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PL ISSN 0137-5083

POLISH      
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Volume 71 Number 9 September 1997
Pages 1213-1373

 
   


Polish Chemical Society 

  

CONTENTS


Page

INORGANIC CHEMISTRY
1213 Synthesis and Spectral Studies on Mononuclear Copper(II) Complexes of Isonitrosoacetyl-acetone Ligand
— El-Tabl A.S.
1223 Reduction Mechanisms of Co(II) Complexes with Diamino Acids and Histidine on the Dropping Mercury Electrode
— Urbanska J.
ORGANIC CHEMISTRY
1232 Synthesis of Some New Pyrimidines
— Assy M.G. and Moustafa H.Y.
1236 2- and 2,7-Substituted Iodonium/Diiodonium Salts Derived from Xanthene, Xanth-9-one, Fluorene, and Fluoren-9-one
— Farhan A.N., Skulski L. and Kryska A.
1246 Synthesis and Properties of New 2-Alkyl-1,4-benzoxazepine Derivatives. Part II. Halogenated
2-Alkyl-2,3,4,5-tetrahydro-1,4-benzoxazepine-3,5-diones

— Kwiecien H. and Baumann E.
1254 Isovellerol and New Isolactarane Sesquiterpenes, Their Structure and Antifeedant Activity
— Daniewski W.M., Gumulka M., Bloszyk E., Jacobsson U. and Norin T.
PHYSICAL CHEMISTRY
1260 Stability of Micelles in Aqueous Salt Solutions of Dodecylpyridinium Halides
— Zielinski R.
1274 Binary Monolayers of Functionalized Long-chained Amphiphiles
— Kucharski S. and Janik R.
1281 Kinetics of Consecutive Reactions Catalyzed by Decaying Catalysts
— Marczewski M. and Marczewska H.
1293 Adsorption of Some Normal Aliphatic Amines on Polycrystalline Gold Electrode
— Brzostowska-Smolska M. and Krysinski P.
1298 The Kinetics of 1-Chloro-2,3-epoxypropane Reaction with Alcohols and Their Adducts in the Presence of Boron Trifluoride
— Chlebicki J. and Pozniak R.
1305 Note on the Capillary Model of Transport through Charged Membranes
— Koter S.
1314 Hydrodechlorination of CF2Cl2 (CFC-12) on Pd/Al2O3 Catalysts
— Juszczyk W., Malinowski A., Bonarowska M. and Karpinski Z.
1321 Molecular Modelling of Three-Dimensional Structure of 1,25-Dihydroxycholecalciferol and Its A-Ring Analogs
— Cholinski J. and Kutner A.
1329 1H and 14N NMR Shielding Constants Differentiate Two Polymorphic Forms of Solid NH4NO3
— Wielogorska E., Jackowski K. and Wozniak K.
1340 Thermoelectric Characteristics of the CuCl2-HCl Electrochemical System with Copper Electrodes
— Tevtul Ya. and Burkun N.
CRYSTAL AND MOLECULAR STRUCTURES
1345 Crystal Structure and Phase Transitions of the Ferroelectric Antimony Sulfoiodide SbSI. Part I. Phase Diagram and Thermal Expansion of SbSI
— Lukaszewicz K., Pietraszko A., Stepien-Damm J. and Kajokas A.
1350 The Crystal Structures of Diaquobis(3-aminopyrazine-2-carboxylato-N,O)magnesium(II)monohydrate and 3-Aminopyrazine-2-carboxylic Acid
— Ptasiewicz-Bak H. and Leciejewicz J.
1359 Molecular Ribbons Composed of Calcium Atoms Bridged by Carboxylate Oxygens in the
X-ray Structure of Calcium Complex with 3-Aminopyrazine-2-carboxylic Acid

— Leciejewicz J., Ptasiewicz-Bak H. and Paluchowska B.
COMMUNICATIONS
1365 Synthesis and Properties of the Complexes of Gadolinium with Nitronyl Nitroxides
— Qi Y.Q., Zou G.Z., Liao D.Z., Jiang Z.H. and Wang G.L.
1370 Systemin - a Polipeptide Inducer of Proteinase Inhibitors Synthesis in Plants: Synthesis and Chemical Stability
— Mucha P., Rekowski P., Szyk A., Kupryszewski G. and Barciszewski J.


