone ammoximation are 84815.4 kg·eq. CO2, 91.58 kg·eq. SO2, and 1.6 × 10−10 kg·eq. R11, respectively. This combination of life cycle environment, thermodynamic and techno-economic evaluation provides a basis for the improvement and sustainable development of the production process of ketoxime.

Determination of hydroxylamine genotoxic impurity by derivatization in penicillamine drug substance by GCHS-MS

The aim of the present research is to develop and validate highly sensitive and selective method for the quantitate determination of hydroxylamine by derivatization with acetone in presence of pyridine as a base in penicillamine drug substance by using hyphenated technique. Hydroxylamine was determined by GCHS-MS method using Gs BP-624, 30 mts × 0.32 mm × 1.8 µm column. Temperature program was set by maintaining 60 °C for 3 min, and then increased by 40 °C per minute to 200 °C and hold for 11.5 min. Methanol and acetonitrile was used as diluents. Injector temperature was 250 °C. Split ratio is 1:5. Head space oven, sample line and transfer line temperatures are 100 °C, 150 °C and 170 °C respectively. Validation of the method was performed as per standard guideline “International Conference on Harmonization” (ICH) guideline Q2(R1). This developed GCHS-MS method is able to quantitate 0.1 ppm of hydroxylamine. Under these GCHS-MS conditions hydroxylamine was quantified by selective reaction monitoring m/z of 73 as its acetone oxime derivative at ppm level. The developed GCHS-MS method was validated and resulting to show the developed method is specific, sensitive, linear, accurate and precise. Hence the GCHS-MS method is well suited for the quantification of hydroxylamine genotoxic impurity as its acetone oxime derivative in penicillamine drug substance.

Formation of Benzodiazepines and Pyrazinylquinoxalines from Aromatic and Heteroaromatic Ketones via Deoximation

The report stated that the treatment of o-phenylenediamine with acetone dicarboxylic acid, acetone and acetophenone afforded 2,4,4-trimethyl-3H-5-hydro-1,5-benzodiazepine. However, direct reactions of o-phenylenediamine with oximes (acetone oxime, acetophenone oxime, and benzophenone oxime) as ketone equivalents did not occur. In the course of present investigations, it is found that dichloroamine-T can be an efficient reagent for the conversion of oximes into the corresponding carbonyl compounds. As a part of a research program related to the synthetic study of pharmacologically interesting benzodiazepine compounds, herein the synthesis of 1H-1,5-benzodiazepine derivatives from heteroaromatic ketones and acetone equivalents obtained using dichloroamine-T. On the other hand, when diamine (1,2-phenylene diamine or 1,2-naphthalene diamine) with heterocyclic ketone (acetyl pyridine or acetyl pyrazines) in the presenece of conc. HCl and SiO2 was refluxed, quinoxaline derivatives as yellow crystalline solids were isolated in high yields

Rhodium-Catalyzed ortho-Alkenylation of Phenols Directed by Acetone Oxime Ether

Rhodium-Catalyzed <i>ortho</i>-Alkenylation of Phenols Directed by Acetone Oxime Ether

Benzyl C–O and C–N Bond Construction via C–C Bond Dissociation of Oxime Ester under Visible Light Irradiation

A photoredox benzyl activation was developed via formidable C(sp3)–C(sp3) bond dissociation of 1‐aryl acetone oxime esters, which were easily prepared from benzyl ketones. Further coupling with O‐ and N‐ nucleophiles successfully forged important benzyl ether and amines derivatives in one pot. In this process, different substitutions on oxime esters were found compatible and various primary and secondary alcohols and amines, as well as amides showed good performance as nucleophiles. Mechanistic studies by control experiments, electrochemical measurements and in‐situ NMR spectra proposed a N–O bond interruption/C–C bond fragmentation/oxidation sequence to provide the key cation intermediate for the next electrophilic SN process. The features of mild condition, short reaction time and broad substrate scope made this new strategy much promising in the transformation of benzyl compounds, which might be valuable in last‐stage functionalizations.

Formation and transformation of nitroso compounds of ketoxime isomers in ketone ammoximation catalyzed by hollow titanium silicalite

2-Nitrosopropane as the isomer of acetoxime was first found in ammoxidation of acetone with hydrogen peroxide catalyzed by hollow titanium silicalite (HTS). Experimental investigation indicates that the formation of 2-nitrosopropane was closely related to the pore size and surface acidity of HTS zeolite and significantly affected by reaction conditions, and further revealed that once formed, this isomer could be easily converted into main product acetoxime and also turned into by-product 2-nitropropane in the presence of excess hydrogen peroxide or O2. Based on the experimental results in combination with the analysis of reaction mechanism, it was suggested that the pathways of acetone ammoxidation catalyzed by HTS could involve both hydroxylamino intermediate and imino intermediate. The former was dominant in the production of acetone oxime, while the latter was mainly responsible for the formation of 2-nitropropane. In the latter case, an acetone first reacted with ammonia to form an imine and then interacted with an active center of Ti-OOH on catalyst to generate an unstable 2-nitrosopropane.

