- Kinetics of hydrolysis in aqueous solution of 1-benzoyl-1,2,4-triazole; the role of pairwise and triplet Gibbs energy interaction parameters in describing the effects of added salts and added alcohols
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Kinetic data are reported for the spontaneous hydrolysis of 1-benzoyl-1,2,4-triazole in aqueous solutions at ambient pressure and 298.2 K, in aqueous solutions containing added ethanol, propanol and sodium chloride.Kinetic data are also reported for the same reaction in aqueous mixtures of sodium chloride and ethanol.When either ethanol or propanol are added the rate constant k decreases, plotes of ln(k) vs. molality of alcohol being linear.The patterns are accounted for using pairwise Gibbs energy interaction parameters.The rate constant k decrease more dramatically when sodium chloride is added.This pattern is accounted for using pairwise and triplet interaction parameters.The dependence of rate constant on molality of added ethanol in solutions containing fixed molalities of sodium chloride deviaties from that predicted using the pairwise interaction parameters indicating a non-additivity of salt and alcohol effects on the rate constant.The deviations increase wirh increase in molalities of both added salt and added solvent in a direction consistent with a disruption of the substrate-alcohol hydrophobic interactions by added salt.
- Noordman, Wouter H.,Blokzijl, Wilfried,Engberts, Jan B. F. N.,Blandamer, Michael J.
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- SURFACTANT-POLYMER INTERACTIONS AND THEIR EFFECTS ON THE MICELLAR INHIBITION OF THE NEUTRAL HYDROLYSIS OF 1-BENZOYL-1,2,4-TRIAZOLE.
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Binding of sodium dodecyl sulfate (SDS) to atactic poly(N-vinylpyrrolidone) (PVP) has been studied by conductivity measurements. It is proposed that in addition to normal micelles of SDS an additional pseudophase of mixed micelles of PVP and SDS is present in solution. The effect of polymer-surfactant binding on the catalytic/inhibitive activity of SDS micelles has been investigated by studying the rates of the pH-independent hydrolysis of 1-benzoyl-1,2,4-triazole (1). Though the polymer itself has no effect on the hydrolysis reaction in water, addition of PVP to SDS solutions decreases the micellar inhibition, and pseudo-first-order rate constants (k//o//b//s//d) are higher than those in the absence of PVP. Ultrafiltration experiments using a model substrate indicate increased solubility of the substrate in the micellar pseudophase upon addition of PVP.
- Fadnavis,Engberts
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- Kinetic Medium Effects of Amphiphilic Cosolutes below Their Critical Micelle Concentration: The Effect of Sodium n-Alkyl Sulfates on the Neutral Hydrolysis of 1-Benzoyl-1,2,4-triazole
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Kinetic medium effects are presented for sodium n-alkyl sulfates (R = methyl to n-octyl) on the neutral hydrolysis of 1-benzoyl-1,2,4-triazole at 298.15 K in highly aqueous solutions below the critical micellar concentration.The observed rate-decreasing effects are quantitatively analyzed in terms of pairwise solute-solute interactions.It is shown that the effect of the alkyl chains cannot be accounted for on the basis of additivity of pairwise group interactions involving individual methylene moieties.Apparently, the sulfate group shields methylene moieties in close proximity for intermolecular interactions.Methylene groups, further away from the ionic functionality, are shielded less effectively.At the critical micellar concentration of the longer-chain sodium n-alkyl sulfates, the observed medium effects change dramatically as expected on the basis of the onset of micellization.No clear indication for premicellar aggregation was found.The medium effect of the sulfate moiety is estimated by extrapolation of kinetic medium effects to zero methylene groups and appears to be rate-retarding as well.
- Noordman, Wouter H.,Blokzijl, Wilfried,Engberts, Jan B. F. N.,Blandamer, Michael J.
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- Effect of Poly(methacrylic acid) Hypercoils on the Neutral and Acid-Catalyzed Hydrolyses of 1-Acyl-1,2,4-triazoles in Aqueous Solution
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Rates and thermodynamic activation parameters have been measured for the neutral and acid-catalyzed hydrolyses of the 1-acyl-1,2,4-triazoles 1-3 in the presence of atactic poly(methacrylic acid) (at-PMAA).Under the employed reaction conditions at-PMAA resides in a coiled, compact conformation.The rates of hydrolysis of the relatively hydrophilic 1-acetyl- (1) and 1-benzoyl-1,2,4-triazole (2) are only little affected by the presence of the polymer.By contrast, the hydrolysis of the hydrophobic 1-benzoyl-3-phenyl-1,2,4-triazole (3) is effectively inhibited as a result of binding of 3 to hydrophobic microdomains within the at-PMAA hypercoil.Only small rate retardations are found for the hydrolysis of 3 in the presence of poly(acrylic acid).The effect of at-PMAA concentration on the rates of hydrolysis of 3 can be described in terms of a kinetic scheme that is essentially a variant of Michaelis-Menten enzyme kinetic formalism.In the presence of at-PMAA, ΔH(excit.) and ΔS(excit.) for the neutral hydrolysis of 3 undergo large and partly compensatory changes, the retardations being dominated by the increase of ΔH(excit.).These findings are interpreted by assuming reduced hydration of the dipolar transition state for hydrolysis in the relatively "dry" hydrophobic microdomains.Comparable results were obtained for the HCl-catalyzed hydrolysis of 3.The inhibitory effect of at-PMAA on this reaction is attenuated in the presence of urea, presumably because of destabilization of the compact conformation of the polymer.
- Jager, Jan,Engberts, Jan B. F. N.
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- Kinetics of hydrolysis of 1-benzoyl-1,2,4-triazole in aqueous solution as a function of temperature near the temperature of maximum density, and the isochoric controversy
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At temperatures above and below the temperature of maximum density, TMD, for water at ambient pressure, pairs of temperatures exist at which the molar volumes of water are equal. First-order rate constants for the pH-independent hydrolysis of 1-benzoyl-1,2,4-triazole in aqueous solution at pairs of such isochoric temperatures show no unique features. Taken together with previously published kinetic data for the hydrolysis of a range of simple organic solutes in both water and D2O near their respective TMDs, we conclude that special significance in the context of rates of chemical reactions in aqueous solutions should not be attached to the isochoric condition.
- Blandamer, Michael J.,Buurma, Niklaas J.,Engberts, Jan B.F.N.,Reis, Joao C.R.
