Effect of preparation method of nickel-zeolite catalysts on their catalytic properties

The effect of the carrier-gas (H₂, N₂, CO₂ and air) and the influence of additives (H₂S and water vapors) in the activation of Ni- and Cr-containing zeolites on their catalytic activity have been studied in toluene disproportionation.

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- (H₂, N₂, CO₂ ) (H₂S ) , Ni Cr, .

     

The triterpene glycosides ofpatrinia intermedia roem et schult

Conclusions It has been established that patrinoside D₁ is the -D-glucopyranosido(13) -D-xylopyranosido(12) -L-rhamnosido(14)--D-xylopyranoside (13) of oleanolic acidKhimiya Prirodnykh Soedinenii, Vol. 5, No. 2, pp. 84–89, 1969     

Complexation of the Non-steroidal Anti-inflammatory Drug Loxoprofen with Modified and Unmodified β-Cyclodextrins

The inclusion complex of the anti-inflammatory drug, loxoprofen, with -cyclodextrin-(CD), sulfated -CD, and glycerol ether -CD was studied by UV-VIS absorption and ¹H-NMR spectroscopy in solution. The inclusion complex of loxoprofen with -CDs was prepared by freeze-drying, and then characterized in the solid state by thermal analysis, X-ray diffraction, FT-IR and FT-Raman spectroscopy, and scanning electron microscopy (SEM). Furthermore, a physical mixture of loxoprofen/-CD (1/1, mol-%) in the solid state was also characterized. The solubility of the loxoprofen increased on addition of -CDs. The solubility enhancement of the loxoprofen with -CDs is in the following order: glycerol ether -CD > sulfated -CD > -CD.     

Cardenolides of the seeds ofCoronilla glauca and ofC. scorpioides. New glycosides alloglaucoside and scorpiosidol

Two new glycosides have been isolated from the seeds ofCoronilla glauca L. and C. scorpioides Koch: 3-(0-D-glucopyranosyloxy)-14. 15-dihydroxy-19-oxo-5-card-20(22)-enolide (alloglaucoside) and 3-(-D-gluco-ucofuranosyloxy)-5,14,19-trihydroxy-5-card-20(22)-enolide (scorpiosidol), together with a glycoside previously unknown for theCoronilla genus — 3-(-D-glucopyranosylo)g)-14-hydroxy-5-card-20(22)-enolide (desglucouzarin) and known aglycons (corotoxigenin, alloglaucotoxigenin, coroglaucigenin) and glycosides (glucocorotoxigenin, coronillobioside, glucocoroglaucigenin, coronillobiosidol and scorpioside).Ukraine Pharmaceutical Academy, Kharkov–2. Translated from Khimiya Prirodnykh Soedinenii, No. 3, pp. 372–376, May–June, 1996. Original article submitted August 14, 1995.     

1-Aryl-6-azauracile, 5. Mitt.: Die Synthese von 1-(β-Pyridyl)-6-azauracil-5-carbonsäure und einiger ihrer Derivate

Zusammenfassung Analog wie in vorherigen Mitteilungen^1–4 wurden -Pyridyl-hydrazono-cyanacetylcarbamidsäureäthylester (1), 1-(-Pyridyl)-5-cyan-6-azauracil (2), 1-(-Pyridyl)-6-azauracil-5-carbonsäure (3), deren Thioamid (4), und Amidoxim (5), welches in 1-(-Pyridyl)-5-[5-methyl-1,2,4-oxdiazolyl(3)]-6-azauracil (6) überge-führt wurde, hergestellt.

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-Pyridylhydrazono-cyanacetylcarbamic acid ethyl ester (1), l-(-pyridyl)-5-cyano-6-azauracil (2), 1-(-pyridyl)-6-azauracil-5-carboxylic acid (3), its thioamide (4) and amidoxime (5) were prepared as described in preceding communications. (5) was converted into l-(-pyridyl)-5-[5-methyl-1,2,4-oxdiazolyl(3)]-6-azauracil (6).

     

Transformations of solasodine

Solasodine (I) has been subjected to a number of transformations. The following compounds have been obtained from it by described procedures: 3-acetoxypregna-5,16-dien-20-one (II), 3-acetoxypregn-5-en-20-ol (III), and 3-acetoxypregn-5-en-20-ol (IV). The oxidation of (III) and (IV), the formation of an oxime, and the reduction of the oxime with sodium in ethanol, followed by Hess methylation, has led to 20-dimethylaminopregn-5-en-3-ol (IX) and to 20-dimethylaminopregn-5-en-3-ol (X). From compounds (IX) and (X), by analogy with (III) and (IV) by their oxidation and the preparation of oximes, which were then reduced and methylated, the following were obtained: 3,20-bisdimethylaminopregnane (XVII) and 3,20-bisdimethylaminopregnane (XVIII), and also quaternary salts of the latter.Institute of the Chemistry of Plant Substances, Academy of Sciences of the Uzbek SSR, Tashkent. Translated from Khimiya Prirodnykh Soedinenii, No. 3, pp. 370–374, May–June, 1980.     

