Second-order Rate Constants K2 Research Articles

Lactone Enolates of Isochroman-3-ones and 2-Coumaranones: Quantification of Their Nucleophilicity in DMSO and Conjugate Additions to Chalcones.

Owing to stereoelectronic effects, lactones often deviate in reactivity from their open-chain ester analogues as demonstrated by the CH acidity (in DMSO) of 3-isochromanone (pKa = 18.8) and 2-coumaranone (pKa = 13.5), which is higher than that of ethyl phenylacetate (pKa = 22.6). We have now characterized the reactivity of the lactone enolates derived from 3-isochromanone and 2-coumaranone by following the kinetics of their Michael reactions with p-quinone methides and arylidenemalonates (reference electrophiles) in DMSO at 20 °C. Evaluation of the experimentally determined second-order rate constants k2 by the Mayr-Patz equation, lg k2 = sN(N + E), furnished the nucleophilicity parameters N (and sN) of the lactone enolates. By localizing their position on the Mayr nucleophilicity scale, the scope of their electrophilic reaction partners becomes predictable, and we demonstrate a novel catalytic methodology for a series of carbon-carbon bond-forming reactions of lactone enolates with chalcones under phase transfer conditions in toluene.

Effect of bovine serum albumin on gallic acid and tannic acid radical scavenging properties and binding kinetics with 2,2-diphenyl-1-picrylhydrazyl

A detailed study on gallic acid (GA), tannic acid (TA) antioxidant properties, and binding kinetics with 2,2-diphenyl-1-picrylhydrazyl radical (DPPH˙) in the presence of bovine serum albumin (BSA) was performed using electronic absorption (UV/Vis), fluorescence, and Fourier transform infrared (FTIR), spectroscopy methods. The effective concentration (EC50), antioxidant reducing power (ARP), stoichiometry (EC100), and the number of reduced DPPH˙(n) were determined using the DPPH˙ assay. It was shown that the antioxidant efficacy of GA/TA reduces slightly in the presence of BSA. However, the duration of the antioxidant activity of GA/TA increases as a result of the complex formation with BSA. The concentration of free and BSA-bound GA/TA was determined using fluorescence spectra. The rate constant (kobs), which describes the main reaction between antioxidant and DPPH˙, and the second-order rate constant (k2) were determined. FTIR studies showed that the binding of GA/TA with BSA causes conformational changes in the secondary structure of the protein (decrease of α-helixes, an increase of β-sheet structures). Moreover, TA induces more pronounced effects compared to GA.

Nucleophilicity of 4-(Alkylthio)-3-imidazoline Derived Enamines.

Imidazolidine-4-thiones (ITOs) are cyclic, secondary amines that were considered as potential prebiotic organocatalysts for light-driven α-alkylations of aldehydes by bromoacetonitrile (BAN). Recent studies showed that the initially supplied ITOs represent the pre-catalyst because they undergo S-alkylation with BAN to give 4-(alkylthio)-3-imidazolines (TIMs). Given that the same reagent mix that undergoes light-driven α-alkylations is also effective in the dark, we synthesized ten ITO- or TIM-derived enamines of aldehydes and characterized their nucleophilic reactivities by kinetic studies in acetonitrile. The experimental second-order rate constants k2 for reactions of enamines with benzhydrylium ions (reference electrophiles) were evaluated by the Mayr-Patz equation, lg k2 (20 °C)=sN (N+E). The determined nucleophilicities N (and sN ) reveal the reactivity profiles of these enamines under prebiotically relevant conditions as well as their potential for use in organocatalytic synthesis.

