Acetophenone Research Articles

Study of the biochemical formation pathway of aroma compound 1-phenylethanol in tea (Camellia sinensis (L.) O. Kuntze) flowers and other plants

After tea leaves, tea (Camellia sinensis) flowers are becoming a second tea plant resource because they contain not only functional metabolites similar to those found in tea leaves, but also predominant amounts of functional metabolites that only occur in tea leaves in small amounts. 1-Phenylethanol (1PE) is a predominant aroma compound found in tea flowers. A 1PE synthase in tea flowers was isolated, functionally characterized, and shown to have the highest catalytic efficiency for the conversion of acetophenone (AP). To determine why 1PE accumulates more in tea flowers than other plants, we compared their 1PE contents and used a stable isotope labeling method to elucidate the 1PE biosynthetic route. Supplementation with [2H8]l-phenylalanine and [2H5]AP suggested that most plants containing the enzyme/gene catalyzed the conversion of AP to 1PE. Furthermore, the availability of AP derived from l-phenylalanine was responsible for the difference in 1PE accumulation between tea flowers and other plants.

Synthesis and photoluminescent properties of orange light emitting Sm(III) complex with 2-hydroxy-4-methoxy-2-(4-chlorophenyl)acetophenone and 2,2?-bipyridine

Synthesis and photoluminescent properties of orange light emitting Sm(III) complex with 2-hydroxy-4-methoxy-2-(4-chlorophenyl)acetophenone and 2,2?-bipyridine

Rapid and selective recovery of acetophenone from petrochemical effluents by crosslinked starch polymer

A porous crosslinked starch polymer (CSTO) using bitolylene diisocyanate as crosslinker was prepared by a facile method and used to selectively recover acetophenone (AP) from petrochemical effluent mainly containing AP and 1-phenylethanol (PE). The theoretical calculation results indicated that AP exhibited the superior affinity toward the adsorption sites of CSTO through noncovalent interactions. The adsorption measurements showed that, due to the large surface area and high affinity of phenyl rings, CSTO displayed an extremely rapid adsorption rate, a desirable adsorption capacity and selectivity to AP. The adsorption kinetics and isotherms in single solute system agreed well with the pseudo-second-order kinetic model and Freundlich isotherm model, and the adsorption was exothermic and spontaneous. Furthermore, CSTO showed excellent reusability for selective adsorption of AP from equimolar mixture of AP/PE, prompting us to further examine its applicability. In the practical application, CSTO also revealed a fast, preferential and reusable adsorption of AP from actual petrochemical effluent.

A New Highly Selective Neodymium(III) Polyvinylchloride Membrane Electrode Based on 4-Hydroxypyrrolidine-2-Carboxylic Acid as an Active Material

The present paper describes the fabrication of a new polyvinylchloride (PVC) membrane electrode for the determination of Nd(III) ion based on 4-hydroxypyrrolidine-2-carboxylic acid (LHP) as an active material along with sodium tetraphenyl borate (NaTPB) as an anionic additive and acetophenone (AP) as solvent mediator. The optimum composition (%, w/w) of the best performing membrane contained 66 AP, 30 PVC, 2 NaTPB and 3 LHP. The basic analytical parameters of this electrode such as slope characteristics, detection limit, response time, selectivity and pH effect were assessed. The electrode displayed a Nernstian response in terms of slope (20.5 ± 0.4 mV per decade) and response time (~8 ± 1 s) over a wide neodymium ion concentration range of 10–6 to 10–2 M with a detection limit of 7.5 × 10−7 M. The potentiometric response of the electrode was constant in the pH range of 3.2‒8.9. According to the selectivity coefficients determined by the matched potential method, the interference of many common alkaline, alkaline earth, transition, heavy metals and specially lanthanide ions in determination of Nd(III) ion was very low. The proposed electrode has been successfully used as an indicator electrode in the potentiometric titration of Nd(III) ion with EDTA and applied for determination of Nd(III) ion in mixtures of different ions.

