J. Serb. Chem. Soc. 63(11) 833-840 (1998)
UDC 547.593.4:547.92
JSCS-2590
Original scientific paper

Stereoselective transformation of cyclodecene-1,4-dione systems, derived from steroids, to the corresponding spiro-g-lactones

LJUBINKA LORENC*,**, LIDIJA BONDARENKO-GHEORGHIU**, VLADIMIR PAVLOVIC*,**, NATALIJA KRSTIC** and MIHAILO LJ. MIHAILOVIC*,**

*Faculty of Chemistry, University of Belgrade, Studentski trg 12-16, P.O.Box 158, YU-11001 Belgrade and
**Center for Chemistry, ICTM, P.O.Box 815, YU-11001 Belgrade, Yugoslavia

 
(Received 4 August 1998)
The thermal and acid-catalyzed intramolecular rearrangement of the (Z)- and (E)-cyclodecene-1,4-dione compounds derived from steroids, 2a,b and 3a,b, respectively, proceeds stereoselectively to give the corresponding configurationally different spiro-g-lactone derivatives, the (5R,9R)-isomers 4a,b (from the (Z)-cyclodecenediones 2a,b) and the (5R,9S)-isomers 5a,b (from the (E)-cyclodecenediones 3a,b). A possible mechanistic pathway of the observed intramolecular process leading to the spiro-g-lactone structures is discussed.

Key words: steroidal cyclodecene-1,4-dione systems, stereoselective transformation, spiro-g-lactones.



J. Serb. Chem. Soc. 63(11) 841-844 (1998)
UDC 547.768:547.587.51
JSCS-2591
Note

N O T E
The preparation of an isoxazole derivative of 4-hydroxycoumarin

LjUBOMIR KRSTIC, SLAVICA SOLUJIC*, SLOBODAN SUKDOLAK*, MILUTIN STEFANOVIC** and DUSAN SLADIC**

*Center for Chemistry, ICTM, Njegoseva 12, POB 815, 11001 Belgrade,
**Faculty of Science, Department of Chemistry, Radoja Domanovica 12, 34000 Kragujevac and
***Faculty of Chemistry, University of Belgrade, POB 158, YU-11001 Belgrade, Yugoslavia

(Received 9 July 1998)
A method for preparation of an isoxazole derivative of 4-hydroxycoumarin, 3-phenyl-5-(4-hydroxy-3-coumarinyl)-isoxazole has been described. The reaction sequence includes addition of bromine to 3-cinnamoyl-4-hydroxycoumarin, and the subsequent treatment of the obtained dibromo derivative with 2 equivalents of sodium azide. Due to steric reasons, the azido group is introduced in the b-position with respect to the side chain carbonyl group, so that an isoxazole ring can be formed. The total yield of the reaction was 58%.

Key words: 4-hydroxycoumarin, isoxazole, azidovinyl ketones.



J. Serb. Chem. Soc. 63(11) 845-850 (1998)
UDC 547.964:546.73-541.428.49
JSCS-2592
Original scientific paper

Investigation of complexes of the tripeptides Leu-Leu-Tyr and Leu-Ser-Phe with Co(III)

LIDIA BARBARA JASIŃSKA, JAN RYSZARD RUMIŃSKI*, PIOTR GUGAc and DOROTA KACZYŃSKA**

*Department of Chemistry, The Ludwig Rydygier Medical University, 85-363 Bydgoszcz, Poland,
**Institute of Chemistry, N. Copernicus University, 87-100 Toru, Poland and
***Centre of Molecular and Macromolecular Studies, Polish Academy of Sciences, 90-363 Lódź, Poland

(Received 17 February, revised 31 August 1998)
Complexes of Co(III) with Leu-Leu-Tyr (LLY) and Leu-Ser-Phe (LSF) peptides were obtained. HPLC chromatograms suggest that the peptides are included into the Co(III) complexes in an intact form. The complex LLY/pentammine Co(III) was isolated by means of RP-HPLC, and characterized using 1H-NMR and LSMS techniques. The obtained NMR spectra indicate that the aromatic ring of tyrosine acts as a ligand to the cobalt cation.

