Synthesis of heterocycles from 1,5-diketones. 3. Alicyclic 1,5-diketones in reaction with phenylhydrazine

8-R-7aH-5,6,7,8,9,10,11,12-Octahydroindolo[3.2.1-d,e]acridines, 1,2,3,4-tetra-hydrocarbazole, 9-R-sym-octahydroacridines, and 9-R,10-phenyl-sym-octahydroacridinium salts are formed by the action of phenyl-hydrazine on alkylidene-2,2-dicyclohexanone or the corresponding 8-R-tricyclo(7.3.1.0^2,7)tridecan-2-ol-13-ones in an acid medium. Postulations were made for the paths of formation of these compounds.2,2-Dimethyl-3-oxa-4a-(2,2-dimethyltetrahydropyran-4-on-5yl-methyl)-4aH-1, 2,3,4-tetrahydrocarbazole, 3,3,14,14-tetramethyl-2-oxa-5a,10b-(methanoxyisobutane)-1,2,3,4,5a,10b,11,11a-octahydroquinindoline, 2,2-dimethyl-3-oxa-1,2,3,4-tetrahydrocarbazole and 3,3,6,6-tetramethyl-2,7-dioxa-sym-octahydroacridine were obtained by the reaction of methylene-3,3-di(6,6-dimethyltetrahydropyran-4-one) with phenylhydrazine in acetic acid. The quinindoline structure was confirmed by the synthesis of this compound from 2,2-dimethyl-3-oxa-4a-(2,2-dimethyl-tetrahydropyran-4-on-5-ylmethyl)-4aH-1,2,3,4-tetrahydrocarbazole by the action of ammonia.For article 2, see [1].Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 1, pp. 46–52, January, 1986.     

Five-membered 2,3-dioxo heterocycles: XLIX. Reaction of methyl 1-aryl-3-aroyl-4,5-dioxo-4,5-dihydro-1<Emphasis Type="Italic">H</Emphasis>-pyrrole-2-carboxylates with N-substituted 3-amino-5,5-dimethyl-2-cyclohexenones

Methyl 1-aryl-3-aroyl-4,5-dioxo-4,5-dihydro-1H-pyrrole-2-carboxylates react with N-substituted 3-amino-5,5-dimethyl-2-cyclohexenones to give 4-hydroxy-1-aryl-3-aroyl-6,6-dimethyl-1, 2,3,4,5,5,6,7-octahydro-1H,2H-indole-3-spiro-2-pyrrole-2,4,5-triones. The structure of the products was proved by the X-ray diffraction data for the 1-cyclohexyl derivative.__________Translated from Zhurnal Organicheskoi Khimii, Vol. 40, No. 12, 2004, pp. 1840–1845.Original Russian Text Copyright © 2004 by Bannikova, Maslivets, Aliev.For communication XLVIII, see [1].     

2,2′-Diphenyl-Δ3,3′-bi-3H-indole-1,1′-dioxide: Competitive demethylation and redox reactions

Competitive demethylation and redox reactions induced by 2,2-diphenyl-^3,3-bi-3H-indole-1,1-dioxide,1 (dinitrone) on several nitrogen bearing compounds (pyridines, amides, indoles, hydrazones and amines) are reported.Es wird über kompetitive Demethylierungen und Redoxreaktionen an stickstoffhaltigen Verbindungen (Pyridine, Amide, Indole, Hydrazone und Amine) berichtet, die durch das Dinitron 2,2-Diphenyl-3,3-bi-3H-indol-1,1-dioxid induziert werden.

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2,2-Diphenyl-3,3t-bi-3H-indol-1,1t-dioxid: Kompetitive Demethylierung und Redoxreaktionen

     

Untersuchungen an 4-Hydroxy-1-thiacumarinen, 3. Mit.: Reaktionen des 4-Hydroxy-1-thiacumarins mit aliphatischen und aromatischen Aldehyden und Dehydratation ihrer Kondensationsprodukte

Es wird die Darstellung einer Anzahl von 3,3-Methylen-bis-(4-hydroxy-1-thiacumarinen), von 3,3-Aryliden-bis-(4-hydroxy-1-thiacumarinen) mit verschiedenen Substituenten im aromatischen Ring und einiger 3,3-Aryliden-4,4-epoxydithiacumarine beschrieben. Die Bildung von Anhydroverbindungen bei Verwendung von Salicyladehyd als Aldehydkomponente bei derartigen Kondensationen wird diskutiert.The synthesis of a number of 3,3-methylene-bis-(4-hydroxy-1-thiacumarins), 3,3-arylidene-bis-(4-hydroxy-1-thiacumarins) carrying various substituents in the arylidene nucleus as well as that of the corresponding 3,3-arylidene-4,4-epoxydithiacumarins is described. The formation of anhydrocompounds when salicylaldehyde is the aldehyde component in such condensations is discussed.