Selective oxidation of histamine H2-Receptor antagonists by peracetic Acid: Kinetics and mechanism

Peracetic acid (PAA) is an emerging substitutive oxidant to chlorine disinfectants owing to the low generation of harmful by-products. Herein, we report PAA-induced oxidation of histamine H2-receptor antagonists (HRAs) via non-radical participation for the first time. Results showed that PAA can selectively oxidize HRAs with high reactivity to ranitidine (RNTD), nizatidine (NZTD), cimetidine (CMTD), and famotidine (FMTD), but low reactivity to roxatidine (RXTD). PAA-induced HRAs oxidation followed the second-order kinetic reaction, the apparent second-order reaction rate constants (k2, app) of RNTD, FMTD, CMTD and NZTD were 18.78 ± (2.4), 37.22 ± (6.1), 36.53 ± (7.8), 30.04 ± (2.4) M−1•s−1, respectively. The value of k2, app decreased as pH increased. Scavenging experiments indicated that PAA-induced HRAs oxidation proceeded via a non-radical process. The theoretical calculation and product analysis further reveal that the reaction involves the double-electron transfer from thioether sulfur in HRAs to peroxide bond. HRAs oxidation by PAA was not affected by water matrices (Cl-, HCO3–, HA), which has good applicability in surface water (SW) and wastewater (WW). Toxicity assessment indicated ecotoxicity of oxidation products was much lower than that of HRAs. This work provided a facile and emerging technology to eliminate the HRAs and their toxicity in the wastewater.

Reactivity and mechanism of the reactions of 4-methylbenzoquinone with amino acid residues in β-lactoglobulin: A kinetic and product investigation

Quinones, produced by the oxidation of phenolic compounds, covalently bind to nucleophilic groups on amino acids or proteins. In this study, the reactions of 4-methylbenzoquinone (4MBQ) with β-lactoglobulin (β-LG) and amino acids at neutral pH were investigated. LC-MS analysis revealed that Cys121 was likely the most modified residue in β-LG. Identification of reaction products by LC-MS/MS showed that Michael addition occurred in all reactions with amino acids tested. The formation of Schiff base and a di-adduct was found in His and Trp samples. Apparent second-order rate constants (k2) were determined at 25 °C and pH 7.0 by stopped-flow spectrophotometry. The rate of reactions decreased in the order: β-LG > His > Trp > Arg > Nα-acetyl His > Nα-acetyl Arg > Nα-acetyl Trp. The rate constants correlated with the pKa values of the amino acids, showing that the amount of unprotonated amine is the major factor determining the reactivity.

Pushing the Upper Limit of Nucleophilicity Scales by Mesoionic N-Heterocyclic Olefins.

A series of mesoionic, 1,2,3-triazole-derived N-heterocyclic olefins (mNHOs), which have an extraordinarily electron-rich exocyclic CC-double bond, was synthesized and spectroscopically characterized, in selected cases by X-ray crystallography. The kinetics of their reactions with arylidene malonates, ArCH=C(CO2 Et)2 , which gave zwitterionic adducts, were investigated photometrically in THF at 20 °C. The resulting second-order rate constants k2 (20 °C) correlate linearly with the reported electrophilicity parameters E of the arylidene malonates (reference electrophiles), thus providing the nucleophile-specific N and sN parameters of the mNHOs according to the correlation lg k2 (20 °C)=sN (N+E). With 21<N<32, the mNHOs are much stronger nucleophiles than conventional NHOs. Some mNHOs even excel the reactivity of mono- and diacceptor-substituted carbanions. It is exemplarily shown that the reactivity parameters thus obtained allow to calculate the rate constants for mNHO reactions with further Michael acceptors and predict the scope of reactions with other electrophilic reaction partners including carbon dioxide, which gives zwitterionic mNHO-carboxylates. The nucleophilicity parameters N correlate linearly with a linear combination of the quantum-chemically calculated methyl cation affinities and buried volumes of mNHOs, which offers a valuable tool to tailor the reactivities of strong carbon nucleophiles.

Reactivity of electrophilic cyclopropanes.

