Stereochemistry of New Nitrogen Containing

Polish J. Chem., 74, 1047–1053 (2000)

INORGANIC CHEMISTRY

Stereochemistry of New Nitrogen Containing Heterocyclic Aldehydes. III. Novel Bis-Bidentate Azodye Compounds by A.F. Shoair, A.A. EI-Bindary, A.Z. El-Sonbati and R.M. Younes Chemistry Department, Faculty of Science (Demiatta), Mansoura University, Demiatta, Egypt (Received February 10th, 2000; revised manuscript April 13th, 2000) New polymeric complexes of Co(II), Ni(II), Cu(II), Fe(II), Fe(III), Zn(II), Cd(II) and UO2(II) with 5-(2-hydroxyphenyldiazo)-8-hydroxy-7-quinolinecarboxaldehyde (LH2) have been synthesized and characterized by analytical, thermal, magnetic, infrared, electronic, 1H NMR, 13C NMR and EPR spectra data. The infrared spectral data of the metal complexes indicate that LH2 act as bis-bidentate towards the metal ions. The electronic spectral data suggest that Co(II) and Mn(II) complexes are octahedral, while Ni(II) complex is square planar. The complexes of Zn(II) and Cd(II) are tetrahedral. The chelating ligand around the copper was expected to be distorted square planar for Cu(II). The electronic absorption and a g||/A|| value are indicative for the beginning of a tetrahedral distortion. The coupling constants of various coordinated nuclei with copper(II) are estimated from EPR spectrum of copper(II) complex.

Polish J. Chem., 74, 1055–1062 (2000)

Synthesis, Characterization and Ferromagnetic Interaction in m-Oxamido Cu(II)–Cr(III) Heterodinuclear Complexes by Y.-T. Li1,2, C.-W. Yan1 and X.-C. Zeng2 1

Department of Chemistry, Qufu Normal University, Qufu Shandong, 273165, P. R. China 2 Department of Chemistry, Sichuan University, Chengdu, Sichuan, 610064, P. R. China (Received February 29th, 2000; revised manuscript April 17th, 2000)

Four new oxamido-bridged heterodinuclear copper(II)–chromium(III) complexes Cu(Me2oxpn)Cr(L)2](NO3)3, where Me2oxpn denotes N,N¢-bis(3-amino-2,2-dimethylpropyl)oxamido dianion and L represents 1,10-phenanthroline (phen), 5-nitro-1,10phenanthroline (NO2-phen), 5-chloro-1,10-phenanthroline (Cl-phen) and 5-bromo-1,10phenanthroline (Br-phen), have been synthesized and characterized by elemental analyses, IR and electronic spectra, magnetic moments at room-temperature and molar conductivity measurements. It is proposed that these complexes extend oxamido-bridged structures, consisting of planar copper(II) and octahedral chromium(III)

ions. The variable temperature magnetic susceptibility (4.2–300 K) of complex [Cu(Me2oxpn)Cr(NO2-phen)2](NO3)3 was measured and the magnetic analysis was carried out by least-square method to fit the data with equation derived from the spin $ = -2JS $ ×S $ , giving the exchange integrals J = +21.5 cm–1, what indicates Hamiltonian, H 1 2 a ferromagnetic interaction between the adjacent chromium(III) and copper(II) ions through the oxamido-bridge within the complex.

Polish J. Chem., 74, 1063–1070 (2000)

Synthesis, Characterization and Magnetism of Heterodinuclear Cu(II)–Fe(II) Complexes Bridged by N,N¢-Oxamidobis(propionato)cuprate(II) by Y.-T. Li1,2, C.-W. Yan1 and X.-C. Zeng2 1

Department of Chemistry, Qufu Normal University, Qufu, Shandong, 273165, P. R. China 2 Department of Chemistry, Sichuan University, Chengdu, Sichuan, 610064, P. R. China (Received March 2nd, 2000; revised manuscript May 4th, 2000)

