Synthesis of novel derivatives of 2-(azolylimino)thiazoline

Successive alkylation of 5-(3-phenylthioureido)-3H-imidazole-4-carboxamides with alkyl halides and chloroacetone gave (N-oxopropylimidazolyl)isothioureas, which were easily converted into derivatives of purine and imidazopyrazinone. In the case of ethyl 5-(3-phenylthioureido)-3H-imidazole-4-carboxylate, primary alkylation occurs at the N atom of the imidazole ring. Reactions of 5-(3-phenylthioureido)-3H-imidazole-4-carboxamides with haloketones afforded a number of 4-hydroxy-2-imidazolyliminothiazolidines and 2-imidazolylimino-Δ⁴-thiazolines.__________Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 10, pp. 2196–2204, October, 2004.     

Adsorption of oxygen-containing aromatics used in petrochemical,pharmaceutical and food industries by means of lignin based active carbons

The adsorption processes of three aromatic chemicals onto activated carbons (ACs) from aqueous solutions have been studied. Eucalyptus kraft lignin obtained from cellulose industry as a residual biomass has been used to prepare activated carbons by physical activation with CO₂. The influences of the activation time on the surface areas and pore volumes of the ACs were analyzed. The physicochemical properties and the surface chemical structure of the adsorbents have been studied by means of N₂ and CO₂ adsorption, ultimate analysis, XPS, TPD and SEM. XPS and TPD spectra of the ACs have suggested the presence of aromatic rings and carbon-oxygen functional groups in the solid surfaces. The potential use of the ACs for the removal of acetaminophen (paracetamol), salicylic acid and benzoic acid has been investigated at different pH, temperature and contact time. The adsorption equilibrium data have been correlated to Langmuir isotherm model. The thermodynamic study has been developed, the values of ΔH, ΔG, and ΔS have been calculated and they indicated that the processes are endothermic for acetaminophen and exothermic for salicylic and benzoic acids. The analysis of the kinetic experiments showed that the effective diffusivities are low; 10⁻¹² to 10⁻¹¹ cm²/s, and they are the corresponding to intraparticle mass transfer, which appears as the controlling step for the net adsorption processes.     

Reactions of <Emphasis Type="Italic">N</Emphasis>-(Perfluorophenyl)carbonimidoyl Dichloride with Aromatic Acids and Their Derivatives in the Presence of AlCl<Subscript>3</Subscript>. Formation of 2-(Perfluorophenyl)isoindoline-1,3-dione and Its Derivatives

Reactions of N-(perfluorophenyl)carbonimidoyl dichloride with benzoic acid, benzoyl chloride, ethyl benzoate, and also with phthalic acid, phthaloyl dichloride, and phthalic anhydride in the presence of AlCl₃ at 170°C afford2-(perfluorophenyl)isoindoline-1,3-dione. With benzoic acid and benzoyl chloride form also 2-(perfluorophenyl)-3-[(perfluorophenyl)imino]isoindolin-1-one. In reactions with compounds of the benzene series arise also derivatives of arylimidoyl chlorides and amide type compounds containing a CONHC₆F₅ moiety.__________Translated from Zhurnal Organicheskoi Khimii, Vol. 41, No. 2, 2005, pp. 228–236.Original Russian Text Copyright © 2005 by Petrova, Platonov.     

Isomer-selective carbon-paste electrodes for the determination of nitrophenol, nitroaniline, and nitrobenzoic acid by adsorption-stripping voltammetry

The preconcentration and voltammetric behavior of aromatic nitro compounds at paste electrodes made of synthetic carbon materials were studied. The relationship between the energies of adsorption of molecules on active carbons and the peak current constants was determined. Conditions for the isomer-selective determination ofo- andp-isomers of nitrophenol, nitroaniline, and nitrobenzoic acid in aqueous solutions were optimized.     

