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.     

Isoflavones of the roots of Lupinus luteus

Conclusions For the first time in the isoflavone series, a compound which has the structure of 5,7-dihydroxy-3,4-methylenedioxyisoflavone (3,4-methylenedioxyorobol) and two of its glucosides — 3,4-methylenedioxyorobol 7-O--D-glucoside and 3,4-methylenedioxyorobol 7-O--D-glucosylglucoside — and also a genistein C-monoglucoside, have been described. The isoflavones were isolated from the roots ofLupinus luteus L. by preparative chromatography on paper and on columns of polyamide. In addition, the previously known genistein, genistein 7-O--D-glucoside (genistin), and genistein 7-O--D-glucosylglucoside have been obtained.V. F. Kuprevich Institute of Experimental Botany, Academy of Sciences of the Belorussian SSR. Translated from Khimiya Prirodnykh Soedinenii, No. 2, pp. 162–166, March–April, 1974.     

Octahedral and tetrahedral configuration changes of nickel(II) chloro complexes from spectrophotometric studies in aprotic solvents

Four NiII chloro complexes were identified spectrophotometrically in aprotic media such as DMSO, DMF and propylene carbonate for the first time. An original multiwavelength numerical treatment, based on a Marquardt method, results in the determination of the individual electronic spectra of the mononuclear chloro complexes and of their stability constants, the values of which indicate the presence of rather weak complexes in DMSO and DMF, much stronger in the less solvating propylene carbonate solvent. The overall stability constants calculated for the NiII chloro complexes are: 1=52, 2=140, 3=160, 4=210 in DMSO, 1=60, 2=110, 3=900, 4=15000 in DMF, 1=1.6×109, 2=6.4×1015, 3=2.7×1021, 4= 5.1×1026 in PC.The solvent effect is discussed in terms of the quantitative results obtained from this spectrophotometric study and reveals that the stability of the complexes is an inverse function of the donor properties of the solvent. This result illustrates the general behavior of complex formation in dipolar aprotic solvents, i.e. the substitution of one solvent molecule in the inner coordination sphere by the ligand is easier if the solvation strength of the solvent is lower. The solvent effect is also described in terms of the variation of shifts of the calculated absorption maxima for the individual electronic spectra of the chloro complexes. This result is used to identify clearly at which step of coordination the octahedral configuration of the nickel ion changes to the tetrahedral configuration, by comparison with the well-known structural properties of these complexes in the solid state.     

New polyhydroxysteroids from the far-eastern starfish Henricia sp.

From the far-eastern starfishHenricia sp. we have isolated and characterized the new polyhydroxysteroid (24S)-5-cholestane-3,4,6,8,15,24-hexaol and three new glycosides: (24S)-5-cholestane-3,4,6,8,15,24-hexaol 3-O-(2,4-di-O-methyl--D-xylopyranoside) (henricioside H₁), 24-methyl-5-cholesta-4,22E-diene-3,6,8,15,16,26-hexaol 3-O-(2,3-di-O-methyl--D-xylopyranoside) (henricioside H₂), and the 22,23-dihydro derivative of henricioside H₂ (henricioside H₃).Pacific Ocean Institute of Bioorganic Chemistry, Far-Eastern Scientific Center, Russian Academy of Sciences, Vladivostok. Translated from Khimiya Prirodnykh Soedinenii, No. 2, pp. 249–253, March–April, 1993.     

Hydrogenation of ethylene and propylene over MgO doped with alkali metals

The hydrogenation of ethylene and propylene over MgO doped with alkali metal vapors has been studied. All the catalysts examined are active in hydrogenation at 150 °C at atmospheric pressure. It is proposed that the catalytic activity of the systems investigated is connected with strong one-electron donor surface sites.

---

MgO . 150°C . , .

     

Über Heterocyclen, 15. Mitt.

Zusammenfassung Bei der Umsetzung von Vinylphenylketonen mit Harnstoffen oder Thioharnstoffen entstehen 2-Oxo- bzw. 2-Thionotetrahydropyrimidine und 2-Oxo- bzw. 2-Thiono-5-(-benzoyläthyl)-6-phenyltetrahydropyrimidine; -Benzoyläthyldimethylamin und analoge Basen geben mit Thioharnstoffen nur 5--Benzoyläthylderivate. 2-Oxo- und 2-Thiono-6-phenyltetrahydropyrimidine sind in der Kernstelle 5 alkylierbar brw. aminoalkylierbar.

---

Vinyl phenyl ketones react with ureas or thioureas to 2-oxo-or 2-thionotetrahydropyrimidines and 2-oxo- or 2-thiono-5-(-benzoylethyl)-6-phenyltetrahydropyrimidines; -benzoylethyldimethylamines and analogous compounds give with thiocarbamides 5--benzoylethyl derivates. 2-oxo- and 2-thiono-6-phenyltetrahydropyrimidines react with 1-phenyl-2-propene-1-ones, -benzoylethylamines resp. formaldehyde and amines to 5-alkyl products.

