Complexation of Na-, Ca-, and Cu-montmorillonites with some parent and methylated cyclodextrins

The uptake of -, -, -, hexakis-2,6-di-O-methyl--(DM--), heptakis-2,6-di-O-methyl--(DM--) and heptakis-2,3,6-tri-O-methyl-- (TM--) cyclodextrins (CD's) by Na-, Ca-, and Cu-montmorillonites has been studied at 25°C. Each of -, DM--, DM--, and TM--CD's forms a complex with all of these montmorillonites in which the guest molecules are arranged as a monolayer with their open faces parallel to the silicate sheet of montmorillonite. On the other hand, -CD is intercalated only by the Na form and -CD cannot be taken up by any of the clays used. The interlayer spacing of the -CD complex varies from 18.0 to 21.5 Å with replacement of the interlayer cation, but those of the methylated -and -CD complexes remain unchanged, beingca. 21 and 18 Å, respectively. The different behaviour of the parent and methylated CD's is explained in terms of the structural and physicochemical characteristics of the individual CD's and interlayer cations.     

Synthesis of 4,5-Seco-Derivatives of Allobetulin

4,5-Seco-19,28-epoxy-18-olean-3,5-dione wasprepared by ozonation of 19,28-epoxy-18-olean-3(5)-ene. The structures of the synthesized compounds were confirmed using spectral data.     

Stereochemie von Metallocenen, 13. Mitt.: Optisch aktive Derivate des Methylcymantrens: Darstellung,Rotationsdispersion und konfigurative Korrelation

Zusammenfassung Optisch aktive Methylcymantren-- und--carbonsäuren wurden durch Racematspaltung ihrer Phenäthylaminsalze erhalten. Bei der Umwandlung in die entsprechenden Acetyl- bzw. Vinyl-methylcymantrene treten charakteristische Drehwertänderungen auf. Aus diesen, vor allem aber aus der Rotationsdispersion, ließ sich auf Grund von Konformationsanalysen und Vergleichen zwischen offenkettigen und cyclischen Verbindungen sowie mit analogen Methylferrocenderivaten für die -substituierten Produkte mit großer Sicherheit die absolute Konfiguration ableiten: (1S) für (+)-Methylcymantren--carbonsäure und ihre Folgeprodukte. Dieser Befund wurde durch kinetische Racematspaltung des Anhydrides der racem. Säure mit (–)--Phenäthylamin gestützt.

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Optically active methylcymantrene-- and--carboxylic acids were obtained by resolution of their salts with -phenethylamine. Upon transformation into the corresponding acetyl and vinyl methylcymantrenes, characteristic shifts of the optical rotation are observed. From these data, and especially from the rotatory dispersions, on the basis of conformational analyses and comparisons between open chain and cyclic compounds as well as with analogous methylferrocene derivatives, the absolute configurations of the -substituted products could be deduced with reasonable probability: (1S) for (+)-methylcymantrenecarboxylic acid and its subsequent products. This result was supported by kinetic resolution of the anhydride of the racemic carboxylic acid with (–)--phenethylamine.

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Mit 3 Abbildungen     

Investigations in the field of lipids

Summary 1. The synthesis of the following neutral plasmalogens has been effected: -O-(octadec-1-enyl)-, distearoylglycerol, -O-(octadec-1-enyl)-, -dipalmitoylglycerol, -O-(hexadec-1-enyl)-, -distearoylglycerol, and -O-(pentadec-1-enyl)-, -dipalmitoylglycerol.2. During the synthesis, the following compounds were isolated and characterized by their physicochemical constants: the -octadec-1-enyl ether of glycerol, -(2-hydroxyoctadecyl) , -isopropylideneglyceryl ether, the tosylate of -(2-hydroxyoctadecyl) , -isopropylideneglyceryl ether, and -O-(2-tosyloxyoctadecyl) glycerol.3. The IR spectra of the -octadec-1-enyl ether of glycerol and the neutral plasmalogens have been studied.Khimiya Prirodnykh Soedinenii, Vol. 2, No. 6, pp. 367–371, 1966     

