Phytoecdysteroids of plants of the genus Silene. XIV. Ecdysterone 20-O-benzoate from Silene tatarica

A new ecdysteroid, which has proved to be ecdysterone 20-O-benzoate, has been isolated from the whole plantSilene tatatica (L.) Pers.Institute of the Chemistry of Plant Substances, Uzbek SSR Academy of Sciences, Tashkent. Translated from Khimiya Prirodnykh Soedinenii, No. 6, pp. 850–852, November–December, 1987.     

Phytoecdysteroids of plants of the genus Silene. IX. Ecdysterone 22-O-benzoate from Silene scabrifolia

An ecdysteroid which has proved to be ecdysterone 22-O-benzoate has been isolated from the epigeal organs ofSilene scabrifolia Kom.Institute of the Chemistry of Plant Substances, Academy of Sciences of the Uzbek SSR, Tashkent. Translated from Khimiya Prirodnykh Soedinenii, No. 1, pp. 77–80, January–February, 1986.     

Phytoecdysteroids of plants of the genus Silene. XVII. Ecdysterone 22,25-di-O-benzoate from Silene scabrifolia

The new phytoecdysteroid ecdysterone 22,25-di-O-benzoate (IV) has been isolated from the epigeal organs ofSilene scabrifolia Kom. The alkaline hydrolysis of (IV) gave ecdysterone 25-O-benzoate and ecdysterone (I). Details of the IR, UV, mass, PMR, and¹³C NMR spectra of compound (IV) are given.     

Phytoecdysteroids of plants of the genus Silene. XVIII. 2-Deoxyecdysterone 20,22-monoacetonide from Silene brahuica

In addition to the known 2-deoxy--ecdysone, 2-deoxyecdysterone, 2-deoxy--ecdysone-22-O-acetate, ecdysterone, integristerone A, and sileneoside A, B, and C, the new ecdysteroid 2-deoxyecdysterone 20,20-monoacetonide has been isolated from the roots of the plantSilene brahuica Boiss.Institute of Chemistry of Plant Substances Academy of Sciences of the Uzbek SSR, Tashkent. Translated from Khimiya Prirodnykh Soedinenii, No. 2, pp. 241–244, March–April, 1991.     

Phytoecdysteroids of plants of the genus Silene. XVI. Viticosterone E 22-O-benzoate from Silene wallichiana

A new phytoecdysteroid, viticosterone E 22-O-benzoate (I), C₃₆H₅₀O₀, mp 147–149°C (methanol-water), [] _D ²⁰ +63.2° (methanol), has been isolated from the epigeal organs ofSilene wallichiana Klotzsch. The alkaline hydrolysis of (I) led to viticosterone E and benzoic acid. The acetylation of (I) gave the 2,3-diacetate (II), C₄₀H₅₄O₁₁, mp 152–153°C (methanol-water), [] _D ²⁰ +65.5° (methanol). Details of the IR, PMR, and mass spectra of (I) and (II) are given.Institute of the Chemistry of Plant Substances, Academy of Sciences of the Uzbek SSR, Tashkent. Translated from Khimiya Prirodnykh Soedinenii, No. 4, pp. 546–549, July–August, 1988.     

Phytoecdysteroids of plants of the genus Melandrium I. Polypodin B 22-acetate from Melandrium turkestanicum

Known ecdysteroids — ecdysterone, ecdysterone 22-acetate, polypodin B, integristerone A, and sileneosides A and D — and a new phytoecdysteroid — polypodin B 22-acetate — have been found in the epigeal parts of the plantMelandrium turkestanicum (Rg1.) Vved. (family Caryophyllaceae).Institute of Chemistry of Plant Substances, Academy of Sciences of the Uzbek SSR, Tashkent. Translated from Khimiya Prirodnykh Soedinenii, No. 4, pp. 480–483, July–August, 1990.     