硅烷化活性炭的吸附性质

本工作测定了25℃和35℃时硅烷化活性炭自水溶液中吸附苯甲酸和苯甲醛的等温线;计算了吸附过程的ΔGⅲ,ΔHⅲ和ΔSⅲ;用Hill-deBoer方程处理了实验结果。所得结果表明:(1)随硅烷化时间延长,苯甲酸和苯甲醛的吸附量(mol.m^-^2)明显增加;-ΔGⅲ和-ΔHⅲ略有升高,ΔSⅲ为正值;(2)吸附分子之间的相互作用很弱,吸附分子与活性炭表面间的作用随硅烷化程度增加而加大;(3)芳香化合物可能是以苯环吸附在炭表面上的。     

The interaction of pyridine with the surface of active carbons

The adsorption and desorption of pyridine on the surface of granulated active carbons was studied. It was shown that pyridine was extracted from aqueous solutions because of physical adsorption and specific adsorption with the formation of H-bonds with oxygen-containing surface groups. The desorption of pyridine at temperatures up to 400°C did not cause its complete removal from the surface of adsorbents. The fraction of pyridine remaining on the surface was proportional to the amount of oxygen-containing surface groups of active carbons of the acid type.     

Effects of micropore size and chemical nature of the surface of carbon adsorbents on the adsorption isotherms of water vapor

Adsorption of benzene and water vapors on activated carbons of various microporous structure was studied. The values of the characteristic energy of adsorption of benzene and water vapors were compared and the affinity coefficients β_H2O for carbons with various degrees of activation were calculated. The values of the β_H2O coefficient for carbons with the same degrees of oxidation remain constant. This makes it possible to use the experimental data on benzene adsorption for prediction of the behavior of microporous activated carbons towards adsorption of water vapor. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 12, pp. 2636–2639, December, 2005.     

Synthesis of 4-(1<Emphasis Type="Italic">H</Emphasis>-Azol-1-ylmethyl)benzohydrazides and Their Acyclic and Heterocyclic Derivatives

4-(1H-Azol-1-ylmethyl)benzohydrazides were prepared from methyl 4-(bromomethyl)benzoate, azoles, and hydrazine hydrate. Reactions of 4-(1H-imidazol-1-ylmethyl)benzohydrazide with carbonyl compounds gave hydrazones whose tautomerism was studied. From the hydrazides, 1,3,4-oxadiazoles, 1,2,4-triazole- 5-thione, and N-benzoyl-N′-alkyl(aryl)sulfonylhydrazines were synthesized.__________Translated from Zhurnal Obshchei Khimii, Vol. 75, No. 1, 2005, pp. 123–129.Original Russian Text Copyright © 2005 by Osyanin, Purygin, Belousova.     

Synthesis and transformations of (imidazolylimino)thiazolidinones

The reaction of ethyl 5-phenylthioureido-3H-imidazole-4-carboxylate with bromoacetic acid afforded (imidazolylimino)thiazolidinones, which were transformed into the corresponding 5-arylidene-4-thiazolidinones by the reactions with aldehydes. Under the conditions of the Knoevenagel reaction, the thiazolidine ring in derivatives of 4-(4-oxothiazolidin-2-ylideneamino)-3H-imidazole-4-carboxamides was opened to form substituted guanidines.     

Synthesis of 2-(imidazolylamino)benzothiazoles

Treatment of derivatives of 5-phenylthioureido-3H-imidazole-4-carboxylic acid with bromine afforded 2-(imidazolylamino)benzothiazoles.     

Adsorption of -histidine on copper surface as evidenced by surface-enhanced Raman scattering spectroscopy

