Research in environmental pollution

Summary Five non-o,o-Cl and 15 mono-o,o-Cl substituted PCB congeners were identified in Hessian human milk by GC-MS. For risk and hazard assessment the concentrations of these analysed PCB congeners were transformed into the corresponding TCDD-equivalents (TE). It was found that the concentrations of the analysed coplanar PCB congeners in human milk expressed in TE are by a factor of about 4 higher than that of the polychlorinated dibenzo-p-dioxins (PCDD's) and dibenzofurans (PCDF's).     

Long chain alkyl-polysiloxanes as non-polar stationary phases in capillary gas chromatography

Summary A new methyl-octadecyl polysiloxane phase with a distinct selectivity in PCB separation and a significantly improved temperature range has been developed. The basic structural element of the separation of PCBs on methyl-octadecyl-polysiloxane is the elution according to the number of the substituents in the ortho-positions 2,2 and 6,6. The 2,2,6,6-substituted congeners are eluted first, while the non-2,2,6,6-substituted coplanar PCB are eluted last. As compared to methyl-phenyl (5%) polysiloxane (SE 54) the standard stationary phase used for the separation of the PCBs, the methyl-octadecyl-polysiloxane has several unique features in an improved PCB separation. The Sil 5–50% C18 column resolves the pair PCB 31/28 and also the sets PCB 5/8, PCB 16/15/32, PCB 25/53, PCB 48/47, PCB 56/60, PCB 118/149, PCB 105, 132, 153, and PCB 170/190. All these separations are not achieved with a SE 54 column. No separation is observed for the pair PCB 138/163 on Sil 5–50% C18. The order of elution of the Cl_xB congeners reveals a rather stringent structure correlation. If the structure/retention correlation is extended to all 209 Cl_xB congeners, 20 groups with one ring fixed / one ring variable substitution can be distinguished.Dedicated to Prof. Dr. V. Krivan on the occasion of his 60th birthday.Presented at 14th International Symposium on Capillary Chromatography, May 25–29, Baltimore, USA.     

Synthetic studies in the field of chlorobium chlorophyll

By the condensation of -halogenomethyl derivatives of pyrroles with -unsubstituted pyrroles the synthesis of the following unsymmetrical dipyrrolylmethanes has been effected: 5-benzyloxycarbonyl-5-ethoxycarbonyl-3, 3-di(-methoxycarbonylethyl)-4,4-dimethyl-2,2-dipyrrolylmethane (IIIa), 5-benzyloxycarbonyl-5-ethoxycarbonyl-3-(-methoxycarbonylethyl)-4, 4-diniethyl-3-n-propyl-2,2-dipyrrolylmethane(IIIb), 3-acetyl-5-benzyloxycarbonyl-4-ethyl-5-methoxycarbonyl-3, 4-dimethyl-2,2-dipyrrolylmethane (IIIc), and 3-bromo-5-benzyloxycarbonyl-4-ethyl-5-methoxycarbonyl-3, 4-dimethyl-2,2-dipyrrolylmethane (IIId). Hydrogenation of the unsymmetrical dipyrrolylmethanes IIIa, b, c, and d has given the corresponding monocarboxylic acids IVa, b, c, and d. The formylation of the dipyrrolylmethanemonocarboxylic acid IVa has given 5-ethoxycarbonyl-5-formyl-3,3-di(-methoxycarbonylethyl)-4, 4-dimethyl-2,2-dipyrrolylmethane (V).For communication II, see [1].Deceased.Translated from Khimiya Geterotsiklicheskikh Soedinenii, Vol. 6, No. 8, pp. 1045–1047, August, 1970.     

Untersuchung des Zerfalls verschiedener Azoinitiatoren in Lösung

The decomposition of various symmetric and unsymmetric azo-initiators (1,1-dichloro-1,1-diphenyl-1,1-azoethane, 2,2-dichloro-2,2-azopropane, 1,1-dichloro-1,1-azocyclohexane, 2,2-diacetoxy-2,2-azopropane, 1,1-diacetoxy-1,1-diphenyl-1,1-azoethane, 1,1-diacetoxy-1,1-azocyclohexane, 2,2-dipropionoxy-2,2-azopropane, 2,2-dicapronoxy-2,2-azopropane, 4,4-dimethyl-1,4-azobutyrolactone, azoisobutyronitrile, 2-t-butylazo-2-cyanobutan, 2-t-bytylazo-1-cyanocyclohexan) in solution was studied in dependence of temperature. Volumetry and differential-scanning-calorimetry (DSC) were used to determine decomposition rates; first order kinetics was found in all cases.

