1H-NMR-spektroskopische Analyse von 2-Chlor-1.3.2-dioxarsolan

The¹H-NMR-spectral data of 2-chloro-1.3.2-dioxarsolane are presented and discussed. The protons of the methylene groups form in concentrated solutions by rapide chlorine exchange anAAAA spin system. In dilute solutions the protons form anAABB spin system, which is changed to anAAAA system by addition of chlorine ions.The vicinal H–C–C–H-coupling constants indicate a twist-envelope conformation.

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Mit 1 Abbildung     

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].     

Mass spectral and thermogravimetric studies of some iron(III) binuclear complexes with bridging thiuram disulfide ligands

Mass spectral and thermal studies by TG and DTG of some iron(III) binuclear complexes of the general type Fe₂(R₂dtc)₂(tds)X₂X/ have been carried out to determine their modes of decomposition. Fragmentation patterns are given and possible mechanisms are discussed.

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Zusammenfassung Massenspektrometrische und thermische Untersuchungen (TG und DTG) einiger zweikerniger Eisen(III)-Komplexe des allgemeinen Typs (R₂dtc)₂(tds)X₂X₂ wurden ausgeführt, um deren Zersetzungsmechanismus zu ermitteln. Fragmentspektren werden angegeben und mögliche Mechanismen diskutiert.

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- ( ) Fe₂(R₂dtc)₂(tds)X₂X₂ . .

     

Solubilization of lanthanide ions by cyclodextrins in basic aqueous solutions

Cyclodextrins form complexes with lanthanide ions in basic aqueous solutions. This complex formation in basic solution dramatically enhances the solubility of lanthanide ions, which are otherwise insoluble due to the formation of hydroxide gels. Solutions of the -cyclodextrin-Ce³⁺ complex effectively hydrolyze 2-deoxyadenosine-5-monophosphate to 2-deoxyadenosine.     

Synthesis of 2,3,7,8-tetramethyldibenzofuran

3,4,3,4-Tetramethyldiphenyl ether readily forms 2,2-dihalo derivatives on bromination and iodination. Heating 2,2-diiodo-4,5,4,5-tetramethyldiphenyl ether with copper powder or oxidation, of 2,2-dilithio-4,5,4,5-tetramethyldiphenyl ether gives 2,3,7,8-tetramethyldibenzofuran, the structure of which was proved by alternative synthesis from 2,2-dinitroand 2,2-diamino-4,5,4,5-tetramethyldiphenyls.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 12, pp. 1597–1599, December, 1972.     

Calorimetric study of dinitrogen adsorption at 310 K on a chromia/silica catalyst

The energetics of dinitrogen adsorption on 310 K on a chromia catalyst has been investigated by adsorption calorimetry. Two types of heats have been detected and assigned to a least two different interactions with Cr^II sites of the catalyst.

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310 . , , - , Cr^II .

     

Kalorische Exzeßcharakteristik flüssiger Nichtelektrolyt-systeme

Zusammenfassung Die mittleren molaren Exzeßenthalpien der ternären Systeme Benzol /n-Heptan/n-Tetradecan, Benzol/n-Decan/n-Tetradecan und Benzol/Toluol/n-Tetradecan sowie die der korrespondierenden binären Systeme wurden titrationskalorimetrisch bei 298.15 K über den gesamten Molenbruchbereich bestimmt. Auf der Grundlage dieser experimentellen Ergebnisse sollte die Anwendbarkeit des Gruppenlösungsmodells von Ratcliff u.a. zur Vorausberechnung mittlerer molarer Exzeßenthalpien an ternären Gemischkombinationen getestet werden. Die Abweichung zwischen den gemessenen und inkrementell berechneten Mischungsenthapien lag bei den hier untersuchten Systemen im Bereich von 0 bis 12%.

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Via a titration calorimetric method the molar enthalpies of mixing for the three ternary systems benzene/n-heptane/n-tetradecane, benzene/n-decane/n-tetradecane and benzene/toluene/n-tetradecane, as well as for all of the corresponding binary systems, were measured over the whole range of mole fractions at 298.15 K. On the basis of the experimental results the applicability of the Group Solution Model, proposed by Ratcliff et al. for predictive calculations of heats of mixing, was tested for the treatment of ternary systems mentioned above.The differences between the measured and incrementally calculated heats of mixing were found to range from 0 to 12 %.

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Résumé Les enthalpies de mélange des trois systèmes ternaires benzène/n-heptane/n-tétradécane, benzène/n-décane/n-tétradécane et benzène/toluène/n-tétradécane ont été mesurées ainsi que celles des systèmes binaires correspondants, à 298.15 K dans le domaine complet des fractions molaires, par une méthode de titrage calorimétrique. En se fondant sur les résultats expérimentaux, on examine la possibilité d'appliquer aux systèmes ternaires, tels que ceux mentionnés ci-dessus, le modèle proposé par Ratcliff et al. pour prévoir les chaleurs de mélange. L'écart entre les chaleurs de mélanges mesurées et celles calculées par incréments varie de 0 à 12%.

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, /-/- , /-/- //- , 298,15 . , , . . 0 12%.

