POLISH JOURNAL OF CHEMISTRY
Volume 73 Number 6 June 1999
Pages 895-1053


CONTENTS

Page

REVIEW ARTICLE
895 Structure of the O-Antigenic Polysaccharide of Proteus Bacteria
— Knirel Y.A., Kaca W., Rozalski A. and Sidorczyk Z
INORGANIC CHEMISTRY
909 Solution Structure of Cu(II) Complexes with Spermine and Nucleosides or Nucleotides in Ternary Systems
— G±sowska A., Łomozik L. and Bregier-Jarzębowska R.
915 Synthesis of a New Naphthol-Derivative Salen and Spectrophotometric Study of the Thermodynamics and Kinetics of Its Complexation with Copper(II) Ion in Binary Dimethylsulfoxide-Acetonitrile Mixtures
— Alizadeh N., Ershad S., Naeimi H., Sharghi H. and Shamsipur M.
927 Complexes of Cadmium(II) and Mercury(II) with Polyamines, Nucleosides and Nucleotides
— Łomozik L. and Bregier-Jarzębowska R.
ORGANIC CHEMISTRY
941 Efficient Synthesis of lactoneo Series Antigen Lewis Y (Ley)
— Hummel G. and Schmidt R.R.
955 Synthesis of Highly Branched Oligomannosides. 3. Synthesis of Trityl Ethers of Mannobiosides and Mannotriosides as Precursors for Higher Mannooligosaccharides
— Backinowsky L.V., Abronina I.P., Nepogodiev S.A., Grachev A.A. and Kochetkov N.K.
967 Regioselective Halogenation of Primary Alcohol Groups of Cyclodextrins with Halomethylenemorpholinium Halides Vilsmeier-Haack Reagents
— Chmurski K. and Defaye J.
973 Stereospecific Synthesis of a Glycosides and a Disaccharides of Ulosonic Acids via Direct Addition of Alcohols to Sugar Ketene Dithioacetal
— Młynarski J. and Banaszek A.
981 Synthesis of Sucrose Derivatives Modified at the Terminal Carbon Atoms
— Jarosz S. and Mach M.
989 Synthesis of 4-Cyanophenyl and 4-Nitrophenyl 2,6-Anhydro-1,2-dithio-D-manno- and altropyranosides and Their Derivatives Possessing Antithrombotic Activity
— Bozó E., Boros S. and Kuszmann J.
1003 The Use of a New Magnesium-Derived Hydride Reagent for Carbohydrate Derivatives
— Szabovik G., Medgyes A., Antal Zs., Varga Zs., Knott W. and Liptak A.
1011 Synthesis and NMR Study of N,N'-Bis(methyl 3,4,6-tri-O-acetyl-2-deoxy-b-D-glucopyranosid-2-yl)urea and Its N'-Nitroso Derivative
— Temeriusz A., Piekarska-Bartoszewicz B., Weychert M. and Wawer I.
1019 Acyclonucleosides of Indazole and Their Rearrangements
— Boryski J.
PHYSICAL CHEMISTRY
1029 Carbon-13 Isotope Effect in the Decarboxylation of Phenylpropiolic Acid in Sulphuric Acid
— Zieliński M., Zielińska A., Paul H., Bernasconi S., Ogrinc N., Kobal I. and Papiernik-Zielińska H.
COMMUNICATIONS
1037 Cyclodextrin - Isocyanate: a New Access from Phosphinimines
— Kovacs J., Pintrr I., Mrszaros P., Kajtar-Peredy M. and Jicsinszky L.
1041 An Improved Calculation of Bond-Dissociation Energies of Organic Compounds Based on the Concept of Stabilization Energy
— Firpo M., Gavernet L. and Castro E.A.
1047 Isothermal Section of the Nd-Co-Sn System at 870 K
— Salamakha P., Demchenko P., Sologub O. and Bodak O.
1051 Synthesis and Magnetism of Manganese(II) Complex with One Dimensional Structure
— Zhu S.C., Xu J.Q., Shi J.M., Wang R.Z., Yang G.Y., Sun H.R., Wang T.G., Cheng P. and Liao D.Z.