     

Five-membered 2,3-dioxo heterocycles: XLVIII. Reaction of 3-aroyl- and 3-heteroyl-2,4-dihydro-1<Emphasis Type="Italic">H</Emphasis>-pyrrolo[2,1-<Emphasis Type="Italic">c</Emphasis>][1,4]-benzoxazine-1,2,4-triones with 3-amino-5,5-dimethyl-2-cyclohexenone

3-Aroyl- and 3-heteroyl-2,4-dihydro-1H-pyrrolo[2,1-c][1,4]benzoxazine-1,2,4-triones react with 3-amino-5,5-dimethyl-2-cyclohexenone to give 3-aroyl-4-hydroxy-1-o-hydroxyphenyl-6,6-dimethyl-2,2,3,4,5,5,6,7-octahydro-1H-indole-3-spiro-2-pyrrole-2,4,5-triones. The structure of the products was proved by X-ray analysis.Translated from Zhurnal Organicheskoi Khimii, Vol. 40, No. 9, 2004, pp. 1405–1409.Original Russian Text Copyright © 2004 by Mashevskaya, Duvalov, Tolmacheva, Aliev, Maslivets.This study was performed under financial support by the Russian Foundation for Basic Research (project nos. 01-03-32641 and 02-03-96411).For communication XLVII, see [1].     

Study of reaction of sulfur halides with unsaturated. Compounds. 24. Reaction of sulfur monochloride with adamantylidene-adamantane

Conclusions In the reaction of adamantylideneadamantane with S₂Cl₂ at an equimolar ratio of the reagents, 2,2-epithio-2-(2-adamantyl)adamantane and 4-chloro-2,2-epithio-2-(2-adamantyl)-adamantane are formed, while with an excess of S₂Cl₂, the products are 4e-chloro- and 4e,4e-dichloroadamantylideneadamantane.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 3, pp. 617–620, March.Article 23, see [1].     

Synthesis of new pyridazino[4′,3′:4,5]-thieno[3,2-d]-1,2,3-triazine and pyrimido[4′,5′:4,5]thieno[2,3-c]pyridazine derivatives

Summary 8,9-Diphenylpyridazino[4,3:4,5]thieno[3,2-d]-1,2,3-triazin-4(3H)-one (2), 3-substituted 8,9-diphenylpyridazino[4,3:4,5]thieno[3,2-d]-1,2,3-triazin-4(3H)-ones (3a–c), 3,4-diphenylpyrimido[4,5:4,5]thieno[2,3-c]pyridazin-8(7H)-one (4), 8-chloro-3,4-diphenylpyrimido[4,5:4,5]thieno[2,3-c]pyridazine (5), 8-substituted 3,4-diphenylpyrimido[4,5:4,5]thieno[2,3-c]pyridazines (6a–h) and 7-substituted 3,4-diphenylpyrimido[4,5:4,5]thieno[2,3-c]pyridazin-8(7H)-ones(7a–c) were synthesized from 5-amino-3,4-diphenylthieno[2,3-c]pyridazine-6-carboxamide (1).

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Synthese neuer Pyridazino[4,3:4,5]thieno[3,2-d]-1,2,3-triazin-und Pyrimido[4,5:4,5]thieno[2,3-c]pyridazin-Derivate

Zusammenfassung Folgende Verbindungen wurden ausgehend von 5-Amino-3,4-diphenylthieno[2,3-c]pyridazin-6-carboxamid (1) synthetisiert: 8,9-Diphenylpyridazino[4,3:4,5]thieno[3,2-d]-1,2,3-triazin-4(3H)-on (2), 3-substituierte 8,9-Diphenylpyridazino[4,3:4,5]thieno[3,2-d]-1,2,3-triazin-4(3H)-one (3a–c), 3,4-Diphenylpyrimido[4,5:4,5]thieno[2,3-c]pyridazin-8[7H]-on (4), 8-Chlor-3,4-diphenylpyrimido[4,5:4,5]thieno[2,3-c]pyridazin (5), 8-substituierte 3,4-Diphenylpyrimido[4,5:4,5]thieno[2,3-c]pyridazine (6a–h) und 7-substituierte 3,4-Diphenylpyrimido[4,5:4,5]thieno[2,3-c]pyridazin-8(7H)-one (7a–c).

