POLISH JOURNAL OF CHEMISTRY
Volume 72 Number 10 October 1998
Pages 2205-2355


CONTENTS

Page

INORGANIC CHEMISTRY
2205 The M(O2)X(YH3)3 Dioxygen Complexes (M = Rh, Co; X = F, Cl, Br, I; Y = N, P): An Ab Initio, DFT and Semiempirical PM3(tm) Study
Dobrowolski J.Cz., Jamróz M.H., Kazimirski J.K., Bajdor K., Borowiak M.A., Manna L., Miglietta M.L. and Aresta M.
2218 New Complexes of 2,4'-Bipyridine with Various Salts of Iron(II)
—Czakis-SulikowskaD.and Kałużna-Czaplińska J.
2226 Coordination Compounds of Pd(II) and Pt(II) with 3,4,5,6-Tetrahydro-2-pyrimidinethiol
Wiśniewski M.Z., Głowiak T. and Surga W.J.
2232 Synthesis and Characterization of Diantipyrylmethanium Salts of Some Pseudo-Tetrahedral Anionic Copper(II) Complexes
Wrzeszcz G., Grodzicki A., Pawlak R. and Rozpłoch F.
ORGANIC CHEMISTRY
2242 Purine Nucleoside Analogues. 8. N2-Acetylation of Guanine Derivatives
—MadreM.,
Zhuk R. and Golankiewicz B.
2247 Selective Synthesis of 1,3-Di- and 1,3,5-Trisubstituted Tetrazolium Salts by Tert-Butylation of Tetrazole, 1- and 5-Monosubstituted Tetrazoles. Isomerization of 1,3-Disubstituted Salts to 1,4-Salts
Gaponik P.N., Voitekhovich S.V., Maruda I.I., Kulak A.A. and Ivashkevich O.A.
2254 Synthesis and Properties of New 2-Alkyl-1,4-benzoxazepine Derivatives. Part III. Synthesis and Cyclization of 2-(2-Carboxyphenoxy)alkanamides
Kwiecień H.
PHYSICAL CHEMISTRY
2261 Quinolinium Fluorochromate Oxidation of -Hydroxy Acids in Perchloric Acid Medium
Subbiah Meenakshisundaram and Sathiyendiran V.
2267 Pyridinium Chlorochromate Oxidation of Arsenic(III) in Hydrochloric Acid
Virkar D.D. and Gokavi G.S.
2272 Digital Simulation of Electrochemical Oscillations and Associated Reagents Concentration Profiles with the Finite Differences Method
Orlik M.
2294 Interaction of Sodium and Potassium Ions with the cis Isomers of Dicyclohexyl-18-crown-6 in Nonaqueous Media
Wagner-Czauderna E., Filipek S. and Kalinowski M.K.
2303 The Influence of Aniline Radicals Concentration in the Stationary Phase on the Retention in Gas Chromatography
Nasuto R.
2312 Langmuir-Blodgett Film Formation by Polymeric Materials
Raźna J., Kucharski S. and Bryjak M.
2321 Kinetics and Mechanism of the Silver Electrode Reaction in Molten AgCl-NaCl Binary
Mixtures

Kisza A., Dzielendziak J. and Kaźmierczak J.
CRYSTAL AND MOLECULAR STRUCTURE
2331 Crystal Structures of 1,2,5-Trimethoxy-3-(1-propenyl)benzene and 1,3,5-Trimethoxy-2-
(1-propenyl)benzene

Wolska I., Popławski J. and Łozowicka B.
COMMUNICATIONS
2342 Structural Investigation of the Complex of Calixresorcarene with Pyridine
Iwanek W. and Froehlich R.
2346 Osmotic Coefficients of Aqueous Solution of Monomer Glycol and Polyethylene Glycol at Various Temperature Gao Z.N., Wen X.L. and Li H.L.
2352 Silver(I) Complexes with 1,2,4-Triazole, 1-Ethyl-1,2,4-triazole, 3-Amino-1,2,4-triazole,
4-Amino-1,2,4-triazole and 3,5-Diamino-1,2,4-triazole

Gabryszewski M. and Wieczorek B.