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- ATTEMPTED GENERATION AND STRUCTURE OF THE 4-(1,2,4-TRIAZOYL) CATION
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4-(and 1-) Amino-1,2,4-triazoles have been treated with nitrosonium tetrafluoroborate or with isoamyl nitrile and acetic acid in the presence of mesitylene.The main product is 1,2,4-triazole, together with a small amount of the 1- and trace amounts of the 4-mesityl derivatives.Ab initio calculations of the putative 4-(1,2,4-triazoyl) cation show the electronic ground state to be a closed shell singlet 1A1 (4? e) (3), with a low-lying 3B1 triplet (4) only 1 kcal/mol above it; the ?-cation (1) is not a local minimum on the potential energy surface.Possible explanations of the results are proposed.
- Abramovitch, Rudolph A.,Gibson, Harry H.,Nguyen, Terry,Olivella, Santiago,Sole, Albert
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- Water-Catalyzed Amide Hydrolysis in Dilute Aqueous Carbohydrate Solutions
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Rates and thermodynamics activation parameters were determined for the water-catalyzed hydrolysis of the activated amide bond in three 1-acyl-1,2,4-triazoles of different hydrophobicity by using dilute aqueous solutions of simple carbohydrates as the reaction medium.The solutions show thermodynamically almost ideal behavior.It appears that the kinetic medium effects, and, in particular, the changes in ΔS. are largely determined by carbohydrate-induced alterations in the three-dimensional hydrogen-bond network of water.The specific, hydration model for carbohydrates, developed by Franks and his associates, appears to provide a key to the understanding of the carbohydrate medium effects on the hydrolytic model reaction
- Nusselder, Jan Jaap H.,Engberts, Jan B. F. N.
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- Kinetics of Neutral Hydrolysis of Two 1-Acyl-1,2,4-triazoles in Binary Aqueous Mixtures: A Critique of the Evans and Polanyi Proposals Concerning Isochoric Activation Parameters
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Kinetic data are reported for hydrolysis of two 1-acyl-1,2,4-triazoles in water and two isodielectric mixtures which belong to different classes of aqueous mixtures.Trends in isothermal and isobaric activation parameters are examined in light of both solute-solvent interactions.Comments by Evans and Polanyi concerning an isochoric constraint are considered.Attention is drawn to the difficulties of satisfying the original criteria and to the possibility of using the internal pressure of the solvent as a way of satisfying in part the requirements of the Evans-Polanyi formalism.
- Haak, Jan R.,Engberts, Jan B. F. N.,Blandamer, Michael J.
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- Water-Catalyzed Hydrolysis of 1-Acyl-1,2,4-triazoles in the Presence of Surfactant-Polymer Mixed Micelles. Substrate Dependence of the Effect of Polymer on the Micellar Inhibition
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The water-catalyzed hydrolysis of 1-benzoyl-1,2,4-triazole (1) is inhibited by SDS micelles.Addition of poly(vinylalcohol)-poly(vinyl acetate) copolymers (17percent and 26percent acetate, respectively) leads to a decreased inhibition.As supported by conductivity measurements, the rate effects are attributed to the formation of SDS-copolymer mixed micelles.Ultrafiltration experiments indicate increased binding of the substrate to the mixed micelles.Therefore the copolymer-induced rate accelerations can be best reconciled with an increase in the micropolarity at the substrate binding sites in the mixed micelles relative to unperturbed SDS micelles.With the aid of a computer, all kinetic data can be fitted into a kinetic scheme assuming hydrolysis of 1 in bulk water and in SDS and SDS-copolymer micellar pseudophases.Hydrolysis in SDS-poly(N-vinylpyrrolidone) (PVP) mixed micelles at low SDS concentrations (3-10 mM) was studied with the more hydrophobic substrate 3-phenyl-1-benzoyl-1,2,4-triazole (3).Now the SDS-induced inhibition is further increased by the polymer.Kinetic analysis shows that 3 is less strongly bound to mixed SDS-PVP micelles than to SDS micelles but that the rate constants in both micellar pseudophases are rather similar.It is argued that the different behavior of 1 and 3 in the mixed micelles primarily reflects the large propensity of 3 for stabilization by hydrophobic interactions.
- Fadnavis, Nitin W.,Berg, Henk-Jan van den,Engberts, Jan B. F. N.
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- Remarkably Distinctive Recognition of α-Alanine and α-Phenylalanine during the Water-Catalyzed Hydrolysis of an Activated Amide
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The rate of the water-catalyzed hydrolysis of three activated amides in aqueous solution is significantly retarded by small amounts of α-phenylalanine as compared with the rate acceleration induced by other common α-amino acids not containing a benzyl group in their side chain.These contrasting effects emphasize the large hydrophobicity of α-phenylalanine and are of relevance for a better quantitative understanding of protein folding and molecular recognition processes involving proteins.
- Streefland, Lisette,Blandamer, Michael J.,Engberts, Jan B. F. N.
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- AN ANALYSIS OF COMPLEX ALKYL-SUBSTITUENT EFFECTS IN THE WATER-CATALYZED HYDROLYSIS OF 1-ACYL-1,2,4-TRIAZOLES
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Pseudo-first-order rate constants and thermodynamic activation parameters have been determined for the water-catalyzed hydrolysis of the 1-acyl-1,2,4-triazoles 1-9 in water and in aqueous acetonitrile .The reaction occurs via water-catlalyzed nucleophilic attack of water at the amide carbonyl group.Variation of the alkyl group in the acyl part of the substrate led to the sequence of reactivities (in water): R= t-Bu > i-Pr > Et > Me > n-Pr > s-Bu > i-Pent > neo-Pent.This complex behaviour strogly suggest the operation of a composite steric effect most likely involving contributions from conformational preference (SE1), change of coordination number at carbonyl carbon (SE2), steric repulsion between O2 and the alkyl group (SE3), and steric inhibition of solvation (SE4)> Modelling of the relative rates in water in terms of the expanded branching equation gave satisfactory results.Two pssible transition states are proposed for the neutral hydrolysis, one involving intramolecular hydrogen bonding between the second water molecule and N2 of the 1,2,4-triazole ring .The different sequence of reactivities for neutral hydrolysis in aqueous acetonitrile as well as the rates for hydroxide-ion-catalyzed hydrolysis in water (BAc2 machanism) support the analysis of substituent effects.
- Mooij, Herman J.,Engberts, B. F. N.,Charton, Marvin
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- Dearomatization of oxa- or selenadiazolopyridines with neutral nucleophiles as an efficient approach to pharmacologically relevant nitrogen compounds
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Highly electrophilic 6-nitro-4-azabenzofuroxan and 6-nitro-4-azabenzo[1,2,5]selenadiazole add π-excessive (het)arenes and other neutral nucleophiles at 7-position to give C–C and N–C-bonded adducts, 1,4-dihydropyridines fused with furoxan or selenadiazole ring.
