YU-ISSN 0352-5139
J.Serb.Chem.Soc. Vol. 67. No. 7 (2002)
CONTENTS
Organic Chemistry
D. Opsenica, G. Pocsfalvi, W. K. Milhous and B. [olaja: Antimalarial
peroxides: the first intramolecular 1,2,4,5-tetraoxane
465
H. Çelik: Synthesis of monoketo and monohydroxy eicosanoic acids and
esters with substituents at odd-numbered (3-13) carbons
473
Physical Chemistry
T. J. Janji}, G. Vu~kovi} and M. B. ]elap: Influence of the stationary
and mobile phase composition on solvent strength parameter eº and SP
system parameter in NP column chromatography
481
M. Radojevi}, V. Jovi} and D. Vitorovi}: Study of sepiolite from Gole{
(Kosovo, Yugoslavia). I. Sorption capacity
489
M. Radojevi}, V. Jovi}, D. Karauli} and D. Vitorovi}: Study of
sepiolite from Gole{ (Kosovo, Yugoslavia). II. Acid activation
499
R. K. Singh and P. M. Dhadke: Extraction and separation of titanium(IV)
with D2EHPA and PC-88A from aqueous perchloric acid solutions
507
Inorganic Chemistry
R. N. Prasad and S. Gupta: Synthesis and characterization of 2,3,13,14tetramethyl (ethyl or p-tolyl)-1,4,12,15-tetraazacyclodocosa-1,3,12,14tetraene complexes of Mg(II), Ca(II), Sr(II) and Ba(II)
523
Electrochemistry
V. D. Jovi} and B. M. Jovi}: Surface reconstruction during the
adsorption/desorption of OH- species onto Cu(111) and Cu(100) in 0.1 M
NaOH solution
531
J.Serb.Chem.Soc. 67(7)465–471(2002)
UDC 616.936:54–39:547.92
JSCS - 2967
Original scientific paper
Antimalarial peroxides: the first intramolecular 1,2,4,5-tetraoxane
DEJAN OPSENICA1, GABRIELLA POCSFALVI2, WILBUR K. MILHOUS3 and
BOGDAN A. [OLAJA4#
1Institute of Chemistry, Technology and Metallurgy, Belgrade,
Yugoslavia, 2Centro di Spettrometria di Massa Proteomica e
Biomoleculare, Istituto di Scienze dell’Alimentazione, Consiglio
Nazionale delle Ricerche, Avellino, Italy, 3Division of Experimental
Therapeutics, Walter Reed Army Institute of Research, Washington, DC
20307-5100, USA and 4Faculty of Chemistry, University of Belgrade, P.
O. Box 158, YU-11001 Belgrade, Yugoslavia
(Received 28 February 2002)
An intramolecular steroidal 1,2,4,5-tetraoxane has been synthesised in
six steps starting from methyl 3-oxo-7a,12a-diacetoxy-5b-cholan-24oate. The synthesised 1,2,4,5-tetraoxane has moderate in vitro
antimalarial activity against P. falciparum strains (IC50 (D6) = 0.35
mg/mL; IC50 (W2) = 0.29 mg/mL).
Keywords: tetraoxane, malaria, peroxide, steroid, intramolecular.
REFERENCES
1. Malaria Foundation International, http://www. malaria. org/, and the
sites given therein
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Andersen, J. M. Grace, V. Wongpanich, C. K. Angerhofer, J. K. Hu, D. L.
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Makler, B. A. [olaja, Steroids 61 (1996) 688, and references cited
therein
5. D. Opsenica, G. Poscfalvi, Z. Jurani}, B. Tinant, J-P. Declercq, D.
E. Kyle, W. K. Milhous, B. A. [olaja, J. Med. Chem. 43 (2000) 3274, and
references cited therein
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J.Serb.Chem.Soc. 67(7)473–480(2002)
UDC 547.295.96+547–326:542.913
JSCS – 2968
Original scientific paper
Synthesis of monoketo and monohydroxy eicosanoic acids and esters with
substituents at odd–numbered (3-13) carbons
HÜLYA ÇEL¤K
Department of Chemistry, Faculty of Engineering, Istanbul University,
34850 Avcilar, Istanbul, Turkey; e-mail: hcelik@istanbul.edu.tr
(Received 28 December 2001, revised 8 April 2002)
In this study, monoketo and monohydroxy eicosanoic acids and their
methyl esters with the position of the substituent on odd numbered
carbon atoms from 3 to 13 were synthesized with high purity.