Investigations in the field of complex lipids

Summary 1. The synthesis of L-(+)--oleoyl--linoleoyl--glycerylphosphorylethanolamine has been effected.2. During the investigations the following substances were isolated and characterized: L--oleoyl--glycerylphosphoryl-N-phthaloylethanolamine and L---linoleoyl--glycerylphosphoryl-N-phthanoylethanolamine.Khimiya Prirodnykh Soedinenii, Vol. 2, No. 2, pp. 80–83, 1966     

Détermination spectrophotométrique de l'analgène au moyen de chlorure de fer(III) et d'α,α'-dipyridyle

Résumé On a élaboré une méthode spectrophotométrique de détermination de l'analgène au moyen de chlorure de fer-III et de l',-dipyridyle. En milieu alcalin, l'analgène réduit le fer-III en fer-II. L',-dipyridyle forme avec le fer-II un composé complexe rouge vif. La densité optique de la solution analysée est proportionnelle à la concentration de l'analgène. On effectue les mesures à 520 nm. Dans l'analyse de 18 substances pharmaceutiques, la détermination de l'analgène fut gêne par le phénylbutazon (le rapport étant supérieur à 1 1) et par le pyramidon.

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Spectrophotometric determination of Analgene by means of iron(III) chloride and ,'-dipyridyl

Summary A spectrophotometric method of determining Analgene by means of iron(III) chloride and, dipyridyl has been worked out. The analgene (in alkaline medium) reduces the Fe(III) to Fe(II). The,-dipyridyl produces a bright red complex compound with Fe(II). The optical density of the solution being analyzed is proportional to the concentration of the analgene. The measurement is made at 520 nm. In 18 pharmaceutical preparations, the determination of the analgene was impaired by phenylbutazone (ratio above 1 1) and by pyramidon.

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Zusammenfassung Eine spektrophotometrische Methode zur Bestimmung von Anaigen [1-Phenyl-2,3-dimethyl-4-(N-methyl-N-methansulfonsäure)-5-pyrazolon] mit Hilfe von Eisen(III)-chlorid und,-Dipyridyl wurde ausgearbeitet. In alkalischem Milieu reduziert Anaigen das Eisen zur zweiwertigen Stufe; dieses bildet dann mit,-Dipyridyl einen lebhaft rot gefärbten Komplex. Die Farbintensität ist der Konzentration proportional. Sie wird bei 520 nm gemessen. Unter 18 geprüften pharmazeutischen Substanzen wird die Reaktion von überschüssigem Phenylbutazon sowie von Pyramidon gestört.

     

Condensation of 2-(1-ethoxyvinyl)oxiranes with sodiomalonic ester and decarboxylation of the reaction products obtained

-(1-Ethoxyvinyl)- and -(1-ethoxyvinyl)--ethoxycarbonyl--butyrolactones were obtained by the reaction of 2-(1-ethoxyvinyl)oxiranes with sodiomalonic ester. Decarboxylation of the -(1-ethoxyvinyl)--ethoxycarbonyl-butyrolactones in DMSO leads to -(1-ethoxyvinyl)--butyrolactones, the hydrolysis of which gives -acetyl-butyrolactones. Ethyl trans-3-acetyl-3-pentenoate was obtained by decarboxylation of -methyl--(1-ethoxyvinyl)--ethoxycarbonyl--butyrolactone in DMSO.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 1, pp. 22–25, January, 1992.     