Cyclopropanes that carry an electron-accepting group react as electrophiles in polar, ring-opening reactions. Analogous reactions at cyclopropanes with additional C2 substituents allow one to access difunctionalized products. Consequently, functionalized cyclopropanes are frequently used building blocks in organic synthesis. The polarization of the C1-C2 bond in 1-acceptor-2-donor-substituted cyclopropanes not only favorably enhances reactivity toward nucleophiles but also directs the nucleophilic attack toward the already substituted C2 position. Monitoring the kinetics of non-catalytic ring-opening reactions with a series of thiophenolates and other strong nucleophiles, such as azide ions, in DMSO provided the inherent SN2 reactivity of electrophilic cyclopropanes. The experimentally determined second-order rate constants k 2 for cyclopropane ring-opening reactions were then compared to those of related Michael additions. Interestingly, cyclopropanes with aryl substituents at the C2 position reacted faster than their unsubstituted analogues. Variation of the electronic properties of the aryl groups at C2 gave rise to parabolic Hammett relationships.

Kinetics of the reaction between Moringa oleifera leaf extracts and 2,2-diphenyl-1-picrylhydrazyl (DPPH) free radical

In this study, an antioxidant-rich extract was obtained by leaching Moringa oleifera leaves. The activity of the extract against the 2,2-diphenyl-1-picrylhydrazyl (DPPH) free radical was measured by determining a second-order rate constant (k2). The reaction between the mixture of antioxidants in the extract and the DPPH was monitored by measuring the absorbance at 517 nm in 30-second intervals for a period of 600 s. The absorbance exhibited a rapid decay within the first 100 s, followed by a slower decay. The absorbance data were fitted to a bi-exponential model. The curve fitting showed a linear relationship between the initial concentration of antioxidants and the reaction rate with the coefficient of determination values greater than 0.9979. The k2 value was 0.0870 ± 0.0007 mg/mL.

Oxidation of Hypophosphorous Acid by a Ruthenium(VI) Nitrido Complex in Aqueous Acidic Solution. Evidence for a Proton-Coupled N-Atom Transfer Mechanism.

The oxidation of hypophosphorous acid (H3PO2) by a ruthenium(VI) nitrido complex, [(L)RuVI(N)(OH2)]+ (RuVIN; L = N,N'-bis(salicylidene)-o-cyclohexyldiamine dianion), has been studied in aqueous acidic solutions at pH 0-2.50. The reaction has the following stoichiometry: 2[(L)RuVI(N)(OH2)]+ + 3H3PO2 + H2O → 2[(L)RuIII(NH2P(OH)2)(OH2)]+ + H3PO3. The pseudo-first-order rate constant, kobs, depends linearly on [H3PO2], and the second-order rate constant k2 depends on [H+] according to the relationship k2 = k[H+]/([H+] + Ka), where k is the rate constant for the oxidation of H3PO2 molecule and Ka is the dissociation constant of H3PO2. At 298.0 K and I = 1.0 M, k = (2.04 ± 0.19) × 10-2 M-1 s-1 and Ka = (6.38 ± 0.63) × 10-2 M. A kinetic isotope effect (KIE) of 2.9 ± 0.1 was obtained when kinetic studies were carried out with D3PO2 at pH 1.16, suggesting P-H bond cleavage in the rate-determining step. On the other hand, when the kinetics were determined in D2O, an inverse KIE of 0.21 ± 0.03 (H3PO2 in H2O vs H3PO2 in D2O) was found. On the basis of experimental results and DFT calculations, the proposed mechanism involves an acid-catalyzed tautomerization of H2P(O)(OH) to HP(OH)2; the latter molecule is the reacting species which reacts with RuVIN via a proton-coupled N-atom transfer pathway.