Theoretical investigation on the oxidation mechanism of dibutyl phthalate by hydroxyl and sulfate radicals in the gas and aqueous phase

A thorough thermodynamic analysis of different DBP conversion paths induced by hydroxyl (OH) and sulfate radicals (SO4−) is performed using Density Functional Theory (DFT) calculations in the gas and aqueous phases. We propose the thermodynamics favorable reaction chains for the major degradation products formation, and the involved reaction mechanisms include radical adduct formation (RAF), formal hydrogen atom transfer (FHAT), OH oxidative cleavage of CCdouble bond, and acid-catalyzed decomposition of C–C single bond. Theoretical results indicate that phthalic anhydride (PA) and acetophenone (ACP) are respectively the dominant and minor products in water, which is consistent with the experimental data. Computational results reveal that the reactivity of OH for the H-abstraction reaction is higher than that of SO4−. Interestingly, the unsaturated CC bonds cleavage reaction can directly occur with OH attack in aqueous solutions. However, it needs to overcome an extra radical adduct formation step when it is attacked by SO4−. The present work opens a new window to illustrate the reaction mechanism and reactivity of OH and SO4− toward different chemical structures of organics from the view of molecular level.

Reaction of N,N-disubstituted hydrazinecarbothioamides with 2-bromo-2-substituted acetophenones

Reaction of N,N-disubstituted hydrazinecarbothioamides with 2-bromo-2-substituted acetophenones

Volatile Compounds in the Leaf of Plane Tree (Platanus orientalis) with Solid Phase Microextraction (SPME) Technique

Plane tree belongs to Platanaceae family. There is a widespread belief that Platanus orientalis leaves (POLs) have beneficial effects on joint disorders. Therefore, many people consume POLs as tea. To our knowledge, as there is no study on volatile compounds (VCs) of POLs, we objected to determine the VCs in POLs obtained from Platanus orientalis trees grown in Hatay province, Turkey. The VCs were extracted using solid phase micro-extraction (SPME) and analyzed by gas chromatography-mass spectrometry (GC-MS). A total of 140 VCs were found in POLs. Aldehydes, alcohols, ketones, terpenes and alkenes were determined in POLs as major VCs groups, which accounted for 32.40 %, 23.51 %, 18.08 %, 10.24 % and 4.82 % of total VCs identified, respectively. Trans , trans -2,4-heptadienal (6.62 %), nonanal (6.46 %), benzaldehyde (6.42 %), cis -3-hexen-1-ol (6.32 %), benzenemethanol (6.13 %) were the most abundant VCs identified in POLs. Trans -2-hexenal (3.46 %), 3-phenyl-2-butanone (2.87 %), trans -3,5-dimethyl-1,6-octadiene (2.80 %), 6-methyl-5-hepten-2-one (2.56 %), octan-1-ol (2.43 %), trans -geranyl acetone (2.17 %), trans -4,8-dimethyl-1,3,7-nonatriene (1.98 %), phenyl methyl ketone (1.69 %), 6-methyl-3,5-heptadiene-2-one (1.57 %) were the second most plentiful compounds found in POLs. 11H-dibenzo[b,e][1,4]diazepin-11-one,5,10-dihydro-5-[3-(methylamino)propyl] (1.38 %), benzeneethanol (1.36 %) and β-ionone (1.02 %) were found as the third most abundant VCs. The above-mentioned VCs were accounted for about 57 % of total VCs identified in POLs. The remaining VCs were below 1.00 % that is, found at trace levels. According to the VCs profiles of POL, its beneficial effects on health may be due to aldehydes, alcohols, ketones and terpenes.

Synthesis of Novel 4-[1-(3-Chlorophenyl)-3-(pyren-1-yl)-1H-pyrazol-4-yl]-6-(substituted phenyl)-1,2-dihydro-2-oxo(imino)pyridine-3-carbonitriles

A novel compounds of 4,6-diaryl-2-oxo(imino)-1,2-dihydro-pyridine-3-carbonitriles has been synthesized by reaction of 1-(3-chlorophenyl)-3-(pyren-1-yl)-1H-pyrazole-4-carbaldehyde with different 1-(substituted phenyl)ethanones and ethyl cyanoacetate or malononitrile in presence of ammonium acetate. Structure of the newly synthesized compounds was elucidated from chemical and spectroscopic data.