The adsorption of -histidine on a copper electrode from H₂O- and D₂O-based solutions is studied by means of surface-enhanced Raman scattering (SERS) spectroscopy. Different adsorption states of histidine are observed depending upon pH, potential, and the presence of the SO²⁻₄ and Cl⁻ ions. In acidic solutions of pH 1.2 the imidazole ring of the adsorbed histidine remains protonated and is not involved in the chemical coordination with the surface. The SO²⁻₄ and Cl⁻ ions compete with histidine for the adsorption sites. In solutions of pH 3.1 three different adsorption states of histidine are observed depending on the potential. Histidine adsorbs with the protonated imidazole ring oriented mainly perpendicularly to the surface at potentials more positive than −0.2 V. Transformation of that adsorption state occurs at more negative potentials. As this takes place, histidine adsorbs through the α-NH₂ group and the neutral imidazole ring. The Cl⁻ ions cause the protonation and detachment of the α-NH₂ group from the surface and the formation of the ion pair NH⁺₃ … Cl⁻ can be observed. In the neutral solution of pH 7.0 histidine adsorbs through the deprotonated nitrogen atom of the imidazole ring and the α-COO⁻ group at E ≥ −0.2 V. However, this adsorption state is transformed into the adsorption state in which the α-NH₂ group and/or neutral imidazole ring participate in the anchoring of histidine to the surface, once the potential becomes more negative. In alkaline solutions of pH 11.9 histidine is adsorbed on the copper surface through the neutral imidazole ring.     

Viscosity behavior of benzoic acid and benzoate ion in aqueous solution

Relative viscosities of aqueous solutions of benzoic acid and benzoates of lithium, sodium, potassium, and ammonium are measured. In the temperature range 25–35°C, the Jones-Dole viscosityB coefficients of the benzoate ion decrease with increasing temperature, indicating a net structure-making effect. The somewhat larger value of theB coefficient for the benzoate ion than that for the benzoic acid molecule confirms similar behavior for the acetate ion and acetic acid in aqueous solutions although the effect is much smaller.     

Calorimetric evaluation of activated carbons modified for phenol and 2,4-dinitrophenol adsorption

Two commercial activated carbons with differences in their superficial chemistry, one granular and the other pelletised, were modified for use in phenol and 2,4-dinitrophenol adsorption. In this paper, changes to the activated carbon surface will be evaluated from their immersion calorimetry in water and benzene, and they will then be compared with Area BET, chemical parameters, micropore size distributions and hydrophobicity factors of the modified activated carbons. The activated carbons were modified using 60 % solutions of phosphoric acid (H₃PO₄), nitric acid (HNO₃), zinc chloride (ZnCl₂) and potassium hydroxide (KOH); the activated carbon/solution ratio was 1:3 and impregnation was conducted 291 K for a period of 72 h before samples were washed until a constant pH was obtained. Water immersion calorimetry showed that the best results were obtained from activated carbons modified with nitric acid, which increased from ?10.6 to ?29.8 J g^?1 for modified granular activated carbon, and ?30.9 to ?129.3 J g^?1 for pelletised activated carbon. Additionally, they showed the best results in phenol and 2.4-dititrophenol adsorption. Those results indicate that impregnation with nitric acid under the employed conditions could generate a greater presence of oxygenated groups on their surface, which favours hydrogen bond formation and the increased adsorption of polar compounds. It should also be noted that immersion enthalpy in benzene for modified activated carbon with nitric acid is the method with the lowest value, which is consistent with the increased presence of polar groups on its surface. Regarding hydrophobicity factors, it was observed that granular carbons modified with nitric acid and potassium hydroxide have the lowest ratios, indicating greater interaction with water.     

Heterogeneous microporous structures and adsorption properties of carbon adsorbents

A theoretical basis for calculating parameters of the pore structure of active carbons is considered. Active carbons are classified into four types according to their dispersion and mesopore surface areas. The parameters of micro- and mesopores of active carbons produced in different countries have been determined from benzene vapor adsorption isotherms at 293 K. The differences in parameters of the Dubinin—Stoeckly equation found from adsorption isotherms of different compounds are noted.For part 11, seeIzv. Akad. Nauk SSSR, Ser. Khim., 1990, 2691 [Bull. Acad. Sci. USSR, Div. Chem. Sci., 1990,39, 2438 (Engl. Transl.)].Deceased July 13, 1993.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 8, pp. 1373–1376, August, 1993.     