ABSTRACTS


2205-2217

The M(O2)X(YH3)3 Dioxygen Complexes
(M = Rh, Co; X = F, Cl, Br, I; Y = N, P):
An Ab Initio, DFT and Semiempirical PM3(tm) Study

by J.Cz. Dobrowolski1, M.H. Jamróz1, J.K. Kazimirski1, K. Bajdor1,
M.A. Borowiak1, L. Manna2, M.L. Miglietta2 and M. Aresta2
1Industrial Chemistry Research Institute, 8, Rydygiera-Street, 01-793 Warsaw, Poland
2Department of Chemistry, University of Bari, 173 via Amendola, 70126 Bari, Italy

(Received April 3rd, 1998; revised manuscript May 26th, 1998)

The molecular structure, energetics and vibrations have been calculated for the MO2 moiety in the M(O2)X(YH3)3 series of metal dioxygen complexes at three levels of theory: ab initio (RHF/3-21G**), DFT (B3PW91/3-21G**) and semiempirical PM3(tm). The methods yielded the O-O distances consistent with the experimental values and similarly predicted the tendencies of geometrical parameters to change. The variation of the enthalpy of formation with the central metal atom, halogen and ligand seems to be in qualitative interconsistency, whereas changes in the MO2 moiety frequencies, found at different levels, disagree substantially.

2218-2225

New Complexes of 2,4'-Bipyridine with Various Salts of Iron(II)

by D. Czakis-Sulikowska and J. Kałużna-Czaplińska
Institute of General and Ecological Chemistry, Technical University,
90-924 Łódź, ul. Żwirki 36, Poland

(Received April 14th, 1998; revised manuscript June 8th, 1998)

New complexes of 2,4'-bipyridine (2,4'-bipy or L) with iron(II) of the formulae FeL2Cl2.2H2O, FeL2Br2.2H2O, FeL2(NCS)2.H2O, FeLSO4.5H2O, FeL4(ClO4)2.2H2O and FeL4(ox).2H2O (ox = C2O4-) have been prepared and their magnetic, spectroscopic, molar conductivity and thermal properties studied. IR measurements show that the 2,4'-bipy behaves as a monodentate ligand. During heating the hydrated complexes lose all crystallization water and next decompose via different intermediate products to Fe2O3.

2226-2231

Coordination Compounds of Pd(II) and Pt(II)
with 3,4,5,6-Tetrahydro-2-pyrimidinethiol

by M.Z. Winiewski1, T. Głowiak2 and W.J. Surga1
1Institute of Chemistry, Pedagogical University, Chęcińska 5, 25-020 Kielce, Poland
2Institute of Chemistry, University of Wrocław, F. Joliot-Curie 14, 50-383 Wrocław, Poland

(Received March 30th, 1998; revised manuscript June 8th, 1998)

Coordination compounds of Pd(II) and Pt(II) with 3,4,5,6-tetrahydro-2-pyrimidinethiol (THPT) of the general formula M(THPT)4Cl2.H2O, where M stands for Pd and Pt, have been obtained and characterized by elemental analysis, X-ray diffraction patterns, derivatography (TG, DTG, DTA), magnetic measurements, and the IR and far-IR spectroscopy. Crystal and molecular structure of the Pd(THPT)4Cl2.H2O have been determined. This compound crystallizes in the monoclinic system with a = 8.555(2), b = 14.999(3), c = 23.324(5), = 91.05(3)°, V = 2832.7(11) 3 and Z = 4; space group P21/c. The two compounds have been found to be isostructural.

2232-2241

Synthesis and Characterization of
Diantipyrylmethanium Salts of Some
Pseudo-Tetrahedral Anionic Copper(II) Complexes

by G. Wrzeszcz1, A. Grodzicki1, R. Pawlak1 and F. Rozpłoch2
1Faculty of Chemistry, Gagarina 7 and 2Institute of Physics, Grudzi±dzka 5/7
Nicolaus Copernicus University, 87-100 Toruń, Poland

(Received April 8th, 1998; revised manuscript June 4th, 1998)

The tetrachlorocuprate(II), tetrabromocuprate(II) and tetrakis(izothiocyanate)cuprate(II) complexes of diantipyrylmethanium cations have been prepared and formulated as (H2DAM)CuCl4, (H2DAM)CuBr4 and (HDAM)2Cu(NCS)4 on the basis of spectral data (IR, UV-VIS) and elemental analysis. The EPR spectra, variable temperature magnetic susceptibility and thermal properties in air have been investigated. The results indicate for all complexes a distorted tetrahedral configuration. All studied complexes exhibited Curie-Weiss behaviour between 80-300 K. Thermal decomposition is a multistage process and yields CuO as final product.