- Starosotnikov, Alexey M.,Shkaev, Dmitry V.,Bastrakov, Maxim A.,Fedyanin, Ivan V.,Shevelev, Svyatoslav A.,Dalinger, Igor L.
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p. 638 - 640
(2018/12/13)
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- Method for synthesizing triazazole
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The invention belongs to the technical field of organic chemical synthesis, particularly relates to a triazole synthesis method and aims at using methyl ethyl ketazine to replace hydrazine hydrate so as to provide a low-cost and high-yield 1,2,4-triazole preparation method. The technical scheme is that the triazole synthesis method comprises the following steps of enabling ammonia, hydrogen peroxide and butanone to react with the presence of formamide to prepare the methyl ethyl ketazine; separating an upper-layer oil phase containing the methyl ethyl ketazine from a water phase containing the formamide, evaporating the ammonia, the butanone and water in the water phase to recover the formamide; rising the temperature of the formamide to be 165 DEG C-190 DEG C, then dropwise adding the oil phase into the formamide, performing heat preservation reaction at the temperature ranging from 165 DEG C to 190 DEG C for 20-60 minutes, recovering incompletely-reacted methyl ethyl ketazine through distillation to obtain 1,2,4-triazole. By means of the triazole synthesis method, the 1,2,4-triazole with purity higher than 95% can be obtained, and the yield is higher than 95% (by formamide).
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Paragraph 0057-0058
(2017/02/23)
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- Synthesizing process of 1H-1,2,4-triazole
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The invention discloses a synthesizing process of 1H-1,2,4-triazole, comprising the following synthesizing steps: (1) adding formic ether, hydrazine hydrate and ammonium salt in sequence into a high-pressure reaction kettle, pressurizing the reaction kettle and gradually heating up to a reaction temperature under a sealed stirring state, gradually lowering down the reaction temperature after the reaction is complete and using the after heat to evaporate the byproduct methyl alcohol, thereby obtaining a white emulsion matter; (2) transferring the white emulsion matter into the reaction kettle, adding ethyl alcohol, heating and refluxing to obtain a mixture solution, hot filtering the mixture solution by a filter cartridge into a crystallization kettle, cooling the filtrate inside the crystallization kettle to room temperature, separating out white crystals, drying by a hot air drying oven after centrifugal separation, thereby obtaining the 1H-1,2,4-triazole. The synthesizing process of the 1H-1,2,4-triazole allows the hydrazine hydrate to react with the formamide which is obtained by direct ammonolysis of the ammonia obtained from the decomposition of the formic ether and the ammonium salt under the high temperature conditions, thereby effectively increasing the entire chemical reaction speed, reducing the reaction temperature and increasing the product output, with simple overall synthesizing process, lower energy consumption and few three-waste discharge.
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Paragraph 0074; 0075; 0076;
(2016/11/28)
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- Exploiting the Imidazolium Effect in Base-free Ammonium Enolate Generation: Synthetic and Mechanistic Studies
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N-Acyl imidazoles and catalytic isothiourea hydrochloride salts function as ammonium enolate precursors in the absence of base. Enantioselective Michael addition–cyclization reactions using different α,β-unsaturated Michael acceptors have been performed to form dihydropyranones and dihydropyridinones with high stereoselectivity. Detailed mechanistic studies using RPKA have revealed the importance of the “imidazolium” effect in ammonium enolate formation and have highlighted key differences with traditional base-mediated processes.
- Young, Claire M.,Stark, Daniel G.,West, Thomas H.,Taylor, James E.,Smith, Andrew D.
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p. 14394 - 14399
(2016/11/11)
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- A new class of bioactivable self-immolative N,O-ligands
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A hexadentate ligand built on an amine-bis(phenol) skeleton with an aminal, self-immolative moiety is presented. Synthesis of the ligand is convenient and relatively high yielded. Moreover, it enables synthesis of many derivatives, both in the amino-phenol and aminal fragment (various heterocycles). Once the final hexadentate ligand is synthesized via the Katritzky reaction, it becomes prone to hydrolysis. Bioactivation by β-galactosidase cleaves the glycosylic bond and a spontaneous collapse of the aminal fragment occurs, thus leading to a pentadentate chelate. This bioactivation has been shown for pyrazole, 1,2,4-triazole and benzotriazole derivatives.
- Ku?nik, Nikodem,Chrobaczyński, Arkadiusz,Mika, Ma?gorzata,Miler, Patrycja,Komor, Roman,Kubicki, MacIej
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supporting information; experimental part
p. 184 - 192
(2012/07/28)
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- The nature of the sodium dodecylsulfate micellar pseudophase as studied by reaction kinetics
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The nature of the rate-retarding effects of anionic micelles of sodium dodecyl sulfate (SDS) on the water-catalyzed hydrolysis of a series of substituted 1-benzoyl-1,2,4-triazoles (1a-f) has been studied. We show that medium effects in the micellar Stern region of SDS can be reproduced by simple aqueous model solutions containing small-molecule mimics for the surfactant headgroups and tails, namely sodium methyl sulfate (NMS) and 1-propanol, in line with our previous kinetic studies for cationic surfactants (Buurma et al. J. Org. Chem. 2004, 69, 3899-3906). We have improved our mathematical description leading to the model solution, which has made the identification of appropriate model solutions more efficient. For the Stern region of SDS, the model solution consists of a mixture of 35.3 mol dm-3 H2O, corresponding to an effective water concentration of 37.0 mol dm-3, 3.5 mol dm -3 sodium methylsulfate (NMS) mimicking the SDS headgroups, and 1.8 mol dm-3 1-propanol mimicking the backfolding hydrophobic tails. This model solution quantitatively reproduces the rate-retarding effects of SDS micelles found for the hydrolytic probes 1a-f. In addition, the model solution accurately predicts the micropolarity of the micellar Stern region as reported by the ET(30) solvatochromic probe. The model solution also allows the separation of the individual contributions of local water concentration (water activity), polarity and hydrophobic interactions, ionic strength and ionic interactions, and local charge to the observed local medium effects. For all of our hydrolytic probes, the dominant rate-retarding effect is caused by interactions with the surfactant headgroups, whereas the local polarity as reported by the solvatochromic ET(30) probe and the Hammett ?? value for hydrolysis of 1a-f in the Stern region of SDS micelles is mainly the result of interactions with the hydrophobic surfactant tails. Our results indicate that both a mimic for the surfactant tails (NMS) and a mimic for the surfactant headgroups (1-propanol) are required in a model solution for the micellar pseudophase to reproduce all medium effects experienced by a variety of different probes. ? 2011 American Chemical Society.