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Teil der DissertationP. S. J. zur Erlangung der Würde eines Ph. D. der Karnatak University.     

Synthesen von N-substituterten o-Methylthioanilinderivaten

Zusammenfassung Methylierung von o-Aminothiophenol lieferte o-Methylmercapto-anilin, dessen Tosylat zur Herstellung des Tosylates der N-(o-Methylmercaptophenyl)--aminopropionsäure verwendet wurde. Cyclisierung von -(2-Methylmercaptodiphenyl)-aminopropionsäure ergab 1-(2-Methylmercaptophenyl)-4-oxo-1,2,3,4-tetrahydrochinolin, dessen Oxim zu 1-(2-Methylmercaptophenyl)-4-amino-1,2,3,4-tetrahydrochinolin reduziert wurde. N-[-(4-Methylpiperazinyl-1)-propyl]-2-methylthiodiphenylamin wurde durch Direktsubstitution van 2-Methylthio-diphenylamin erhalten.

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Methylation of o-aminothiophenol gave o-methyl-mercaptoaniline, the tosylate of which was used for the preparation of N-(o-methylmercaptophenyl)--aminopropionic acid tosylate. Cyclization of -(2-methylmercapto-diphenyl)-aminopropionic acid yielded 1-(2-methylmercaptophenyl)-4-oxo-1,2,3,4-tetrahydroquinoline, the oxime of which was reduced to 1-(2-methylmercaptophenyl)-4-amino-1,2,3,4-tetrahydroquinoline. N-[-(4-Methylpiperazino-1)-propyl]-2-methylmercapto-diphenylamine was prepared by direct su stitution of 2-methylmercapto-diphenylamine.

     

Synthesis of some 5′-O-amino acid derivatives of uridine as potential inhibitors ofUDP-glucuronosyltransferase

Summary In an attempt to develop potential inhibitors ofUDP-glucuronosyltransferase, some 5-O-amino acid derivatives of uridine were synthesized. N-protectedL-amino acids were coupled at the 5-O-position of 2,3-O-isopropylideneuridine by esterification employing the method of symmetrical anhydrides in presence of 4-dimethylaminopyridine, 5-O-(N-benzyloxycarbonyl-O-tert.butyl-L-threonl)-23-O-isopropylideneuridine (1), 5-O-(N-tert.butyloxycarbonyl-O-benzyl-L-seryl)-2,3-O-isopropylideneuridine and (2), 5-O-(N-tert.butyloxycarbonyl-L-valyl)-2,3-O-isopropylideneuridine (3), and 5-O-(N-tert.butyloxycarbonyl-L-valyl)-2,3-O-isopropylideneuridine (4) were obtained in good yield after column chromatography on silica gel. The treatment of2 withTFA/CH₂Cl₂ (6:1) at room temperature for 30 min led to a selective removal of theBoc group without deblocking of the 2,3-O-isopropylidene group of uridine. Treatment of2 withTFA/H₂O (5:1) at room temperature for 1 h, however, released bothBoc and 2,3-isopropylidene groups. TheZ group of1 was deprotected by catalytic hydrogenolysis over 10% Pd/C/ammonium formate.

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Synthese von 5-O-Aminosäurederivaten des Uridins als potentielle Inhibitoren derUDP-Glukuronosyl-Transferase

