POLISH JOURNAL OF CHEMISTRY
Volume 72 Number 6 June 1998
Pages 971- 1130


CONTENTS

Page

REVIEW ARTICLE
971 Stable Thioaldehydes and Selenoaldehydes: Synthesis, Structure and Reactivity
— Tokitoh N. and Okazaki R.
INORGANIC CHEMISTRY
1001 Rare Earth(III) Complexes with an Amido Acid Derived from Isonicotinic Acid Hydrazide: Syntheses, Characterization and Antifungal Activities
— Shen X., Shi X.F., Liu Y.S., Yao T.M. and Xie Y.Y.
1009 The Synthesis, Crystal, Molecular and Electronic Structure of [ReCl3(NO)(OPPh3)(PPh3)] Complex
— Dziegielewski J.O., Machura B., Kupka T., Bartczak T.J. and Czurak W.
ORGANIC CHEMISTRY
1017 Synthesis of Human Heat Shock Protein 70 (29-42) Fragment and Evaluation of Its Immunogenicity
—Karawajczyk B., Wysocki J., Kunikowska D., Mackiewicz Z., Glosnicka R., Korzeniowski A., Gorski J. and Kupryszewski G.
1021 The Ritter Reaction of Terpenes. Part 2. The Fenchyl System
— Welniak M.
1028 Reversed Imidazole Nucleosides. Alternative Pathways of Synthesis
— Walczak K. and Suwinski J.
PHYSICAL CHEMISTRY
1037 The Kinetics of the Sn(II)/Sn Electrode Reaction in Pure Molten Tin Dichloride
— Kazmierczak J. and Kowalczewska K.
1045 Wetting Behavior of Molten Alkali Carbonates on Au Interface under Various Gas Atmo-spheres
— Godula-Jopek A. and Suski L.
1054 Prediction of Tautomeric Equilibrium Constant in the Gas Phase for Simple Compounds Containing the Amidine Group
— Raczynska E.D. and Taft R.W.
1068 Chiral Recognition Studies of Amino Acids by Chiral Calix[4]resorcinarenes in Langmuir Films
— Pietraszkiewicz M., Prus P. and Fabianowski W.
1076 Effect of High-Molecular-Weight Polymers on Sedimentation Behavior and Stability of Fine Suspensions
— Nowicki W. and Nowicka G.
1089 The Chemical Properties of Zn and Ag Composite Electrodes for Power Sources
— Koval'chuk E.P., Artymyshyn O.R., Reshetnyak O.V. and Pankevych R.V.
1096 Adsorption of Tyrosine on Ag(110) and Ag(111) Surfaces
— Milkowska M. and Jurkie-wicz-Herbich M.
CRYSTAL AND MOLECULAR STRUCTURES
1106 Crystal Structure of meso-4,4'-Di[2.2]paracyclophane
— Jones P.G. and Kus P.
COMMUNICATIONS
1112 The Ag2GeS3-CdS System
— Piskach L.V. and Parasyuk O.V.
1116 Voltammetry at Platinum Microelectrodes of Binary Liquids Based on Methanol
—Gadomska J. and Stojek Z.
1120 Isobaric Vapor-Liquid Equilibria of the Hexamethyldisiloxane-1-Butanol System
— Kaczmarek B.
1124 Force Field Studies of Some XY3Z Type Molecules
— Palaniappan PL.RM. and Rajamannan B.
1127 1,4-Dihydro-1-methyl-4-thioxo-3-quinolinesulfonamides
— Skrzypek L., Folwarczna J., Janiec W., Kaczmarczyk-Sedlak I., Maslankiewicz A. and Pytlik M.


ABSTRACTS


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971-1000

Stable Thioaldehydes and Selenoaldehydes:
Synthesis, Structure and Reactivity

by N. Tokitoh and R. Okazaki
Department of Chemistry, Graduate School of Science, The University of Tokyo,
7-3-1 Hongo, Bunkyo-ku, Tokyo 113, Japan
E-mail:okazaki@chem.s.u-tokyo.ac.jp

(Received November 28th, 1997)

Recent progress in the synthesis, structure, and reactivity of thio- and selenoaldehydes kinetically stabilized by steric protection are reviewed with emphasis on the authors' work.

