JSCS Vol 69, No. 6
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Impresum |
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J. Serb. Chem.
Soc. 69 (6) 413–420 (2004) |
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Photochemical and
Beckmann rearrangement of (Z)-cholest-4-en-6-one oxime
NATALIJA M. KRSTIC*, MIRA S. BJELAKOVIC*, MILAN
M. DABOVIC*, LJUBINKA B. LORENC*,** and VLADIMIR D. PAVLOVIC*,**
*Center for Chemistry,
ICTM, P. O. Box 473, 11001 Belgrade and
**Faculty of Chemistry, University of Belgrade, Studentski trg 12–16, P. O. Box
158, 11001 Belgrade, Serbia and Montenegro
(Received 27 November
2003)
Beckmann rearrangement of (Z)-cholest-4-en-6-one
oxime (4) (prepared in 4 steps starting from cholest-5-en-3b-ol (1)) with thionyl chloride in dioxane solution afforded
an enAMide-type lactAM, i.e., 7-aza-B-homocholest-4-en-6-one (6)
as a single product. Photoreaction of the sAMe compound in methanol or
benzene-acetic acid solution gave a mixture of products, with the formation of
the parent ketone 3 and the occurrence of Z/E isomerization,
while the lactAM 6 was obtained only when the reaction was performed in
methanol and then in very low yield (7 %).
Keywords: (Z)-cholest-4-en-6-one oxime, 7-aza-B-homocholest-4-en-6-one,
Beckmann rearrangement, photoreaction.
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J. Serb. Chem.
Soc.69 (6) 421–429 (2004) |
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Regioselectivity of the bromination of 1-oxo-1,2,3,4-tetrahydronaphthalene and
6,7-dimethyl-1-oxo-1,2,3,4-tetrahydronaphthalene, and thiabiscyclanones
synthesis on their basis
ALEXEI N. PANKRATOV, OLGA V. FEDOTOVA, ANTONINA
V. BARABANOVA, TAT’YANA V. ALYONKINA* and YURI YU. ELISEEV*
Department of Chemistry,
N. G. Chernyshevskii Saratov State University, 83 Astrakhanskaya Street,
Saratov 410012, Russia and
*Russian Antiplague Research Institute “Microbe”, 46 Universitetskaya Street,
Saratov 410005, Russia
(Received 6 August,
revised 21 November 2003)
Abstract: On the basis of quantum chemical (PM3
and RHF/6-31G*) study, the regioselectivity of the bromination of 1-oxo-1,2,3,4-tetrahydronaphthalene
(1) and 6,7-dimethyl-1-oxo-1,2,3,4-tetrahydronaphthalene (2) at
their alicyclic and aromatic fragments was quantum chemically substantiated and
confirmed experimentally. It was found that the above compounds undergo
aromatic at the a-methylene position. The conditions for bromination at the
positions 5, 8 of benzannelated ring were established. For the first time, non-
and 2,2’-dibromosubstituted with respect to the oxo group
bis(6,7-dimethyl-1-oxo-1,2,3,4-tetrahydronaphth-2-yl) sulphides (7, 8a, b)
were obtained. The latter were found to show promise as stabilizing agents for
the storage of cholera sera.
Keywords: 1-oxo-1,2,3,4-tetrahydronaphthalene, bromination, reactivity,
quantum chemical study, sulphur-containing 1,5-diketones.
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J. Serb. Chem.
Soc. 69 (6) 431–439 (2004) |
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An approach to quantum chemical consideration of "hydride" transfer
reactions
ALEXEI N. PANKRATOV and BORIS I. DREVKO
Department of Chemistry,
N. G. Chernyshevskii Saratov State University, 83 Astrakhanskaya Street,
Saratov 410012, Russia
(Received 6 August,
revised 27 November 2003)
An approach to the quantum chemical study of "hydride ion" transfer
has been proposed, according to which the sequences of changes in ionization
potentials, enthalpies and free energies of the affinities to the hydride ion,
to the hydrogen atom and to the proton of substrates molecules and their
derivatives (cations, radicals, anions), are compared with the experimentally
substantiated series of "hydride" mobility. It has been established
that the experimental series of "hydride" mobility for six
chalcogenopyrans based on "semicyclic" 1,5-diketones is in conformity
with the computed ionization potentials of the molecules, and with the affinity
of the corresponding radicals to the hydrogen atom involved in the transfer.