Zusammenfassung In einem Versuch, potentielle Inhibitoren derUDP-Glukuronosyl-Transferase zu entwickeln, wurden einige 5-O-Aminosäurederivate des Uridins synthetisiert. N-GeschützteL-Aminosäuren wurden durch Veresterung mit der 5-O-Position des 2,3-isopropylidenuridins gekuppelt (Methode der symmetrischen Anhydride in der Gegenwart von 5-Dimethylaminopyridin). Solcherweise wurden 5-O-(N-Benzyloxycarbonyl-O-tert.butyl-L-threonly)-2,3-O-isopropylidenuridin (1), 5-O-(N-tert.Butyloxycarbonyl-O-benzyl-L-seryl)-2,3-O-isopropylidenuridin (2), 5-O-(N-tert.Butyloxycarbonyl-L-leucyl)-2,3-O-isopropylidenuridin (3) und 5-O-(N-tert.Butyloxycarbonyl-L-valyl)-2,3-O-isopropylidenuridine (4) nach Säulenchromatographie (Kieselgel) in guter Ausbeute hergestellt. Die Behandlung von2 mitTFA/CH₂Cl₂ (6:1) bei Zimmertemperatur (30 min) führte zu einer selektiven Abspaltung derBoc-Gruppe ohne Deblockierung der 2,3-O-Isopropylidengruppe des Uridins. Eine Behandlung von2 mitTFA/H₂O (5:1) bei Zimmertemperatur für 1 Stunde führte hingegen zur Abspaltung sowohl derBoc als auch der 2,3-O-Isopropylidengruppe. DieZ-Gruppe von1 wurde durch katalytische Hydrogenolyse auf 10% Pd/C/Ammoniumformiat abgespalten.

     

Bisindoles. 28. Synthesis of 7,7′-dimethyl-5,5′-bis-1H-indole

Cyclization of the 3,3-dimethyl-4,4-diphenylendihydrazone of ethyl pyruvate in polyphosphoric ester gave 7,7-dimethyl-2,2-dicarbethoxy-5,5-bis-1H-indole which was hydrolyzed and decarboxylated to give 7,7-dimethyl-5,5-bis-1H-indole.For Communication 27 see [1].Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 3, pp. 343–345, March, 1990.     

Kinetics of the alkaline hydrolysis of flavonoid glycosides

Summary 1. In a study of the kinetics of the alkaline hydrolysis of flavone glycosides it has been found that derivatives of 3,3,4,5,7-pentahydroxyflavone hydrolyze faster than derivatives of 3,4,5,7-tetrahydroxyflavone and of 3,4,5,7-tetrahydroxy-3-methoxyflavone.2. In the hydrolysis of diglycosides of 3,3,4,5,7-pentahydroxyflavones the maximum amount of intermediate product is formed after 2 min (3,4,5,7-tetrahydroxyflavone glycoside), and in the case of 3,4,5,7-tetrahydroxy-3-methoxyflavone glycosides after 120–150 min.I. V. Kutateladze Institute of Pharmacochemistry, Academy of Sciences of the Georgian SSR, Tbilisi. Translated from Khimiya Prirodnykh Soedinenii, No. 5, pp. 646–649, September–October, 1977.     

2,2′-Diphenyl-Δ3,3′-bi-3H-indole-1,1′-dioxide: Molecular interactions and crystal structure

The Dinitrone 2,2-diphenyl-^3,3-bi-3H-indole-1,1-dioxide acts as a demethylating and dehydrogenating agent. The mechanism of interaction of the dinitrone with donors and acceptors does not involve intermediate charge-transfer complexes probably due to a self association between dinitrone molecules (as supported by X-ray determinations). The crystal structure of the dinitrone was obtained by direct methods;a=9.967 (2),b=19.817 (3),c=10.875 (2) Å, =111.2 (2)°, space group P2₁/n. The finalR andR _w were 0.089 and 0.063 for all measured reflexes.

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2,2-Diphenyl-^3,3-bi-3H-indol-1,1-dioxid: Molekulare Wechselwirkungen und Kristallstruktur

Zusammenfassung Das Dinitron 2,2-Diphenyl-^3,3-bi-3H-indol-1,1-dioxid wirkt als Demethylierungs- und Oxydationsmittel. Die Wechselwirkung des Dinitrons mit Elektronen-Acceptoren und Elektronen-Donatoren geht wegen der Selbstassoziation zwischen den Dinitron-Molekülen ohne die dazwischenliegende Bildung eines Charge-Transfer-Komplexes vor sich; das wird auch von Röntgenstrukturuntersuchungen gestützt. Die Kristallstruktur wurde mit direkten Methoden ermittelt:a=9.967 (2),b=19.817 (3),c=10.875 (2) Å; =111.2 (2)°. P2₁/n. Die endgültigen WerteR undR _w waren 0.089 und 0.063 für alle gemessenen Reflexe.