2242-2246

Purine Nucleoside Analogues. 8.
N2-Acetylation of Guanine Derivatives

by M. Madre1, R. Zhuk1 and B. Golankiewicz2
1Latvian Institute of Organic Synthesis, 21 Aizkraukles, 226006 Riga, Latvia
2Institute of Bioorganic Chemistry, Polish Academy of Sciences,
Noskowskiego 12/14, 61-704 Poznań, Poland

(Received April 28th, 1998; revised manuscript May 26th, 1998)

A method for the acetylation of the exocyclic amino group of guanine derivatives has been developed. A series of N2-acetylguanines was synthesized by reacting of N9(7)-alkoxyalkylguanines with an excess of acetic anhydride in the presence of 4-dimethylaminopyridine. The method has been used successfully also for N2-acetylation of guanosine and its 8-bromo derivative although in the latter case a partial substitution of bromine for a hydroxy group at the position 8 of the heterocycle occurred.

2247-2253

Selective Synthesis of 1,3-Di- and 1,3,5-Trisubstituted
Tetrazolium Salts by Tert-Butylation of Tetrazole,
1- and 5-Monosubstituted Tetrazoles. Isomerization
of 1,3-Disubstituted Salts to 1,4-Salts

by P. N. Gaponik, S.V. Voitekhovich, I.I. Maruda,
A.A. Kulak and O.A. Ivashkevich
Research Institute for Physical-Chemical Problems of the Belarusian State University,
14 Leningradskaya str., 220050 Minsk, Belarus

(Received April 27th, 1998; revised manuscript June 9th, 1998)

Tetrazole and its 1- and 5-monosubstituted derivatives are found to react with tert-butyl alcohol in 72% perchloric acid media, yielding selectively 1,3-di- and 1,3,5-trisubstituted tetrazolium salts. 1,3-Disubstituted salts are slowly converted under the same conditions into the corresponding 1,4-disubstituted salts. This transformation may be used for selective synthesis of the latter.

2254-2260

Synthesis and Properties of New 2-Alkyl-1,4-benzoxazepine Derivatives. Part III.
Synthesis and Cyclization of 2-(2-Carboxyphenoxy)alkanamides

by H. Kwiecień
Department of Organic Synthesis, Technical University of Szczecin,
Al. Piastów 42, 71-065 Szczecin, Poland

(Received February 16th, 1998; revised manuscript June 15th, 1998)

A series of novel 2-(2-carboxyphenoxy)alkanamides 4a-f have been obtained as result of condensation of salicylaldehydes with 2-halo esters, amination of prepared esters 1a-f with methylamine followed by oxidation of amides 3a-f with sodium chlorite. The intramolecular cyclization of amides 4a-f to 1,4-benzoxazepin-3,5-dione system has been investigated.

2261-2266

Quinolinium Fluorochromate Oxidation of
-Hydroxy Acids in Perchloric Acid Medium

by Subbiah Meenakshisundaram and V. Sathiyendiran
Department of Chemistry, Annamalai University, Annamalainagar - 608 002, India

(Received November 3rd, 1997; revised manuscript April 27th, 1998)

The kinetics of oxidation of -hydroxy acids (mandelic, lactic and glycolic) with a recently developed new mild Cr(VI) reagent quinolinium fluorochromate (QFC) has been investigated in perchloric acid medium. First-order dependence with respect to [oxidant] is observed. Increase in [substrate] increases the rate proportionally. The acidity dependence is fractional order throughout the entire range of acidities studied. Decrease in dielectric constant of the medium increases the oxidation rate considerably. Kinetic solvent isotope effect studies indicate a pre-equilibrium fast proton transfer. Absence of polymerization with acrylonitrile rules out a free radical mechanism. An intermediate formed between protonated oxidant and substrate decomposes in a slow rate-limiting step giving the products.