Furthermore, the semicarbazone and anilide derivatives of the obtained
keto acids were prepared. They were characterized by TLC, IR and 1H-NMR
spectroscopy and their physical and chemical properties were
established.
Keywords: monoketo, monohydroxy, eicosanoic acid methyl ester.
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J.Serb.Chem.Soc. 67(7)481–487(2002)
UDC 543.544.7+541.8:541.121/.123
JSCS – 2969
Original scientific paper
Influence of the stationary and mobile phase composition on solvent
strength parameter eº and SP system parameter in NP column
chromatography
T. J.JANJI], G. VU^KOVI]# and M. B. ]ELAP#
Faculty of Chemistry, University of Belgrade, P. O. Box 158, YU-11001
Belgrade, Yugoslavia
(Received 31 January 2002)
It is shown that SP system parameters, previously used for the
linearization of log k values in RP chromatography, can also be used in
NP chromatography. A very good linear correlation between SP parameter
and the earlier described Snyder solvent strength parameter has been
established. It was also found that the phase equilibrium constant K is
independent of the polarity and concentration of the more polar
component of binary solvent mixtures.
Keywords: NP chromatography, SP parameter, solvent strength parameter
eº.
REFERENCES
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(2000) 725
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(2001) 671
3. T. J. Janji}, G. Vu~kovi}, M. B. ]elap, J. Serb. Chem. Soc. 67
(2002) 179
4. F. Geiss, Fundamentals in Thin-Layer Chromatography (Planar
Chromatography) Huthig Verlag, Heidelberg, 1987, p. 257
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7. As reference 4, p. 254
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Chromatography Library, Vol 35, 1989, p. 100, Oxford, Russ. transl,
Mir, Moscow
10. L. R. Snyder, J. L. Glajch, J. Chromatogr. 214 (1981) 1 and
references cited therein.
J.Serb.Chem.Soc. 67(7)489–497(2002)
UDC 553.673(497.115):66.081
JSCS – 2970
Original scientific paper
Study of sepiolite from Gole{ (Kosovo, Yugoslavia). I.
Sorption capacity
MARINA RADOJEVI]a, VIDOJKO JOVI]b, and DRAGOMIR VITOROVI]c
aInstitute of General and Physical Chemistry, P. O. Box 551, Studentski
trg 12, YU-11000 Belgrade, bFaculty of Mining and Geology, Dju{ina 7,
YU-11000 Belgrade and cCenter of Chemistry –ICTM, Njego{eva 12, YU11000 Belgrade, Yugoslavia
(Received 8 February 2002)
The sorption of molecules of different size and polarity (water, nhexane, isooctane, benzene, toluene, cyclohexane, carbon tetrachloride,
isopropanol, isobutanol, methanol, ethanol) by sepiolite from Gole{,
i.e. from the biggest to-date known Yugoslav deposit, was studied in
this work. The BET surface area observed with different sorbates varied
from 227 to 314 m2/g, due to only partial migration of sorbate
molecules into the pores or to imperfect packing of the sorbate
molecules. The value of the outer surface area suggested that the
average thickness of the fibers of Gole{ sepiolite was approximately 15
nm.
Keywords: sepiolite, Gole{, sorption capacity, BET surface area,
alcohols, alkanes, aromatics, carbon tetrachloride.
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347.
J.Serb.Chem.Soc. 67(7)499–506(2002)
UDC 553.673(497.115):66.094.6
JSCS – 2971
Original scientific paper
Study of sepiolite from Gole{ (Kosovo, Yugoslavia). II.
