Diphenylacetic Acid Research Articles

Late-stage Functionalization using a Popular Titrating Agent: Aryl-Chlorides and -Fluorides Activation by the Diphenylacetic Acid Dianion.

Aryl-chlorides and -fluorides are common building blocks, but their use in synthesis is limited by the high stability of their Ar-X bonds. The generation of aryl radicals via activation of strong Ar-X bonds is possible through the irradiation of tailor-made organic anions, which become reductants stronger than lithium metal. We report that the combination of visible light with the cheap diphenylacetic acid dianion is an even better tool, showing excellent activity across a variety of complex substrates and providing opportunities for late-stage drug modification. Ar-X bonds are chemoselectively activated in the presence of more easily reducible functions, such as Alk-Cl ones and carbonyl groups. These results pave the way to original synthetic strategies that would be otherwise considered impossible.

Attenuation of phenylnaphthenic acids related to oil sands process water using solar activated calcium peroxide: Influence of experimental factors, mechanistic modeling, and toxicity evaluation

Refractory naphthenic acids (NAs) are among the primary toxic compounds in oil sands process water (OSPW), a matrix with a complex chemical composition that poses challenges to its remediation. This study evaluated the effectiveness of calcium peroxide (CaO2) combined with solar radiation (solar/CaO2) as an advanced water treatment process for degrading model NAs (1,2,3,4-tetrahydronaphthalene-2-carboxylic acid, pentanoic acid, and diphenylacetic acid) in synthetic water (STW) and provide preliminary insights in treating real OSPW. Solar light and CaO2 acted synergistically to degrade target NAs in STW (>67 of synergistic factor) following a pseudo-first-order kinetic (R2 ≥ 0.95), with an optimal CaO2 dosage of 0.1 g L–1. Inorganic ions and dissolved organic matter were found to hinder the degradation of NAs by solar/CaO2 treatment; however, the complete degradation of NAs was reached in 6.7 h of treatment. The main degradation mechanism involved the generation of hydroxyl radicals (•OH), which contributed ∼90% to the apparent degradation rate constant (K), followed by H2O2 (4–5%) and 1O2 (0–5%). The tentative transformation pathways of three NAs were proposed, confirming an open-ring reaction and resulting in short-chain fatty acid ions as final products. Furthermore, a reduction in acute microbial toxicity and genotoxic effect was observed in the treated samples, suggesting that solar/CaO2 treatment exhibits high environmental compatibility. Furthermore, the solar/CaO2 system was successfully applied as a preliminary step for real-world applications to remove natural NAs, fluorophore organic compounds, and inorganic components from OSPW, demonstrating the potential use of this technology in the advanced treatment of oil-tailing-derived NAs.

Experimental and Machine-Learning-Assisted Design of Pharmaceutically Acceptable Deep Eutectic Solvents for the Solubility Improvement of Non-Selective COX Inhibitors Ibuprofen and Ketoprofen.

Deep eutectic solvents (DESs) are commonly used in pharmaceutical applications as excellent solubilizers of active substances. This study investigated the tuning of ibuprofen and ketoprofen solubility utilizing DESs containing choline chloride or betaine as hydrogen bond acceptors and various polyols (ethylene glycol, diethylene glycol, triethylene glycol, glycerol, 1,2-propanediol, 1,3-butanediol) as hydrogen bond donors. Experimental solubility data were collected for all DES systems. A machine learning model was developed using COSMO-RS molecular descriptors to predict solubility. All studied DESs exhibited a cosolvency effect, increasing drug solubility at modest concentrations of water. The model accurately predicted solubility for ibuprofen, ketoprofen, and related analogs (flurbiprofen, felbinac, phenylacetic acid, diphenylacetic acid). A machine learning approach utilizing COSMO-RS descriptors enables the rational design and solubility prediction of DES formulations for improved pharmaceutical applications.