The direct splitting-out of the hydride ion and the primary deprotonation of
the substrates followed by the withdrawal of two electrons was elucidated to be
unlikely. Feasible are the mechanisms of "hydride" mobility, the
first step of which consists of electron or hydrogen atom transfer from the
chalcogenopyrans molecules.
Keywords: "hydride" transfer, reaction mechanisms, theory –
experiment correlation, quantum chemical consideration, chalcogenopyrans.
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J. Serb. Chem.
Soc. 69 (6) 441–453 (2004) |
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DynAMical mechanical analysis of
photocrosslinked hyperbranched urethane acrylates
ENIS DZUNUZOVIC, SRBA TASIC*, BRANISLAV BOZIC*,
DRAGAN BABIC and BRANKO DUNJIC*
The "Vinca"
Institute of Nuclear Sciences, The Laboratory of Radiation Chemistry and
Physics "GAMa", P. O. Box 522, 11001 Belgrade and
*DugaNova Ltd., Viline vode 6, 11000 Belgrade, Serbia and Montenegro
(Received 17 October
2002, revised 17 December 2003)
A series of acrylate functionalized sAMples
based on hyperbranched hydroxy-terminated polyesters with different molecular
weights and different degrees of acrylation were synthesized. The obtained
urethane acrylates were slightly yellow viscose liquids. Their composition was
characterized by FTIR and 1H-NMR spectroscopy and their molecular
weights were measured by GPC. All the synthesized sAMples were diluted with 25
wt.% 1,4-butanediol dimethacrylate (BDDM). The rheological properties of the
uncured sAMples and the dynAMic mechanical properties of the UV cured sAMples
were exAMined. All the sAMples exhibit Newtonian behavior, which indicates the
absence of physical entanglements in these polymers. The viscosity increases
with increasing number of acrylic groups per molecule. The glass transition
temperature of the UV cured sAMples increases with increasing the number of
acrylic groups per molecule. The value of the storage modulus in the
rubber-elastic plateau and the cross-link density increase with increasing
number of acrylic groups per molecule. The formed networks are inhomogeneous
and the residual unsaturation is the highest in the sAMples with the largest
number of acrylic groups per molecule.
Keywords: urethane acrylate, hyperbranched hydroxy-terminated polyester,
FTIR, 1H-NMR, GPC, rheology, UV curing, dynAMic mechanical
properties.
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J. Serb. Chem.
Soc. 69 (6) 455–460 (2004) |
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Noble metals binding on macroporous
poly(GMA-co-EGDMA) modified with ethylenediAMine
ALEKSANDRA NASTASOVIC, SLOBODAN JOVANOVIC*,
DRAGICA JAKOVLJEVIC, SLAVKA STANKOVIC* and ANTONIJE ONJIA**
ICTM - Center for
Chemistry, Njegoseva 12, Belgrade
*Faculty of Technology and Metallurgy, Karnegijeva 4, Belgrade and
**Vinca Institute of Nuclear Sciences, Chemical DynAMics Laboratory, P. O. Box
522, Belgrade, Serbia and Montenegro
(Received 28 July 2003,
revised 8 January 2004)
Macroporous crosslinked poly(glycidyl
methacrylate-co-ethylene glycol dimethacrylate), p(GME), was synthesized by
suspension copolymerization and modified by reaction of the pendant epoxy
groups with ethylenediAMine. The sorption rate and capacity of the modified
copolymer, p(GME)-en for Rh(III), Au(III) and Pt(IV) ions were determined in
batch experiments under non-competitive conditions. The uptake of Rh(III) was
faster than those of Au(III) and Pt(IV). The sorption capacity for Pt(IV) was
determined in the pH range 0.9–6.0. The maximum Pt(IV) uptake capacity onto
p(GME)-en at pH 5.5 was 1.30 mmol/g.