ABSTRACTS


895-907 Structure of the O-Antigenic Polysaccharides of Proteus Bacteria

by Y.A. Knirel1, W. Kaca2,3, A. Rozalski2 and Z. Sidorczyk2
1N.D. Zelinsky Institute of Organic Chemistry, Russian Academy of Sciences,Leninsky Prospekt 47, Moscow 117913, Russia
2Institute of Microbiology and Immunology, University of Łódź, Banacha 12/16, 90-237 Łódź, Poland
3Center of Microbiology and Virology, Polish Academy of Sciences, Lodowa 106, 93-232 Łódź, Poland

(Received December 23rd, 1998)

Data on the composition and structure of the O-specific polysaccharides (O-antigens) of the lipopolysaccharides of the genus Proteus are summarized and discussed as the molecular basis for serotyping of these medically important bacteria.

909-913 Solution Structure of Cu(II) Complexes with Spermine and Nucleosides or Nucleotides in Ternary Systems

by A. G±sowska, L. Łomozik and R. Bregier-Jarzębowska
Faculty of Chemistry, A. Mickiewicz University, Grunwaldzka 6, 60-780 Poznań, Poland

(Received January 20th, 1999)

The mode of coordination of the complexes formed in the systems Cu/spermine/nucleoside (or nucleotide) was proposed on the basis of the equilibrium and spectral studies. Significant differences were found in the coordination character of nucleosides and nucleotides. In the systems with adenosine or cytidine, mixed-ligand complexes are formed with the N5 type coordination. On the other hand, in the systems with their monophosphates, molecular complexes are formed with metal ions coordinated through oxygen atoms from the phosphate groups. Spermine, left outside the inner coordination sphere, is involved in non-covalent interactions with nitrogen atoms from the nucleotide bases.

915-925 Synthesis of a New Naphthol-Derivative Salen andSpectrophotometric Study of the Thermodynamics and Kinetics of Its Complexation with Copper(II) Ion inBinary Dimethylsulfoxide-Acetonitrile Mixtures

by N. Alizadeh1, S. Ershad1, H. Naeimi2, H. Sharghi2 and M. Shamsipur3
1Department of Chemistry, Tarbiat Modarres University, Tehran, Iran
2Department of Chemistry, Shiraz University, Shiraz, Iran
3Department of Chemistry, Razi University, Kermanshah, Iran

(Received December 3rd, 1998; revised manuscript February 8th, 1999)

A synthetic procedure has been developed for the preparation of new salen (2,2'- [1,2-ethanediyl bis (nitriloethylidyne)] bis (1-naphthalenol)). The thermodynamics and kinetics of complexation reaction between the new salen and Cu2+ ion were investigated spectrophotometrically in different dimethylsulfoxide-acetonitrile mixtures. Formation constant of the resulting 1:1 complex was determined from the absorbance-mole ratio data and found to increase with increasing acetonitrile content of the solvent mixtures. Enthalpy and entropy data for complexation were determined from the temperature dependence of the formation constant. In all solvent mixtures, the salen–copper complex is entropy stabilized but enthalpy destabilized. Order of reaction, rate constants and activation parameters for the complexation reaction in different solvent mixtures were also investigated. The Arrhenius plots showed a distinct isokinetic temperature at about 88°C, at which the reaction rate is approximately independent of the solvent composition. Activation parameters are strongly solvent dependent.

927-940 Complexes of Cadmium(II) and Mercury(II)with Polyamines, Nucleosides and Nucleotides

by L. Łomozik and R. Bregier-Jarzębowska
Faculty of Chemistry, A. Mickiewicz University, Grunwaldzka 6, 60-780 Poznań, Poland

(Received December 28th, 1998; revised manuscript March 5th, 1999)

Computer analysis of potentiometric titration data was applied for determination of stability constants of Cd(II) and Hg(II) complexes in binary systems with polyamines (PA), nucleosides (Nuc) and nucleotides (NMP). For the systems of Hg(II) and PA an untypical increase in the complex stability with increasing ring size was observed and interpreted as the mercury preference to formation of linear complexes. Results of the potentiometric and 13C NMR studies for the complexes of both metals indicate the involvement of all donor nitrogen atoms of di- and triamines in the coordination, leading to formation of N2 and N3 type chromophores, respectively. Monodentate complexes of Hg(II) with Cyd are formed already at very low pH (complexes with Cd from pH of about 4). In the systems with AMP apart from nitrogen donor atoms, also the phosphate groups are involved in coordination. In the solid complexes of Cd(II) and Hg(II) with PA all donor atoms from the polyamines were found to be involved in the coordination and the presence of nitrate ions was established both in the inner and in the outer coordination spheres.