New Monofunctionalized Fluorescein Derivatives for the Efficient High‐Throughput Screening of Lipases and Esterases in Aqueous Media

Monoalkylation or acylation of fluorescein ( 1 ) with various acyloxymethyl or acyl halides afforded, respectively, a series of ether‐ ( 2 ) and ester‐functionalized ( 3 ) fluorogenic probes. The highly reactive and water‐soluble substrates release fluorescein ( 1 ) upon reaction with lipases and esterases within seconds or minutes, both under fully aqueous conditions or in the presence of DMSO (20%) as a co‐solvent. The most‐reactive substrates in the two series were the octanoic acid derivatives 2f (= 2‐{6‐[(octanoyloxy)methoxy]‐3‐oxo‐3H‐xanthen‐9‐yl}benzoic acid) and 3a (= 2‐[6‐(octanoyloxy)‐3‐oxo‐3H‐xanthen‐9‐yl]benzoic acid). Esterases were found to generally react faster under aqueous conditions, while lipases were more reactive in the presence of DMSO as a co‐solvent.     

Enantioseparation of Some New 1-(2-Naphthyl)-1-ethanol Ester Derivatives by HPLC on Chiralcel OD

The direct enantiomeric resolution of racemic 2-(1H-imidazole-1-yl)-1-naphthalene-2-yl)ethanol esters, 1-(naphthalene-2-yl)ethanol esters, and 1-(1-hydroxynaphthalene-2-yl)-2-(1H-imidazole-1-yl)ethanol on silica-based cellulose tris(3,5-dimethylphenylcarbamate) (Chiralcel OD) column is described. The separations were performed using mobile phases which consist of alcohol (methanol, ethanol or 2-propanol)/n-hexane in various proportions. The effect of structural features of the solutes along with the nature and concentration of alcohol in the mobile phase on the discrimination between the enantiomers was examined for different mobile phase compositions. The results suggest that not only the structure and concentration of alcohol in the mobile phase, but also the subtle structural differences in racemates can have a pronounced effect on enantiomeric separation and retention. Baseline separations were obtained for 2-(1H-imidazole-1-yl)-1-naphthalene-2-yl)ethanol esters carrying imidazole ring in addition to ester functional group in their structures. The α values of the resolved enantiomers of 2-(1H-imidazole-1-yl)-1-naphthalene-2-yl)ethanol esters were in the range of 1.49–1.62 while the R _s values varied from 4.20 to 6.75 when methanol/n-hexane (70:30 v/v) was used as mobile phase.

     

Synthesis and Selected Transformations of 1H‐Imidazole 3‐Oxides Derived from Amino Acid Esters

A series of new optically active 1H‐imidazole 3‐oxides 5 with a substituted acetate group at N(1) as the chiral unit were prepared by the reaction of α‐(hydroxyimino) ketones, α‐amino acid methyl esters, and formaldehyde. In an analogous reaction, ethyl 2‐(hydroxyimino)‐3‐oxobutyrate and 1,3,5‐trialkylhexahydro‐1,3,5‐triazines gave 3‐oxido‐1H‐imidazole‐4‐carboxylates 14 , which easily rearranged into the 2‐oxo derivatives 15 . Selected examples of N‐oxides 5 could be transformed into the corresponding 2,3‐dihydro‐1H‐imidazole‐2‐thione derivatives 10 via a ‘sulfur‐transfer reaction’, and the reduction of the histidine derivative 5i with Raney‐Ni yielded the optically active 2,3‐bis(imidazolyl)propanoate 12 . Furthermore, reaction of the (1H‐imidazol‐1‐yl)acetates with primary amines yielded the corresponding acetamides.     

