POLISH JOURNAL OF CHEMISTRY
Volume 72 Number 4 April 1998
Pages 655-813


CONTENTS

Page

INORGANIC CHEMISTRY
655 Synthesis and Characterization of Chromium(III) Chelates of Some Lawsones
— Kelkar V.D. and Gokhale R.R.
660 Angular Overlap Treatment of cis-Bis(2,2'-bipyridyl)dichlorochromium(III) Chloride Dihydrate in Aqueous Solution
— Kurzak K. and Biernacki K.
ORGANIC CHEMISTRY
667 The 1H and 13C NMR Assignment of 4-Oxo-1,4-dihydro-3'-methylsulfinyl-3,4'-diquinolinyl Sulfides and Their 6- and 8-Nitro and 1-Methyl Derivatives
— Maslankiewicz M.J.
678 Reactions of Ethyl Diazoacetate with Thioketones
— Kaegi M., Mloston G. and Heimgartner H.
688 Reaction of Acetyliron Anion with Terminal Halogeno-deoxysugars
— Bartnicka E. and Zamojski A.
694 New Isomeric N-Substituted Hydrazones of ortho, meta and para Hydroxybenzaldehydes
— Wyrzykiewicz E. and Prukala D.
703 Synthesis of Deoxyglycosyl Dithiocarbonic Acid Derivatives
— Wandzik I. and Szeja W.
710 Reaction of Allylic Alcohols with Aliphatic Alcohols in the Presence of Cerium(III) Chloride. Part II
— Uzarewicz A., Dresler R. and Scianowski J.
719 Mass Spectrometry of 2,4-Dialkoxy-5-bromopyrimidines
—Plaziak A.S.,Wojtowicz-Rajchel H. and Golankiewicz K.
725 Mass Spectrometry of Some Derivatives of 5-(Indol-2-yl)pyrimidine
— Celewicz L., Franski R., Urjasz W. and Plaziak A.S.
735 Synthesis of Some Novel Nitrogenous Furocoumarin Derivatives
— Elgamal M.H.A., Shalaby N.M.M. and Shaban M.A.
PHYSICAL CHEMISTRY
746 Description of Vapour-Liquid Equilibria of Some Binary Mixtures with Compounds Containing Oxygen
— Antosik M. and Gierycz P.
756 The Adsorption Character and Desorption Kinetics of the Weakly Bound Oxygen on Thin Iron, Palladium and Titanium Film Surfaces
— Lisowski W.
766 Electrochemical Reactions of 1,8-Anthraquinonedisulphonate Potassium Salt
— Socha A.
777 Kinetics and Mechanism of the Acid-Catalyzed Hydrolysis of [Carbonatotetra(1-methyl- imidazole)cobalt(III)]+ Ion
— Chatlas J., Danilczuk E. and Nasiadko M.
CRYSTAL AND MOLECULAR STRUCTURES
786 Oxime-Carboxyl Hydrogen Bonds: The Preferred Interaction Determining Crystal Packing. II. Crystal Structure of 5ß-Cholanic Acid 3-Oxime
— Maurin J.K.
793 Crystal and Molecular Structure of 7-Chloropropyl-8-aminotheophylline Semibenzene Solvate
— Karczmarzyk Z. and Pawlowski M.
COMMUNICATIONS
799 Sesquiterpene Lactones from Roots of Lactuca quercina
— Kisiel W. and Szneler E.
803 Carbon-13 NMR Study of 4-Tetracarbonylchromium Complexes of Bicyclo[2.2.1]hepta-2,5—diene Derivatives. Interligand 1H-13C Spin-Spin Couplings
— Krawczyk H. and Gryff-Keller A.
808 Isothermal Section of the Phase Diagram of the Ce-Ge-Sn System at 670 K
—Stetskiv A.O., Pavlyuk V.V. and Bodak O.I.
BOOK REVIEW
812 Sigmund F. Zakrzewski: Podstawy Toksykologii Srodowiska (in Polish) (Principles of Environmental Toxicology), Wydawnictwo Naukowe PWN, Warszawa 1997.
— Pawlowski L.