Key words: peptides, cobalt(III) complexes, HPLC.



J. Serb. Chem. Soc. 63(11)851-862(1998)
UDC 541.124-16:546.76'77''78'''/54-31/
JSCS-2593
Original scientific paper

A thermoanalytical study of the solid state reactions in Li2CO3 - MexOy systems

N. COLOVIC, M. ANTONIJEVIC and S. MILIC

Technical Faculty Bor, University of Belgrade, P.O. Box 50 YU-19210 Bor, Yugoslavia

(Received 13 December 1997, revised 17 June 1998)
The results of a study of the kinetics of the reaction between lithium carbonate and the oxides of some transition metals (Cr, Mo, W) are presented in this work. The reactions were carried out under non-isothermal conditions, in an air atmosphere. The transformation degree, a, was surveyed by thermogravimetric analysis. It was established by analysis of the experimental data that the reaction between lithium carbonate and chromium(III) oxide occurs in one stage, and that the reactions of molybdenum and wolfram oxides with lithium carbonate are more complex. The values of the basic kinetic parameters (energy of activation and pre-exponential factor) for all stages of the examined reaction were also determined. The energy of activation for the reaction between Li2CO3 and Cr2O3 is 97.3 kJ/mol, for the reaction between Li2CO3 and MoO3 (I stage) 120.6 kJ/mol, and for the reaction between Li2CO3 and WO3 (I stage) 167.1 kJ/mol. Based on the values of the energies of activation and the pre-exponential factors, a compensation effect was observed.

Key words: solid state reactions, lithium carbonate, chromium, molybdenum and wolfram oxide, compensation effect.



J. Serb. Chem. Soc. 63(11)863-868(1998)
UDC 546.34'822'':541.65
JSCS-2594
Original scientific paper

The optical properties of non-annealed LiNbO3

ALEKSANDAR GOLUBOVIC, RADOS GAJIC* and ANDREJA VALCIC**

Institute of Chemistry, Technology and Metallurgy, Njegoseva 12, YU-11000 Belgrade,
*Institute of Physics, P.O.Box 57, YU-11001 Belgrade and
**Faculty of Technology and Metallurgy, Karnegijeva 4, YU-11000 Belgrade, Yugoslavia

(Received 11 March, revised 30 June 1998)
Single crystals of LiNbO3were grown by the Czochralski technique. X-ray measurements were performed on the powder to obtain the lattice parameters. The optical properties of non-annealed samples LiNbO3 single crystals were studied to investigate the effect of non-annealing on the optical properties. Obtained results are discussed and compared with published data.

Key words: Czochralski technique, LiNbO3, single crystals, optical properties, non-annealing.



J. Serb. Chem. Soc. 63(11) 869-875 (1998)
UDC 546.776:547.565.3
JSCS-2595
Original scientific paper

Spectrophotometric study of the reaction of molybdenum(VI) with sodium-pyrogallol-5-sulphonate. The determination of molybdenum

MIRJANA V. OBRADOVIC, SNEZANA S. MITIC, DRAGAN S. VESELINOVIC* and
DANIELA C. NASKOVIC**

Department of Chemistry, Faculty of Philosophy, University of Nis, Cirila i Metodija 2, YU-18000 Nis,
*Faculty of Physical Chemistry, University of Belgrade, P.O.Box 137, YU-11001 Belgrade and
**D.D. Zdravlje, Leskovac, YU-16000 Leskovac, Yugoslavia

(Received 17 April, revised 10 July 1998)
On the basis of spectrophotometric measurements and applying the Job, Harvey-Manning, mole ratio and the Franck-Ostwald methods it has been found that, in acid media, molybdenum(VI) and sodium-pyrogallol-5-sulphonate (PS) form a complex SMoO3(PS)2C2-. The wide absorption maxima of this complex is at 314-375 nm. The stability constants of this complex were calculated by using the Job and the Franck-Ostwald methods. The thermodynamic values, D H°, DG°, and DS°, of the complex have also been calculated. A spectrophotometric method for molybdenum determination has been developed. The method is applied for the determination of molybdenum in steel.

