1,1′-Disubstituted 2,2′-di(n-perfluoropropyl)-5,5′-bibenzimidazolyls

The synthesis of 4,4-di(methylamino)- and 4,4-dianilino-3,3-diaminobiphenyls is described. The condensation of the tetraaminobiphenyls mentioned with phenyl perfluorobutyrate has given, respectively, 1,1-dlmethyl- and 1,1-diphenyl-2,2-(n-perfluoropropyl)-5, 5-bibenzimidazolyls. A study of the thermal stability of the 2-perfluoroalkylbenzimidazoles has shown that the replacement of the hydrogen of the imino group in these compounds by a methyl or a phenyl radical considerably increases their heat stability.     

Synthesis of 2,3-disubstituted 4-oxo-3,4,5,6-tetrahydrospiro-(benzo[h]quinazoline-5,1′-cyclopentanes)

3-Substituted 4-oxo-2-thioxo-1,2,3,4,5,6-hexahydrospiro(benzo[h]quinazoline-5,1-cyclopentanes) were obtained by the reaction of 4-amino-3-ethoxycarbonyl-1,2-dihydrospiro(naphthalene-2,1-cyclopentane) with methyl, phenyl, and benzyl isothiocyanates and cyclization of the obtained thioureas. Condensation of the products with various halides gave 2,3-substituted 4-oxo-3,4,5,6-tetrahydrospiro(benzo[h]quinazoline-5,1-cyclopentanes). The reaction of 4-oxo-2-thioxo-1,2,3,4,5,6-hexahydrospiro(benzo[h]quinazoline-5,1-cyclopentane) with 1,2-dibromoethane and 1,3-dibromopropane led to 6-oxo-7,8-dihydrospiro(benzo[h]thiazolidino[2,3-b]quinazoline-7,1-cyclopentane) and 7-oxo-8,9-dihydrospiro(benzo[h]-perhydrothiazino[2,3-b]quinazoline-8,1-cyclopentane) respectively.A. L. Mndzhoyan Institute of Fine Organic Chemistry, National Academy of Sciences of the Republic of Armenia, Erevan. Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 5, pp. 663–667, May, 2000.     

Synthesis of 10-(N′-phenyl)imidoyl derivatives of phenothiazine,and their reactions with o,o-dialkylthio- and dithiophosphates

Condensation of phenothiazine with phenyl isocyanide dichloride has given 10(N-phenylchloroformimidoyl)phenothiazine, exchange reactions of which with salts of diakylthio- and dithiophosphoric acids result in rearrangement of the initially formed 10-[N-phenyldialkoxy(thio)phosphorylthioformimidoyl]phenothiazines to 10-{N-phenyl-N-[dialkoxy(thio)phosphoryl]thiocarbamoyl}phenothiazines, while reaction with diisopropyl dithiophosphoric acid affords diisopropyl chlorothiophosphate, phenyl isothiocyanate, and phenothiazine. 10-(N-Phenylethoxyformimidoyl)phenothiazine alkylates dithiophosphoric acid to give 10-(N-phenylcarbamoyl)phenothiazine, while N²-phenyl-N¹,N¹-diethyl-(10-phenothiazinyl)formamidine reacts with diisopropyl dithiophosphoric acid, affording the salt N²-phenyl-N¹,N¹-diethyl-(10-phenothiazinyl)formamidinium O,O-diisopropyl dithiophosphate.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 11, pp. 2596–2601, November, 1989.     

Synthesis and some properties of the methyl ester and N,N-diethylamide of 2-azido-5-phenyl-4-thiazolecarboxylic acid

The methyl ester and N,N-diethylamide of 2-azido-5-phenyl-4-thiazolecarboxylic acid were obtained by the reaction of the corresponding 4-substituted 2-hydrazino-5-phenylthiazole with NaNO₂ in acid media. IR and UV spectroscopy were used to show that the compounds synthesized retain azide form in both the crystalline state and in solution. The reaction of azides with dicarbonyl compounds gave derivatives of 2-[5-methyl-4-acetyl-or 2-[5-methyl-4-ethoxycarbonyl-1,2,3-triazol-1-yl]-5-phenylthiazole-4-carboxylic acid.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 5, pp. 710–714, May, 1993.     

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.

     

Photophysical and Photochemical Properties of Ru(bpy)3 2+ in Si-Ti Mixed Oxides Xerogels Prepared by the Sol-Gel Process

The luminescence spectra and lifetime of tris(2,2-bipyridine)ruthenium(II), Ru(bpy)₃ ²⁺, were studied in sol-gel reaction systems of tetramethoxysilane (TMOS) and titanium(IV) isopropoxide (TTIP) with HCl. Luminescence lifetime in the TMOS system increased as the sol-gel reaction proceeded, because diffusion-controlled luminescence quenching such as oxygen and collisional quenching with solvent molecules were suppressed in the rigid matrices. On the other hand, luminescence lifetime in the TTIP system decreased during the sol-gel reaction. The decrease in lifetime was ascribed to electron transfer from photoexcited Ru(bpy)₃ ²⁺ to the conduction band of the TiO₂ xerogels. Extended X-ray absorption fine structure (EXAFS) measurements were done to associate lifetime in the Si-Ti xerogels with the structures of Ti⁴⁺ sites in the xerogels.     