Co-CRYSTAL OF 2-AMINO-6-METHYL PYRIDINE WITH DIPHENYLACETIC ACID: SYNTHESIS, X-RAY STRUCTURE, QUANTUM CHEMICAL CALCULATION, HIRSHFELD SURFACE ANALYSIS AND ANTIBACTERIAL ACTIVITY

A new co-crystal of 2-amino-6-methyl pyridine with diphenylacetic acid has been synthesized and characterized using various spectroanalytic techniques. The co-crystal structure features a bifurcated N–H∙∙∙O intermolecular hydrogen bond. The intermolecular N–H∙∙∙O, O–H∙∙∙O, and C–H∙∙∙π hydrogen bonds play a significant role in stabilizing the structure of the co-crystal. The density functional theory approach has been employed to carry out a detailed quantum chemical analysis, employing a 6-311++G(d,p) basis set and the B3LYP method. The molecular interactions have been investigated by using the Hirshfeld surface method. The co-crystal demonstrates effective antibacterial efficacy against bacterial pathogens when compared to the standard antibiotic variant of ciprofloxacin.

Transforming micropores to mesopores by heat cycling KOH activated petcoke for improved kinetics of adsorption of naphthenic acids

Formation of activated carbon from petroleum coke by KOH, results in high specific surface area materials that are predominantly microporous. This initial microporosity means that the adsorption kinetics of target species are not as rapid as they could be, thus limiting environmental remediation applications for the material. To address this problem a series of additional heat cycles with no additional chemical inputs were applied after activation but prior to the removal of activating agents. This process resulted in the oxidation of residual potassium metal from the initial activation which allows it to function again as an activating agent for the subsequent cycles. The heat cycling resulted in an increase in mesoporosity by 10–25% with each successive cycle independent of the KOH to feedstock ratio. This was shown to be demonstrably different than equivalently extended heating times, thus identifying the importance of thermal cycling. Adsorption kinetics of three model naphthenic acids showed faster kinetics for the pore widened activated carbon. The t1/2 times dropped from 20 to 6.6 min for diphenyl acetic acid, 34.3 to 4.5 min for cyclohexane acetic acid, and 51.4 to 12.0 min for heptanoic acid.

Bis-Rhodamines Bridged with a Diazoketone Linker: Synthesis, Structure, and Photolysis.

Two fluorophores bound with a short photoreactive bridge are fascinating structures and remained unexplored. To investigate the synthesis and photolysis of such dyes, we linked two rhodamine dyes via a diazoketone bridge (−COCN2−) attached to position 5′ or 6′ of the pendant phenyl rings. For that, the mixture of 5′- or 6′-bromo derivatives of the parent dye was prepared, transformed into 1,2-diarylacetylenes, hydrated to 1,2-diarylethanones, and converted to diazoketones Ar1COCN2Ar2. The high performance liquid chromatography (HPLC) separation gave four individual regioisomers of Ar1COCN2Ar2. Photolysis of the model compound—C6H5COCN2C6H5—in aqueous acetonitrile at pH 7.3 and under irradiation with 365 nm light provided diphenylacetic acid amide (Wolff rearrangement). However, under the same conditions, Ar1COCN2Ar2 gave mainly α-diketones Ar1COCOAr2. The migration ability of the very bulky dye residues was low, and the Wolff rearrangement did not occur. We observed only moderate fluorescence increase, which may be explained by the insufficient quenching ability of diazoketone bridge (−COCN2−) and its transformation into another (weaker) quencher, 1,2-diarylethane-1,2-dione.

Visible-light photoredox-catalyzed selective carboxylation of C(sp3)−F bonds with CO2

Visible-light photoredox-catalyzed selective carboxylation of C(sp3)−F bonds with CO2

Development and Assembly of a Flow Cell for Single‐Pass Continuous Electroorganic Synthesis Using Laser‐Cut Components

AbstractFlow electrolysis cells are essential for the scale up of synthetic organic electrochemistry. We have developed a simple and inexpensive parallel plate flow cell that can be easily assembled using a stack of laser‐cut Mylar foils, which act as gaskets, insulating material, interelectrode gap and flow channel. The ease with which the laser‐cutting pattern can be customized has enabled the development of interelectrode separators with mixing geometries, which improve the mass transfer and thus the current efficiency. The performance of the flow electrolysis cell has been evaluated using the anodic decarboxylative methoxylation of diphenylacetic acid as model transformation. Very high conversions and selectivities have been achieved with single‐pass processing, with nearly quantitative current efficiency in some cases.