1001-1008

Rare Earth(III) Complexes with an Amido Acid Derived from Isonicotinic Acid Hydrazide:
Syntheses, Characterization and Antifungal Activities

by X. Shen1, X.F. Shi1, Y.S. Liu1, T.M. Yao1 and Y.Y. Xie2
1Department of Chemistry, Tongji University, Shanghai 200092, China 2Shanghai Institute of Materia Medica, Chinese Academy of Sciences, Shanghai 200031, China

(Received September 30th, 1997; revised manuscript November 19th, 1997)

Rare earth(III) complexes, RE2(CPI)3.nH2O (RE = La, Ce, Pr, Sm, Gd, Tb, Dy, Er, Yb, Sc, n = 3; RE = Nd, Eu, n = 4; H2CPI = 1-[(N-carboxymethyl-N-phenyl)amino]acetyl-isonicotinic acid hydrazide), have been synthesized and characterized by IR, UV and 1H NMR spectroscopy, magnetic susceptibility, elemental analysis, molar conductivity and TGA measurement. Preliminary pharmacological tests showed that these complexes exhibit definite inhibition activities against S. Sake Yake and C. Albicans (Robin) Berkh 50.

1009-1016

The Synthesis, Crystal, Molecular and Electronic
Structure of [ReCl3(NO)(OPPh3)(PPh3)] Complex

by J.O. Dziegielewski1, B. Machura1, T. Kupka1,
T.J. Bartczak2* and W. Czurak2
1Department of Inorganic and Radiation Chemistry, Institute of Chemistry, University of Silesia,
9th Szkolna St., 40-006 Katowice, Poland
2X-ray Crystallography Laboratory, Institute of General and Ecological Chemistry,
Technical University of Lodz, 116 Zeromski St., 90-924 Lodz, Poland
E-mail: tjbartcz@lodz1.p.lodz.pl.

(Received December 18th, 1997; revised manuscript February 5th, 1998)

A new rhenium(II) nitrosyl complex has been synthesized and characterized by IR, UV-VIS, NMR (1H and 31P) and magnetochemical measurements. Its ligand field parameters have been determined (Dq = 2810, Ds = -3712 and Dt = 822 cm-1). The crystal and molecular structure of [ReCl3(NO)(OPPh3)(PPh3)] has been solved by the heavy atom method and refined anisotropically to R = 5.52% for 7525 unique observed reflections. The crystals of [ReCl3(NO)(OPPh3)(PPh3)] contain distorted octahedral molecules, in which the triphenylphosphine ligand is trans with respect to one chlorine atom and O-triphenylphosphine ligand is trans to nitrosyl group. The PPh3 and OPPh3 groups are cis. Re-Cl bond trans to PPh3 [2.377(2) Å] is longer than the mutually trans Re-Cl bonds [2.358(2) and 2.350(2) Å]. The rhenium atom is pushed by 0.12 Å towards nitrosyl ligand out of the least-squares plane defined by the atoms: Cl(1), Cl(2), Cl(3) and P(2).

1017-1020

Synthesis of Human Heat Shock Protein 70 (29-42) Fragment and Evaluation of Its Immunogenicity

by B. Karawajczyk1, J. Wysocki2, D. Kunikowska2, Z. Mackiewicz1,
R. Glosnicka2, A. Korzeniowski2, J. Gorski2 and G. Kupryszewski1,3
1Faculty of Chemistry, University of Gdansk, 80-952 Gdansk, Poland
2Institute of Maritime and Tropical Medicine, 81-519 Gdynia, Poland
3Institute of Oceanology, Polish Academy of Sciences, 81-712 Sopot, Poland

(Received January 19th, 1998)

The 29-42 fragment of human heat shock protein 70 (hsp70) was synthesized by the solid phase method. As determined by enzyme-linked immunosorbent assay (ELISA), the synthetic hsp70(29-42)peptide generated relatively strong immune response in immunized rabbits. Antibody titers were comparable with anti hsp70 antibody serum level that was induced by immunization with recombinant protein (hsp70). It was established that antibodies directed against hsp70(29-42)peptide could be applied in ELISA for detecting hsp70 in body fluids and tissues.

1021-1027

The Ritter Reaction of Terpenes. Part 2.
The Fenchyl System

by M. Welniak
Faculty of Chemistry, Nicolaus Copernicus University, 87-100 Torun, Poland

(Received August 4th, 1997; revised manuscript February 2nd, 1998)

The Ritter reaction of fenchyl alcohols 2a-f was examined. Surprisingly, in the case of alcohols 2a-d, formation of the corresponding alkenes 3 was observed. These compounds underwent, in turn, Namietkin and Wagner-Meerwein rearrangements, followed by endo-6,2-hydrogen shift to give acetamides 8 and 9. The alcohol 2e gave a mixture of hydrocarbons 11 and 12 as well as an anti acetamide 9e. For secondary endo-2-fenchol (2f) exo-isofenchyl acetamide (15) was the only product as a result of endo-6,2-hydrogen shift and subsequent reaction with acetonitrile.