2267-2271

Pyridinium Chlorochromate Oxidation of Arsenic(III)
in Hydrochloric Acid

by D.D. Virkar and G.S. Gokavi
Department of Chemistry, Shivaji University, Kolhapur - 416004, India

(Received March 30th, 1998; revised manuscript May 19th, 1998)

The reaction between pyridinium chlorochromate and As(III) was studied in hydrochloric acid medium. The reaction was found to be overall second order and the added product As(V) was found to decrease the rate. The hydrogen ion was found to catalyse the reaction and it was predicted that both protonated and free pyridinium chlorochromate are active to a different extent. The active species of the reductant was H3AsO3 and the mechanism is dicussed in terms of these species. The retardation by the added product is predicted to be due to a competitive ester formation.

2272-2293

Digital Simulation of Electrochemical Oscillations
and Associated Reagents Concentration Profiles
with the Finite Differences Method

by M. Orlik
Laboratory of Electroanalytical Chemistry, Department of Chemistry,
University of Warsaw, Pasteura 1, 02-093 Warsaw, Poland
E-mail: morlik@chem.uw.edu.pl

(Received March 13th, 1998; revised manuscript May 21st, 1998)

A classical finite differences algorithm of simulation of electrode processes was applied for strict modelling of electrochemical oscillations induced by interplay of ohmic drops and negative polarization resistance of the charge-transfer process. The linear and spherical geometry of diffusion was implemented. A numerical way of incorporating constant and potential-dependent double layer capacitances is described. Examples of shapes of oscillations and associated full diffusion profiles of electroactive species are presented. A comparison of this strict modelling of oscillations and typical approximated way of calculations, suggesting the importance of precise calculations, was outlined.

2294-2303

Interaction of Sodium and Potassium Ions
with the cis Isomers of Dicyclohexyl-18-crown-6 in Nonaqueous Media

by E. Wagner-Czauderna, S. Filipek and M.K. Kalinowski
Department of Chemistry, University of Warsaw, 1 Pasteur St., 02-093 Warszawa, Poland

(Received May 21st, 1998)

The formation constants, Ks, for 1:1 complexes of the cis-syn-cis and cis-anti-cis isomers of dicyclohexyl-18-crown-6 with sodium and potassium cations have been electrochemically determined in 10 nonaqueous (protic and aprotic) media. Linear correlations were obtained for log Ks with standard Gibbs transfer energies of the cation from water to a given solvent. The cis-anti-cis isomer was found to be a weaker complexer than the cis-syn-cis one and this was elucidated in terms of the ligand solvation. Energy-minimized structures of the ligands and complexes surrounded by methanol and acetonitrile molecules were established by molecular dynamics computations.

2303-2311

The Influence of Aniline Radicals Concentration
in the Stationary Phase on the Retention in Gas Chromatography

by R. Nasuto
Faculty of Chemistry, M. Curie-Skłodowska University, 20-031 Lublin, Poland

(Received September 25th, 1997; revised manuscript June 4th, 1998)

Four adsorbents with chemically bounded aniline radicals on silica gel surface of concentration 2.94; 5.86; 6.47 and 7.81 µ mole/m2 were prepared. On packed chromatographic column with unmodified silica gel Si 100 and obtained adsorbents the retention times of aliphatic (C6-C12) and aromatic (benzene, toluene and m-xylene) hydrocarbons and polar organic compounds (chloroform, ethylene chloride, chlorobenzene, p-chlorotoluene and ethyl benzene) were measured. Retention times, obtained on column with packing of the highest concentration of the bounded phase, were shorter than those on column with unmodified silica gel Si 100. Thus, there exists a possibility of optimization of retention of chemical compounds by change of their phase concentration on the support surface.

2312-2320

Langmuir-Blodgett Film Formation by Polymeric Materials

by J. Raźna, S. Kucharski and M. Bryjak
Institute of Organic and Polymer Technology, Wroclaw Technical University,
ul. Wyspiańskiego 27, 50-370 Wrocław, Poland
E-mail: kucharski@itots.ch.pwr.wroc.pl

(Received February 27th, 1998; revised manuscript June 8th, 1998)

Polymeric materials such as: poly(n-octadecyl methacrylate), poly(n-octadecyl metha-crylate-co-N-p-nitrophenylmaleimide) and poly(n-octadecyl methacrylate-co-N-p-nitrophenylacrylamide) were synthesized to investigate their ability for monolayer film formation and deposition. It was found that polymerization of n-octadecyl methacrylate yielded the material with improved ability of film formation as compared with the monomer, and the surface pressure-area isotherm showed a distinct solid film phase formation with a high value of film collapse pressure of ca. 56 mN/m. The incorporation of a co-monomer resulted in a shift of the surface pressure isotherm towards higher area values, still with a distinct solid film phase region and high film collapse pressure. The thickness of the poly(n-octadecyl methacrylate) film deposited onto a solid subphase was ca. 3 nm per monolayer (as determined by surface plasmon resonance) and this value corresponded to the length of the monomer molecule.