Effects of Cyclodextrins on Deodoration of ``Aging Odor'

Hexenal, octenal and nonenal are known causes of unpleasant body odor and are present at markedly increased levels in the middle-aged and elderly. The odor of such unsaturated aldehydes is therefore called ``aging odor'. The present study investigated the effects of cyclodextrins (CDs) on deodoration of crotonaldehyde, pentenal, hexenal, heptenal, octenal, nonenal, decenal, undecenal and dodecenal. -, - and -CD formed inclusion complexes with the majority of unsaturated aldehydes in aqueous solution. The -CD inclusion complex contained the highest amount of guest molecule. One molecule of -CD was estimated to include 1 molecule of short chain aldehyde and 2 molecules of long chain aldehyde. Deodorant testing was conducted by headspace gas analysis using sealed vials. All CDs decreased the concentrations of unsaturated aldehyde. With nonenal, the deodorant power of parent CDs was -CD > -CD > -CD, and that of chemically modified CD was Me-CD > HP-CD > G2-CD > MCT-CD. CDs were demonstrated to reduce ``aging odor'. Me-CD was the most effective type of CD for the deodoration of ``aging odor'.     

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.     

Structure of psolusoside B — A nonholostane triterpene glycoside of the holothurian genus Psolus

The structure of psolusoside B — a minor triterpene oligoglycoside from the holothurianPsolus fabricii and the main glycoside fromPsolus sp. has been determined by the methods of partial acid hydrolysis, methylation,¹³C NMR, and FAB mass spectrometry as 20S-acetoxy-3-{2-O-[O--D-glucopyranosyl-(1 4)-O--D-glucopyranosyl]-4-O-(6-O-sulfato--D-glucopyranosyl)--D-xylo-pyranosyloxy}holosta-7,25-diene-18,16-carbolactone. 3-[O-(3-O-Methyl-6-O-sulfato--D-glucopyranosyl)-(1 3)-O-(6-O-sulfato--D-glucopyranosyl)-(1 4)-O--D-quinovopyranosyl-(12)--D-xylopyranosyloxy]holosta-9(11),25-dien-16-one (psolusoside A), known previously forPsolus fabricii, has been identified in a holothurian —Psolus sp. — from Kraternaya Bay (island of Ushishir).Pacific Ocean Institute of Bioorganic Chemistry, Far Eastern Branch, Academy of Sciences of the USSR, Vladivostok. Translated from Khimiya Prirodnykh Soedinenii, No. 3, pp. 361–368, May–June, 1989.     

Determination of the Association Constant of 6-Thiopurine and Chitosan Grafted β-Cyclodextrin

The equilibrium constants (K) for the inclusion complex formationof -cyclodextrin (-CD) with Methyl Orange (MO) and substituted azoanilinium chlorides were determinedspectrophotometrically. Based on the results, the substituent effecton the inclusion complexation of -CD with azoanilinium chlorides was discussed indetail. Further, the solvent effects on the inclusion complexation of MO with -CD andheptakis(2,6-di-O-methyl)--cyclodextrin (DM--CD) wereexamined in aqueous organic mixtures with water-miscible organic compounds(dimethylsulfoxide, acetonitrile, N,N-dimethylformamide, and acetone). It was found that the K value for the inclusion complexformation with -CD and DM--CD decreases remarkably with increasing ratioof organic solvents, dependent of the surface tension of solvent mixtures.     

Improvement of Solubility and Dissolution of 19-Norprogesterone via Inclusion Complexation

In an effort to modify the solubility and dissolution rate of the contraceptive steroid, 19-norprogesterone in order to improve its bioavailability, the cyclodextrin complexation approach was chosen. In solution, the complex formation with -cyclodextrin (-CD), hydroxyethyl -cyclodextrin (HE--CD) and hydroxypropyl -cyclodextrin (HP--CD) was confirmed by using solubility, UV, IR and ¹H-NMR spectrophotometric techniques. The phase solubility diagrams were categorized as A_L-type. The complexing affinity of the CDs investigated were ranked as follows: -CD > HP--CD > HE--CD. The complexation thermodynamic parameters were obtained from the temperature dependence of the dissociation constants. In the solid state, differential scanning calorimetery (DSC) and optical microscopy methods were utilized to characterize the complexes. Dissolution studies showed that such molecularly encapsulated forms offered a marked improvement in the dissolution rate compared to the parent drug.     

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.     

Rearrangement ofα -trifluoromethyl-β-dialkylamino-β-fluoroacrylic acid N.N-dialkylamides

Conclusions When heated in the presence of a catalytic amount of BF₃ etherate,-trifluoromethyl--diethylamino--fluoroacrylic acid N, N-dimethylamide is reversibly isomerized to-trifluoromethyl--dimethylamino--fluoroacrylic acid N, N-diethylamide. The methyl esters of-trifluoromethyl--diethylammo--fluoroacrylic acid and-trifluoromethyl--phenoxy--fluoroacrylic acid N,N-dimethylamide are not isomerized under the same conditions.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No.1, pp.137–141, January, 1976.     