Key words: molybdenum determination, spectrophotometry, sodium-pyrogallol-5-sulphonate, complex.



J. Serb. Chem. Soc. 63(11) 877-882 (1998)
UDC 541.135:66.087
JSCS-2596
Original scientific paper

Elimination of nucleation exclusion zones by electrodeposition at a reversing current

N. D. NIKOLIC, E. R. STOJILKOVIC*, K. I. POPOV** and M. G. PAVLOVIC

ICTM-Institute of Electrochemistry, Njegoseva 12, YU-11000 Belgrade,
*Faculty of Agriculture, University of Belgrade, Nemanjina 6, YU-11080 Zemun-Belgrade and
**Faculty of Technology and Metallurgy, University of Belgrade, Karnegijeva 4, YU-11000 Belgrade, Yugoslavia

(Received 10 July 1998)
Elimination of nucleation exclusion zones by electrodeposition at a reversing current (RC) in the seconds time range is considered. It is shown that nucleation exclusion zones formed in constant regimes can be eliminated by a reversing current only if the deposition process is under full diffusion control.

Key words: metal deposition, reversing current, exclusion zones.



J. Serb. Chem. Soc. 63(11) 883-889 (1998)
UDC 582.886:66.066.1:661.97
JSCS-2597
Original scientific paper

Extraction of Oenothera biennis seed oil with supercritical carbon dioxide - determination of the content of gamma linolenic acid in seed oil

IRENA ZIZOVIC, DEJAN SKALA and MIHAJLO RISTIC*

Faculty of Technology and Metallurgy, Karnegijeva 4, YU-11000 Belgrade and
*Institute for Medical Herbs "Dr Josif Pancic", Tadeusa Koscuska 1, YU-11000 Belgrade, Yugoslavia

(Received 4 March, revised 8 July 1998)
Oenothera biennis oils can be extracted from seeds using usual organic solvents or by applying the modern method of extraction based on supercritical carbon dioxide as the solvent. The solubility of oil in supercritical carbon dioxide depends on the temperature and pressure conditions of the extraction, i.e., on the density of the carbon dioxide. The fatty acids content of the extracted oils was analyzed after hydrolysis of the oil and the preparation of their methyl esters using conventional procedures.

Key words: supercritical extraction, Oenothera biennis, gamma linolenic acid.



J. Serb. Chem. Soc. 63(11) 891-901 (1998)
UDC 541.183.5:628.3:62.001.57
JSCS-2598
Original scientific paper

Modelling of a fixed bed adsorption column for waste water treatment

VERA D. MESHKO, LJILJANA T. MARKOVSKA, MIRJANA B. MINCEVA and VIOLETA V. CIBULIC*

Faculty of Technology and Metallurgy, University "St. Cyril and Methodius", Ruger Boskovic 16, 91000-Skopje,
Republic of Macedonia and
* Public - Health Institute, Leskovac, Yugoslavia

(Received 6 June 1998)
A fixed bed adsorption column for purification of waste water from textile fibres colouring has been studied. All investigations were performed under dynamic conditions at a constant temperature on united collective composite waste water samples. A natural zeolite was used as the adsorbent. The mathematical model of the fixed bed adsorption column, used for computer simulation, is based on mass balance of the column and mass balance of a particle in the column. The positions and shape of the breakthrough curve profile depend on several factors, including the physical and chemical properties of both the sorbate and sorbent, the influent concentration of sorbate, the particular rate limiting mechanism, the nature of the equilibrium conditions, the height of the column and the flow rate. The relative effects of these factors are highly specific to a particular sorbent-sorbate system which constitutes one of the major difficulties in designing such a process.

Key words: adsorption column design, purification, waste water, textile dyeing.


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