Reaction Of Benzoic Acid Research Articles

Hexagonal-prismatic metal‒organic cages and metal‒organic polymers based on 1,1'-(5-methyl-1,3-phenylene)bis(1H-imidazole) ligand: Synthesis, structural characterization and magnetic property

A serial of hexagonal-prismatic metal organic cages (MOCs), [Co6(OH)2(HCOO)6(pbim)6(H2O)6]·SO4·2HCOO·8H2O (1·2HCOO·8H2O), [Ni6(OH)2(HCOO)6(pbim)6(H2O)6]·SO4·2HCOO·8H2O (2·HCOO·8H2O), {[Co6(μ3-OH)2(μ-HCOO)6(pbim)6(H2O)6]·ClO4}3+·3HCOO·solvent (3·3HCOO·solvent) and {[Ni6(μ3-OH)2(μ-HCOO)6(pbim)6(H2O)6]·ClO4}3+·3HCOO·solvent (4·3HCOO·solvent), was constructed from shuttlecock-like C3-symmetric [M3(μ3-OH) (μ-HCOO)3(H2O)3] (M = Co2+ or Ni2+) clusters generated in situ and a clip-like ligand 1,1'-(5-methyl-1,3-phenylene)bis(1H-imidazole) [pbim]. Interestingly, one SO42− or ClO4− anion was encapsulated in each cage of MOCs 1–4 through cooperative O–H⋯O and C–H⋯O hydrogen-bonding interactions. It was also found that those SO42‒-/ClO4−-encapsulated MOCs, especially SO42‒-encapsulated MOC of Ni2+, displayed quite stability in methanol. Notably, when the crystal parent solution of MOC 1 was disturbed or MOC 1 was immersed in its parent solution for a long time, it resulted in the formation of a 2D coordination polymer [Co(pbim)2(H2O)2]·2HCOO (5) with helical architecture. Unexpectedly, a novel 2D coordination polymer [Ni4(pbim)2(CH3O)4(C6H5COO)4]·2H2O (6·2H2O) based on in-situ produced cubane-like [Ni4(μ3-CH3O)4(μ-COO)2] cluster was solvothermally synthesized through the reaction of benzoic acid with relatively stable MOC 2 in DMF. Magnetic studies show that there are antiferromagnetic coupling exchanged by mixed hydroxyl/carboxylate bridges in shuttlecock-like [M3(μ3-OH) (μ-HCOO)3(H2O)3] clusters of 1 and 2 or in cubane-like [Ni4(μ3-CH3O)4(μ-COO)2] cluster of 6. The best fits for their magnetic behaviours gave the following coupling constants: J = −2.05 cm−1 for 1, J = −1.74 cm−1 for 2, and J1 = −2.85 cm−1 and J2 = −4.01 cm−1 for 6.

Ein‐Topf‐Synthese von 1,3‐Cyclohexadienen durch Birch‐Reduktion in Gegenwart von Carbonylverbindungen

Ein‐Topf‐Synthese von 1,3‐Cyclohexadienen durch Birch‐Reduktion in Gegenwart von Carbonylverbindungen

One-Pot Synthesis of 1,3-Cyclohexadienes by Birch Reduction in the Presence of Carbonyl Compounds.

Birch reductions are well-known transformations of arenes, applied for large scale synthesis of 1,4-cyclohexadienes. Herein, we describe first reactions of benzoic acids in the presence of carbonyl compounds, affording aldol products in moderate to high yields. Alkyl aldehydes give the expected nonconjugated dienes by reaction at the α-position. Interestingly, the intermediately formed enolate attacks aryl aldehydes and ketones from its γ-position, which can be explained by steric hindrance. This opens the door for the one-pot synthesis of 1,3-cyclohexadienes, which are not accessible by classical Birch reductions. Our method is applicable to benzoic, m- and p-toluic acid and various carbonyl compounds, and more than 25 new products were isolated in up to 93 % yield. Prochiral aryl aldehydes afford diastereomeric mixtures in ratios of about 4 : 1, but in the cyclohexadiene ring only trans isomers are formed with high selectivity. Finally, the 1,3-cyclohexadienes are suitable precursors for further transformations, which we have demonstrated in first examples. Thus, aromatization affords products of a formal meta selective Friedel-Crafts alkylation, and four new stereocenters were generated by cycloaddition of singlet oxygen with excellent selectivity.

Polyethylene Film Surface Modification via Benzoic Acid Grafting.