Solving the Computational Puzzle: Toward a Pragmatic Pathway for Modeling Low-Energy Vibrational Modes of Pharmaceutical Crystals

Five pharmaceutically relevant compounds with increasing molecular complexity, benzoic acid, diphenylacetic acid, l-tyrosine, celecoxib (form III), and carvedilol (form II), were investigated using...

Thermal kinetics, 3D-FMOs and spectral phase matching of 2-aminopyridinium diphenylacetate diphenylacetic acid crystal

The bulk size title crystal is grown by adopting temperature lowering technique. The intermolecular charge transfer reactions, frontier molecular energy gaps and nonlinear optical properties have been calculated theoretically by density functional theory. The investigations on the transfer of charge occurring in the molecular system are revealed through natural bonding orbital analysis. Polarizability of the 2APD compound has been found utilizing Penn gap analysis and Claussius–Mossotti relation. Microhardness measurements were taken along three different planes to look into the anisotropicity of the grown crystal. Further, properties affecting the mechanical behaviour of the grown crystal were also discussed. The estimation of thermodynamic specifications has been calculated. The specific heat capacity of 2APD is observed to be 2.36 J g−1 K−1 to 4.62 J g−1 K−1 in the deliberate temperature range varying from 32 to 230 °C. The output signal of the 2APD sample was recorded along different angles. Bulk 2APD sample exhibits maximum intensity at θm = 28° ± 1°.

Bimetallic Ni(II) complex with carboxylate bridging for homogeneous hydrogenation of alkenes with NaBH4

In this study, we present the synthesis and full characterization of the dimer Ni(II) complex, [Ni2(dpaa)2(bpy)2(SO4)(H2O)]CH3OH, (dpaa = diphenyl acetic acid, bpy = 2,2′-bipyridine) with an N2O4 donor set and its hydrogenation activity on linear and cyclic alkenes (1-octene, t-2-octene, 1-hexene, cyclohexene, cyclopentene, benzene and styrene) with NaBH4 as a hydrogen source. 1-Octene and 1-hexene were reduced to the corresponding alkanes as the major products (81.3 and 91.2%, respectively), and the substrate isomerized the terminal alkenes to a mixture of internal alkenes as minor products (1–4%) under the studied conditions (subs/cat/reduct. 100/1/1 in methanol, 40 °C, 6 h). To optimize the reaction conditions for the reduction of styrene to ethyl benzene in methanol, the effect of subs./NaBH4 ratio, solvent and temperature were also investigated.

Synthesis, characterization, geometric optimization and multi-target therapeutic evaluation of new homoleptic and heteroleptic Cd(II) carboxylates

In this study, nine Cd(II) carboxylates including three homoleptic and six heteroleptic complexes were synthesized in water at ambient conditions. Five different ligands (4-chlorophenylacetic acid, 3-chlorobenzoic acid, diphenyl acetic acid, 1,10-phenanthroline and 2,2-bipyridine) were used to form the Cd(II) coordination complexes. The carboxylate complexes were characterized by analytical techniques (SCXRD, 1H NMR, 13C NMR, FTIR, DRS and melting point). These complexes were investigated for anti-bacterial activity (against six different multidrug resistant bacterial strains of Staphylococcus aureus), anti-leishmanial activity and anti-glycation activity. The complexes were also evaluated for their inhibition potential against the pharmacologically important enzymes such as alkaline phosphatase, urease, α-glucosidase and acetyl cholinesterase. Various computational features explored by DFT calculations indicated that these materials could be potentially employed in biological, optoelectronic and electrical applications.

Kinetic Resolution of Racemic 2‐Hydroxyarylketones by Asymmetric Esterification: Investigation of the Influence of the Co‐Base on the Selectivity

AbstractAn efficient kinetic resolution of a variety of racemic 2‐hydroxyarylketone derivatives was developed by asymmetric esterification protocol using diphenylacetic acid, pivalic anhydride, and a catalytic amount of (R)‐benzotetramisole ((R)‐BTM). It was revealed that employing a tertiary amine as a co‐base in this reaction is not necessary to achieve high s‐values. All conducted reactions proceeded smoothly with good s‐values under the optimized reaction conditions, irrespective of the steric and electronic nature of the substituents on the aromatic rings of the substrates. The most stable transition state of the reaction was determined by density functional theory (DFT) calculations.

