Reaction Of Acetophenone Research Articles

Synthesis, Characterization, Anti-Inflammatory, and Antimicrobial Evaluation of New 2-Pyrazolines Derivatives Derived from Guaiacol

Abstract:
 Chalcones were used to synthesis series of 2-pyrazoline derivatives and evaluated their antimicrobial and anti-inflammatory activities
 (E)-1,3-diphenylprop-2-en-1-one (1-5) were synthesized by Claisen-Schmidt Condensation method through the reaction of acetophenone with five various para substituted benzaldehyde in presence of KOH, the reaction monitoring by TLC and the result intermediates were checked by melting point and FT-IR
 Various 2-Pyrazoline derivatives were prepared by one pot reaction that involved the refluxing of (E)-1,3-diphenylprop-2-en-1-one (1–5) and Hydrazine monohydrate in the presence of glacial acetic acid for 24 hours at a temperature of (45–50) °C for a duration 24 hrs. pyrazoline II (1-5) was formed, then antioxidant compound (guaiacol) was added reflex for 24-48 hours, monitoring by TLC to ensure the reaction was completed. The final mixture was cooled in ice-water bathe until the formation of crystals were completed, added to crushed ice, kept in refrigerator overnight, filter, recrystallized and then dried to get 2-pyrazoline derivatives, IIIa, IIIb, IIIc, IIId and, IIIe. based on the spectral data 2-pyrazoline derivatives structures have been confirmed. The synthesized compounds were screened for their antimicrobial activity and anti-inflammatory.

Synthesis, Characterization and biological activity of some novel heterocyclic β-lactam/thiazol compounds derived from 4-phenyl-4,5-dihydrothiazol-2-yl-imino

An efficient and convenient synthesis of β-lactam/ thiazol derivatives has been achieved by the reaction of acetophenone, substituted aromatic aldehyde and thiourea yield substituted schiff’s bases which further undergo the cyclization in the presence of chloroacetyl chloride, triethyl amine/ZnCl2, thioglycoolic acid. All the synthesized novel derivatives have been established by % of C, N, S elements, FT-IR, 1H NMR and Mass spectral studies. Further in-vitro antimicrobial activity of novel derivatives was carried out against some Gram-positive and Gram-negative bacteria by serial dilution method. The activity of IIIc, IIId, IIc, IId, IIf derivatives showed significant response against the tested microbes.

Regio- and Chemoselective Formal (4+1) Carbocyclization of Chalcones with Internal Alkynes via Rhodium(III) Catalysis.

A rhodium(III)-catalyzed oxidative cyclization of chalcones with internal alkynes is reported, generating biologically important 3,3-disubstituted 1-indanones along with reusable aromatic aldehydes. This transformation features unique (4+1) reaction mode, excellent regioselectivity in alkyne insertion, broad substrate scope, allows for the construction of quaternary carbon centers, and is scalable. Steric hindrance from substrate and ligand probably controls the chemoselectivity of this carbocyclization. Importantly, this discovery enables a practical two-step protocol switching the overall reaction of acetophenones with internal alkynes from a (3+2) to a (4+1) annulation.

Regio‐ and Chemoselective Formal (4+1) Carbocyclization of Chalcones with Internal Alkynes via Rhodium(III) Catalysis

AbstractA rhodium(III)‐catalyzed oxidative cyclization of chalcones with internal alkynes is reported, generating biologically important 3,3‐disubstituted 1‐indanones along with reusable aromatic aldehydes. This transformation features unique (4+1) reaction mode, excellent regioselectivity in alkyne insertion, broad substrate scope, allows for the construction of quaternary carbon centers, and is scalable. Steric hindrance from substrate and ligand probably controls the chemoselectivity of this carbocyclization. Importantly, this discovery enables a practical two‐step protocol switching the overall reaction of acetophenones with internal alkynes from a (3+2) to a (4+1) annulation.

