POLISH JOURNAL OF CHEMISTRY
Volume 73 Number 11 November 1999
Pages 1757-1924

CONTENTS

INORGANIC CHEMISTRY

Synthesis and Crystal Structure of Bis(2-iminopent-2-en-4-onato)nickel(II)

— Nowak E., Gdaniec M., Gierczyk B. and Urbaniak W.

1763

Spectroscopic and Thermal Studies of Silver(I) Complexes with Aliphatic Carboxylates and Triphenylphosphine

—Szłyk E., Łakomska I., Surdykowski A. and Goliński A.

1771

Synthesis and Structure of Di-m-iodo-bis(phthalocyaninato)bismuth(III)

— Kubiak R. and Ejsmont K.

ORGANIC CHEMISTRY

1777

Chiral Calixarenes Derived from Resorcinol. Part 5: Crystal Structure of Chiral Aminomethyl Derivative of Resorcarene

— Iwanek W.

1783

The Reaction of Some Dithiinodiquinolines with Potassium Methoxide as a Source of 4-Quinolinones with 3-Sulfide Function

— Maślankiewicz A. and Bębenek E.

1791

Synthesis and Reactions of Organic Compounds with a Nitrogen Atom. Part XV. Reactions of (+)-3-Chloro-2(10)-pinene and (–)-1-Chloro-2-pinene with Phenyltelluro- and Phenylselenosodium

— Uzarewicz A., Ścianowski J. and Bąkowska-Janiszewska J.

1797

Simple Synthesis of D-erythro- and L-erythro-D-gluco-octoses

— Jarosz S., Skóra S. and Kościołowska I.

1803

Enantiomers of Hepatitis B Virus (HBV) Surface Antigen (140–146)S Region Fragment:  Synthesis and Studies on Immunological Properties

— Kunikowska D., Dera-Tomaszewska B., Dziadziuszko H., Wysocki J., Wolańska I., Maćkiewicz Z., Głośnicka R. and Kupryszewski G.

PHYSICAL CHEMISTRY

1811

Electrooxidation of Nicotinic Hydrazide Catalyzed by  2,2,6,6-Tetramethyl-4-hydroxypiperidine-1-oxyl and Its Analytical Application

— Gong X. and Li H.L.

1819

Sphere-Rod Transition of Micelles in Aqueous NaBr Solutions of Hexadecyltrimethyl-ammonium Bromide

— Zieliński R.

1827

Vanadium(V) Catalysis of Perborate Oxidation of Iodide Ion

— Karunakaran C. and Muthukumaran B.

1837

Kinetics of Interaction Between Methanediol and (+)-Tartrate  in Alkaline Solutions

— Norkus E., Pauliukait R. and Vaškelis A.

1845

pH Dependent Enantiomeric Recognition of Amino Acids by Mannich-Type Calix[4]resorcinarenes in Langmuir Monolayers

— Pietraszkiewicz M., Prus P. and Bilewicz R.

1855

Electrochemical and UV-VIS Spectroscopic Study of Inclusion of Azobenzene Derivative by b-Cyclodextrin

— Wang Z., Zhang H.L. and Li H.L.

1863

Prototropic Tautomerism in 2- and 4-Hydroxypyridines. Halogen Substituent Effects
in the Gas Phase Calculated by Semiempirical (AM1) Method

— Raczyńska E.D.

CRYSTAL AND MOLECULAR STRUCTURES

1877

Crystal and Molecular Structure of (–)-(S)- and (+)-(R)-Bromofosfamide

— Karolak-Wojciechowska J., Wieczorek M., Grynkiewicz G. and Kutner A.

1887

Crystal and Molecular Structure of a Zn(II) Complex with Pyrazine-2,3-dicarboxylate Ligand

— Ptasiewicz-Bąk H. and Leciejewicz J.

1895

Crystal and Molecular Structure of 1,3,5-Trimethoxy-2,4,6-trinitrobenzene. Mesomeric Effects for Out-of-plane Twisted Substituents

— Anulewicz-Ostrowska R., Krygowski T.M., Cyrański M.K. and Matuszewska M.P.

COMMUNICATIONS

1903

Synthetic Studies on Pseudosterallin A

— Himaja M., Haris Kumar K., Ramana M.V. and Belagali S.L.