Structures of four new triterpene glycosides from the holothurian Cucumaria japonica

Four new triterpene glycosides of the holostane series have been isolated from an alcoholic extract of the economically important Pacific Ocean holothurianCucumaria japonica: cucumariosides A₁-2 (I), A₂-3 (II), A₂-4 (III), and A₄-2 (IV). The structures of these substances have been established by the methods of carbohydrate chemistry and¹³C NMR spectroscopy.Pacific Ocean Institute of Bioorganic Chemistry, Far Eastern Branch, Academy of Sciences of the USSR, Vladivostok. Translated from Khimiya Prirodnykh Soedinenii, No. 6, pp. 787–793, November–December, 1990.     

Phytoecdysteroids of plants of the genus Silene. XIV. Ecdysterone 20-O-benzoate from Silene tatarica

A new ecdysteroid, which has proved to be ecdysterone 20-O-benzoate, has been isolated from the whole plantSilene tatatica (L.) Pers.     

Neptunium-237 in the marine environment determination in animal and plant species in the English Channel: Biological indicators and trophic relationships

We have studied the uptake of²³⁷Np in marine plants and animals belonging to several phyla, and collected samples from the end of January 1986 to March 1986, in a sampling station situated near the outlet of the irradiated fuel reprocessing plant at La Hague.We determined the²³⁷Np by neutron activation analysis. This method is very sensitive, with a limit of detection of 5×10^–10 mg, 1.3×10^–2 mBq. The method consists of the following steps:Reduction of the neptunium to the tetravalent state by treatment with a mixture of hydrazine sulfate and ferrous iron-chromatographic separations on Dowex 1×10 resin in a nitric medium, then in a hydrochloric medium-neutron irradiation in a nuclear reactor-purification of the neptunium by chromatography on Dowex 1×10 resin in a nitric then hydrochloric medium-measurement of the isotope²³⁸Np by gamma ray spectrometry using a Ge(Li) detector. The species were collected at Goury, at the northwest extremity of the Cotentin Peninsula, 5 km from the outlet of the reprocessing plant at La Hague. The levels of²³⁷Np were as follows: red algaeCorallina officinalis 64 mBq kg^–1 wet weight; andChondrus crispus 18 mBq kg^–1 wet weight; the spongeHalichondria panicea 14 mBq kg^–1 wet weight; the ascidianDendrodoa grossularia 12 mBq kg^–1 wet weight. The bivaive molluscsPatella vulgata andGibbula umbilicalis (the flesh ofP. vulgata andG. umbilicalis: 4 and 7 mBq kg^–1 wet weight respectively) also prove to be interesting biological indicatorsThe transfer modes of²³⁷Np to the various species as a function of their trophic levels are discussed as well as the distribution among the organs in the species consumed and the radiological impact of human consumption.     

Phytoecdysteroids of Plants of the Silene Genus. 2-Dehydroxyecdysterone-3-O-benzoate from Silene wallichiana

The known ecdysteroids 2-dehydroxyecdysone, 2-dehydroxyecdysterone, ecdysterone-22-O-benzoate, ecdysterone, integristerone A, and a new ecdysteroid identified as 2-dehydroxyecdysterone-3-O-benzoate are isolated from roots ofSilene wallichianaKlotzsch     

Co-hydrolysis products of tetraethoxysilane and methyltriethoxysilane in the presence of tetramethylammonium ions: Part 2 [1]

²⁹Si NMR peaks due to species with the double four-membered ring siloxane backbone composed of both Si(O^–)_4/2 and CH₃Si(O^–)_3/2 units, (CH₃) _n Si₈O _{20 – n} ^{/(8 – n) –} (n=1–3), formed by co-hydrolysis of tetraethoxysilane and methyltriethoxysilane in the presence of tetramethylammonium ions in methanol have been assigned. It has been found that ²⁹Si NMR peaks due to Si(OSi)₃(O^–) units shift to lower frequencies by replacement of the adjacent Si(O^–)_4/2 units by CH₃Si(O^–)_3/2 units, in other words, with increasing m value in Si[OSi(O^–)₃]_{3 – m} [OSi(CH₃) (O^–)₂] _m (O^–) (m=0–2). Peaks from CH₃ Si(OSi)₃ units in the species have also appeared as separated due to the kind of neighbor structural units. On the basis of the assignments, positions of CH₃Si(O^–)_3/2 units in the cubic octameric siloxane framework of (CH₃) _n Si₈O _{20 – n} ^{/(8 – n) –} (n=2, 3), for both of which three isomers are present, have been estimated.     

