Reaction Of Benzoic Acid Research Articles

Investigation of MWNTs/PBO nanocomposite polymerization mechanism with model compound

AbstractA model compound was obtained by reaction of benzoic acid and 4,6‐diamino‐1,3‐dihydroxybenzene dihydrochloride (DADHB · 2HCl) in the presence of functionalized multiwall carbon nanotubes (FMWNTs). FMWNTs were formed on raw multiwall carbon nanotubes (MWNTs) by chemical modification. The model compound was rinsed by chloroform and MWNTs were separated by centrifuge. The sediment yielded was denoted as graft multiwall carbon nanotubes (GMWNTs). Then X‐ray photoelectron spectroscopy (XPS), Raman spectroscopy, and Fourier‐transform infrared (FTIR) were used to investigate the existence of covalent bond between DADHB and FMWNTs. The results of XPS showed that nitrogen atoms amounted to about 3.3% except for oxygen and carbon on the surface of GMWNTs. Meantime, the reaction of COOH of the FMWNTs and themonomer DADHB occurred, and benzoxazole was formed predominantly by Raman spectroscopy analysis. FTIR spectroscopy confirmed the covalent grafting of monomer to FMWNTs in the processing procedure. As a result, the mechanism of the reaction of the poly(p‐phenylenebenzoxazole) (PBO) oligomer and FMWNT composites was deduced according to the reaction of the model compound. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007

An Efficient Waste-Free Oxidative Coupling via Regioselective C−H Bond Cleavage: Rh/Cu-Catalyzed Reaction of Benzoic Acids with Alkynes and Acrylates under Air

[structure: see text]. The direct oxidative coupling of benzoic acids with internal alkynes proceeds efficiently in the presence of a rhodium/copper catalyst system under air to afford the corresponding isocoumarin derivatives. The reaction forms no wastes except for water. Under similar conditions, the aerobic coupling with acrylates also takes place smoothly to produce 7-vinylphthalide derivatives via divinylation and subsequent cyclization.

Synthesis, X-ray crystal structures and biomimetic and anticancer activities of novel copper(II)benzoate complexes incorporating 2-(4′-thiazolyl)benzimidazole (thiabendazole), 2-(2-pyridyl)benzimidazole and 1,10-phenanthroline as chelating nitrogen donor ligands

Cu(BZA) 2(EtOH) 0.5 ( 1) was generated by the reaction of copper(II) hydroxide with benzoic acid (BZAH). [Cu(TBZH) 2(BZA)](BZA) · 0.5TBZH · H 2O ( 2) and [Cu(2-PyBZIMH)(2-PyBZIM)(BZA)] · 1.66EtOH ( 3) were obtained when 1 reacted with Thiabendazole (TBZH) and 2-(2-pyridyl)benzimidazole (2-PyBZIMH), respectively. [Cu(BZA) 2(phen)(H 2O)] ( 4) was isolated from the reaction of benzoic acid and 1,10-phenanthroline (phen) with copper(II)acetate dihydrate. Molecular structures of 2, 3 and 4 were determined crystallographically. 2 and 3 are hydrogen bonded dimers and trimers, respectively. The copper centres in complexes 2 and 3 are bis-chelate derivatives that have N 4O ligation and their geometry is very similar being approximately square-pyramidal. However whereas in complex 2 both TBZH ligands are neutral in 3 one of the 2-PyBZIMH chelators is deprotonated on each copper. The structural results for 4 represent a re-examination of this crystallographically known compound for which no hydrogen atom coordinates have been previously reported. It crystallises as a hydrogen bonded dimmer and is a mono-chelate of phen with each copper centre possessing N 2O 3 ligation and square pyramidal geometry. The catalase and superoxide dismutase (SOD) activities of the four complexes along with those of the known phenanthroline complexes [Cu(mal)(phen) 2] and [Cu(phendione) 3](ClO 4) 2 (malH 2 = malonic acid and phendione = 1,10-phenanthroline-5,6-dione) were investigated. Complexes 1– 4, the metal free ligands and a simple copper(II) salt were assessed for their cancer chemotherapeutic potential against the hepatocellular carcinoma (Hep-G 2) and kidney adenocarcinoma (A-498) cell lines. TBZH, 2-PyBZIMH and benzoic acid when uncoordinated to a metal centre offer poor chemotherapeutic potential. copper(II) benzoate is significantly more active than the free acid. The bis-chelate derivatives [Cu(TBZH) 2(BZA)](BZA) · 0.5TBZH · H 2O ( 2) and [Cu(2-PyBZIMH)(2-PyBZIM)(BZA)] · 1.66EtOH ( 3) elicit a significant cytotoxic response to the cancer cell lines tested. Replacing TBZH and 2-PyBZIMH with phen to give [Cu(BZA) 2(phen)(H 2O)] ( 4) does not significantly increase the anti-cancer activity.