     

A new coumarin, pranferol, from the roots ofPrangos ferulacea

Summary A new coumarin, pranferol C₁₆H₁₆O₅, has been isolated from the roots ofPrangos ferulacea (L.) Lindl.The structure 5-(2-hydroxy-3-methylbutoxy)furo-2,3:7,6-coumarin has been proposed for pranferol.Khimiya Prirodnykh Soedinenii, Vol. 9, No. 5, pp. 310–315, 1966     

Synthesis of 2,3,7,8-tetramethyldibenzofuran

3,4,3,4-Tetramethyldiphenyl ether readily forms 2,2-dihalo derivatives on bromination and iodination. Heating 2,2-diiodo-4,5,4,5-tetramethyldiphenyl ether with copper powder or oxidation, of 2,2-dilithio-4,5,4,5-tetramethyldiphenyl ether gives 2,3,7,8-tetramethyldibenzofuran, the structure of which was proved by alternative synthesis from 2,2-dinitroand 2,2-diamino-4,5,4,5-tetramethyldiphenyls.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 12, pp. 1597–1599, December, 1972.     

Study of furan compounds

Research on synthesis of polycyclic spirans of the 1, 6-dioxaspiro-[4, 4]nonane group is continued. Electrolysis of methanol solutions of 2-furylcyclopentanol, 2-(5-methyl-furfuryl)cyclopentanol, and 2-furfuryl-1-indanol, gives, by intramolecular alkoxylation, spiro{perhydrocyclopenta[b]furan-2, 2-(5dihydrofuran)}, spiro{perhydrocyclopenta[b]furan-2, 2-(5-methoxy-5-methyl-2, 5-dihydrofuran)}, and spiro{2, 3, 3a, 8b-tetrahydro-4H-indeno[1, 2-b]furan-2, 2-(5-methoxy-2, 5-dihydrofuran)}, hitherto undescribed in the literature. Depending on the conditions, catalytic hydrogenation of these gives: spiro{perhydiocyclopenta[b]furan-2, 2-(5-methoxytetrahydrofuran)}, spiro{2, 3a, 8b-tetrahydro-4H-indeno[1, 2-b]furan-2, 2-(5-methoxytetrahydrofuran)}, spiro{perhydrocyclopenta[b]furan-2, 2-tetrahydrofuran}, and spiro{2, 3, 3a, 8b-tetrahydro-4H-indeno[1, 2-b]furan-2, 2-tetrahydrofuran}.For Part XXXI see [1].     

Spaltungen mittels Diazoniumverbindungen und Chinonimidchlorid, 6. Mitt.: Über Hydroxychalkone

Zusammenfassung Es wird über die Reaktion verschieden methylsubstituierter 4-Hydroxychalkone mittels Chinonimidchlorid berichtet und gezeigt, daß die Ausbeute an 2,6-Dimethylphenol-indophenol bei der Spaltung von 4,4-Dihydroxy-3,5,3-trimethylchalkon (VII) am RingB dreimal so groß ist als beim 4,4-Dihydroxy-3,3,5-trimethylchalkon (III) am RingA.

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The reaction between several methyl-4-hydroxy-chalkones and p-benzoquinone-monochloroimine has been studied. It has been shown that the yield of 2.6-dimethylphenol-indophenol from the cleavage of 4.4-dihydroxy-3.5.3-trimethyl-chalkon (VII) at ringB is three times the yield resulting from the cleavage of 4.4-dihydroxy-3.3.5-trimethylchalkon (III) at ringA.

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Herrn Prof. Dr.H. Bretschneider zum 60. Geburtstag gewidmet.     

Spectrophotometric determination of vanadium with 4-(1′H-1′,2′,4′-Triazolyl-3′-azo)-2-methylresorcinol

Summary 4-(1H-1,2,4-Triazolyl-3-azo)-2-methylresorcinol reacts with vanadium(V) at pH 8.10 (Tris-HClO₄ buffer solution) to produce a pink-violet 11 complex ( _max=525 nm,=2.55×10⁴l·mol^–1· cm^–1) in a 50% (v/v) methanol-water medium, which allows the spectrophotometric determination of 0.1 to 1.51 ppm of vanadium. The method has been applied for the determination of the vanadium content in low alloy steels.

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Spectrophotometriscbe Bestimmung von Vanadin mit 4-(1H-1,2,4-triazo-lyl-3-azo)-2-methylresorcin

Zusammenfassung Vanadin bildet bei pH 8,10 (Tris-HClO₄-buffer) mit 4-(1H-1,2,4-tri-azolyl-3-azo)-2-methylresorcin ein rosenrot-violettes Chelat, dessen Absorptionsmaximum bei 525 nm in Gegenwart von 50% Methylalkohol gemessen wird. Dieser 11-Komplex entspricht bei einer Vanadin-Konzentration von 0,1–1,51g/ml dem Beerschen Gesetz; seine molare Absorptivität ist 2,55×10⁴l·mol^–1·cm^–1. Das Verfahren wurde zur Bestimmung des Vanadins in Stahl verwendet.