Acid activation
MARINA RADOJEVI]a, VIDOJKO JOVI]b, DRAGOMIR KARAULI]a and DRAGOMIR
VITOROVI]c
aInstitute of General and Physical Chemistry, P. O. Box 551, Studentski
trg 12, YU-11000 Belgrade, bFaculty of Mining and Geology, Dju{ina 7,
YU-11000 Belgrade and cCenter of Chemistry –ICTM, Njego{eva 12, YU11000 Belgrade, Yugoslavia
(Received 8 February 2002)
The changes in the pore structure and adsorption properties of
sepiolite from Gole{ resulting from treatment with 4 M HCl for various
periods of time were investigated. The BET method specific surface
areas, pore volumes and f – plots were determined by nitrogen
adsorption. The surface area progressively increased during the 70
hours of acid treatment, when a maximum was attained. The differences
in the adsorption properties of the original and the acid treated
sepiolite were evaluated by comparison of adsorption isotherms obtained
with benzene, n-hexane, methanol and isooctane. The enhanced adsorption
of isooctane was of great interest, since the sorption of this compound
on natural sepiolites is generally very limited. The results suggest
that chemical treatment of sepiolite with 4 M HCl for 70 h produces an
adsorbent of optimal porosity and other adsorption properties.
Keywords: sepiolite, Gole{, acid activation, surface area, pore volume,
f – plot, adsorption.
REFERENCES
1. K. Brauner, A. Preisinger, Tschermaks Miner. Petr. Mitt. 6 (1956)
120
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568
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5. A. J. Dandy, J. Phys. Chem. 72 ( 1968) 334
6. A. J. Dandy, M. S. Nadiye-Tabbiruka, Clays Clay Miner. 23 (1975) 428
7. A. J. Dandy, M. S. Nadiye-Tabbiruka, Clays Clay Miner. 30 (1982) 347
8. S. Inagaki, Y. Fukushima, H. Doi. O. Kamigaito, Clay Miner. 25
(1990) 99
9. T. Hibbino, A. Tsunashima, A. Yamazaki, R. Otsuka, Clays Clay Miner.
43 (1995) 391
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4 (1989) 411
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18. H. Abdul-Latif, C. E. Weaver, Clays Clay Miner. 17 (1969) 169
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Interf. Sci. 109 (1986) 150
20. M. A. Vicente Rodriguez, J. de D. López Gonzalez, M. A. BaZares
MuZoz, Clay Miner. 29 (1994) 361
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MuZoz, J. Casado Linarejos, Clay Miner. 30 (1995) 315
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J. M. Martin Pozas, Appl. Clay Sci. 10 (1995) 247
23. Z. Maksimovi}, G. Raduki}, Geolo{ki anali Balkanskog poluostrva 28
(1961) 309 (in Serbian)
24. M. Ili}, M. Ba~anac, Z. Miladinovi}, Tehnika 52 (1997) 150 (in
Serbian)
25. M. Radojevi}, V. Jovi}, D. Vitorovi}, J. Serb. Chem. Soc. 67 (2002)
482
26. S. Brunauer, P. Emmett, E. Teller, J. Amer. Chem. Soc. 60 (1938)
309
27. J. H. DeBoer, B. C. Lippens, B. G. Linsen, J. C. P. Broekhoff, A.
van den Heuval, Th. J. Osinga, J. Colloid Interface Sci. 21 (1966) 405
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Clay Miner. 19 (1984) 93.