ABSTRACTS


655-659

Synthesis and Characterization of Chromium(III)
Chelates of Some Lawsones

by V.D. Kelkar and R.R. Gokhale
Department of Chemistry, University of Pune, Pune 411 007, India

(Received October 7th, 1997)

Chelates of chromium(III) with phthiocol (3-methyllawsone), lawsone (2-hydroxy-1,4—naphthalenedione), 3-chlorolawsone and their 1-oxime derivatives have been synthesized and characterized. They exhibit the general formula CrL3.3H2O and magnetic moments close to 3.87 B.M. indicating trivalent chromium. IR spectral data suggest that lawsone derivatives exhibit coordinating O-O system, while lawsone-1-oxime derivatives present N-O system. Octahedral geometry for chelates has been suggested.

660-666

Angular Overlap Treatment of cis-Bis(2,2'-bipyridyl)dichlorochromium(III) Chloride Dihydrate
in Aqueous Solution

by K. Kurzak and K. Biernacki
Department of Chemistry, Pedagogical University, PL-08110 Siedlce, Poland

(Received October 6th, 1997; revised manuscript December 19th, 1997)

Six-coordinate cis-[CrCl2(bipy)2]+ complex (bipy = 2,2'-bipyridyl) has been prepared. Electronic spectrum of aqueous solution of this complex has been recorded and explained by the angular overlap model (AOM), assuming C2v symmetry. All transition energies are derived from Gaussian analysis of the spectrum. The calculations of the ligand field parameters take into account all the transitions required in the ligand field (LF) theory (except those energetically higher than the range of the spectrum recorded).

667-677

The 1H and 13C NMR Assignment of 4-Oxo-1,4-
dihydro-3'-methylsulfinyl-3,4'-diquinolinyl Sulfides
and Their 6- and 8-Nitro and 1-Methyl Derivatives

by M. J. Maslankiewicz
Institute of Chemistry, Silesian University, Szkolna 9, 40-006 Katowice, Poland

(Received July 18th, 1997; revised manuscript October 17th, 1997)

Reaction of 1-methyl-4-oxo-1,4-dihydro-3'-methylthio-3,4'-diquinolinyl sulfide 1b with a nitrating mixture caused the monooxidation of 3'-methylthio group followed by C6- and C8- nitration and led to the sulfoxide 2b, and then to the mixture of 3b and 4b. The 1H and 13C NMR spectra of 1H and 1-methyl-4-oxo-1,4-dihydro-3'-methylsulfinyl- 3,4'-diquinolinyl sulfides 2-4 were fully assigned using a combination of NMR techniques. H-2' protons in sulfoxides 2-4 are deshielded by ortho methylsulfinyl group by about 0.4 ppm. H-2 protons in sulfoxides 2a, 2b, 3a, 3b and 4b are deshielded by about 0.4-0.6 ppm.

678-687

Reactions of Ethyl Diazoacetate with Thioketones

by M. Kaegi1, G. Mloston2, and H. Heimgartner1
1Organisch-chemisches Institut der Universitaet Zuerich,
Winterthurerstrasse 190, CH-8057 Zuerich, Switzerland
2Department of Organic and Applied Chemistry, University of Lodz,
Narutowicza 68, PL-90-136 Lodz, Poland

(Received November 3rd, 1997)