     

A new vicinal-dioxime and its mono and trinuclear complexes containing the monoazatetraoxa macrocyclic moiety

Mononuclear [Co(HL)2LCl)], [Co(LBF2)2LCl] or [Cu-(HL)2] H2L = {N,N-bis (4-N-phenylaza [15]crown-5)diaminoglyoxime} and a trinuclear, [Cu(L)2(CuL)2](NO3)2, complex of the ligand were synthesized and characterized. The mononuclear copper(II) species coordinates to two copper(II) ions through the deprotonated oximate oxygens to yield a trinuclear structure cis-bridged by the oximate groups, with 1,10-phenanthroline as an end-cap ligand. The terminal copper adopts an essentially planar configuration with the nitrogen atoms of H2L. The structure of the ligand and its complexes is proposed and formulated according to the elemental analyses, 1H- and 13C-n.m.r, i.r. and m.s. spectral data.     

Relation between the catalytic and acidic properties of zeolite catalysts

Influence of the strength and concentration of non protic centers on the catalytic activity of metal-zeolite catalysts in isomerization of n-butane has been studied. A relationship between the specific activity and the center strength is suggested.

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-. , .

     

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.     

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.     

Reactions of dichloro-bis-[N(1)-benzyl-2-(arylazo)imidazole] ruthenium(II) with tertiary phosphines

The title reaction proceeds smoothly in MeOH-H2O togive the salts [RuCl(P)L2](ClO4), H2O (1, 2) or [Ru(PP)L2](ClO4)2, H2O (3, 4) where L=N(1)-benzyl-2-(arylazo)imidazole, P=PPh3, or PPh2Me, and PP=Ph2P(CH2)2PPh2 (dppe) or Ph2P(CH2)3PPh2(dppp). The complexes have been characterised by physico-chemical and spectroscopic methods.     

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.     

Synthesis of 9-diazo-4-azafluorenes

Stable diazo compounds of the azafluorene series, viz., 9-diazo-4-azafluorenone and 1,3-diphenyl-4-azafluorene, were obtained from 4-azafluorenone and 1,3-diphenyl-4-azafluorene tosylhydrazones. 1,2-Dicarbomethoxyspiro(4-azafluorene-9,3-cyclopropane) was obtained from 4-azafluorenone tosylhydrazone, and 4,5-dicarbomethoxyspiro(4-azafluorene-9,3-pyrazolenine) was obtained from 9-diazo-4-azafluorene. It is assumed that the product in the latter case is obtained as a result of reaction of a carbene, viz., 4-azafluorenylidene carbene, which is formed from 9-diazo-4-fluorene, with dimethyl acetylenedicarboxylate.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 7, pp. 951–953, July, 1979.     

Synthesis of obtusinin and 7-(3′-hydroxymethylbut-2′-enyloxy)-6-methoxy-2H-1-benzopyran-2-one

Obtusinin (1) has been synthesised by the reaction of 6-methoxy-7-(3-methylbut-2-enyloxy)-2H-1-benzopyran-2-one (3) with OsO₄. Synthesis of 7-(3-hydroxymethylbut-2-enyloxy)-6-methoxy-2H-1-benzopyran-2-one (2) has been achieved by the regiospecific oxidation of3 with SeO₂ followed by reduction of the formed aldehyde with KBH₄.

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Synthese von Obtusinin und 7-(3-Hydroxymethylbut-2-enyloxy)-6-methoxy-2H-1-benzopyran-2-on

Zusammenfassung Obtusinin (1) wurde über 6-Methoxy-7-(3-methylbut-2-enyloxy)-2H-1-benzopyran-2-on (3) mit OsO₄ synthetisiert. Die Darstellung von 7-(3-Hydroxymethylbut-2-enyloxy)-6-methoxy-2H-1-benzopyran-2-on (2) wurde mittels regioselektiver Oxidation von3 mit SeO₂, gefolgt von Reduktion des gebildeten Aldehyds mit KBH₄, bewerkstelligt.

     

Investigations in the field of the chemistry of 2-hetarylbenzimidazoles. 6. Synthesis and properties of 1-methyl-2-(2′-selenienyl)benzimidazole

2-(2-Selenienyl)benzimidazole has been synthesized by a Weidenhagen reaction and converted into the N-methylated derivative. Electrophilic-substitution reactions (nitration, sulfonation, bromination, chloromethylation, and acylation) in the selenophene ring have been studied. It has been shown that the substituent enters the position of the selenophene ring in most cases. The bromination of 1-methyl-2-(2-selenienyl)benzimidazole in acetic acid produces the 3,5-dibromo derivative, whereas 1-methyl-5(or 6)-bromo-2-(3,5-dibromo-2-selenienyl)benzimidazole is obtained in polyphosphoric acid.For Report 5, see [1].Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 11, pp. 1531–1534, November, 1983.     

Coumarins of theLibanotis buchtormensis

Conclusions From the roots ofLibanotis buchtormensis (Fisch.) D.C. have been isolated the furocoumarins bergapten, isoimperatorin, a pyranocoumarin, xanthogallol, and a new coumarin buchtormin C₁₉H₂₀O₅, for which the structure (+)-3-(,-dimethylacryloxy)-2,2-dimethyl-3, 4-dihydropyrano-5, 6:8, 7-coumarin has been proposed and confirmed by synthesis.Khimiya Prirodnykh Soedinenii, Vol. 4, No. 3, pp. 145–149, 1968     

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.