A Strategy for Trapping Molecular Guests in MOF-5 Utilizing Surface-Capping Groups

We have developed a simple strategy allowing molecular guests to be trapped within MOF-5 using carboxylic acids bearing sterically demanding substituents as capping reagents. We demonstrate that introducing triphenylacetic acid or diphenylacetic acid onto the surface of crystals of MOF-5 loaded with crystal violet (CV) prevents CV from escaping by blocking the openings of pores. In this study, MOF-5 was capped with four carboxylic acids and two 3° amines, and diffusion of CV out of capped MOFs was monitored using UV–vis spectroscopy to assess how variation in the steric demand of substituents affected retention of CV.

Synthesis, Characterization and DNA Binding Studies of Zn(II)/Cu(II) Complexes with 2,2`-Diphenyl Acetic Acid/2-(4-Hydroxyphenyl)Acetic Acid Ligand Precursors and Nitrogen Bases

The hydrated complexes 1, 3, 7 and 8 with the general formula (RCOO)2M.xH2O (where M = Zn & x = 6; M = Cu & x = 5,6) were synthesized by the reaction of sodium salt of 2,2`-diphenyl acetic acid or 2-(4-hydroxyphenyl)acetic acid (RCOONa) with Zn(NO3)2.6H2O or CuSO4.5H2O in an aqueous medium. The addition of methanolic solution of either bipyridine (bpy) or 1,10-phenanthroline (phen) to an aqueous suspension of 1, 3, 7 and 8 (produced in situ) result in the formation of mixed ligand products with the general formulae (RCOO)2M(bpy).xH2O (2, 4, 9 and 10) and (RCOO)2M(phen).xH2O (5 and 6). The complexes were characterized by microanalysis, FTIR and NMR (1H and 13C) spectroscopic techniques. The FTIR data suggested a bidentate coordination mode of the carboxylate ligand and complexes exhibited four/six-coordinated geometry in the solid state. The spectroscopic data also revealed the presence of coordinated water molecules in all complexes. 1H and 13C NMR data demonstrated the coordination between ligand and the metal in complex 1. The complexes were tested for their binding with salmon sperm DNA (SS-DNA). The DNA binding potential of the complexes owed to the presence of zinc metal and the nature of the incorporated ligand. The complexes showed a significant hypochromic effect and an intercalating mode of binding with SS-DNA. The complexes were screened against various bacterial and fungal strains to check their biological activity. All the complexes showed significant antibacterial activity but none of complex exhibit antifungal activity.

Continuous column adsorption of naphthenic acids from synthetic and real oil sands process-affected water (OSPW) using carbon-based adsorbents

In this study, activated petroleum coke (APC) and commercial activated carbon (CAC) were used in a continuous adsorption column for removal of model naphthenic acids and organics from real oil sands process-affected water (OSPW). Diphenylacetic acid and 2-naphthoic acid, two model naphthenic acid (NA) compounds, were removed completely by the APC in a continuous column operation. Due to the complex nature of organics in OSPW, total organic carbon (TOC) was measured to determine the effectiveness of OSPW treatment by APC. The removal of TOC from OSPW at its natural pH 8 by APC was only 25%, whereas acidification at pH 4 followed by APC adsorption removed 96% of the initial TOC. When compared to a commercial activated carbon, the APC showed an average of 20% higher organics removal. The experimental breakthrough curves were better fitted by Thomas model in comparison to Adams-Bohart and Yoon-Nelson models. The regeneration of APC was conducted using methanol with 0.01 wt% NaOH (pH = 11.7) and a total of four cycles of adsorption and regeneration were conducted with marginal loss of adsorption sites.