Fabrication of highly efficient mesoporous NaBiO3/ZnO nanocomposites for recyclable photocatalytic degradation of organic pollutants

A novel nanocomposite photocatalyst NaBiO3/ZnO with three different molar ratios (0.5%, 1%, 1.5% of NaBiO3) were synthesized successfully by hydrothermal precipitation-deposition method and characterized by UV–vis diffuse reflectance spectroscopy (DRS), X-ray diffraction (XRD), scanning electron microscopy (SEM), energy dispersive spectroscopy (EDS), high resolution transmission electron microscopy (HR-TEM) with SAED pattern, Brunauer-Emmett-Teller surface analysis (BET) and photoluminescence spectroscopy (PL) techniques. The λmax of the prepared nanocomposite was highly red shifted from wavelength 390nm to 520nm compared to bare metal oxides. The degradation of organic pollutants such as Nitrobenzene (NB) and Acetophenone (AP) were studied by using the prepared nanocomposite. The nanocomposite with molar ratio of 1% NaBiO3/ZnO photocatalyst possess excellent photocatalytic activity than the nanocomposite with molar ratio 0.5% NaBiO3/ZnO, 1.5% NaBiO3/ZnO, and the individual components NaBiO3, ZnO. The band edges of materials have been theoretically calculated on the basis of Mulliken electronegativity of atoms. The effect of operational parameters such as pollutant concentration, pH, catalyst dosage, OH radical trapping and COD have been investigated in details. The kinetics of photodegradation reactions were correlated with the pseudo-first-order model. The stability of nanocomposite was examined by recycling experiments.

Computational study on acetophenone in amorphous polyethylene.

Polyethylene (PE) is widely used as an electrical insulating material. Acetophenone (AP) is a major residue in PE and is considered one of the causes of insulation deterioration. However, the physicochemical explanation of the influence of AP is still unknown. Therefore, in the present study, the behavior of AP molecules in amorphous PE was investigated using molecular dynamics (MD) simulations and quantum chemical calculation. First, the basic properties of the AP molecule were evaluated from the viewpoint of molecular electrostatic potential (MEP), molecular orbitals, and energy levels. Subsequently, an amorphous PE system containing AP molecules was studied using MD simulations. The results clearly indicate that AP does not greatly change the density and radius of gyration of amorphous PE. Quantum computations were performed using a part of the structure obtained from the MD simulations, suggesting that AP acts as a trap site in amorphous PE. It was also revealed that under the external electric field, the total density of state (DOS) changes with a dependence on the applied direction. Results of these calculations help in explaining previous experimental results.

Synthesis and characterization of cobalt-supported catalysts on modified magnetic nanoparticle: Green and highly efficient heterogeneous nanocatalyst for selective oxidation of ethylbenzene, cyclohexene and oximes with molecular oxygen

In this study, a new supported cobalt nanocatalyst has been described. The Fe3O4 magnetic nanoparticles (Fe3O4 MNPs) modified by SiO2/aminopropyl trimethoxy silane/cyanuric chloride (Fe3O4@SiO2-APTMS/CC) utilized for anchoring metformin-cobalt complex (Fe3O4 Ms@SiO2-APTMS/CC/Met@Co(II)). The structure of novel complex well defined by elemental analysis, ICP, AAS, BET, FT-IR, EDX, SEM, TEM, DLS, XRD, TG-DTG, VSM and XPS. The catalytic efficiency of the synthesized cobalt nanocatalyst was studied in the oxidation of ethylbenzene (EB), cyclohexene (CYHE) and various oximes using molecular oxygen as ecofriendly oxidant and high catalytic activity and selectivity toward oxidation is observed. Selective aerobic oxidation of EB and CYHE and various oximes catalyzed by the cobalt nanocatalyst without any reducing agent by using N-hydroxyphthalimide (NHPI), gave acetophenone (AcPO), 2-cyclohexene-1-one and corresponding carbonyl compounds respectively, as major products. To achieve high level of efficiency of heterogeneous nanocatalyst, various parameters such as the ratio and amount of nanocatalyst/NHPI, reaction time, temperature and solvents were evaluated. The easily preparation from inexpensive and commercially available reagent, thermal stability, suitable performance in reusability, high efficiency and selectivity in oxidation reactions, short reaction time, easy recovery and separation from reaction mixture, are advantages of this novel catalyst.

