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.     

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.     

Proanthocyanidins of Polygonum coriarium. I

Six proanthocyanidins have been isolated from the roots ofPolygonium coriarium. The structures of three oligomeric proanthocyanidins have been established: taranin, consisting of [epigallocatechin gallate]-(48)-[epigallocatechin gallate]-(48)-[epigallocatechin-(48)-epigallocatechin₂-(48)-epigallocatechin; taranoside A - [epigallocatechin gallate]-7-0-[-(16)--D-Glcp]₃-(48)-[epigallocatechin-(48)-epigallocatechin]₂-(48)-gallocatechin; and taranoside B - [epigallocatechin gallate]-7-O-[-(16)--D-Glcp]₄-(48)-[epigallocatechin-(48)-epigallocatechin]₂-(48)-epigallocatechin-(48)-[epigallocatechin gallate).Institute of the Chemistry of Plant Substances, Uzbekistan Republic Academy of Sciences, Tashkent. Translated from Khimiya Prirodnykh Soedinenii, No. 1, pp. 59–67, January–February, 1992     

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.     

New cardenolides from the seeds ofCoronilla hyrcana

Summary Four substances have been isolated from the seeds ofCoronilla hyrcana: hyrcanoside, deglucohyrcanoside, hyrcanogenin, and substance E.It has been established that hyrcanoside (I) has the structure 3-(O--D-xylopyranosyl- <4 1 > -O--D-glycopyranosyl)-14-hydroxy-19-oxocard-4, 20 (22)-dienolide; deglucohyrcanoside (VII) is 3-(O--D-xylopyranosyl)-14-hydroxy-19-oxocard-4, 20 (22)-dienolide; and hyrcanogenin (V) is 3, 14-dihydroxy-19-oxocard-4, 20 (22)-dienolide. Both the aglycone hycanogenin (V) and its glycosides (I) and (VII) are new compounds.Khimiya Prirodnykh Soedinenii, Vol. 2, No. 4, pp. 251–257, 1966     

Steroid glycosides from the starfish Crossaster papposus

Two new steroid glycosides have been isolated from an ethanolic extract of the starfishCrossaster papposus — crossasterosides P₁ and P₂. On the basis of chemical transformations and spectral characteristics, the structure of crossasteroside P₁ has been established as (24R)-24-ethyl-5-cholestane-3,6,8,15,16,29-hexaol 29-O-[2-O-methyl--D-xylopyranosyl-(1 2)--D-galactofuranoside]. Crossasteroside P₂ is its 4-hydroxy analogue.Pacific Ocean Institute of Bioorganic Chemistry, Far Eastern Branch, Academy of Sciences of the USSR, Vladivostok. Translated from Khimiya Prirodnykh Soedinenii, No. 5, pp. 669–673, September–October, 1989.     

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     

Unsaturated esters of N-(β-hydroxyethyl) lactams

A general method is developed for synthesizing methacrylic esters with a 5-, 6-, or 7-membered lactam ring to the carboxyl group, by reacting the sodio-derivatives of the lactams with -chloroethyl methacrylate. The esters synthesized are prone to thermal polymerization, and able to copolymerize with other monomers in the presence of azodiisobutyronitrile. The following copolymers are prepared; -(N-pyrrolidonyl) ethyl acrylate with methyl acrylate, -(N-pyrrolidonyl) ethyl, -(N-2-oxotetramethyleneimino) ethyl, and -(N-2-oxopentamethyleneimino) ethyl methacrylates withmethyl methacrylate.     

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.     

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.     

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.

---

-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).

     

Comparative basicities of substituted pyridines and electronegativity series for substituents in the pyridine series

Relationships between basicity of the pyridine ring and the nature and position of substituents are found. Comparative electronegativity series are constructed for substituents (, , and ) in the pyridine series. In isolated cases transmission of an effect from the position by a M effect is found.     

Synthesis of pyridine and quinoline derivatives of ferrocene from β-chloro-β-ferrocenylacrolein

2-Ferrocenylquinolines that contain a hydroxy or methoxy group in the 7 position were obtained by the reaction of -chloro--ferrocenylacrolein with m-anisidine and with m-aminophenol. The introduction of aniline in this reaction leads to the formation of -ferrocenyl--phenylaminoacrolein anil hydrochloride, which cannot be converted to 2-ferrocenylquinoline. 2,3,6-Trisubstituted pyridines that contain a ferrocenyl substituent in the 6 position were obtained by condensation of -chloro--ferrocenylacrolein with -dicarbonyl compounds.Deceased.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 10, pp. 1376–1378, October, 1981.     

