Mechanism of the hydrolysis of N-aryliminotriphenylphosphoranes

Hydrolysis reactions of N-aryliminotriphenylphosphoranes (I) at varying pH have been investigated kinetically. The reactions produced aniline derivatives and triphenylphosphine oxide as the products. The reactions are first-order, and the Hammett values are -0.29 and -0.63 at pH 3.0 and 8.0, respectively. The reaction rate increased linearly with acetate ion concentration at [AcO^–] < 0.05 M and approached a limiting value at higher base concentration. The plot of logk _t versus pH shows that there are two different regions in the rate profile; one part in which logk _t increases with hydronium ion concentration and the other where k _t is a constant regardless of pH. On the basis of these results, a plausible hydrolysis mechanism is proposed. At pH < 8.0, the reaction proceeds by protonation of the iminophosphorane nitrogen atom, followed by the addition of a water molecule. At pH > 8.0, the proton transfer from water to -nitrogen of the iminophosphorane becomes the rate limiting step.From Kinetika i Kataliz, Vol. 46, No. 1, 2005, pp. 26–34.Original English Text Copyright © 2005 by Pyun, Lee, Kim.This article was submitted by the authors in English.     

Synthesis of Novel Thioethers from Polyhalobutadienes and Thiols

Abstract

Substituted perchlorobutadienes were synthesized from the reactions of hexachloro-1,3-butadiene with some thiols in ethanol in the presence of sodium hydroxide. The oxidation products were obtained from the reactions of thioethers with m-chloroperbenzoic acid. The structures of the new compounds were characterized by microanalysis and spectroscopic data.

GRAPHICAL ABSTRACT      

Spectrophotometric Determination of Acyclovir and Amantadine Hydrochloride through Metals Complexation1

A simple spectrophotometric method for determination of some antiviral drugs, such as acyclovir and amantadine hydrochloride in pure and dosage forms, have been developed. The proposed method is based on the reactions of the selected drugs and metals. Acyclovir was reacted with copper (II) and cobalt (II) using a borax/sodium pH 9 hydroxide buffer, and in a non-aqueous medium using 1% pyridine in methanol, respectively.The formed complexes were absorbed maximally at A, 290 nm and at X 287 nm. The method determined from 112–1620 g/mL of acyclovir, with a mean percentage of recovery of 99.32 ± 0.63 and of 98.77 ± 0.70 for copper (II) and cobalt (III), respectively.The suggested method was applied to a Novirus capsule, and its validity was ascertained by the standard addition technique. In addition, amantadine hydrochloride was allowed to react with iron (III) at pH 3 adjusted with 0.1 M ammonium hydroxide. The formed complex absorbed maximally at 295 nm. This method determined from 94–940 g/mL of amantadine hydrochloride with a mean percentage of recovery of 99.49 ± 0.57. The suggested method was applied to an Adamine capsule, and its validity was ascertained by the standard addition technique.     

Imidazoline ring cleavage in 1,3,6,10-tetraazatetracyclo-[7.3.1.02,7.06,13]trideca-4, 11-dienes,leading to the formation of diquinoxalino[1,2-a∶2′,3′-d]pyrrole derivatives

Dibenzo[d,k]-1,3,6,10-tetraazatetracyclo[7.3.1.0^2,7.0^6,13]trideca-4,11-dienes undergo addition reactions at the C₍₂₎ carbon atom with alcohols and thiols, accompanied by cleavage of the C-N bond of the imidazoline ring, to generate diquinoxalino[1,2-a2,3-d]pyrrole derivatives.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 4, pp. 513–522, April, 1987.     

α,β-Acetylenic Acids and Their Derivatives in Reactions with Hydrogen Sulfide and Thiols

Results of the research into reactions of ,-acetylenic acids and their derivatives with hydrogen sulfide and thiols are summarized. The addition direction and stereochemistry depend on whether there is an activating group at the triple bond, as well as on the structure of the thiol. The reactions not infrequently provide not only monothiylation products, but complete with intramolecular cyclization yielding polyfunctional heterocyclic compounds.     