Selective C(sp3)−H and C(sp2)−H Fluorination of Alcohols Using Practical Auxiliaries

AbstractSelective introduction of fluorine into molecules by the cleavage of inert C−H bonds is of central academic and synthetic interest, yet remains challenging. Given the central role of alcohols in organic chemistry as the most ubiquitous building blocks, a versatile and selective C(sp3)−H and C(sp2)−H fluorination of simple alcohols, enabled by novel designed exo‐directing groups, is described. C(sp2)−H bond fluorination was achieved by using a simple acetone oxime as auxiliary, whereas a new, modular and easily accessible bidentate auxiliary was developed for the efficient and site‐selective fluorination of various primary methyl, methylene, and benzylic C(sp3)−H bonds. Fluorinated alcohols can readily be accessed by the removal of auxiliaries, and significantly expands the synthetic prospect of the present procedure.

Selective C(sp3)−H and C(sp2)−H Fluorination of Alcohols Using Practical Auxiliaries

Selective introduction of fluorine into molecules by the cleavage of inert C-H bonds is of central academic and synthetic interest, yet remains challenging. Given the central role of alcohols in organic chemistry as the most ubiquitous building blocks, a versatile and selective C(sp3 )-H and C(sp2 )-H fluorination of simple alcohols, enabled by novel designed exo-directing groups, is described. C(sp2 )-H bond fluorination was achieved by using a simple acetone oxime as auxiliary, whereas a new, modular and easily accessible bidentate auxiliary was developed for the efficient and site-selective fluorination of various primary methyl, methylene, and benzylic C(sp3 )-H bonds. Fluorinated alcohols can readily be accessed by the removal of auxiliaries, and significantly expands the synthetic prospect of the present procedure.

Nitrate formation during ozonation as a surrogate parameter for abatement of micropollutants and the N-nitrosodimethylamine (NDMA) formation potential

In this study, nitrate formation from ammonium and/or dissolved organic nitrogen (DON) was investigated as a novel surrogate parameter to evaluate the abatement of micropollutants during ozonation of synthetic waters containing natural organic matter (NOM) isolates, a natural water and secondary wastewater effluents. Nitrate formation during ozonation was compared to the changes in UV absorbance at 254 nm (UVA254) including the effect of pH. For low specific ozone doses UVA254 was abated more efficiently than nitrate was formed. This is due to a relatively slow rate-limiting step for nitrate formation from the reaction between ozone and a proposed nitrogen-containing intermediate. This reaction cannot compete with the fast reactions between ozone and UV-absorbing moieties (e.g., activated aromatic compounds). To further test the kinetics of nitrate formation, two possible intermediates formed during ozonation of DON were tested. At pH 7, nitrate was formed during ozonation of acetone oxime and methyl nitroacetate with second-order rate constants of 256.7 ± 4.7 M−1 s−1 and 149.5 ± 5.8 M−1 s−1, respectively. The abatement of the selected micropollutants (i.e., 17α-ethinylestradiol (EE2), carbamazepine (CBZ), bezafibrate (BZF), ibuprofen (IBU), and p-chlorobenzoic acid (pCBA)) was investigated for specific ozone doses ≤1.53 mgO3/mgDOC and its efficiency depended strongly on the reactivity of the selected compounds with ozone. The relative abatement of micropollutants (i.e., EE2 and CBZ) with high ozone reactivity showed linear relationships with nitrate formation. The abatement of micropollutants with intermediate-low ozone reactivity (BZF, IBU, and pCBA) followed one- and two-phase behaviors relative to nitrate formation during ozonation of water samples containing high and low concentrations of nitrate-forming DON, respectively. During ozonation of a wastewater sample, the N-nitrosodimethylamine formation potential (NDMA-FP) during chloramination decreased with increasing specific ozone doses. A good correlation was obtained between NDMA-FP abatement and nitrate formation. Therefore, nitrate formation after pre-ozonation may be a useful parameter to estimate the reduction of the NDMA-FP during post-chloramination. Overall, the results of this study suggest that nitrate formation (possibly in combination with UVA254 abatement) during ozonation of DON-containing waters may be a good surrogate for assessing the abatement of micropollutants and the NDMA-FP.