Catalytic activity of Cu-BTC metal organic framework for borrowing hydrogen and tandem reactions of an alcohol under solvent and base free condition

The Cu-BTC (copper(II)-benzene-1,3,5-tricarboxylate) metal–organic framework was found to be a potential, stable and reusable catalyst for the solvent- and base-free borrowing hydrogen and tandem reactions of an alcohol. The Cu-BTC exhibited borrowing hydrogen activity in N-alkylation of aniline with benzyl alcohol, a model reaction of borrowing hydrogen, giving the saturated product (N-alkylated aniline). However, the formation of unsaturated product (chalcone) in the reaction of acetophenone with benzyl alcohol for α-C-alkylation, another model reaction of borrowing hydrogen, showed potential of Cu-BTC for the catalysis of tandem reactions to synthesize unsaturated products utilizing alcohols as a reagent. The study shows that the Cu-O pair sites of Cu-BTC are involved in the catalysis of borrowing hydrogen and tandem reactions.

Farklı Kalkon, Ftalonitril ve Periferal Tetra Çinko Ftalosiyanin Türevlerinin In Vitro Layşmanyasidal Aktivitesi

In this study, in vitro leishmanicidal activity of different chalcone compounds (5-8), phthalonitrile derivatives (5a-8a), and zinc phthalocyanine (5b-8b) complexes bearing chalcone compound in peripheral positions were investigated. Phthalonitrile derivatives were obtained in the reaction of 4-nitrophthalonitrile with chalcone compound obtained by the reaction of acetophenone and various aldehydes. Zinc phthalocyanine complexes containing chalcone in the peripheral position were obtained as a result of the reaction of the synthesized phthalonitrile derivative with Zn(CH₃COO)₂ metal salt. The characterization of the synthesized original compounds (8, 8a and 8b) was performed by various spectroscopic methods (IR, 1H and 13C NMR, MALDI-TOF-MS and UV-Vis). Leishmaniasis is a disease lead to by parasites of the genus Leishmania, which can result in death as well as various clinical syndromes, generally in developing countries. New drug studies are needed because the drugs used in the treatment are toxic and resistance develops against them. In this study, the leishmaniacidal activities of synthesized chalcone, phthalonitrile and phthalocyanine series substances against Leishmania infantum and Leishmania major parasites were evaluated for the first time.

Synthesis and Characterisation of a Heterobimetallic N-heterocyclic Carbene Rhodium Ruthenium Complex as Catalyst for Transfer Hydrogenation

The heterobimetallic N-heterocyclic dicarbene (NHDC) rhodium ruthenium complex [Ru(OAc)(Mes-NHC-methyl-PPh2)(Mes-aNHC-methyl-PPh2)RhCl(cod)] (4) is obtained from a mixed normal/abnormal bis-NHC ruthenium complex via transmetallation by addition of [RhCl(cod)]2 in THF at 40 °C, applying Ag2O as base. Crystallization is achieved by layering a solution of 4 in THF with Et2O. The complex is applicable as a catalyst in the transfer hydrogenation (TH) reaction of acetophenone, exhibiting a turnover frequency (TOF) of 6 700 h−1 with 80% conversion after 25 min (0.10 mol% catalyst, iPrOH, 80 °C, 2.00 mol% NaiOPr). These results are compared to an analogous iridium ruthenium NHDC complex.

Cyclization Reactions of Non-Conjugate Ynones with Propargyl Amine in the Presence of a Catalyst

In this study, acetate derivatives were obtained from the reaction of acetophenones using diethyl carbonate. The acidic proton of CH2 moiety was abstracted using a suitable base and α-propargyl-β-ketoester (non-conjugated ynone) derivatives 3a-c were obtained from the reaction of the acetate derivatives with propargyl bromide. By removing the ester group of α propargyl-β-ketoester derivatives under suitable conditions, α-propargyl acetophenones (non-conjugated ynone) 4a-c were obtained. In this study, 6 different unconjugated ynone derivatives were synthesized as starting material with yield in a range of 60-95%. Cyclization reactions with propargyl amine in the presence of three different unconjugated ynone derivatives, metal catalysts were investigated. The synthesis of propargyl pyrroles 7a-c having substituents on C-2 and C-5 was completed.