Biosorption of heavy metals: Transferability between batch and column studies

The design of an industrial water treatment system using sorption is based on laboratory column tests. To verify the applicability of a column sorption system at industrial scale, it is necessary to determine the system's breakthrough time (BT) in a laboratory setting. In a laboratory column set-up, BT is referred to as the time taken by the adsorbate to appear at column outlet for the first time. This is when the mass transfer zone (MTZ), where the equilibrium sorption occurs, reaches the end of the sorbent bed. However, such laboratory set-up requires significant resources including laboratory space, time and multiple trials, which is the opposite to the batch experimental approach that is commonly used to assess efficiency of sorbents. This study identified batch sorption parameters that can be used to determine BT for a column sorption setting for three toxic heavy metals commonly found in industrial wastewater, namely, Pb2+, Cd2+ and Cu2+. The study conducted a comprehensive evaluation of the relationships between column BT and its key influential factors, namely, equilibrium sorption capacity (qe), pseudo second-order kinetic rate constant (k2) and initial sorption rate (h). The results revealed that BT can be better estimated using h compared to qe and k2. As such, a batch experiment which is more resource efficient could be undertaken for an initial estimation of the experimental BT of a column system. Moreover, a simulation model developed to replicate column sorption could demonstrate the behaviour of the breakthrough curve, which is a key to the selection and assessment of the performance of a sorbent in an adsorbent column. The estimation errors in qe and k2 were found to influence the simulation outcomes. Hence, it is necessary to further investigate the other factors that can potentially influence sorption behaviour.

C(sp3)-H bond activation by the carboxylate-adduct of osmium tetroxide (OsO4).

The reaction of osmium tetroxide (OsO4) and carboxylate anions (acetate: X- = AcO- and benzoate: X- = BzO-) gave 1 : 1 adducts, [OsO4(X)]- (1X), the structures of which were determined by X-ray crystallographic analysis. In both cases, the carboxylate anion X coordinates to the osmium centre to generate a distorted trigonal bipyramidal osmium(VIII) complex. The carboxylate adducts show a negative shift of the redox potentials (E1/2) and a red shift of the νOsO stretches as compared to those of tetrahedral OsO4 itself. Despite the negative shift of E1/2, the reactivity of these adduct complexes 1X was enhanced compared to that of OsO4 in benzylic C(sp3)-H bond oxidation. The reaction obeyed the first-order kinetics on both 1X and the substrates, giving the second-order rate constant (k2), which exhibits a linear correlation with the C-H bond dissociation energy (BDEC-H) of the substrates (xanthene, 9,10-dihydroanthracene, fluorene and 1,2,3,4-tetrahydronaphthalene) and a kinetic deuterium isotope effect (KIE) of 9.7 (k2(xanthene-h2)/k2(xanthene-d2)). On the basis of these kinetic data together with the DFT calculation results, we propose a stepwise reaction mechanism involving rate-limiting benzylic hydrogen atom abstraction and subsequent rebound of the generated organic radical intermediate to a remaining oxido group on the osmium centre.

Amino Reactivity of Glutardialdehyde andMonoaldehydes─Chemoassay Profile vs Skin Sensitization Potency.

Chemoassay profiling of organic electrophiles through the direct peptide reactivity assay has become an OECD-accepted nonanimal component in the REACH evaluation of potential skin sensitizers. For aldehydes forming imines (Schiff bases), however, existing chemoassays yielded inconclusive results, indicating issues with their NH2 sensitivity and the reversibility of the reaction. In the present study, a new kinetic chemoassay employing the N terminus of glycine-para-nitroanilide, Gly-pNA, as a model nucleophile for protein NH2 groups is introduced and applied to nine aliphatic monoaldehydes and glutardialdehyde (1,5-pentanedial) that have log Kow (octanol/water partition coefficient) values from 0.63 to 3.99. The Gly-pNA second-order rate constants k1 range from 8.56 to 150 L·mol-1·min-1 for the monoaldehydes. Interestingly, glutardialdehyde with a k1 of 17 731 L·mol-1·min-1 is 170-fold more reactive than its monoaldehyde counterpart pentanal. This can be rationalized by hydration or tautomerization of the dialdehyde to monoaldehydic forms, now facilitating Schiff base formation through an intramolecular H bond. Comparison with murine local lymph node assay data from the literature reveals that adduct stability in terms of reaction thermodynamics (K = k1/k-1pseudo) rather than formation kinetics (k1) governs the skin sensitization potency of Schiff-base-forming aldehydes. The discussion includes analytically determined adduct patterns, and the impact of α- and β-carbon substitution as well as hydrophobicity on aldehyde reactivity.

