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PL ISSN 0137- 5083

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Volume 71 Number 8 August 1997
Pages 1037- 1211

 
   


Polish Chemical Society 

   

CONTENTS


Page

ORGANIC CHEMISTRY
1037 The Anhydrous Lagochiline: Three Ways of Preparation and Crystal Structure
— Izotova L.Yu., Beketov K.M., Talipov S. A. and Ibragimov B.T.
1045 Meso-ionic 4-Benzyl-2-phenyl-1,3-oxazolium-5-olate By-product Found in Carbodiimide-mediated Peptide Synthesis
— Slebioda M.
1049 Synthesis and Antiinflammatory Activity of 3-Substituted-4-(3-aryloxymethyl-7H-s-triazolo[3,4- b]
[1,3,4]thiadiazin-6-yl)-sydnones

— Kalluraya B. and Rahiman A.M.
1053 Influence of Base and Solvent on the Reaction between p-Cresol and Formaldehyde Leading to p-Methylcalix[n]arenes
— Ostaszewski R., Lipkowski P. and Jurczak J.
1060 Sulfanolysis of Tris(2-cyanoethyl)phosphine Chalcogenides. X-ray Structure Analysis of OP(CH2CH2CONH2)3 and OP(CH2CH2CSNH2)3 — Kamenicek J., Kasparek F., Posolda M., Bekarek V. and Marek J.
1066 Synthesis of N,N'-Carbonyl-bis-amino Acids and N,N'-Carbonyl-bis-peptides
— Izdebski J. and Pawlak D.
1075 A New Method for the Preparation of 4-Substituted Pyrazoles
— Soloducho J. and Musgrave R.P.
1082 Conformational Study of Scyliorhinin I by NMR and Molecular Dynamics Calculations
— Qi X.F., Rodziewicz S., Zboinska J. and Rolka K.
1093 Ceric Ammonium Nitrate Oxidation of Aldoximes in Aliphatic Nitriles as Solvents: a New Way for Synthesis of 1,2,4-Oxadiazoles
— Giurg M. and Mlochowski J.
1102 Structure of 5-Imino-9-methyl-3-nitrodipyrido[1,2-a:3',2'-e]pyrimidine Hydrochloride
— Pniewska B., Rykowski A. and Pucko W.
1108 The Reaction of Acyliron Anions with Deuterium Oxide
— Bartnicka E. and Zamojski A.
PHYSICAL CHEMISTRY
Papers presented at Fourth International Microsymposium
on Electrochemical Impedance Analysis
held 10-14 June, 1996, in Madralin near Warsaw, Poland.
1113 A.C. Four-Probe Impedance Measurements on Solid Electrolytes with High Impedance
— Fafilek G. and Breiter M.
1120 The Kinetics of Ag(I)/Ag Electrode Reaction in Pure Molten Silver Chloride
— Kisza A., Dzielendziak J. and Kazmierczak J.
1133 Deviation from Linearity in Electrochemical Impedance Spectroscopy
— Darowicki K.
1140 Temperature Effects in Thin Film Polyaniline Electrodes
— Poks P. and Grzeszczuk M.
1151 Potential Dependence of the AC Impedance Response at an Ultramicrodisc
— Los P. and Bruce P.G.
1160 A New Experimental Device for Magnetoelectrochemical (M.E.C.) Transfer Function Measurements
— Devos O., Aaboubi O., Chopart J.P., Merienne E., Olivier A., Gabrielli C.
and Tribollet B.
1171 Investigation of Electrochemical Processes by A.C. Quartz Electrogravimetry

— Gabrielli C., Keddam M., Minouflet-Laurent F., Nadi N. and Perrot H.
1183 An Electrochemical Impedance Study of the Oxygen Reduction on Non-Porous NiO and LiCoO2 in Molten Carbonate
— Plevier G.A.J.M., Prins-Jansen J.A., Hemmes K. and de Wit J.H.W.
1196 Differential Impedance Analysis on Single Crystal and Polycrystalline Yttrium Iron Garnets
— Vladikova D., Stoynov Z. and Ilkov L.
1204 Differential Impedance Analysis - an Insight into the Experimental Data
— Stoynov Z.
BOOK REVIEW
1211 Water Disinfection and Natural Organic Matter. Characterization and Control.
Edited by: Roger A. Minear and Gary L. Amy. ACS Symposium Series 649, American Chemical Society, Washington DC, 1997 — Pawlowski L.