Tetraaqua(1,10-phenanthroline-N,N′)manganese(II) dinitrate

The title compound, [Mn(C12H8N2)(H2O)4](NO3)2, was obtained from the reaction of benzoic acid, 1,10-phenanthroline and manganese nitrate tetrahydrate. The Mn atom is coordinated in a distorted octahedral arrangement by four water mol­ecules and two N atoms from the phenanthroline ligand.

Substituted styrenes-maleic anhydride copolymers?Measurements of the reactivity ratios with high conversions and relations between molecular masses and viscosity

Three substituted styrenes were respectively synthesized by reaction of benzoic acid, acetic acid, and methanol with vinylbenzylchloride, then copolymerized with maleic anhydride. The measurements of the reactivity ratios of these three copolymerizations were carried out with a method using high conversions of the reactions. The results show a good correlation between a linear alternating structure for one of the copolymers and an alternating and a partially crosslinked structure for the two others. The copolymerizations were also performed with various percentages of initiator, giving similar proportions of incorporated monomers in the resulting products, and a relation between their viscosities and their weight molecular masses was presented.

NMR Identification of an Acyl-adenylate Intermediate in the Aryl-aldehyde Oxidoreductase Catalyzed Reaction

A new one-pot synthesis was designed to prepare benzoyl-AMP under anhydrous conditions in N,N-dimethylformamide. Reaction of benzoic acid with N,N'-carbonyldiimidazole and subsequently with 5'-adenosyl monophosphate gave the mixed anhydride in 76% isolated yield. The structure of benzoyl-AMP was confirmed by mass spectroscopy and 1H-, 31P-, and 13C-NMR. The purity of the preparation was greater than 98% as indicated by 31P- and 13C-NMR. Purified aryl-aldehyde oxidoreductase was incubated in NMR tubes together with either carboxy-13C-benzoyl-AMP or carboxy-13C-benzoic acid to demonstrate that benzoyl-AMP is an active intermediate during the enzymatic reduction of benzoic acid to benzaldehyde.

Oxidative Cross-Coupling of N-(2‘-Phenylphenyl)benzene- sulfonamides or Benzoic and Naphthoic Acids with Alkenes Using a Palladium−Copper Catalyst System under Air

N-(2‘-Phenylphenyl)benzenesulfonamides react with acrylate esters accompanied via cleavage of the C−H bond at their 2‘-position in the presence of a catalyst system of Pd(OAc)2 and Cu(OAc)2 and a base under air to produce 5,6-dihydro-5-(benzenesulfonyl)phenanthridine-6-acetate derivatives in high yields. The reactions of benzoic acid with butyl acrylate and styrene can also give 3-[(butoxycarbonyl)methyl]phthalide and 3-phenylisocoumarin, respectively.

Natural formation of chlorobenzoic acids (CBA) and distinction between PCB-degraded CBA

Mono- and dichlorobenzoic acid (CBA) could be found in samples of remote bog pond water and sediment. The 2,4-CBA always had the highest concentrations. In bog water samples the concentrations ranged between 0.11 and 0.48 μg/I. Besides 2,4-CBA, most only 2,5-CBA could be found as dichlorobenzoic acid. In all samples we could detect also trichloroacetic acid (TCAA). The TCAA concentrations correlate with the CBA concentrations. As TCAA is known as a naturally produced organohalogen, this correlation can be seen as an indication to a natural formation of CBA. A confirmation of this presumption is our detection of CBA in a reaction of benzoic acid with the chlorinating enzyme chloroperoxidase (CPO).

The reaction ofn-butyllithium with benzoic acid: is nucleophilic addition competitive with deprotonation?

An evaluation of a branching vs sequential mechanism for the reaction of benzoic acid with n-butyllithium favors the latter. © 1997 John Wiley & Sons, Ltd.

ChemInform Abstract: Catalysis Using Phosphorus Compounds in the Reaction of Benzoic Acid with Aniline.

AbstractChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 100 leading journals. To access a ChemInform Abstract of an article which was published elsewhere, please select a “Full Text” option. The original article is trackable via the “References” option.