Keywords: macroporous copolymers, modification, sorption, noble metals.
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J. Serb. Chem.
Soc. 69 (6) 461–475 (2004) |
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Changes of refractive indices in ternary
mixtures containing
chlorobenzene + n-hexane + (n-heptane or n-octane) at 298.15 K
A. TOURIÑO, M. HERVELLO, V. MORENO, G. MARINO
and M. IGLESIAS*
Laboratorio de
Propiedades Fisicas. Centro de Apoyo Cientifico y Tecnólogico a la
Investigación (C.A.C.T.I.),
Universidad de Vigo, 36200 Vigo, España and
*DepartAMent d’Enginyeria Quimica, Escola TPcnica Superior d’Enginyeria
Quimica, Universitat Rovira i Virgili,
Avinguda Països Catalans 26, CAMpus Sescelades, 43007 Tarragona, España
(Received 11 August,
revised 5 December 2003)
The refractive indices of ternary mixtures of
chlorobenzene + n-hexane + (n-heptane or n-octane) have
been measured at 298.15 K and at atmospheric pressure over the whole
composition diagrAM. ParAMeters of polynomial equations which represent the
composition dependence of physical and derived properties are gathered. The
experimental refractive indices and the ternary derived properties are compared
with the data obtained using several predictive semi-empirical models. The use
of the Soave–Redlich–Kwong (SRK) and the Peng–Robinson (PR) cubic equations of
state with the Van der Waals one-fluid mixing rule, which incorporate different
combining rules to predict refractive indices on mixing, are tested against the
measured results, good agrement being obtained.
Keywords: refractive index, chlorobenzene, alkanes, cubic equation of state.
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J. Serb. Chem.
Soc. 69 (6) 477–483 (2004) |
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Kinetic determination of morin nanoAMounts
D. A. KOSTIC, S. S. MITIC and G. Z. MILETIC
Faculty of Natural
Science and Mathematics, Department of Chemistry, University of Nis,
Visegradska 33, 18000 Nis, Serbia and Montenegro
(Received 22. September,
revised 10 December 2003)
A kinetic-spectrophotometric method is proposed
for the determination of morin. The method is based on the inhibition effect of
morin on the oxidation of C6H5COONa by hydrogen peroxide
in the presence of the complex Fe(II)-AA(ascorbic acid), which acts as a
catalyst. The concentration range for the determination of morin is one of the
lowest achieved so far (a linear calibration graph was obtained for morin from
2.255–22.55 ng cm-3). The limit of detection of the method is 0.28
ng cm-3. The relative error ranges between 1.42 to 5.10 % for the
given concentration interval. Kinetic equations are proposed for the
investigated process. The effects of certain foreign ions upon the reaction
rate were determined in order to assess the selectivity of the method. The
major advantages of this kinetic-spectrophotometric assay are its sensitivity,
selectivity, reproducibility, speed and simplicity.
Keywords: kinetic method, morin, determination.
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J. Serb. Chem.
Soc. 69 (6) 485–491 (2004) |
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Spectrophotometric investigation of fAMotidine-Pd(II) complex and its
analytical application in drug analysis
ZAGORKA KORICANAC, TATIJANA JOVANOVIC, JELENA
PETKOVIC* and DRAGICA MINIC*
Institute of Inorganic Chemistry, Faculty of Pharmacy, University of
Belgrade, Vojvode Stepe 450, 11000 Belgrade and
*Faculty of Physical Chemistry, University of Belgrade, Studentski trg 12-14,
Belgrade, Serbia and Montenegro
(Received 12 September
2003, revised 19 January 2004)
By using different spectrophotometric methods,
it was found that fAMotidine and palladium(II) ions form a complex, Pd(II) :
fAMotidine = 1:1, which has an absorption maximum at 345 nm. The formation of
the complex between fAMotidine and palladium(II) chloride in Britton–Robinson
buffer solution in the pH range 2.23–8.50 was studied. The conditional
stability constant of the complex at the optimum pH 2.62 and ionic strength 0.5
M was found to be log K’ = 3.742 ± 0.025. The Beer’s law was verified over the
fAMotidine concentration range from 5×10-5 – 6×10-4 M.