The reaction of ethyl diazoacetate (10) with 9H-fluorene-9-thione (2a), thiobenzophenone (2b), and adamantanethione (2c), respectively, in THF yielded 1,3-dithiolane carboxylates (Scheme 2). Whereas in the first two cases the reaction proceeded at room temperature, heating to 60oC was necessary when the less reactive 2c was used. The additions with 2a and 2c occurred in a regioselective way, yielding 1,3-dithiolane-2-carboxylate 11a and 1,3-dithiolane-4-carboxylate 12c, respectively, with opposite regiochemistry. On the other hand, a mixture of the two regioisomeric cycloadducts 11b and 12b was formed in the case of 2b. The analogous reaction of 10 with the sterically crowded thione 13 gave thiirane 14 as the sole product, and with the corresponding dithione 16, a mixture of the cis- and trans-dithiiranes 17 and 18 was formed (Scheme 3). Desulfurization with tris(dimethylamino)phosphine yielded the ,ß-unsaturated esters 15 and 19/20, respectively. The ,ß-unsaturated ester 22 was the only product in the reaction of 10 with 9H-xanthene-9-thione (21), which had to be carried out at 60oC.

688-693

Reaction of Acetyliron Anion
with Terminal Halogeno-deoxysugars

by E. Bartnicka and A. Zamojski
Institute of Organic Chemistry, Polish Academy of Sciences, 01-224 Warsaw, Poland

(Received November 7th, 1997)

Reaction of the anion (2) generated from acetyliron complex (1) with methyl 5-bromo-5-deoxy-2,3-O-isopropylidene-ß-D-ribofuranoside (3) led to a Grob-type fragment-ation of the furanoside to open-chain aldehyde (7) which, in situ, reacted with 2 to form a mixture of stereoisomeric complexes 4. Decomplexation furnished methyl esters of 2,6,7-trideoxy-4,5-O-isopropylidene-heptonic acid of D-ribo and D-arabino configur-ation. Analogously, from methyl 2,3,4-tri-O-benzyl-6-bromo-6-deoxy--D-galactopyranoside (8) methyl 4,5,6-tri-O-benzyl-2,7,8-trideoxy-L-manno-oct-7-enoate (10) was obtained. Methyl 6-bromo (iodo)-6-deoxy-hexopyranosides 12-15 did not undergo Grob fragmentation in the presence of 2.

694-702

New Isomeric N-Substituted Hydrazones
of ortho, meta and para Hydroxybenzaldehydes

by E. Wyrzykiewicz and D. Prukala
Faculty of Chemistry, Adam Mickiewicz University, Grunwaldzka 6, 60-780 Poznan, Poland

(Received August 21st, 1997; revised manuscript November 26th, 1997)

27 unknown N-(E)-stilbenyloxyalkylcarbonyl- and N-(E)-stilbenyloxyalkylcarbonyl-
aminoalkylcarbonyl- substituted hydrazones of ortho, meta and para hydroxybenzaldehydes were prepared. From 1H-NMR (in DMSO-d6) was established that the N-substituted hydrazones occurred as E geometrical isomers and cis/trans amide conformers.

703-709

Synthesis of Deoxyglycosyl Dithiocarbonic
Acid Derivatives

by I. Wandzik and W. Szeja
Silesian Technical University, Department of Chemistry, 44-100 Gliwice, Poland

(Received October 27th, 1997; revised manuscript December 1st, 1997)

Dithiocarbonic acid esters of deoxy sugars (6-10) can be prepared by treatment of reducing deoxy monosaccharides (1-5) with diphenylphosphoryl chloride and sodium diethyldithiocarbamate or potassium O-ethyldithiocarbonate under phase-transfer conditions (procedure A) or with sodium hydride in anhydrous tetrahydrofuran (procedure B). Good yields and selectivity are reported for acetylated and benzylated derivatives of deoxy sugars, applying procedure B. The probable way of the reaction is discussed.

710-718

Reaction of Allylic Alcohols with Aliphatic Alcohols
in the Presence of Cerium(III) Chloride. Part II

by A. Uzarewicz, R. Dresler and J. Scianowski
Faculty of Chemistry, Nicolaus Copernicus University, 87-100 Torun, Poland

(Received October 27th, 1997; revised manuscript December 4th, 1997)

The reactions of selected allylic alcohols with methanol, ethanol, n-propanol, isopropanol and tert-butanol in the presence of catalytic amounts of cerium(III) chloride are described. Allylic alkyl ethers, bis-allylic ethers and 1,3-dienes were obtained depending on the structure of the reacting alcohols.

