POLISH JOURNAL OF CHEMISTRY
Volume 74 Number 1 January 2000
Pages 1-162


CONTENTS

REVIEW ARTICLE


1

Electrochemical Properties of Fullerene Based Solid Thin Layers

—- Winkler K., Costa D.A. and Balch A.L.


INORGANIC CHEMISTRY


39

Ce–Ag–P System

- Demchyna R.O., Chykhrij S.I. and Kuz'ma Yu.B.

45

Preparation and Properties of Rare Earth Element 2,3-Dihydroxybenzoates

—- Kula A. and Brzyska W.


ORGANIC CHEMISTRY


51

Synthesis of 7-Substituted 5-Dethia-5-oxacephams via [2+2]Cycloaddition of Chlorosulfonyl Isocyanate to Sugar Vinyl Ethers

—- Łysek R., Furman B., Kałuża Z. and Chmielewski M.

61

The Complexation of Protonated Amines, Diaza-18-crown-6 and Cryptand (222) by 18-Crown-6 in Different Solvents

—- Buschmann H.-J., Mutihac L., Wego A.  and Schollmeyer E.


PHYSICAL CHEMISTRY


67

Electrochemistry of Diazonium Salts. Pathways of Electrochemically Initiated Polymerization Processes

—- Koval'chuk E.P., Kozłowska Z.E., Jóźwiak L. and Błażejowski J.

79

The Kinetics of Chloromethyloxirane Reaction with Alcohols and Their Adducts in the Presence of Stannic Chloride

—- Chlebicki J. and Poźniak R.

89

QSAR Studies on Bioorganic and Pharmacological Effects of the Antidepressants

—- Pietrzycki W.

109

Fenton Reaction of Iron Chelates Involving Polyazacyclononane. The Ligand StructureEffect

—- Szulbiński W.S.


COMMUNICATIONS


125

Crystal and Molecular Structure of Pinane Derivatives with C2 Symmetry. Part I. 10,10'-Biisopinocampheol

—- Karolak-Wojciechowska J. and Markowicz S.W.

131

New Compounds of Indium(III) with 2,4'-Bipyridine

—- Czakis-Sulikowska D. and Kałużna-Czaplińska J.

137

Synthesis and Crystal Structure of Tris-(1,10-phenanthroline) Nickel(II) Dichromate

- — Tang J.K., Gao E.Q., Liao D.Z., Jiang Z.H. and Yan S.P.

141

Synthesis and Properties of New 2-Alkyl-2,3,4,5-tetrahydro-1,4-benzoxazepine Derivatives. Part IV. Reduction of 2-Alkyl- 2,3,4,5-tetrahydro-1,4-benzoxazepin-3,5-diones

—- Kwiecień H. and Baumann E.

147

Synthesis and Characterization of a New Cyclobutane Substituted Schiff Base Ligand and Its Cd(II), Co(II), Ni(II) and Zn(II) Complexes

—- Cukurovali A. and Yilmaz I.

153

Neolignan Glycosides from a Cell Suspension Culture of Lactuca virosa

—- Stojakowska A. and Kisiel W.


DISCUSSION


157

Comment on the Polymorphic Forms of Metal-Free Phthalocyanine. Refinement of the Crystal Structure of a-H2Pc at 160 K

—- Janczak J.


1-37

Electrochemical Properties of Fullerene BasedSolid Thin Layers

by K. Winkler1, D.A. Costa2 and A.L. Balch3

1Institute of Chemistry, University of Bialystok, Pilsudskiego 11/4, 15443 Bialystok, Poland

2Los Alamos National Laboratory, Los Alamos, New Mexico 87545 , USA

3Department of Chemistry, University of California, Davis, California 95616, USA

(Received August 30th, 1999)

This paper reviews the results of investigations into the electrochemical properties of fullerenes and their derivatives in solid state. These systems can be divided into three groups: (i) polycrystalline thin layers, (ii) non-crystalline films, and (iii) fullerene based polymers. The effects of the supporting electrolyte and solvent on the electrochemical behavior of polycrystalline fullerene thin layer films are discussed. The redox properties of fullerene based self-assembled monolayers, Langmuir-Blodgett films, and fullerene incorporated bilayer lipid membranes are presented. Special emphasis is placed on the electrochemistry of fullerene based polymers. Several different methods for the electrochemical polymerization of fullerene systems are described and the properties of these systems are discussed.


