POLISH JOURNAL OF CHEMISTRY
Volume 72 Number 12 December 1998
Pages 2519-2672-


CONTENTS

Page

INORGANIC CHEMISTRY
2519 Synthesis and Characterization of the Copper(II) Complexes with 3-Amino-1,2,4-triazole,
4-Amino-1,2,4-triazole and 3-Amino-5-methylthio-1,2,4-triazole

— Gabryszewski M.
2524 Spectral and Thermal Studies of Yttrium and Heavy Lanthanide 2,6-Dihydroxybenzoates
— Brzyska W., Kula A., Rzączyńska Z. and Jaroniec M.
ORGANIC CHEMISTRY
2531 13C CP MAS NMR Study of Some 4,4',-Disubstituted-trans-azobenzenes
— Maciejewska D., Koleva V. and Wawer I.
2537 Analogue of Cucurbita maxima Trypsin Inhibitor III (CMTI-III) with All L-Cysteine Residues Substituted by L-Penicillamine (Pen). Synthesis and Evaluation of Trypsin
Inhibitory Activity

— Jaśkiewicz J., Lesner A., Różycki J., Kupryszewski G. and Rolka K.
2541 Reactions of N-Aryl-N-(4,5-dihydro-1H-imidazol-2-yl)hydroxylamines with Methanesulfonyl Chloride. Synthesis and Acylation of 2,3-Dihydro-1H-imidazo[1,2-a]benzimidazoles
— S±czewski F. and Dębowski T.
2546 Reactions of Aza-ortho-xylylenes with 1,4-Naphthoquinone
— Kosiński Sz. and Wojciechowski K.
PHYSICAL CHEMISTRY
2551 13C Kinetic Isotope Effects in the Decarboxylation of Phenylpropiolic Acid (PPA) Assisted with Formic Acid and 13C KIE in the Decarbonylation of Formic Acid in the Presence of PPA
— Zieliński M., Zielińska A., Paul H. and Papiernik-Zielińska H.
2556 Chronopotentiometry as a Method for Determining Stability Constants of Metal Complexes
— Kublanovsky V.S., Litovchenko K.I. and Nikitenko V.N.
2564 A Contribution to ZSM-5 Zeolite Modified with Niobia
— Romotowski T., Komorek J. and Terskikh V.V.
2573 Electrochemical Studies of 1,8-Dihydroxy-9,10-anthraquinone Derivatives in Acetonitrile
— Salimi A., Tamaddon F., Sharghi H., Mousavi M.F., Golabi S.M. and Shamsipur M.
2583 A Cyclic Voltammetric and Coulometric Study of a Modified Electrode Prepared by
Electrooxidative Polymerization of Nickel Complex of 1,5-Diaminonaphthalene in Acetonitrile

— Yousef U.S. and Abdel-Azzem M.
2598 Probing Palladium-Silica Interactions in Pd/SiO2 Catalyst Subjected to High Temperature Reduction
— Łomot D.
2606 Phosphorus Losses in VPO Catalysts
— Stoch J., Stoch A., Mikołajczyk M. and Brożek A.
2610 Thermal Degradation of Epoxy Polymers. Method of the Evaluation of Kinetic Parameters on the Base of Thermogravimetric Data
— Zakordonskiy V.P., Hnatyshin S.Y. and Soltys M.M.
2621 Characterization of Cu-Ni Alloys by Temperature-Programmed Reduction Method
— Zieliński J.
CRYSTAL AND MOLECULAR STRUCTURE
2629 Structural Investigation of Nifuroxazide, p-Hydroxy-N',-(5-nitrofurfurylidene)benzhydrazide
— Pniewska B. and Januchowski M.
COMMUNICATIONS
2635 Alkaline Poly(vinyl alcohol)-KOH-H2O Solid Polymer Electrolyte
— Lewandowski A. and Skorupska K.
2639 Reaction of 1,1,2,3-Tetramethylallyl Cation with 2,3-Dimethyl-2-butene: Intermediates and Reaction Pathway
— Baran J. and Sośnicki J.
2642 Adsorption of Nitrogen on Iron Surface
— Arabczyk W. and Narkiewicz U.
2649 ANNUAL INDEXES
2649  - CONTENTS
2649   -- Review Articles
2649   -- Inorganic Chemistry
2651   -- Organic Chemistry
2653   -- Physical Chemistry
2656   -- Crystal and Molecular Structures
2657   -- Communications
2659   -- Supplement in Honor of Włodzimierz Kołos
2660   -- Book Reviews and IUPAC Recommendations
2662   - AUTHOR INDEX
2672   - SUBJECT INDEX