Six new copper(II)–iron(II) heterodinuclear complexes bridged by dianions of N,N¢oxamidobis(propionato)cuprate [Cu(obp)] and end-capped with 2,2¢-bipyridine (bpy), 1,10-phenanthroline (phen), 5-nitro-1,10-phenanthroline (NO2-phen), 5-chloro-1,10-phenanthroline (Cl-phen), 5-bromo-1,10-phenanthroline (Br-phen) or 5-methyl-1,10phenanthroline (Me-phen); namely [Cu(obp)FeL2] (L = bpy, phen, NO2-phen, Cl-phen, Br-phen, Me-phen), have been synthesized and characterized. Based on the elemental analyses, magnetic moments (at room temperature) and molar conductivity measurements, and spectroscopic studies, extended oxamido-bridged structures consisting of a copper(II) ion and an iron(II) ion, which have a square-planar environment and an octahedral environment, respectively, are proposed. The Cu(obp)Fe(bpy)2 (1) and Cu(obp)Fe(phen)2 (2) complexes have been further characterized by variable temperature magnetic susceptibility (4.2~300 K) and the observed data were least-squares fitted to the susceptibility equation derived from the spin Hamiltonian including single-ion $ = -2JS $ ×S $ - DS $ 2 , giving the exchange integzero-field interaction for the iron(II) ion, H 1 2 Z1 rals J = –17.9 cm–1 for (1) and J = –18.8 cm–1 for (2). These results indicated that the spin coupling between the adjacent copper(II) and iron(II) ions through oxamido-bridge in both complexes (1) and (2) is antiferromagnetic.

Polish J. Chem., 74, 1071–1077 (2000)

Synthesis and Magnetic Studies of m-Iodanilato-Bridged Binuclear Oxovanadium(IV) Complexes by Y.-T. Li1 and C.-W. Yan2 1

Department of Chemistry, Qufu Normal University, Qufu Shandong, 273165, P. R. China

2

Department of Biology, Qufu Normal University, Qufu Shandong, 273165, P. R. China (Received March 6th, 2000; revised manuscript May 4th, 2000)

Six novel oxovanadium(IV) binuclear complexes of the formula [(VO)2(IA)L2]SO4, where IA represents the dianion of iodanilic acid and L denotes 5-methyl-1,10-phenanthroline (Me-phen); 2,9-dimethyl-1,10-phenanthroline (Me2-phen); 5-chloro-1,10-phenanthroline (Cl-phen); 5-bromo-1,10-phenanthroline (Br-phen); diaminoethane (en) and 1,3-diamino-propane (pn), have been synthesized and characterized by elemental analyses, molar conductance and magnetic moments of room-temperature measurements, IR and electronic spectral studies. It is proposed that these complexes have IA-bridged structures and consist of two vanadium(IV) ions in a square-pyramidal environment. The complexes [(VO)2(IA)-(Me-phen)2]SO4 (1) and [(VO)2(IA)(Me2-phen)2]SO4 (2) were characterized by variable temperature magnetic susceptibility measurements (4.2~300 K) and the observed data were fitted to the modified Bleaney-Bowers equation by the least-squares method, giving the exchange parameters J = –18.9 cm–1 for (1) and J = –14.3 cm–1 for (2). This result indicates that there is an antiferromagnetic spin-exchange interaction between the two VO2+ ions within each molecule.

Polish J. Chem., 74, 1079–1083 (2000)

ORGANIC CHEMISTRY

Synthesis and Reactions of Organic Compounds with a Nitrogen Atom. Part XVI. Reactions of (–)-4-Chloro-3(10)-carene and (+)-10-Chloro-3-carene with Phenyltelluro- and Phenylselenosodium by A. Uzarewicz, J. Œcianowski and J. B¹kowska-Janiszewska Faculty of Chemistry, Nicolaus Copernicus University, 87-100 Toruñ, Poland (Received March 9th, 2000; revised manuscript March 21st, 2000) The reaction of (–)-4-chloro-3(10)-carene (1) and (+)-10-chloro-3-carene (2) with phenylselenosodium (3) or phenyltellurosodium (4) and chloramine-T produced Ntrans-[3¢(10¢)-caren-4¢-yl]toluenesulfonamide (6), which was reduced with sodium in liquid ammonia to (+)-trans-4-amino-2-carene (7) and trans-4-amino-3(10)-carene (8). Carenal (9) and trans-3(10)-caren-4-ol (10) were obtained from 10-phenyltelluro-3carene by the air oxidation.