Operating mechanism of the electrolyte cathode atmospheric glow discharge

Cathode fall (U_cf), cathodic current density and atomic emission intensities originating from metal salts in the electrolyte cathode were measured as a function of different discharge parameters. Emission intensities in function of cathode fall indicate a potential barrier in the sputtered mass flux. This means that the primary particles of the cathode sputtering are of positive charge and the cathode fall including its internal variables is the most important factor. The measured current density and the U_cf as a function of pressure are in accordance with the low pressure data in the literature. The observed decrease of the U_cf with decreasing pH was explained by a model in that the secondary electron emission coefficient of the cathode () is controlled through a reaction net of competing reactions of different electron scavengers involving the hydroxonium ions of the cathode solution. The model revealed two different electron emission processes of the electrolyte cathode, an emission coupled with hydrated electrons is dominating below pH 2.5 while a proton-independent emission of poor efficiency is working above pH 3. Our model fits to the reported yields of the ultimate products both in the solution and in the gas phase and offers a calculation of and U_cf in the function of the cathode acidity. The model provides two other independent calculation methods based on product analysis data.     

Synthesis and Complex-Forming Properties of N-Substituted Diazacrown Ethers

N-Substituted mono- and diazacrown ether with ethoxycarbonylmethyl, 7-phenyl-3,6-dioxaheptyl, p-methoxy, and p-nitrobenzyl groups in the side chain have been synthesized. Their reactions with alkali and alkaline-earth metals have been studied. Substituents affect the complex-forming ability of the base macrocycle by changing the basicity of the nitrogen atoms and coordinating with the complexing ion.     

Reactions ofβ, β-dichlorovinyl organyl sulfides with thiols and the synthesis of bis(organylthio)acetylenes

Conclusions ,-Dichlorovinyl organyl sulfides can react with thiols and KOH by several pathways, depending on the conditions, leading to different unsaturated sulfides. We have found a simple preparative route to bis(alkylthio)acetylenes with identical or different radicals.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 2, pp. 426–431, February, 1978.We thank V. V. Keiko for the preparative separation of isomers (I) and (III).     

Synthesis of caprolactamates of group II metals

Caproiactamates of alkaline-earth metals and magnesium of the general formula , where M = Mg, Ca, Sr, and Ba, were synthesized from alkoxides, hydrides, and organometallic compounds of these metals and -caprolactam. The catalytic activities of caprolactamates obtained under conditions of anionic polymerization of -caprolactam were compared. It was demonstrated that the purest caprolactamates and, hence, the most effective catalysts of anionic polymerization of lactams can be obtained from organometallic and hydride compounds of these metals. The reactivities of alkoxides of the alkaline-earth metals and magnesium increase in metallation reactions of -caprolactam in the order Mg < Ca < Sr < Ba.Translated fromIzyestiya Akademii Nauk. Seriya Khimicheskaya, No. 11, pp. 2272–2275, November, 1995.The work was supported by the Russian Foundation for Basic Research (Project No. 93-03-4252).     

The Synthesis of Novel S-, S,S-, S,S,S-, and N,S-Substituted Nitrodienes from Polyhalonitrodienes and Thiols

Abstract

The novel S-, S,S-, and S,S,S-substituted nitrobutadienes were synthesized from the reactions of 2-nitrobutadiene compounds with some thiols. The new N,S-substituted nitrobutadienes were obtained from the reaction of the mono-thiosubstituted butadienes with morpholine, thiomorpholine, homopiperazine, and piperazine derivatives. The structures of new compounds were determined by spectroscopic techniques.

