JSCS Vol 61, No. 10
J. Serb.
Chem. Soc. 61 (10) 841-848 (1996)
UDC 547.512
JSCS-2301
Original scientific
paper
1,3-MIGRATION
OF PHENYLTHIO GROUP IN THE REARRANGEMENT OF TERTIARY CYCLOPROPYLMETHANOLS
POSSESSING AN a-PHENYLTHIO GROUP
RADOMIR N. SAICIC, JOVICA BADJIC and ZIVORAD CEKOVIC
Faculty of
Chemistry, University, of Belgrade, Studeintski trg 16, P. O Box 158, and
ICTM Centre for
Chemistry, Njegoseva 12, YU-11000 Belgrade,
Yugoslavia
(Received 16 January, revised 5 June 1996)
The acid catalysed ring opening of tertiary cyclopropylmethanols
1 (R = H, vinyl, Ph), possessing a phenylthio group
on the adjacent carbon atom proceeds, regioselectively
and homoallylic halides 2 are obtained in 49 - 86%
yields. Depending on the structure of 1 (R= Ph, SPh)
and the acid used the cyclopropane ring opening
follows the Immigration of phenylthio group and the
corresponding 1-halo-3-phenylthio-4-pcntene derivatives 3 are obtained in 54 -
76 % yields.
Key words: cyclopropylcarbinyl
carbocation, cyclopropane
ring opening, 1,3-mmigration of phenylthio
group
J. Serb. Chem. Soc. 61(10) 849-856 (1996)
UDC 547.823
JSCS-2302
Original scientific
paper
THE SYNTHESIS OF
3,3-DIMETHYL FENTANYL AND ITS LACTAME ANALOGUE
IVAN V. MICOVIC1, GORAN M. ROGLIC1,
D. IVANOVIC2, LJILJANA DOSEN-MICOVIC1, VESNA D.
KIRICOJEVIC2 and JELENA B. POPOVIC3
1Faculty of Chemistry, University, of
Belgrade, Studentski trg
16, P. O Box 158, YU-11001, Belgrade,
2ICTM Centre for Chemistry, Njegoseva 12, YU-11000 Belgrade, Yugoslavia and
3Faculty of Agriculture, University
of Belgrade, Nemanjina 6, 11080 Zemun,
Yugoslavia
(Received 30 December. 1995)
An efficient synthesis
of seine novel analogues of fentanyl, a well known
central analgesic, has been developed. Thus, 3,3-dimethyl
fentanyl (9) and its 2-oxo derivative 7 were prepared
in 9 and 8 steps, respectively. In the first step, fentanyl
amine was selectively added to one equivalent of methyl acrylate
to afford the corresponding amino-ester 1. N-acylation
of this intermediate with dimethyl malonate yielded an amido-ester
2, which was further. subjected to a Dieckmann-type cyclization, to
produce a six-membered cyclic intermediate 3a. The cyclization was effected under
phase transfer conditions, utilising potassium
carbonate as the base and 18-crown-6 as the catalyst. In the next step, acid
hydrolysis and decarboxylation furnished the
corresponding N-pheilethyl-2,4-dioxo piperidine (4) as a single, pure product. Bialkation of this active methylene
derivative with methyl iodide and potassium carbonate in DMSO gave the 3,3-dimethyl derivative 5. After reductive amination of this substrate with aniline and Zn-AcOH acid or NaBH3CN, pure 3,3-dimethyl
4-anilino2-piperidone (6) was obtained. The synthesis of the lactame analogue of fentanyl was
completed by N-acylation with propionyl
chloride in ethylene chloride. When the reduction of the lactam
function was conducted (NaBH4/BF3 Et2O) prior
to the acylation, the reduced analogue, 3,3-dimethyl fentanyl (9) was
obtained. The method appears to be fairly general for various
4-anilido-2-piperidones and 4-anilido piperidines.
Key words: fentanyl,
2,4-piperidinedione, 3,3-dimethyl fentanyl.
