Coumarins of Smyrniopsis aucheri

Chemical transformations and spectral characteristics have enabled us to establish the structure and configurations of three coumarins: (+)-2,2-dimethyl-3-hydroxy-3,4-dihydropyrano(5,6:6,7)coumarin (I); (+)-4-hydroxy-5-(1-hydroxy-1-methylethyl)-4,5-dihydrofuro(2,3:6,7)coumarin (II); and (+)-4-hydroxy-5-(1-glucopyranosyloxy-1-methylethyl)-4,5-dihydrofuro(2,3:6,7)-coumarin (III) isolated from the roots ofSmyrnopsis aucheri Karjag. This is the first time that these compounds, which have been called smyrinol, smyrindiol, and smyrindioloside, have been detected in nature.Institute of Chemistry of Plant Substances, Uzbekistan Republic Academy of Sciences, Tashkent. Azerbaidzhan State University, Baku. Translated from Khimiya Prirodnykh Soedinenii, No. 1, pp. 36–40, January–February, 1992.     

Cobalt(II) and nickel(II) chloride complexes with some 2-(4′-Methyl-2′-pyridyl and 2′- or 8′-quinolyl)benz-X-azoles

Summary Complexes of general formula ML_mCl₂ · nH₂O, where M=cobalt(II) or nickel(II); L=2-(4-methyl, 2-pyridyl)-benzimidazole (mpbi), 2-(4-methyl, 2-pyridyl)benzothiazole (mpbt), 2-(4-methyl, 2-pyridyl)benzoxazole (mpbo), 2-(4-methyl, 2-quinolyl)benzoxazole (mqbo), or 2-(4-methyl, 8-quinolyl)benzoxazole (mqbo); m=1,2; n=0–3, were prepared and characterized by t.g.a., conductance and magnetic measurements, i.r. and diffuse-reflectance electronic spectra.All the ligands behave as bidentate and coordinate through the pyridine- and isoxazole-nitrogen atoms.The nickel complexes have distorted octahedral or fivecoordinate structures. The cobalt complexes arepseudo-tet- rahedral except Co(mpbo)₂Cl₂·2H₂O where the metal is six-coordinate.     

1,2-bis(2',6'-dimethyl-i',3'-dioxa-6'-aza-2'-silacyclooctyl-2')ethane and the corresponding ethylene and acetylene derivatives

Conclusions The reaction of 1,2-bis(methyldimethoxysilyl)ethane and the corresponding ethylene and acetylene derivatives with bis(2-hydroxyethyl)methylamine gives 1,2-bis(2,6-dimethyl-1,3-dioxa-6-aza-2-silacyclooctyl-2)ethane and the corresponding ethylene and acetylene derivatives. Analogously, 1,2-bis(vinyldimethoxysilyl)acetylene gave 1,2-bis(2-vinyl-6-methyl-1,3-dioxa-6-aza-2-silacyclooctyl-2)acetylene.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 6, pp. 1420–1421, June, 1988.     

1,1′,2,2′,6,6′-Hexaphenyl-4,4′-bipyridinium cation radical

Aniline reacts with 2,2,6,6-tetraphenyl-4,4-bipyrilium perchlorate to form 1,1,2,2,6,6-hexaphenyl-4,4-bipyridine perchlorate. A relatively stable cation radical is formed in the first stage of electrochemical reduction of this compound, which has been examined by ESR, where there are splittings from two nitrogen nuclei and the four protons in the 3,3,5,5 positions: a_N=0.38; a_H=0.14 mT.Translated from Teoreticheskaya i Éksperimental'naya Khimiya, No. 1, pp. 61–64, January–February 1992.     

X-ray spectral investigation by synchrotron radiation of supported Re/SiO2 and (Re+Pt)/SiO2 catalysts prepared via triethoxyrhenium

Using synchrotron radiation L_III absorption spectra of rhenium in Re/SiO₂ and (Re+Pt)/SiO₂ catalysts prepared via triethoxyrhenium have been studied. The conclusion has been drawn that reduced catalysts contain lowvalent rhenium ions and their composition is more uniform than that of the previously examined catalysts Re/Al₂O₃ and (Re+Pt)/Al₂O₃ prepared by a conventional impregnation technique.

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L_III- Re/SiO₂ (Re+Pt)/SiO₂, . , , Re/Al₂O₃ (Re+Pt)/Al₂O₃, .

     

Synthesis of aminoacyl derivatives of nucleosides,nucleotides, and polynucleotides

Conclusions The possibility has been shown of extending the method of synthesis of O-aminoacyl derivatives of nucleotides and nucleoside triphosphates to prepare 3(2)-O-peptidyI-micleoside-5-triphosphates.TranslatedfromlzvestiyaAkademii Nauk SSSR, Seriya Khimicheskaya, No. 6, pp. 1369–1372, June, 1970.     