GRAPHICAL ABSTRACT      

Some Colloidal and Chemical Aspects of Biotransformation of Heavy Metal Citrate Complexes

It was established that chemically stable water-soluble citrate complexes of heavy metals, which are widespread forms of their occurrence under natural conditions, can be mineralized in the course of metabolism of citrate ligand by Basillus cereus AUMC 4368 metallophilic bacterial culture. Biodegradation of metal citrate complexes is not directly related to their stability constants and corresponds to the Ca (Mg, Sr) > Fe(III) > Zn (Cu, Ni, Co, Cd) > U(VI) series. As a result of biomineralization of water-soluble metal citrate complexes, pH of dispersion medium increases and water-insoluble salts, mainly carbonates and hydroxides, can be formed; correspondingly, the disperse state of metals can be changed. Exception is uranium(VI) that forms (at pH 8) water-soluble stable uranyl carbonate complex. It was shown that the bound forms of metals (water-soluble complexes, insoluble precipitants) are nontoxic for microorganisms.     

Disparate behavior of ketones and thioketones on reaction with organolithiums

The reactions of alkyllithiums with ketones and thioketones proceed in fundamentally different ways. Whereas alkyllithiums add to the carbonyl carbon of ketones to give tertiary alcohols, the reaction with thioketones proceeds to give secondary thiols by reduction of the CS group. Transition states for the addition and reduction reactions of acetone and thioacetone in ethereal solution have been located and the computed activation free energies are in agreement with the observed behavior of ketones and thioketones in reactions with alkyllithiums.     

Study of the kinetics of the transport of Cu(II), Cd(II) and Ni(II) ions through a liquid membrane

The coupled transport of Cu(II), Cd(II) and Ni(II) ions through a bulk liquid membrane (BLM) containing pyridine-2-acetaldehyde benzoylhydrazone (2-APBH) as carrier dissolved in toluene has been studied. Once the optimal conditions of extraction of each metal were established, a comparative study of the transport kinetics for these metals was performed by means of a kinetic model involving two consecutive irreversible first-order reactions. The kinetic parameters (apparent rate constants of the metal extraction and re-extraction reactions (k ₁, k ₂), the maximum reduced concentration of the metal in the liquid membrane (), the time of the maximum value of R _o ( t _max) and the maximum entry and exit fluxes of the metal through the liquid membrane ( and ) of the extraction and stripping reactions were evaluated and results showed good agreement between experimental data and theoretical predictions. Complete transport through the membrane took place according to the following order: Cd(II)>Cu(II)>Ni(II), with similar kinetic parameters obtained for Cu(II) and Cd(III). The transport behaviour of Ni(II) was different to that of Cu(II) and Cd(III), probably due to the different stoichiometry of the nickel complex compared to those of the other metal ions and the different chemical conditions required for its formation. The influence of the sample salinity on the transport kinetics was studied. k ₁ values decreased slightly when the feed solution salinity was increased for Cu(II) and Ni(II), but not for Cd(II). Values of k ₂ were practically unaffected. The proposed BLM was applied to the preconcentration and separation of metal ions (prior to their determination) in water samples with different saline matrices (CRM, river water and seawater), and good agreement with the certified values was obtained.     

New methodology for the preparation of 3-hydroxy-2-pyridinone (3,2-HOPO) chelators and extractants. Part 2: Reactions of alcohols, phenols, and thiols with an electrophilic 3,2-HOPO reagent

The reactions of the electrophilic iminium ester mesylate salt 1 with alcohols, phenols, and thiols have been investigated. In the presence of base, thiols, phenols, and thiophenol react with 1 to give the corresponding ether linked HOPO derivatives in good yields. However, the ring opening of salt 1 with alcohols could only be accomplished efficiently using a large excess of the alcohol in the presence of methanesulfonic acid at 80 °C. The synthetic utility of HOPO precursor, 1, has been demonstrated by the synthesis of two polyHOPO chelators 7 and 9.     

Biosorption of copper(II) and cadmium(II) by a novel exopolysaccharide secreted from deep-sea mesophilic bacterium