1909

Structure of [Cu(phen)₂]₂[{Cu(phen)₂Mo₈O₂₆]×H₂O

— Wang R.Z., Xu J.Q., Yang G.Y., Bu W.M., Xing Y.H., Li D.M.,  Liu S.Q., Ye L. and Fan Y.G.

1917

Novel Synthesis of Anomeric Peroxides and Hydroperoxides

— Grynkiewicz G. and Priebe W.

DISCUSSION

1921

Some Remarks on Prof. Siekierski's, Review of “Homonuclear Chemical Structures” by Z. Gontarz, A. Górski and Reviewer's Comments by S. Siekierski

1757-1762

Synthesis and Crystal Structure
of Bis(2-iminopent-2-en-4-onato)nickel(II)

by E. Nowak, M. Gdaniec, B. Gierczyk and W. Urbaniak

Faculty of Chemistry, Adam Mickiewicz University, 60-780 Poznań, Poland

(Received May 17th, 1999; revised manuscript July 2nd, 1999)

Synthesis and crystal and molecular structure of the title compound have been performed. It crystallizes in the space group Ccca with 12 molecules in the unit cell. There are two crystallographically independent molecules located on special positions with symmetry 2 or 222. Each molecule is  disordered over two sites. The Ni²⁺ ion, chelated by two 2-iminopent-2-en-4-onate anions, exhibits a planar square coordination. The neighbouring molecules are connected by pairs of N–H...O hydrogen bonds forming a ribbon motif. Isostructurality of the crystal studied with 2,4-pentadionato-Li complex is discussed.

1763-1769

Spectroscopic and Thermal Studies of Silver(I) Complexes with Aliphatic Carboxylates and Triphenylphosphine

by E. Szłyk, I. Łakomska, A. Surdykowski and A. Goliński

Nicholas Copernicus University, Faculty of Chemistry, 87-100 Toruń, Poland

(Received May 12th, 1999; revised manuscript July 19th, 1999)

Silver(I) complexes with triphenylphosphine and aliphatic carboxylates of formula [Ag₂(PPh₃)₂(µ-RCOO)₂], where R = C₂H₅, izo-C₃H₇, n-C₄H₉, izo-C₄H₉, tert-C₄H₉, Ph = C₆H₅ have been prepared and characterized with ¹H, ¹³C, ³¹P NMR and vibrational spectra. Results of spectral analysis are in favour of Ag(I) trigonal coordination with unidentately bonded triphenylphosphine and bidentate carboxylates, forming bridges between silver(I) ions. Thermal decomposition was studied in 293–973 K range in nitrogen. The multistage decomposition initiates with the detachment of carboxylates and is followed by triphenylphosphine dissociation. The final product is metallic silver, formed between 605–683 K.

1771-1775

Synthesis and Structure
of Di-m-iodo-bis(phthalocyaninato)bismuth(III)

by R. Kubiak¹ and K. Ejsmont^1,2

¹W. Trzebiatowski Institute of Low Temperature and Structure Research,
Polish Academy of Sciences, P.O.Box 1410, 50-950 Wrocław 2, Poland

²Institute of Chemistry, University of Opole, Oleska 48, 45-052 Opole, Poland
E-mail: kubiak@int.pan.wroc.pl

(Received March 10th, 1999; revised manuscript June 30th, 1999)

A new phthalocyanine dinuclear complex of bismuth, di-m-iodo-bis(phthalocyanin- ato)bismuth(III) has been obtained by the reaction of Bi₂Se₃ and 1,2-dicyanobenzene under  iodine vapour. The crystal structure of the complex was determined by X-ray diffraction method. The dinuclear complex is centrosymmetric with two dependent symmetrically BiPcI (Pc = C₃₂H₁₆N₈^2–) units. The bismuth atom is coordinated by four isoindole nitrogen atoms and two bridged iodine atoms. The formation and structural features of (BiPcI)₂ are related to other iodo–phthalocyaninato–bismuth(III) complexes from literature.