ABSTRACTS

1213-1222

Synthesis and Spectral Studies on Mononuclear Copper(II)
Complexes of Isonitrosoacetylacetone Ligand

by A.S. El-Tabl
Department of Chemistry, Faculty of Science, Menoufia University, Shebin El-Kom, Egypt

(Received November 13th, 1996; revised manuscript February 28th, 1997)

Reaction of isonitrosoacetylacetone (Hinaa) with CuX2.nH2O, (X = CH3CO2, Cl or NO3, n = 1, 2 or 3) led to complexes of types (inaa)2Cu.3H2O and (Hinaa)2CuX2.H2O, (X = Cl or NO3). The octahedral complexes have been postulated due to elemental analysis, IR, VIS-U.V spectra, magnetic susceptibility, conductivity and ESR spectra. Molar conductance of the complexes in DMF indicates non-ionic character. ESR spectrum of (inaa)2Cu.3H2O in CD3OD/D2O (10%) at 77 K shows axial type symmetry (dx2-y2). However, the spectrum of the solid (Hinaa)2CuCl2.H2O at room temperature with gperpend >> g|| >> 2.002 indicates a compressed tetragonal distortion along the Z-axis with the unpaired electron in dz2 orbital.

1223-1231

Reduction Mechanisms of Co(II) Complexes
with Diamino Acids and Histidine
on the Dropping Mercury Electrode

by J. Urbanska
Faculty of Chemistry, University of Wroclaw, F. Joliot-Curie 14, 50-383 Wroclaw, Poland

(Received February 10th, 1997; revised manuscript March 17th, 1997)

DC and DP polarography were used to study the reduction of Co(II) in the presence of potentially terdentate diamino acids (2,3-diaminopropionic acid, 2,4-diaminobutyric acid, histidine). The stoichiometry of the species discharging on a mercury electrode and the relevant electrochemical kinetic parameters were determined. The electrochemical behaviour of particular species strongly depends on the donor system bound to the metal ion.

1232-1235

Synthesis of Some New Pyrimidines

by M.G. Assy and H.Y. Moustafa
Chemistry Department, Faculty of Science, Zagazig University, Zagazig, Egypt

(Received November 14th, 1996; revised manuscript April 16th, 1997)

Chlorolysis of pyrimidinethione 1 yielded chloropyrimidine 3, which reacted with arylamines to yield 4-arylaminopyrimidines 4a-c. Compounds 4a,b were condensed with benzaldehyde to afford pyridopyrimidines 6a,b, which underwent cyclization to pyirmidoquinazoline 7. Compound 3 reacted with ethyl glycinate to give pyrrolopyrimidine 9. Chloropyrimidine 3 reacted with acid hydrazide to afford hydrazides 10a,b that underwent intramolecular cyclodehydration to triazolopryimidine 11. Synthesis of furopyrimidine 13, thienopyrimidine 14 and 4-ethoxypyrimidine 15 was also described.

1236-1245

2- and 2,7-Substituted Iodonium/Diiodonium Salts
Derived from Xanthene, Xanth-9-one, Fluorene,
and Fluoren-9-one

by A.N. Farhan, L. Skulski and A. Kryska
Chair and Laboratory of Organic Chemistry, Faculty of Pharmacy, Medical Academy,
Banacha 1, 02-097 Warsaw, Poland

(Received May 6th, 1997; revised manuscript June 5th, 1997)

Thirty three new 2- and 2,7-substituted iodonium/diiodonium salts derived from xanthene, xanth-9-one, fluorene, and fluoren-9-one are reported in this paper. Their structures were supported analytically and by their 1H NMR and IR interpreted spectra.

