Synthetic studies in the field of chlorobium chlorophyll

By the condensation of -halogenomethyl derivatives of pyrroles with -unsubstituted pyrroles the synthesis of the following unsymmetrical dipyrrolylmethanes has been effected: 5-benzyloxycarbonyl-5-ethoxycarbonyl-3, 3-di(-methoxycarbonylethyl)-4,4-dimethyl-2,2-dipyrrolylmethane (IIIa), 5-benzyloxycarbonyl-5-ethoxycarbonyl-3-(-methoxycarbonylethyl)-4, 4-diniethyl-3-n-propyl-2,2-dipyrrolylmethane(IIIb), 3-acetyl-5-benzyloxycarbonyl-4-ethyl-5-methoxycarbonyl-3, 4-dimethyl-2,2-dipyrrolylmethane (IIIc), and 3-bromo-5-benzyloxycarbonyl-4-ethyl-5-methoxycarbonyl-3, 4-dimethyl-2,2-dipyrrolylmethane (IIId). Hydrogenation of the unsymmetrical dipyrrolylmethanes IIIa, b, c, and d has given the corresponding monocarboxylic acids IVa, b, c, and d. The formylation of the dipyrrolylmethanemonocarboxylic acid IVa has given 5-ethoxycarbonyl-5-formyl-3,3-di(-methoxycarbonylethyl)-4, 4-dimethyl-2,2-dipyrrolylmethane (V).For communication II, see [1].Deceased.Translated from Khimiya Geterotsiklicheskikh Soedinenii, Vol. 6, No. 8, pp. 1045–1047, August, 1970.     

Cardiac glycosides of Cheiranthus allioni. IX

Summary From the seends ofCheiranthus allioni hort. another three cardiac glycosides have been isolated. One of them has been identified as cheirotoxin. It has been established that in cheirotoxin the D-glucose is attached to C₄ of the D-gulomethylose and this glycoside therefore has the structure of strophanthidin 3-O-[4-O--D-glucopyranosyl--D-gulomethylopyranoside]. The two other glycosides, which have been named sarmentogulomethyloside and gulosarmentoglucoside are new and are, respectively, sarmentogenin-3-O--D-gulomethylopyranoside and sarmentogenin 3-O-[4-O--D-glucopyranosyl--D-gulomethylopyranoside].For Communication VIII see [1].Khar'kov Scientific-Research Institute of Pharmaceutical Chemistry. Translated from Khimiya Prirodnykh Soedinenii, No. 5, pp. 607–611, September–October, 1974.     

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).

     

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.     

The structure of yuccoside E from Yucca filamentosa

Summary From the roots ofYucca filamentosa L. we have isolated a new sarsasapogenin glycoside, yuccoside E, which is 3-O-{[O--D-galactopyranosyl(1 2)]-[-O--D-galactopyranosyl(1 6)]-O--D-glucopyranosyl-(1 4)--D-glucopyranosyl}-(25S), 5 -spirostan-3-ol.Institute of Chemistry, Academy of Sciences of the Moldavian SSR. Translated from Khimiya Prirodnykh Soedinenii, No. 6, pp. 747–750, November–December, 1975.     

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.     

New cardenolides from the leaves ofGomphocarpus fruticosus

Two new glycosides, gomphotin (1) and gomphotoxin (13), and also the known gomphoside (9) have been isolated from the leaves ofGomophocarpus fruticosus. Compounds (1) and (9) contain a 4,6-dideoxyhexosulose residue as the sugar component, and (13) a 6-deoxyhexosulose, which are attached to glycolic OH groups of the aglycons by 3-O-1,2-O-2 (9, 13) and 3-O-1,4-O-2 (1) acetal-ketal bonds. The structures of the new compounds are represented by the names (3-O-1,4-O-2)-(2,3-dihydroxy-4, 6dideoxyhexulosido)-14-hydroxy-5-card-20(22)-enolide* (1) and (3-O-1,2-O-2)-(2,3,4-trihydroxy-6-deoxyhexulosido)-14-hydroxy-5-card-20(22)-enolide* (13).State Scientific Center for Drugs of the Ministry of Health and the National Academy of Sciences of the Ukraine, Kharkov, fax 441118. Translated from Khimiya Prirodnykh Soedinenii, No. 6, pp. 824–832, November–December, 1995. Original article submitted May 22, 1995.     

Transformed steroids. 160. Reaction of 20,20-dimethoxy-16α,17α-epoxypregn-5-ene-3β, 21-diol-20-one with pyridine thiocyanate and carbethoxyhydrazine

Conclusion The reaction of 20,20-dimethoxy-16,17-epoxypregn-5-ene-3,21-diol-20-one with pyridine thiocyanate in the presence of carbethoxyhydrazine proceeds by two competing paths: cisopening of the oxide ring by a -SCN ion at the C¹⁷ atom, and substitution of one of the methoxyl groups by -NCS ion. As a result 2,20-dicarbethoxyhydrazones of pregn-5-ene-3,21-diol-20-one-[17,16-d]-1,3-oxathiolan-2-one and 20-methoxy-16,17-epoxypregn-5-ene-3-ol-[20,21-d]-1,3-oxazolidine-2-thione are formed.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 4, pp. 911–914, April, 1987.     