     

1,2-Dimethylimidazobenzo-1′, 2′, 3′-thiadiazoles and derived cyanine dyes

New tricylic heterocyclic systems and their methyl derivatives are synthesized. They are 2-methylimidazo[5, 4-e]benzo-1, 2, 3-thiadiazole, 2-methylimidazo[5, 4-g]benzo-1, 2', 3-thiadiazole, 1, 2-dimethylimidazo[5, 4-g]benzo-1, 2, 3-thiadiazole, and 1, 2-dimethylimidazo[5, 4-g]benzo-1, 2, 3-thiadiazole. Quaternary salts of the 1, 2-dimethyl derivatives are used to prepare symmetrical and unsymmetrical trimethinecyanines and dimethinemerocyanines containing rhodanine groups. The absorption maxima of the dyes are displaced towards the long wavelength region compared with imidacarbocyanines. It is shown that when 1, 2-dimetnyl-5-aminobenzoimidazole is thiocyanated, the thiocyano group enters the benzoimidazole ring at position 4, and that 1, 2-dimethylimidazo[5, 4-e] benzo-1, 2, 3-thiadiazole is less basic than its isomer 1, 2-dimethylimidazo[5, 4-g]benzo-1, 2, 3-thiadiazole.     

Convenient synthesis of 5′-methyl-2′-desoxyuridines

A convenient method has been developed for the synthesis of 5-methyl-2-desoxyuridines. Chlorination of 5-O-benzoyl-5-methyluridines with a mixture of Ph₃P and CCl₄ in DMF affords the 2-desoxy-2-chloro-derivatives, which are then reduced with tributyltin hydride. The crystalline 5-O-benzoyl-5-methyl-2-desoxyuridines were obtained in overall yields of 40–60%. In a similar way, 5-O-benzoyluridine has given 5-O-benzoyl-2-desoxyuridine.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 2, pp. 246–248, February, 1989.     

Studies of 2,3′-biquinolyl. 6. Regioselectivity of nucleophilic addition of organometallic compounds to 1-aklyl-3-(2-quinolyl)quinolinium halides

Nucleophilic addition of organometallic lithium and magnesium compounds to 1-alkyl-3-(2-quinolyl)quinolinium cations produces a mixture of the corresponding 1-alkyl-2-R-1,2-dihydro-2,3-biquinolyls and 1-alkyl-4-R-1,4-dihydro-2,3-biquinolyls. The portion of the latter decreases with increasing hardness of the organometallic compound.For No. 5, see [1].Stavropol State University, Stavropol'355009, Russian Russian Chemical Technology University Moscow 125190 Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 7, pp. 919–923, July, 1999.     

Benzoylation of 1,4-diaza-1,3-butadienes: Synthesis of representatives of a new chemical class—1,2-diamino-1-chloroethylenes

Trans-N,N-dialkyl-N,N-dibenzoyl-1,2-diamino-1-chloroethylenes — the first representatives of a new chemical class — and N,N-dialkyl-N,N-dibenzoyl-1,2-diaminoethylenes were obtained by benzoylation of N,N-dialkyl-1,4-diaza-1,3-butadienes. On increase in pressure to 10,000 atm, the yields of the N,N-dibenzoylated 1,2-diamino-1-chloroethylenes increase, and those of the N,N-dibenzoylated 1,2-diaminoethylenes decrease.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 9, pp. 2038–2041, September, 1989.     

Nitration,amination, and halogenation of Di-O-methylphloracetophenone

Chlorination of the title compound gave 5- and 3-chloro-2-hydroxy-4,6-dimethoxyacetophenone. The nitration of its acetate, followed successively by reduction, diazotization, and reaction with cuprous chloride, gave the 3-substituted series, 2-acetoxy-4,6-dimethoxy-3-nitroacetophenone, 3-amino-2-hydroxy-4,6-dimethoxyacetophenone, and 3-chloro-2-hydroxy-4,6-methoxyacetophenone, respectively. The orientation of substituents in the products was proved. The amino and chloro members of the isomeric 5-substituted series were availablevia 2-hydroxy-4,6-dimethoxy-5-phenylazoacetophenone, the product of the reaction of the title compound with benzenediazonium chloride.

