Structure of some components of the roots of Prangos ferulacea

Summary From a methanolic extract of the roots ofPrangos ferulacea (L) Lindl., growing in the Nakhichevan ASSR, in addition to the compounds found previously, another six substances (I–VI) have been isolated, of which (I) and (VI) have been identified as, respectively, meransin hydrate monoacetate, found for the first time in nature, and umbelliferone: and in the study of a crystalline mixture obtained from the resin of the roots of the plant under investigation collected in Armenia, two coumarins — (VII) and (VIII) — have been isolated.On the basis of a study of IR, NMR, and mass spectra and chemical properties, the structures of the six new cumarin derivatives (II–V, VII, and VIII) have been established. Compound (II) has the structure of 8-(3-methylbutenyloxy)furo-2,3:7,6-coumarin and has been called feruliden; (III) is 7-hydroxy-8-(3-hydroxy-2-senecioyloxyisopentyl) coumarin and has been called ferudiol; (IV) is 7-hydroxy-8-(3-methoxy-2-senecioyloxyisopentyl) coumarin; (V) is 5-[1-(2,3-dihydroxy-3-methylbutyroyloxy)-1-methylethyl]-4,5-dihydrofuro-2,3:7,6-coumarin and has been called lindiol; (VII) is 8-(2-hydroxy-3-methylbut-3-enyloxy)-7-methoxycoumarin and has been called ferudenol; (VIII) is 7-methoxy-8-(3-methyl-2-oxobut-3-enyl)coumarin and has been called prangone.Leningrad Sanitary-Hygenic Medical Institute. Translated from Khimiya Prirodnykh Soedinenii, No. 5, pp. 568–574, September–October, 1974.     

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.

     

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.     

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.

     

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.     

Transformed steroids. 160. Reaction of 20,20-dimethoxy-16α,17α-epoxypregn-5-ene-3β, 21-diol-20-one with pyridine thiocyanate and carbethoxyhydrazine

Conclusion The reaction of 20,20-dimethoxy-16,17-epoxypregn-5-ene-3,21-diol-20-one with pyridine thiocyanate in the presence of carbethoxyhydrazine proceeds by two competing paths: cisopening of the oxide ring by a -SCN ion at the C¹⁷ atom, and substitution of one of the methoxyl groups by -NCS ion. As a result 2,20-dicarbethoxyhydrazones of pregn-5-ene-3,21-diol-20-one-[17,16-d]-1,3-oxathiolan-2-one and 20-methoxy-16,17-epoxypregn-5-ene-3-ol-[20,21-d]-1,3-oxazolidine-2-thione are formed.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 4, pp. 911–914, April, 1987.     

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.     

Selectivity of toluene disproportionation over zeolite catalysts

Three decationated zeolites (H-Y, H-ZSM-5 and H-ZSM-11) were tested in different conditions. Selectivities (to xylenes, S_x, and to para-isomer, S_p) were evaluated, together with activity, vs. time-on-stream. H-ZSM-5 proved to be the best catalyst, showing S_x1 and S_p-values larger than for the equilibrium gaseous mixture.

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(H-Y, H-ZSM-5 H-ZSM-11) . ( , S_x, , S_p) . H-ZSM-5 , S_x1 S_p, .

     

ESR measurements of concentration for strong surface acceptor centers on zeolites and Al2O3 using nitroxide radical TEMPON

A method to measure concentrations of strong surface acceptor centers on aluminosilicate catalysts by their titration with a solution of TEMPON (2,2,6,6-tetramethyl-4-oxypiperidine-1-oxyl) is suggested. The concentration of these centers corresponds to that of CO test molecules for the strongest acceptor centers (_CO 2210 cm^–1) obtained using IR spectroscopy. It is shown that for ZSM-5 zeolites most of these centers are localized on their external surface.

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. - - CO (_CO 2210 cm^–1). , ZSM-5 .

     

New route for the synthesis of 2-thiouracil analogues of 3′-azido-2′,3′-dideoxy nucleosides

Summary Reaction of 3-azido-5-O-tert-butyldiphenylsilyl-2,3-dideoxy-D-erythro-pentofuranoside (5) with silylated 2-thiouracil and 5-alkoxy-2-thiouracils in the presence of trimethylsilyl trifluoromethanesulfonate afforded an anomeric mixture of the corresponding 3-azido-2,3-dideoxy-2-thiouridine derivatives with the -anomer as the main product. Deprotected nucleosides were obtained by treatment with tetrabutylammonium fluoride.