2321-2330

Kinetics and Mechanism of the Silver Electrode Reaction
in Molten AgCl-NaCl Binary Mixtures

by A. Kisza, J. Dzielendziak and J. Kaźmierczak
Faculty of Chemistry, University of Wrocław, ul. F. Joliot-Curie 14, 50-383 Wrocław, Poland

(Received April 17th, 1998; revised manuscript June 19th, 1998)

Kinetics and mechanism of the silver electrode reaction in six melts of the binary AgCl-NaCl system were determined at several temperatures by Electrochemical Impedance Spectroscopy (EIS) and Relaxation Method with galvanostatic perturbation (RM). The exchange current density for this electrode process ranges from 2.5 to 4.5 A cm-2 for different melt composition. The diffusion coefficient of the silver ion and the activation parameters are also determined in melts containing 80 and 90 mol % of NaCl.

2331-2341

Crystal Structures of
1,2,5-Trimethoxy-3-(1-propenyl)benzene
and 1,3,5-Trimethoxy-2-(1-propenyl)benzene

by I. Wolska1, J. Popławski2 and B. Łozowicka2
1Faculty of Chemistry, Adam Mickiewicz University, Grunwaldzka 6, 60-780 Poznań, Poland
2Institute of Chemistry, University of Białystok, Al. J. Piłsudskiego 11/4, 15-443 Białystok, Poland

(Received March 30th, 1998; revised manuscript May 25th, 1998)

The crystal structures of 1,2,5-trimethoxy-3-(1-propenyl)benzene (D) and 1,3,5-trimethoxy-2-(1-propenyl)benzene (F) have been determined by X-ray diffraction methods. The compounds crystallize in the monoclinic system, space group P21/c for (D) with a = 8.173(2), b = 11.725(2), c = 12.275(2) , = 102.48(3)°, V = 1148.5(4) 3, and P21/n for (F) with a = 7.433(1), b = 18.225(4), c = 8.854(2) , = 108.51(3)°, V = 1137.4(4) 3. Both, (D) and (F), carry E-propenyl side chains. The double bond lengths observed in the propenyl groups of the compounds examined (1.307(3) and 1.281(4) ) deviate from the expected value (~1.34 ). The angular deformation parameters were used in the analysis of the deformations of angles in the benzene ring. The existence of intra- and intermolecular C-H....O hydrogen bonds was observed.

2342-2345

Structural Investigation of the Complex
of Calixresorcarene with Pyridine

by W. Iwanek1 and R. Fr<148>hlich2
1Institute of Chemistry, Pedagogical University, Chęcińska 5, 25-020 Kielce, Poland
2Institut fuer Organische Chemie, Universitaet Muenster, Corrensstrasse 40, 48149, Germany

(Received April 20th, 1998; revised manuscript May 28th, 1998)

2346-2351

Osmotic Coefficients of Aqueous Solution of Monomer >br> Glycol and Polyethylene Glycol at Various Temperature

by Z.N. Gao, X.L. Wen and H.L. Li
Department of Chemistry, Lanzhou University, Lanzhou 730000, P. R. China

(Received March 30th, 1998; revised manuscript June 3rd, 1998)

2352-2355

Silver(I) Complexes with 1,2,4-Triazole,
1-Ethyl-1,2,4-triazole, 3-Amino-1,2,4-triazole,
4-Amino-1,2,4-triazole and 3,5-Diamino-1,2,4-triazole

by M. Gabryszewski and B. Wieczorek
Institute of Chemistry, Pedagogical University, 25-020 Kielce, Chęcińska 5, Poland

(Received March 27th, 1998; revised manuscript June 15th, 1998)


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