- Onel, Lavinia,Buurma, Niklaas J.
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experimental part
p. 13199 - 13211
(2012/02/14)
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- Heterocyclization of 3-(R-amino)-3-methylthio-1-phenylpropenones and 5-benzoyl-6-methylthio-1,2-dihydropyridin-2-ones with 1,2- and 1,3-dinucleophilic reagents
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The interaction of 3-(R-amino)-3-methylthio-1-phenylpropenones and 1-alkyl-5-benzoyl-3-ethoxy-carbonyl-6-methylthio-1,2-dihydropyridin-2-ones with N,N- and N,C-1,2- and 1,3-dinucleophiles proceeded regioselectively by [3+2] and [3+3] cyclocondensation with the formation of derivatives of pyrazole, benzimidazo[1,2-a]-pyridine, benzimidazo[1,2-a]pyrimidine, imidazo[1,2-a] pyrimidine, [1,2,4]triazolo[4,3-b]pyridazine, and 6,7-dihydro-2H-pyrazolo[3,4-b] pyridine. The regioselectivity of the reactions carried out was analyzed.
- Britsun,Pikun,Ryabitskii,Lozinskii
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experimental part
p. 970 - 976
(2012/03/26)
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- Synthesis of amides of 2,4-dioxothiazolidin-5-yl acetic acid with 1,2,4-triazole substituents
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In the reaction of (2,4-dioxothiazolidin-5-yl)acetyl chloride with 1,2,4-triazole, 4-phenyl-1,2,4-triazolin-5-one and 4-phenyl-1,2,4-triazolin-5- thione, the new corresponding amides (2-4) were obtained. For compounds 2 and 4 effects on central nervous system (CNS) of mice were studied.
- Trotsko, Nazar,Dobosz, Maria,Chodkowska, Anna,Jagiello-Wojtowicz, Ewa
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body text
p. 217 - 221
(2009/04/04)
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- The nature of the micellar Stern region as studied by reaction kinetics. 2
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The nature of rate-retarding effects of cationic micelles on the water-catalyzed hydrolyses of a series of para-substituted 1-benzoyl-1,2,4-triazoles (1a-f) and 1-benzoyl-3-phenyl-1,2,4-triazole (2) has been studied using kinetic methods. A comparison is drawn between medium effects in the micellar Stern region and in model solutions for the micellar Stern region. Simple model solutions involving concentrated aqueous solutions of a small ionic molecule resembling the surfactant headgroup, as reported before, were improved. New model solutions for alkyltrimethylammonium bromide micelles contain both tetramethylammonium bromide (TMAB), mimicking micellar headgroups, and 1-propanol, mimicking hydrophobic tails. The rate-retarding effect of micelles on the hydrolysis of 1a-f and 2 is caused by the high concentration of headgroups as well as by hydrophobic tails in the Stern region where 1a-f and 2 bind to the micelle. Individual contributions of these interactions are quantified. Rate-retarding effects found for different probes, with different sensitivities for interactions as they occur when the probe binds to the micellar Stern region, as well as the micellar Stern region's micropolarity as reported by the ET(30) probe, are satisfactorily reproduced by new model solutions containing both TMAB and 1-propanol.
- Buurma, Niklaas J.,Serena, Paola,Blandamer, Michael J.,Engberts, Jan B. F. N.
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p. 3899 - 3906
(2007/10/03)
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- Substituted amino methyl factor Xa inhibitors
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The present application describes substituted-aminomethyl substituted compounds and derivatives thereof, or pharmaceutically acceptable salt forms thereof, which are useful as inhibitors of factor Xa.
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- Oxazole PPAR antagonist
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A method is disclosed for rational design of a PPAR, FXR, LXR-alpha, or LXR-beta antagonist comprising chemical modification of a PPAR, FXR, LXR-alpha, or LXR-beta agonist to: a) prevent formation of a hydrogen bond between the agonist and tyrosine or histidine, or tryptophan involved in receptor activation; and/or b) displace the tyrosine or histidine, or tryptophan involved in receptor activation from its agonist bound position. Preferably, little or no additional changes are made in the structure of the agonist so that the resulting antagonist is a close structural analogue of the agonist. Specific examples of PPAR gamma antagonists designed and prepared using the method of this invention are compounds of Formula (I) or (II), or pharmaceutically acceptable salts or solvates thereof, where in Formula (I) X is O, S, or NH; and R is methyl, ethyl, n-propyl, i-propyl, cyclopropyl, n-butyl, phenyl, or —CH2OCH3and wherein in Formula (II) X is C or N; and R is methyl, ethyl, n-propyl, i-propyl, —CH2OCH3, or —CO2CH3.
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- Anti-HCV nucleoside derivatives
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The present invention comprises novel and known purine and pyrimidine nucleoside derivatives which have been discovered to be active against hepatitis C virus (HCV). The use of these derivatives for the treatment of HCV infection is claimed as are the novel nucleoside derivatives disclosed herein.
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- Trisubstituted heterocyclic compounds and their use as fungicides
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Compounds of general formula (I): in which:Het represents a five or six membered saturated, partially unsaturated or aromatic ring containing between one and six heteroatoms of the group N, O, S, in which the heterocycle is substituted in an adjacent manner with -P-Q1-T-Q2, -GZ and Y, such that the substituant -GZ is adjacent to both. the other substituants being as defined in the description,process for preparing these compounds,fungicidal compositions comprising these compounds,processes for treating plants by applying these compounds or compositions.
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- Heteroaryl-phenyl substituted factor Xa inhibitors
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The present application describes heteroaryl-phenyl substituted compounds and derivatives thereof, or pharmaceutically acceptable salt or prodrug forms thereof, which are useful as inhibitors of factor Xa.
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- Heteroaryl- phenyl heterobicyclic factor Xa inhibitors
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The present application describes heteroaryl-phenyl heterobicycles and derivatives thereof, or pharmaceutically acceptable salt forms thereof, which are useful as inhibitors of factor Xa.