941-954 Efficient Synthesis of lactoneo SeriesAntigen Lewis Y (Ley)

by G. Hummel and R.R. Schmidt
Faculty of Chemistry, University of Konstanz, M 725, D-78457 Konstanz, Germany

(Received January 29th, 1999)

The synthesis of glycosphingolipid Lewis Y (1) could be efficiently carried out, based on the connection of building blocks 27. Reaction of fucosyl donor 2 with azidoglucose derivative 4 as acceptor gave a(1–3)-linked disaccharide 8, which was transformed to acceptor 9; ensuing reaction with galactosyl donor 3 furnished Lewis X trisaccharide derivative 10. This compound could be transformed into the LeY hexasaccharide 16 either via transformation into glycosyl donor 12, connection with lactose moiety 5, and then reaction with fucosyl donor 2a, or, alternatively by transformation of 10 into acceptor 18, reaction with fucosyl donor 2, and then attachment of lactose moiety 5. Application of the azidosphingosine glycosylation procedure to 16, i.e. first transformation into O-acyl protected hexaosyl donor 33, then reaction with azidosphingosine 6 and fatty acid (7), and finally O-acyl deprotection, afforded target molecule 1 in high purity.

955-965 Synthesis of Highly Branched Oligomannosides. 3. Synthesis of Trityl Ethers of Mannobiosides and Mannotriosides as Precursorsfor Higher Mannooligosaccharides

by L.V. Backinowsky1, P.I. Abronina1, S.A. Nepogodiev2, A.A. Grachev3 and N.K. Kochetkov1
1N.D. Zelinsky Institute of Organic Chemistry, Russian Academy of Sciences, Leninsky prosp. 47, 117913 Moscow, Russian Federation (Fax: 7 (095) 135 5328)
2The University of Birmingham, School of Chemistry, Edgbaston, Birmingham, B15 2TT, UK
3Higher Chemical College, Russian Academy of Sciences, Miusskaya pl. 9, 125190, Moscow, Russian Federation

(Received December 29th, 1998)

Synthesis of mono- and ditrityl ethers of mannobiosides and mannotriosides as precursors for higher mannooligosaccharides is described. Advantage is taken of selective glycosylation of primary-secondary ditrityl ethers and selective removal of O-acetyl protective groups in the presence of O-benzoyl protective groups.

967-971 Regioselective Halogenation of Primary Alcohol Groups of Cyclodextrins with Halomethylenemorpholinium Halides Vilsmeier-Haack Reagents

by K. Chmurski and J. Defaye
CNRS (EP 811) and Université Joseph Fourier - Grenoble 1, Département de Pharmacochimie Moléculaire/Glucides, BP 138, F-38243 Meylan, France.
e-mail: Jacques.Defaye@ujf-grenoble.fr

(Received January 18th, 1999)

Per(6-bromo-6-deoxy)cyclomalto-hexaose, -heptaose, and -octaose and the corresponding per(6-chloro-6-deoxy) derivatives were prepared in high yield by reaction of bromomethylenemorpholinium bromide or chloromethylenemorpholinium chloride, respectively, with cyclomaltohexaose, cyclomaltoheptaose and cyclomaltooctaose in dimethylformamide.

973-979 Stereospecific Synthesis of a Glycosides and a Disaccharides of Ulosonic Acids via Direct Addition of Alcohols to Sugar Ketene Dithioacetal

by J. Młynarski and A. Banaszek
Institute of Organic Chemistry, Polish Academy of Sciences, Kasprzaka 44/52, 01-224 Warsaw, Poland, (e-mail: mlynar@ichf.edu.pl)

(Received January 21st, 1999)

A new direct route to the stereospecific construction of aglycosides and adisaccharides of ulosonic acids is presented. Addition reaction of alcohols and/or "sugar alcohols" to the quaternary double bond of sugar ketene dithioacetal 1 mediated by trimethylsilyl triflate led to the corresponding O-glycosides. Subsequent hydrolysis of dithianyl residue afforded the title compounds.

981-988 Synthesis of Sucrose Derivatives Modified atthe Terminal Carbon Atoms

by S. Jarosz and M. Mach
Institute of Organic Chemistry, Polish Academy of Sciences,ul. Kasprzaka 44, 01-224 Warszawa 42 P.O.Box 58; e-mail: sljar@ichf.edu.pl

(Received January 11th, 1999)

The methodology for the preparation of various derivatives of sucrose modified at C1', C6, and C6'-positions is presented. 6-Amino-, 6'-amino-, and 6,6'-diamino-penta-O-benzylsucroses (16, 17 and 18 respectively), as well as appropriate uronic acids (characterized as methyl esters: 19–22), have been obtained from 2,3,4,3'4'-penta-O-benzyl-sucrose (1). The usefulness of this approach was exemplified by the preparation of 1'-O-benzyloxymethyl-6-deoxy-6-C-(2-furyl)-2,3,4,3'4'-penta-O-benzylsucrose (26).