     

Spektrophotometrische Bestimmung von Dehydrokondensationsprodukten der Pyrazine und Chinoxaline

Zusammenfassung Die Absorptionsspektren folgender Verbindungen: Chinoxalin, 2,2-Dichinoxalyl, 2-Methylchinoxalin, 3,3-Dimethyl-2,2-dichinoxalyl, Pyrazin, 2,2-Dipyrazyl, 2-Methylpyrazin und 5,5-Dimethyl-2,2dipyrazyl wurden in Methanol im Bereich von 225–360 nm bestimmt.Eine Methode zur quantitativen Bestimmung der genannten Verbindungen wurde ausgearbeitet, um den Herstellungsprozeß von 2,2Dichinoxalyl, 3,3-Dimethyl-2,2-dichinoxalyl, 2,2-Dipyrazyl und 5,5-Dimethyl-2,2-dipyrazyl aus den entsprechenden Monomeren durch direkte Photometrierung von Proben der Reaktionsgemische, die in einem beliebigen Stadium der Synthese dem Reaktor entnommen wurden, verfolgen zu können.

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Spectrophotometric determination of dehydrocondensation products of pyrazines and quinoxalines

Summary The absorption spectra of the following compounds: quinoxaline, 2,2-diquinoxalyl, 2-methylquinoxaline, 3,3-dimethyl-2-2-diquinoxalyl, pyrazine, 2,2-dipyrazyl, 2-methylpyrazine and 5,5-dimethyl-2,2-dipyrazyl were determined in methanol in the region of 225–360 nm. A method was developed for the quantitative determination of these compounds in order to be able to follow the preparation methods of 2,2-diquinoxalyl, 3,3-dimethyl-2,2-diquinoxalyl, 2,2-dipyrazyl and 5,5-dimethyl-2,2-dipyrazyl from the corresponding monomers through direct photometration of samples of the reaction mixture, which can be taken from the reactor at a selected stage of the synthesis.

     

Flotations-spektrophotometrische Methode zur Bestimmung von Zirkonium mittels Eriochromazurol B

Zusammenfassung Eine flotations-spektrophotometrische Methode zur Bestimmung des Zirkoniums in Stählen mittels des Dinatriumsalzes der 2,6-Dichlor-4-hydroxy-3, 3-dimethylfuchson-5,5-dicarbonsäure (CAB) wurde ausgearbeitet. Der molare Extinktionskoeffizient beträgt 3,3×10⁴, die spezifische Absorptiona=0,33. Der Vorteil der bearbeiteten Methode ist die Möglichkeit, Zirkonium (IV) neben der hundertfachen Menge Hf(IV) zu bestimmen.

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Flotation spectrophotometric method for determination of zirconium by means of eriochrome azurol B

Summary A flotation spectrophotometric method for determining zirconium in steels by means of the disodium salt of 2, 6-dichloro-4-hydroxy-3,3-dimethylfuchsone-5, 5-dicarbonic acid (CAB) was worked out. The molar extinction coefficient is 3.3×10⁴. The specific absorption wasa=0.33. The advantage of the method is the possibility of determining zirconium(IV) besides the hundredfold amount of Hf(IV).

     

Synthesis of some 1 -oxo-1h-2,3,4,5-tetrahydro-benzofuro [3, 2-c]azepines

Condensation of O-phenylhydroxylamine with 1H-2,3,4,5,6,7-hexahydroazepine-2,4-dione in alcoholic hydrogen chloride solution gave 1-oxo-1H-2,3,4,5-tetrahydrobenzofuro[3,2-c]-azepine, while a similar condensation with 6,6-dimethyl-1H-2,3,4,5,6,7-hexahydroazepine-2,4-dione gave a mixture of 4,4-dimethyl-1H-2,3,4,5-tetrahydrobenzofuro[3,2-c]azepine and 2-oxo-3-(3,3-dimethyl-5-pyrrolidylidene)benzofuran. Tetrahydrobenzofuroazepines were also synthesized by Beckmann rearrangement of oximes of 1-oxo-1,2,3,4-tetrahydrobenzofuran and 3,3-dimethyl-1-oxo-1,2,3,4-tetrahydrodibenzofuran, which were obtained in turn by condensation of O-phenylhydroxylamine with dihydroresorcinol and dimedone.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 2, pp. 149–153, February, 1973.     

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.     