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- The 1,2,4-triazolyl cation: Thermolytic and photolytic studies
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The generation of the 1,2,4-triazolyl cation (1) has been attempted by the thermolysis and photolysis of 1-(1,2,4-triazol-4-yl)-2,4,6-trimethylpyridinium tetrafluoroborate (2) and the thermolysis of 1- and 4-diazonium-1,2,4-triazoles, using mainly mesitylene as the trapping agent. Thermolysis of 2 gave mostly 1,2,4-triazole, together with 3-(1,2,4-triazol-4-yl)-2,4,6-trimethylpyridine, 4-(1,2,4-triazol-4-ylmethyl)-2,6-dimethylpyridine, and 4-(2,4,6-trimethylbenzyl)-2,6-dimethylpyridine. Thermolysis, of each of the diazonium salts in the presence of mesitylene again gave mainly triazole together with very low yields of 1-(1,2,4-triazol-1-yl)-2,4,6-trimethylbenzene and the corresponding -4-yl isomer in about the same ratio. On the other hand, photolysis of 2 in mesitylene gave mainly 1-(1,2,4-triazol-1-yl)-2,4,6-trimethylbenzene. A photoinduced electron transfer from mesitylene to 2 has been observed and preliminary laser flash photolyses of 2 and the corresponding 2,4,6-triphenylpyridinium salt have been carried out. The observed transients are explained as arising from the first excited states of the pyridinium salts rather than from 1. Ab initio MO calculations are reported and indicate that the predicted electronic ground-state of the triazolyl cation is a triplet state of B1 symmetry with five π electrons, which corresponds to a diradical cation (1c). Possible mechanisms for the formation of the various products are proposed.
- Abramovitch,Beckert,Gibson Jr.,Belcher,Hundt,Sierra,Olivella,Pennington,Sole
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p. 1242 - 1251
(2007/10/03)
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- Benzimidazolinones, benzoxazolinones, benzopiperazinones, indanones, and derivatives thereof as inhibitors of factor Xa
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The present application describes inhibitors of factor Xa of formula I: or pharmaceutically acceptable salt forms thereof, wherein W, W1, W2, and W3may be N or C and J, Ja, and Jbcombine to form a substituted carbocycle or heterocycle.
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- Hydrolysis of N-cyanoazoles
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The hydrolysis kinetics of N-cyanoazoles in alkaline solutions is described by a first-order kinetic equation with respect to the substrate and concentration of hydroxide ions. The hydrolysis rate constants increase with increasing number of nitrogen atoms in the heterocyclic moiety and decrease with introduction of the annelated benzene ring.
- Pan'kov,Belyakova,Vishnyakov,Purygin
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p. 763 - 766
(2007/10/03)
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- 6-membered aromatics as factor Xa inhibitors
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The present application describes 6-membered aromatics of formula I: or pharmaceutically acceptable salt forms thereof, wherein D may be CH2NH2 or C(=NH)NH2, which are useful as inhibitors of factor Xa.
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- Orthoamides. LIV. Contributions to the chemistry of azavinylogous orthoformic acid amide derivatives
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The azavinylogous aminalester 3 reacts with primary amines to give amidines 5 and 6. In the reaction of 3 with aniline the azavinylogous amidine 7 is produced additionally to the amidine 5c. Ethylendiamine is formylated at both aminogroups, the bis-amidine 8 thus formed is transformed to the salts 9a,b. Benzoxazole and benzimidazole can be prepared from 3 and o-aminophenol and o-phenylenediamine, resp. Carboxylic acid amides, urea, thiourea, aromatic acid hydrazides 17 and the sulfonylhydrazide 19 are formylated by 3 at nitrogen to give N-acylated formamidines 14, 16, 18, 20. From 3 and aliphatic acid hydrazides 17 and alkylhydrazines, resp., can be obtained 1,2,4-triazole 21 and 1-alkyl-1,2,4-triazoles 22a,b, resp. N.N-Dimethylcyanacetamide (32) reacts with 3 and the orthoamide 4a, resp., to give a mixture of the formylated compound 34 and the amidine 33. The reaction conditions are of low influence on the ratio in which 33 and 34 are formed. The orthoamide 4b and 32 react to afford a mixture of the amidine 35 and the enamine 36. Hydrogen-sulfide acts on 3 giving N,N-dimethylthioformamide (37). From 3 and 1-alkynes 41 can be prepared the amidines 42. Hydrolysis of 42b affords phenylpropiolaldehyde (43). The alkylation of the aminalester 3 gives rise to the formation of vinylogous amidinium salts 1c and 1d, resp., additionally is formed the amide acetal 2a. The salt 1d can also be prepared from 3 and borontrifluoride-ether. Iodide reacts with N,N-dimethylformamide acetals 12a,b in an unclear, complicated manner giving orthoesters 53, N,N-dimethylformamide, alkyliodides, alcohols, ammonium iodides 46 and carbondioxide. The action of halogens on 3 affords the salts 1a,b,c,e,f depending on the chosen stoichiometric ratio. Aromatic aldehydes are suited for trapping azavinylogous carbenes formed on thermolysis of 3; 1,3-oxazoles 69 are the reaction products. From 3 and propionaldehyde the amidine 65 can be obtained with low yield. Carbondisulfide transforms 3 to the azavinylogous salt 66. The preparation of the azavinylogous orthoamide 4a is described. The thermolysis of 3 and 4a, resp., gives rise to the formation of the triaminopyrimidine 67. Treatment of 1a with lithium diisopropylamide affords the triaminopyrazine 68, which can also be obtained by thermolysis of 3 in the presence of sodium hydride. Azavinylogous carbenes are thought to be the intermediates. Wiley-VCH Verlag GmbH, 2000.
- Kantlehner, Willi,Hauber, Michael,Haug, Erwin,Schallenmueller, Claus,Regele, Claudia
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p. 682 - 699
(2007/10/03)
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- Pairwise Gibbs energies of interaction involving N-alkyl-2- pyrrolidinones and related compounds in aqueous solution obtained from kinetic medium effects
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Kinetic solvent effects of N-alkyl-2-pyrrolidinones and structurally related compounds on the water-catalyzed hydrolysis reactions of p- methoxyphenyl dichloroacetate (MPDA), 1-benzoyl-3-phenyl-1,2,4-triazole (BPhT), and 1-benzoyl-1,2,4-triazole (BT) in highly dilute aqueous solutions at pH 4 and 298.15 K have been determined by UV/vis spectroscopy. Using a thermodynamic description of solute-solute interactions in aqueous solutions, the kinetic results have been analyzed in terms of pairwise Gibbs energy interaction parameters: G(c) values. These are negative, indicating that hydrophobic interactions in the initial state dominate the medium effects. The interaction parameters increase in the order MPDABT>BPhT. However, when differences in reactivity and transition state effects are taken into account, it appears that BPhT is more successful in establishing hydrophobic interactions with the cosolutes than are MPDA and BT. Using the SWAG-approach for additivity of group interactions, additivity is observed for the first three consecutive CH2 groups in the cosolute in all three hydrolysis reactions. Larger alkyl substituents cause larger retardations than anticipated on basis of this additivity. The results are explained by intramolecular destructive overlap of the polar hydration shell of the amide functionality and the apolar (hydrophobic) hydration shell of the alkyl group, which extends to the third CH2 group in the N-alkyl group of the cosolute molecule. The inner apolar groups, therefore, have a reduced apparent hydrophobicity. More remote CH2 groups develop independent hydrophobic hydration shells. The effect of the position of a CH2 group in the cosolute molecule is also considered. Kinetic solvent effects with structurally related esters show that amide-amide, ester-ester, and amide- ester group interactions affect the transition state in different ways. Finally, the effects of PVP polymers on the three hydrolysis reactions have been examined. The data presented enhance the understanding of pairwise hydrophobic interactions in aqueous solutions. In addition the results provide insights into the interactions between hydrophobic and hydrophilic hydration shells as well as into the energetics of amide hydration and interactions involving amides in aqueous solution, both playing important roles in protein stabilization.