Triterpene glycosides ofCauliphyllum robustum. The structures of caulosides B and C

Summary Two triterpene glycosides — caulosides b and c — have been isolated from a methanolic extract of the leaves ofCaulophyllum robustum maxim. Cauloside b has been identified as hederagenin 3--L-rhamnopyranosyl-(12)--L-arabinopyranoside, while cauloside c has the structure of hederagenin 3-0--L-arabinopyranosyl(13)--L-pyranosyl-(12)--L-arabinopyranoside.Pacific Ocean Institute of Bioorganic Chemistry, Far Eastern Scientific Center of the Academy of Sciences of the USSR, Vladivostok. Translated from Khimiya Prirodnykh Soedinenii, No. 2, pp. 174–176, March–April, 1979.     

Synthesis of substituted hydroxypyrazines

Conclusions A new method was developed for the synthesis of substituted hydroxypyrazine derivatives by reacting the hydrochlorides of-amino ketones with the acid chlorides of N-phthaloyl--amino acids in acetone in the presence of diethylaniline, and subsequent treatment of the intermediate N-(N-phthaloyl--aminoacyl)--amino ketones with aqueous sodium acetate solution at 100°.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 10, pp. 2417–2421, October, 1978.     

Steroid glycosides of the seeds ofNicotiana tabacum. II. The structures of nicotianosides C and F

From the seeds of tobacco Nicotiana tabacumL. we have isolated two new steroid glycosides, nicotianosidesC andF. The structures of the glycosides have been shown on the basis of chemical transformations and spectral characteristics. Nicotianoside C is a steroid glycoside of the spirostan series and has the structure of (25S)-5-spirostan-3ß-ol3-O-[-L-rhamnopyranosyl-(1 2)]-[-L-rhamnopyranosyl-(1 4)]-ß-Dglucopyranoside), and nicotianoside F is (25S)-5 furostan-3ß, 22, 26-triol 3-O-[-L-rhamnopyranosyl-(1 2)1-[-L-rhamnopyranosyl-(1 4)1-ß D-glucopyranoside) 26-O-ß-D-glucopyranoside.Institute of Genetics, Academy of Sciences of the Republic of Moldova, 277022, Kishinev, ul. Pédurilor, 20. Translated Khimiya Prirodnykh Soedinenii, No. 3, pp. 396–401, May–June, 1995. Original article submitted August 29, 1994.     

Preparation and thermoanalytic studies of yttrium poly(acrylate)

A new process for the production of advanced ceramic powders has been studied. The process involves the chelation of a metal ion in solution by an organic acid polymer. Using FTIR, TG, DTG and DTA, the process for the formation of the organo-metallic complex and the decomposition to the metal oxide is reported. Effects of packing density on DTA are also discussed.

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Zusammenfassung Ein neues Verfahren zur Herstellung von Keramikpulvern wurde untersucht. Das Verfahren beinhaltet die Chelatisierung eines in Lösung befindlichen Metallions mittels einer polymeren organischen Säure. Unter Zuhilfenahme von FTIR, TG, DTG und DTA wurde der Vorgang der organometallischen Komplexbildung und der Zersetzung zu Metalloxid beschrieben. Der Einfluss der Packungsdichte auf die DTA wird ebenfalls beschrieben.

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, - . - , , , - . .

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The authors would like to acknowledge the BF Goodrich Co. for supplying the polyacrylic acid used in this study. Rong Sheng Zhou is also acknowledged for his assistance using the GRAFIT plotting program.     

Mass spectrometric study of monoalkyl-substituted thiacyclanes

Monosubstituted - and -alkylthiophans and -, -, and -alkylthiacyclohexanes were subjected to a comparative mass spectrometric study. The stability of the M⁺ ion increases on passing from - to -alkylthiophans and from - to - and -alkylthiacyclohexanes. In the case of -alkylthiophans and - and -alkylthia-cyclohexanes the principal process is associated with ejection of the substituent as a whole, whereas a portion of the alkyl substituent, with retention of one CH₂ group in the composition of the charged fragment, is eliminated from the molecular ions of -alkylthiophans and -alkylthiacyclohexanes.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 2, pp. 176–181, February, 1978.     