ABSTRACTS


2519-2523

Synthesis and Characterization of the Copper(II)
Complexes with 3-Amino-1,2,4-triazole, 4-Amino-1,2,4-
-triazole and 3-Amino-5-methylthio-1,2,4-triazole

by M. Gabryszewski
Institute of Chemistry, Pedagogical University, Chęcińska 5, 25020 Kielce, Poland

(Received June 23rd, 1998)

The complexes of Cu(II) with 3-amino-1,2,4-triazole, 4-amino-1,2,4-triazole and 3-amino-5-methylthio-1,2,4-triazole have been prepared and characterized by metal and CHN analyses, infrared and visible spectral and magnetic susceptibility data. It has been found, that the first two ligands form mononuclear species, while the third ligand forms the polynuclear complex. All the complexes have pseudo-octahedral configuration with a tetragonal distortion.

2524-2530

Spectral and Thermal Studies of Yttrium and Heavy Lanthanide 2,6-Dihydroxybenzoates

by W. Brzyska1, A. Kula1, Z. Rz±czyńska1 and J. Jaroniec2
1Department of Inorganic and General Chemistry, Marie Curie Skłodowska University,
20-031 Lublin, Poland
2Department of Chemistry, Kent University, Kent OH 44242, USA

(Received June 1st, 1998; revised manuscript July 22nd, 1998)

The complexes of Y(III) and heavy lanthanides(III) (Gd-Lu) with 2,6-dihydroxybenzoic acid have been prepared and their IR spectra, solubilities in water and thermal decomposition have been investigated. The complexes [Ln(C7H5O4)3(H2O)4].2H2O, when heated, lose their crystallization water in two steps and then decompose to the oxides Ln2O3 and Tb4O7 with intermediate formation of Ln(C7H5O4)(C7H4O4). In the complexes prepared, the carboxylate groups act as monodentate and bidentate chelating ligands. The water molecules are linked in inner and outer spheres. The complexes of Y(III) and heavy lanthanides (Gd-Lu) are isostructural.

2531-2536

13C CP MAS NMR Study of Some
4,4'-Disubstituted-trans-azobenzenes

by D. Maciejewska1, V. Koleva2 and I. Wawer1
1Department of Physical Chemistry, Faculty of Pharmacy, Medical University of Warsaw,
1 Banacha, 02-097 Warsaw, Poland
E-mail: wawer@farm.amwaw.edu.pl
2Department of Chemistry, University of Sofia, 1126 Sofia, Bulgaria

(Received June 23rd, 1998)

Azobenzenes with para-dimethylamino group at aromatic ring and various para substituents to another phenyl have been studied by 13C CP MAS NMR spectroscopy followed by semi-empirical AM1 MO calculations. The locked trans-configuration around N=N bond in the solid state results in non-equivalence of ortho carbons (C2 and C6, also C2' and C6') and the difference in chemical shifts is 12.9-22.0 ppm. The separation of meta carbons resonances is less manifested but in 1, 3, 4, 8 the non-equivalence of C3' and C5' is enhanced by the orientation of X-substituents at C4'.

2537-2540

Analogue of Cucurbita maxima Trypsin Inhibitor III (CMTI-III) with All L-Cysteine Residues Substituted by L-Penicillamine (Pen). Synthesis and Evaluation of Trypsin Inhibitory Activity

by A. Jaśkiewicz, A. Lesner, J. Różycki, G. Kupryszewski and K. Rolka
Faculty of Chemistry, University of Gdańsk, ul. Sobieskiego 18, 80-952 Gdańsk, Poland

(Received July 28th, 1998)

A 29-peptide, [Pen3,10,16,20,22,28]CMTI-III, an analogue of Cucurbita maxima trypsin inhibitor from squash seeds was synthesized by the solid phase method using the Fmoc chemistry. The inhibitory activity of the analogue, as measured by the association equilibrium constant (Ka) with bovine -trypsin, is of the same order of magnitude as that for the wild CMTI-III.