ABSTRACTS

1037-1044

The Anhydrous Lagochiline:
Three Ways of Preparation and Crystal Structure

by L.Yu Izotova, K.M. Beketov, S.A. Talipov and B.T. Ibragimov
Institute of Bioorganic Chemistry, Kh. Abdullaev Str. 83, 700143, Tashkent, Uzbekistan

(Received August 5th, 1996; revised manuscript February 26th, 1997)

In order to find a new crystal modification of lagochiline with a better water solubility instead of the well known insoluble monohydrate form, the information of crystalline products has been investigated under various conditions. The modification searched is shown to exist indeed in an anhydrous form. It is possible to obtain it by: 1) crystallization from solutions with no traces of water, 2) crystallization at 120oC from solutions in butylacetate and 3) dehydration of the hydrate form. Water solubility of the form obtained is 20 mg/ml and, unfortunately, still insufficient for the practical use of lagochiline as an effective bloodstopping remedy. Crystal data of anhydrous lagochiline are: C20H36O5, monoclinic, space group P21, a = 8.306(1), b = 17.443(2), c = 14.028(3) Å, ß = 106.85o (1), V = 1943(1) Å 3, Z = 4, Dx = 1.22 g/cm3. The structure has been refined to the final R value of 0.049 for 1984 observed reflections.
The complicated system of the intermolecular H-bonds incorporates lagochiline molecules to the three dimensional H-bonded network. The realization of this network is possible due to the adoption, by one of two lagochiline molecules, of the conformation unusual for an isolated molecule.

1045-1048

Meso-ionic 4-Benzyl-2-phenyl-1,3-oxazolium-5-olate
By-product Found in Carbodiimide-mediated
Peptide Synthesis

by M. Slebioda
Department of Organic Chemistry, Technical University of Gdansk, 80-952 Gdansk, Poland

(Received April 11th, 1997)

Formation of 4-benzyl-2-phenyl-1,3-oxazolium-5-olate was observed during carbodiimide-mediated N-benzoyl- phenylalanyl-leucine methyl ester synthesis. This meso- ionic compound can also be obtained by tautomeric transformation of 4-benzyl-2-phenyl-5(4H)-oxazolone in yield (3% to 60%) depending on the type of solvent and tertiary amine catalyst used.

1049-1052

Synthesis and Antiinflammatory Activity
of 3-Substituted-4-(3-aryloxymethyl-7H-s- triazolo
[3,4-b][1,3,4]thiadiazin-6-yl)-sydnones

by B. Kalluraya1 and A.M Rahiman2
1Department of Studies in Chemistry, Mangalore University,
Mangalagangothri-574 199, Karnataka, India
2Department of Chemistry, Government Science College, Hassan-573 201, India

(Received February 7th, 1997; revised manuscript April 24th, 1997)

A series of triazolothiadiazines with an aryloxymethyl substituent at the 3-position and an aryl sydnone at the 6- position were synthesized. Several compounds showed antiinflammatory activity.

1053-1059

Influence of Base and Solvent on the Reaction
between p-Cresol and Formaldehyde Leading
to p-Methylcalix[n]arenes

by R. Ostaszewski,1 P. Lipkowski1 and J. Jurczak1,2
1Institute of Organic Chemistry, Polish Academy of Sciences, 01-224 Warsaw, Poland
2Department of Chemistry, Warsaw University, 02-093 Warsaw, Poland

(Received February 7th, 1997; revised manuscript April 24th, 1997)

Effects of solvent and base on the reaction of p-cresol with formaldehyde were studied using a liquid SIMS method. In all cases, complex mixtures of p-methylcalix[n]arenes were obtained and selectivities depended on the cation type and solvent used. Two pure products, p-methylcalix[7]arene and p-methylcalix[8]arene, were isolated.