1777-1782

Chiral Calixarenes Derived from Resorcinol. Part 5:
Crystal Structure of Chiral Aminomethyl
Derivative of Resorcarene

by W. Iwanek

Institute of Chemistry, Pedagogical University, Chęcińska 5, 25-020 Kielce, Poland

(Received March 30th, 1999; revised manuscript June 11th, 1999)

Crystal and molecular structure of the hydrochloride salt of the chiral aminomethyl derivative of resorcarene, (–)-2, was determined by X-ray diffraction. Crystal data for (–)-2: C₇₁H₉₂C_l4N₄O₁₁, orthorhombic, C222₁, a = 24.169(3) ,  b = 24.410(3) , c = 26.865(3) , a  = b = g = 90°, Z = 8, R = 0.1049, for 14263 reflections. The effect of the solvent type on the ¹H- and ¹³C-NMR spectra was also discussed.

1783-1789

The  Reaction  of  Some Dithiinodiquinolines with
Potassium Methoxide as a Source of 4-Quinolinones
with  3-Sulfide  Function

by A. Maślankiewicz and E. Bębenek

Department of Organic Chemistry, Silesian School of Medicine,
Jagiellońska 4, 41-200 Sosnowiec, Poland

(Received December 11th, 1998; revised manuscript June 11th, 1999)

Reaction of thioquinanthrene 1 and isothioquinanthrene 6 with 6 molar excess of potassium methoxide produces dipotassium salts 3-A and  8-A respectively, which were converted after 3'- (or 4')-alkylation followed by neutralization into 3,4'- or 3,3'-diquinolinyl sulfides 4 or 9 with total yield up to 99%. 4-Quinolinones 4 were N₁-alkylated in DMSO/aqueous alkaline solution to N,S-dialkyl derivatives 5.

1791-1796

Synthesis and Reactions of Organic Compounds
with a Nitrogen Atom. Part XV.
Reactions of (+)-3-Chloro-2(10)-pinene and (–)-10-Chloro-2--pinene with Phenyltelluro- and Phenylselenosodium

by A. Uzarewicz, J. Ścianowski and J. Bąkowska-Janiszewska

Faculty of Chemistry, Nicolaus Copernicus University, 87-100 Toruń, Poland

(Received May 26th, 1999; revised manuscript June 23rd, 1999)

1797-1802

Simple Synthesis of D-erythro- and L-erythro-D-gluco-octoses

by S. Jarosz, S. Skóra and I. Kościołowska

Institute of Organic Chemistry, Polish Academy of Sciences,
01-224 Warszawa 42, P.O.Box 58, Poland (e-mail: sljar@ichf.edu.pl)

(Received July 5th, 1999)

Synthesis of the previously unknown methyl 2,3,4-tri-O-benzyl-L-erythro-b-D-gluco- and D-erythro-a-D-gluco-oct-1,5-pyranosides (1 and 2) was accomplished on two independent routes via either cis-hydroxylation of stereoisomeric 6-C-vinyl-L-glycerob-D-gluco- and D-glycero-a-D-gluco-pyranosides (9 and 10 respectively) or by epoxidation (following by the opening of the three membered ring) of methyl 2,3,4-tri-O-benzyl-6,7-dideoxy-oct-6(E)-eno-a-D-gluco-pyranoside (11).

1803-1809

Enantiomers of  Hepatitis B Virus (HBV) Surface
Antigen (140–146)S Region Fragment: Synthesis
and Studies on Immunological  Properties

by  D. Kunikowska¹,  B. Dera-Tomaszewska¹,  H. Dziadziuszko¹,  J.  Wysocki¹,
I. Wolańska²,  Z. Maćkiewicz²,  R. Głośnicka¹ and G. Kupryszewski²

¹Department of Immunology, Institute of  Maritime and Tropical  Medicine,
Powstania Styczniowego 9b, 81-519 Gdynia, Poland
²Faculty of Chemistry, University of Gdańsk, Sobieskiego 18, 80-952 Gdańsk, Poland

(Received June 11th, 1999; revised manuscript July 22nd, 1999)

Enantiomers of  HBV surface antigen (140–146)S region fragment were synthesized  by  the solid phase method  using Boc/Bzl chemistry. Immunological properties of enantiomers were investigated. The peptides induced both humoral and  cellular response after subcutaneous immunization of guinea pigs. Slight prevalence of the immunological response to  the L-peptide was observed. Per os  route of antigen administration resulted in the presence  of antibodies in the sera of the immunized animals and the organs of the mucosal  immune system.  The  L-peptide induced more intensive production of the antibodies  in the sera of the immunized guinea pigs, whereas the D-peptide evoked much stronger response in the mucosal tissues, particulary in  Peyer’s patches.