2541-2545

Reactions of N-Aryl-N-(4,5-dihydro-1H-imidazol-2-yl) hydroxylamines with Methanesulfonyl Chloride.
Synthesis and Acylation of 2,3-Dihydro-1H-imidazo
[1,2-a]benzimidazoles

by F. Sączewski and T. Dębowski
Department of Organic Chemistry, Medical University of Gdańsk,
Al. Gen. Hallera 107, 80-416 Gdańsk, Poland
E-mail: saczew@eniac.farmacja.amg.gda.pl

(Received July 3rd, 1998; revised manuscript August 28th, 1998)

Reactions of N-aryl-N-(4,5-dihydro-1H-imidazo-2-yl)-hydroxylamines 1a-d with methanesulfonyl chloride in the presence of triethylamine afforded 2,3-dihydroimid-
azo[1,2-a]benzimidazoles 2a-d. The latter compounds treated with acetic anhydride, methane or phenylsulfonyl chlorides gave N-1 acetyl or N-1 methane or phenylsulfonyl derivatives 3a-d and 4a-b, respectively.

2546-2550

Reactions of Aza-ortho-xylylenes with 1,4-Naphthoquinone

by Sz. Kosiński and K. Wojciechowski
Institute of Organic Chemistry, Polish Academy of Sciences,
ul. Kasprzaka 44/52, PL 01-224 Warszawa 42, P.O.Box. 58, Poland
e-mail: kris@ichf.edu.pl

(Received September 14th, 1998; revised manuscript September 23rd, 1998)

Reactions of 1,4-naphthoquinone with aza-ortho-xylylenes generated via thermal extrusion of SO2 from 2,1-benzisothiazoline 2,2-dioxides (benzosultams) lead to tetrahydronaphthalene-2-spiro-2'-dihydroindole derivatives. Aza-ortho-xylylene generated via thermal ring opening of 1-phenylbenzazetidine gave with naphthoquinone benzo[b]acridine derivative 15.

2551-2555

13C Kinetic Isotope Effects in the Decarboxylation of Phenylpropiolic Acid (PPA) Assisted with Formic Acid and 13C KIE in the Decarbonylation of Formic Acid
in the Presence of PPA

by M. Zieliński1, A. Zielińska1, H. Paul2 and H. Papiernik-Zielińska1
1Laboratory of Nuclear Chemistry, Faculty of Chemistry, Jagiellonian University, 30-060 Kraków, Poland
2Laboratory of Stable Isotopes, Institute of Geology, ETH, Zuerich, Switzerland

(Received May 6th, 1998; revised manuscript July 3rd, 1998)

Carbon-13 kinetic isotope effects,13C-KIE, in the decarboxylation of phenylpropiolic acid (carboxyl C-13) in formic acid medium and 13C KIE in the decarbonylation of liquid formic acid assisted with PPA and acetophenone have been studied in the 70-100°C temperature interval. The kinetic and isotope results have been discussed and interpreted as indicating that the formation of C-H bond, preceded by the protonation of acetylenic bond of PPA, is the rate determining step followed by carbon dioxide splitting. The 13CO-KIE in the carbon monoxide generation assisted with PPA is much larger than the 13CO-KIE observed in the generation of CO in the presence of phenylacetylene. Thus the decarboxylation of PPA and decarbonyl

2556-2563

Chronopotentiometry as a Method for Determining
Stability Constants of Metal Complexes

by V.S. Kublanovsky, K.I. Litovchenko and V.N. Nikitenko
Institute of General and Inorganic Chemistry, 32-34 Prospekt Palladina, 252680 Kiev 142, Ukraine

(Received May 22nd, 1998; revised manuscript July 21st, 1998)

The complex formation of cadmium(II) with ethylenediaminetetraacetate (H4Edta), iminodiacetate (H2Imda) and glycine (HGl) has been studied by chronopotentiometry. It has been found that cadmium(II) forms with the above ligands complex ions of the compositions: CdHEdta-, CdEdta2-, CdImda, Cd (Imda)22- CdGl+ and CdGl2. The stability constants of the above complexes have been determined.

