1,4-bis(4′-hydroxy-1′,2′,5′-trimethyl-4-piperidyl)-1,3-butadiyne and its derivatives

1.4-Bis(4-hydroxy-1,2,5-trimethyl-4-piperidyl)-1.3-butadiyne has been synthesized from the individual isomers of 4-ethynyl-1,2,5-trimethyl-4-piperidol. Hydrogenation, bromination, and cleavage have given, respectively, 1,4-bis(4-hydroxy-1,2,5-trimethyl-4-piperidyl)butane, 1,4-bis(4-nydroxy-1,2,5-trimethyl-4-piperidyl)-1,2,3,4-tetrabromo-1, 3-butadiene, and 4-(1,3-butadiynyl)-1,2,5-trimethyl-4-piperidol.     

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.

     

Chemistry of 2-hetarylbenzimidazoles. 8. Synthesis and properties of 1-methyl-2-(5′-methyl-2′-selenienyl)benzimidazole

1-Methyl-2-(5-methyl-2-selenienyl)benzimidazole was synthesized and subjected to electrophilic-substitution reactions: nitration, bromination, sulfonation, chloromethylation, formylation, and acylation. The substituent usually enters the 4 position of the selenophene ring, but nitration with acetyl nitrate leads to a mixture of 5-nitro and 4-nitro derivatives. Oxidation of 2-selenienylbenzimidazole with potassium permanganate leads to the 5-carboxy derivative, while oxidation with selenium dioxide leads to the 5-hydroxymethyl and 5-formyl derivatives.See [1] for Communication 7.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 12, pp. 1636–1639, December, 1987.     

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.     

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.

     

A differential scanning calorimetric study of some phenol derivatives

Differential scanning calorimetry has been applied to derive the fusion enthalpies and entropies of series of mono and dimethylphenols, mono and dichlorophenols, and mono and dinitrophenols.

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Zusammenfassung DSC wurde verwendet zur Ermittlung der Schmelzenthalpie und Entropie der Reihen von Mono- und Dimethylphenolen, Mono- und Dichlorphenolen, Mono- und Dinitrophenolen.

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- , - , - .

     

Crystal and molecular structure of 1-aza-6′-(3′-oxo-5′, 5′-dimethyl-δ1′-pyrrolin-3′-yl)methylidene-2,2,7,7-tetramethyl-4-hydroxybicyclo-[2.2.21azaoctane

An x-ray structural study has shown that 6-(3-oxo-5,5-dimethyl-¹-pyrrolin-3-yl)methylidene-2,2,7, 7-tetramethyl-4-hydroxybicyclo[2.2.2]azaoctane is formed as a low-molecular-weight byproduct of the solid-phase polymerization of 1,4-bis(2,2,6,6-tetramethyl-4-hydroxy-4-piperidyl)butadiyne.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 3, pp. 585–587, March, 1990.     

Zur Mannich-Reaktion von Dihydro-6-methyl-2(1H)-pyrimidinonen

Zusammenfassung Dihydro-4,4,6-trimethyl-2(1H)-pyrimidinone reagieren mit Formaldehyd und sekundären bzw. primären Aminen zu 6-Dialkylaminoäthylidentetrahydro-2(1H)-pyrimidinonen bzw. Hexahydro-2(1H)-pyrido[4,3-d]Pyrimidinonen. Mit Succindialdehyd bzw. Glutardialdehyd und primären Aminen entstehen 5,7-Äthanohexahydro-2(1H)-pyrido[4,3-d]pyrimidinone bzw. Tetrahydro-6,8-propano-6H-pyrimido[1,6-c]pyrimidin-1(2H)-one. Die 6-Dialkylaminoäthylidentetrahydro-2(1H)-pyrimidinone geben mit Phenolen Tetrahydrospiro([1]benzopyran-2,4(1H)-pyrimidin)-2(3H)-one, mit cycl. -Dicarbonylverbindungen Hexahydrospiro([1]benzopyran-2,4(1H)-pyrimidin)-2,5(3H, 6H)-dione bzw. Tetrahydrospiro(2H,5H-pyrano[3,2-c][1]benzopyran-2,4(1H)-pyrimidin)-2(3H),5-dione bzw. mit Malonestern -(Tetrahydro-4,4-dimethyl-2-oxo-6-pyrimidyl)-äthylmalonester.Zusammenfassung Dihydro-4.4.6-trimethyl-2(1H)-pyrimidinones react with formaldehyde and sec. and prim. amines resp. to 6-dialkylaminoethylidentetrahydro-2(1H)-pyrimidinones and hexahydro-2(1H)-pyrido[4.3-d]pyrimidinones, resp. succindialdehyde and glutaraldehyde with primary amines give 5.7-ethanohexahydro-2(1H)-pyrido[4.3-d]pyrimidinones and tetrahydro6.8-propano-6H-pyrimido[1.6-c]pyrimidin-1(2H)-ones, resp. 6-Dialkylaminoethylidentetrahydro-2(1H)-pyrimidinones react with phenols to tetrahydrospiro([1]benzopyran-2.4(1H)-pyrimidin)-2(3H)-ones, with cyclic -dicarbonyl compounds to hexahydrospiro([1]benzopyran-2.4 (1H)-pyrimidin)-2,5 (3H), 6H)-diones and tetrahydrospiro(2H,5H-pyrano[3.2-c][1]benzopyran-2.4(1H)-pyrimidin)-2(3H),5-diones, resp., with malonates -(tetrahydro-4.4-dimethyl-2-oxopyrimidyl-6)-ethylmalonates.