Synthesis of 2-O-ethyl analogues of 3′-azido- and 3′-fluoro-2′,3′-dideoxyuridines and evaluation of their biological activity against HIV

Summary 2-O-Ethyluracil and 2-O-ethylthymine were silylated with 1,1,1,3,3,3-hexamethyldisilazane and condensed in the presence ofTMS triflate with 2,3-dideoxy-3-fluoro-D-erythro-pentofuranoside, 3-azido-2,3-dideoxy-D-erythro-pentofuranoside, and 2,3-dideoxy-3-phthalimido--D-erythro-pentofuranose derivatives to give the corresponding 2-O-ethyl nucleosides. Deprotection with saturated methanolic ammonia afforded the 2,3-dideoxy-3-fluoro-2-O-ethyluridines, whereas 3-azido-2,3-dideoxy-3-O-ethyluridine was obtained by deprotection with tetrabutylammonium fluoride in tetrahydrofuran. 3-Amino-2,3-dideoxy-3-O-ethyluridine could be obtained only by treatment of the corresponding 3-azido nucleoside with triphenylphosphine in pyridine. 3-Deoxy-2-O-ethyl-3-fluorothymidine (6b) showed moderate activity against HIV-1.

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Synthese von 2-O-Ethyl-Analogen von 3-Azido- und 3-Fluor-23-dideoxyuridinen und Bestimmung ihrer biologischen Aktivität gegenüber HIV

Zusammenfassung 2-O-Ethyluracil und 2-O-Ethylthymin wurden mit 1,1,1,3,3,3-Hexamethyldisilazan silyliert und in Gegenwart vonTMS-triflat mit 2,3-Dideoxy-3-fluoro-D-erythro-pentofuranosid, 3-Azido-2,3-dideoxy-D-erythro-pentofuranosid und 2,3-Dideoxy-3-phthalimido--D-erythro-pentofuranosederivaten zu den entsprechenden 2-O-Ethyl-Nucleosiden umgesetzt. Entfernung der Schutzgruppe mit gesättigter methanolischer Ammoniaklösung lieferte 2,3-Dideoxy-3-fluor-2-O-ethyluridin; 3-Azido-2,3-dideoxy-3-O-ethyl-uridin wurde durch Entschützung mit Tetrabutylammoniumfluorid in Tetrahydrofuran erhalten. 3-Amino-2,3-dideoxy-3-O-ethyl-uridin konnte nur durch Behandeln des entsprechenden 3-Azido-Nucleosids mit Triphenylphosphin in Pyridin hergestellt werden. 3-Deoxy-2-O-ethyl-3-fluor-thymidin (6b) zeigt geringe Aktivität gegenüber HIV-1.

     

New chiral acyclic analogs of 2′-deoxynucleosides

Convenient methods for the synthesis of chiral 2,3-seco-2-deoxynucleosides were developed. An isopropylidene protective group was used to block the 3,5-hydroxy groups in 2,3-seco-uridine. Conversion of the hydroxymethyl group to a methyl group was accomplished by chlorination with a mixture of CCl₄ and Ph₃P with subsequent reduction with n-Bu₃SnH. 2,3-seco-2-Deoxyuridine was obtained after deacetonation. The (S) enantiomer was similarly synthesized starting from 1-(-D-arabinofuranosyl)uracil. 3-O-tert-Butyldimethylsilyl-5-O-(p-monomethoxytrityl)-2,3-seco-2-deoxyuridine, which has optically active centers at C₍₁₎ and C₍₄₎, was also synthesized.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 6, pp. 822–826, June, 1988.The authors thank Professor M. Ya. Karpeiskii for his constant interest in this research.     

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].     

Contributions to silica gel application in pesticide residue analysis

Summary An on-line method for the extraction and isolation of pesticides in milk and dairy products is discussed. Milk and aqueous dairy products are homogenized with silica gel. This sample having a water content of approximately 40% is brought into a column, which is filled with the 10% water silica gel necessary for the clean-up. Extraction and clean-up of the pesticides occurs on-line with light petroleum — dichloromethane 80+20 (v/v). The pesticides move with the solvent front from the upper silica gel to the lower 10% water column, where they are cleaned up. Quantitative identification of the pesticides is performed by glass capillary gas chromatography (ECD) as well as by mass spectroscopy. HCB, -HCH, -HCH, -HCH, -Heptachloroepoxide, p,p-DDE, Dieldrin, o,p-DDT, p,p-DDT, 2,4,5,2,4,5-Hexachlorobiphenyl and 2,3,4,2,4,5-Hexachlorobiphenyl were identified in milkThe hexachlorobiphenyl concentrations in milk are about 20 times the value of o,p-DDT and p,p-DDT.