39-44

Ce–Ag–P System

by R.O. Demchyna, S.I. Chykhrij and Yu.B. Kuz'ma

Department of Analytical Chemistry, Ivan Franko L'viv State University,
Kyryla and Mefodia str. 6. 290005 L'viv, Ukraine

(Received July 13th, 1999; revised manuscript August 10th, 1999)

Phase equilibria were established in the Ce–Ag–P ternary system up to 80 at.% of P and the CeP–CeP2–Ag region (30–70 at.% of P) for isothermal sections at 400°C and 800°C, respectively. The isothermal sections have been formed basing on X-ray analysis. The existence of the CeAgP2 ternary phosphide at 800°C and its decomposition to CeP, Ag3P11 and Ag, when decreasing the temperature to 400°C, has been established. Its crystal structure has been investigated using X-ray single crystal and powder methods. The CeAgP2 compound exhibits crystal structure with tetragonal symmetry (I4/mmm space group, a = 0.4002(1) nm, c = 2.042(2) nm).


45-50

Preparation and Propertiesof Rare Earth Element 2,3-Dihydroxybenzoates

by A. Kula and W. Brzyska

Department of General Chemistry, Marie Curie Sklodowska University, 20-031 Lublin, Poland

(Received May 14th, 1999; revised manuscript October 1st, 1999)

Complexes of lanthanide(III) (La–Lu) and Y(III) with 2,3-dihydroxybenzoic acid were prepared and their IR spectra, solubility in water at 293 K and thermal decomposition were investigated. When heated, the complexes with a general formula Ln(C7H5O4)3×nH2O, where n = 0 for La–Tb, n = 4 for Dy–Tm and Y, n = 2 for Yb–Lu decompose to the oxides Ln2O3, CeO2, Pr6O11 and Tb4O7 with intermediate formation of Ln(C7H5O4)(C7H4O4) (with the exception of cerium complex).


51-60

Synthesis of 7-Substituted 5-Dethia-5-oxacephams via [2+2]Cycloaddition of Chlorosulfonyl Isocyanateto Sugar Vinyl Ethers

by R. Łysek, B. Furman, Z. Kałuża and M. Chmielewski

Institute of Organic Chemistry of the Polish Academy of Sciences,

Kasprzaka 44/52, 01-224 Warsaw, PolandE-mail: chmiel@ichf.edu.pl

(Received October 7th, 1999)

[2+2]Cycloaddition of chlorosulfonyl isocyanate (CSI) to (Z) prop-1'-enyl, (Z) and (E) 4'-trimethylsilyl-but-1'-enyl ethers of 1,2-O-isopropylidene-5-O-trityl-a-D-xylofuranose proceeds with high stereoselectivity to afford respective azetidin-2-ones. Subsequent transformations of adducts consisting in detritylation, tosylation of a terminal hydroxy group and intramolecular alkylation of the nitrogen atom give corresponding tetracyclic 5-oxacephams.


61-66

The Complexation of Protonated Amines, Diaza-18-crown-6 and Cryptand (222)by 18-Crown-6 in Different Solvents

by H.-J. Buschmann1, L. Mutihac2, A. Wego1 and E. Schollmeyer1

1Deutsches Textilforschungszentrum Nord-West e.V., Frankenring 2, D-47798 Krefeld, Germany

2Department of Analytical Chemistry, Faculty of Chemistry, University of Bucharest,

4-12 Blvd. Regina Elisabeta, Bucharest 703461, Romania

(Received October 29th, 1998; revised manuscript August 20th, 1999)

The formation of complexes between protonated amines and macrocyclic ligands is known. However, the diprotonated ligands diaza-18-crown-6 and cryptand (222) themselves are able to act as guest molecules. As a result they form complexes with 18-crown-6. The complex formation has been studied by calorimetric titrations and 1H NMR measurements. As the macrocyclic ligands diaza-18-crown-6 and cryptand (222) contain two nitrogen atoms, they are able to form 1:1 and 2:1 complexes with 18-crown-6. The macrocyclic and macrobicyclic structure of these ammonium ions has no influence on the formation of 1:1 complexes. From the results in methanol, propylene carbonate, acetonitrile and acetone as solvents some indirect conclusions about the structure of the diprotonated ligands in solution can be drawn. The reaction between diprotonated diazacrown ethers or cryptands with crown ethers can be used for the self-assembly of larger aggregates.