The proposed method was found to be suitable for accurate and sensitive
analysis of fAMotidine both as the substance (RSD = 1.02–1.80 %) and its dosage
forms (RSD = 1.75–1.83 %).
Keywords: fAMotidine, palladium(II) chloride, complexometry,
spectrophotometry, drug determination.
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J. Serb.Chem.
Soc. 69 (6) 493–502 (2004) |
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Phonon anomalies in optical spectra of LiNbO3 single crystals
ALEKSANDAR GOLUBOVIC*, RADOS GAJIC*,**,
IVANA HINIC* and ANDREJA VALCIC***
*Institute of Physics,
Pregrevica 118, P. O. Box 68, 11080 Zemun, Serbia and Montenegro,
**Institute of Physics, Montanuniversitaet Leoben, Franz Josef Strasse 18, 8700
Leoben, Austia and
***Faculty of Technology and Metallurgy, Karnegijeva 4, 11000 Belgrade, Serbia
and Montenegro
(Received 29. October,
revised 25 December 2003)
LiNbO3 single crystals were grown by
the Czochralski technique in an air atmosphere. The critical crystal diAMeter Dc
= 1.5 cm and the critical rate of rotation wc = 35 rpm were calculated by equations from the
hydrodynAMics of the melt. The domain inversion was carried out at 1430 K using
a 3.75 V/cm electric field for 10 min. The obtained crystals were cut, polished
and etched to determine the presence of dislocations and single domain
structures. The optical properties were studied by infrared and RAMan spectroscopy
as a function of temperature. With decreasing temperature, an atypical
behaviour of the phonon modes could be seen in the ferroelectrics LiNbO3.
The obtained results are discussed and compared with published data.
Keywords: litium niobate, Czochralski tecnique, single crystal, RAMan
spectroscopy, infrared spectroscopy, ferroelectrics.
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BOOK REVIEW
CHEMISTRY AND
MATHEMATICS: TWO SCIENTIFIC LANGUAGES OF THE 21st CENTURY
Nova Acta Leopoldina,
No. 330, Vol. 88
Deutsche Akademie der Naturforscher Leopoldina, Halle (Saale), 2003 ISBN
3–8047–2038–2, 160 pages, price: 28.80 Eur
This publication may be viewed as an issue of Nova Acta
Leopoldina, in particular its number 330 and volume 88, but (as this reviewer
prefers) also as a separate book. Anyway, it contains papers presented at a
scientific conference, held in Göttingen on October 11 to 13, 2001, under the
auspices of the German Academy of Natural Sciences Leopoldina, the Göttingen
Academy of Sciences, and the French Academy of Sciences, The book contains 8
articles (that this reviewer will refer to as chapters), preceded by in
introduction written by Herbert W. Roesky,
In the "Introduction" (pp. 7–9) Roesky
recalls that a language is a system of verbal signs which are typical for a
community of people who want to express what they think and who want to be
understood by the other members of the community. Because modern chemistry and
mathematics began... to discover that there are a lot of things they share, the
purpose of this conference was to bring chemists and mathematicians together,
in order that they could better understood each other. This is best expressed
by Peter Deuflhard, who, by studying the relations of the scientific languages of
chemistry and mathematics, concludes: The common clear message from these
comparisons is that chemical intuition may pave the way for mathematical
concepts just as chemical concepts may gain from mathematical precisioning.
Along this line, significant improvements in chemical research and engineering
have already been possible -- and can be further expected in the future from
the dialogue between the two scientific languages.
The first chapter is "Chemistry as an
Ideographic Language" by Guy Ourisson (pp. 11-18). It briefly outlines the
wealth of information contained in a structural formula of an organic compound.
What the paper does not mention is that such formulas have also a mathematical
content, recognized already in the middle of the 19th century.