2564-2572

A Contribution to ZSM-5 Zeolite Modified with Niobia

by T. Romotowski1, J. Komorek1 and V.V. Terskikh2
1Institute of Catalysis and Surface Chemistry, Polish Academy of Sciences,
ul. Niezapominajek, 30-239 Kraków, Poland
2Institute of Catalysis, Siberian Branch of Russian Academy of Sciences, Novosibirsk, Russia

(Received June 17th, 1998; revised manuscript July 23rd, 1998)

ZSM-5 zeolite modified with Nb was investigated by XRD, IR and MAS NMR spectroscopies. Niobium atoms were introduced by calcination of NH4ZSM-5 zeolite with Nb2O5. The last samples showed Broensted and Lewis acidity and can catalyse m-xylene ammoxidation to nitriles. Thermal treatment of ZSM-5 and Nb2O5 mixtures leads to dealumination of zeolite framework. The addition of Nb2O5 decreases the amount of aluminium atoms eliminated from the lattice and preserves the framework.

2573-2582

Electrochemical Studies of 1,8-Dihydroxy-9,10-
-anthraquinone Derivatives in Acetonitrile

by A. Salimi1, F. Tamaddon2, H. Sharghi2, M.F. Mousavi1,
S.M. Golabi3 and M. Shamsipur4
1Department of Chemistry, Tarbiat Modarres University, Tehran, Iran
2Department of Chemistry, Shiraz University, Shiraz, Iran
3Electroanalytical Chemistry Laboratory, Faculty of Chemistry, University of Tabriz, Tabriz, Iran
4 Department of Chemistry, Razi University, Kermanshah, Iran

(Received April 30th, 1998; revised manuscript July 27th, 1998)

The electrochemical reductions of some recently synthesized 1,8-dihydroxy-9,10-anthraquinone derivatives in acetonitrile were investigated. In the absence of proton donors, the anthraquinones reduced in two successive one-electron steps. The first step is reversible or nearly reversible, while the second step is quasireversible or irreversible, depending on the electrode used. The influence of molecular structure on the reduction potential is addressed. The diffusion coefficients of the anthraquinone derivatives were determined from chronoamperometric measurements on the GC, Au and Pt electrodes. The heterogeneous electron transfer rate constants and charge transfer diffusion coefficients were evaluated from rotating disc voltammetry measurements. Dependence of the rate constants on the anthraquinone structure and the electrode materials is discussed.

2583-2597

A Cyclic Voltammetric and Coulometric Study
of a Modified Electrode Prepared by Electrooxidative Polymerization of Nickel Complex
of 1,5-Diaminonaphthalene in Acetonitrile

by U.S. Yousef and M. Abdel-Azzem
Electrochemistry Laboratory, Chemistry Department, Faculty of Science,
E1 Menoufia University, Shebin EI-Kom, Egypt

(Received April 22nd, 1998; revised manuscript August 10th, 1998)

The electrooxidative polymerization of nickel complex of 1,5- diaminonaphthalene was performed in acetonitrile containing lithium perchlorate, using cyclic voltammetry and controlled potential electrolysis. The film coated electrode showed an electroactive redox response in acidic aqueous solutions only. The stability of the redox response towards repetitive cyclic voltammetry was studied. The formal redox potential of the resulting film electrode was about 0.28 V vs. Ag/Ag+ in 1.0 M acidic chloride aqueous solution (pH = 0). The electrical conductivity of the film was measured in 0.01 M KC1 aqueous solution and was found as (2.2 ± 0.02) × 10-4 S cm-1. The morphology of the film and the factors affecting its electroactivity were studied in detail.

2598-2605

Probing Palladium-Silica Interactions in Pd/SiO2
Catalysts Subjected to High Temperature Reduction

by D. Łomot
Department of Catalysis on Metals, Institute of Physical Chemistry, Polish Academy of Sciences,
ul. Kasprzaka 44/52, 01-224 Warszawa, Poland

(Received June 2nd, 1998; revised manuscript August 11th, 1998)

Metal-support interactions in silica-supported palladium catalyst have been re-investigated. In addition to the already recognized model reaction of 2,2-dimethylpropane with hydrogen, where the isomerization selectivity appears as a useful indication in diagnosing changes in the catalyst, another effective probe has been used: a variable capability of differently modified palladium to form the hydride phase. High temperature reduction at 600°C of 1.6 wt% Pd/SiO2 results in the formation of palladium silicide. However, the prove of this fact by X-ray diffraction is ambiguous or impossible, because of a low content of highly dispersed Pd-containing phase. On the other hand, the formation (stability) of Pd hydride provides an interesting diagnostic tool: Pd/SiO2 transformed into Pd silicide does not form the metal hydride phase. The stability of the Pd hydride phase and the catalytic conversion of 2,2-dimethylpropane are complementary methods in probing silica-supported palladium catalysts.