Investigations in the field of acyl group carriers

Conclusions Two representatives of phosphate ester derivatives of pantothenonitrile have been obtained: the methyl ester of D-(+)-4-C-[2-O-mesylpantothenonitrilyloxy(phenoxy)phosphonyl]-N-benzyloxycarbonylserine and the ethyl ester of D-(+)-4-C-[2-O-mesylpantothenonitrilyl(phenoxy)phosphonyl]-N-benzyloxycarbonylserylglycine.Khimiya Prirodnykh Soedinenii, Vol. 5, No. 3, pp. 174–176, 1969     

Reaction of 2,2-bis(4′-hydroxy-3′-N,N-diethylaminomethylphenyl) propane with triethyl phosphite

Conclusions The reaction of 2,2-bis(4-hydroxy-3-N,N-diethylaminomethylphenyl)propane with triethyl phosphite gave 2,2-bis(4-ethoxy-3-diethylphosphonomethylphenyl)propane via the intermediate formation of a compound with a pentacovalent phosphorus atom. In the presence of acetic acid the reaction leads to 2,2-bis(4-hydroxy-3-diethylphosphonomethylphenyl)propane.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 7, pp. 1621–1624, July, 1978.     

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.     

Darstellung von 2′,3′-Dideoxy-2′-hydroxymethyl-nucleosiden

Zusammenfassung Die Synthese von geschützten 2,3-Dideoxy-2-hydroxymethyl-nucleosiden wird beschrieben. Die durch ein Mehrstufenverfahren aus Isopropylidenglycerol erhaltenen Nucleoside können als Bausteine zur Darstellung von Oligonucleotiden verwendet werden, deren 2- und 5-Positionen über eine Etherbrücke verbunden sind.

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Synthesis of 2,3-dideoxy-2-hydroxymethyl nucleosides

Summary The synthesis of protected 2,3-dideoxy-2-hydroxymethyl nucleosides is presented. The nucleosides, obtained in a multi-step procedure starting from isopropylideneglycerol, may be used as building blocks for the synthesis of 2,5-ether linked oligonucleotides.

     

Networks based on aromatic glycidylamines: 1. Effect of curing conditions on the crosslinking of N,N-diglycidylaniline with 4,4′-diaminodiphenylmethane and of N,N,N′,N′-tetraglycidyl-4,4′-diaminodiphenylmethane with 4,4′-diaminodiphenylmethane

The effect of time and temperature of curing on the conversion of epoxy groups, on the relative change of some other functional groups (–OH, –NH₂, RNH), glass transition temperatureT _g , and equilibrium modulusG _e was investigated for epoxy networks having various initial ratios of N,N-diglycidylaniline to 4,4-diaminodiphenylmethane (DDM) and of networks with various ratio of N,N,N,N-tetraglycidyl-4,4-diaminodiphenylmethane and DDM. Curing conditions were found under which the conversion of minority groups is maximal at the minimal extent of degradation reactions for networks prepared both in the excess of amine and in the excess of epoxide. For networks prepared in the excess of epoxide the degree of the etherification reaction was found to depend on time and temperature.     

Furazane disulfilimines

The reaction of 3,4-diaminofurazane and 4,4-diamino-3,3-difurazanyl with dimethyl sulfide ditriflate provided the first syntheses for 3,4-bis(dimethylsulfilimino)furazane and 4,4-bis(dimethylsulfilimino)-3,3-difurazanyl.N. D. Zelinskii Institute of Organic Chemistry, Russian Academy of Sciences, 117913 Moscow. Translated from Izvestiya Akademii Nauk, Seriya Khimicheskaya, No. 8, pp. 1922–1923, August, 1992.     

Investigations in the region of 2,3′-biquinolyl 5. Investigation of the reaction of stabilized C-nucleophiles with 1-alkyl-3-(2-quinolyl)-quinolinium halides

The regioselectivity of the nucleophilic addition of stabilized C-nucleophiles to 1-alkyl-3-(2-quinolyl)quinolinium halides was investigated. The reaction of the latter with enolates, indolesodium, and cyanide ion leads to 4-substituted 1-alkyl-1, 4-dihydro-2,3-biquinolyls.For communication 4, see [1].Stravropol State University, Stavropol 355009, Russia. Russian Chemical Technology University 125190, Moscow. Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 9, pp. 1218–1222, September, 1998.     