     

Chemical modification of furanoeremophilan-14β,6α-olide

On performing the modification of furanoeremophilan-14,6-olide at the most reactive fragments of the molecule, the lactone and furan rings, it was established that in an alkaline medium furanoeremophilan-14,6-olide isomerizes into the 14,6-olide; the oxidation of furanoeremophilan-14,6-olide to a dilactone in the presence of Rose Bengal takes place with high yield under mild conditions — atmospheric oxygen, without heating and irradiation; on the interaction of furanoeremophilan-14,6-olide with selenium dioxide in glacial acetic acid a selenium-containing dimer is formed.Institute of Chemical Sciences of the Kazakh SSR Academy of Sciences, Alma-Ata. Translated from Khimiya Prirodnykh Soedinenii, No. 2, pp. 189–193, March–April, 1989.     

Photochemistry of Some Codeinones and Morphinones

Irradiation of 5-benzyl-, 5-methoxymethyl-, and 5-allyl-substituted codeinones and morphinones with UV light ( 366 nm) leads to formation of the corresponding 18-phenyl, 18-methoxy, and 18-vinyl derivatives of 4,5-epoxymethanomorphin-7-en-6-one.     

Triterpene glycosides of Pulsatilla dahurica structures of glycosides A,B, C,and D

The isolation of four triterpene glycosides from the roots of the dahurian anemonePulsatilla dahurica (Fisch. ex DC) Spreng, is described together with their identification, on the basis of chemical transformations, spectral characteristics, and literature analogies, as hederagenin 3-O--L-arabinoside, hederagenin 3-O-[O--D-glucopyranosyl-(12)--L-arabinopyranoside], hederagenin 3-O--L-arabinopyranoside 28-O-[O--L-rhamnopyranosyl-(14)--D-glucopyranosyl-(16)--D-glucopyranoside], and hederagenin 3-O-[O--D-glucopyranosyl-(14)--L-arabinopyranoside] 28-O-[O--L-rhamnopyranosyl-(14)--D-glucopyranosyl-(16)--D-glucopyranoside].Pacific Ocean Institute of Bioorganic Chemistry, Far Eastern Branch, Russian Academy of Sciences, Vladivostok. Translated from Khimiya Prirodnykh Soedinenii, Nos. 3,4, pp. 349–356, May–August, 1992.     

Binding of vitamin A byβ-cyclodextrin and heptakis(2,6-O-dimethyl)-β-cyclodextrin

Inclusion complexation of all-trans-retinol, retinal and retinoic acid with -cyclodextrin (-CD) and heptakis(2,6-O-dimethyl)--cyclodextrin (DM--CD) were investigated by means of UV-vis spectroscopy. The association constants (K _a) obtained for vitamin A with DM--CD is greater than with -CD. On the other hand, for the same host compoundK _a values of retinol, retinal and retinoic acid are very close to each other.     

Molecular Recognition Based on Roof-shaped Diol Hosts. X-Ray Crystal Structures of Inclusion Compounds with Methanol, Pyridine and Toluene

Three crystalline inclusion compounds of roof-shapedtrans-11,12-bis(diaryl-hydroxymethyl)-9,10-dihydro-9,10-ethanoanthracene host molecules [where aryl is 4-methyl-phenyl (3) or4-t-butylphenyl (4)] have been studied by X-ray diffraction.The crystals of both the 3methanol (2 : 1) [a = 10.755(1),b = 11.571(1), c = 14.697(2) Å, = 75.12(1), = 89.67(1), = 87.13(1) °] and the 4-pyridine (2 : 3) compounds[a = 14.045(3), b = 14.366(3), c = 15.607(3) Å, = 91.62(1), = 103.65(1) and =116.05(1)°] are triclinic (P–1),while the 3toluene (1 : 1) complex has orthorhombic (Fddd) symmetry [a = 16.041(1), b = 25.008(1), c = 40.440(4) Å]. The host–guest interactions in both triclinic crystals are characterised by hydrogen bonds, with different patterns however. The determined crystal structures indicate a compromise between the requirement of hydrogen bonding on the one hand and close packing on the other. The highly symmetrical host framework in the toluene (1 : 1) complex of 3 seems to be the result of shape recognition, although atendency towards weak (C_methyl)H _arylinteractions [C_methyl = 3.533(7) and 3.674(6) Å] between the hosts was observed. The present roof-shaped diol hosts give excellent examples of molecular recognition by exhibiting two significantly different conformations, mostly depending on the proton donor/acceptor ability of the guest component. (O)H O intramolecular bonding between the two alcoholic groups characterises the so-called active form, whereas weaker (O)H and interactions stabilise the `inactive'conformation.     