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Ein neuer Weg zur Synthese von 2-Thiouracil-Analogen von 3-Azido-2,3-dideoxy-Nucleosiden

Zusammenfassung Die Reaktion von 3-Azido-5-O-tert-butyldiphenylsilyl-2,3-dideoxy-D-erythro-pentofuranosid (5) mit silyliertem 2-Thiouracil und 5-Alkoxy-2-thiouracil in Gegenwart von Trimethylsilyltrifluormethansulfonat ergab eine anomere Mischung der entsprechenden 3-Azido-2,3-dideoxy-2-thiouridin-Derivate, wobei das -Anomer das Hauptprodukt darstellte. Die ungeschützten Nucleoside wurden mittels Behandlung mit Tetrabutylammoniumfluorid erhalten.

     

Kinetic analysis of thermogravimetric data. XX. Study of the thermal decomposition of some tetrathiocyanato-diamino-chromate complexes with derivatograph

The thermal decompositions of 8 complexes of the type A · H[Cr(NCS)₄(am)₂] (A=NH₃, pyridine,-picoline or aniline, andam=NH₃ or aniline) and of 14 complexes of the type M[Cr(NCS)₄(am)₂] (M=K, Ag, Tl, 1/2 Cd, 1/2 Pb or 1/3 Bi, andam=NH₃, benzylamine or aniline derivatives) were studied by means of a derivatograph. In the case of the A · H salts the formation of Cr(NCS)₃ was observed as a labile intermediate. Characteristic temperatures are discussed in terms of the polarizing effect of the outer sphere cations and of the nucleophilic character of the ligands. The results are compared with those obtained in the thermal decompositions of the analogous salts of the complex acid H₃[Cr(NCS)₆].

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Zusammenfassung Die thermische Zersetzung von 8 Komplexverbindungen des Typs A ·H[Cr(NCS)₄(am)₂] (A=NH₃, Pyridin, -Picolin, Anilin und am=NH₃ und Anilin) und von 14 Komplexen des Typs M[Cr(NCS)₄(am)₂] (M=K, Ag, Tl, 1/2 Cd, 1/2 Pb, 1/3 Bi und am=NH₃, Anilin und Anilinderivate) wurde mit dem Derivatographen untersucht. Im Falle der A. H Salze wird die Bildung von Cr(NCS)₃ als labiles Zwischenprodukt beobachtet. Die charakteristischen Temperaturen und kinetischen Parameter werden abgeleitet und auf der Basis der molekularen Struktur erörtert. Im Falle der M Salze werden die DTAPeaks aufgrund des Polarisationseffektes der Kationen der äußeren Sphäre und des nukleophilen Charakters der Liganden diskutiert. Die Ergebnisse werden mit jenen der thermischen Zersetzung der analogen Salze des H₃[Cr(NCS)₆] Komplexes verglichen.

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A. H[Cr(NCS)₄ ()₂], — , , - , «» . M[Cr(NCS)₄ ()₂], -, Ag, Tl, 1/2 Cd, 1/2Pb 1/3 Bi, « » — , . . Cr(NCS)₃, . , . , - . H₃[Cr(NCS)₆].

     

Conditions for the appearance of thermal oscillations during the catalytic oxidation of methanol

The experimental conditions in which thermal oscillations may be detected during methanol oxidation on palladium catalyst were determined for methanol concentration, oxygen flow rate, temperature of the gaseous reaction mixture and weight of the catalyst sample. Catalyst powder disposal may influence the characteristics of oscillations.

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, , , , , , . .

     

Isoflavones of the roots of Lupinus luteus

Conclusions For the first time in the isoflavone series, a compound which has the structure of 5,7-dihydroxy-3,4-methylenedioxyisoflavone (3,4-methylenedioxyorobol) and two of its glucosides — 3,4-methylenedioxyorobol 7-O--D-glucoside and 3,4-methylenedioxyorobol 7-O--D-glucosylglucoside — and also a genistein C-monoglucoside, have been described. The isoflavones were isolated from the roots ofLupinus luteus L. by preparative chromatography on paper and on columns of polyamide. In addition, the previously known genistein, genistein 7-O--D-glucoside (genistin), and genistein 7-O--D-glucosylglucoside have been obtained.V. F. Kuprevich Institute of Experimental Botany, Academy of Sciences of the Belorussian SSR. Translated from Khimiya Prirodnykh Soedinenii, No. 2, pp. 162–166, March–April, 1974.     