Cembrenolides of a soft coral Lobophytum sp. (coelenterata, octocorallia, alcyonacea)

The known cembrenolide sarcophin and its new acetoxy derivative — 13-acetoxy-7,8-epoxycembra-1(15),3,11-trien-2,16-olide — have been isolated from the soft coralLobophytum sp.. The compounds isolated are inhibitors of the activity of Na⁺K⁺-ATPase and are membranotropic agents. The structures of the compounds have been shown on the basis of the results of NMR spectroscopy.Pacific Ocean Institute of Bioorganic Chemistry, Far Eastern Branch, Academy of Sciences of the USSR, Vladivostok. Translated from Khimiya Prirodnykh Soedinenii, No. 6, pp. 762–765, November–December, 1990.     

Polysaccharides of Eremurus. XXVI. Study of the structure of the pectin from the leaves of Eremurus regelii

The partial acid hydrolysis of the homogeneous fraction C of the pectin fromEremurus regelii Vved. leaves has given a galacturonan. Its structure has been established on the basis of the results of periodate-nitric acid oxidation, methylation, and¹³C NMR spectroscopy.Institute of Chemistry of Plant Substances, Uzbekistan Republic Academy of Sciences, Tashkent. Translated from Khimiya Prirodnykh Soedinenii, No. 2, pp. 191–194, March–April, 1993.     

Alkaloids of Stephania hernandifolia VI. Hernandifoline

Summary A new hasubanan alkaloid with the composition C₂₉H₃₃O₉N, mp 128–129°C₉ from ether), [] _D ²⁰ – 25° (c 2; ethanol) containing an ester group has been isolated from the herbStephania hernandifolia and has been called hernandifoline.All-Union Scientific-Research Institute for Medicinal Plants. Translated from Khimiya Prirodynkh Soedinenii, No. 2, pp. 158–164, March, 1971.     

Triterpene glycosides of Astragalus and their genins. XX. Cycloorbigenin from Astragalus orbiculatus

A new genin — cycloorbigenin (I), C₃₀H₄₈O₅, mp 217–219°C, [] _D ²⁰ +28.3° (c 1.19; ethanol) has been obtained from a glycoside isolated from the epigeal parts of the plantAstragalus orbiculatus (Leguminosae), and on the basis of chemical transformation and spectral characteristics its structure has been established as 16,23:16,24-diepoxy-23(R),24(S)cycloartane-3,7,25-triol. The acetylation of (I) with acetic anhydride in pyridine yielded its diacetate (II), C₃₄H₅₂O₇, mp 148–150°C, [] _D ²⁰ +32.6° (c 0.92; methanol) and its triacetate (III), C₃₆H₅₄O₈, mp 137–139°C, [] _D ²⁰ +75° (c 0.4; methanol). The Jones oxidation of (I) led to a diketone (IV), C₃₀H₄₄O₅, mp 155–158°C, [] _D ²⁰ -73° (c 0.63; methanol). Details of the PMR, IR, and mass spectra are given for all the compounds.Institute of The Chemistry of Plant Substances, Academy of Sciences of the Uzbek SSR, Tashkent. Translated from Khimiya Prirodnykh Soedinenii, No. 4, pp. 455–460, July–August, 1986.     

Alkaloids of Aconitum rubricundum

The known alkaloids isolappaconitine (I), 9-deoxylappaconotine (II), lycaconitine (III), puberaconitine (IV), lycoctonine (V), ranaconitine (VI), ajacine (VII), and septentriodine (VII), and an unidentified alkaloid with mp 203–205°C have been isolated from the epigeal part of the Far-Eastern plantAconitum rubricundum. Institute of Chemistry of Plant Substances, Academy of Sciences of the Uzbek SSR, Tashkent. Translated from Khimiya Prirodnykh Soedinenii, No. 3, pp. 403–407, May–June, 1991.     