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Mannich reaction with dihydro-6-methyl-2(1H)-pyrimidinones

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Herrn Prof. Dr.F. Kuffner zum 65. Geburtstag gewidmet.     

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     

Synthesis of spiro[9,10-dihydro-10-sila-2-azaanthracene-9,1′-cyclopropanes

The Z- and E-isomers of 9,14dihydro-10,10-&-methyl-2-trimethylsilyl(2phenyl-3 fornryl)spiro[IO-sila-2-azaanthracene-9,1 -cyclopropane] have been obtained by heating 9-diazo-9,10-dihydro-10,10-dimethyl-10-sila-2azaanthracene with trimethylvinylsilane and with cinnanuaidehyde.     

Phenolic derivatives of 2-pyrone

The cyclization of 1,1-dichloro-5-(2,5-dimethoxyphenyl)-1,3-pentadien-5-one and the product of its partial demethylation leading to the corresponding derivatives of 2-pyrone and 2-(,-dichlorovinyl)-6-methoxy-4-chromanone has been studied. Irradiation causes the dimerization of 1,1-dichloro-5-(2,5-dimethoxyphenyl)-1,3-pentadien-5-one.For part I, see [1].     

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 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.

     

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.     

Natural product chemistry. Part 121. Synthesis of dicoumarinyl ethers with the structures proposed for fatagarine and oreojasmine

Synthesis of the 7,8-dicoumarinyl ethers: 7-methoxy-7,8-oxydicoumarin and 6,7-dimethoxy-7,8-oxydicoumarin, established that the structures of fatagarine and oreojasmine for which these two structures have been proposed, have to be revised. Synthesis of 7-methoxy-5,7-oxydicoumarin and 8-methoxy-7,7-oxydicoumarin exclude the possibility of these dicoumarinyl ether structures for fatagarine.

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Naturstoffchemie. 121. Mitt.: Synthese von Dicumarinylethern mit den für das Fatagarin und das Oreojasmin vorgeschlagenen Strukturen

Zusammenfassung Durch die Synthese der 7,8-Dicumarinylether: 7-Methoxy-7,8-oxydicumarin und 6,7-Dimethoxy-7,8-oxydicumarin, ließ sich nachweisen, daß die für das Fatagarin und Oreojasmin vorgeschlagenen Strukturen revidiert werden müssen. Die Darstellung des 8-Methoxy-7,7-oxydicoumarin und 7-Methoxy-5,7-oxydicumarin schließen die Möglichkeit dieser Strukturen für das Fatagarin aus.

     

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.     

Acid properties and stability of operation of vanadium catalysts in benzene oxidation to phenol

Catalytic properties of V₂O₅/SiO₂ in benzene oxidation by N₂O were examined. Sodium additive was shown to affect the catalyst operation stability.

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V₂O₅/SiO₂ N₂O. .

     

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.     

Kinetic and mechanistic studies on the oxidation of sulfanilic acid by peroxomonophosphoric acid

Oxidation of sulfanilic acid to the corresponding azoxy derivative by peroxomonophosphoric acid (PMPA) has been studied in aqueous medium. The observed bell-shaped pH-rate profile has been rationalized on the basis of protonation of the amino group and ionization into different PMPA species and a suitable rate law has been proposed. The mechanism of oxidation involves the nucleophilic attack of nitrogen on the electrophilic peroxo oxygen.

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- (PMPA) . pH— , PMPA . .

     

Quantitative measurement of isomeric cyclic nucleotides from T-lymphocytes by HPLC

Summary The influence of thymic factors on the levels of different cyclic nucleotides in human lymphoblastic lymphoma cells has been studied. A single-step HPLC method for the simultaneous determination of 2,3-cGMP, 3,5-cGMP, 2,3-cAMP and 3,5-cAMP from biological cell materials is described. Concentrations even in the picomolar range could be determined quantitatively.

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Quantitative HPLC-Messung isomerer cyclischer Nucleotide aus T-Lymphocyten