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Beiträge zur Verwendung von Kieselgel in der PesticidanalytikIII. On-Line-Verfahren zur Extraktion und zur Isolierung von Chlorkohlenwasserstoff-Pesticiden und polychlorierten Biphenylen aus Milch und Molkereiprodukten

Zusammenfassung Eine on-line-Methode zur Extraktion und Isolierung der Chlorkohlenwasserstoff-Pesticide in Milch und Milchprodukten wird beschrieben. Milch und wäßrige Milchprodukte werden zuerst mit Kieselgel homogenisiert. Diese Probenhomogenisate mit einem Wassergehalt von etwa 40% werden anschließend in eine Chromatographiesäule gefüllt, in der sich bereits das für den clean-up erforderliche Kieselgel mit 10% Wasserbelegung befindet. Die Extraktion bzw. der clean-up der Pesticide erfolgt on-line mit Petrolether-Dichlormethan 80+20 (v/v). Die Pesticide werden in der Lösungsmittelfront von der oberen auf die untere Kieselgelsäule (10% Wassergehalt) transportiert, an welcher schließlich die Abtrennung der Pesticide von den Störkomponenten erfolgt. Die Identifizierung und Quantifizierung der Pesticide erfolgt sowohl gas-chromatographisch (ECD) an Capillarsäulen als auch massenspektrometrisch. HCB, -HCH, -HCH, -HCH, -Heptachlorepoxid, p,p-DDE, Dieldrin, o,p-DDT, p,p-DDT, 2,4,5,2,4,5-Hexachlorbiphenyl und 2,3,4,2,4,5-Hexachlorbiphenyl wurden in der Milch gefunden. Die Gehalte der beiden Hexachlorbiphenylkomponenten sind etwa 20mal so groß wie die von o,p-DDT und p,p-DDT.

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Part II: see [2]     

Spektrophotometrische und fluorometrische Bestimmung von Myricetin (3,3′,4′,5,5′,7-Hexahydroxy-Flavon)

Zusammenfassung Myricetin (3,3,4,5,5,7-Hexahydroxyflavon) wird aus Pflanzenextrakten chromatographisch abgetrennt, mit Methanol eluiert. Das gelbgrüne Fluoreszenzlicht seines Aluminiumchelats wird in Gegenwart von Essigsäure und Ammoniumacetat gemessen. 10^–4% Myricetin lassen sich mit einem relativen Fehler von ±4% bestimmen.

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Spectrophotometric and fluorometric determination of myricetin (3,3,4,5,5,7 -hexahydroxyflavone)

Summary Myricetin (3,3,4,5,5,7-hexahydroxyflavone) is separated chromatographically from plant extracts and eluted with methanol. The yellow-green fluorescent light of its aluminium chelate is measured in the presence of acetic acid and ammonium acetate. 10^–4% Myricetin can be determined with a relative error of ±4%.

     

Oxidative cyclisation of chalcones with thallium(III)nitrate: Synthesis of (Z)-2-phenylmethylene-7-nitro-3(2H)-benzofuranones

Oxidation of 2-hydroxy-3-nitrochalcones with thallium(III) nitrate gives (Z)-2-phenylmethylene-7-nitrobenzofuran-3(2H)-one derivatives, rather than the more usual 1,2-diaryl-3,3-dimethoxypropan-1-ones or the corresponding isoflavones.

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Oxydative Cyclisierung von Chalconen mit Thallium(III)nitrat: Synthese von (Z)-2-Phenylmethylen-7-nitro-3(2H)-benzofuranonen (Kurze Mitteilung)

Zusammenfassung Die Oxidation von 2-Hydroxy-3-nitrochalconen mit Thallium(III)nitrat ergab (Z)-2-Phenylmethylen-7-nitro-3(2H)-benzofuranon-Derivate und nicht die üblichen 1,2-Diaryl-3,3-dimethoxypropan-1-one bzw. die entsprechenden Isoflavone.

     

Synthesis,structure, and physico-chemical properties of 3-methyl and 3,3-dimethyl derivatives of l-(4′,4′-dimethyl-2′,6′-dioxocyclohex-1′-yl)-3,4-dihydroisoquinoline

3,3-Dimethyl- and 3-methyl-1-(4,4-dimethyl-2,6-dioxocyclohex-1-yl)-3,4-dihydroisoquinolines have been synthesized. Crystal and molecular structures of the 3,3-dimethyl derivative have been determined. In the crystalline state this compound exists as a tautomeric form where a hydrogen atom is located at the N atom of the dihydroisoquinoline fragment of the molecule. The tautomeric equilibrium does not shift noticeably in solutions, as shown by IR, UV, and NMR spectroscopy.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 2, pp. 331–336, February, 1993.