1028-1036

Reversed Imidazole Nucleosides.
Alternative Pathways of Synthesis

by K. Walczak and J. Suwinski
Institute of Organic Chemistry and Technology, Silesian Technical University,
Krzywoustego 4, 44-100 Gliwice, Poland

(Received November 7th, 1997; revised manuscript February 9th, 1998)

The reversed imidazole nucleosides were obtained on three independent routes: a) by the nucleophilic substitution of terminal tosylate group in sugar derivatives with imidazole-1,8-diazabicyclo[5.4.0]undec-7-ene (DBU) salts, b) from monosugar derivatives with unprotected terminal hydroxy group and substituted imidazoles, under the Mitsunobu reactions conditions, c) by the reaction of monosugars possessing terminal primary amino group with 1,4-dinitroimidazoles. Limitations of these routes are discussed.

1037-1044

The Kinetics of the Sn(II)/Sn Electrode Reaction
in Pure Molten Tin Dichloride

by J. Kazmierczak1 and K. Kowalczewska2
1Faculty of Chemistry, Wroclaw University, F. Joliot-Curie 14, 50-383 Wroclaw, Poland
2Department of Inorganic Chemistry,University of Medicine, 50-139 Wroclaw, Poland E-mail: jukka@wchuwr.chem.uni.wroc.pl

(Received October 10th, 1997; revised manuscript January 28th, 1998)

Results of electrochemical investigation of the Sn(II)/Sn electrode reaction in pure molten tin(II) chloride are presented. The exchange current density has been determined by relaxation and impedance methods as 1.6 A cm-2 for the anodic and 1.2 A cm-2 for the cathodic process, both exhibiting a weak temperature dependence. Both, the inductive model of a double layer of a metallic electrode immersed in its pure molten salt, and a barrierless electron transition have been confirmed.

1045-1053

Wetting Behavior of Molten Alkali Carbonates
on Au Interface under Various Gas Atmospheres

by A. Godula-Jopek and L. Suski
Institute of Physical Chemistry, Polish Academy of Sciences, Molten Salts Laboratory,
ul. Zagrody 13, 30-318 Krakow, Poland

(Received December 1st, 1997; revised manuscript February 9th, 1998)

Wettability of gold by molten (Li+Na), (Li+K) and (Li+Na+K) carbonate eutectic systems has been measured by sessile-drop method, as relevant to the problem of adhesion at the molten electrolyte/solid interfaces in molten carbonate fuel cell. The parameters determined and the literature surface tension data have been used for calculation of the adhesion work parameters for the interfaces under study.

1054-1067

Prediction of Tautomeric Equilibrium Constant
in the Gas Phase for Simple Compounds Containing
the Amidine Group

by E.D. Raczynska1 and R.W. Taft2
1Institute of General Chemistry, Agricultural University, 02528 Warszawa, Poland
2Department of Chemistry, University of California, Irvine, CA 92717, USA

(Received December 12th, 1997; revised manuscript February 9th, 1998)

Prototropic tautomerism together with conformational and configurational isomerism with respect to the C-N single and C=N double bond have been considered for simple compounds containing the amidine group, -NH-C(R)=N-. General methods, based on the theoretical (AM1) calculations for prediction of the tautomeric equilibrium constant (as pKT) in the gas phase have been discussed and illustrated by their application to cyclic and acyclic N,N'-disubstituted amidines containing substituent(s) without heteroatoms. The results obtained for simple cyclic amidines are similar to those reported in solution. The pKT values calculated for simple acyclic amidines are in good agreement with those found on the basis of the experimental substituent effects observed for non tautomerizing amidines in the gas phase.

1068-1075

Chiral Recognition Studies of Amino Acids by Chiral Calix[4]resorcinarenes in Langmuir Films

by M. Pietraszkiewicz1, P. Prus1 and W. Fabianowski2
1Institute of Physical Chemistry, Polish Academy of Sciences, 01-224 Warsaw, Kasprzaka 44/52, Poland
2Warsaw University of Technology, Department of Chemistry, 00-664 Warsaw, Noakowskiego 3, Poland
E-mail:pietrasz@ichf.edu.pl

(Received October 29th, 1997; revised manuscript February 13th, 1998)

Two chiral, lipophilic calix[4]resorcinarenes of Mannich-base type, containing (S)(-)-phenylethylamine (CAL11-PhEt), and (1R,2S)(-)-norephedrine (CAL11-EPh) form Langmuir monolayers on water surface. Chiral discrimination of amino acids: alanine, valine, leucine and tryptophan was observed by the changes in the surface area, which was different for D- and L-forms.

1076-1088

Effect of High-Molecular-Weight Polymers
on Sedimentation Behavior and Stability
of Fine Suspensions

by W. Nowicki and G. Nowicka
A. Mickiewicz University, Faculty of Chemistry, Department of Physical Chemistry,
60-780 Poznan, Poland
E-mail: gwnow@chem.amu.edu.pl (both authors)

(Received October 27th, 1997; revised manuscript February 13th, 1998)

Our previous model of colloidal stability of a system containing aggregates composed of several fine colloidal particles attached to a single, very long polymer chain [1] is extended to include the nonuniform distribution of particles among macromolecules. Both the reversible and irreversible polymer - particle attachment was considered. The predictions of the model are confronted with experimental results of the flocculation of silver iodide hydrosol by very-high-molecular weight polyacrylamide.