Tripenoid glycosides of alfalfa. VII. Medicosides E and F

Two hederagenin glycosides — medicosides E and F — have been isolated from the roots ofMedicago sativa L. (Leguminosae). Medicoside E has the structure of hederagenin 28-O--D-glucopyranoside 3-O-[O--G-glucopyranosyl-(13)--D-xylopyranoside]. Medicoside F has the structure of hederagenin 28-O--D-glucopyranoside 3-O-[O--D-glucopyranosyl-(12)--L-arabinopyranoside].Institute of the Chemistry of Plant Substances, Academy of Sciences of the Republic of Uzbekistan, Tashkent. Institute of Organic Chemistry, Russian Academy of Sciences, Moscow. Translated from Khimiya Prirodnykh Soedinenii. No. 5, pp. 701–705, September–October, 1993.     

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).     

Synthesis of dihalopicoline N-oxides and their 4-nitro derivatives

Three aminohalo-substituted - and -picolines, six dihalo-substituted - and -picolines, six dihalo-substituted - and -picoline N-oxides and six respective dihalo-4-nitropicoline N-oxides were synthesized in excellent yields. Some properties of the products were reported.Academy of Economics, Department of Organic Chemistry, PL 53-423, Wroclaw. Published in Khimiya Geterotsiklicheskikh Soedinenii, No. 10, pp. 1366–1371, October, 1996. Original article submitted November 15, 1995.     

Phytoecdysteroids of Rhaponticum carthamoides. II. Rhapisterone B

A new ecdysteroid (rhapisterone B) has been isolated from the seeds ofRhaponticum cathamoides (Willd.) Iljin. (familyCompositae). It has been shown that it is 2, 3, 11, 14, 20R, 24-hexahydroxy-5-cholest-7-en-6-one.Institute of the Chemistry of Plant Substances, Uzbek Academy of Sciences, Tashkent. Translated from Khimiya Prirodnykh Soedinenii, No. 6, pp. 806–808, November–December, 1991.     

Steroids of the furostan and spirostan series from Nolina microcarpa II. structures of nolinospiroside D and nolinofurosides D, E, and F

Proofs are given of the structures of two new glycosides of the furostan series isolated from the leaves of the plantNolina microscarpa S. Wats. (family Dracaenaceae). Nolinofuroside D is (25S)-furost-5-ene-1,3,22,26-tetraol 1-O--D-galactopyranoside 26-O--D-glucopyranoside (I), and nolinofuroside F is (25S)-furost-5-ene-1,3,22,26-tetraol 1-O--D-fucopyranoside 26-O--D-glucopyranoside 3-O--L-rhamnopyranoside (VII). The latter was characterized as its 22-O-methyl ether (VIII). Nolinofuroside E (IV) has the structure of (25S)-furost-5-ene-1,3,22,26-tetraol 26-O--glucopyranoside 1-O-[O--L-rhamnopyranosyl-(12)--D-fucopyranoside], which followed from the structure of the fermentation product (VI). The products of the fermentation of the above-named compounds were present in the plant in only trace amounts. Only one of them — nolinospiroside D (III) — has not been described previously. This monoside of the spirostan series is (25S)-spirost-5-ene-1,3-diol 1-O--D-galactopyranoside.M. V. Frunze Simferopol' State University. Institute of Chemistry of Plant Substances, Uzbek Academy of Sciences, Tashkent. Translated from Khimiya Prirodnykh Soedinenii, No. 5, pp. 678–686, September–October, 1991.     

Excess enthalpies of aqueous solutions of small peptides at 25°C

Heats of dilution of aqueous solutions of the following di-and tripeptides were determined at 25°C over a wide concentration range: -alanyl-glycine, -alanyl--alanine, DL--alanyl-glycine, glycyl-DL--alanine, L--alanyl-L-alanine, DL--alanyl-DL--alanine, DL--alanyl-DL-valine, DL--alanyl--alanine, glycyl--aminobutyric acid, glycyl-L-leucine and DL--alanyl-glycylglycine. The excess enthalpies H^ex and partial molar relative enthalpies L₂ were calculated and enthalpy coefficients of intermolecular interaction were analysed using the additivity principle of Savage and Wood. The concentration dependence of the enthalpic characteristics of peptide-peptide interactions is discussed based on of their hydrophobicity and hydrophilicity. The three-stage model of peptide association is described using enthalpic coefficients of intermolecular interactions.