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Nitrierung, Aminierung und Halogenierung von Di-O-methylphloracetophenon

Zusammenfassung Chlorierung der Titelverbindung gab 5- und 3-Chlor-2-hydroxy-4,6-dimethoxyacetophenon. Die Nitrierung des Acetats, gefolgt von Reduktion, Diazotierung und Reaktion mit CuCl ergab die 3-substituierte Reihe: 2-Acetoxy-4,6-dimethoxy-3-nitroacetophenon, 3-Amino-2-hydroxy-4,6-dimethoxyacetophenon und 3-Chlor-2-hydroxy-4,6-dimethoxyacetophenon. Die Orientierung der Substituenten wird diskutiert. Die Amino- und Chlorderivate der isomeren 5-substituierten Reihe sind über 2-Hydroxy-4,6-dimethoxy-5-phenylacetophenon zugängig, dem Produkt der Reaktion der Titelverbindung mit Phenyldiazoniumchlorid.

     

Anomalous nucleosides

A preparative synthesis of the antimetabolite 6-azacytidine is described which involves the amination under mild conditions without the use of an autoclave of 2, 3, 5-tri-O-acyl-4-thip-6-azauridines with the isolation of the intermediate 2, 3, 5-tri-O-acyl-6-azacytidines and subsequent elimination of the protective groups at room temperature.For communication VI, see [10].     

The electronic structure of groups of isomeric hetero-aromatic systems

The electronic structure of the configurational isomers of 3-3-, 3-5- and 5-5-bis-oxadiazole, and of trans-,-di-(3-3)-, -(3-5)- and -(5-5)-diazolyl-ethylene, was studied by using the ASMO, SCF, CI procedure developed by Pariser, Parr and Pople. The total -electron energy is taken as the measure for ranging the various isomers and their different configurations in a given order of stability.Predictions based on charge distributions and bond orders are in agreement with the chemical behaviour of the known 3-3 and 5-5 isomers, and are therefore regarded as reliable also for the 3-5 compounds, not described in the literature so far.The calculated value of the lowest singlet transition energy agrees with the observed spectra, with a scatter of ±0.20 eV depending on the particular procedure chosen for calculating the _pqand (App) integrals. The calculated second singlet transition is found to depend on the procedure chosen for those integrals to such an extent as to make the prediction unreliable.

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Zusammenfassung Die Elektronenstruktur der Konfigurationsisomere von 3,3-, 3,5- und 5,5-bis-Oxadiazol und trans-,-di-3,3-, -3,5- und -5,5-Diazolyläthylen wurde mit Hilfe der ASMO-SCF-CI-Methode studiert. Die totale -Elektronenenergie wurde als Maß für die Stabilität der verschiedenen Isomere und ihrer Konfigurationen gewählt.Voraussagen, die auf Ladungsverteilungen und Bindungsordnungen basieren, sind in Übereinstimmung mit dem chemischen Verhalten der bekannten 3,3- und 5,5-Isomere und wurden deshalb auch als zuverlässig für die 3,5-Verbindungen angesehen, die bis jetzt in der Literatur nicht beschrieben sind.Der berechnete Wert für die niedrigste Singulett-Anregungsenergie stimmt mit den beobachteten Spektren bis auf ±0,2 eV überein, abhängig von der Berechnungsart für die _pqund (App). Die Anregungsenergie für den zweiten Singulettübergang läßt sich in diesem Rahmen nicht vorhersagen.

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Résumé La structure électronique des isomères configurationales des 3-3-, 3-5- et 5-5-bis-oxadiazole, et des trans---di-(3-3)-, -(3-5)- et -(5-5)-diazolyl-ethylène a été étudiée par la méthode ASMO, SCF, CI sélon la forme développée par Pariser, Parr et Pople. L'énergie totale des électrons a été prise comme étalon pour classifier les isomères et leurs differentes configurations sélon un ordre de stabilité.Les déductions que l'on peut tirer de la distribution des charges et des ordres de liaison sont en accord avec les observations chimiques des isomères connus, 3-3 et 5-5; par conséquent on peut considérer raisonables les prédictions que ont été faites sur les isomères 3-5, qui ne sont pas décrites dans la literature jusqu'ici.La valeur calculée pour la première transition de singulet est en bon accord avec le spectre d'absorption observé, l'incertitude due à la procedure choisie pour les integrales _pqet (App) étant ±0.20 eV. La deuxième transition de singulet apparait dépendre presque entièrement de la choix faite pour les dites integrales.

     

Derivatives of 3-aminopiperidine-2, 6-dione

Several N-substituted 3-phthalimidopiperidine-2,6-diones and 3-(3phthalimido-2,5-dioxopyrrolid-1-yl)piperidine-2,6-dione have been synthesized.