Pheromones of insects and their analogs. XX. Methyl-branched pheromones based on 4-methyltetrahydropyran.

A synthesis is proposed of 4,8-dimethyldecanal (VIII) — a pheromone of the flour beetlesTribolium confusum andT. castaneum. By heating 71.2 g of 4-methyltetrahydropyran (I), 83.2 g of AcBr and 1.57 g of ZnCl₂ (45°C), then 120°C, 2 h), 1-acetoxy-5-bromo-3-methylpentane (II) was obtained. The hydrolysis of 19.8 g of (II) (MeOH-H₂O, TsOH, 20°C, 15 h) gave 5-bromo-3-methylpentan-1-ol (III). From 18.1 g of (III) and 38.9 ml of 2,3-dihydropyran (Et₂O, TsOH, 20°C, 20 h) was obtained the 2-THPL ester of (III), (IV), which was converted into 3-methyloct-7-en-1-ol (V) by the treatment of the corresponding Grignard reagent with allyl bromide (THF, CuI-bi-2-pyridyl, 2°C, 4 h, Ar). The interaction of 1.42 g of (V) with Et₃Al (hexane, 20°C, Cp₂ZrCl₂, Ar) gave 3,7-dimethylnonan-1-ol (VI), boiling which with 48% HBr in the presence of concentrated H₂SO₄ gave 1-bromo-3,7-dimethylnonane (VII) which was then converted into the desired (VIII) by the reaction of the corresponding Grignard reagent with DMFA (0–2°C, 1 h; 20°C, 2 h; Ar). The characteristics of the compounds — yield (%), n_D (°C): (I), 79, 1.4340 (22); (III) 89, 1.4660 (23); (IV), 82, 1.4739 (23); (V), 85, —; (VI), 90, 1.4483 (20); (VII), 88, 1.4409 (22); (VIII), 88, 1.4589 (22). Details of the IR and PMR spectra of compounds (II)–(VII) are given.Institute of Chemistry, Bashkir Scientific Center, Urals Branch, USSR Academy of Sciences, Ufa. Translated from Khimiya Prirodnykh Soedinenii, No. 2, pp. 272–276, March–April, 1989.     

Triterpene glycosides of alfalfa. III. Medicoside I

On the basis of chemical transformations and with the aid of physicochemical results, the structure of glycoside I isolated from the roots of the plantMedicago sativa has been established as hederagin 3-O-[O--L-arabinopyranosyl-(1 2)--D-glucopyranosyl-(1 2)--L-arabinopyranoside] 28-O--D-glucopyranoside. Compound (I), C₅₂H₈₄O₂₂, mp 210–212°C, [] _D ²¹ +38.4° (c 1.48; methanol). Acid hydrolysis of (I) led to hederogenin (II) — C₃₀H₄₈O₄, mp 326–330°C, [] _D ²³ +84.2° (c 0.19; pyridine. The Hakomorimethylation of glycoside (I) yielded the permethylate (IV) — C₆₅H₁₁O₂₂ [] _D ²³ +41.6° (c 1.79; methanol). The GLC analysis of the products of the methanolysis of compound (IV) showed the presence of 3,4,6-tri-O-methyl-D-glucopyranose, 2,3,4,6-tetra-O-methyl-D-glucopyranose, 3,4-di-O-methyl-L-O-arabinopyranose, and 2,3,4-tri-o-methyl-L-arabinopyranose. The alkaline hydrolysis of glycoside I gave compound (III) with mp 230–233°C, [] _D ²¹ +35.2° (c 0.21; methanol), which was identified as medicoside C. Details of the PMR spectrum are given for compound (IV) and of the IR spectrum for compound (I).Institute of the Chemistry of Plant Substances of the Uzbek Academy of Sciences, Tashkent. Translated from Khimiya Prirodnykh Soedinenii, No. 5, pp. 607–610, September–October, 1986.