- Apperloo, Joke J.,Streefland, Lisette,Engberts, Jan B. F. N.,Blandamer, Michael J.
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p. 411 - 418
(2007/10/03)
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- α-branched anilines, toluenes, and analogs thereof as factor Xa inhibitors
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The present application describes m-amidino phenyl analogs of formula I: wherein D can be amidino and E can be phenyl, which are useful as inhibitors of factor Xa.
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- N-(AMIDINOPHENYL) CYCLOUREA ANALOGS AS FACTOR XA INHIBITORS
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The present application describes N-(amidinophenyl)cyclourea analogs of formula I: STR1 which are useful as inhibitors of factor Xa.
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- INHIBITORS OF FACTOR XA WITH A NEUTRAL P1 SPECIFICITY GROUP
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The present application describes inhibitors of factor Xa with a neutral P1 specificity group of formula I: STR1 or pharmaceutically acceptable salt forms thereof, wherein R and E may be groups such as methoxy and halo.
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- Nucleophilic activation of hydrogen peroxide. On the formation and the reactivity of 1H-1,2,4-triazoleperoxycarboxylic acid and O-p-nitrophenylmonoperoxycarbonic acid
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Measurements of the infrared phosphorescence of singlet molecular oxygen (1O2) at 1270 nm have been employed to demonstrate the formation of 1O2 in the system N,N′-carbonyldi-1,2,4-triazole (CDT)-hydrogen peroxide and in the system 1H-1,2,4-triazolecarboxylic acid p-nitrophenyl ester (TCNP)-hydrogen peroxide in tetrahydrofuran. At hydrogen peroxide concentrations of [H2O2] ≥ 2 [CDT] or ≥ 2 [TCNP] one molecule of 1O2 is generated per molecule of CDT and TCNP, respectively. In both systems a very reactive peroxy-intermediate is formed. In the system CDT-H2O2 the 1H-1,2,4-triazoleperoxycarboxylic acid (1) is generated, in TCNP-H2O2 the p-nitrophenylmonoperoxy-carbonic acid (4). For the epoxidation of cyclohexene in THF by 1 a rate constant k15 ≈3 x 100 dm3 mol-1 s-1 can be estimated. For 4 the corresponding rate constant was found to be k20 ≈ 6 x 10-2 dm3 mol-1 s-1. The Arrhenius parameters of the formation of 1 and 4, respectively, and in addition of their consecutive reactions with hydrogen peroxide were determined. The results are consistent with the assumption that the nucleophilic displacements by hydrogen peroxide at the carbonyl carbon atom are addition-elimination processes, which take the form of a BAC2-mechanism.
- Bender, Carsten,Brauer, Hans-Dieter
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p. 2579 - 2587
(2007/10/03)
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- Method of producing 1,2,4-triazole
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A method of producing 1,2,4-triazole, comprising a step of subjecting a ketazine, water and formamide to a cyclization reaction. The ketazine and water are added simultaneously to formamide kept at a cyclization temperature. Then, ketone by-produced during the cyclization reaction is distilled off while maintaining the reaction mixture at a cyclization temperature to complete the cyclization reaction, thereby obtaining 1,2,4-triazole. The use of the ketazine in place of hydrazine makes the energy-consuming hydrolysis step in the conventional hydrazine production unnecessary. Therefore, the method of the invention is advantageous over the known methods in energy consumption and production cost.
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- Alkoxy isothiocyanates, RO-N=C=S
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Methoxy isothiocyanate has been identified as a product of pyrolysis of the silver salt of N-methoxydithiocarbamic acid. It is also formed on FVT of 1-(N-methoxythiocarbamoyl)imidazole and 1-(N-methoxythiocarbamoyl)-1,2,4-triazole. Methoxy isothiocyanate was identified by IR spectroscopy in argon matrices at 10 K supported by good agreement with the ab initio and DFT calculated spectrum. Isopropoxy isothiocyanate was generated from the corresponding silver salt in a similar manner. The oligomerization of MeONCS to trithiolanes and tetrathianes is also described.
- Bech, Allan T.,Flammang, Robert,Pedersen, Carl Th.,Wong, Ming Wah,Wentrup, Curt
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p. 1869 - 1873
(2007/10/03)
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- QUINOXALINEDIONE NMDA RECEPTOR ANTAGONISTS
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Compounds of formula (I): STR1 and their pharmaceutically acceptable salts, wherein R 1 and R 2 are each independently Cl, Br, CH 3, CH 2 CH 3 or CF 3 ; R 3 is H, CH 3 or CH 2 CH 3 ; and X is a 5-membered heterocyclic group containing up to four nitrogen atoms, attached via a nitrogen atom, the said group being optionally substituted by C 1-C 6 alkyl or (CH 2) n NR 4 R 5, wherein n is an integer from 1 to 5 and R 4 and R. sup.5 are each independently H, C. sub.1-C 6 alkyl, C 3-C 6 cycloalkyl or C 1-C 4 alkyl substituted by phenyl or pyridyl, or R 4 and R 5 are linked to form, together with the nitrogen atom to which attached, a pyrrolidine, piperidine, piperazine, N-(C 1-C. sub.4 alkyl) piperazine, morpholine or azepine group, or, when X is triazolyl, said group may optionally be benzofused, are NMDA antagonists of value in the treatment of acute neurodegenerative disorders, e.g. arising from stroke or traumatic head injury and in chronic neurological disorders, e.g. senile dementia and Alzheimer's disease.