J. Serb. Chem. Soc. 61 (10) 859-863 (1996)
UDC 547.564.2:543.94
JSCS-2303
Original scientific
paper
REDUCTION OF p-NITROSOPHENOL
BY NADH CATALYSED BY EQUINE LIVER ALCOHOL DEHYDROGENASE
MILICA PANTELIC1, SVETLANA TRIVIC2 and VLADIMIR LESKOVAC1
1Faculty of Technology, University of
Novi Sad, and
2Faculty of Science, University of
Novi Sad, YU-21000 Novi Sad, Yugoslavia
(Received 15 August 1995, revised 9 May 1996)
p-Nitrosophenol is easily reduced by NADH in the
presence of equine liver alcohol dehydrogenase (EC
1.1.1.1.). In this work we report the steady-state kinetic parameters for this
enzymatic reaction at pH 7.0, and the pH-profile of its catalytic constant. In
addition, the minimal chemical mechanism of this reaction is postulated.
Key words: p-nitrosophenol,
reduction.
J Serb. Chem. Soc. 61 (10 )865-872 (1996)
UDC
547.236.1/.2:543.544.25
JSCS-2304
Original scientific
paper
GAS CHROMATOGRAPHIC
RETENTION INDICES FOR N-SUBSTITUTED AMINO S-TRIAZINES ON CAPILLARY
COLUMNS.
PART
III. N-CYCLOALKYLAMINO
DERIVATIVES OF S-TRIAZINES
OLGA S. RAJKOVIC, DUSAN G. ANTONOVIC, BRATISLAV Z. JOVANOVIC and
GORDANA A. BONCIC-CARICIC
Department of
Organic Chemistry, Faculty of Technology and Metallurgy, University of
Belgrade, P. O. Box 494, YU-11001, Belgrade, Yugoslavia
(Received 1 March, revised 17 June 1996)
Gas chromatographic
retention indices (I) for a series of 10 synthesised N-substituted
cycloalkylamino s-triazines
on DB-1, DB-5 and DB-WAX capillary columns isothermal at 190, 210 and 230oC,
and using temperature programmed gas chromatography (TPGC) were determined
within a standard deviation of 0.2 i.u. The
isothermal data obtained on these columns and TPGC data were compared and a
comparison of the retention indices, deltaI
and dI/dT values presented as linear
regression equation with correlation coefficients greater than 0.9992 within a
standard deviation of 0.6 i.u. The best resolution of
the N-cycloalkylamino derivatives of s-triazines was obtained using the DB-WAX capillary column.
Key words: gas chromatography,
retention indices, N-substituted cycloalkylamino s-triazines, isothermal and TPGC, linear regression.
J. Serb. Chem. Soc. 61 (10) 873-879 (1996)
UDC 539.126.34:547,62
JSCS-2305
Original scientific
paper
CORRELATIONS BETWEEN
N-ELECTRON PROPERTIES OF PHENYLENES AND THEIR HEXAGONAL SQUEEZES
IVAN GUTMAN, SVETLANA MARKOVIC, ALEKSANDRA STAJKOVIC and SLAVICA KAMIDZORAC
Faculty of Science,
University of Kragujevac, P. 0. Box.
60, YU-34001 Kragujevac.
(Received 20 April 1996)
The recent discovery
that the algebraic structure count of phenylenes (PH)
coincides with the number of Kekule structures of the
corresponding hexagonal squeezes (HS) suggests that there might exist a
deep-lying congruence between the topological properties of PH and their HS. In
order to gain more information about this congruence we have investigated
relations between a few topology-based properties of PH and HS. Very good
linear correlation is found for the total
-electron energy and HOMO-LUMO
separation of PH and HS. In the case of Kekule
structure count such a correlation is much weaker.
Key words: phenylenes,
hexagonal squeeze
J Serb. Chem. Soc. 61 (10) 881-886 (1996)
UDC 539.194:513.83/.84
JSCS-2306
Original scientific
paper
ON THE ORIGIN OF HIGH
HIICKEL MOLECULAR ORBITAL DEGENERACY
I.GUTMANa,b and T. P. RADHAKRISHNANa,c
alnstitute for Advanced Studies, The
bpermanent address: Faculty of Science,
cpernament address.