Soluble polysaccharides of Rhodotorula flava

Conclusions 1. Xanthalin has been shown to have the structure of 2, 2-dimethyl-3, 4,-diangeloyloxy-3, 4-dihydropyrano-5, 6:6, 7-coumarin on the basis of the preparation of a number of derivatives and cleavage products.2. The following products of the alkaline hydrolysis of xanthalin have been isolated and characterized for the first time: (±)-3, 4-dihydroxy-3, 4-dihydroxanthyletin (isokhellactone), C₁₄H₁₄O₅, with mp 213–215° C and (–)-trans-3-hydroxy-4-methoxy-3, 4-dihydroxanthyletin (isomethylkhellactone, C₁₅H₁₆O₅, with mp 136.5–138° C and [] _D ²⁰ –47.7 (ethanol).Khimiya Prirodnykh Soedinenii, Vol. 6, No. 1, pp. 14–19, 1970     

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.

     

Solid-gas reactions: Study of sulphation of limestone using thermogravimetry

Comparative data are presented on the absorption rate and capacity for SO₂ capture by a natural Polish limestone with and without sodium chloride additive. Two sets of experiments were carried out, under dry and wet conditions during limestone calcination and sulphation.The presence of water vapour brought about a higher reactivity of the sorbent, probably as a result of an effect on the sintering of lime and through the influence of the CaSO₄ layer. Further morphological investigations could provide confirmation of the present hypothesis.

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Zusammenfassung Absorptionsgeschwindigkeit und -kapazität für SO₂ an einem polnischen Kalkstein mit oder ohne NaCl-Zusatz werden verglichen. Zwei Reihen von Experimenten wurden in trockener bzw. wasserdampfhaltiger Atmosphäre bei der Calcination und Sulfatbildung durchgeführt. In Gegenwart von Wasserdampf wird die Reaktivität des Absorbens infolge Sinterung des Kalks und trotz des Einflusses der CaSO₄-Schicht erhöht. Künftige morphologische Untersuchungen sollen diese Hypothese eventuel bestätigen.

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The author would like to thank Prof. E. M. Bulewicz of this Institute for valuable discussions, and Mr. W. Balcerowiak for making available the facilities of the Laboratory of the Institute of Heavy Organic Synthesis in Kdzierzyn-Kole.     

Investigations of 2,3′-biquinolyl. 8. Reduction of 1-alkyl-3-(2-quinolyl)-quinolinium halides with sodium borohydride

Reduction of 1-alkyl-3-(2-quinolyl)quinolinium halides with sodium borohydride leads to 1-alkyl-1,2-dihydro-2,3-biquinolyls which, except for the ethoxycarbonyl derivative, undergo rearrangement to 1-alkyl-1,4-dihydro-2,3-biquinolyls. The last can be synthesized by the alkylation of the corresponding 1,4-dihydro-2,3-biquinolyls under conditions of interphase catalysis and in the system KOH-DMSO.For Communication 7, see [1].Stavropol' State University, Stavropol' 355009, Russia; nauka@stavsu.ru. Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 8, pp. 1084–1087, August, 2000.     

Structure of ursinoic acid and ursinin

Conclusions On the basis of UV, IR, and NMR spectroscopy, and the preparation of derivatives, the most probable structures of ursinoic acid and ursinin, aromatic oxo acids isolated previously from the roots ofAngelica ursina Rupr. et Schmalh., have been established. It has been shown that the former has the structure 2,2-dimethylpyrano-5, 6:5, 6-(2, 4-dimethoxy)benzoylacetic acid while the second is 2,2-dimethylpyrano-5,6:5, 6-(2-methoxy)benzoylacetic acid.Khimiya Prirodnykh Soedinenii, Vol. 6, No. 4, pp. 421–424, 1970     

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.     

Investigations in the field of oxygen-containing heterocycles

2-(4-Chloro-2-methyl-2-butenyl)tetrahydropyran and 2-(4-chloro2, 3-dimethyl-2-butenyl)tetrahydropyran react with organomagnesium compounds and also with sodium amalgam with the formation of mixtures of the 2-(2-alkenyl)tetrahydropyrans corresponding to the initial chlorides and the 2-(3-alkenyl)tetrahydropyrans corresponding to the allyl isomers of the initial chlorides. The structure and composition of the products have been established by IR and NMR spectroscopy and by gas-liquid chromatography.For part V, see [1].     