Polish J. Chem., 74, 1085–1090 (2000)

Synthesis of Hepatitis C Virus Protein Fragments and Evaluation of Their Immunogenicity. Part II by K. Klugmann1, B. Karawajczyk1, D. Kunikowska2, R. G³oœnicka2 and Z. Maækiewicz1

1

Faculty of Chemistry, University of Gdañsk, Sobieskiego 18, 80-952 Gdañsk, Poland 2 Department of Immunology, Institute of Maritime and Tropical Medicine, Powstania Styczniowego 9b, 81-519 Gdynia, Poland e-mail: [email protected] (Received March 8th, 2000; revised manuscript April 3rd, 2000)

Three polypeptide fragments of hepatitis C virus protein were synthesized using the solid-phase method. The immunogenicity of the peptides was tested. All the peptides exhibit immunological activity.

Polish J. Chem., 74, 1091–1099 (2000)

A Comparison of Solution Conformations of Scyliorhinin I and Its Analogue with N-Methyl-L-phenylalanine in Position 7 by L. Klaudel, S. Rodziewicz-Motowid³o, A. Liwo and K. Rolka Faculty of Chemistry, University of Gdañsk, Sobieskiego 18, PL-80-952 Gdañsk, Poland (Received February 18th, 2000; revised manuscript April 5th, 2000) Conformational studies on scyliorhinin I (ScyI), a member of tachykinin family and its analogue with N-methyl-L-phenylalanine in position 7 in DMSO-d6 were performed using a combination of the two-dimensional NMR technique and theoretical conformational analysis. Their solution structures are characterized by families consisting of 7 and 8 conformers, respectively, with statistical weights higher than 2%. The 3D structure of ScyI is rather flexible, whereas the presence of a local constraint (MePhe) in position 7 significantly rigidifies the whole molecule. The comparison of conformers with the greatest statistical weights obtained for both peptides revealed the similarities in the fragment 1–7, whereas C-terminal segments are quite different (RMSD = 2.26 Å). We postulate that this can be connected with the differences of the pharmacological profiles of both peptides (ScyI full agonist of both NK1 and NK2 tachykinin receptors; [MePhe7]ScyI is practically inactive).

Polish J. Chem., 74, 1101–1114 (2000)

Reactions of Secondary b-Ketothioamides with Ethyl Bromoacetate and Ethyl 2-Bromopropionate. The Synthesis of N-Substituted 2-Acylmethylidene-1,3-thiazolidin-4-ones by T.S. Jagodziñski, A. Weso³owska and J.G. Soœnicki Department of Organic Chemistry, Technical University of Szczecin, 71-065 Szczecin, Aleja Piastów 42, Poland

(Received February 3rd, 2000; revised manuscript April 14th, 2000) 4-Morpholinocoumarin (2) was obtained in the reaction of 4-(2-hydroxythiobenzoyl)morpholine (1) with ethyl bromoacetate in the presence of triphenylphosphine and triethylamine. Analogous reactions of 3-keto thioamides with ethyl bromoacetate and ethyl 2-bromopropionate, carried out in THF or acetone, yielded cyclic derivatives of N-substituted 2-acylmethylidene-1,3-thiazolidin-4-ones (4, 7, 8). In the reaction with ethyl 3-bromopropionate only S-alkylation of the thioamide was observed. The reaction of the indandione-derived thioamides 6 with ethyl bromoacetate in acetone gave the condensation products of 2-acylmethylidene-1,3-thiazolidin-4-ones with acetone. 2-Acylmethylidene-1,3-thiazolidin-4-ones 4, 7, 8 condensed with benzaldehyde to give the 5-benzylidene derivatives.