1246-1253

Synthesis and Properties of New 2-Alkyl-1,4-
-benzoxazepine Derivatives. Part II.
Halogenated 2-Alkyl-2,3,4,5-tetrahydro-1,4-
-benzoxazepine-3,5-diones

by H. Kwiecien1 and E. Baumann2
1Department of Organic Chemistry, Technical University of Szczecin, 71-065 Szczecin, Poland 2Hauptlaboratorium BASF-AG, 67-056 Ludwigshafen, Germany

(Received April 17th, 1997; revised manuscript June 9th, 1997)

Novel bromo and iodo substituted 2-alkyl-2,3,4,5-tetrahydro-1,4-benzoxazepine-3,5- -diones 5 have been prepared by cyclodehydratation of 2-(2-carbamoilphenoxy) alkanoic acids 4 and as the result of the reaction of halogenated salicylamides 1 with 2-bromo

1254-1259

Isovellerol and New Isolactarane Sesquiterpenes,
Their Structure and Antifeedant Activity

by W.M. Daniewski1, M. Gumulka1, E. Bloszyk2, U. Jacobsson3 and T. Norin3
1Institute of Organic Chemistry, Polish Academy of Sciences, Kasprzaka 44, 01-224 Warsaw, Poland
2Department of Medicinal Plants, Academy of Medicine, 60623 Poznan, Poland
3Royal Institute of Technology, Department of Chemistry, Organic Chemistry,
SE-100 44 Stockholm, Sweden

(Received June 10th, 1997; revised manuscript June 23th, 1997)

High antifeedant activity of isovellerol, a gamma-hydroxy-aldehyde sesquiterpene of marasmane skeleton prompted us to synthesize the same type of compounds with the isolactarane skeleton, and to check their antifeedant activity. LiAlH4 reduction of isolactarorufin gave the desired compound, besides the tetraol (a compound with open lactone ring). Extensive spectroscopic investigation (including X-ray) indicated that the desired gamma-hydroxy-aldehyde in chloroform solution existed in the cyclic (lactol) form. Antifeedant activities of both compounds against the storage pests were moderate.

1260-1273

Stability of Micelles in Aqueous Salt Solutions
of Dodecylpyridinium Halides

by R. Zielinski
Department of General Technology, Faculty of Commodity Science, Poznan University of Economics, Aleja Niepodleglosci 10, 60-967 Poznan, Poland

(Received January 17th, 1997; revised manuscript March 13th, 1997)

Stability of spherical and rod-like micelles of cationic surfactants in aqueous salt solutions have been treated on the basis of a statistical thermodynamic theory, corrected by incorporation of the micellar surface energy term. The modified equations for the double logarithmic relationship between micellar aggregation number and ionic strength of the solution have been derived. The newly derived equations have been applied to aqueous sodium halides solutions of dodecylpyridinium halides including those of chloride, bromide and iodide. Effect of salt concentration on the degree of ionization and the energy of hydration of both spherical and rod-like micelles have been demonstrated. Degree of ionization of the micellar associates decreases with increasing salt concentration for all surfactants studied. Energy of hydration of both spherical and rod-like micelles is negative and it increases with increasing salt concentration.

1274-1280

Binary Monolayers of Functionalized
Long-chained Amphiphiles

by S. Kucharski and R. Janik
Institute of Organic and Polymer Technology, Wroclaw Technical University,
ul. Wyspianskiego 27, 50-370 Wroclaw, Poland; E-mail: kucharski@itots.ch.pwr.wroc.pl

(Received March 17th, 1997)

Monolayer films of binary systems were investigated with reference to miscibility of the components described in terms of excess surface area, Aexc, and excess free energy of mixing, DELTAGexc. The binary systems contained at least one component able to generate nonlinear optical effects or (and) to show semiconductive ability. The materials tested were: poly(n-octadecylthiophene), p-(1-n-octadecylpyrryl-2-azo)benzenesulfonic acid, (p-(1-n-octadecylpyrryl-2-azo)benzoic acid, and 2,4-dinitrophenylhydrazone of 3-n- -octadecanoylpyrrole. As film builders there were used 1-n-octadecylimidazole and 3-n-octadecylpyrrole. On the basis of surface excess area, Aexc, and surface excess free energy, DELTAGexc, the regions of positive synergic interactions between film components were determined.

1281-1292

Kinetics of Consecutive Reactions Catalyzed
by Decaying Catalysts

by M. Marczewski and H. Marczewska
Warsaw University of Technology, Faculty of Chemistry,
Noakowskiego 3, 00-664 Warsaw, Poland

(Received March 13th, 1997; revised manuscript April 3rd, 1997)

The kinetics of complex catalytic reaction of A -> B -> C type proceeding in the presence of decaying catalyst in a batch reactor is discussed. Calculated model correlations between reactant conversions and reaction time/total conversion were used to analyze n-pentane transformation in the presence of solid superacid Al2O3-SbF5 catalyst.