J.Serb.Che.Soc. 67(7)507–521(2002)
UDC 546.824+546.137-32:66.061+620.168.3
JSCS – 2972
Original scientific paper
Extraction and separation of titanium(IV) with D2EHPA and PC-88A from
aqueous perchloric acid solutions
RAJEEV K. SINGH and PURSHOTTAM M. DHADKE
Inorganic Chemistry Laboratory, Applied Chemistry Division, Department
of Chemical Technology,
University of Mumbai, Matunga, Mumbai – 400 019, India
(Received 20 August 2001, revised 1 March 2002)
The liquid-liquid extraction of Ti(IV) from perchlorate media using,
di(2-ethylhexyl) phosphoric acid (D2EHPA) and 2-ethylhexyl prosphonic
acid mono-2-ethylhexyl ester (PC-88A) in toluene as the extractant was
studied. Quantitative extraction of Ti(IV) was observed in the lower
acidity range of 0.01 to 0.1 mol dm-3 with 0.003 mol dm-3 D2EHPA and
0.01 mol dm-3 PC-88A in toluene, respectively, and in the higher
acidity range of 9.0 to 10.0 mol dm-3 with 0.1 mol dm-3 D2EHPA and PC88A in toluene. Ti(IV) was completely stripped from the metal loaded
organic phase of both the extractants with 3 % H2O2 in 1 M H2SO4 and
determined spectrophotometrically. The stoichiometry of the extracted
species was determined on the basis of slope analysis. The extraction
in the lower acidity range was found to proceed by a cation-exchange
mechanism with the extracted species being TiOR2.2HR, while in the
higher acidity range it was by solvation with the extracted species
being Ti(OH)3ClO4.4HR. Separation of Ti(IV) was also carried out from
some associated metals like Fe(III), Al(III), V(V), Ce(IV), Mg(II) and
Mn(II). The developed methods were extended for the determination of
Ti(IV) in real samples like ilmenite, magnetite and red mud in order to
show the practical utility of the extractants.
Keywords: extraction, titanium, separation, D2EHPA, PC-88A and
stripping.
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J.Serb.Chem.Soc. 67(7)523–530(2002)
UDC 547.7+669–034.89:543.422.25
JSCS - 2973
Original scientific paper
Synthesis and characterization of 2,3,13,14-tetramethyl (ethyl or ptolyl)-1,4,12,15-tetraazacyclodocosa-1,3,12,14-tetraene
complexes of Mg(II), Ca(II), Sr(II) and Ba(II)
RAGHU N. PRASAD and SEEMA GUPTA
Department of Chemistry, University of Rajasthan, Jaipur 302004, India
(Received 28 January 2002)
2+2 Cyclocondensation of 1,7-diaminoheptane with a-diketones, viz. 2,3butanedione, 3,4-hexanedione or 4,4’-dimethylbenzil, in the presence of
Mg2+, Ca2+, Sr2+ and Ba2+ ions as templates yields a series of
complexes of the type [ML(X2)] (where L = N4 macrocycle having a 22membered ring and X = Cl or NCS). The resulting complexes were
characterized by elemental analysis, conductance measurements and IR
and 1H-NMR spectral studies.
Keywords: macrocyclic complexes, alkaline earth metal complexes,
conductances, IR spectra, NMR spectra.
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UDC 546.56+546.33–36:541.183
JSCS – 2974
Original scientific paper
Surface reconstruction during the adsorption/desorption of OH– species
onto Cu(111) and Cu(100) in 0.1 M NaOH solution
V. D. JOVI]# and B. M. JOVI]
Department of Materials Engineering, Drexel University, Philadelphia,
PA 19104, USA
(Received 1 April 2002)
The process of adsorption/desorption of OH- species onto Cu(111) and
Cu(100) in 0.1 M NaOH solution has been investigated by cyclic
voltammetry and the potentiostatic pulse technique. Investigation of
the electrochemical behavior of the Cu(100) face in 0.1 M NaOH solution
was performed for the first time in this work. It was shown that the
adsorption/desorption of OH- species occurs in the potential range
between –1.13 V vs. SHE and – 0.83 V vs. SHE forming an adsorbate of
low coverage. It was shown that in 0.1 M NaOH solution irreversible
surface reconstruction of the Cu(111) face occurs as a consequence of
the adsorption/desorption of OH- species. The original surface cannot
be restored even if the electrode is exposed to potentials more
positive than – 0.53 V vs. SHE for some time. If this time is, in the
case of repetitive pulse experiments, equal or smaller than 10 s
reconstruction does not occur. Adsorption of OH- species takes place in
the potential range more negative than – 0.6 V vs. SHE only on
reconstructed surfaces. For this process to occur onto nonreconstructed, original Cu(111) surfaces, higher overpotentials are
needed.
Keywords: Cu(111), Cu(100), OH- adsorption, surface reconstruction.
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