1060-1065

Sulfanolysis of Tris(2-cyanoethyl)phosphine Chalcogenides.
X-ray Structure Analysis of OP(CH2CH2CONH2)3
and OP(CH2CH2CSNH2)3

by J. Kamenicek1, F. Kasparek1, M. Posolda1, V. Bekarek2 and J. Marek3
1Department of Inorganic and Physical Chemistry, Palacky University,
Krizkovskeho 10, 771 47 Olomouc, Czech Republic
2Department of Organic Chemistry, Palacky University,
Tr. Svobody 8, 771 46 Olomouc, Czech Republic
3Department of Inorganic Chemistry, Masaryk University,
Kotlarska 2, 611 37 Brno, Czech Republic

(Received January 27th, 1997; revised manuscript April 25th, 1997)

Sulfanolysis of tris(2-cyanoethyl)phosphine oxide (chalcogenide) gave new compounds of tris(2- thiocarbamoylethyl)phosphine oxide (chalcogenide) type, alkaline hydrolysis of which afforded sodium salts of tris(2-carboxyethyl)phosphine chalcogenides. Two compounds, OP(CH2CH2CONH2)3 and OP(CH2CH2CSNH2)3were studied by X-ray structure analysis. The coordination sphere around phosphorous atom is in both cases approximately tetrahedral.

1066-1074

Synthesis of N,N'-Carbonyl-bis-amino
Acids and N,N'-Carbonyl-bis-peptides

by J. Izdebski and D. Pawlak
Department of Chemistry, University of Warsaw, ul. Pasteura 1, 02-093 Warsaw, Poland

(Received April 2nd, 1997; revised manuscript May 12th, 1997)

A new method for the preparation of N,N'-carbonyl-bis-amino acid esters by reaction of bis(4-nitrophenyl)carbonate with amino acid esters is described. When the carbonate reacts with two equivalents of a peptide ester, N,N'-carbonyl-bis(peptide ester) is obtained but, a hydantoin derivative is formed as a side product. The hydantoin derivative is a major product, when equimolar amounts are allowed to react. Usefulness of this method for preparation of larger N,N'-carbonyl-bis-peptides is demonstrated by the synthesis of the respective product from C-terminal hexapeptide of Substance P linked to the Merrifield resin.

1075-1081

A New Method for the Preparation
of 4-Substituted Pyrazoles

by J. Soloducho1 and R.P. Musgrave2
1Institute of Organic Chemistry, Biochemistry and Biotechnology, Technical University of Wroclaw, Wybrzeze Wyspianskiego 27, 50-370 Wroclaw, Poland
2Center for Heterocyclic Compounds, University of Florida,
Gainesville, FL 32611-7200, USA

(Received April 25th, 1997)

3,5-Dimethyl-4-(benzotriazol-1-ylmethyl)-1-phenylpyrazole (5) and 1,3,5-trimethyl-4-(benzotriazol-1- ylmethyl)pyrazoles (17) were prepared and alkylated with various alkyl bromides. Treatment of these compounds with alkyl Grignards led to a variety of 4-substituted-3,5-dimethylpyrazoles.

1082-1092

Conformational Study of Scyliorhinin I
by NMR and Molecular Dynamics Calculations

by X.F. Qi, S. Rodziewicz, J. Zboinska and K. Rolka
Faculty of Chemistry, University of Gdansk, Sobieskiego 18, PL-80-952 Gdansk, Poland

(Received July 8th, 1996; revised manuscript May 19th, 1997)

A detailed conformational analysis of an equipotent agonist of NK-1 and NK-2 tachykinin receptors - scyliorhinin I in DMSO-d6 was carried out by 1H NMR (DQF-COSY, TOCSY, NOESY and ROESY) and molecular dynamics calculation methods. Two groups of conformations (major and minor) were obtained based on the experimental data. Characteristic of the lowest energy conformer of the major species is the presence of two beta-turns: the first one, type IV at the N-terminus in the 1-4 fragment, the second one, type III', with Lys5 and Phe6 in positions i + 1 and i + 2, respectively. The other conformers of this group contain an additional type IV ß-turn with Phe6 and Tyr7 in the centre. Minor species represents a more extended structure with one type VI beta-turn present in the fragment 2-5. The common motive for all low energy conformers obtained is the presence of a bent structure in the fragment 4-8 of the peptide backbone. The results obtained were compared with the published conformations of selective NK- 1 and NK-2 tachykinin agonists.