Optimisation and kinetic modelling of atenolol degradation by ZnO under solar irradiation

ABSTRACT The aim of this study is to investigate the atenolol (ATL) degradation in aqueous suspension using commercial ZnO photocatalysts under solar irradiation. Effects of various operating parameters such as the ZnO dosage (0.025 to 0.075 g L−1), as well as pH ranges (3–12), and the ATL concentration (5–30 mg L−1) were also studied in a batch system. Results show that alkaline medium favoured the photocatalytic degradation of ATL (pH~7) and the best value of ZnO dosage occurred in 0.075 g L−1. Also, the removal rate increased with increasing ATL concentration. Kinetic data indicated that the photocatalytic kinetics followed the second-order model at high concentration of ATL, third-order model at low concentration, and first order model when adjusted pH. The second-order rate constant (k2) increases from 0.064 to 0.13 L mg−1 mn−1 when ZnO dosage increases from 0.025 to 0.2 g L,−1 respectively. As well, the pH rises from 3 to 7 the first-order rate constant (k1) increases from 0.35 to 1.56 mn−1. Then, at pH = 12 the rate constant (k1) decreases to 0.74 mn−1. The biodegradability, based on the BOD5 to COD ratio, increased with the increased photocatalysis time.

Mass-transfer kinetics of CO2 in a hybrid choline-2-pyrrolidine-carboxylic acid/polyethylene glycol/water absorbent

Understanding the mass-transfer kinetics of CO2 in novel hybrid absorbents with physical and chemical contributions is essential for process design and evaluation. In this study, the liquid-side mass-transfer coefficients (kL) and second-order reaction rate constants (k2) of CO2 in hybrid absorbents (namely, choline-2-pyrrolidine-carboxylic acid salt/polyethylene glycol/water ([Cho][Pro]/PEG200/H2O)) were determined. The kL values for the hybrid absorbents were obtained from the CO2 diffusion coefficients (DCO2) and the kL values in PEG200/H2O. The DCO2 value was calculated from the density and viscosity of the hybrid absorbents, whereas the kL values in PEG200/H2O were measured experimentally. The k2 values of CO2 in the hybrid absorbents were estimated according to the reaction mechanism, the enhancement factor, and the kL values, and compared with those of other commercialized absorbents. The results showed that 30 wt% [Cho][Pro] + 70 wt% H2O had the highest kL and k2 values at atmospheric pressure, whereas the values of kL and k2 of CO2 in 30 wt% [Cho][Pro]/H2O + PEG200 were comparable to those in diethanolamine aqueous and amino-functionalized ILs. The hybrid absorbent of [Cho][Pro]/PEG200/H2O could be promising for CO2 separation considering its thermodynamic and kinetic properties.

Low-Spin and High-Spin Perferryl Intermediates in Non-Heme Iron Catalyzed Oxidations of Aliphatic C-H Groups.

The selectivity patterns of iron catalysts of the Fe(PDP) family in aliphatic C-H oxidation with H2 O2 have been studied (PDP=N,N'-bis(pyridine-2-ylmethyl)-2,2'-bipyrrolidine). Cyclohexane, adamantane, 1-bromo-3,7-dimethyloctane, 3,7-dimethyloctyl acetate, (-)-acetoxy-p-menthane, and cis-1,2-dimethylcyclohexane were used as substrates. The studied catalyst systems generate low-spin (S=1/2) oxoiron(V) intermediates or high-spin (S=3/2) oxoiron(V) intermediates, depending on the electron-donating ability of remote substituents at the pyridine rings. The low-spin perferryl intermediates demonstrate lower stability and higher reactivity toward aliphatic C-H groups of cyclohexane than their high-spin congeners, according to the measured self-decay and second-order rate constants k1 and k2 . Unexpectedly, there appears to be no uniform correlation between the spin state of the oxoiron(V) intermediates, and the chemo- and regioselectivity of the corresponding catalyst systems in the oxidation of the considered substrates. This contrasts with the asymmetric epoxidations by the same catalyst systems, in which case the epoxidation enantioselectivity increases when passing from the systems featuring the more reactive low-spin perferryl intermediates to those with their less reactive high-spin congeners.