(Received 8 April 1996)
The previously observed high
("unusual") degeneracy of Huckel M0s in
certain conjugated-electron systems is rationalised by
means of graph spectral theory. Rules are given, enabling the prediction of the
degeneracy of MOs in the majority of cases of chemical interest. These generalise previously noticed regularities. It is shown
that the high degeneracy of the M0s is not caused by summetry,
but rather by certain peculiarities of the connectedness of the respective
molecules.
Key words: molecular orbitals, Huckel MOs, orbital degeneracy.
J. Serb. Chem. Soc. 61 (10) 885-891 (1996)
UDC 541.124.2:541.127.546.154
JSCS-2307
Original scientific paper
THE BRAY-LIEBHAFSKY REACTION.
VI. KINETICS IN IODIDE
OSCILLATIONS
SLOBODAN ANIC and LJILJANA KOLAR-ANIC
Faculty of Physical
Chemistry, University of Belgrade, P. O. Box 137, YU-l 1001 Belgrade,
Yugoslavia
(Received 16 April 1996)
The rate constants and
activation energies of the dominant reactions in characteristic kinetic
branches of iodide oscillations in the Bray-Liebhafsky
system are determined. In the part of the phase space considered the decisive
role of nonradical processes in the appearance of
oscillations is suggested.
Key words: Bray-Liebhafsky reaction, oscillatory reactions, chemical
kinetics, non-equilibrium phenomena.
J. Serb. Chem. Soc. 61 (10) 893-902 (1996)
UDC
541.143.3:546.155:541.12.017
JSCS-2308
Original scientific
paper
THE BRAY-LIEBHAFSKY
REACTION.
VII. CONCENTRATIONS OF
THE EXTERNAL SPECIES H+ AND I03-
ZELJKO CUPIC*, SLOBODAN ANIC#, and DJURO MISLJENOVIC^&
*ICTM-Department of
Catalysis and Chemical Engineering, Njegoseva 12,
YU-11000 Belgrade,
#Faculty of Physical Chemistry,
University of Belgrade, Studentski trg 16, YU-11000 Belgrade and
&Faculty of Mathematics, University
of Belgrade, Studentski trg
16, YU-11000 Belgrade, Yugoslavia
(Received 13 May 1996)
A procedure to evaluate
pseudo-equilibrium concentration of hydrogen and iodate
ions, the two ionic species important in the Bray-Liebhafsky
oscillatory system, is considered. The values of the concentrations are found
to be predominantly determined by the equilibrium dissociation reactions of sulphuric and iodic acids, and
much less by the dimerization of the iodate ion.
Key words: chemical equilibrium,
Bray-Lebhafsky reaction, numerical approximation
calculations.
J. Serb. Chem. Soc. 61 (10) 903-910 (1996)
UDC
549.313.2.66.094.41:546.41'131
JSCS-2309
Original scientific
paper
STUDY OF THE
CHLORINATION KINETICS OF ANTIMONY(III)SULPHIDE BY CALCIUM CHLORIDE
R. VRACAR, K. CEROVIC, B. DJURKOVIC and I. ILIC
Department of
Nonferrous Metallurgy, Faculty of Technology and Metallurgy, University of
Belgrade, Karnegijeva 4, YU-11001 Belgrade,
Yugoslavia
(Received 27 December 1995, revised 17 May 1996)
The conditions for the
chlorination of antimony(lll)
sulphide by calcium chloride in the presence of
oxygen were studied, both experimentally and theoretically. The negative values
of Gibbs energy change show that the chlorination process of antimony(lll) sulphide by calcium chloride
in the presence of oxygen is thermodynamically feasible within the temperature
range of 298-773 K. The activation energy of 64 kJ mol-1
was determined. The chlorination process of antimony(III)
sulphide is diffusion controlled.