Di and monocarbonyl complexes of rhodium(I) containing singly charged bidentate ligands

Summary A series of neutral square planar rhodium(I) dicarbonyls containing singly charged bidentate ligands (salicylaldoxime, -benzoinoxime, -furildioxime, -benzildioxime, dimethylglyoxime, cupferron) has been prepared from three sources: (i) tetracarbonyl--dichlorodirhodium(I), (ii) solutions of hydrated rhodium chloride in DMF held under reflux and (iii) a carbonylated solution of hydrated rhodium chloride in boiling absolute alcohol. These dicarbonyls react with triphenylphosphine,-arsine and -stibine to yield monocarbonyl derivatives. The monocarbonyls form 1 : 1 adducts with TCNE. All complexes have been characterized by elemental analysis, i.r. and uv-visible spectra.     

Influence of carbon dioxide and carbon monoxide on the kinetics of propylene polymerization

Retardation effect of the carbon oxides on propylene polymerization, catalyzed by the TiCl₃/AlEt₂Cl system, can be described in terms of a Langmuir type equation as selective adsorption of the carbon oxides on the polymerization sites.

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, TiCl₃/AlEt₂Cl, , .

     

Triterpene glycosides ofHedera canariensis. I. Structures of glycosides L-A,L-B1, L-B2, L-C,L-D,L-E1 1, L-G1, L-G2, L-G3, L-G4, L-H1, L-H2, AND L-I1 from the leaves ofHedera canariensis

From the leaves of Algerian ivyHedera canariensis Willd. (fam. Aralaceae) we have isolated 13 triterpene glycosides: the 3-O--L-arabinopyranosides of oleanolic acid (A), of echinocystic acid (B₁), and of hederagenin (B₂); the 3-O-[O--L-rhamnopyranosyl-(2)--L-arabinopyranoside]s of oleanolic acid (C), of echinocystic acid (D), and of hederagenin (E₁); the 3-O--L-rhamnopyranoside] 28-O-[O--L-rhamnopyranosyl-(14)--gentiobioside of hederagenin (G₁); the 3-O-[O--L-rhamnopyranosyl-(12)--L-arabinopyranoside] 28-O--gentiobioside of hederagenin (G3); the 3-O-[O--L-rhamnopyranosyl-(12)--L-arabinopyranoside] 28-O-[O--L-rhamnopyranosyl-(14)--gentiobioside]s of oleanolic acid (G₂), of echinocystic acid (H₁), and of hederagenin (H₂); the 3-O-[O--L-rhanmopyranosyl-(12)--D-glucopyranoside] 28-O-(O--L-rhamno-pyranosyl-(14)--gentiobioside] of hederagenin (H₂); and the 3-O-(O--L-rhamnopyranosyl-(12)-O-gentiobiosyl)-O-(14)--L-rhamnopyranosyl-(12)-a-L-arabinopyranoside] of hederagenin (G₄). The structures of the substances isolated have been established on the basis of chemical transformations and¹³C NMR spectroscopy.Translated from Khimiya Prirodnykh Soedinenii, No. 3, pp. 377–383, May–June, 1996. Original article submitted December 3, 1995.     

Lactam and acid amide acetals. 64. Acylation of enamino ketones of the indolin-3-one and 2-pyrrolin-4-one series and synthesis of 2-indolyl- and 5-pyrrolylacrylic acid derivatives

The reaction of 2-(N,N-dimethylaminomethylene)indolin-3-one and 2-methyl-3-ethoxycarbonyl-5-(N,N-dimethyl aminomethylene)-2-pyrrolin-4-one with acyl halides was used to synthesize immonium salts, the aqueous hydrolysis of which leads to 2-formyl-3-hydroxyindole and 4-hydroxy-5 formylpyrrole derivatives. -Cyano--(2-indolyl)- and -cyano--(5-pyrrolyl)acrylic acid derivatives were synthesized by reaction of immonium salts of the pyrrole series, 4 acyloxy-5-formylpyrrole and 2-formyl-3-acyloxyindole derivatives, with compounds that contain an active methylene group.See [1] for Communication 63.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 3, pp. 343–348, March, 1991.     