Synthesis, characterization and application of chitosan conjugated heterocyclic compounds

Derivatives of formyl pyrazole were synthesized by the reaction of acetophenone, 4-methyl acetophenone, 3-acetyl furan, 3-acetyl thiophen and phenyl hydrazine derivatives. The product was treated with Vilsmeier reagent producing different formyl pyrazole derivatives which were characterized by FT-IR, 1HNMR, Elemental analysis and Mass spectroscopy. The formyl pyrazole derivatives were reacted with chitosan to produce chitosan/ pyrazole Schiff base. These Schiff bases were characterized by FT-IR and TGA.The antimicrobial activity of chitosan/ pyrazol Schiff base (CSB) was evaluated against Gram-positive bacteria (Staphylococcus aureus and Bacillus cereus), gram negative bacterium (Escherichia coli) and fungus (Aspergillus niger). Results indicated agood inhibitory activity for CSB-14 when tested against B.cereus that gave inhibition zone of 7.5 ± 0.6 (mm), however CSB-18 gave a pronounced inhibitory activity against S. aureus and recorded 25 ± 2.0 (mm). All synthesized derivatives have no inhibitory activity against Gram negative E. coli. CSB-14, and CSB-15 exhibited inhibitory activity against tested A. niger that was used as a fungal model which gave 19 ± 0.9 and 18 ± 1.0 inhibition zone (mm) respectively. Thus, these results showed that, functionalization of chitosan with the hetero-cyclic compounds created biological activities of the synthesized derivatives; hence the synthesized pyrazole derivatives have not recorded any inhibitory activity before its immobilization onto chitosan.

An Approach in Synthesis of 1-Morpholino-2-phenylethane-1,2-dione Catalyzed by Copper (II) Bromide

A novel approach towards synthesis of α-Ketoamides was serendipitously found in acetophenone's reaction with a secondary amine catalyzed by copper (II) bromide. This methodology is a promising simple alternative to access biologically active compounds containing α-Ketoamides. Reactions were carried out at room temperature using dimethyl sulfoxide (DMSO) as solvent and catalyst loading at 10 mol %. The products were purified using a chromatographic method and analyzed extensively by spectroscopic methods, namely 1D (1H and 13C) and 2D NMR (HMBC and HSQC). The reaction of acetophenone and morpholine furnished a yield of 6%. Acetophenone derivatives bearing benzyl and acetyl groups were prepared from para-hydroxy acetophenone with 25% and 99% yields, respectively. The products were analyzed by spectroscopic method, namely 1H and 13C NMR. The presence of substituents, namely hydroxyl, benzyl, acetyl group, prevent the formation of α-Ketoamides. Formation of α-Ketoamides in this reaction condition was proposed as the result of the oxidation product in the catalytic cycle of Cu (II).

Highly Efficient Ultrasound Promoted Synthesis of 2-phenylquinoxaline in Glycerol- Water

Quinoxalines show diversified applications in the field of medicinal chemistry. Therefore, we have designed a highly efficient, environmentally benign and one-pot protocol for the synthesis of 2-phenylquinoxaline from the reaction of Acetophenone, N-bromosuccinimide and 1,2-phenylenediamine under ultrasound irradiation in glycerol-water. We observed that, although the reaction efficiently completed in all of these solvents, the use of glycerol-water with different ratios gives consistently higher yields (89-94%) and decreases reaction times. The main advantages of this protocol are that it is a green method, avoids the use of toxic catalysts and volatile organic medium and the product is obtained with excellent yield.

Efficient Catalytic Performance of Calcined Tungstophosphoric Acid for the Claisen-Schmidt Condensation under Solvent-Free Reaction

Effect of calcination of tungstophosphoric acid catalyst was evaluated in terms of the synthesis of chalcone derivatives via Claisen-Schmidt condensation using the reaction of acetophenone and several substituted aldehydes. The catalyst was characterized before and after calcination by FT-IR to assess the effectiveness of the synthesis of the desired products. The calcined tungstophosphoric acid catalyst (HPW-CL) showed a better performance and high yield of Claisen-Schmidt products in a short period of time. It was also found out that the calcined tungstophosphoric acid provides a chemo selective, efficient and environmentally benign synthesis of chalcone in an excellent yield in a solvent-free system.