1293-1297

Adsorption of Some Normal Aliphatic Amines
on Polycrystalline Gold Electrode

by M. Brzostowska-Smolska and P. Krysinski
Department of Chemistry, University of Warsaw, 02-093 Warsaw, Poland

(Received January 24th, 1997; revised manuscript April 10th, 1997)

The adsorption of n-octylamine, n-dodecylamine, n-hexadecylamine and n-octadecyl-amine on a polarized Au electrode from LiClO4 methanolic solutions has been studied by capacity measurements. Some adsorption parameters for the potential near to the potential of maximum adsorption have been calculated, according to Frumkin's and Damaskin's theory. A discussion of the results connected with the literature data concerning the adsorption of alcohol molecules has been provided.

1298-1304

The Kinetics of 1-Chloro-2,3-epoxypropane Reaction
with Alcohols and Their Adducts
in the Presence of Boron Trifluoride

by J. Chlebicki and R. Pozniak
Institute of Organic and Polymer Technology, Technical University of Wroclaw,
50-370 Wroclaw, Poland

(Received December 20th, 1996; revised manuscript April 11th, 1997)

Rate constants for the reaction of 1-chloro-2,3-epoxypropane with n-, sec-, tert-butyl, n-hexyl, n-octyl, and n-decyl alcohols in the presence of boron trifluoride were studied at 30, 40, and 50oC. The reaction rate is first order with respect to 1-chloro-2,3-epoxypropane and independent of alcohol concentration. The rate constant is proportional to the catalyst concentration. The rate constants increase in the homologous series of C4-C10 alcohols. The reaction rates of 1-chloro-2,3-epoxypropane with 1-alkoxy-3- -chloro-2-propanols are considerably larger than that with corresponding alcohols.

1305-1313

Note on the Capillary Model of Transport
through Charged Membranes

by S. Koter
Faculty of Chemistry, N. Copernicus University, 7 Gagarin Street, PL-87100 Torun, Poland

(Received January 17th, 1997; revised manuscript April 18th, 1997)

The capillary model of transport through charged membranes has been reformulated by transport equations of non-equilibrium thermodynamics. Two geometries of pores has been considered - a capillary and a slit. It has been assumed that the distribution of mobile components is governed by the zero components of forces in the plane perpendicular to the direction of transport. It has been shown that the part of transport coefficients, describing the motion of the center of mass, depends on the distribution of species inside the capillary and on the viscosity of the solution. The transport coefficients, averaged over the cross-section, are symmetrical.

1314-1320

Hydrodechlorination of CF2Cl2 (CFC-12)
on Pd/Al2O3 Catalysts

by W. Juszczyk, A. Malinowski, M. Bonarowska and Z. Karpinski
Department of Catalysis on Metals, Institute of Physical Chemistry,
Polish Academy of Sciences, ul. Kasprzaka 44/52, 01-224 Warszawa, Poland

(Received April 22nd, 1997)

The reaction of hydrodechlorination of CF2Cl2 was studied in the presence of similarly dispersed alumina-supported palladium catalysts. Catalytic activity of alpha-Al2O3- and gamma-Al2O3-supported palladium does not depend on the fact, which type of alumina was used as a support. However, palladium supported on alpha-Al2O3 appeared more selective towards CF2H2 than Pd/gamma-Al2O3. Since alpha-Al2O3 is markedly less porous carrier than gamma-Al2O3, lower selectivity towards partial hydrodehalogenation on Pd/gamma-Al2O3 may result from a consecutive reaction of CF2H2 to methane. High temperature pretreatment supposedly eliminates narrow pores in gamma-Al2O3, what, in consequence, leads to higher selectivity to CF2H2. Carbiding palladium surfaces takes place during the reaction. After carbon removal, Pd/Al2O3 shows a similar catalytic behaviour as fresh samples.