67-78

Electrochemistry of Diazonium Salts. Pathways ofElectrochemically Initiated Polymerization Processes

by E.P. Koval'chuk1, Z.E. Kozłowska1, L. Jóźwiak2 and J. Błażejowski2

1Department of Physical and Colloid Chemistry, Ivan Franko L'viv State University,

Kyryla and Mefodiy 6, 290 005 L'viv, Ukraine

2Department of Chemistry, University of Gdańsk,

J. Sobieskiego 18, 80-952 Gdańsk, Poland

(Received April 30th, 1999; revised manuscript July 29th, 1999)

The electrochemical reduction of several diazonium cations was examined on drop and stationary Hg-electrodes immersed in 1 M NaClO4 background electrolyte and water, acetone or water–acetone mixtures. Features of ongoing processes were investigated at various reduction potentials and in the presence of acrylamide as a radical scavenger. The products of electrochemical reduction are mainly polymeric substances containing hydrogen, carbon and nitrogen. The polymerization pathways were discovered on the basis of a thorough analysis of thermochemical data obtained at the level of the semiempirical PM3 method and statistical thermodynamics. Possible applications of the electrochemical reduction of diazonium cations as polymerization (polycondensation) initiators are suggested.


79-88

The Kinetics of Chloromethyloxirane Reactionwith Alcohols and Their Adductsin the Presence of Stannic Chloride

by J. Chlebicki and R. Poźniak

Institute of Organic and Polymer Technology, Wrocław University of Technology, 50-370 Wroclaw, Poland

(Received July 6th, 1999; revised manuscript September 9th, 1999)

Rate constants of the reaction of chloromethyloxirane (epichlorohydrin) with methyl, n-propyl, isopropyl, n-, sec-, tert-butyl, n-hexyl, n-octyl, and n-decyl alcohols in the presence of stannic chloride were studied at 30, 40, and 50°C. Reaction is not first order in respect to epichlorohydrine and is particularly fast at the beginning and its rate constants are proportional to the concentration of the catalyst. The rate constants increase in the homologous series of C1–C10 alcohols. The reaction rates of 2-chloromethyloxirane with 1-chloromethyl-2-alkoxyethanols are ca. 2.5-times larger than that with corresponding alcohols.


89-108

QSAR Studies on Bioorganic and PharmacologicalEffects of the Antidepressants

by W. Pietrzycki

Department of Chemistry, University of Agriculture, 31-120 Kraków, Mickiewicz Avenue 21, Poland

(Received April 12th, 1999; revised manuscript September 20th, 1999)

Quantitative Structure – Activity Relationship (QSAR) studies on 19 most important antidepressants were performed using the PM3 quantum chemical parameters. The ground state population analysis was performed for all the antidepressants (Antds), norepinephrine (NA) and serotonin (5-HT) neurotransmitters, imipramine---NA complex and  its ionic forms, asparaginate anion as active moiety in  TM III  helix of  a1-adrenergic receptors, serine – active species in TM V helix of a2-adrenergic receptors and  phenylalanine as actvive in TM VI  helix of  both a1- and  a2-adrenergic receptors of  brain frontal cortex. With the use of experimental data: Ki(j) inhibitor constants, Aj affinities and IC50(j) inhibitory activities, a linear dependence of  ln 1/Ki(j), ln Aj and ln 1/IC50(j) on  electronic density parameters and charge-transfer frontier orbital parameters was found. Four aspects on the biochemical and pharmacological  effects of antidepressants  are examined: (i) Blockade of  NA uptake into presynaptic nerve endings is followed by the formation of Antd---NA inactive complexes. (ii) Analogous blockade of  5-HT  uptake into presynaptic surface is accompanied by a formation of Antd---5-HT inactive complexes. (iii) Up-regulation effect of the postsynaptica1-adrenergic receptors is followed  by high affinities of Antd---NA complexes and Antd---NA-H+ transition state forms for a receptor surface, accompanied by small affinities of  the antidepressants for  NA-H+ agonist.  (iv) Down-regulation of  the presynaptica2-adrenergic receptors (autoreceptors) is followed by an impossibility of  formation of  Antd---NA-H+ ionic transition states  on  the a2-receptor  surface.