A polyethylene (PE) film surface modification method is proposed via benzoic acid (BA) alkylation grafting to improve the surface affinity to polar substances. The procedure involves sequentially spraying AlCl3 and BA onto the heat-softened PE surface. The occurrence of the alkylation reaction was evaluated through comparative chemical, morphological, and thermal analyses. It was demonstrated that the grafting reaction of BA onto the PE film surface took place, limited to the surface layer, while preserving the bulk properties of PE. The reaction resulted in the formation of aluminum benzoate complexes, which improved the surface affinity to polar compounds. The impact of grafting on the surface properties of PE was further assessed by comparing the behavior of PE films treated with BA and untreated PE films when painted with watercolors. The PE film grafted with BA exhibited increased affinity towards watercolors, providing strong evidence of a change in surface polarity from hydrophobic to hydrophilic. These findings indicate that the proposed methodology effectively renders the PE surface paintable, even with non-toxic water-based inks, making it suitable for applications such as packaging.

Mechanistic insights into Criegee intermediates with benzoic acid at gas-phase and air-water interface and nucleation of product

Since the detection of Criegee intermediates (CIs) in the gas phase, there has been a growing recognition of the important role of CIs in atmospheric oxidation. Further mechanistic investigations are required to fully elucidate the bimolecular reactions of CIs with atmospheric species, such as OH, RO2/HO2, and carbonyl compounds. This article primarily focused on the reactions of benzoic acid (BA) with syn- and anti- CH3CHOO (C2 CI) in both gas-phase and gas-liquid interface using density functional theory (DFT) and Born-Oppenheimer molecular dynamics (BOMD). The results reveal that the reactions of BA and anti-CH3CHOO represent the principal pathway in the gaseous phase, whereas the water-involved reactions exhibit higher energy barriers, rendering them less favorable for occurrence. At the air-water interface, the reactions of BA and C2 CI as well as the BA-catalyzed hydration take place on the picosecond scale, conforming to the stepwise mechanism. The direct reaction between BA and anti- CH3CHOO remains the main sink for C2 CI at the gas-liquid interface. Molecular dynamics (MD) simulations were employed to investigate the nucleation capabilities of the reaction products and to examine the influence of temperature and water molecules on the nucleation process. The product molecules of BA and C2 CI can form stable clusters with sulfuric acid, ammonia molecules, and water molecules within 30 ns? The nucleation ability tends to decrease with the elevation of temperature, and the presence of water molecules promotes the new particles formation (NPF). Therefore, BA and its products with CIs affect the budget of secondary organic aerosols (SOAs).

Electrochemistry-enabled Rh-catalyzed regioselective [4 + 1] and [4 + 2] cycloaddition of benzoic acid with alkynyl esters/amides

The reaction of benzoic acids with alkynyl esters/amides in the presence of a Rh-catalyst and AcOH as an additive to give phthalides by [4 + 1] annulation. In contrast, the additive NaOAc exclusively affords isocoumarins through the [4 + 2] pathway.

N-Formamide as a carbonyl precursor in the catalytic synthesis of Passerini adducts under aqua and mechanochemical conditions.

A new simple, efficient, and environmentally friendly protocol is presented for the catalytic synthesis of α-acyloxycarboxamides using N-formamides as a carbonyl precursor under aqua and mechanochemical conditions. Immobilized sulfuric acid on silica gel was employed for the synthesis of desired products, via the reaction of benzoic acid, 1-napthylisocyanide and various heterocyclic N-formamides. After a careful optimization of the reaction conditions, the desired Passerini products were obtained in high to excellent yields in short reaction times (10-30 min) at room temperature. The highly efficient and environmentally friendly method provides a facile access to a library of α-acyloxycarboxamides derivatives for future research on bioactivity screening.

Insights into ultrasound-promoted degradation of naphthenic acid compounds in oil sands process affected water. Part II: In silico quantum screening of hydroxyl radical initiated and propagated degradation of benzoic acid

In Part I, we outlined the importance of sustainable sonochemical treatment to intensify oil sands process affected water (OSPW) treatment empirically and hypothesized degradation pathways. Herein, we elucidate the formation of intermediate products with well-defined molecular level solutions. Proposed mechanisms describe hydroxylation, decarboxylation and bond scission which drive the degradation of intermediates towards mineralization. This comprehensive first study on in silico screening of sonochemical degradation investigates quantum methods using density functional theory to explain the postulated degradation mechanisms through a theoretical radical attack approach, based on condensed Fukui reactivity indicators. A nudged elasticity band (NEB) approach is applied to find a minimum energy path (MEP), allowing the determination of intermediate products and energy barriers associated with naphthenic acid degradation. This approach provides structures and energies of the breakdown compounds formed along the reaction pathway enabling the determination of molecular reaction kinetics.In continuation of Part 1, the focus of this study is to evaluate sonochemically-induced hydroxyl radical (OH•) reactions of benzoic acid using density functional theory. Hydroxylation and decarboxylation mechanisms of the model naphthenic acid compound and its intermediates were simulated to determine the prospective pathway to ideal mineralization. DFT was applied to calculate interaction energies, Mulliken charges, Hirshfeld population analysis, dipole moments, frontier orbitals, and polarizability. Electronic properties and frontier orbital trends were also compared to computational work by Riahi et al.[1] to confirm the transition states by Nudged Elastic Band Transition State theory (NEB-TS). In combination with Hirshfeld Population analysis, Fukui indices suggest a more linear degradation pathway narrowed down from earlier experimental work by Singla et al.[2]. The linear free energy relationship for the newly suggested computational benzoic acid degradation can be determined by lnkTST/W=-1.677ΔG-15.41 with a R2 of 0.9997 according to classic transition state theory and Wigner tunneling. This computational method can be used to explore possible degradation pathways of other NAs and bridges molecular-to-macroscale sonochemical degradation of NA’s through a manifestation of molecular solutions.