719-724

Mass Spectrometry of 2,4-Dialkoxy-5-bromopyrimidines

by A.S. Plaziak1,2, H. Wojtowicz-Rajchel1 and K. Golankiewicz1
1Faculty of Chemistry and 2Instrumental Laboratory,
Adam Mickiewicz University, 60-780 Poznan, Poland
E-mail: golan@chem.amu.edu.pl

(Received November 14th, 1997; revised manuscript December 5th, 1997)

The electron impact (EI) and collisionally-induced dissociation (CID) mass spectra of 2,4-dialkoxy-5-bromopyrimidines are discussed. In 5-bromouracil upon EI conditions the cleavage of pyrimidine ring occurs. Fragmentation of 2,4-dialkoxy-5-bromopyrimidines always begins on 2- or 4-alkoxy substituents.

725-734

Mass Spectrometry of Some Derivatives
of 5-(Indol-2-yl)pyrimidine

by L. Celewicz1, R. Franski2, W. Urjasz1 and A.S. Plaziak1,2
1Faculty of Chemistry and 2Instrumental Laboratory, Adam Mickiewicz University,
60-780 Poznan, Poland, E-mail: celewicz@chem.amu.edu.pl

(Received October 31st, 1997; revised manuscript December 5th, 1997)

The electron impact (EI) and liquid secondary ion (LSI) mass spectra of 5-(indol-2- -yl)pyrimidine derivatives are discussed. It was established that 5-(indol-2-yl)uracils, instead of the cleavage of the single carbon-carbon bond between uracil and indole ring, form stable ions with additional linkage between 4O-oxygen of uracil and CH2 group at the 3 position of indole moiety. Similarly, 5-(indol-2-yl)cytosines yield stable tetracyclic ions with new linkage between 4N-nitrogen of cytosine and CH2 group at the 3 position of indole ring.

735-745

Synthesis of Some Novel Nitrogenous
Furocoumarin Derivatives

by M.H.A. Elgamal, N.M.M. Shalaby and M.A. Shaban
Laboratory of Natural Products, National Research Centre, Dokki, Cairo, Egypt

(Received July 4th, 1997; revised manuscript December 9th, 1997)

Reaction of 5-chloro-6-formylfurocoumarins (3 and 4) with heterocyclic amines and hydrazine derivatives yields corresponding 5-N-substituted and 5-chloro-6-hydrazine derivatives 7a-h and 8a-h, respectively. Bergapten(5,6-c)isoxazole (9) or 6-oxime derivative 10 were obtained by reaction of 3 and 4 with hydroxylamine hydrochloride. Also, reaction of 5-hydroxybergapten (1) and 5-hydroxyisopimpinellin (2) with aliphatic, heterocyclic and aromatic amines beside benzenesulphonamide derivatives affords some novel 5- and 6-substituted aminofurocoumarins 11a-o, 12a-f, and 13a-f. The antimicrobial activity of all compounds was studied.

746-755

Description of Vapour-Liquid Equilibria of Some Binary Mixtures with Compounds Containing Oxygen

by M. Antosik and P. Gierycz
Institute of Physical Chemistry, Polish Academy of Sciences, ul. Kasprzaka 44/52, 01-224 Warsaw, Poland

(Received September 25th, 1997; revised manuscript November 18th, 1997)

The new local composition model for excess Gibbs energy (NRTLmKW) has been applied for vapour-liquid equilibria in six binary mixtures with compounds containing oxygen: tert-amyl methyl ether + 2,2,4-trimethylpentane, tert-amyl methyl ether + methylcyclohexane, tert-amyl methyl ether + toluene, 2-ethoxyethanol + methanol, 2-ethoxyethanol + n-valeraldehyde, 2-ethoxyethanol + dipropyl ether. The obtained results prove the superiority of the proposed model over Redlich-Kister, Wilson, UNIQUAC, NRTL, AEOS and PRSV models. Recommendation for a global thermodynamic description of associating mixtures by this model is given.