ChemInform Abstract: Direct ortho‐C—H Functionalization of Aromatic Alcohols Masked by Acetone Oxime Ether via exo‐Palladacycle.

AbstractAn oxime ether directing group for the Pd‐catalyzed selective ortho‐olefination of aromatic alcohols is developed.

Fast and low-temperature sintering of silver complex using oximes as a potential reducing agent for solution-processible, highly conductive electrodes

Highly conductive, solution-processed silver thin-films were obtained at a low sintering temperature of 100 °C in a short sintering time of 10 min by introducing oximes as a potential reductant for silver complex. The thermal properties and reducibility of three kinds of oximes, acetone oxime, 2-butanone oxime, and one dimethylglyoxime, were investigated as a reducing agent, and we found that the thermal decomposition product of oximes (ketones) accelerated the conversion of silver complex into highly conductive silver at low sintering temperature in a short time. Using the acetone oxime, the silver thin-film exhibited the lowest surface resistance (0.91 Ω sq−1) compared to those sing other oximes. The silver thin-film also showed a high reflectance of 97.8%, which is comparable to evaporated silver films. We also demonstrated inkjet printed silver patterns with the oxime-added silver complex inks.

Synthesis of 3,5-isoxazolidinediones and 1H-2,3-benzoxazine-1,4(3H)-diones from aliphatic oximes and dicarboxylic acid chlorides.

The synthesis of the title compounds was carried out by reacting dicarboxylic acid chlorides with oximes in the presence of excess triethylamine. Disubstituted malonyl chlorides gave 2-alkenyl-4,4-dialkyl-3,5-isoxazolidinediones (8a–f) and 2,2′-ethylidene-bis[4,4-dialkyl-3,5-isoxazolidinedione]s (9a–f). Compounds 9 were formed from 8 and its N-unsubstituted 3,5-isoxazolidinedione decomposition product. Phthaloyl chlorides reacted with acetone oxime to yield 3-(1-methylethenyl)-1H-2,3-benzoxazine-1,4(3H)-diones (16a–e). Products 16 spontaneously decomposed to give N-unsubstituted 1H-2,3-benzoxazine-1,4(3H)-diones (17a–e) at rates that were dependent on temperature and solvent. Kinetic studies showed that two of the compounds decomposed by zero-order kinetics under neutral conditions. Butanedioyl chloride did not produce a cyclic product.

Reaction Mechanism of an Intramolecular Oxime Transfer Reaction: A Computational Study

Density functional theory (PBE0/def2-TZVPP) calculations in conjunction with a polarizable continuum model were used to assess the mechanism of the intramolecular oxime transfer reaction that leads to the formation of isoxazolines. Different diastereomers of the intermediates as well as different oximes (formaldehyde and acetone oxime) were considered. The computed reaction profile predicts the water-addition and -expulsion steps as the highest barriers along the pathway, a conclusion that is in line with the experimental evidence obtained previously for these reactions.

Experimental and theoretical study on corrosion inhibition of oxime compounds for aluminium in HCl solution

The inhibition effect of three oxime compounds of acetone oxime (AO), 2-butanone oxime (BO) and cyclohexanone oxime (CO) on the corrosion of aluminium in HCl solution was studied by weight loss, potentiodynamic polarization curves, electrochemical impedance spectroscopy (EIS), quantum chemical calculation and molecular dynamics (MD) simulation methods. The results show that all oxime compounds are good inhibitors, and inhibition efficiency follows the order: CO>BO>AO. The adsorption of each inhibitor on aluminium surface obeys Langmuir adsorption isotherm. All these oxime compounds act as cathodic inhibitors. The probable inhibitive mechanism is proposed from the viewpoint of adsorption theory.

Liquid–Liquid Equilibrium for the Ternary System Acetone Oxime Methyl Ether–Acetone–Water

In the production of acetone oxime methyl ether (AOME) and its related products, AOME usually needs to be separated from the AOME, acetone, and water mixture. As the base data, the liquid–liquid equilibrium data for the AOME–acetone–water ternary system were measured at 293.15 K, 303.15 K, 313.15 K, and 323.15 K, respectively, under atmospheric pressure. Then, the nonrandom two-liquid (NRTL) and T-K-Wilson models were used to correlate the experimental data. The root-mean-square deviation (RMSD) between the calculated values and the experimental data is less than 0.0054 for the NRTL equation, and the RMSD is up to 0.046 for T-K-Wilson equation. Therefore, for this ternary system, the NRTL equation is more suitable than the T-K-Wilson equation for predicting liquid activity coefficients of the system. At the same time, the experimental data also show that the temperature has little effect on the miscibility gap within the experimental temperature range.