Dielectric study of H-bonded interactions in amyl alcohols with ketones and DMSO at T = 298.15 K

This paper reports the role of hydrogen bonding and other electrostatic interactions on the dielectric behaviour, excess parameters, and structure properties of the binary systems containing 1-pentanol isomers (H-bond donors) and dipolar aprotic liquids at T=298.15K. The dipolar aprotic liquids were four H-bond acceptor, i.e. dimethyl ketone (acetone), methyl ethyl ketone (2-butanone), methyl phenyl ketone (acetophenone), and dimethyl sulfoxide (DMSO). In order to make a coherent discussion, the dielectric data were analyzed with various approaches in terms of intermolecular interactions between like and unlike molecules. In order to obtain valuable information about hetero interaction and structure occurring in the studied systems, the effective and corrective Kirkwood correlation factors were calculated using Kumbharkhane et al. approach. The Winkelmann-Quitzsch theory was employed to obtain excess Helmholtz energies of dipole-dipole interactions. The Reis and Iglesias approach was applied to calculate excess Kirkwood correlation factors.

SOLVENT EXTRACTION OF IRON IONS FROM HYDROCHLORIC ACID SOLUTIONS

In this study Methyl Isobutyl Ketone (MIBK) and acetophenone (Methyl Phenyl Ketone) are presented as suitable agents for removal of Fe(III) from concentrated hydrochloric acid solutions. An extensive study applying 4 parameters was carried out: Time (5, 10,15,20,30 and 60 minutes), Stirring rate (200, 300, 400 and 500 r.p.m), Solvent to HCl Ratio (5%, 10%, 14% and 16%), and initial concentration of Fe ions in crude HCl (95.24, 126 ppm, 330 ppm and 1955 ppm).The best Condition was found to be 30 min – 400 r.p.m – 14 %. The distilled water was used to strip Fe ions out of MIBK; In order to get most of the MIBK dissolved in both the concentrated HCl and water. Diluents were used such as benzene, kerosene and xylene. Xylene gives better recovery of about 96%.

Biosorption and selective separation of acetophenone and 1-phenylethanol with polysaccharide-based polymers

A polysaccharide-based polymer (abbrev., SMP) was prepared via the crosslinking of starch with 4,4-methylene diphenyl diisocyanate and employed as an adsorbent for selective separation of acetophenone (AP) and 1-phenylethanol (PE) which coexist extensively in petrochemical by-products and effluents. The successful crosslinking was proved by FTIR and XPS, and the rough morphology as well as porous structure was also demonstrated in XRD, SEM and N2 adsorption-desorption analysis. Using SMP as adsorbent, the adsorption kinetics and isotherms were both investigated in single-component system. Both kinetic and thermodynamic parameters of the adsorption process were obtained. Further thermodynamic investigation indicated that the adsorption was exothermic and spontaneous. Compared to the starch-based polymers whose frameworks contain no phenyl ring, SMP exhibits both higher selectivity and capacity for AP in the competitive adsorption. Additionally, increasing the level of crosslinking in SMP favors its adsorption performance. Furthermore, continuous adsorption-desorption indicated high separation ability and regeneration efficiency of SMP. Finally, the mechanism studies suggested that the adsorption mechanisms may be physisorption involving noncovalent interactions, permitting preference to AP over PE.