756-765

The Adsorption Character and Desorption Kinetics
of the Weakly Bound Oxygen on Thin Iron,
Palladium and Titanium Film Surfaces

by W. Lisowski
Institute of Physical Chemistry, Polish Academy of Sciences,
Kasprzaka 44/52, 01-224 Warszawa, Poland

(Received June 6th, 1997; revised manuscript December 5th, 1997)

New data concerning the electrical nature of adsorption as well as the kinetics of desorption of weakly bound oxygen state on thin metal films, obtained in situ under controlled UHV conditions, are presented. The measurements of surface potential (SP) have been carried out to distinguish between elementary steps of surface processes, accompanying the formation of weakly bound oxygen states on thin Fe, Pd and Ti films at 78 and 298 K. These states appear under the oxygen pressure higher than 10-4 Torr, following a strong chemisorption of oxygen adatoms. Both adsorption and desorption phenomena have been carried out under isothermal conditions. It has been found that weakly bound (activation energy of desorption <18 kJ/mol), positively polarized oxygen admolecules (+), are present on Fe, Pd and Ti surfaces at 78 K, covering more than 65% of the monolayer located on the top of strongly chemisorbed oxygen adatoms. Weakly bound oxygen admolecules were also observed at 298 K on thin Ti and Fe films (activation energy of desorption was in the range 80-95 kJ/mol). These admolecules are located on the top of strongly preadsorbed oxygen adatoms, forming low-coverage ( ~ 0.25), negatively polarized oxygen state ( -). The electrical nature of O2 ordering in the weakly bound oxygen layer at both temperatures has also been considered.

766-776

Electrochemical Reactions of
1,8-Anthraquinonedisulphonate Potassium Salt

by A. Socha
Institute of General and Ecological Chemistry, Technical University of Lodz, 90-924 Lodz, Poland

(Received August 1st, 1997; revised manuscript December 22nd, 1997)

Electrochemical reduction of 1,8-anthraquinonedisulphonate potassium salt forms anion radicals (EPR) and anthraquinone after oxidation of reduction products. Linear dependence of E1/2 of quinone moiety reduction on LUMO energy was used for estimation of reduction potential of probable reaction products. Reduction of quinone moiety is quasireversible and two electrons are exchanged. Desulphonation proceeds in consecutive electrode steps of reduction.

777-785

Kinetics and Mechanism
of the Acid-Catalyzed Hydrolysis
of [Carbonatotetra(1-methylimidazole)cobalt(III)]+ Ion

by J. Chatlas, E. Danilczuk and M. Nasiadko
Faculty of Chemistry, Nicolaus Copernicus University, 87-100 Torun, Poland

(Received October 27th, 1997; revised manuscript December 22nd, 1997)

The kinetics of acid-catalyzed hydrolysis of the [Co(1-Meim)4(CO3)]+ ion follows the rate law -d ln[complex]/d t = k1K[H+]/(1 + K[H+]) (25-45oC, [H+] = 0.05-1.0 M and I = 1.0 M (NaClO4)). The reaction course consists of a rapid pre-equilibrium protonation followed by a rate determining ring opening process and the subsequent fast release of monodentate carbonato ligand. Kinetic parameters, k1 and K, at 25oC are 5.1 x 10-3 s-1 and 0.48 M-1 respectively, and activation parameters for k1 are H 1+ = 84.4 ± 0.8 kJ mol-1 and S1+ = -5.8 ± 3.7 J mol-1 K-1. The hydrolysis rate increases with the ionic strength. The results are compared with those for similar cobalt(III) complexes.