1093-1101

Ceric Ammonium Nitrate Oxidation of Aldoximes
in Aliphatic Nitriles as Solvents:
a New Way for Synthesis of 1,2,4-Oxadiazoles

by M. Giurg and J. Mlochowski
Institute of Organic Chemistry, Biochemistry and Biotechnology, Technical University of Wroclaw, Wybrzeze Wyspianskiego 27, PL-50 370 Wroclaw, Poland

(Received April 22nd, 1997; revised manuscript May 20th, 1997)

Oxidation of aromatic aldoximes with one-electron oxidant ceric ammonium nitrate CAN in acetonitrile and propionitrile, has been investigated. Aromatic nitrile oxides, formed in situ, underwent 1,3- cycloaddition with aliphatic nitriles and 5-alkyl-3-aryl-1,2,4-oxadiazoles are produced in moderate to high yields. The mechanism of the reaction based on the transformations of intermediate aldazine di-N- oxides is discussed.

1102-1107

Structure of 5-Imino-9-methyl-3-nitrodipyrido[1,2-
- a:3',2'-e]pyrimidine Hydrochloride

by B. Pniewska1, A. Rykowski1 and W. Pucko2
1Institute of Chemistry, Agricultural and Teachers University, 3 Maja 54, 08-110 Siedlce, Poland
2Institute of Organic Industry, PP Department, Annopol 6, 03-236 Warszawa, Poland

Received April 24th, 1997; revised manuscript May 21st, 1997)

Title compound, C12H9N5O2.HCl, was obtained by reaction of 2-amino-5-methylpyridine with 2-chloro-3-cyano-5-nitropyridine. The crystals belong to the monoclinic system, space group P21/c. Lattice parameters are: a = 6.8072(5) Å, b = 22.453(1) Å, c = 8.2083(7) Å, ß = 97.725(7)o. The organic cation is essentially planar except of the nitro group, which forms interplanar angle of 19.0(1)o with the adjacent ring plane. A conjugation of the double bonds is observed within the protonated imino group. The salt molecules, related by a center of symmetry, form dimers bonded via the N-H...Cl and C-H...Cl type hydrogen bonds.

1108-1112

The Reaction of Acyliron Anions with Deuterium Oxide

by E. Bartnicka and A. Zamojski
Institute of Organic Chemistry, Polish Academy of Sciences, 01-224 Warsaw, Poland

(Received May 22nd, 1997)

Alkylation of the anions, generated from propionyl and butyryliron complexes, is highly stereoselective whereas reaction of the anions with deuterium oxide is non-stereoselective and leads to both stereoisomers of RS/SR and RR/SS configuration.

1113-1119

A.C. Four-Probe Impedance Measurements
on Solid Electrolytes with High Impedance

by G. Fafilek and M.W. Breiter
Institut fuer Technische Elektrochemie, TU Wien, Getreidemarkt 9, A-1060 Wien, Austria

(Received July 18th, 1996; revised manuscript February 3rd, 1997)

An a.c. four-probe setup was built to measure impedance spectra between 1 Hz and 100 kHz on solid electrolytes up to impedance values of 10 G ohm. A solution to minimize the source of errors by means of preamplifiers for current and voltage signals is presented. A special construction of the sample holder is necessary to give the best results in conjunction with the preamplifiers. The holder is designed for measurements on solid electrolytes in a wide temperature range. The performance of the setup and the residual error sources are determined. Measurements of the four-probe impedance spectra on yttria stabilized zirconia in the temperature range between room temperature and 750oC are given as an example.