Measurement of the Absorption Rates of Carbon Dioxide in Aqueous Solutions of Piperazine and Sulfolane Using the Stopped-flow Technique

With the accelaration of the exploitation of natural gas reservoirs, the efficient removal of contaminants such as CO2, H2S, RSH, and COS is becoming of critical importance. In recent years, there is a growing interest in using amine blends or mixed solvents instead of a single amine for gas sweetening processes. Mixed solvents composed of a chemical solvent and a physical solvent take advantage of the benefits of both physical and chemical absorptions. The study of the absorption kinetics of the mixed solvent are necessary for designing and optimizing the process for removal of CO2 from natural gas, synthesis gas, or reformer gas. As a physical solvent, Sulfolane has excellent stability and low corrosiveness, in addition to a high capability for CO2 absorption. Sulfinol is a comercially successful process used in more than 200 plants and based on the use of Sulfolane as a physical solvent and either Diisopropanolamine (DIPA) or Methyldiethanolamine (MDEA) as chemical solvents. Mixed Sulfolane-based solvents have recently been proposed for post-combustion CO2 capture. In this study, the reaction kinetics of carbon dioxide (CO2) in aqueous solutions of aqueous piperazine (PZ) and an aqueous mixed solvent of (PZ + Sulfolane) were measured using the stopped flow technique resulting in the meaurement of observed pseudo-first-order rate constants (k0) allowing for the calculation of the second-order reaction rate constants (k2). The experiments were carried out over) concentration ranges of (10 to 60) for PZ, and (10 to 40, 10 to 200) (mol/m3) for PZ and Sulfolane, respectively and temperatures ranging from (298.15 to 313.15) K. Results show that the kinetic rates of the mixed solvent (PZ + Sulfolane + Water) were higher than those in aqueous PZ at all temperatures. The reaction kinetics in aqueous mixed solents of (PZ + Sulfolane) in reaction with CO2 increase with increasing temperature and concentration. The Termolecular mechanisms correlated the aqueous mixed systems of (PZ + Sulfolane) successfully. The reaction kinetics increased with the increase in temperature and concentration. The addition of Sulfolane to aqueous PZ resulted in increased absorption rates. Thus, the mixed solvent of PZ, Sulfolane and water can be considered an attractive alternative to aqueous amines for the enhancement of CO2 capture.

C-H Activation by an Iron-Nitrido Bis-Pocket Porphyrin Species.

High-valent iron-nitrido species are nitrogen analogues of iron-oxo species which are versatile reagents for C-H oxidation. Nonetheless, C-H activation by iron-nitrido species has been scarcely explored, as this is often hampered by their instability and short lifetime in solutions. Herein, the hydrogen atom transfer (HAT) reactivity of an Fe porphyrin nitrido species (2 c) toward C-H substrates was studied in solutions at room temperature, which was achieved by nanosecond laser flash photolysis (LFP) of its FeIII -azido precursor (1 c) supported by a bulky bis-pocket porphyrin ligand. C-H bonds with bond dissociation enthalpies (BDEs) of up to ≈84 kcal mol-1 could be activated, and the second-order rate constants (k2 ) are on the order of 102 -104 s-1 m-1 . The Fe-amido product formed after HAT could further release ammonia upon protonation.