1321-1328

Molecular Modelling of Three-Dimensional
Structure of 1,25-Dihydroxycholecalciferol
and Its A-Ring Analogs

by J. Cholinski and A. Kutner
Pharmaceutical Research Institute, Rydygiera 8, 01-793 Warsaw, Poland

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

Two major force fields (Tripos and MMX) were used to calculate three dimensional structures, steric energies and Boltzmann distribution of low energy conformers of 1,25-dihydroxycholecalciferol and its A-ring analogs. Molecular modelling revealed that out of a series of analogs substituted at carbon atom C(4), (4R)-4-methyl-1,25-dihydroxycholecalciferol might be expected to exist in a solution preferentially in a ß-type of conformation of an A ring. This analog, compared to the (4S) isomer, is to be used for further structure - activity study of the ß-type conformation of an A-ring as a hypothetical active form in which vitamin D compound interacts with vitamin D receptor.

1329-1339

1H and 14N NMR Shielding Constants Differentiate
Two Polymorphic Forms of Solid NH4NO3

by E. Wielogorska, K. Jackowski and K. Wozniak
Department of Chemistry, The University of Warsaw, ul. Pasteura 1, 02-093 Warszawa, Poland
E-mail: kwozniak@chem.uw.edu.pl

(Received May 20th, 1997)

The gauge-independent atomic orbital (GIAO) approach has been used within the coupled Hartree-Fock approximation to compute 1H and 14N NMR shielding constants in selected ion pairs of solid NH4NO3. Assuming additivity of intermolecular effects the shielding constants of NH4+ ions in two different polymorphic forms of ammonium nitrate have been determined. According to our calculations condensation of NH4NO3 leads to small deshielding effects for 1H and 14N nuclei. Geometry of the central NH4+ cation is the most important factor influencing results of calculations of nuclear shielding constants. This geometry reflects the role of intermolecular interactions in the crystal lattice. Our results show that the GIAO approach at the Hartree-Fock level differentiates two polymorphic forms of ammonium nitrate. Some results on temperature dependences for 1H and 14N shielding constants are included. There is a linear dependence between the 1H and 14N shielding constants.

1340-1344

Thermoelectric Characteristics of the CuCl2-HCL
Electrochemical System with Copper Electrodes

by Ya. Tevtul and N. Burkun
Chernovtsy State University, Faculty of Chemistry, Department of Physical Chemistry,
Kotsybinski Str., 2, Chernovtsy 274012, Ukraine

(Received November 20th, 1996; revised manuscript May 23rd, 1997)

The non-isothermal system of copper electrodes in aqueous solution of CuCl2 + HCl has been studied. The interval of HCl concentrations with a linear dependence of non-isothermal electromotive force (emf) on the temperature difference has been determined. Thermoelectric potentials and phenomenological coefficients have been evaluated. The contribution of particle fluxes caused by temperature gradient to the total flux of charged particles is estimated to 15-20%.

1345-1349

Crystal Structure and Phase Transitions
of the Ferroelectric Antimony Sulfoiodide SbSI.
Part I. Phase Diagram and Thermal Expansion of SbSI

by K. Lukaszewicz1, A. Pietraszko1, J. Stepien-Damm1 and A. Kajokas2
1Institutte of Low Temperature and Structure Research, Polish Academy of Sciences,
Okolna 2, 50-950 Wroclaw, Poland
2Department of Physics, University of Vilnius, Sauletekio al. 9/3. 2054 Vilnius Lithuania

(Received February 3rd, 1997; revised manuscript March 21st, 1997)

Precise lattice parameters of antimony sulfoiodide SbSI single crystals have been determined by the Bond method between 95-460 K. Apart from the ferroelectric phase transition at 298 K, a high temperature phase transition was found at 410 K. In the ferroelectric phase the lattice parameter c increases with decreasing temperature and reaches the maximum value at about 150 K. There is also a small anomaly of the temperature dependence of lattice parameter a, which increases below the Curie point, reaches the maximum value at 290 K and decreases at lower temperatures. No anomalies of thermal expansion were observed between 210-260 K, where a low temperature phase transition was reported by some authors.