Proton‐Conductive 3D LnIII Metal–Organic Frameworks for Formic Acid Impedance Sensing

Metal‐organic frameworks (MOFs) as new classes of proton‐conducting materials have been highlighted in recent years. Nevertheless, the exploration of proton‐conducting MOFs as formic acid sensors is extremely lacking. Herein, we prepared two highly stable 3D isostructural lanthanide(III) MOFs, {(M(μ₃‐HPhIDC)(μ₂‐C₂O₄)_0.5(H₂O))?2 H₂O}_n (M=Tb ( ZZU‐1 ); Eu ( ZZU‐2 )) (H₃PhIDC=2‐phenyl‐1H‐imidazole‐4,5‐dicarboxylic acid), in which the coordinated and uncoordinated water molecules and uncoordinated imidazole N atoms play decisive roles for the high‐performance proton conduction and recognition ability for formic acid. Both ZZU‐1 and ZZU‐2 show temperature‐ and humidity‐dependent proton‐conducting characteristics with high conductivities of 8.95×10^?4 and 4.63×10^?4 S cm^‐1 at 98 % RH and 100 °C, respectively. Importantly, the impedance values of the two MOF‐based sensors decrease upon exposure to formic acid vapor generated from formic aqueous solutions at 25 °C with good reproducibility. By comparing the changes of impedance values, we can indirectly determine the concentration of HCOOH in aqueous solution. The results showed that the lowest detectable concentrations of formic acid aqueous solutions are 1.2×10^?2 mol L^?1 by ZZU‐1 and 2.0×10^?2 mol L^?1 by ZZU‐2 . Furthermore, the two sensors can distinguish formic acid vapor from interfering vapors including MeOH, N‐hexane, benzene, toluene, EtOH, acetone, acetic acid and butane. Our research provides a new platform of proton‐conductive MOFs‐based sensors for detecting formic acid.     

1,7′-dimethyl-2′-propyl-1<Emphasis Type="Italic">H</Emphasis>,3′<Emphasis Type="Italic">H</Emphasis>-2,5′-bibenzo[<Emphasis Type="Italic">d</Emphasis>]imidazole as a corrosion inhibitor of mild steel in 1 M HCl

Inhibition effect of imidazole derivative 1,7′-dimethyl-2′-propyl-1H,3′H-2,5′-bibenzo[d]imidazole (DPBI) against mild steel corrosion in 1 M HCl solutions was evaluated using the conventional mass loss method, potentiodynamic polarization, linear polarization, and electrochemical impedance spectroscopy. The mass loss results showed that DPBI is an excellent corrosion inhibitor; electrochemical polarizations data revealed the mixed mode of inhibition; and the results of electrochemical impedance spectroscopy showed that the change in the impedance parameters, charge transfer resistance, and double layer capacitance with the change in the concentration of the inhibitor is due to the adsorption of the molecule leading to the formation of a protective layer on the surface of mild steel. The inhibition action of this compound was assumed to occur via adsorption on the steel surface through the active centers of the molecule.     

Effect of the carbon surface layer chemistry on benzene adsorption from the vapor phase and from dilute aqueous solutions

We present a complex study of benzene adsorption on chemically modified commercial activated carbons. The porosity of studied carbons is almost the same, whereas the chemical composition and the acid-base properties of surface layers differ drastically from amphoteric (initial de-ashed carbon D43/1, Carbo-Tech, Essen, Germany) and acidic (carbon modified with concentrated HNO3 and fuming H2SO4) to strongly basic (carbon modified with gaseous NH3). Benzene adsorption isotherms measured from aqueous solution at three temperatures (298, 313, and 323 K) and at the neutral pH level are reported. They are supported by studies of water and benzene adsorption from the gaseous phase (volumetric and calorimetric data) and the data of benzene temperature-programmed desorption (TPD). Moreover, the data of the enthalpy of immersion in water and benzene are also presented. Obtained data of benzene adsorption from the gaseous phase are approximated by applying the method of Nguyen and Do (ND) and the Dubinin-Astakhov (DA) equation. The data of adsorption from solution are described by the hybrid DA-Freundlich (DA-F) model. We show that there are similarities in the mechanisms of benzene adsorption from the gaseous phase and from aqueous solutions and that the pore-blocking effect is the main stage of the adsorption mechanism. This effect strongly depends on the polarity of the carbon surface. The larger the ratio of the enthalpy of carbon immersion in water to the enthalpy of immersion in benzene, the larger the reduction in adsorption from solution, compared to that in the gaseous phase, that is observed.