Palladium(II) and platinum(II) chloride and bromide complexes with some 2-methylpyridyl- or methylquinolyl-benzimidazole,benzoxazole, or benzthiazole

Summary Palladium(II) and platinum(II) complexes [MLX₂], where L=2-(4-methyl-2-pyridyl)benzimidazole (mpbi), 2-(4-methyl-2-pyridyl)benzoxazole (mpbo), 2-(4-methyl-2-quinolyl)benzoxazole (mpbo), 2-(4-methyl-8-quinolyl)benzoxazole (mq'bo), X=Cl. Br, together with M(mqbo)₂Br₂ and Pt₂(mpbt)Cl₄, where mpbt=2-(4-methyl-2-pyridyl)benzthiazole, have been synthesized and characterized by conductivity and magnetic measurements as well as by i.r. and electronic spectra. The ligands are bidentate chelates through the pyridine or quinoline and isoxazole or imidazole nitrogen atoms. The [MLX₂] derivatives arecis, square planar.     

Ruthenium(III) ion complexes with nucleotides

Summary Complexes of adenosine-5-monophosphate (5-AMP), guanosine-5-monophosphate (5-GMP), inosine-5-monophosphate (5-IMP) and cytidine-5-monophosphate (5-CMP) with ruthenium trichloride have been prepared and studied by i.r. spectroscopy, diffuse reflectance spectra and magnetochemical measurements.All complexes are probably polymeric as indicated by their insolubility in polar solvents.The i.r. spectra suggest that the ruthenium(III) ion interacts with the ligands through N(7) of the purine mononucleotides and through N(3) of the pyrimidine mononucleotide from one side and with the phosphate group of another mononucleotide molecule from another side. The formation of hydrogen bonds reinforces the interaction.The complexes have normal magnetic moments close to the spin-only value. The electronic spectra confirm their octahedral structure.     

Convenient synthesis of 5′-methyl-2′-desoxyuridines

A convenient method has been developed for the synthesis of 5-methyl-2-desoxyuridines. Chlorination of 5-O-benzoyl-5-methyluridines with a mixture of Ph₃P and CCl₄ in DMF affords the 2-desoxy-2-chloro-derivatives, which are then reduced with tributyltin hydride. The crystalline 5-O-benzoyl-5-methyl-2-desoxyuridines were obtained in overall yields of 40–60%. In a similar way, 5-O-benzoyluridine has given 5-O-benzoyl-2-desoxyuridine.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 2, pp. 246–248, February, 1989.     

Studies of 2,3′-biquinolyl. 6. Regioselectivity of nucleophilic addition of organometallic compounds to 1-aklyl-3-(2-quinolyl)quinolinium halides

Nucleophilic addition of organometallic lithium and magnesium compounds to 1-alkyl-3-(2-quinolyl)quinolinium cations produces a mixture of the corresponding 1-alkyl-2-R-1,2-dihydro-2,3-biquinolyls and 1-alkyl-4-R-1,4-dihydro-2,3-biquinolyls. The portion of the latter decreases with increasing hardness of the organometallic compound.For No. 5, see [1].Stavropol State University, Stavropol'355009, Russian Russian Chemical Technology University Moscow 125190 Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 7, pp. 919–923, July, 1999.     

Zur Kenntnis der Dioxyditolylsulfone

Zusammenfassung Es wird der Verlauf der Sulfurierung des m-Kresols auf Grund der zwei dabei gebildeten Sulfone, dem - und -m-Oxytolylsulfon vonZehenter, geklärt. Die Konstitution des -m-Oxytolylsulfons wird als die des 2,2-Dioxy-4,4-dimethyldiphenylsulfons erkannt; für das -m-Oxytolylsulfon wird die Konstitution des 4,2-Dioxy-2,4-dimethyldiphenylsulfons wahrscheinlich gemacht.     

New cardenolides from the leaves ofGomphocarpus fruticosus

Two new glycosides, gomphotin (1) and gomphotoxin (13), and also the known gomphoside (9) have been isolated from the leaves ofGomophocarpus fruticosus. Compounds (1) and (9) contain a 4,6-dideoxyhexosulose residue as the sugar component, and (13) a 6-deoxyhexosulose, which are attached to glycolic OH groups of the aglycons by 3-O-1,2-O-2 (9, 13) and 3-O-1,4-O-2 (1) acetal-ketal bonds. The structures of the new compounds are represented by the names (3-O-1,4-O-2)-(2,3-dihydroxy-4, 6dideoxyhexulosido)-14-hydroxy-5-card-20(22)-enolide* (1) and (3-O-1,2-O-2)-(2,3,4-trihydroxy-6-deoxyhexulosido)-14-hydroxy-5-card-20(22)-enolide* (13).State Scientific Center for Drugs of the Ministry of Health and the National Academy of Sciences of the Ukraine, Kharkov, fax 441118. Translated from Khimiya Prirodnykh Soedinenii, No. 6, pp. 824–832, November–December, 1995. Original article submitted May 22, 1995.