Formation of Supramolecular Polymers Constructed by Cyclodextrins with Cinnamamide

-Cyclodextrin having cinnamamide at 6- or 3-positions (6-CiNH--CD, 3-CiNH--CD) and -cyclodextrin with cinnamamide on 6-position (6-CiNH--CD) have been prepared. Supramolecular structures were formed in the solid state or aqueous solutions and characterized by measurements of NMR and vapor pressure osmometry (VPO). The results indicate that 6-CiNH--CD formed insoluble supramolecular polymers in the solid state, while 6-CiNH--CD and 3-CiNH--CD formed supramolecular complexes in aqueous solutions. 6-CiNH--CD was found to form a dimer in an aqueous solution. 3-CiNH--CD formed intermolecular complexes to give supramolecular polymers. The differences of the position of guest part on cyclodextrins caused to give a variety of supramolecular structures in aqueous solutions.     

Synthesis and transformations of the 20-substituted derivatives of 16α,17α-epoxy-5α-pregnane-3Β,21-diol-20-ones

A new and more effective sequence of reactions is proposed for the production of 16,17-isopropylidenedioxy-5-pregnane-3,21-diol-20-one. It uses methods previously unused for 5-H-steroids and involves 21-hydroxylation of 16,17-epoxy-5-pregnan-3-ol-20-one with diacetoxyiodobenzene and cis-opening of the obtained 21-hydroxy-16,17-epoxy-5-pregnane-3,21-diol-20-one by acetic acid in the presence of epoxycarbonylhydrazine, followed by condensation of the obtained product with acetone.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 5, pp. 1185–1188, May, 1991.     

<Superscript>1</Superscript>H and <Superscript>13</Superscript>C NMR spectra of some drimanic sesquiterpenoids

One- and two-dimensional homo- and heteronuclear correlation proton, carbon, proton—proton, and proton—carbon NMR spectra of fifteen drimanic sesquiterpenoids: 11,12-dibromodrima-5,8-dien-7-one, drim-8-en-7-one, 11-hydroxydrim-8-en-7-one, 11,12-dihydroxydrim-8-en-7-one, 11-hydroxy-11,12-epoxydrim-8-en-7-one, 11-hydroxy-11,12-epoxydrim-8-en-7-one, 8,9-epoxydriman-7-one, 8,9-epoxydriman-7-ol, 11,12-diacetoxydrim-8-en-7-ol, drimane-7,8,11-triol, 7,8-isopropylidenedioxydriman-11-al, 9, 11-dihydroxydrim-7-en-6-one, drimane-7,8,9-triol, drimane-7,8,11-triol, and drim-8-ene-7,11,12-triol were studied. The proton and carbon chemical shifts were assigned.__________Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 12, pp. 2589–2594, December, 2004.     

Synthesis and Investigation of Ring-chain Isomerism of the Derivatives of N-Amino-5-hydroxy-1,2,3-triazole-4-carboxylic Acid

A series of sodium salts of 4-substituted 1-amino-5-hydroxy-1,2,3-triazoles was obtained by the diazo transfer reaction to arylmethylene-protected -ethoxycarbonyl- and -(methylcarbamoyl)-acetohydrazides. In DMSO solution the corresponding neutral hydroxytriazoles exist in equilibrium with the isomeric diazo compounds with an open chain. Electron-donating substituents stabilize the cyclic form. A good correlation was obtained between the equilibrium constants and the Hammett -constants. During the diazotization of benzaldehyde -amino--cyanoacetylhydrazone the initially formed diazo compound undergoes spontaneous cyclization in solution to hydroxytriazole. Removal of the arylmethylene protection leads to N-unsubstituted sodium salts of 1-amino-5-hydroxytriazoles, but acidification of the latter leads to diazoacetohydrazides with an open chain.