One‐Pot Sequential Synthesis of 2‐Amino‐4, 6‐Diaryl Pyrimidines Involving SO3H‐Functionalized Piperazinium‐Based Dicationic Ionic Liquids as Homogeneous Catalysts

AbstractA new series of –SO3H functionalized dicationic ionic liquids based on N, N, N′, N′ ‐ tetrasulfopiperazinium cation [TSPi]+ and various anions [X]− (X=Cl, CF3SO3, TsO) is synthesized and characterized by 1H NMR, 13C NMR, FTIR, elemental analysis and thermogravimetric studies. Brönsted acidity of these ionic liquids is determined by Hammett plot using UV‐Visible absorbance spectra. Further they are examined as acidic catalyst for one‐pot preparation of 2‐amino‐4, 6‐diaryl pyrimidines through Biginelli‐like reaction of acetophenone, aromatic aldehyde and urea followed by condensation‐aromatization reaction with phenylhydrazine under solvent‐free grinding method. The most acidic [TSPi][CF3SO3]2 catalyst offers good to satisfactory yield within 15–25 min reaction time. Easy recyclability, simple and mild reaction conditions represent the advantages of this method.

Raney® nickel-catalyzed hydrodeoxygenation and dearomatization under transfer hydrogenation conditions—Reaction pathways of non-phenolic compounds

Abstract Catalytic reduction of oxygen-containing aromatic compounds has been studied under transfer hydrogenation (TH) conditions at 150 °C in 2-PrOH as a hydrogen donor. Raney® nickel is used as a heterogeneous catalyst. The reaction of aromatic non-phenolic carbonyl compounds is most likely to proceed through the pathway “aromatic ketone (aldehyde)→aromatic alcohol→alkylaromatics→saturated alkylcyclohexane”. One of the main reactions under the TH conditions is a hydrodeoxygenation (HDO) process. Unexpectedly, the hydrodeoxygenation of aromatic ketones to alkylaromatics (C O → CH2) occurs faster than of corresponding aromatic alcohols (HC OH → CH2) that means either additional reaction pathway of its hydrodeoxygenation missing for the corresponding aromatic alcohols or specific interaction of OH functionality with Raney® nickel surface obstructing (hindering) the further reduction. Benzaldehyde is shown to be less reactive than the aromatic ketones under the same reaction conditions. The main reason is proposed to be carbon monoxide release resulted from the decarbonylation of the aldehyde. Carbon monoxide demonstrates a poisoning effect on Raney® nickel surface that is evidenced in the catalyzed TH reaction of acetophenone. The HDO reaction of anisole under the same reaction conditions was a little slowly than of oxygen-containing non-phenolic aromatics.

LaFeO3 perovskite nanoparticles as high-performance reusable catalyst for convenient synthesis of β-amido ketones under mild conditions

Perovskite-type LaFeO3 nanoparticles were successfully prepared by a simple sol–gel method and used as a highly active, heterogeneous, and reusable nanocatalyst. The prepared catalyst was characterized by scanning electron microscopy, powder X-ray diffraction analysis, energy-dispersive X-ray spectroscopy, and Fourier-transform infrared (FT-IR) spectroscopy. The catalytic activity of LaFeO3 nanocatalyst was investigated in synthesis of β-amido ketone derivatives by reaction of acetophenone, different substituted aldehydes, nitriles, and acetyl chloride. This method offers several advantages such as environmental sustainability, low catalyst loading, easy workup and purification of products, excellent yield, and catalyst reusability of at least four times without any remarkable change in catalytic activity. Perovskite-type LaFeO3 nanoparticles were prepared by a citric acid-based sol–gel route and successfully used as a heterogeneous and reusable nanocatalyst for convenient synthesis of β-amido ketones derivatives.

Synthesis, Characterization and Cytotoxic Studies of New Thiazolidinones

A new series of substituted aromatic thiazolidinones [1-4]were synthesized by the reaction of acetophenone and its derivatives [5-8]with hydrazine hydrate and merceptoacetic acid in absolute ethanol in one pot manner. The striking feature of this reaction is the formation of hydrazone in situ which in turn undergoes the cyclization with mercepto acetic acid, leading to the formation of new thiazolidinones. Thus, the thiazolidinone ring closes at carbonyl carbon, by the attack of sulfur of mercaptoacetic acid moiety, preferentially from the front (I², axial) so that the nitrogen has an equatorial orientation (I±, equatorial) to avoid steric repulsion, giving minimum steric hindrance. The new compounds were characterized by spectral (IR, 1H NMR,13C NMR, MS) and analytical methods. The new compounds were screened for cytotoxicity (MTT assay) as well as genotoxicity (Comet assay) studies against different cancer cell lines, during which the new compounds depicted potential anticancer behaviour.