Crystal engineering, structural and optical properties of 2-aminopyridinium diphenylacetate diphenylacetic acid crystal

Organic crystal of 2-aminopyridinium diphenylacetate diphenylaetic acid with dimensions 22 × 13 × 11 mm3 was grown by slow cooling technique. The structural confirmation has been done using single crystal X-ray diffraction study. The title compound crystallizes in the monoclinic crystal system with noncentrosymmetric space group P21. The C-H-O, N-H-O type of packing for the title compound has been reported. Optical transmittance shows a wide transparency in the visible region with lower cutoff wavelength at 349 nm. The four independent tensor coefficients of dielectric permittivity were found to be ε11 = 12.16, ε22 = 10.68, ε33 = 11.90 and ε13 = −4.24 from the dielectric measurements. The thermal stability of the 2APD compound was found to be 128˚C assessed by TG-DTA analyses. The particle size SHG of the 2APD reveals that it is a phase-matchable NLO crystal.

Preparation of activated petroleum coke for removal of naphthenic acids model compounds: Box-Behnken design optimization of KOH activation process

This study employed Box-Behnken design and response surface methodology to optimize activation parameters for the production of activated petroleum coke (APC) adsorbent from petroleum coke (PC) to achieve highest adsorption capacity for three model naphthenic acids. Activated petroleum coke (APC) adsorbent with a BET surface area of 1726 m2/g and total pore volume of 0.85 cc/g was produced at the optimum activation conditions (KOH/coke mass ratio) of 3.0, activation temperature 790 °C, and activation time 3.47 h). Effects of the activation parameters on the adsorption pefromances (adsortion capaciy and kinetics) were investigated. With the APC obtained at the optimum activation condition, the maximum adsorption capacity of 451, 362, and 320 (mg/g) was achieved for 2-naphthoic acid, diphenylacetic acid and cyclohexanepentanoic acid (CP), respectively. Although, generally APC adsorbents with a higher specific surface area and pore volume provide better adsorption capacity, the textural properties (surface areas and pore volume) are not the only parameters determining the APC adsorbents’ adsorption capacity. Other parameters such as surface functionalities play effective roles on the adsorption capacity of the produced APC adsorbents for NAs. The KOH activation process, in particular the acid washing step, distinctly reduced the sulfur and metals contents in the raw PC, decreasing the leaching potential of metals from APC adsorbents during adsorption.

Crystal structure, molecular packing, FMO, NBO, nonlinear optical and optical limiting properties of an organic imidazolium diphenylacetate diphenylacetic acid single crystal

A new organic nonlinear optical material, imidazolium diphenylacetate diphenylacetic acid, with excellent structural characterization and nonlinear optical activity has been reported.

Zeolite Encapsulated Fe-poprhyrin for Catalytic Oxidation with Iodobenzene Diacetate (PhI(OAc)2)

meso-Tetrakis(3-pyridyl)porphyrinatoiron(III) chloride encapsulated on NaY Zeolite [Fe(T-3-PyP)@NaY] was synthesized as a heterogeneous “ship-in-a-bottle” type catalyst and characterized by Fourier transform infrared (FT-IR), atomic absorption (AA), diffused reflectance UV-Vis (DR UV-Vis), X-ray diffraction (XRD) and scanning electron microscopy (SEM) analysis. The catalytic activity of Fe(T-3-PyP)@NaY was examined for the epoxidation of cyclohexene by PhI(OAc)2 in CH3CN/H2O (5:1) and compared to that of Fe(T-3-PyP) as a homogenous catalyst. We found that the heterogeneous catalyst Fe(T-3-PyP)@NaY was stable and reusable for several times, and provided a mild condition and exhibited high activity and selectivity in the oxidation of alkenes to epoxides(16-94%). As representative examples for the use of Fe(T-3-PyP)@NaY/ PhI(OAc)2 in organic oxidations, oxidation of 4-nitrobenzylalcohol to 4-nitrobenzaldehyde (97 %), oxidative dehydrogenation of diethyl 4-(2,6-dichlorophenyl)-2,6-dimethyl- 1,4-dihydro-3,5-pyridinedicarboxylate to the corresponding pyridine (100 %), diphenylacetic acid to benzophenone (64 %) was achieved.