Polish J. Chem., 74, 1115–1122 (2000)

Allylation of Sugar Diols Under Phase Transfer Conditions Using Potassium Carbonate as a Base. Unexpected Formation of Cyclic Carbonates by S. Jarosz and K. Szewczyk Institute of Organic Chemistry, Polish Academy of Sciences, ul. Kasprzaka 44, 01-224 Warszawa 42, P.O.Box 58 Poland; e-mail: e-mail: [email protected] (Received March 17th, 2000; revised manuscript April 17th, 2000) Allylation of sugar vic-diols (with a primary and secondary OH groups) under the phase transfer conditions (allyl bromide, K2CO3, 18-crown-6, toluene) afforded a mixture of both monosubstituted allyl ethers and small amounts of the di-allyl derivative. Interestingly, the cyclic carbonate was also isolated from the post reaction mixture. Its formation may be explained by reaction of the di-allyl carbonate, formed in situ under the reaction conditions, with the 1,2-diol. The structure of mono-allylated isomers can be easily assigned from the chemical shift (dC) of the CH2OR group (for R = H; All).

Polish J. Chem., 74, 1123–1128 (2000)

A Useful Synthesis of Diethyl 1-Substituted Vinylphosphonates by H. Krawczyk, J. Koszuk and R. Bodalski Institute of Organic Chemistry, Technical University, 90-924 £ódŸ, ul.¯eromskiego 116, Poland (e-mail: [email protected]) (Received March 27th, 2000; revised manuscript April 17th, 2000)

A variety of diethyl 1-substituted vinylphosphonates 8 has been conveniently synthesized by piperidine catalyzed decarboxylative condensation of 2-diethoxyphosphorylalkanoic acids and 2-diethoxyphosphorylalkenoic acids 7 with formaldehyde.

Polish J. Chem., 74, 1129–1141 (2000)

Cyclic Analogues of Proline-Rich Protein Fragments. Part III. Synthesis of New Analogues, Conformational Studies and Evaluation of Immunotropic Activity by I. Wirkus-Romanowska1, S. Rodziewicz-Motowid³o1, H. Miecznikowska1, K. Rolka1, M. Janusz2, S. Szymaniec2, A. Zab³ocka2, W. Fortuna2, R. Miêdzybrodzki2, J. Lisowski2 and G. Kupryszewski1,3 2

1 Faculty of Chemistry, University of Gdañsk, 80-952 Gdañsk, Poland Institute of Immunology and Experimental Therapy, Polish Academy of Sciences, 53-114 Wroc³aw, Poland 3 Institute of Oceanology, Polish Academy of Sciences, 81-712 Sopot, Poland

(Received March 21st, 2000; revised manuscript April 20th, 2000) Two new cyclic analogues of proline-rich protein (PRP) fragments: Cys-Tyr-Val-Pro-Leu-Phe-Pro-Cys (1) and Ac-Glu-Val-Glu-Ser-Tyr-Val-Pro-Leu-Phe-Pro-Lys-NH2 (2) were synthesized by the solid phase method. These peptides were designed based on the immunoregulatory activity of a linear nonapeptide isolated from products of PRP chymotrypsic digestion. Conformational studies in DMSO-d6 of peptides 1 and 2 performed by the 1H-NMR method have shown that the solution structure of peptide 1 is more rigid than that obtained for the second analogue. Nevertheless, the lowest-energy conformations of both peptides revealed similarities in the fragment Tyr-Val-Pro-LeuPhe-Pro (root mean squere deviation – RMSD of a-carbons is 0.94 Å). The immunotropic activity of peptides studied evaluated in the murine system indicated that they are as active as the linear precursor in the resistance to hydrocortisone, but did not shown activity in the human system. As reported previously, similar immunotropic profiles were observed in the case of two cyclic analogues. Superposition of most representative conformations of all four peptides in the fragment mentioned above (RMSD of a carbons is 0.86 Å) leads to the conclusion that this hexapeptide segment might be considered as bioactive.

