Spectral characteristics of C-methylflavones

A study has been made of natural C-methylflavones and their dealkylated analogues: 5-hydroxy-4,7-dimethoxy-7-methylflavone (noreucalyptin); 4,5,7-trihydroxy-6-methylflavone; 5-hydroxy-4,7-dimethoxy-6,8-dimethylflavone (eucalyptin); 4,5-dihydroxy-7-methoxy-6,8-dimethylflavone (sideroxylin); 4,5,7-trihydroxy-6,8-dimethylflavone; 4,5,6-trihydroxy-3-methoxy-8-methylflavone (silpin) and 3,4,5,6-tetrahydroxy-8-methylflavone.All-Union Scientific-Research Institute of Medicinal Plants, Moscow. Translated from Khimiya Prirodnykh Soedinenii, No. 3, pp. 306–309, May–June, 1984.     

Antimicrobial activity studies of mononuclear and binuclear mixed-ligand copper(II) complexes derived from Schiff base ligands and 1,10-phenanthroline

Mixed-ligand complexes of copper(II) with 1,10-phenanthroline and various Schiff bases have been prepared and characterized by elemental analysis, electronic and i.r. spectra, magnetic moment and molar conductance data. The Schiff base behave as bidentate ligands, and the mixed-ligand copper(II) complexes of the ligands HL1, HL2 and HL4 are binuclear. The conductivity data for all the complexes are consistent with those expected for an electrolyte. Antimicrobial activities of some of the ligands and complexes have been tested against Bacillus megaterium and Candida tropicalis. 1H and 13C n.m.r. spectra have been recorded in order to solve the solution structure of the ligands. Thermal properties of all complexes have been studied by the d.t.a. and t.g.a. techniques.     

Vanadyl ion complexes with nucleotides

Summary Complexes of adenosine-5-triphosphate, adenosine-5-monophosphate, guanosine-5-monophosphate, inosine-5-monophosphate, cytidine-5-monophosphate and uridine-5-monophosphate with vanadyl ion, have been studied in the solid state by i.r. spectroscopy and magnetochemically. All complexes have normal magnetic moments, very close to the spin-only values. From the i.r. spectra it is suggested that the vanadyl ion is interacting with adenosine-5-triphosphate, through the N-1 of the purine ring, with adenosine-5-monophosphate, guanosine-5-monophosphate, inosine-5-monophosphate, through the N-7 of the purine ring, with cytidine-5-monophosphate through the N-3 of the pyrimidine ring, and most probably through the phosphate group with uridine-5-monophosphate. The complexes of vanadyl ion with the nucleotides are probably polymeric.     

Investigations in the field of complex lipids

Summary 1. The synthesis of L-(+)--oleoyl--linoleoyl--glycerylphosphorylethanolamine has been effected.2. During the investigations the following substances were isolated and characterized: L--oleoyl--glycerylphosphoryl-N-phthaloylethanolamine and L---linoleoyl--glycerylphosphoryl-N-phthanoylethanolamine.Khimiya Prirodnykh Soedinenii, Vol. 2, No. 2, pp. 80–83, 1966     

1-Aryl-6-azauracile, 5. Mitt.: Die Synthese von 1-(β-Pyridyl)-6-azauracil-5-carbonsäure und einiger ihrer Derivate

Zusammenfassung Analog wie in vorherigen Mitteilungen^1–4 wurden -Pyridyl-hydrazono-cyanacetylcarbamidsäureäthylester (1), 1-(-Pyridyl)-5-cyan-6-azauracil (2), 1-(-Pyridyl)-6-azauracil-5-carbonsäure (3), deren Thioamid (4), und Amidoxim (5), welches in 1-(-Pyridyl)-5-[5-methyl-1,2,4-oxdiazolyl(3)]-6-azauracil (6) überge-führt wurde, hergestellt.

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-Pyridylhydrazono-cyanacetylcarbamic acid ethyl ester (1), l-(-pyridyl)-5-cyano-6-azauracil (2), 1-(-pyridyl)-6-azauracil-5-carboxylic acid (3), its thioamide (4) and amidoxime (5) were prepared as described in preceding communications. (5) was converted into l-(-pyridyl)-5-[5-methyl-1,2,4-oxdiazolyl(3)]-6-azauracil (6).

     

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.

     

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].     

New terpenoid coumarins from Ferula tadshikorum

Summary Two new terpenoid coumarins — tadzhiferin (I) and tadzhikorin (II) — have been isolated from the fruit ofFerula tadshikorum M. Pimen.On the basis of physicochemical and spectral investigations, the structure of 7-(9-hydroxy-3,7,11-trimethyldodeca-2,6,10-trienyloxy)coumarin is proposed for (I) and that of 7-(4-acetoxy-9-hydroxy-3,7,11-trimethyldodeca-2,6,10-trienyloxy)coumarin for (II).All-Union Scientific-Research Institute of Medicinal Plants, Moscow. M. V. Lomonosov State University. Botanical Garden, Moscow. Translated from Khimiya Prirodnykh Soedinenii, No. 5, pp. 593–599, September–October, 1976.     