109-124

Fenton Reaction of Iron Chelates Involving Polyazacyclononane. The Ligand Structure Effect

by W.S. Szulbiński

Central Institute of Mining, Department of Environmental Monitoring,

40-166 Katowice, Plac Gwarków 1, Poland

(Received August 6th, 1999; revised manuscipt October 1st, 1999)

A Fenton-like reaction of two ferrous macrocyclic complexes, one with the pentadentate ligand DPC, (DPC = N, N'-di-2-picolyl-4,7-diaza-1-oxacyclononane), and the other with the hexadentate ligand TPC, (TPC = N, N', N''-tri-2-picolyl-1,4,7-triazacyclononane) has been studied, using spectroscopic, electrochemical and kinetic analysis. Even though redox potentials of these complexes are quite similar, the rate constant of H2O2/[Fe2+DPC]2+ (k = 650 ± 80 M–1 s–1, at pH = 5.6 and 25°C) is three orders of magnitude higher than that of H2O2/[Fe2+TPC]2+. Because the oxidation of [Fe2+DPC]2+ ([Fe2+TPC]2+) by H2O2 is thermodynamically unfavourable, production of a highly reactive oxidizing intermediate, such as hydroxyl radicals (OH·) or a kinetically equivalent ferryl species ([OFe4+L]2+), is postulated. The resonance Raman spectrum of [Fe2+DPC]2+ treated with H2O2 shows a frequency at 854 cm–1, ascribable to n(O–O) vibration modes of an iron peroxide complex with side-on geometry. The electron spin resonance spectrum of this reaction mixture, acquired at 77 K, exhibits the resonance transition, due to a low-spin Fe3+ complex with axial symmetry. It has been concluded that the rate of H2O2/[Fe2+TPC]2+ is limited by substitution of peroxide anion for one of the ligating 2-picoline. On the other hand, H2O2/[Fe2+DPC]2+ proceeds via rapid bonding of H2O2 to an open coordination site on the central cation.


125-129

Crystal and Molecular Structure of Pinane Derivatives with C2 Symmetry. Part I. 10,10''-Biisopinocampheol

by J. Karolak-Wojciechowska1and S.W. Markowicz2

1Institute of General and Ecological Chemistry and

2Institute of Organic Chemistry,Technical University of Łódź,

ul. Żeromskiego 116, 90-924 Łódź, Poland

(Received July 9th, 1999; revised manuscript September 3rd, 1999)


131-136

New Compounds of Indium(III) with 2,4'-Bipyridine

by D. Czakis-Sulikowska and J. Kałużna-Czaplińska

Institute of General and Ecological Chemistry, Technical University,90-924 Łódź, ul. Żwirki 36, Poland

(Received June 28th, 1999; revised manuscript September 13th, 1999)


137-140

Synthesis and Crystal Structure of Tris-(1,10-phenanthroline) Nickel(II) Dichromate

by J.-K. Tang, E.-Q. Gao, D.-Z. Liao, Z.-H. Jiang and S.-P. Yan

Department of Chemistry, Nankai University, Tianjin, 300071, P. R. China

(Received July 19th, 1999; revised manuscript September 28th, 1999)


141-145

Synthesis and Properties of New 2-Alkyl-2,3,4,5-tetrahydro-1,4-benzoaxazepine Derivatives. Part IV. Reduction of 2-Alkyl-2,3,4,5-tetrahydro-1,4-benzoaxazepin-3,5-diones

by H. Kwiecień1 and E. Baumann2

1Dep. Organic Synthesis, Technical Univ. of Szczecin, Al. Piastów 42, 71-065 Szczecin

2Hauptlaboratorium, BASF-AG, 67056 Ludwigshafen, Germany

(Received July 27th, 1999; revised manuscript October 4th, 1999)


147-151

Synthesis and Characterization of a New Cyclobutane Substituted Schiff Base Ligand and Its Cd(II), Co(II), Ni(II) and Zn(II) Complexes

by A. Çukurovalland I. Yllmaz

Firat University, Faculty of Arts and Sciences, Chemistry Department, 23119 Elazig, Turkey

(Received August 5th, 1999; revised manuscript October 7th, 1999)


153-155

Neolignan Glycosides from a Cell SuspensionCulture of Lactuca virosa

by A. Stojakowska and W. Kisiel

Department of Phytochemistry, Institute of Pharmacology, Polish Academy of Sciences,

Smętna 12, 31-343 Kraków, Poland

(Received August 25th, 1999; revised manuscript October 8th, 1999)


157-162

Comment on the Polymorphic Formsof Metal-Free Phthalocyanine.Refinement of the Crystal Structure of a-H2Pc at 160 K

by J. Janczak

W. Trzebiatowski Institute of Low Temperatures and Structure Research, Polish Academy of Sciences, P.O. Box 1410, 50-950 Wrocław, Poland; email: janczak@highscreen.int.pan.wroc.pl

(Received August 19th, 1999; revised manuscript October 1st, 1999)




Return to main page.


© 1999 Polish Journal of Chemistry

prepared by (aws)