Enantiomer separations with chromatographic supports based on β-cyclodextrin polymers immobilized on porous silica. Role of the polymer structure in separating ability

Summary Two -cyclodextrin (-CD)-containing polymers have been prepared either by condensation of -CD molecules with a bifunctional reagent or by grafting a -CD derivative on to a linear polymer (polyvinylimidazole). HPLC stationary phases were obtained by adsorption of the -CD polymers on to silica. The ability of these chromatographic supports to resolve racemic mixtures of organic compounds such as amino acid derivatives, phenylhydantoins, barbiturates, and hydroxycoumarin derivatives has been investigated. Results were found to depend on the chemical structure of the -CD polymers     

The reaction of hypophosphorous acid with chloral

Conclusions The condensation of chloral with hypophosphorous acid has given,,-triebloro--hydroxyethyl phosphonous and bis-(, ,-trichloro--hydroxyethyl)-phosphinic acids.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 6, p. 1095, June, 1966.     

<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.     

Indole derivatives

The synthesis of -lactams containing an indole ring was accomplished by the reaction of acyl chlorides with Schiff bases in the presence of triethylamine. 3-Indolylacetyl chloride reacts with benzylideneaniline to give a mixture of cis- and trans--lactams. Schiff bases obtained from N-substituted indole-3-aldehyde and aniline derivatives form phthalimido--lactams by reaction with phthalimidoacetyl chloride, while the azomethines of indole-3-aldehyde itself are acylated at the NH group under these conditions. Hydrazinolysis of the phthalimido--lactams gives amino--lactams. The reaction of 3-[-(benzylideneamino) ethyl]indole and phthalimidoacetyl chloride leads to a -lactam and a carboline derivative, the yields of which depend on the order of addition of the reacting compounds. The configurations of the -lactams were established from the NMR data.See [18] for Communication LIX.Translated from Khimiya Geterotsikliches kikh Soedinenii, No. 12, pp. 1626–1630, December, 1970.The authors sincerely thank K. F. Turchin for interpreting the NMR spectra.     

Über einige β,β,β-Trichlor-α-[dichlor-phenyl]-äthanole

Zusammenfassung Unter Verwendung derGrignardschen Reaktion wurden aus 2,4-, 2,5-und 3,4-Dichlor-jodbenzol und Chloral die entsprechenden ,,-Trichlor--[dichlor-phenyl]-äthanole synthetisiert und als Acetate charakterisiert. Das ,,-Trichlor--[3,4-dichlor-phenyl]-äthanol (IV) läßt sich schneller und in besserer Ausbeute aus dem Produkt der Umsetzung von o-Dichlorbenzol mit Chloral in Gegenwart von Aluminiumchlorid isolieren. IV besitzt insektizide Wirksamkeit (Testtiere: Drosophila melanogaster, Blatta orientalis, Phyllodromia germanica, Calandra granaria, Acanthoscelides obtectus, Musca domestica).     

The effects of cyclodextrin inclusion of the ferrocenemonocarboxylate anion on the kinetics of its oxidation by bis(pyridine-2,6-dicarboxylato)cobaltate(III) in aqueous solution

The effects of -, -, dm-(heptakis(2,6-di-O-methyl)--) and -cyclodextrins (CD) on the kinetics of the electron-transfer reaction of the ferrocenemonocarboxylate anion (FCA^–) with bis(pyridine-2,6-dicarboxylato)cobaltate(III) have been investigated in aqueous solution (0.20 M Na₂HPO₄, pH 9.2) at 25.0°C. Substantial decreases in the rate constants for the electron-transfer reactions were observed upon cyclodextrin inclusion of the reductant, due to an increase in the FCA^0/– reduction potential and to the insulation of the reductant from oxidant. The inclusion stability constants for {FCA·CD}^– were evaluated from the¹H NMR and kinetic data, and the order of the stability constants was found to be -CDdm-CD-CD>-CD.     

Condensation of aldehydes and ketones

The alkaline condensation of -aceto-and -propionaphthalenes with furfural has given, respectively, 2-(-furfuryl)-1, 3-di(-naphthoyl)-propane and 3-(-furyl)-2,4-di(-naphthoyl)pentane; both -diketones have also been obtained by the Michael condensation. Under more severe conditions, two molecules of furfural condense with three molecules of -acetonaphthalene to form 2, 4-di(-furyl)-1, 3, 5-tri(-naphthoyl)pentane. Under similar conditions, benzaldehyde exhibits only a feeble capacity for triketone condensation with -acetonaphthalene. The condensation of -propionaphthalene with furfural has given the new compound furylidenepropionaphthalene. It has been shown that both under the conditions of the improved Chichibabin pyridine synthesis and under the conditions of the Leuckhardt reaction, 3-(-furyl)-1, 3-di(-naphthoyl)propane gives 4-(-furyl)-2, 6-di(-naphthyl)pyridine.