1120-1132

The Kinetics of Ag(I)/Ag Electrode Reaction
in Pure Molten Silver Chloride

by A. Kisza, J. Dzielendziak and J. Kazmierczak
Faculty of Chemistry, University of Wroclaw, 50-383 Wroclaw, Poland

(Received September 20th, 1996; revised manuscript February 10th, 1997)

Application of the relaxation and impedance methods to the study of kinetics of the electrode reaction of silver electrode in pure molten silver chloride is presented. Basing on the inductive model of the double layer of metallic electrodes in their pure molten salts, the kinetic and activation parameters of the electrode reaction are determined. The exchange current density at 600oC equals 4 A cm-2, and is slightly temperature dependent, what indicates a possible barrierless charge transfer. This has been also confirmed by a kinetic type approach.

1133-1139

Deviation from Linearity in Electrochemical
Impedance Spectroscopy

by K. Darowicki
Department of Anticorrosion Protection, Technical University of Gdansk,
Narutowicza 11/12, 80-952 Gdansk, Poland

(Received July 18th, 1996; revised manuscript February 10th, 1997)

The analysis of the effect of the sinusoidal voltage perturbation signal on an electrode process has been studied. The necessity of resolving of the effective and generated sinusoid perturbation signal has been shown. The influence of the amplitude and frequency of the voltage perturbation signal on the value of the effective potential, the value of the modulus of current harmonic components and the magnitude of the electrode impedance has been discussed.

1140-1150

Temperature Effects
in Thin Film Polyaniline Electrodes

by P. Poks and M. Grzeszczuk
Faculty of Chemistry, University of Wroclaw, 50-383 Wroclaw, Poland

(Received July 18th, 1996; revised manuscript February 13th, 1997)

The impedance of thin film polyaniline electrodes was measured in the frequency range 0.1 Hz to 50 kHz at dc potentials corresponding to the reversible reduced and oxidized forms of the polymer. Electrical, statistical, and physical models of the thin film polymer electrode were analyzed. The reversibly reduced and oxidized polyaniline was studied from 273 to 298 K. The activation energies found for the hf and lf conductivity parameters are from 0.2 eV to 0.6 eV, respectively. In spite of the hysteresis, the activation energy was found to depend insignificantly on the direction of the dc potential scan between the reversible redox forms of polyaniline.

1151-1159

Potential Dependence of the AC Impedance
Response at an Ultramicrodisc

by P. Los1 and P.G. Bruce2
1Laboratoire de Synthese et d'Electrosynthese Organometalliques,
UMR 5632 du CNRS, Faculte des Sciences Gabriel, 6 bd Gabriel, 21000 Dijon, France
2School of Chemistry, University of St. Andrews, St. Andrews, Fife KY16 9ST, Scotland

(Received September 20th, 1996; revised manuscript February 13th, 1997)

Ac impedance spectroscopy at ultramicrodisc electrodes is a potentially powerful technique for the investigation of electrochemical reactions, since it provides an excellent means of measuring and separating all the faradaic and non-faradaic processes occurring at the interface. In this paper we describe the theory and practice of the dc potential dependence of such measurements.

1160-1170

A New Experimental Device for Magnetoelectrochemical (M.E.C.)
Transfer Function Measurements

by O. Devos1, O. Aaboubi1, J-P. Chopart1, E. Merienne1,
A. Olivier1, C. Gabrielli2 and B. Tribollet2
1)EP 120-CNRS Dynamique des Transferts aux Interfaces
UFR Sciences - B.P.1039 - 51687 Reims Cedex 2, France
2)UPR15-CNRS Physique des Liquides et Electrochimie, Universite P. & M. Curie,
Tour 22 - 4, Place Jussieu - 75252 Paris Cedex 05, France

(Received July 18th, 1996; revised manuscript February 14th, 1997)

A new home-made experimental device has been developped to get accurate magnetoelectrochemical transfer functions (dI/dB)V or (dV/dB)I without an electromagnet and its limitations. First experiments were carried out with the ferri-ferrocyanide system onto platinum electrode. They confirm the experimental and theoretical results for steady-state as well as dynamic studies.