Cyclization reactions of nitriles. 28. Synthesis and reactions of 3β-acetoxy-2′-methyl-5′-cyanoandrost-5-eno[17,16-c]pyridine-6′ (1′H)-thione

3-Acetoxy-2-methyl-5-cyanoandrost-5-eno[17,16-c]pyridine-6(1H)-thione was obtained by thiylation of 16-dicyanomethyl-3-hydroxypregn-5-en-20-one acetate, and its alkylation by chloroacetonitrile and phenacyl bromide was studied. The same thione was also synthesized by treating the corresponding 6-bromo-2-methyl-5-cyanoandrost-5-eno[17,16-c]pyridine with urea.Communication 27, see [1].Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 7, pp. 943–946, July, 1988.     

Über Inhaltstoffe der Iris germanica (Schwertlilie)

Acetovanillon and the known flavonoids irisolidone, irigenin, irisolone, tectorigenin and dihydroquercetin-7.3-dimethylether were detected in the rhizomes of Iris germanica. Also a few unknown compounds could be isolated and their structure elucidated; 9-methoxy-7-(3.4.5-trimethoxyphenyl)-8H-1.3-dioxolo[4.5-g] [1]-benzopyran-8-on (=5.3.4.5-tetramethoxy-6.7-methylenedioxyisoflavone (III A); 9-methoxy-7-(3.4-dimethoxyphenyl)-8H-1.3-dioxolo[4.5-g] [1]-benzopyran-8-on (=5.3.4-trimethoxy-6.7-methylenedioxyisoflavone(III B); 9-hydroxy-7-(p-hydroxyphenyl)-8H-1.3-dioxolo[4.5-g] [1]-benzopyran-8-on (=5.4-dihydroxy-6.7-methylenedioxyiosoflavone (IX); 5.7-dihydroxy-3-(3-hydroxy-4-methoxyphenyl)-6-methoxy-4H-1-benzopyran-4-on (=5.7.3-trihydroxy-6.4-dimethoxyisoflavone (XI B); 5.7-dihydroxy-3-(4-hydroxy-3-methoxyphenyl)-6-methoxy-4H-1-benzopyran-4-on (=5.7.4-trihydroxy-6.3-dimethoxyisoflavone (XI C).The structure determination was effected by combined spectroscopical and chemical methods.

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Herrn Prof. Dr.F. Hecht mit den besten Wünschen zum 70. Geburtstag gewidmet.     

9-(2′,5′-Dimethyl-4′-pyridyl)fluorene in syntheses of fluorospirodihydrofuropyridine and pyridofluoranthene

1,2,5-Trimethyl-4-(9-fluorenylidene)piperidine, which is formed by condensation of fluorene with 1,2,5-trimethyl-4-piperidone, is converted catalytically to 9(2,5-dimethyl-4-pyridyl)fluorene, from which 2-methylpyrido[4,5-a]fluoranthene and its demethylated analog were obtained by catalytic dehydrocyclization. Oxidation of 9-(2,5-dimethy1-4-pyridyl)fluorene gave 9-(2,5-dimethyl-4-pyridyl)9-fluorenol and fluorene-9-spiro-4-(6-oxo-2-carboxypyrido[4,5-c]-4-6-dihydrofuran). 6-Methyl-2-phenyl-7-(9-fluorenyl)indolizine was synthesized by the Chichibabin method.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 8, pp. 1087–1090, August, 1978.     

Pyrimidines. 70. Relative reactivities of the chlorine atoms of 2,2′,4-trichloro-4′,5-dipyrimidinyl in its reaction with piperidine

2,2,4-Trichloro-6-phenyl-4,5-dipyrimidinyl, for which nucleophilic substitution with piperdine under various conditions was studied, was obtained from 2,2,4-trioxo-6-phenyl-1, 1,2,2,3,4-hexahydro-4,5-dipyrimidinyl. It is shown that there is an appreciable difference in the rates of substitution of the first, second, and third chlorine atoms, and this made it possible to obtain reaction products that contain one, two, and three piperidino groups. The chlorine atom in the 4 position is replaced initially, after which the chlorine atom in the 2 position undergoes substitution. The structures of the compounds were proved by chemical transformations and analysis of the PMR spectra.See [1] for communication 69.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 6, pp. 821–826, June, 1979.