1811-1817

Electrooxidation of Nicotinic Hydrazide Catalyzed
by 2,2,6,6-Tetramethyl-4-hydroxypiperidine-1-oxyl
and Its Analytical Application

by X. Gong and H.L. Li

Chemistry Department, Lanzhou University, Lanzhou 730000, P.R. China

(Received March 22nd, 1999; revised manuscript May 24th, 1999)

The electrochemical oxidation of nicotinic hydrazide (NH) catalyzed by 2,2,6,6-tetramethyl-4-hydroxypiperidine-1-oxyl (TMHPO) on a glassy carbon electrode has been studied. Addition of TMHPO reduces remarkably the overpotential necessary for the oxidation of NH at the GCE and the catalytic current is affected by the concentration of the catalyst and the pH of the solution. A non-toxic and convenient method for detecting NH in the concentrations range 4.0´10^–6–1.2´10^–3 M has been developed.

1819-1826

Sphere-Rod Transition of Micelles in Aqueous NaBr
Solutions of Hexadecyltrimethylammonium Bromide

by R. Zieliński

Department of Technology and Environmental Protection, Faculty of Commodity Science,
Poznań University of Economics, Aleja Niepodległości 10, 60-967 Poznań, Poland

(Received  March 3rd, 1999; revised manuscript May 26th, 1999)

Effect of temperature on the formation of micelles in aqueous NaBr solutions of hexadecyltrimethylammonium bromide, C₁₆TAB, has been studied within the range 25–50°C. The critical surfactant concentrations for sphere-rod transition of the micellar shape, C_tr, were determined from the intersections of two straight line portions of the plots of the relationship between ultrasound velocity in the solutions and surfactant concentration. C_tr shift towards lower surfactant concentrations with the increase in NaBr concentration and the decrease in temperature.

1827-1836

Vanadium(V) Catalysis of Perborate
Oxidation of Iodide Ion

by C. Karunakaran and B. Muthukumaran

Department of Chemistry, Annamalai University, Annamalainagar 608 002, India

(Received March 16th, 1999; revised manuscript May 31st, 1999)

Vanadium(V) catalyzes perborate oxidation of iodide ion in acidic solution, being 1.6 order with respect to the oxidant, first order in the catalyst, inhibited by H⁺ and displays Michaelis-Menten kinetics on the reductant. In aqueous solution perborate generates hydrogen peroxide and the kinetic results reveal formation of  oxodiperoxovanadium(V)–iodide ion complex.

1837-1844

Kinetics of Interaction Between Methanediol
and (+)-Tartrate in Alkaline Solutions

by E. Norkus, R. Pauliukait and A. Vaškelis

Department of Chemical Kinetics and Catalysis, Institute of Chemistry,
A. Goštauto 9, LT-2600 Vilnius, Lithuania, E-mail: Norkus@ktl.mii.lt

(Received April 23rd, 1999; revised manuscript June 7th, 1999)

The reaction:

                    COO^–                                                            COO^–
                     |                                                                     |
                 HC-OH                                            k₁ HC-O
                     |               +         H₂C(OH)₂         <=>        |         >CH₂   +   2H₂O
                HC-OH                                             k_-1      HC-O
                     |                                                                      |
                    COO^–                                                             COO^–

has been studied by direct current polarography and cyclic voltammetry. The equilibrium constant of reaction (K_e) and  reaction rate constants were determined at   20°C in alkaline aqueous solutions: logK_e = 2.1 ± 0.1 l mol^–1,     k₁ = (8.53 ± 0.3) × 10^–5 mol^–1 l s^–1 and k_–1 = (0.06 ± 0.01) × 10^–5 s^–1. The cyclic acetal formed may have influence on the anodic oxidation of formaldehyde on copper, as well as on the adsorption phenomena taking place at the interface copper–solution, and is important for understanding of the processes taking place during the electroless copper deposition.