Isobaric vapor–liquid equilibria of the binary system acetone + acetone oxime methyl ether at 101.3 kPa

Isobaric vapor–liquid equilibria (VLE) were measured for the binary system acetone+acetone oxime methyl ether (AOME) at 101.3kPa. The activity coefficients were correlated satisfactorily with NRTL and Wilson models. The thermodynamic consistency of the obtained VLE data was checked by Herington method and passed the test. The results show that the correlated data of NRTL and Wilson models are both in keep with the experimental data, and the UNIFAC parameters of the new group (CN) were determined using the obtained VLE data. The azeotrope behavior is not happen for the binary system of acetone+AOME, which can provide the basis data to design the separation process, and promote the development of new technology to produce O-methylhydroxyamine hydrochloride effectively and economically.

H/D Isotopic and Temperature Effects in the Polarized IR Spectra of Hydrogen-Bond Cyclic Trimers in the Crystal Lattices of Acetone Oxime and 3,5-Dimethylpyrazole

Polarized IR spectra of hydrogen-bonded acetone oxime and 3,5-dimethylpyrazole crystals were measured at 293 and 77 K in the ν(X-H) and ν(X-D) band frequency ranges. These crystals contain molecular trimers in their lattices. The individual crystal spectral properties remain in a close relation with the electronic structure of the two different molecular systems. We show that a vibronic coupling mechanism involving the hydrogen-bond protons and the electrons on the π-electronic systems in the molecules determines the way in which the vibrational exciton coupling between the hydrogen bonds in the trimers occurs. A strong coupling in 3,5-dimethylpyrazole trimers prefers a "tail-to-head"-type Davydov coupling widespread via the π-electrons. A weak through-space exciton coupling in acetone oxime trimers involves three adjacent hydrogen bonds in each cycle. The relative contribution of each exciton coupling mechanism in the trimer spectra generation is temperature and the molecular electronic structure-dependent. This explains the observed difference in the temperature-induced evolution of the compared spectra. The mechanism of the H/D isotopic "self-organization" processes in the crystal hydrogen bonds was also analyzed. The two types of the hydrogen-bond trimers exhibit the same way, in which the H/D isotopic recognition mechanism occurs. In acetone oxime and 3,5-dimethylpyrazole trimers, identical hydrogen isotope atoms exist in these entire hydrogen-bond systems.

PtII-Mediated Imine–Nitrile Coupling Leading to Symmetrical (1,3,5,7,9-Pentaazanona-1,3,6,8-tetraenato)Pt(II) Complexes Containing the Incorporated 1,3-Diiminoisoindoline Moiety

Treatment of trans-[PtCl(2)(NCR)(2)] (1; R = Et (1a), Ph (1b)) with 1,3-diiminoisoindoline (2) gives access to the corresponding symmetrical (1,3,5,7,9-pentaazanona-1,3,6,8-tetraenato)Pt(II) complexes [PtCl{NH═C(R)N═C(C(6)H(4))NC═NC(R)═NH}] (3). The reactions of 1 with one equivalent of 1,1,3,3-tetramethylguanidine (4), 1,3-diphenylguanidine (6), or acetone oxime (8) leads to the formation of mixed asymmetrical Pt(II) complexes trans-[PtCl(2){NH═C(R)N═C(NMe(2))(2)}(NCR)] (5), [PtCl{NH═C(R)NC(NHPh)═NPh}(NCR)] (7), or trans-[PtCl(2){NH═C(Ph)ON═CMe(2)}(NCPh)] (9), respectively, as a result of nucleophilic addition to one of the nitrile ligands in 1. Treatment of 5, 7, and 9 with one equivalent of 2 leads to complexes 3. The complexes were characterized by IR, (1)H, (13)C{(1)H}, and (195)Pt NMR (for 3) spectroscopies, ESI(+)-MS, elemental analyses, and X-ray diffraction (for 3). Complex 3a has an asymmetric unit with five independent Pt molecules of the same chemical composition and two molecules of water, resulting in a total of 40 molecules of the complex and sixteen guest water molecules per unit cell. Theoretical calculations revealed that the most plausible mechanism of formation of complexes 3 includes stepwise nucleophilic addition of 2 to one of the nitrile ligands in 1, a first cyclization upon formation of the Pt-N bond and elimination of HCl, and a second nucleophilic addition/cyclization.