Reactions of pennogenin and related compounds. IV. Formation of (25R,22′R,25′R)-3β,3′β-diacetoxy-26,22′-epoxy-16,16′-bifurosta-5,20(22),5′,17′(20′)-tetraen-26′-ol from pennogenin diacetate under the action of BF3·Et2O

A new direction of the reaction of pennogenin diacetate with BF₃·Et₂O has been discovered in which a previously unknown dimeric steroid is formed — (25R,22R,25R)-3,3-diacetoxy-26,22-epoxy-16,16-bifurosta-5,20(22), 5,17(20)-tetraen-26-ol, the structure of which has been established as the result of an analysis of IR, UV,¹H and¹³C NMR, and mass spectra. A probable mechanism for the formation of the title compound from pennogenin diacetate is suggested.Pacific Ocean Institute of Bioorganic Chemistry, Far Eastern Branch, USSR Academy of Sciences, Vladivostok. Institute of Chemistry of Plant Substances, Uzbek SSR Academy of Sciences, Tashkent. Translated from Khimiya Prirodnykh Soedinenii, No. 2, pp. 202–208, March–April, 1990.     

Intramolecular cyclization of N-phthalyl-β-aryl-β-alanine phenylhydrazide

The reaction of N-phthalyl--aryl--alanine N-methyl-N-phenylhydrazides with phosphorus oxychloride (at80 °C) is accompanied by further transformations of the initially formed 2-aminoindole derivatives and leads to isoindolo[1,22,3]-pyrimido[5,6-b]indole derivatives. Intermediate 2-aminoindoles were isolated at lower reaction temperatures. The hydrolysis of the isoindolo[1,22,3]pyrimido [5, 6-b]indole derivatives was studied. The structures of the compounds obtained were established on the basis of the PMR, IR, and UV spectra and the results of elementary analysis.Deceased.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 7, pp. 926–929, July, 1982.     

Organozinc compounds of the RZnR′ and ArZnAr′ classes

Conclusions Some unsymmetrical organozinc compounds of the RZnR class (R=phenyl or benzyl, R=2-thienyl) and a number of unsymmetrical aliphatic organozinc compounds were synthesized.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 3, pp. 587–590, March, 1967.     

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.

     

The effect of zinc(II) on the formation of 2,2′- and 2,3′-bipyridine complexes of [Ru2II(ttha)]2−(ttha6−=triethylenetetraminehexaacetate)

Ru2II(ttha)(H2O)2]2– (ttha6–= triethylene tetramine hexa-acetate), prepared by the reduction of the ruthenium(III) precursor, reacts with 2,2-bipyridine (2,2-bpy) in a multi-step fashion. The first 2,2-bpy equivalent (1:1) adds with bidentate chelation at one ruthenium(II) site as revealed by separate ruthenium(II)/(III) waves at 0.03 and 0.54V vs. n.h.e. A second equivalent of 2,2-bpy (1:2) is initially stored and retained as the [Zn(2,2-bpy)]2+ complex. Further addition of 2,2-bpy initiates coordination at the second ruthenium(II) site. [Ru2(ttha)-(2,2-bpy)(H2O)]2– forms a strong ion-pair with zinc(II) that is in rapid equilibrium with the Zn(H2O)62+/Zn(2,2-bpy)]2+ pool. The solubility of the ion-pair is low. The ion-pair exhibits a shifted ruthenium(II)/(III) wave at 0.60V. Higher amounts of 2,2-bpy recomplex the zinc(II), solubilizing the complex and returning the E1/2 value to 0.54V. Other ligands which either have a higher affinity for ruthenium(II) centres than for zinc(II) as bidentate donors (1,10-phenanthroline), or ligands that cannot form bidentate zinc(II) complexes [(2-methylpyrazine, 4,4-bipyridine (4,4-bpy), and 2,3-bipyridine (2,3-bpy)] do not exhibit the unusual competition by zinc(II). These ligands all add statistically to the ruthenium(II) centres forming 1:2 complexes with 1:2 stoichiometries. 1H-n.m.r. studies of the Ru(II)polyaminopolycarboxylate complexes [RuII(hedta)(H2O)]– complex, and [Ru2(ttha)(H2O)2]2– itself, reveal that substitution of 2,3-bpy at ruthenium(II) sites occurs with an initial kinetic split between the pyridyl rings of the 3- less-hindered and 2-more-hindered ring. A slower rearrangement occurs, producing the isomer of the more-hindered 2-substituted ring. A process is driven by forming a more -accepting system when ruthenium(II) binds to the 2-ring of 2,3-bpy. Understanding the unusual influence of zinc(II) on the substitution of 2,2-bpy with [Ru2(ttha)(H2O)2]2– clarifies the nature of the 1:1 complex – namely that the 2,2-bpy becomes bidentate at one ruthenium(II) centre rather than serving as a trans-bridging ligand between both ruthenium(II) centres within one [Ru2(ttha)]2– unit.     

Some transformations of 3,4:3'2 tetrahydrofurano-1,2,3,4-tetrahydroquinolines

Conclusions Under the action of KMnO₄ in acetone on derivatives of 3,43,2-tetrahydrofurano-1,2,3,4-tetrahydroquinoline, the nitrogen ring is dehydrogenated with a simultaneous opening of the furan ring, resulting in the formation of quinolylethyl alcohols. Hydrogenated furanoquinolines, containing the vinyl group in the 2-position, are oxidized to-quinolones in this case.     

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.