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.

     

Reaction of dibepin with amino acids on chromatographic paper

A method was developed for the development of amino acids and some of their derivatives on Chromatographic paper by means of dibepin-8-[2,3(CO),6,5(CO)-dibenzoylene-4-pyridyl]-l-naphthoyl chloride. The sensitivity was 2 g in the case of glycine ethyl ester hydrochloride.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 3, pp. 357–358, March, 1972.     

Reaction of Cytisine with 4″-Substituted Dibenzo-18-crown-6 Sulfonylchlorides

Sulfamides were synthesized via the reaction of cytisine with 4,4(5)-dibenzo-18-crown-6-disulfonyl-, 4-sec-butyl-4(5)-dibenzo-18-crown-6-sulfonyl-, and 4-acetyl-4(5)-dibenzo-18-crown-6-sulfonylchlorides. The structures of the prepared compounds were confirmed by PMR.     

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.     

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].     

Oxidation of 2,6-disubstituted phenols as a route to 3,5,3′,5′-tetrasubstituted diphenoquinones and 4,4′-dihydroxydiphenyls

Conclusions Oxidation of 2,6-disubstituted phenols by atmospheric oxygen in the presence of a cuprammonium complex gave 3,3,5,5-tetraalkyldiphenoquinones which were converted to the corresponding 4,4-dihydroxydiphenyls.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 8, pp. 1808–1810, August, 1987.     

Podand-porphyrins with peripheral chelates

Alkylation of 5-(3-nitro-4-hydroxyphenyl)-10,15,20-triphenylporphyrin with chloropyridines[2,6-dichloromethyl-and 2-chloromethyl-6-(2-nitrophenoxymethylpyridine)] as well as condensation by a mixed-aldehyde method starting with formylpyridines [2-(2-nitro-4-formylphenoxymethyl)-6-(2-nitrophenoxy-methyl-) or 2,6-di(2-nitro-4-formylphenoxymethyl)pyridine], benzaldehyde, and pyrrole are used to synthesize previously unknown podand-porphyrins containing from one to four peripheral chelates.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 4, pp. 475–481, April, 1991.     

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.

     

Coordination polymers of cobalt(II) involving 4,4′-bipyridyl and its dioxide

Summary Analytical data, room temperature magnetic moment values, electronic and i.r. spectral measurements down to 200 cm^–1 on the coordination compounds formed by the interaction of cobalt(II) chloride, bromide, thiocyanate, acetate and nitrate with 4,4-bipyridyl and 4,4-bipyridylN,N-dioxide indicate that the isolated compounds are coordination polymers having tetrahedral or octahedral stereochemistry around cobalt(II) involving bridging 4,4-bipyridyl/4,4-bipyridylN,N-dioxide molecules. Terminally bonded acetato- and nitrato-ligands and bridging or terminally bonded chloro-, bromo- and thiocyanato-groups in the solid state.     

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.

     

Diazabicycloalkanes with nitrogen atoms in bridgehead positions. 16. Synthesis and properties of benzo[b]-1,4-diazabicyclo[2.2.2]octene and dibenzo[b,e]-1,4-diazabicyclo[2.2.2]octadiene,containing primary aromatic amino acids

4-Aminobenzo[1,2-b]-1,4-diazabicyclo[2.2.2]octene and 4-aminodibenzo[1,2-b, e]-1,4-diazabicyclo[2.2.2]octadiene have been prepared by cyclization reactions of N--chloroethyl derivatives of 1,2,4-triaminobenzene and aminophenazine, and subsequent catalytic hydrogenation of the corresponding 4-nitrobenzo[1,2-b]-1,4-diazabicyclo[2.2.2]octene and 4-benzylaminodibenzo[1,2-b,e]-1,4-diazabicyclo[2.2.2]-octadiene. Using the conversion of these compounds to azides as an example, we have demonstrated the feasibility of applying these primary aromatic amines for the synthesis of derivatives of these heterocycles.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 6, pp. 831–837, June, 1988.     

Synthesis and study of L-arabinopyranosides of 5- and 6-nitroindoles

Condensation of 5- or 6-nitroindoline with L-arabinose gave 1--L-arabinopyranosyl-5 (or 6)-nitroindolines, which, after acetylation, dehydrogenation, and removal of the protective groups, are converted to 1--L-arabinopyranosyl-5(or 6)-nitroindoles and then to the corresponding amino derivatives. 1--L-Arabinopyranosyl-6-nitro-3-bromo-(iodo)indoles were obtained. The selective 2-O- and 3-O-deacetylation of 1-(2, 3, 4-tri-O-acetyl)--L-arabinopyranosyl-6-nitroindole was accomplished.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 2, pp. 224–229, February, 1979.