2606-2609

Phosphorus Losses in VPO Catalysts

by J. Stoch1, A. Stoch2, M. Mikołajczyk1 and A. Brożek2
1Institute of Catalysis and Surface Chemistry, Polish Academy of Sciences,
ul. Niezapominajek 1, Kraków 30-239, Poland
2University of Mining and Metallurgy, Faculty of Materials Science and Ceramics,
Department of Crystallochemistry and Chemistry of Silicates, al. Mickiewicza 30, Kraków 30-059, Poland

(Received May 21st, 1998; revised manuscript August 28th, 1998)

During oxidation of n-butane to maleic anhydride on VPO catalysts phosphorus is carried out from the catalyst by gas phase. The transport medium is likely an organic compound of phosphorus. An active role of phosphorus in the n-butane transformation is suggested.

2610-2620

Thermal Degradation of Epoxy Polymers.
Method of the Evaluation of Kinetic Parameters
on the Base of Thermogravimetric Data

by V.P. Zakordonskiy, S.Y. Hnatyshin and M.M. Soltys
Department of Physical and Colloid Chemistry, Ivan Franko Lviv State University,
Kyryla & Mefodia St. 8, Lviv 290005, Ukraine

(Received May 4th, 1998; revised manuscript September 16th, 1998)

A new evaluation of kinetic parameters of the thermal degradation of cross-linked polymers is proposed. The DTG-peaks separation is the base for this method. The application of this approach to thermal degradation of epoxypolymers is discussed with respect to chemical transformations and structure of the polymer matrix.

2621-2628

Characterization of Cu-Ni Alloys by
Temperature-Programmed Reduction Method

by J. Zieliński
Institute of Physical Chemistry, Polish Academy of Sciences,
ul. Kasprzaka 44/52, 01-224 Warsaw, Poland

(Received May 11th, 1998; revised manuscript October 6th, 1998)

Reduction of surface oxide preformed on unsupported and alumina supported Cu-Ni alloys was examined at a linearly increasing temperature. The obtained TPR spectra exhibited two peaks of H2 consumption, connected with the reduction of surface copper and surface nickel oxides. The size of these peaks was used to estimate surface compositions of the alloy. The results obtained agree with the surface composition calculated from a semiempirical equation.

2629-2634

Structural Investigations of Nifuroxazide,
p-Hydroxy-N'-(5-nitrofurfurylidene)benzhydrazide

by B. Pniewska1 and M. Januchowski2
1Institute of Chemistry, Agricultural and Teachers University, ul. 3 Maja 54, 08-110 Siedlce, Poland
2POLFA, ul. Poniatowskiego 5, 05-825 Grodzisk Mazowiecki, Poland

(Received June 23rd, 1998; revised manuscript August 26th, 1998)

The crystal and molecular structure of the antibacterial compound Nifuroxazide was carried out by X-ray diffraction methods. The crystals belong to the triclinic system, space group P1. The lattice parameters are: a = 6.879(6) , b = 8.164(5) , c = 11.410(7) , = 78.87(5)°, = 78.91(5)°, = 69.68(7)°. The molecule is essentially planar except of the phenyl ring somewhat twisted with respect to the residual part of the molecule. In the crystal structure, the molecules are hydrogen bonded, forming infinite planar sheets.

2635-2638

Alkaline Poly(vinyl alcohol)-KOH-H2O
Solid Polymer Electrolyte

by A. Lewandowski and K. Skorupska
Institute of Chemistry, Poznań University of Technology, PL-60 965 Poznań, Poland

(Received June 24th, 1998; revised manuscript August 10th, 1998)

2639-2642

Reaction of 1,1,2,3-Tetramethylallyl Cation with
2,3-Dimethyl-2-butene: Intermediates and
Reaction Pathway

by J. Baran and J. Sośnicki
Institute of Fundamental Chemistry, Technical University, Al. Piastów 42, PL-71-065 Szczecin, Poland

(Received October 14th, 1997; revised manuscript August 17th, 1998)

2642-2648

Adsorption of Nitrogen on Iron Surface

by W. Arabczyk and U. Narkiewicz
Institute of Inorganic Chemical Technology, Technical University of Szczecin,
ul. Pułaskiego 10, 70-322 Szczecin, Poland
Email:un@mailbox.tuniv.szczecin.pl

(Received May 25th, 1998; revised manuscript September 7th, 1998)


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