Gas chromatography-mass spectrometry in the study of the adsorption of sulfur-containing amino acids on graphitized thermal carbon black

Summary Gas chromatographic — mass spectrometric study of the trifluoroacetyl-methyl esters of sulfur- and hydroxyl-containing amino acids such as methionine, cysteine, D-,-dimethylcysteine (D-penicillamine), serine, and threonine was carried out. Sterling hydrogen treated graphitized thermal carbon black (HTGTCB) was used as the adsorbent. The Henry's constants, and the initial differential adsorption heats of these amino acid derivatives were determined on the HTGTCB surface by gas chromatography.Introduction of two methyl groups into the -position of a cysteine molecule (,-dimethylcysteine) stimulates the intramolecular nonvalent interactions increasing the internal rotation barriers in the molecule. This is revealed in the sharply reduced retention of the ,-dimethylcysteine derivative on the HTGTCB surface (as compared to the cysteine derivative) and it also influences the fragmentation pathways under electron impact.Deceased.     

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.     

Self organization of fluorescent molecular necklaces in aqueous solution

N-Fluoresceinyl-N-(mono-6-desoxy-6--cyclodextrinyl)-thiourea2 was synthesized from mono-6-amino-6-desoxy--CD1 and fluorescein isothiocyanate. The fluorescent CD derivative2 was threaded on a water soluble polymer, poly(N,N-dimethylammoniumhexamethylene-N,N-dimethyl-ammoniumdecamethylene dibromide)3. The existence of the molecular necklace was visualized by gel electrophoresis.     

Synthesen von kernsubstituierten N,N-Diphenyl-β-alaninen

Zusammenfassung N,N-Diphenyl--alanine mit Substituenten in einem oder in beiden Phenylresten wurden durch Umsetzung von entsprechenden Diphenylaminderivaten mit -Propiolacton erhalten. In ähnlicher Weise reagierte Diphenylamin mit -Butyrolacton zu -(N,N-Diphenylamino)-buttersäure. 4,4-Diäthyldiphenylamin und 2-Chlor-6-methyl-diphenylamin wurden als Ausgangsmaterialien für die entsprechenden -Alanine hergestellt.

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N.N-Diphenyl--alanines with substituents in one or in both of the phenyl groups were synthesized by reactions of the corresponding diphenylamine derivatives with -propiolactone. Similarly diphenylamine reacted with -butyrolactone to give -(N.N-diphenylamino)-butyric acid. 4.4-Diethyldiphenylamine and 2-chloro-6-methyldiphenylamine were prepared as starting materials for the corresponding -alanines.

     

Synthesis of the bis(2′-chloroethyl) amide of β-(8-guanyl)propionic acid

The synthesis of -(8-guanyl)propionic acid and its chloride, methyl ester, bis(2-hydroxyethyl)amide, and bis(2-chloroethyl)amide has been effected. The latter readily rearranges under certain conditions into 2-chloroethylaminoethyl -(8-guanyl)propionate.     

Preparation and stereochemical characterization of some N-acyl-[1]benzopyrano[3,4-c]pyrazole derivatives from rotenoids

Summary Several new N-acyl derivatives of 1-(4-hydroxy-2,3-dihydrobenzofuran-5-yl)-7,8-di methoxy-1,9 b,2,3,3 a,4-hexahydro-[1]benzopyrano[3,4-c]pyrazole-1-ene have been prepared by appropriate chemical transformation of isohydrazones of rotenone and amorphigenin. A study of their¹H- and¹³C-NMR spectra confirmed the presence of the twocis 3a, 9b, 2 and 3a, 9b, 2 diastereomers in the parent isohydrazones and revealed the strong predominance of the conformers withendo orientation of the 3-NAc group. The conformations due to rotation about the 1,5-bond between rings C and D in the 4-OH and 4-O-substituted compounds were also determined by taking into account the anisotropic effect of aromatic rings A and D, and the hydrogen bond between 4-OH and the 2-N atom, as well as by inspecting the Dreiding models.