989-1001 Synthesis of 4-Cyanophenyl and 4-Nitrophenyl 2,6-Anhydro-1,2-dithio-D-manno- andaltropyranosides and Their DerivativesPossessing Antithrombotic Activity,

by É. Bozó, S. Boros and J. Kuszmann
Institute for Drug Research, P.O.B. 82, H-1325-Budapest, Hungary

(Received November 11th, 1998; revised manuscript February 26th, 1999)

1,3,4-Tri-O-acetyl-2,6-anhydro-2-thio-D-manno- and -D-altropyranose as well as 1,4-di-O-acetyl-2,6-anhydro-3-azido-3-deoxy-2-thio-D-mannopyranose were synthesized and used as donors in the synthesis of the corresponding 4-cyano- and 4-nitrophenyl-thioglycosides, which showed significant oral antithrombotic activity in rats.

1003-1009 The Use of a New Magnesium-Derived HydrideReagent for Carbohydrate Derivatives

by G. Szabovik1, A. Medgyes1, Zs. Antal1, Zs. Varga1, W. Knott3 and A. Lipták2
1Department of Biochemistry, Kossuth L. University and
2Carbohydrate Research Group of the Hungarian Academy of Sciences,H-4010 Debrecen, P.O.Box 55, Hungary
3Zentralbereich Forschung der Th. Goldschmidt AG, D-45116 Essen,Goldschmidtstraße 100, Germany

(Received January 4th, 1999)

The magnesium hydride based reagent in THF solution is an excellent tool for the stereoselective reduction of different uloside derivatives. Sugar azides, sulfonyl esters give aminosugars and methylose derivatives without affecting other functionalities. Halogenated sugars or methylene derivatives are stable under these conditions. The reagent can be applied in the presence of a wide variety of blocking groups (acetals, benzyl and allyl ethers, imides, C=C bonds) generally used in the carbohydrate chemistry.

1011-1018 Synthesis and NMR Study of N,N'-Bis(methyl 3,4,6-tri-O-acetyl-2-deoxy-b-D-glucopyranosid-2-yl)urea and Its N'-Nitroso Derivative

by A. Temeriusz1, B. Piekarska-Bartoszewicz1, M. Weychert2 and I. Wawer2
1Department of Chemistry, Warsaw University, Pasteura 1, 02-093 Warsaw, Poland
2Department of Physical Chemistry, Faculty of Pharmacy, Medical Academy, Banacha 1, 02-097 Warsaw, Poland

(Received December 10th, 1998; revised manuscript February 26th, 1999)

N,N'-Bis(methyl 3,4,6-tri-O-acetyl-2-deoxy-b-D-glucopyranosid-2-yl)urea 1 and its N'-nitroso derivative 2 were synthesized from methyl 2-amino-3,4,6-tri-O-acetyl-2-deoxy-b-D-glucopyranoside and di(4-nitrophenyl)carbamate. The nitrosation was carried out using N2O3 in dichloromethane. The structure of compounds was analyzed by 1H , 13C, 15N NMR in CDCl3 and 13C CP MAS in the solid state. The assignments of resonances were done by COSY 1H, 13C, HETCOR and the 1H, 15N 2D correlation spectroscopy. Compound 1 gives one set of 1H/13C resonances in solution, but exhibits polymorphism in the solid state.

1019-1027 Acyclonucleosides of Indazole andTheir Rearrangements

by J. Boryski
Institute of Bioorganic Chemistry, Polish Academy of Sciences,ul. Noskowskiego 12/14, 61-704 Poznań, PolandE-mail: jboryski@ibch.poznan.pl

(Received December 28th, 1998)

2-[(2-Acetoxyethoxy)methyl]indazole (3), a kinetic product formed in the reaction of indazole (1) with 2-acetoxyethyl acetoxymethyl ether (2), undergoes an irreversible, acid-catalyzed isomerization of the 2 -> 1 transglycosylation type to the respective 1-regioisomer (4). In contrast to the purine acyclonucleosides series, however, product 4 undergoes a further rearrangement to the dimer 5. On the basis of products distribution and kinetics of their formation, a mechanism of these conversions has been proposed and compared to the facile anomerization reactions of indazole ribofuranosides.