New asterosaponins from the starfishDismolasterias nipon

Three new glycosides, D₁, D₂, and D₃, have been isolated from the Far Eastern starfishDistolasterias nipon. They have been identified by chemical and physicochemical methods as 5-cholestane÷3,6,8,15,24-pentaol 3,24-di-O--D-xylopyranoside, t-cholest-22-ene-3,6,8,15,24-pentaol 3,24-di-O--D-xylopyranoside (II), and 5-cholestane-3,6,8,15,24-pentaol 24-O--D-glucopyranoside 3-O--D-xylopyranoside (III).Pacific Ocean Institute of Bioorganic Chemistry, Far Eastern Scientific Center, Academy of Sciences of the USSR, Vladivostok. Translated from Khimiya Prirodnykh Soedinenii, No. 2, pp. 250–255, March–April, 1987.     

Steroid saponins and sapogenins ofAllium IX. The structure of aginoside

Summary From a methanolic extract of the skins of the bulbs ofAllium giganteum Rgl, a new steroid glycoside has been isolated — aginoside, which is (25R)-5-spirostan-2, 3, 6-triol 3-0-{[0--D-xylopyranosyl-(13)-]-[0--D-glucopyranosyl-(12)]-0--D-glucopyranosyl-(14)-0--D-galactopyranoside}.Institute of the Chemistry of Plant Substances, Academy of Sciences of the Uzbek SSR, Tashkent. Translated from Khimiya Prirodnykh Soedinenii, No. 4, pp. 480–486, July–August, 1976.     

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     

On the nature of surface sites for heterolytic dissociation of hydrogen on Al2O3

A quantum-chemical analysis of the models for geminal OH groups of Al₂O₃ and of the processes of their dehydroxylation with further dissociative chemisorption of hydrogen has been carried out. Calculations were performed by the SCF MO LCAO method using STO-3G basis set in terms of the cluster approach.

---

OH- Al₂O₃ . , STO-3G .

     

Researches on 2, l, 3-thia- and selenadiazole

4-(,-Dicarboethoxy--acetylamino) ethyl-7-aminobenzo-2,1, 3-thiadiazole (IV) and ethylene oxide form mainly the 7-(-hydroxyethyl) amino derivative (V); the 7- di (-hydroxyethyl) amino derivative VII was isolated in low yield. Action of POCl₃ on compound VII gave the 7-di (-chloroethyl) amino derivative VIII, which was converted into 4-(-amino--carboxy)-ethyl-7 -di (-chloroethyl) aminobenzo-2, 1, 3-thiadiazole (IX). 5-(, -dicarboethoxy--acetylamino) ethyl-4-nitrobenzo-2, 1, 3-thiadiazole (XI) was converted to 5-(-carboxy--amino) ethyl-4-nitrobenzo-2, 1, 3-thiadiazole hydrochloride (XII), from which was prepared, by known routes, and in satisfactory yield, 5-(-carboxy--amino) ethyl-4-di (-chloroethyl)-aminobenzo-2, l, 3-thiadiazole hydrochloride (XVII).For Part XXXIX see [8].     

Polyhydroxysteroids from the Far-Eastern starfishCtenodiscus crispatus

Four new polyhydroxysteroids, 5-cholesta-3,5,6,15,16,25,26-heptaol, 24-ethyl-5-cholesta-3,5,6,15,28,29-heptaol-29-sulfate, (22E)-24-methyl-5-cholest-22-ene-3,5,6,15,25,26-hexaol-26-sulfate, 24-propyl-5-cholesta-3,5,6,8,15,28,29-heptaol, and the known 5-cholesta-3,5,6,15,16,26-hexaol, have been isolated from the starfishCtenodiscus crispatus.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 10, pp. 1821–1825, October, 1994.     

Steroid saponins X. Glycosides of Allium narcissiflorum the structure of glycosides A and B

Summary FromAllium narcissiflorum Wells have been isolated for the first time trillin and a glycoside B, which proved to be 3-O-[-O-D-glucopyranosyl-(1 3)-O--D-glucopyranosyl-(1 6)-O--D-glucopyranosyl-(1 ]-26-O-[-D-glucopyranosyl-(1 ]-25R-furost-5-ene-3,22 , 26-triol.Institute of Chemistry, Academy of Sciences of the Moldavian SSR, Kishinev. Translated from Khimiya Prirodnykh Soedinenii, No. 1, pp. 55–58, January–February, 1976.     

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.     

Chemistry of the lipids

Conclusions 1. A. new route for the synthesis of optically active ,-diglycerides has been developed.2. D- and L-, -Distearins and D-, -dilinolenin have been synthesized from the readily accessible L- and D--O-tritylglycerols.Khimiya Prirodnykh Soedinenii, Vol. 5, No. 4, pp. 210–214, 1969