786-792

Oxime-Carboxyl Hydrogen Bonds: The Preferred
Interaction Determining Crystal Packing. II.
Crystal Structure of 5ß-Cholanic Acid 3-Oxime

by J.K. Maurin
Institute of Atomic Energy, 05-400 Otwock-Swierk, Poland
Drug Institute, Chelmska 30/34, 00-725 Warsaw, Poland
E-mail: e08jm@cx1.cyf.gov.pl.

(Received October 28th, 1997; revised manuscript December 3rd, 1997)

ß-Cholanic acid oxime, C24H39NO3, Mr = 389.56, hexagonal, P65, a = b = 14.564(3) , c = 20.282(5) , = ß = 90o, = 120o, V = 3725.7(14) 3, Z = 6. Crystal structure is composed from infinite hydrogen bonded chains of molecules forming bihelical arrangements along sixfold screw axes. Oxime-carboxyl hydrogen bonds are observed. Structure is both chiral and polar.

793-798

Crystal and Molecular Structure of
7-Chloropropyl-8-aminotheophylline
Semibenzene Solvate

by Z. Karczmarzyk1 and M. Pawlowski2
1Department of Chemistry, Agricultural and Teachers University, ul. 3 Maja 54, 08-110 Siedlce, Poland
2Department of Pharmaceutical Chemistry, Jagiellonian University, Collegium Medicum,
ul. Medyczna 9, 30-688 Krakow, Poland

(Received November 3rd, 1997; revised manuscript December 12th, 1997)

The title compound, 8-amino-7-chloropropyl-1,3-dimethyl-3,7-dihydro-1H-purine-2,6-dione semibenzene solvate, C10H14N5O2Cl.1/2C6H6, crystallizes in the triclinic system, space group P1, with cell constants a = 8.291(7), b = 9.224(6), c = 11.098(3) , = 72.31(4), ß = 78.39(4) and = 63.95(7)o. Asymmetric unit of the unit cell contains a molecule of 7-chloropropyl-8-aminotheophylline and a half of the benzene molecule; the centre of the benzene ring lies in the center of symmetry. The fused rings of the purine system are planar and are inclined with respect to each other at an angle 0.8(1)o. The chloroalkyl group in the 7 position of the theophylline has a gauche - gauche - trans conformation. The crystal structure is stabilized by a network of intermolecular hydrogen bonds. Moreover, theophylline skeletons and benzene rings show significant stacking.

799-802

Sesquiterpene Lactones
from Roots of Lactuca quercina

by W. Kisiel1 and E. Szneler2
1Department of Phytochemistry, Institute of Pharmacology, Polish Academy of Sciences,
Smetna 12, 31-343 Krakow, Poland
2Department of Chemistry, Jagiellonian University, Ingardena 3, 30-060 Krakow, Poland

(Received October 13th, 1997)

803-807

Carbon-13 NMR Study of 4-Tetracarbonylchromium Complexes of Bicyclo[2.2.1]hepta-2,5-diene Derivatives. Interligand 1H-13C Spin-Spin Couplings

by H. Krawczyk and A. Gryff-Keller
Warsaw University of Technology, Faculty of Chemistry, Noakowskiego 3, 00-664 Warsaw, Poland

(Received November 25th, 1997; revised manuscript December 23rd, 1997)

808-811

Isothermal Section of the Phase Diagram
of the Ce-Ge-Sn System at 670 K

by A.O. Stetskiv, V.V. Pavlyuk and O.I .Bodak
Department of Inorganic Chemistry, Ivan Franko Lviv State University,
Kyryla and Mefodia str. 6, 290005, Lviv, Ukraine

(Received October 31st, 1997; revised manuscript December 23rd, 1997)

812-813

Sigmund F. Zakrzewski: PODSTAWY TOKSYKOLOGII SRODOWISKA (in Polish)
(PRINCIPLES OF ENVIRONMENTAL TOXICOLOGY),
Wydawnictwo Naukowe PWN, Warszawa 1997, Paperback pp. 281

reviewed by L.Pawlowski

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