Polish J. Chem., 74, 1143–1148 (2000)

PHYSICAL CHEMISTRY

Carbon-13 Isotope Fractionation in the Decarboxylation of Phenylpropiolic Acid (PPA) Below and Above Its Melting Point and in the Decarboxylation of PPA in Phenylacetylene Medium

by M. Zieliñski, A. Zieliñska and H. Papiernik-Zieliñska Faculty of Chemistry, Jagiellonian University, 30-060 Kraków, Poland (Received January 28th, 2000; revised manuscript March 2nd, 2000) C-13 isotope fractionation in the decarboxylation of pure phenylpropiolic acid (PPA) below and above its melting point and the decarboxylation of PPA in phenylacetylene solutions has been investigated in sealed under vacuum reaction vessels. The reactive PPA undergoing decarboxylation polymerizes with the liquid product, phenylacetylene in reaction cage producing a condensation compound, which does not decarboxylate measurably in the 120–190°C. Especially low final carbon dioxide yields (about 11%) have been obtained in the decarboxylation of PPA in phenylacetylene solution at 132°C and below this temperature. The carbon dioxide is depleted in carbon-13. The ratio of the carbon isotope ratios of carboxylic carbon of PPA before decarboxylation, R(13C/12C)so, and of the first portions of carbon dioxide obtained at partial decarboxylations, R(13C/12C)pf, located in the range 1.007–1.010, indicates that the pure kinetic fractionation of 13C in the elementary decarboxylation step is negligible and the C-13 fractionation in the condensed phase dimer/monomer equilibria contributes mainly to the resultant experimental carbon isotope fractionation. A preliminary discussion of the experimental isotope findings is presented.

Polish J. Chem., 74, 1149–1161 (2000)

Aqueous Basicity and Proton Affinity of Zwitterionic w-(N-Methylpiperidine)-alkanocarboxylates and w-(N-Piperidine)-alkanocarboxylic Acids by P. Barczyñski, Z. Dega-Szafran, E. Dulewicz, M. Petryna and M. Szafran Faculty of Chemistry, A. Mickiewicz University, 60-780 Poznañ, Poland E-mail: [email protected] (Received December 27th, 1999; revised manuscript March 20th, 2000) The pKa values of 5 w-(N-methylpiperidine)-alkanocarboxylates (N-methylpiperidine betaines) and 5 w-(N-piperidine)-alkanocarboxylic acid were determined by potentiometric titration of their hydrohalides with KOH. Semiempirical geometry optimizations were performed for gaseous betaines. Four conformers were characterized and their PA values estimated. The PA values fulfilled the linear correlation with the aqueous pKa values estimated in ref. 1. A linear correlation between the calculated heat of formation (DHf) and the sum of the N···O1 and N···O2 distances, for the conformers containing the same number of CH2 groups, indicates that they are stabilized by the intramolecular electrostatic interactions between the positively charged nitrogen atom and oxygen atoms of the carboxylate group.

Electroreduction of Dioxygen Catalyzed by Ferric Carboxymethylene–Cyclam Complex by W.S. Szulbiñski Central Institute of Mining, Department of Environmental Monitoring, 40-166 Katowice, Plac Gwarków 1, Poland (Received February 24th, 2000; revised manuscript April 25th, 2000) Electrochemical analysis of a Fe3+ macrocyclic complex, involving N-carboxymethylene-1,4,8,11-tetraazacyclotetradecane, {Fe3+[14]aneN4Ac–}2+, under aerobic conditions, shows a similar behaviour to that previously observed for the catalysts of O2-

Complexes of cadmium(II) and mercury(II)...

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C-substituents. More stable derivatives condense with the nitroso intermediates to yield azoxycompounds. Less stable hydroxylamines undergo rearrangements, azole ring reduction and decomposition. Some products of these transformations, following the electrochemical reduction, were isolated and their structures were fully characterized by standard methods.