The second chapter "Transition Metal-Based
Machines and Motors at the Molecular Level" (pp. 19–38) is written by
Jean-Paul Collin and four coauthors. It contains exactly what the title says
and is nothing but a well–written (chemical) review article.
The next chapter is "Virtual
Crystallography" by Olaf Delgado-Friedrichs (pp. 39–49). It describes the
author's original and interesting combinatorial and geometric researches,
related to crystallography.
Follows "A Comparison of Related Concepts
in Computational Chemistry and Mathematics" by Peter Deuflhard (pp.
51–66). This text goes to the very center of the theme. It considers three
mathematical concepts (intrinsic low-dimensional manifolds, Galerkin's method
for constructing special Hilbert spaces, and geometrical conformations) and
connects them with three fields of physico-chemical research (quasistationary
state approximation in chemical kinetics, lumping in polymer kinetics, and
molecular conformational analysis).
The fifth chapter "The Essence of Chemical
Thinking Beyond Mathematical Equations" by Jerzy Haber (pp. 67–80) has the
AMbition to demonstrate that chemistry is based on an interplay of theory,
comprising phenomenological inductive laws and deductive theory, experiments,
and chemical intuition, and that chemistry developed its own ideographic
language, whose semiotic rules permit to understand reaction mechanisms. In
spite of these abstract claims, the article mainly outlines the author's own
(experimental) research of catalytic oxidation of hydrocarbons. A few
philosophical thoughts are found only at the end of the text, whereas
mathematics is completely absent.
The next chapter is “Analysis of Chemical
Reaction Systems – What Are Mathematics Able to Do, How Far Has Chemistry to
Help?” by Jürgen Warnatz (pp. 81–108). It provides exAMples for how complex
phenomena encountered in chemical and industrial processes are modelled by
mathematical methods. These will be found interesting by both chemists and
mathematicians.
The "Poetic Suggestion in Chemical
Science" (pp. 109–139), written by (Sir) John Meurig Thomas, expresses
some thoughts on the artistic and poetic aspects of both mathematics and
chemistry, richly illustrated by facts and pictures from their past and
present. Although the entire book is full of high-quality and beautiful
figures, this chapter is really a piece of art. It would be good to make this
article available to high-school students, before they decide what they will be
studying – the number of those choosing chemistry would increase significantly.
The last chapter "Combustion: From
Mathematical Models to Practical Devices", by Jürgen Wolfrum (pp.
141–160), is a fine survey of the physical chemistry of combustion, however
with very few details on its mathematical modelling.
There is a total of 218 references quoted in
this book. Not a single one is from the Journal of Mathematical Chemistry or
MATCH Communications in Mathematical and in Computer Chemistry, the only two
journals devoted to mathematics-related researches in chemistry. Not a single
quotation is from the Journal of Computational Chemistry or Journal of Chemical
Information and Computer Sciences or Computers &AMp; Chemistry, the three
main journals for publishing computer-aided researches in chemistry. Not a
single quotation is from Theoretical Chemistry Accounts (former Theoretica
Chimica Acta) or International Journal of Quantum Chemistry, the leading
journals for theoretical chemistry. This says something about the modes by
which the authors of the book were invited or selected, and the connection of
the contents of the book to contemporary scientific activities, lying on the
border between mathematics and chemistry, sometimes referred to as Mathematical
Chemistry.
In spite of the above, there is no doubt that
the book “Chemistry and Mathematics: Two Scientific Languages of the 21st
Century” is a valuable attempt to improve understanding, communication, and
cooperation between mathematicians and chemists. From a technical point of
view, the book is a masterpiece.
Ivan Gutman
Faculty of Science, University of Kragujevac
Kragujevac, Serbia and Montenegro
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The Devision of Analytical Chemistry
of the Federation of European Chemical Societies
and Professional Institutions (FECS)
European Analytical
Column No. 32
(January 2004)
Copyright &AMp; copy; SHD 2004.
June 24, 2004.
For
more information contact: SHD@tmf.bg.ac.yu