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Darstellung und stereochemische Charakterisierung einiger N-Acyl-[1]benzopyrano[3,4-c]pyrazol-Derivate von Rotenoiden

Zusammenfassung Mittels geeigneter chemischer Transformationen von Isohydrazonen von Rotenon und Amorphigenin wurden einige neue N-Acyl-Derivate von 1-(4-Hydroxy-2,3-dihydrobenzofuran-5-yl)-7,8-dimethoxy-1,9 b,2,3,3 a,4-hexahydro-[1]benzopyrano[3,4-c]pyrazol-1-en hergestellt. Eine Untersuchung ihrer¹H und¹³C-NMR-Spektren zeigt die Gegenwart von zweicis 3a, 9b, 2- und 3a, 9b, 2-Diastereomeren in den Ausgangs-Isohydrazonen und eine starke Bevorzugung der Konformeren mitendo-Orientierung der 3-NAc-Gruppe. Die Konformationen bezüglich der Rotation um die 1,5-Bindung zwischen Ring C und D werden für die 4-OH und 4-O-substituierten Verbindungen unter Berücksichtigung von Anisotropie-Effekten der aromatischen A- und D-Ringe, der Wasserstoffbrücken zwischen 4-OH und dem 2-N Atom und auch der Betrachtung der entspechenden Dreiding-Modelle diskutiert.

     

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.     

Radiation-induced reactions of cholesterol in an aqueous medium

⁶⁰Co -ray radiolysis of cholesterol /3-hydroxy-5-cholestene/ /I/ in the two-phase system /water-ethyl acetate/ and in the presence of air has been studied using TLC and GC methods. The following products were observed in the irradiated mixture: 3, 7-dihydroxy-5-cholestene /II/, G O. 36, 3-hydroxy-7-keto-5-cholestene /III/, G 1.48, 3-hydroxy-7-keto-5-cholestane /IV/, G 0.22, 3,5,6-trihydroxy-5-cholestane /V/, G 0.83, 5,6-epoxy-3-hydroxy-5-cholestane /VIa/, G 0.26, 5,6-epoxy-3-hydroxy-5-cholestane /VIb/, G 0.24, and 2, 3-dihydroxy-5-cholestene /VII/, G 0.22. The dose dependence of the formation of these products shows that the cholesterol derivatives substituted in the position 7 /II–IV/ are formed from a common precursor — the radical Ia. On the other hand, the products of the 5–C=C double bond reactions /V and VI/ are formed independently. Also the product VII is formed independently. A reaction scheme that is in agreement with these results is proposed.     

The influence of second-nearest neighbor interactions on the thermodynamic properties of B2 phases with substitutional defects

In order to explain some discrepancies between the theoretical predictions and the experimental data for the thermodynamic properties of substitutional B 2 phases,Chang's theoretical model is extended by including the influence of second-nearest neighbor interactions. For this purpose a new parameter is introduced which is defined as the ratio of the interchange energies between second-nearest and first-nearest neighbors. Theoretical equations are derived for the compositional dependence of the activity and the partial molar enthalpy. Using literature data, the following phases are re-evaluated in terms of the disorder parameter and the newly introduced parameter : -AuZn, -AuCd, -AgMg, and -NiZn. Very good agreement is found between the theoretical curves and the experimental data for the four systems. The values of obtained range from 0.0 for -NiZn to 0.5 for -AuZn. The inclusion of second-nearest neighbor interactions has little influence on the values of . It is shown that the behavior of the activity curve in -AuZn can be explained in a physically more meaningful way by including interactions between all second-nearest neighbors rather than interactions between gold substitutional defects only, as was done byLibowitz.With 5 Figures     

Steroid compounds from the starfish Lysastrosoma anthosticta collected in the Sea of Japan

Six polyhydroxylated steroids and their derivatives were isolated from the starfish Lysastrosoma anthosticta collected in the Posyet Bay, Sea of Japan. These include a new glycoside of the steroid polyol, lysastroside A (1), which was identified as (25S)-26-O--d-xylopyranosyl-5-cholestane-3,6,8,15,16,26-hexaol, and the previously known pycnopodioside C monoglycoside (2), marthasterone sulfate (3), (25S)-5-cholestane-3,6,8,15,16,26-hexaol (4), (25S)-5-cholestane-3,6,7,8,15,16,26-heptaol (5), and (25S)-5-cholestane-3,6,7,8,15,16,26-heptaol (6). The compounds were tested for the haemolytic activity and the action on the embryogenesis of the sea urchin Strongylocentrotus intermedius.     

New glycosides from plants of the genus Phlojodicarpus

From plants of the genusPhlojodicarpus have been isolated the new coumarins umbelliferone -D-apiosyl (1 6)--D-glucopyranoside (I) and 8-(2,3-dihydroxy-3-methylbutyl)umbelliferone 7-O--D-glucopyranoside (II) and also the flavone glycoside diosmetin 7-O--D-glucopyranoside (III). The result of IR, UV, PMR, and¹³C NMR spectroscopy are given.Institute of Chemistry, Academy of Sciences of the Mongolian Peoples' Republic, Ulan-Bator; Irkutsk Institute of Organic Chemistry, Siberian Branch, Academy of Sciences of the USSR. Translated from Khimiya Prirodnykh Soedinenii, No. 1, pp. 36–39, January–February, 1986.