1089-1095

The Chemical Properties of Zn and Ag
Composite Electrodes for Power Sources

by E.P. Koval'chuk, O.R. Artymyshyn, O.V. Reshetnyak and R.V. Pankevych
Department of Physical and Colloid Chemistry, Ivan Franko Lviv State University,
Kyryla & Mefodia St. 6, Lviv 290005, Ukraine

(Received August 7th, 1997; revised manuscript February 16th, 1998)

Chemical properties of composite electrodes for the silver-zinc (Ag-Zn) battery have been studied. The instability of the supersaturated zincate electrolyte solutions is related to the formation of polynuclear zincate complexes. In accordance with quantum-mecha-nical calculations it was shown that most stable is the complex with the linear structure. The influence of polyacrylamide, both on the stability of the electrolyte solutions and on the inhibition of dendrite formation, has been studied.

1096-1105

Adsorption of Tyrosine on Ag(110) and Ag(111) Surfaces

by M. Milkowska and M. Jurkiewicz-Herbich
Department of Chemistry, Warsaw University, ul. Pasteura 1, 02-093 Warsaw, Poland

(Received November 24th, 1997; revised manuscript February 19th, 1998)

The adsorption of tyrosine at Ag(110) and Ag(111) single crystal electrodes has been studied in aqueous solutions of 0.1 M LiClO4. The standard Gibbs energies of adsorption, DELTAGads0, at the potential of maximum adsorption and the interaction parameters, A, using Frumkin's isotherm were calculated. The orientation of the adsorbed tyrosine molecules is different on Ag(111) and Ag(110) electrodes. At Ag(111) the molecules adsorb flat with the benzene ring parallel to the electrode, whereas at Ag(110) electrode the orientation is probably vertical with OH group towards the metal. The origin of that difference is probably the different atomic structure of both electrodes.

1106-1111

Crystal Structure of meso-4,4'-Di[2.2]paracyclophane

by P.G. Jones1 and P. Kus2
1Institut fuer Anorganische und Analytische Chemie, Technische Universitaet Braunschweig,
Postfach 3329, 38023 Braunschweig, Germany
2Department of Chemistry, Silesian University, 9, Szkolna Street, 40-006 Katowice, Poland

(Received January 15th, 1998)

Of the two possible racemates formed on the dimerization of [2.2]paracyclophane, the title compound C32H30 is the meso (RS/SR) isomer. It crystallizes in monoclinic system in space group P21/n with Z = 4 and unit cell dimensions: a = 13.7612(12), b = 11.2530(10), c = 14.6974(12) Å, ß = 99.668(8)o (at -100oC). The conformation is described by the interplanar angle between the linked rings, 48.67(8)o. Some widened angles in the region of C4-C4' may indicate steric congestion.

1112-1115

The Ag2GeS3-CdS System

by L.V. Piskach and O.V. Parasyuk
Department of Inorganic and Physical Chemistry, Volyn State University, Voli av.13, Lutsk 263009, Ukraine

(Received November 25th, 1997; revised manuscript February 4th, 1998)

1116-1119

Voltammetry at Platinum Microelectrodes
of Binary Liquids Based on Methanol

by J. Gadomska and Z. Stojek
Department of Chemistry, University of Warsaw, ul. Pasteura 1, PL 02-093 Warsaw, Poland

(Received November 26th, 1997; revised manuscript February 4th, 1998)

1120-1123

Isobaric Vapor-Liquid Equilibria
of the Hexamethyldisiloxane-1-Butanol System

by B. Kaczmarek
Department of Physical Chemistry, Medical University of Gdansk, Al. Gen. Hallera 107, 80-416 Gdansk, Poland

(Received December 1st, 1997; revised manuscript February 5th, 1998)

1124-1126

Force Field Studies of Some XY3Z Type Molecules

by PL.RM. Palaniappan and B. Rajamannan
Department of Physics, Annamalai University, Annamalainagar - 608 002, India

(Received October 31st, 1997; revised manuscript February 6th, 1998)

1127-1130

1,4-Dihydro-1-methyl-4-thioxo-3-quinolinesulfonamides

by L. Skrzypek1, J. Folwarczna2, W. Janiec2,
I. Kaczmarczyk-Sedlak2, A. Maslankiewicz1 and M. Pytlik2
1Department of Organic Chemistry and 2Department of Pharmacology, Pharmaceutical Faculty,
Silesian School of Medicine, Jagiellonska 4, 41-200 Sosnowiec, Poland

(Received December 31st, 1997; revised manuscript February 11th, 1998)


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