Key words: antimony(lll)sulphide, calcium chloride,
chlorination, kinetics
J. Serb. Chem. Soc. 61 (10 )911-915 (1996)
UDC
541.44:546.73/546.98/:66.094.25/258
JSCS-2310
Original scientific
paper
HYDRIDING OF PURE AND
PALLADIUM-DOPED COBALT SAMPLES
MILENKO V. SUSIC and
University of
Belgrade, P.O. Box 137, YU-11001 Belgrade, Yugoslavia
(Received 16 April
1996)
The processes of hydridiiig
and dehydriding of both cobalt metal and cobalt doped
with 0.02 percent of palladium were investigated in thc range of 30oC to 350oC.
Introduction of the dopant substantially increases
the ability of hydrogen absorption and decreases its energy of activation.
Thermodynamic and kinetic analyses of the processes were performed. The maximum
H/Co mole ratio reached in the absorbents was 29.
Key words: cobalt metal, cobalt
hydrides, palladium doping, hydrogen storage.
J. Serb. Chem. Soc. 61 (10) 917-922 (1996)
UDC
546.72:620.197.2:543.257.1
JSCS-2311
Original scientific
paper
A STUDY OF THE
REACTIVATION OF PROCESS OF IRON IN ACID SOLUTION
XIAO-LIANG CHENG, CHAO WANG, HIAO CHEN and SHEN-HAO CHEN
Deptament o Chemistry, Shandong University, Jinan, Shandong 250100, P.R. China
(Received I April 1996)
The reactivation
process of iron in 0.5 mol dm-3 H2SO4 solution was studied by potentiodynamic
sweep and holographic microphotography techniques. An anodic peak was observed
before the iron was reactivated. This anodic peak is caused by the anodic
dissolution of iron in the reactivation process. The holographic
microphotography technique proved to be useful in-situ method in studying the
dissolution process of the passive film. The reactivation process of iron is
influenced by both the passivation time and passivation potential and can be used to study the
structure and dissolution process of the passive film in acid solutions.
Key words: iron, passive film,
reactivation, dissolution.
J. Serb. Chem. Soc. 61 (10) 923-930 (1996)
UDC 546.72+661.2:541.138
JSCS-2312
Original scientific
paper
THE INFLUENCE OF
SULPHUR-CONTAINING COMPOUNDS ON THE ANODIC PROCESSES ON IRON AND STAINLESS
STEELS IN STRONG ACIDS
XIAO-LIANG CHENG, CHANG-YI LIU, HUA DING and SHEN-HAO CHEN
Deptament o Chemistry, Shandong University, Jinan, Shandong 250100, P.R. China
(Received I April 1996)
The effects of sulphur-containing compounds on anodic processes on iron
and stainless steels have been studied using the electrochemical method. The
results show that in the low potential range KSCN can catalyse
the anodic dissolution of iron in 0.5 mol dm-3 H2S04.
The influence of KSCN decreases with increasing electrode potential. In the
corrosion-catalysis process of KSCN, the desorption
of KSCN increases with the anodic dissolution current of iron. The catalysis of
KSCN on the anodic dissolution of austenitic SS is much stronger than on
ferrite SS. KSCN has no influence on the reactivation process of iron in sulphuric acid, while the reactivation potential of ferrite
SS is improved notably by KSCN.
Key words: stainless steel,
anodic dissolution, thiocyanate, reactivation.
Serb. Chem. Soc. 61 (10) 931-935 (1996)
UDC 621.01:621.3.027
JSCS-2313
Note
NOTE
MODIFICATION OF THE
LIELMEZS-ASTLEY-MCEVOY VAPOUR PRESSURE RELATION
ANDJELA B. KNEZEVIC-STEVANOVIC and DUSAN K. GROZDANIC
Faculty of
Technology and Metallurgy, University, of Belgrade, Karnegijeva
4, P. O. Box 494, YU-l 1001 Belgrade, Yugoslavia