1350-1358

The Crystal Structures of Diaquobis(3-aminopyrazine-2-
-carboxylato-N,O)magnesium(II)monohydrate and
3-Aminopyrazine-2-carboxylic Acid

by H. Ptasiewicz-Bak and J. Leciejewicz
Institute of Nuclear Chemistry and Technology, ul. Dorodna 16, 03-195 Warszawa, Poland

(Received February 4th, 1997; revised manuscript April 29th, 1997)

Diaquobis(3-aminopyrazine-2-carboxylato-N,O)magnesium(II)monohydrate, MgC10H14N6O7 crystallizes in the monoclinic system, space group Cc. Lattice parameters: a = 12.225(5), b = 8.286(1), c = 15.964(2) Å, ß= 112.50(3) deg., Z = 4. The structure is composed of monomeric molecules. The Mg+2 ion is coordinated by two acid molecules and two water molecules. The coordination octahedron of the Mg+2 ion consists of two heteroring nitrogens (Mg-N = 2.255 Å) and two oxygen atoms belonging to two monodentate carboxylic groups (Mg-O = 2.070 Å) donated by two acid molecules plus two oxygen atoms of water molecules (Mg-O = 2.040 Å). A network of hydrogen bonds is operative between the monomers and solvation water molecules.
Crystals of 3-aminopyrazine-2-carboxylic acid, C5H5N3O2 belong to the monoclinic system, space group P21/c. Lattice parameters: a = 3.751(1), b = 14.184(3), c = 10.906(2) Å, ß = 99.17(3) deg., Z = 4. The structure contains two-dimensional molecular layers in which the molecules are held by short hydrogen bonds of 2.765 Å. They join the carboxylic oxygens and the heteroring nitrogens of the adjacent molecules to make zig-zag chains. Additional weak interaction with the distance of 3.112 Å operates between the aminogroup nitrogen and the heteroring nitrogen. Every second pair of molecules belonging to the adjacent chains is linked by two weak hydrogen bonds of 2.997 Å. The interlayer spacing is 3.751(1) Å.

1359-1364

Molecular Ribbons Composed of Calcium Atoms
Bridged by Carboxylate Oxygens in the X-ray
Structure of Calcium Complex with
3-Aminopyrazine-2-carboxylic Acid

by J. Leciejewicz1, H. Ptasiewicz-Bak 1 and B. Paluchowska2
1Institute of Nuclear Chemistry and Technology, ul. Dorodna 16, 03-195 Warszawa, Poland
2Institue of Atomic Energy, Swierk, Poland

(Received April 10th, 1997; revised manuscript May 8th, 1997)

The crystals of monoaquabis(miu-3-amino-2-pyrazinato)calcium(II) are monoclinic, space group Cc, a = 22.787(5), b = 6.367(1), c = 9.906(2) Å, ß = 110.58(3) deg., Z = 4. Each calcium atom is coordinated by two aminopyrazinate molecules via their heteroring nitrogens (Ca-N = 2.594 Å ) and the nearest to them two oxygens of the carboxylate groups (Ca-O = 2.385 Å) and by one water molecule with Ca-O = 2.344 Å, making with aminopyrazinate ligands a planar "step". Two other oxygen atoms are chelated to the calcium atom, each contributed by the second oxygen atom of the carboxylic group situated in the "step" above and below (mean Ca-O = 2.363 Å). The carboxylic groups are bidentate and bridge the "steps" into ribbons propagating along the c axis. The ribbons are linked by strong hydrogen bonds of 2.71(1) and 2.74(1) Å operating between the coordinated water oxygen and the carboxylic oxygens in the adjacent ribbons.

1365-1369

Synthesis and Properties of the Complexes
of Gadolinium with Nitronyl Nitroxides

by Y.Q. Qi, G.Z. Zou, D.Z. Liao, Z.H. Jiang and G.L. Wang
Department of Chemistry, Nankai University, Tianjin 300071, P.R. China

(Received January 27th, 1997; revised manuscript April 9th, 1997)

1370-1373

Systemin - a Polipeptide Inducer of Proteinase
Inhibitors Synthesis in Plants:
Synthesis and Chemical Stability

by P. Mucha1, P. Rekowski1, A. Szyk1, G. Kupryszewski1 and J. Barciszewski2
1Faculty of Chemistry, University of Gdansk, Sobieskiego 18, 80-952 Gdansk, Poland
2Institute of Bioorganic Chemistry, Polish Academy of Sciences, Noskowskiego 12, 61-709 Poznan, Poland

(Received May 9th, 1997; revised manuscript June 9th, 1997)


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