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- Photodegradation of Azole Fungicide Triadimefon
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To examine the photostability of the fungicide triadimefon [1-(4-chlorophenoxy)-3,3-dimethyl-1H-(1,2,4-triazol-1-yl)butan-2-one] in the field, model experiments with organic solvents were performed. Photolysis in methanol, hexane, and acetone resulted in considerable formation of 1-(4-chlorophenoxy)-3,3-dimethylbutan-2-one, 1-[(4-chlorophenoxy)methyl]-1H-1,2,4-triazole, 1H-(1,2,4-triazol-1-yl)-3,3-dimethylbutan-2-one, and 1-phenoxy-3,3-dimethyl-1H-(1,2,4-triazol-1-yl)butan-2-one. The rate of photodegradation in different solvents followed first-order rate kinetics with a significant correlation coefficient.
- Nag, Subir K.,Dureja, Prem
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p. 294 - 298
(2007/10/03)
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- L-2',3'-dideoxy nucleoside analogs as anti-hepatitis B (HBV) and anti-HIV agents
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The present invention relates to the surprising discovery that certain dideoxynucleoside analogs which contain a dideoxy ribofuranosyl moiety having an L-configuration (as opposed to the naturally occurring D-configuration) exhibit unexpected activity against Hepatitis B virus (HBV). In particular, the compounds according to the present invention show potent inhibition of the replication of the virus in combination with very low toxicity to the host cells (i.e., animal or human tissue). Compounds according to the present invention exhibit primary utility as agents for inhibiting the growth or replication of HBV, HIV and other retroviruses, most preferably HBV. The compound 1-(2,3-dideoxy-beta-L-ribofuranosyl)-5-fluorocytosine is shown to be a potent anti-HIV agent with low toxicity to host cells.
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- Kinetic medium effects of cationic cosolutes in aqueous solution: The effects of alkylammonium bromides on the neutral hydrolysis of 1-benzoyl-1,2,4-triazole
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We have investigated the kinetic effects of alkylammonium, alkyldimethylammonium, alkyltrimethylammonium and tetraalkylammonium bromides on the water-catalysed hydrolysis of 1-benzoyl-1,2,4-triazole at pH 4 and 25 °C. All cosolutes retard the reaction. The retardation is attributed to a dominant stabilisation of the initial state through hydrophobic interactions with the cosolute. The results are analysed in terms of pairwise Gibbs energy interaction parameters. These G(C) values show that alkyl groups shorter than propyl have no significant influence on the medium effect. The extensively hydrated ammonium groups prevent the formation of a well developed hydrophobic hydration shell by methylene moieties in its vicinity. We observe additivity of kinetic effects of methylene groups outside the ionic hydration sphere on the hydrolysis reaction. Pairwise group interaction parameters were obtained for the CH2-group of the different cosolutes; the contribution of the CH2-group to the overall cosolute effect is -94 J kg mol-2 for both alkylammonium bromides and alkyldimethylammonium bromides, and -110 J kg mol-2 for alkyltrimethylammonium bromides. Ammonium bromide, which is primarily hydrophilic, also retards the reaction. We suggest that competition between ammonium bromide and the transition state for water molecules results in the strict orientational requirements for the water molecules in the activated complex not being met. Hence the hydrolysis is retarded.
- Hol, Peter,Streefland, Lisette,Blandamer, Michael J.,Engberts, Jan B. F. N.
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p. 485 - 488
(2007/10/03)
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- Method for treating HBV infections with L-2',3'-didehydro-dideoxy-5-fluorocytidine
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The present invention relates to the surprising discovery that certain dideoxynucleoside analogs which contain a dideoxy ribofuranosyl moiety having an L-configuration (as opposed to the naturally occurring D- configuration) exhibit unexpected activity against Hepatitis B virus (HBV). In particular, the compounds according to the present invention show potent inhibition of the replication of the virus in combination with very low toxicity to the host cells (i.e., animal or human tissue). Compounds according to the present invention exhibit primary utility as agents for inhibiting the growth or replication of HBV, HIV and other retroviruses, most preferably HBV.
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- Synthesis and antiviral evaluation of 3'-substituted thymidine analogues derived from 3'-amino-3'-deoxythymidine
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To assess the structure-activity relationship for antiviral activity, a series of 3'-deoxy-3'-N-functionalized thymidine analogues were synthesized. Several of these thymidine analogues show moderate in vitro activity against HIV-1 and HIV-2.
- Pannecouque,Van Poppel,Balzarini,Claes,De Clercq,Herdewijn
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p. 541 - 544
(2007/10/02)
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- Oxidative Alkylation of Azoles. III. Reaction of N-Chloro-1,2,4-triazole with Methyl Iodide
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Reaction of 1-chloro-1,2,4-triazole with methyl iodide in methylene chloride or chloroform at 20-40 deg C results in formation of products of mono- and dialkylation of the ring at positions 1 and 4.Under the same conditions, the 1,4-dimethyltriazolium salt gives rise to 5-iodo derivative.
- Kurenkov, A. A.,Pevzner, M. S.
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p. 1118 - 1121
(2007/10/03)
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- On the Photodegradation of 1-(4-Chlorophenyl)-4,4-dimethyl-3-(1H-1,2,4-triazol-1-ylmethyl)-pentan-3-ol (Folicur)
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The photodegradation of the 1,2,4-triazole fungicide Folicur 1 in different organic solvents (benzene, ether, methylene chloride, methanol) and water, in absence and in presence of a singlet oxygen sensitizer (methylene blue) has been studied.The photometabolites formed in organic solvents, have been separated by column chromatography (with isolation of 4-7, 13 and 14) and in case of benzene as solvent as well with the aid of HPLC (isolated: 4-7, and five additional products 8-12).Photodegradation of 1 in water leads to the formation of only two photoproducts: 4 and 17 (separated only by HPLC).Identification has been achieved by spectroscopic methods and comparison (of retention times, UV and mass spectra) with authentic samples.Furthermore, the kinetics of the photodegradation of 1 in benzene and water (also after addition of titanium dioxide) has been established by HPLC-UV/VIS-technique.The interpretation of the kinetics allows conclusions towars the photodegradation-mechanism, which is discussed in the paper.As expected, the addition of the photocatalyst titanium dioxide leads to a significant acceleration of the photodegradation. - Keywords: Folicur, Photoabbau, Kinetik, HPLC-Separation
- Wamhoff, Heinrich,Koch, Helmut,Foerster, Rolf,Herrmann, Christiane,Atta, Sanaa M. S.,et al.