1845-1853

pH Dependent Enantiomeric Recognition
of Amino Acids by Mannich-Type
Calix[4]resorcinarenes in Langmuir Monolayers

by M. Pietraszkiewicz¹, P. Prus¹ and R. Bilewicz²

¹Institute of Physical Chemistry, Polish Academy of Sciences, 01224 Warsaw, Kasprzaka 44/52, Poland
²Department of Chemistry, University of  Warsaw, 02093 Warsaw, Pasteura 1, Poland
E-mail: pietrasz@ichf.edu.pl, bilewicz@chem.uw.edu.pl, viayner@ichf.edu.pl

(Received April 30th, 1999; revised manuscript June 21st, 1999)

Calix[4]resorcinarenes of Mannich-type derived from L(-)-norephedrine, piperidine and dimethylamine display, contrary to nonderivatized calix[4]resorcinarene, distinct differences in the parameters of their Langmuir  monolayers, depending on the pH of the subphase. The surface potential of these compounds is distinctly higher in the presence of substituents and its further increase upon decreasing the pH of the subphase is observed only for  the derivatized calixarenes. This  means that protonation on the amine centers is the factor determining the properties of the monolayer.  Enantiomeric recognition of D- and L-amino acids was found also to depend on the pH of the subphase with the former isomer, recognized at low pH and the latter in neutral solutions, hence by the nonprotonated form of the chiral calixarene.

1855-1861

Electrochemical and UV-VIS Spectroscopic Study
of Inclusion of Azobenzene Derivative by b-Cyclodextrin

by Z. Wang, H.L. Zhang and H.L. Li

Department of Chemistry, Lanzhou University, Lanzhou, 730000, People’s Republic of China

(Received April 13th, 1999; revised manuscript June 30th, 1999)

The inclusion of 4-methoxy-4'-carboxylic azobenzene (MCA) by b-cyclodextrin (b-CD) in aqueous solution was investigated by electrochemical and UV-VIS spectroscopic methods. Cyclic voltammetry results showed that the cathodic peak potential for MCA was shifted towards negative values and the peak current was decreased, when the b-CD concentration was increased. MCA is adsorbed strongly on the glassy carbon electrode. The surface concentration of MCA was determined by chronocoulometry. The UV-VIS spectroscopy measurement confirmed the inclusion and demonstrated that MCA formed a 1:1 complex with b-CD of the formation constant, K_f = 417 mol^–1 L

1863-1876

Prototropic Tautomerism in 2- and 4-Hydroxypyridines. Halogen Substituent Effects in the Gas Phase Calculated by Semiempirical (AM1) Method

by E.D. Raczyńska

Institute of General Chemistry, Agricultural University, Rakowiecka 26/30, 02-528 Warszawa, Poland

(Received May 20th, 1999; revised manuscript July 5th, 1999)

Tautomeric equilibrium constants (pK_T) were calculated in the gas phase for unsubstituted, mono- and tetrahalogenated 2-hydroxypyridines and for unsubstituted, mono-, di- and tetrahalogenated 4-hydroxypyridines using semiempirical method (AM1). Influence of position of halogen (F, Cl, Br) on the pK_T is studied and compared with that found previously in solution. Observed differences in the pK_T between the gas phase and solution are explained by differences in dipole moments calculated for the hydroxy- and oxo-forms. Influence of intramolecular hydrogen bonding on the pK_T is also discussed.

1877-1885

Crystal and Molecular Structure of (–)-(S)-
and (+)-(R)-Bromofosfamide

by J. Karolak-Wojciechowska¹, M. Wieczorek ¹, G. Grynkiewicz²
and A. Kutner²

¹Technical University of  ŁódŸ, Chemistry Department, 36 Żwirki, 90-924 ŁódŸ, Poland
            ²Pharmaceutical Research Institute, 8 Rydygiera, 01-793 Warszawa, Poland

(Received January 11th, 1999)

The  crystal and molecular  structures of (–)-(S)- and (+)-(R)-bromofosfamide were determined as a part of our research on therapeutically useful oxazaphosphorines. Both compounds crystallized in strictly enantiotropic crystals. The six-membered oxazaphosphorine ring adopts chair-forms with P=O phosphoryl oxygen atom in equatorial orientation. Two halogen atoms (Cl and Br) at the terminus of  aminoethyl substituents are differently anchored in the crystals. The crowded surrounding of around chlorine atom results in a H-bond formation of Cl…H–C, while bromine atom is much more separated from  H-atom. Both compounds undergo partial decomposition during diffractometric exposition with emission of free bromine.