Quantum chemical modeling of superbase-catalyzed reactions of acetophenone and methyl mesityl ketone with acetylene

The mechanisms of furan formation and the competitive reaction of 1,5-diketone formation from 1-mesitylbut-2-en-1-one (1a) and 1-phenylbut-2-en-1-one (1b) were studied using the B3LYP/6-311++G**//B3LYP/6-31+G* quantum chemical approach taking into account solvation effects in terms of the IEFPCM model. The addition to 1a of the ethynide ion to form β-acetylene enolate ion (2a) occurs with the activation energy ΔG≠ = 13.3 kcal mol–1, while the further intramolecular O-vinylation with the closure of 2a to the dihydrofuran cycle of the dihydrofuran carbanion is the rate-determining step in the reaction pathway of substituted furan formation needing the activation energy G≠ = 19.5 kcal mol–1. The alternative addition of the mesitylethenolate ion to 1a to form the 1,5-diketone carbanion is associated with a higher (by 3.4 kcal mol–1) free activation energy than that of ethynide ion addition. In contrast, in the case of 1b, the addition at the C=C bond of the phenylethenolate ion rather than of the ethynide ion to form the 1,5-diketone carbanion is more preferable, since its activation free energy is 1.5 kcal mol–1 lower. The quantum chemical calculation results are consistent with the experimental data.

DFT-based prediction of reactivity of short-chain alcohol dehydrogenase

The reaction mechanism of ketone reduction by short chain dehydrogenase/reductase, (S)-1-phenylethanol dehydrogenase from Aromatoleum aromaticum, was studied with DFT methods using cluster model approach. The characteristics of the hydride transfer process were investigated based on reaction of acetophenone and its eight structural analogues. The results confirmed previously suggested concomitant transfer of hydride from NADH to carbonyl C atom of the substrate with proton transfer from Tyr to carbonyl O atom. However, additional coupled motion of the next proton in the proton-relay system, between O2′ ribose hydroxyl and Tyr154 was observed. The protonation of Lys158 seems not to affect the pKa of Tyr154, as the stable tyrosyl anion was observed only for a neutral Lys158 in the high pH model. The calculated reaction energies and reaction barriers were calibrated by calorimetric and kinetic methods. This allowed an excellent prediction of the reaction enthalpies (R2 = 0.93) and a good prediction of the reaction kinetics (R2 = 0.89). The observed relations were validated in prediction of log Keq obtained for real whole-cell reactor systems that modelled industrial synthesis of S-alcohols.

SYNTHESIS OF 5-(PYRAZOL-1-YL)-1,2,3-THIADIAZOLES

A method is proposed for the synthesis of ethyl 5-(3-aryl-4-formyl-1H-pyrazol-1-yl)-1,2,3-thiadiazole-4-carboxylates by a reaction of acetophenone (4-ethoxycarbonyl-1,2,3-thiadiazol-5-yl)hydrazones with a Vilsmeier–Haack complex. The obtained heterocyclic assemblies provide interesting substrates for further modification and study of biological activity. Authors: Olga A. Vysokova, Tatiana A. Kalinina, Marina A. Tokareva, Tatiana A. Pospelova, Tatiana V. Glukhareva*, Yuri Yu. Morzherin

Synthesis of 5-(pyrazol-1-yl)-1,2,3-thiadiazoles

A method is proposed for the synthesis of ethyl 5-(3-aryl-4-formyl-1H-pyrazol-1-yl)-1,2,3-thiadiazole-4-carboxylates by a reaction of acetophenone (4-ethoxycarbonyl-1,2,3-thiadiazol-5-yl)hydrazones with a Vilsmeier–Haack complex. The obtained heterocyclic assemblies provide interesting substrates for further modification and study of biological activity.