Ruthenium(ii)-catalyzed synthesis of CF3-isoquinolinones via C–H activation/annulation of benzoic acids and CF3-imidoyl sulfoxonium ylides

The synthesis of 3-trifluoromethylisoquinolinones by a ruthenium(ii)-catalyzed C–H activation/annulation reaction of benzoic acids and CF3-imidoyl sulfoxonium ylides has been achieved.

THIONYL CHLORIDE INDUCED CONVENIENT SYNTHESIS OF BENZAMIDES FROM 3-BROMO-5-NITROBENZOIC ACID AND AMINES UNDER SOLVENT FREE CONDITIONS

A new method of thionyl chloride induced convenient synthesis of novel benzamides under solvent free conditions has been developed using benzoic acid and amines. The benzamides were synthesized through a coupling reaction of benzoic acid and different amines using thionyl chloride at room temperature. The abovementioned technique assists in the preparation of substituted benzamides which were obtained in good yields within 2-4 h using conventional heating. The developed method is flexible, economic, environment friendly; also is catalyst, ligand and solvent free and has major importance in industry and laboratory.

Kinetic modeling of benzoic acid esterification using functionalized silica gel

ABSTRACTIn our study, we synthesized two types of solid acid catalysts. Silica gel with a particle size of 0.063–0.2 mm was silanized first at reflux (S1) and second at room temperature (S3) using (3-mecaptopropyl)trimethoxysilane in toluene, and further oxidized with H2O2, and methanesulfonic acid. Characterization of the synthesized catalysts was performed using adsorption/desorption of nitrogen (BET), Fourier transform infrared spectroscopy, scanning electron microscopy, and thermogravimetric analysis. Both catalysts were used in esterification reactions of benzoic acid with methanol. All reactions were performed in a batch reactor at temperatures, ϑ = 55, 60, and 64.5°C, stirrer speed, fs = 400 min−1, and catalyst loading, m = 5, 10, and 15 g. The concentration of produced methylbenzoate was determined by HPLC. The study was supplemented with a kinetic study of the reaction. First-order kinetics was confirmed for this esterification reaction. Using catalyst S1, higher conversion was reached, while catalyst S3 is much more suitable for reuse.

ChemInform Abstract: Rhodium‐Catalyzed Tandem Dehydrogenative Coupling—Michael Addition: Direct Synthesis of Phthalides from Benzoic Acids and Alkenes.

AbstractThis new method provides access to phthalides by reaction of benzoic acids with vinyl ethyl ketone, methyl acrylate, N,N‐dimethylacrylamide, ethyl and phenyl vinyl sulfones with interesting regio‐ and chemoselectivity though often in moderate yields only.

ChemInform Abstract: Ruthenium‐Catalyzed Hydrocarboxylation of Internal Alkynes.

AbstractThe reaction of benzoic acids and alkynes proceeds with excellent E/Z‐selectivity furnishing the E‐isomers of the respective alkenylbenzoates only.

Synthesis and Biological Evaluation of Novel Mono Acid Esters Derived from the Constituents of Urtica pilulifera.

New mono acid esters have been synthesized from the reaction of benzoic acid and mono-hydroxybenzoic acids with 2-phenoxyethanol separated from Urtica pilulifera, characterized, and screened for possible antioxidant, antifungal, antimicrobial and anticancer activities. These phenolic acid esters gave various degrees of free radical scavenging, but the values were lower than that of α-tocopherol. The concentrations of the tested compounds needed to reduce DPPH absorption by 50% at 517 nm were nearly in the range of 900-1100 µg/mL. While for α-tocopherol was 40 µg /mL. The compounds were tested in-vitro against six bacterial species which are known to cause dermic and mucosal infections in human. 2-phenoxyethyl benzoate showed significant activity in the range of 30% against P. aeruginosa to 70% against E. coli compared with the activity of Streptomycin. On the other hand 2-phenoxyethyl 2-hydroxybenzoate reveals 70% of gentamicin against K. pneumoniae. The tested compounds also showed complete inhibition at a concentration less than 37.5 µg/mL against M. canis and less than 50 µg/mL against T. rubrum. 2-phenoxyethyl 4-hydroxybenzoate showed considerable activity against MCF-7 with IC50 is less than 62.5 µg/mL.