1029-1036 Carbon-13 Isotope Effect in the Decarboxylationof Phenylpropiolic Acid in Sulphuric Acid

by M. Zieliński1, A. Zielińska1, H. Paul2, S. Bernasconi2, N. Ogrinc3,I. Kobal3 and H. Papiernik-Zielińska1
1Faculty of Chemistry, Jagiellonian University, 30-060 Kraków, Poland
2Laboratory of Stable Isotopes, Institute of Geology, ETH-Zurich, Switzerland
3Jozef Stefan Institute, Ljubljana, Slovenia

(Received November 9th, 1998; revised manuscript February 19th, 1999)

C-13 isotope effect in the decarboxylation of phenylpropiolic acid in diluted aqueous sulphuric acid and in its concentrated solution has been studied in vacuum reaction vessels. The (k12/k13) KIEs are located in the range 1.0042–1.0046 in the temperature interval 90–110oC in the case of decarboxylation of PPA in H2SO4 diluted with water. C-13 KIEs in the decarboxylation of PPA in the concentrated H2SO4 were found to be 1.060–1.050 between 16–60oC. A discussion of the negligible C-13 KIE in the decarboxylation of PPA in diluted aqueous sulphuric acid (1:4/V:V/H2SO4:H2O) has been given and the discussion of the large C-13 KIE, exceeding the values of C-13 KIE calculated for this temperature interval, assuming the "full" C–*C bond rupture in the T.S., has been presented. The kinetic parameters, deduced from the temperature dependence of the absolute rate constants of decarboxylation reaction and the C-13 KIE data, have been interpreted as the result of the loose T.S. in the case of decarboxylation of PPA in aqueous solution of H2SO4 and as the result of the "chelate-like" T.S. in the decarboxylation of PPA in concentreted sulphuric acid. The protonation of the triple bond and/or formation of he Ca–H bond are the rate and the C-13 KIE determining processes in 3.75 M H2SO4, while in the case of decarboxylation of PPA in concentrated H2SO4, the phenylpropiolic acid is fully protonated and the rupture of the C–*C bond, preceded by preequilibria, determines the large C-13 isotope effect observed.

1037-1039 Cyclodextrin-Isocyanate: a New Access from Phosphinimines

by J. Kovács1, I. Pintér1, P. Mészáros2, M. Kajtár-Peredy3 and L. Jicsinszky4
1Prochem Research and Development Ltd., H-1525 Budapest, P. O. Box 17, Hungary
2Gedeon Richter Ltd., H-1475 Budapest 10, P. O. Box 27, Hungary
3Chemical Research Center, Hungarian Academy of Sciences, H-1525 Budapest, P. O. Box 17, Hungary
4Cyclolab, Cyclodextrin Research and Development Ltd., H-1525 Budapest, P. O. Box 435, Hungary

(Received December 21st, 1998)

1041-1045 An Improved Calculation of Bond-DissociationEnergies of Organic Compounds Based on theConcept of Stabilization Energy

by M. Firpo, L. Gavernet and E.A. Castro
CEQUINOR, Departamento de Química, Facultad de Ciencias Exactas,Universidad Nacional de La Plata, C.C. 962, La Plata 1900, Buenos Aires, Argentina

(Received October 22nd, 1998; revised manuscript February 18th, 1999)

1047-1050 Isothermal Section of the Nd–Co–Sn System at 870 K

by P. Salamakha, P. Demchenko, O. Sologub and O. Bodak
Inorganic Chemistry Department, L'viv State University, L'viv, Ukraine

(Received February 1st, 1999; revised manuscript March 3rd, 1999)

1051-1053 Synthesis and Magnetism of Manganese(II)Complex with One Dimensional Structure

by S.C. Zhud1, J.Q. Xu2, J.M. Shi1, R.Z. Wang2, G.Y. Yang2, H.R. Sun2, T.G. Wang2, P. Cheng3 and D.Z. Liao3
1Department of Chemistry, Shandong Normal University, Jinan 250014, P. R. China
1State Key Laboratory of Crystal Materials, Shandong University, Jinan 250100, P. R. China
2Department of Chemistry, Jilin University, Changchun 130023, P. R. China
3Department of Chemistry, Nankai University, Tianjin 300071, P. R. China

(Received November 30th, 1998; revised manuscript March 8th, 1999)


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