1171-1182

Investigation of Electrochemical Processes by
A.C. Quartz Electrogravimetry

by C. Gabrielli, M. Keddam, F. Minouflet-Laurent, N. Nadi and H. Perrot
Laboratoire Physique des Liquides et Electrochimie, UPR 15 CNRS - Tour 22, 5eme etage,
Universite Pierre et Marie Curie, 4 Place Jussieu - 75252 Paris, Cedex 05 - France

(Received September 20th, 1996; revised manuscript March 10th, 1997)

A general approach is proposed to investigate an electrochemical reaction mechanism by simultaneous electrochemical and electrogravimetric impedance measurements. Our approach shows that a.c. electrogravimetry may provide some useful information on the chemical nature of the species involved, in addition to the information obtained by using electrochemical impedance analysis alone. Application of a.c. electrogravimetry to passive iron in sulfuric acid solution showed that the major part of the charge transferred during a transient potential change, within the Fe passive potential range, contributes to iron corrosion rather than to the film growth. In the case of electropolymerization of polypyrrol in the presence of sodium dodecylsulfate, it was shown that the electropolymerization is followed by an oxidation process, which occurred in pores crossing the polymer.

1183-1195

An Electrochemical Impedance Study of the Oxygen
Reduction on Non-Porous NiO and LiCoO2
in Molten Carbonate

by G.A.J.M. Plevier, J.A. Prins-Jansen, K. Hemmes and J.H.W. de Wit
Laboratory for Materials Science, Delft University of Technology,
2628 Al Delft, The Netherlands

(Received September 20th, 1996; revised manuscript March 10th, 1997)

Non-porous electrodes of NiO and LiCoO2 are examined in molten carbonate half cells using electrochemical impedance spectroscopy. With this technique the charge-transfer resistance and diffusion properties of the oxygen reduction were measured as a function of gas composition and compared to theoretical predictions. For both electrodes the super oxide mechanism yields the best fit results, but the difference with the peroxycarbonate mechanism is very small. The exchange current densities of electrode processses are estimated from the Rct and found to be approximately the same for both materials. By using potentiometry we showed that both electrode materials are not inert in molten carbonate. The stoichiometry of the samples depends on the Li content in the melt due to Li-doping of NiO and the Li-insertion reaction in LiCoO2.

1196-1203

Differential Impedance Analysis on Single Crystal
and Polycrystalline Yttrium Iron Garnets

by D. Vladikova1, Z. Stoynov1 and L. Ilkov2
1Central Laboratory of Electrochemical Power Sources,
Bulgarian Academy of Sciences, 1113 Sofia, Bulgaria
2Higher Institute of Chemical Technology, 1756 Sofia, Bulgaria

(Received July 4th, 1996; revised manuscript March 26th, 1997)

The resistivity of single crystal and polycrystalline Yttrium Iron Garnet was investigated by the Complex Impedance Method, distinguishing the resistivity of the bulk material rho b from the resistivity of the grain boundaries rhogb. Two different approaches are used for the determination of the model structure: (i) a theoretical, in which the structure is assumed apriori as a Voight- type model and (ii) a structural, in which the model is extracted from the experimental data. The second approach is based on the recently developed Differential Impedance Analysis. The results obtained illustrate the advantages of the new method, which can give information about the mechanism of the ferrite conductivity and may enhance the knowledge of the physical nature of the process.

1204-1210

Differential Impedance Analysis - an Insight
into the Experimental Data

by Z. Stoynov
Central Laboratory of Electrochemical Power Sources, Bulgarian Academy of Sciences,
1113 Sofia, Bulgaria

(Received July 4th, 1996; revised manuscript March 26th, 1997)

A new method for analysis of the experimental data of the impedance spectroscopy is presented. The method is based on the assumption of a local operating model. Using the derivatives of the impedance with respect to frequency, the model parameters and their effective time-constants are calculated for each frequency. The analytical equations are used as a moving estimator over the entire frequency range. Important properties of the studied system can be derived.

1211

WATER DISINFECTION AND NATURAL ORGANIC MATTER
Characterization and Control


Edited by: Roger A. Minear and Gary L. Amy
ACS Symposium Series 649, American Chemical Society, Washington DC 1997
Hardcover, 394 pp. price GBP 109,95


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