Polymer-Supported Bases. XI. Esterification and Alkylation in the Presence of Polymer-Supported Bicyclic Amidine or Guanidine Moieties

Abstract Polymer-supported 1,5,7-triazabicyclo[4.4.0]deca-5-ene (TBD) was prepared by the reaction of chloromethylated polystyrene resins, cross-linked with 2 mol% of divinylbenzene, with TBD. The reaction of benzoic acid with bromobutane was carried out in toluene or acetonitrile in the presence of polymer-supported TBD or polymer-supported 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU). The rate of esterification was dependent on the ring substitution of the supported bases and the solvent. The reduced ring substitution resulted in the increased swellability of the polymeric beads containing benzoate or bromide ions for toluene and thereby in the increased reaction rate. The rate with the high ring-substituted bases increased in acetonitrile, because of the high swellability of the immobilized salts and the high nucleophilicity of benzoate anion in the solvent. The supported bases were also effective for alkylation of an active methylene compound with bromoalkane.

Mass spectrometric synthesis—III Gas phase ion/molecule reaction between benzoic acid and some substituted phenols

AbstractThe reaction of benzoic acid with some substituted phenols, carried out in the chemical ionization source of a mass spectrometer and under high pressure conditions leads to phenyl benzoate. This has been proved by accurate mass measurements and collision activated dissociation mass‐analysed ion kinetic energy spectra. The intimate mechanisms of this reaction are discussed in detail.

Direct polyesterification promoted by a complex of phosphorus oxychloride with LiCl monohydrate

AbstractThe reaction of benzoic acid and p‐chlorophenol with phosphorus oxychloride (POC) was significantly affected by the presence of metal salt hydrates or a mixture of metal salts and water sufficiently aged. Among metal salts examined, LiCl was most effective for the reaction to give quantitative yield of the benzoate. The reaction was assumed to proceed via a complexation of POC with LiCl monohydrate followed by selective hydrolysis of POC by water bound to LiCl. The reaction promoted by a complex derived from POC and LiCl monohydrate in pyridine was successfully used as a new condensing agent for the synthesis of aromatic polyesters by the direct polycondensation or aromatic dicarboxylic acids and bisphenols. Under favorable conditions for aging of POC with LiCl monohydrate and for addition of bisphenols, polymers of moderate to high molecular weights were obtained in quantitative yield. The reaction was applied with limited success to the preparation of a copolymer of high molecular weight from hydroxybenzoic acids.

Reaction kinetics of the reaction of terephthalic acid and ethylene carbonates

AbstractThe kinetics of the reaction of terephthalic acid with a number of ethylene carbonates in the presence of an amine catalyst were examined. All reactions apparently follow first‐order kinetics; therefore, the solution rate of TPA is not rate‐limiting. With minor adjustments, the mechanism appears to be in accord with that of the model reaction of benzoic acid and ethylene carbonate previously reported. Attack of the carboxylate on the carbonate ring must be the rate‐limiting step. Substituent effects (owing to substituents on the carbonate ring) appear to be mostly steric in nature; surprisingly, an n‐octyl group causes the slowest reaction. Besides being strongly influenced by steric hinderance, the transition state appears to be highly polar. Activation energy (16.0 kcal/mol) and activation entropy (−23.6 cal/deg) are very similar to those of the model reaction.

Study of step‐growth polymerizations using epoxy‐carboxy reaction, 3. General analysis of the results obtained on models in various solvents

AbstractA global analysis of the kinetic results relating to a model reaction of epoxy‐carboxy polycondensation is reported. The model is the reaction of benzoic acid with 1‐phenoxy‐2,3‐epoxypropane carried out in the presence of N,N‐dimethyldodecylamine as catalyst. The hypothesis concerning the contribution of two competitive ractions as suggested in the two preceding parts of this series is subjected to a mathematical treatement. This allowed the determination of the rate constants of each reaction. All the kinetic characteristics obtained in a broad range of experimental conditions fit the reaction scheme, which is described in detail. Exceptions are found for borderline cases. The rate constants of the reaction of the classical dependence on dielectric constant and temperature. Activation parameters of each reaction are reported.

Synthesis of 4H‐3,1‐benzoxazin‐4‐ones and 4‐(3H)quinazolinones from anthranilic acids and their derivatives by the use of triphenyl phosphite and pyridine

AbstractA series of 2‐substituted 4H‐3,1‐benzoxazinones and 2,3‐disubstituted 4‐(3H)quinazolinones have been synthesized in mild conditions by the use of triphenyl phosphite and pyridine as cyclising medium. Benzox‐azinones are produced either by ring closure of 2‐(acylamino)benzoic acids or in the reaction of benzoic acid with anthranilic acids. In the presence of aniline, the reaction leads to quinazolinones.