1887-1885

Crystal and Molecular  Structure  of  a Zn(II)
Complex  with  Pyrazine-2,3-dicarboxylate Ligand

by H. Ptasiewicz-Bąk and J. Leciejewicz

Institute of Nuclear Chemistry and Technology, ul. Dorodna 16, 03-195 Warszawa, Poland

(Received May 26th, 1999; revised manuscript July 5th, 1999)

Crystals of trisaquo(µ-pyrazine-2,3-dicarboxylato N,O,O')zinc(II) monohydrate contain  molecular ribbons composed of zinc(II) ions bridged by molecules of pyrazine-2,3-dicarboxylate (2,3-PZDC) ligand via its N,O bonding moiety  [Zn–O(1)  2.065(3) ,  Zn–N(1) 2.170(3) ]. The second carboxylic group of the ligand contributes only one oxygen atom to bonding the  adjacent zinc ion [Zn–O(3)^II   2.097(3) ].  Distorted octahedral coordination around the zinc ion is completed by three water molecules [Zn–O(5)  2.049(3) ,  Zn–O(6) 2.072(3) ,  Zn–O(7)  2.161(3) ]. The ribbons are interconnected by an extensive network of hydrogen bonds operating via the coordinated and solvate water molecules.

1895-1901

Crystal and Molecular Structure of 1,3,5-Trimethoxy-2,4,6-trinitrobenzene.
Mesomeric Effects for Out-of-plane Twisted Substituents

by R. Anulewicz-Ostrowska, T.M. Krygowski, M.K. Cyrański
and M.P. Matuszewska

Department of Chemistry, University of Warsaw, ul. Pasteura 1, 02-093 Warsaw, Poland

(Received June 14th, 1999; revised manuscript July 7th, 1999)

Crystal and molecular structure of 1,3,5-trimethoxy-2,4,6-trinitrobenzene has been determined by X-ray diffraction technique. Crystal data for C₉H₉N₃O₉: triclinic, P1, a  = 7.507(2) ,  b = 9.218(2) , c = 10.426(2) , a = 108.58(3)°, b = 90.24(3)°, g = 110.77(3)°, Z = 2,  R = 0.0629 for 2568 reflections.  Both substituents, OCH₃ and NO₂, exhibit a significant mesomeric effect in spite of their twist of about 70°.

1903-1907

Synthetic Studies on Pseudostellarin A

by  M. Himaja², K. Harish Kumar, M.V. Ramana² and S.L. Belagali¹

¹Department of Studies in Chemistry, Mangalore University, Mangalagangothri-574 199, Karnataka, India

²NGSM Institute of Pharmaceutical Sciences, Nanthoor, Mangalore-575 005, Karnataka, India

(Received February 3rd, 1999; revised manuscript June 18th, 1999)

1909-1916

Structure of [Cu(phen)₂]₂[{Cu(phen)}₂Mo₈O₂₆]×H₂O

by R.Z. Wang¹, J.Q. Xu¹, G.Y Yang¹, W.M. Bu², Y.H. Xing¹, D.M. Li¹,
S.Q. Liu¹, L. Ye² and Y.G. Fan²

¹Department of Chemistry, Jilin University, Changchun 130023, P.R China
²Key Laboratory for Supramolecular Structure and Spectroscopy, Jilin University, 130023, P.R China

(Received February 9th, 1999; revised manuscript July 5th, 1999)

1917-1920

Novel  Synthesis  of  Anomeric  Peroxides
and  Hydroperoxides

by G. Grynkiewicz¹ and W. Priebe²

¹Pharmaceutical Research Institute, Rydygiera 8, 01-793 Warszawa, Poland
²The University of Texas M.D. Anderson Cancer Center, 1515 Holcombe Blvd., Houston, TX, 77030, USA