Assessing the nucleophilic character of 2-amino-4-arylthiazoles through coupling with 4,6-dinitrobenzofuroxan: Experimental and theoretical approaches based on structure-reactivity relationships

A kinetic study of the reactions of potentially bioactive 2-amino-4-arylthiazoles with highly reactive 4,6-dinitrobenzofuroxan (DNBF) is reported herein in acetonitrile solution. The complexation reaction was followed by recording the UV–vis spectra with time at λmax = 482 nm. Electronic effects of substituents influencing the rate of reaction have been studied using structure-reactivity relationships. It is shown that the Hammett plot relative to the reaction of DNBF with 2-amino-4-(4-chlorophenyl)thiazole exhibit positive deviation from the log k1 versus σ correlation, while it showed excellent linear correlation in terms of Yukawa–Tsuno equation. It has be noticed that the nonlinear Hammett plot observed for 2-amino-4-(4-chlorophenyl) thiazole is not attributed to a change in rate-determining step but is due to nature of electronic effect of substituent caused by the resonance of stabilization of substrates. The second-order rate constant (k1) relating to the bond C–C and C-N forming step of the complexation processes of DNBF with 4-substituted-aminothiazoles and 2-amino-5-methyl-4-phenylthiazole, respectively, is fit into the linear relationship log k = sN (N + E), thereby permitting the assessment of the nucleophilicity parameter (N) of the 2-amino-4-arylthiazoles of the range (4.90 < N < 6.85). 2-amino-4-arylthiazoles is subsequently ranked by positioning its reactivity on the general nucleophilicity scale developed recently by Mayr and coworkers (2003) leading an interesting and a direct comparison over a large domain of π-, σ -, and n-nucleophiles. The global electrophilicity/nucleophilicity reactivity indexes of the 2-amino-4-arylthiazoles have been investigated by means of a density functional theory (DFT) method. .

Kinetic modeling and evaluation of free radical-scavenging behavior in oils: application to four tropical and subtropical fruits in a DPPH system

Abstract A kinetic model was developed to represent the radical-scavenging capacity (RSC) for the oxidation of oils. The model was developed using second-order rate constants (k2) to represent the RSC. The RSC of the oils can be compared by the k2 values indicating their scavenging capacity. Furthermore, the k2 values can be used to determine the decay kinetic of oils prone to attack by free radicals and to determine the amount of antiradicals that should be added as protective agent to these oils. As a case study, the antiradical capacity of four oils produced from tropical and subtropical fruits (avocado, nance, palm and peach palm) were studied using the DPPH• assay.

N-(Hydroxybenzyl)benzamide Derivatives: Aqueous pH-Dependent Kinetics and Mechanistic Implications for the Aqueous Reactivity of Carbinolamides.

The rate constants for the aqueous reaction, between pH 0 and 14, have been determined for a series of amide substituted N-(hydroxybenzyl)benzamide derivatives, in H2O, at 25 °C, I = 1.0 M (KCl). The N-(hydroxybenzyl)benzamide derivatives were found to react via three distinct mechanisms with the kinetically dominant mechanism being dependent on the pH of the reaction solution. It has been shown that the carbinolamides react via a specific-base-catalyzed mechanism (E1cB-like) under basic and pH neutral conditions. At lower pH values, an acid-catalyzed mechanism was kinetically dominant and, last, a water reaction was postulated at pH values where neither the hydroxide-dependent nor the general-acid-catalyzed mechanism was dominant. Contrary to earlier studies with N-(hydroxymethyl)benzamide compounds, no evidence for mechanistic variation based upon the nature of the amidic substituent was observed for any of the N-(hydroxybenzyl)benzamide derivatives studied between pH values of 0-14. The rate for the acid-catalyzed reaction (kH, ρ = -1.17), the apparent second-order hydroxide rate constant (k1', ρ = 0.87), the hydroxide-independent rate (k1, ρ = 0.65), and the pKa's of the hydroxyl group of the carbinolamide (ρ = 0.23) are reported.