The reaction of benzoyl peroxide with trimethylphenyltin: a polar mechanism of formation of trimethyltin benzoate

The mechanism of the reaction which gives trimethyltin benzoate by thermal decomposition of benzoyl peroxide in the presence of trimethylphenyltin was investigated. Reaction of benzoic acid, which was derived from the peroxide, with the tin compound was shown to give the benzoate.

The separation of polar and steric effects. Part XIII. Kinetics of the reactions of cinnamic acid and meta-substituted cinnamic acids with diazodiphenylmethane in various alcohols and in aprotic solvents

Rate coefficients have been determined for the reactions at 30 °C of diazodiphenylmethane with cinnamic acid and meta-substituted cinnamic acids (substituents: Me, Cl, or NO2) in 12 alcohols, in ethyl acetate, and in acetone.The reactions of cinnamic acid with diazodiphenylmethane in alcohols show a good linear free-energy relationship with the corresponding reactions of benzoic acid. The solvent effect can be interpreted in terms of the dielectric constant and the influence of hydrogen bonding. Multiple linear correlation with three suitable solvent parameters is quite successful. Comparisons are made with the benzoic and the phenylacetic acid system.The Hammett ρ-values (ρ3) for the reactions of cinnamic acids are correlated with solvent parameters and comparisons are made with ρ-values for the benzoic (ρ1) and the phenylacetic (ρ2) acid system. The expressions ρ3= 0.39ρ1, and ρ2= 0.60 (ρ1– 0.25) hold, and are interpreted in terms of Bowden, Chapman, and Shorter's treatment of the transmission of polar effects through side-chains.

The Reaction of Benzoic Acid with Phenyl Glycidyl Ether

The reaction of phenyl glycidyl ether (PGE) with benzoic acid (BA) catalyzed by tertiary amines and quarternary ammonium salts has been studied. The reaction catalyzed by quarternary ammonium salts is in goed agreement with second-order kinetics, according to-d[PGE]/dt=-d[BA]/dt=k, [PGE], [Cat. ]The tertiary amine catalyzed reaction, especially at the beginning ef the reaction, proceeds at a slewer rate than the reaction in the presence of quaternary ammonium salts. ln the reaction of PGE with BA in the prescnce of tertiary amines, catalyst amines react with PGE to form quarternary ammonium carboxylate salts, which is the actual catalyst in this reaction. The strtcture of the alkyl groups of amines has a large influence on the catalytic activity. ln the case of quarternary ammonium catalyst, the structure of alkyl groups does no affect the catalytic activity, but the type ef aniori associated with quarternary salt is very important.

The separation of polar and steric effects. Part XII. The influence of protic and aprotic solvents on the kinetics of the reactions of benzoic acid with diazodiphenylmethane

Rate coefficients have been determined for the reactions at 30 °C of diazodiphenylmethane with benzoic acid in 10 alcohols so that, with earlier work, results are now available for this reaction in 20 alcohols of very varied structures. The kinetic solvent effect can be interpreted in terms of the dielectric constant of the solvent and the influence of hydrogen bonding (solvent basicity or acidity). Multiple linear correlation of log k with the Kirkwood function of dielectric constant and the Taft σ* value for the alkyl group of the alcohol is highly successful (r= 0·983), but an additional parameter is necessary to express the rate enhancing effect of branching at the β-carbon atom of the alcohol. The most useful third parameter is nγH, the number of γ-hydrogen atoms in the alcohol molecule, giving r= 0·991.Apparent second-order rate coefficients have also been determined for the reactions at 37 °C of diazodiphenylmethane with benzoic acid in 22 aprotic solvents. Values determined for a range of initial concentrations of acid have been extrapolated to obtain values of k0, the rate coefficient at [acid]= 0. The effect of solvent on k0 can be interpreted in terms of the effect of the dielectric constant and the basicity of the solvent, but multiple linear correlation of log k0 with a suitable function of dielectric constant and a measure of solvent basicity (two are available) is only moderately successful (r=ca. 0·91). Attempts to improve the correlations by including the refractive index as a measure of ‘dynamic dielectric constant’ have met with little success. Detailed examination of the pattern of results suggests the relevance of other factors but at present these cannot be incorporated as additional parameters in the correlations.In both protic and aprotic solvents the specific role of the solvent is more important than its general electrostatic effect.