Polish J. Chem., 74, 1185–1189 (2000)

Application of Spatially Resolved NMR Spectroscopy for High Resolution Spectra of Heterogeneous Samples by W. KoŸmiñski Laboratory of NMR Spectroscopy, Department of Chemistry, Warsaw University, ul. Pasteura 1, 02-093 Warszawa, Poland, e-mail [email protected] (Received March 13th, 2000; revised manuscript April 17th, 2000) An improved method for acquisition of high resolution NMR spectra, exclusively in an arbitrarily chosen volume element of the sample, is presented. The proposed pulse sequence utilizes the Double Pulsed Field Gradient Selective Echo (DPFGSE) element, that offers a high selectivity and superior phase and baseline properties of the resulted spectra. The discussed experiment is applicable in all NMR spectrometers, equipped with at least a single-axis PFG accessory. The effectiveness of the proposed technique is demonstrated by acquisition of 1H NMR spectra from different volume elements of a heterogeneous CDCL3/D2O sample.

Polish J. Chem., 74, 1191–1196 (2000)

COMMUNICATION

Investigation of the Inclusion Complex of Ferrocenyl Derivative with b-Cyclodextrin by Z.X. Liao1,2, X.Y. Ma1, Z.X. Shi2 and Y.Z. Chen1,3 1

Department of Chemistry, National Laboratory of Applied Organic Chemistry, Lanzhou University, Lanzhou 730000, P.R. China 2 Northwest Plateau Institute of Biology, Chinese Academy of Science, Xining 810001, P.R. China 3 Institute of Organic Chemistry, Zhejiang University, Hangzhou 310072, P.R. China (Received December 20th, 1999; revised manuscript March 17th, 2000)

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L. £omozik and R. Bregier-Jarzêbowska

Polish J. Chem., 74, 1197–1200 (2000)

COMMUNICATION

Isomerization of Allyl-Aryl Ethers Catalyzed by Ruthenium Complexes by S. Krompiec1, N. KuŸnik2, T. Bieg3, B. Adamus4, J. Majnusz5 and M. Grymel2 1

Institute of Inorganic Chemistry, Technology and Electrochemistry, Silesian Technical University, Krzywoustego 6, 44-101 Gliwice, Poland 2 Institute of Organic Chemistry and Technology, Silesian Technical University, Krzywoustego 4, 44-101 Gliwice, Poland 3 Department of Chemical Technology of Coal and Petroleum, Silesian Technical University, Krzywoustego 8, 44-101 Gliwice, Poland 4 Centre of Polymer Chemistry, M. Sk³odowskiej-Curie 34, 41-800 Zabrze, Poland 5 Department of Physical Chemistry and Technology of Polymers, Silesian Technical University, M. Strzody 9, 44-101 Gliwice, Poland (Received November 22nd, 1999; revised manuscript March 27th, 2000)

Polish J. Chem., 74, 1201–1205 (2000)

COMMUNICATION

Spectral and Thermal Studies of Rare Earth Element Pivalates by W. Brzyska, A. Nosal-Wierciñska, W. Kaliszczak, W. Dudek and M. Kulczyk-Stañko Department of General Chemistry, Faculty of Chemistry, Marie Curie Sklodowska University, 20 031 Lublin, Poland (Received December 22nd, 1999; revised manuscript March 27th, 2000)

Polish J. Chem., 74, 1207–1209 (2000)

COMMUNICATION

Catalytic Hydrogen Transfer Over Magnesia. XIII. Liquid Phase Reduction of Substituted 1-Phenyl-1-alkanones by 2-Octanol

Complexes of cadmium(II) and mercury(II)...

by M. Gliñski Faculty of Chemistry, Warsaw University of Technology, Laboratory of Catalytic Synthesis, Noakowskiego 3, 00-664 Warsaw, Poland E-mail: [email protected] (Received February 29th, 2000; revised manuscript April 21st, 2000)

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