The Rational Synthesis of Fenidronate

The synthesis of the disodium salt of fenidronate by the reaction of benzoic acid with phosphorus trichloride and phosphorous acid in methanesulfonic acid was investigated and optimized. It was enough to use 3.2 equivalents of phosphorus trichloride and there was no need to apply phosphorous acid. Both the one-step and two-step versions led to similar results giving the product in ca. 45% yield and in high purity. It was also possible to start directly from benzoyl chloride or ethyl benzoate. The work-up included in all cases hydrolysis and pH adjustment followed by purification. The fenidronic acid standard that was necessary for the analysis of our samples was prepared by another approach, by the addition of dimethyl phosphite to the carbonyl group of the -oxophosphonate, followed by hydrolysis of the tetramethyl ester so formed. Keywords: Dronic acid, dronate, synthesis, intermediate, optimization, titration.

ChemInform Abstract: Synthesis and Antibacterial Activity of Isochromene and Isoquinoline Derivative.

AbstractNovel thiazolylisochromene derivative (VII) is synthesized by reaction of benzoic acid (V) with benzoin, and transformed into corresponding isoquinoline derivatives (IX).

New insights into the acid mediated disproportionation of pentavalent uranyl

The reaction of benzoic acid with the uranyl(V) complex [(UO(2)Py(5))(KI(2)Py(2))] in pyridine leads to immediate disproportionation with formation of a hexanuclear U(IV) benzoate cluster, a bis-benzoate complex of uranyl(VI) and water.

Catalytic and noncatalytic esterification and transesterification by subcritical methanol

The model reactions of benzoic acid (BA) esterification and ethyl benzoate (EB) transesterification by subcritical methanol were carried out for the first time at 220° C without catalysts in order to decrease the acid wastes from an industrially important reaction of the synthesis of biodiesel components. Methanol under these conditions is both a solvent and a catalyst. Benzoic acid is esterified in quantity even when the ratio of BA to methanol is 1: 3. Benzoic acid transesterification occurs with 82% conversion and a BA-to-methanol ratio of 1: 10. A process is proposed for biodiesel manufacturing from vegetable oil under the specified conditions and in the presence of a solid acid catalyst (sulfated TiO2, SnO2, or Al2O3). With the use of sulfated TiO2, biodiesel fuel yields can reach 98% at 170 °C. Our results can be used in the large-scale production of biodiesel fuel components because they show a way to seriously decrease costs for recycling acid emissions and the load on the environment.

Effect of reaction components on the hydrolytic stability of tetrabutoxytitanium as the catalyst of benzanilide synthesis

Tetrabutoxytitanium reacts with vebzoic acid and benzanilide in o-xylene under reflux to form complexes resistant to water. Indirect evidence for the composition of such complexes was obtained by IR spectral analysis of their hydrolysis products. Under comparable conditions, tetrabutoxytitanium and its complexes with aniline, butanol, and butyl benzoate undergo fast hydrolysis yielding hydrated titanium oxide that precipitates. In the reaction of benzoic acid with aniline, catalyzed by tetrabutoxytitaniumom, the latter, forming complexes with benzoic acid and benzanilide, is not prone to hydrolysis and changing its catalytic activity due to reaction with the liberated water.

DFT study of the structure of hydroxybenzoic acids and their reactions with [rad]OH and [formula omitted] radicals

B3LYP/6-31++G(d) method was used for the structural study of 3,4,5-trihydroxybenzoic acid (3,4,5-THBA), 3,4-dihydroxybenzoic acid (3,4-DHBA), and 4-hydroxybenzoic acid (4-HBA). Calculated structures agree with available X-ray experimental data within 2%. The phenolic O H bond dissociation enthalpy (BDE) of all sites in each benzoic acid were determined and compared with those of phenol (for 4-HBA) and catechol (for 3,4-DHBA). The consistency between the calculated values and experimental ones are within 5.4% and 9.2%, respectively, for 4-HBA and 3,4-DHBA. The reactions of benzoic acids with O 2 - and OH radicals were studied and it turns out that benzoic acids react differently with both radicals. We have shown that the reaction of hydroxybenzoic acids with the hydroxyl radical was governed by a phenolic hydrogen (H + + e −) transfer from the acid to the radical, while for the superoxide radical, the reaction is governed by a proton (H +) transfer from the acid to the radical. The first reaction is evidenced by the delocalization of the radical on the entire quinone moiety, and the second reaction is evidenced by the negative NBO charge on the phenoxide moiety as well as the localization of the radical on the hydroperoxy (O 2H) moiety.