Design, synthesis, antibacterial activity and docking study of some new trimethoprim derivatives

In present study, nineteen novel trimethoprim (TMP) derivatives were designed, synthesized and evaluated for their antibacterial potential. Hydroxy trimethoprim 2 (HTMP) was synthesized by following the demethylation of 4-methoxy group at trimethoxy benzyl ring of TMP. Structure–activity relationship (SAR) studies were explored on HTMP by incorporating various substituents leading to the identification of some new compounds with improved antibacterial activities. The results revealed that the introduction of benzyloxy (4a–e) and phenyl ethanone (5a–e) group at 4-position of dimethoxy benzyl ring leads to overall increase in the antibacterial activity. The most potent antibacterial compound discovered is benzyloxy derivative 4b with MIC value of 5.0μM against Staphylococcus aureus and 4.0μM against Escherichia coli strains higher than the standard TMP (22.7μM against S. aureus and 55.1μM against E. coli). Substitution at 4-NH2 group was not tolerated and the resulting Schiff base derivatives 3a–h demonstrated very little or no antibacterial activity in the tested concentration domain. We further performed exploratory docking studies on dihydrofolate reductase (DHFR) to rationalize the in vitro biological data and to demonstrate the mechanism of antibacterial activity. For the ability to cross lipophilic outer membrane, logP was computed. It was found that the compounds possessing high hydrophobicity have high activity against E. coli.

Prediction of Static Dielectric Constant (ε<sub>0</sub>) and Refractive Index (n) Using Various Models for Binary Mixtures (Acetophenone with N-Hexanol)

Static dielectric constant (ε0) and refractive index (n) have been experimentally determined for binary liquid mixture of n-Hexanol (HxOH) with Acetophenone (ACP) over the entire concentration range of mixture composition (0.0 →1.0) at constant temperature 303.15 K. Static dielectric constant (ε0) and refractive index (n) for the binary mixture have been measured using high precision LCR meter (0.2 MHz) and Abbe’s refractometer respectively. Excess of static dielectric constant (ε0)E and refractive index (n)E are determined and fitted with Redlich-Kister polynomial equation to derive the binary coefficients and standard deviations. Deviations of these parameters are discussed in terms of terms of molecular interaction between the constituent species. In the present work, comparative study of various mixing models for static dielectric constant (ε0) [Böttcher-Bordewijk (BOTT), Bruggeman (BRUG), Kraszewski (KRAZ), Looyenga (LOOY), Peon–Iglesias (P-I)] and for refractive index (n) [Oster (OST), Weiner (W), Eykman (EYK), Lorentz–Lorentz (L-L), Arago–Biot (A-G), Newton (Nw), Gladstone–Dale (G-D) and Erying–John (EJ)] have been carried out and their validity has been tested for the (n-HxOH+ACP) binary mixtures. The objective of the present work is to report the influence of nonassociative molecule on the molecular dynamics of associative molecules and validation mixing models.

Study of Molecular Interaction in Binary Mixtures (1-Propanol + Acetophenone)

Studies on Physico-chemical properties of binary liquid mixtures provide information on the nature of interactions between the constituent of the binaries. Literature provides extensive data on the static dielectric constant (ε0) and refractive index (n) of liquid compounds, but the combined study of all is quite scarce. In the present work static dielectric constant (ε0) and refractive index (n) have been experimentally determined for binary liquid mixture of 1-Propanol (PrOH) with Acetophenone (ACP) over the entire concentration range of mixture composition (0.0 →1.0) at constant temperature 303 K. Static dielectric constant (ε0) and refractive index (n) for the binary mixture have been measured using high precision LCR meter (0.2 MHz) and Abbe’s refractometer respectively. Excess of static dielectric constant (ε0)E and refractive index (n)E are determined and fitted with Redlich-Kister polynomial equation to derive the binary coefficients and standard deviations. For interaction and structural information various parameters namely, Kirkwood correlation factor (g), Kirkwood effective correlation factor (geff), Kirkwood angular correlation factor (gF) and Bruggeman parameter (fB) are determined for the binary mixtures. Variations of these parameters against the concentration of constituents are discussed in terms of molecular interaction between the constituent species.

ChemInform Abstract: Remarkable Differences in Reactivity Between Benzothiazoline and Hantzsch Ester as a Hydrogen Donor in Chiral Phosphoric Acid Catalyzed Asymmetric Reductive Amination of Ketones.