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p. 280 - 287
(2007/10/02)
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- Azolylmethyloxabicyclohexane derivatives and fungicidal compositions thereof
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Disclosed herein is a process for preparing a cis-azole derivative represented by the general formula (I) STR1 wherein R1 and R2 denote each a hydrogen atom or an alkyl group, R denotes a halogen atom, a nitro group, a cyano group, an alkyl group, a haloalkyl group or a phenyl group, A denotes a nitrogen atom or a methine group, and n stands for an integer of 1-5, which comprises reducing an azolylmethyloxabicyclohexane derivative represented by the general formula (VI) STR2 wherein R1, R2, R, A and n have the same meanings as defined above. A fungicidal composition comprising the azolylmethyloxabicyclohexane derivative represented by the above-mentioned general formula (VI) is also desclosed.
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- Di(hydroxyphenyl)-1,2-4-triazole monomers
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The di(hydroxyphenyl)-1,2,4-triazole monomers were first synthesized by reacting bis(4-hydroxyphenyl) hydrazide with aniline hydrochloride at 250° C. in the melt and also by reacting 1,3 or 1,4-bis-(4-hydroxyphenyl)phenylene-dihydrazide with 2 moles of aniline hydrochloride in the melt. Purification of the di(hydroxyphenyl)-1,2,4-triazole monomers was accomplished by recrystallization. Poly(1,2,4-triazoles) (PT) were prepared by the aromatic nucleophilic displacement reaction of di(hydroxyphenyl)-1,2,4-triazole monomers with activated aromatic dihalides or activated aromatic dinitro compounds. The reactions were carried out in polar aprotic solvents such as sulfolane or diphenylsulfone using alkali metal bases such as potassium carbonate at elevated temperatures under nitrogen. This synthetic route has provided high molecular weight PT of new chemical structure, is economically and synthetically more favorable than other routes, and allows for facile chemical structure variation due to the availability of a large variety of activated aromatic dihalides.
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- A novel synthesis of diarylacetylenes from N-arylmethylheteroarenes and N-arylmethyleneanilines
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Aromatic enamines and diarylacetylenes may be obtained in a novel one-step synthesis involving the condensation of N-arylmethyl heterocycles with aromatic imines in the presence of a strong base. The enamines are isolable intermediates on the route to diarylacetylenes via the elimination of the nitrogen heterocycle.
- Paventi, Martino,Elce, Edmund,Jackman, Rebecca J.,Hay, Allan S.
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p. 6405 - 6406
(2007/10/02)
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- 4-(1,2,4-Triazolyl) Cation: Possible Generation and Reactions
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Thermolysis of N-(1,2,4-triazol-4-yl)-2,4,6-trimethylpyridinium tetrafluoroborate 3 in mesitylene-hexafluoroisopropyl solution gives a variety of products, but none derived from attack of the free nitrenium ion upon mesitylene; a possible explanation is a SET from trimethylpyridine to the nitrenium ion within the solvent cage.
- Abramovitch, Rudolph A.,Beckert, Joseph M.,Pennington, William T.
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p. 1761 - 1762
(2007/10/02)
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- Hydroxyalkinyl-azolyl derivatives
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Novel hydroxyalkinyl-azolyl derivatives of the formula STR1 in which Ar represents optionally substituted aryl, R represents alkyl, optionally substituted aryl or optionally substituted aralkyl, X1 represents halogen, X2 represents hydrogen or halogen, X3 represents hydrogen or halogen, X4 represents hydrogen or halogen and n represents 0 or 1, and acid addition salts and metal salt complexes thereof, are outstandingly effective as fungicides.
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- Tri- and tetra-substituted-oxetanes and tetrahydrofurans and intermediates thereof
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This invention relates to tri- and tetra-substituted-oxetanes, e.g. (±)-cis- and (±)-trans-2-[(4-(4-isopropylpiperazin-1-yl)phenoxy)methyl]-4-(2,4-dihalophenyl)-4-[1H-1,2,4-triazol-1-yl)-methyl]oxetane and tri- and tetra-substituted-tetrahydrofurans, e.g. (±)-cis- and (±)-trans-1-[4-[[2-(2,4-dihalophenyl)tetrahydro-2-[(1H-azol-1-yl)methyl]-5-furanylmethoxy]phenyl]-4-yl-1-substituted piperazine-3-one and related derivatives which exhibit antifungal and antiallergy activities, pharmaceutical composition thereof, methods of their use in treating or preventing susceptible fungal infections and allergic reactions in a host including warm-blooded animals such as humans.
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- Isomerization process
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Transformation of specified 4H-substituted-1,2,4-triazoles into their 1H-substituted isomers by heating at a temperature of 150° C. to 300° C. in the presence of a base and, essentially, in the absence of a polar aprotic solvent.
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- Benzo-fused cyclic compounds
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Herbicidal benzo-fused cyclic compounds of the formula STR1 wherein Q is STR2 Y is O or S, W is STR3 T is O, S, --NH-- or STR4 and R4 may represent, together with T, chlorine, Z is O or S, X is hydrogen or halogen, n is 0 or 1 and R is C3-6 cycloalkyl, an optionally substituted 5-membered heterocyclic group or an optionally substituted 6-membered heteroaromatic group which contains one to three nitrogen atoms, and salts thereof.
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- Preparation of the diastereomeric mixture 2R,4S-1-[2-(2,4-dichlorophenyl)-4-n-propyl-1,3-dioxolan-2-ylmethyl]-1H-1,2,4-triazole
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The 2R,4S-isomer of formula I and the 2RS,4S-diastereoisomeric mixture of formula Ia of 1-[2-(2,4-dichlorophenyl)-4-n-propyl-1,3-dioxolan-2-ylmethyl]-1H-1,2,4-triazole STR1 and the preparation thereof are described. The compounds of formulae I and Ia have pronounced microbicidal activity without having phytotoxic side-effects. They are used as active ingredients in microbicidal compositions, especially as seed dressings.
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- Phosphorsulfide derivatives of deoxynucleosides or deoxynucleotides and their uses
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Novel phosphorsulfide derivatives of deoxynucleosides or deoxynucleotides are provided, which have the general formula: STR1 wherein R1 is a hydroxy-protecting group; R2 is a phosphate-protecting group; R3 is an aryl group; B1 and B2 may be the same or different and each are a base residue which may have a protecting group; and n is zero or a positive integer, provided that if n is 2 or larger, the respective R2 may be the same or different. They are prepared by reacting a deoxynucleoside or deoxynucleotide with a 1,2,4-triazolylphosphine compound and are useful as intermediates for the preparation of oligodeoxy-nucleotides.
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