The biosorption behaviors and mechanisms of a novel exopolysaccharide (EPS), which is secreted by a mesophilic bacterium (namely Wangia profunda (SM-A87)) isolated from deep-sea sediment, for heavy metals Cu(II) and Cd(II) have been studied in this paper. The effects of SM-A87 EPS concentration, solution pH and ionic strength on the metal uptake were investigated by employing batch adsorption techniques, respectively. The optimum biosorption capacities were observed at pH 5.0 for Cu(II) with 48.0 mg/g and pH 6.0 for Cd(II) with 39.75 mg/g, respectively. Addition of salts decreased Cu(II) or Cd(II) uptake in the order of K⁺ < Na⁺ < Ca²⁺. Langmuir and Freundlich models were employed to describe the biosorption equilibrium data, indicating the favorable biosorption occurs and larger biosorption capacity and intensity for Cu(II) than for Cd(II). The biosorption kinetics for both metals can be well described by pseudo-second-order kinetic model, compared with pseudo-first-order and intraparticle diffusion kinetic models. The competitive biosorption was also studied, indicating that in two-component solution with different metal ratios, the selective biosorption of SM-A87 EPS for Cu(II) was much higher than for Cd(II). The Fourier transform infrared spectroscopy (FT-IR) analysis indicated possible functional groups (e.g., OH, COO and COC) of SM-A87 EPS involved in metal biosorption process, which indicated the potential of using SM-A87 EPS as an effective sorbent for Cu(II) or Cd(II) removal from water.     

A thermometric titration study of the interaction of Al3+, Co2+, Ni2+ and Zr4+ with xylenol orange

A thermometric titrimetry study of the interaction in aqueous solution of A1³⁺, Co²⁺, Ni²⁺ and Zr⁴⁺ with xylenol orange has revealed in each case a linear reaction heat/[Mⁿ⁺] relationship at a specified pH, thereby suggesting the potential of metallochromic indicators for the analytical determination of these metals in water. The effect of pH on the reaction heat is investigated and is interpreted in terms of the ability of these metal cations to complex with the known xylenol orange species existing at the various pH studied. An interference study, involving transition and non-transition metal ions, is also reported and the interference effect, as measured by the deviation ofQ/Q from unity (Q andQ are the relevant reaction heats in the presence and absence of interfering ion), is partially explained in terms of the coordination numbers, relative sizes and crystal field stabilization energies of the cations studied and the known behaviour of xylenol orange in aqueous solution.     

N-Trifluoroacetyl arenesulfenamides, effective precursors for synthesis of unsymmetrical disulfides and sulfenamides

N-Trifluoroacetyl arenesulfenamides (3) were effective precursors for the synthesis of unsymmetrical disulfides (4) and sulfenamides (5). Reactions of 3 with a variety of aromatic thiols at room temperature were generally complete within 5 min and gave unsymmetrical diaryl disulfides in high yields. Aralkyl disulfides were isolated in high yields from the reaction of 3 with aliphatic thiols. The nucleophilic substitution reactions of 3 with amines proceeded smoothly and provided N-substituted sulfenamides in good to excellent yields.     

Synthesis of β-Aryl-β-sulfanyl Ketones by a Sequential One-Pot Reaction Using KF/Al2O3 in Glycerol

The title compounds were synthesized by a sequential one-pot reaction of aryl aldehydes, aryl-methyl ketones, and thiols promoted by KF/Al₂O₃. This methodology affords a large number of β-aryl-β-sulfanyl ketone derivatives from aliphatic and aromatic thiols in good yields and is also applicable for solid substrates.

[Supplementary materials are available for this article. Go to the publisher's online edition of Synthetic Communications® for the following free supplemental resource(s): Full experimental and spectral details.]     

Solvent Extraction Separation of Th(IV) and U(VI) with PC-88A

Liquid-liquid extraction of Th(IV) and U(VI) has been investigated by commercial extractant PC-88A in toluene. The optimum conditions for extraction of these metals have been established by studying the various parameters like acid concentration/pH, reagent concentration, diluents and shaking time. The extraction of Th(IV) was found to be quantitative with 0.1–1.0M HNO₃ acid and in the pH range 1.0–4.0 while U(VI) was completely extracted in the pH range 1.0–3.5 with 2.5·10^–2M and 2.·10^–2M PC-88A in toluene, respectively. The probable extracted species have been ascertained by log D-log C plot as ThR₄·4HR and UO₂R₂·2HR, respectively. The method permits separation of Th(IV) and U(VI) from associated metals with a recovery of 99.0%.