AbstractAttempted asymmetric reductive amination of benzyl methyl ketones with benzothiazoles (II) as hydrogen donor does not give any yields of the expected β‐arylamine whereas phenyl methyl ketone gives the reductive amination product (VII) with moderate e.e.

Catalyst-Free Aldol Reaction in a Water Medium

Background: With growing interest in developing environmentally friendly reactions and atom-economic processes in recent years, the utilization of water as a solvent has attracted a great deal of attention. This is not only for its low-cost, safe and environmentally benign nature, but also the unique properties of water in promoting reactions. Moreover, it may afford new access to the compounds that required harsh reaction conditions under traditional approaches. The aldol reaction is one of the most useful and widely employed methods for carbon - carbon bond formation in organic synthesis. Aldols can be acted as the raw materials used for the production of lubricants, surface coatings, synthetic resins and the important intermediates in the synthesis of polyols. Methods: p-nitrobenzaldehyde (100 mg), acetone (1.5 ml) and water (2 ml) was added into a round bottom at N2 atmosphere. The suspension was stirred vigorously at 50°C for 48 h. Then the reaction mixture was diluted with brine (10ml) and extracted with 3 × 15 ml ethyl acetate. The organic layer was dried over anhydrous MgSO4. Then the ethyl acetate solution was filtered and evaporated in vacuum. The crude mixture was purified by flash column chromatography on silica gel using petroleum/ ethyl acetate (2/1) as the eluent to give the desired aldol product in 92.0%. All the compounds were spectroscopically characterized (IR, 1H NMR). Results: In the examination of electron-withdrawing groups, a pronounced steric effect was more evident in the ortho position than other positions of nitrobenzaldehydes. The electronic effect influenced the reactions dramatically. No reaction progress was detected when p-methyl benzaldehyde was employed in the identical reaction condition. With increase of carbon number of ketones the yields decreased noticeably, although the temperature was elevated to reflux situations. This was partially for the increase of substrate’s steric bulk. When the acetyl benzene was used as substrate, the reaction gave poor yield. Compared to acetone, cyclic ketones reacted more slowly in reactions. When cyclic ketones were used as substrate at 50°C, only trace amounts of the desired product were obtained. Luckily, when increasing the reaction temperature to reflux conditions, for cycloheptanone, cyclohexanone and cyclopentanone, the yields reached to 86.1%, 91.4% and 56.1% respectively. The decrease was possibly due to the influence of ring strain. More interestingly, an excellent yield was obtained when 4-methylcyclohexanone was used in the reaction. In addition, nicotinaldehyde was used to react with cyclohexanone and afforded the target product in a good yield. Conclusion: In summary, a new methodology has been developed using water as solvent and promoter that is associated with non-flammable, non-toxic reaction medium, mild conditions, easy operation and good yields. The attractive function of water in aldol reaction was observed compared with many organic solvents. The approach was expanded successively to a wide range of substrates, especially cyclic ketones. Keywords: Aldehydes, aldol reaction, catalyst-free, cyclic ketones, eco-friendly, water.

Preparation of Pd-Loaded Hierarchical FAU Membranes and Testing in Acetophenone Hydrogenation.

Pd-loaded hierarchical FAU (Pd-FAU) membranes, containing an intrinsic secondary non-zeolitic (meso)porosity, were prepared and tested in the catalytic transfer hydrogenation of acetophenone (AP) to produce phenylethanol (PE), an industrially relevant product. The best operating conditions were preliminarily identified by testing different solvents and organic hydrogen donors in a batch hydrogenation process where micron-sized FAU seeds were employed as catalyst support. Water as solvent and formic acid as hydrogen source resulted to be the best choice in terms of conversion for the catalytic hydrogenation of AP, providing the basis for the design of a green and sustainable process. The best experimental conditions were selected and applied to the Pd-loaded FAU membrane finding enhanced catalytic performance such as a five-fold higher productivity than with the unsupported Pd-FAU crystals (11.0 vs. 2.2 mgproduct gcat−1·h−1). The catalytic performance of the membrane on the alumina support was also tested in a tangential flow system obtaining a productivity higher than that of the batch system (22.0 vs. 11.0 mgproduct gcat−1·h−1).