Biosyntheis of the alkaloids of Ammodendron karelinii

Summary The biosynthesis of the alkaloids ofAmmodendron karelinii Fisch. et Mey has been studied by feeding the plant with labelled [1,5-¹⁴C]cadaverine. It has been shown that cadaverine is a precursor of anagyrine, pachycarpine, ammodendrine, N-methylcytisine, and cytisine. Possible routes of interconversions have been considered by feeding the plant with the tritium-labelled [³H]pachycarpine, [³H]lupanine, [³H]anagyrine, and [³H]ammodendrine.V. I. Lenin Tashkent State University. Institute of Plant Biochemistry, Academy of Sciences of the GDR, Halle. Translated from Khimiya Prirodnykh Soedinenii, No. 2, pp. 247–250, March–April, 1977.     

Synthesis of tritium-labeled components of nucleic acids of the hypoxanthine series

The synthesis of [8-³H] and [2,8-³H]hypoxanthine, inosine, inosine 5-mono-, -di-and -triphosphates, and also of 2-deoxy[2,2-8-³H]inosine from the corresponding labeled compounds of the adenine series with the aid of the de-amination reaction is described. De-amination was carried out with sodium nitrite in the presence of acetic acid. In the case of bases and nucleosides, the separation of the reaction mixtures with simultaneous desalting of the final products was achieved by column chromatography on Sephadex G-10 or SE C-25 with elution by water. For nucleotides, the isolation process included chromatography on DEAE-Sephadex A-25 (HCOO^– or Cl^–) and Dowex 1×8 (Cl^–) followed by desalting with the aid of reprecipitation or adsorption on Carboraffin activated carbon. The molar radioactivities of the compounds synthesized amounted to 370–2220 TBq/mole (10–60 kCi/mole) and corresponded to the molar radioactivities of the initial compounds of the adenine series.V. G. Khlopin Radium Institute, Leningrad. Translated from Khimiya Prirodnykh Soedinenii, No. 1, pp. 128–131, January–February, 1987.     

Ornithine-containing lipid from Actinomyces globisporus

Conclusions From the cell lipids ofActinomyces globisporus 1131 a lipo amino acid has been isolated which is a N²-[L-(3-acyloxy)acyl]-L-ornithine. The configurations of all the asymmetric centers in an ornithino lipid have been established for the first time.M. M. Shemyakin Institute of the Chemistry of Natural Compounds, Academy of Sciences of the USSR. Translated from Khimiya Prirodnykh Soedinenii, No. 1, pp. 3–10, January–February, 1974.     

Phytoecdysones ofSilene praemixta. I. Silenosterone

In addition to known ecdysteroids (2-deoxy--ecdysone and 2-deoxyecdysterone) fromSilene praemixta (Caryophyllaceae) we have isolated new ones — premixisterone and selenosterone (I), C₂₇H₄₂O₇, mp 115–117°C (from MeOH), [] _D ²⁸ +86.9 ± 2° (c 0.92, MeOH), yield 0.003%. The acetylation of (I) with (CH₃CO)₂O in Py gave 22-acetyl-selenosterone (II), C₂₉H₄₄O₆, mp 210–212°C (MeOH-C₆H₁₄), [] _D ²⁷ +45.5 ± 3° (c 0.16; MeOH). On the basis of physiocochemical and spectral characteristics it has been established that (I) has the structure of 14,22R,25-trihydroxy-5-cholest-7-ene-3,6-dione. The IR, PMR, and mass spectra of (I) and (II) are presented.Institute of the Chemistry of Plant Substances, Academy of Sciences of the Uzbek SSR, Tashkent. Translated from Khimiya Prirodnykh Soedinenii, No. 6, pp. 793–797, November–December, 1979.     

Structure and stereochemistry of pallinin

The roots ofFerula pallida Korov. have yielded pallinin, C₂₅H₃₈O₅, mp 79–80°C, []D²⁰ –148.5° (c 0.1; CHCl₃) — an ester of the new carotane alcohol pallinol and angelic acid. A structure and absolute configuration have been proposed for it on the basis of chemical transformations and spectral characteristics.Institute of the Chemistry of Plant Substances, Academy of Sciences of the Uzbek SSR, Tashkent. Translated from Khimiya Prirodnykh Soedinenii, No. 1, pp. 53–56, January–February, 1986.     

Structure and configuration of a new diterpenoid lactone fromLagochilus hirsutissimus

The epigeal part of the plantLagochilus hirsutissimus has yielded a new diterpenoid lactone — lagohirsidin, C₂₂H₃₄O₅, mp 144–145°C, [] _D ²² – 17.5° (c 1; ethanol). Reduction with LiAlH₄ has yielded a diol C₂₂H₃₈O₅, mp 165–166°C [] _D ²⁰ –1.2 (c 0.6; ethanol). Acid hydrolysis of the diol has led to the formation of lagochilin, C₂₀H₃₆O₅, mp 167–168°C, [] _D ²⁰ –3.9° (c 1; ethanol). The synthesis of lagohirsidin from lagochilin has been effected.V. I. Lenin Tashkent State University. Translated from Khimiya Prirodnykh Soedinenii, No. 6, pp. 788–792, November–December, 1979.     

The biosynthesis of the alkaloids of Goebelia pachycarpa

Summary 1. Qualitative and quantitative compositions of the main alkaloids in five development phases of theGoebelia pachycarpa C. A. Mey. have been determined.2. The radioactivities of the alkaloids isolated after feeding the plant with assumed precursors -[2-¹⁴C] lysine and [1,5-¹⁴C] cadaverine — show that vigorous synthesis of alkaloids takes place in the flowering and budding periods.3. The results of an investigation of the oxidation products and of the alkaloids introduced and isolated after the feeding of plants with labelled matrine and labelled sophocarpine show that the alkaloids undergo interconversion without intramolecular changes.V. I. Lenin Tashkent State University. Translated from Khimiya Prirodnykh, Soedinenii, No. 4, pp. 549–552, July–August, 1977.     

Biotinylation of amines with the pentafluorophenyl ester of D-biotin

The synthesis has been effected of the pentafluorophenyl ester of D-biotin by the reaction of D-biotin with bispentafluorophenyl carbonate or pentafluorophenyl trifluoroacetate. The possibility has been shown of using the ester obtained for the biotinylization of amino acids and NH₂-containing macromolecules, and D-biotinyl--aminocaproic acid and -[¹⁴C]glycine have been synthesized. It is proposed to use the biotinyl-[¹⁴C]glycine for measuring the activity of avidin.Institute of Molecular Biology, Academy of Sciences of the USSR, Moscow. Translated from Khimiya Prirodnykh Soedinenii, No. 3, pp. 404–408, May–June, 1989.     

Triterpene glycosides ofSilphium perfoliatum. IV. Structure of siliphioside C

The epigeal part ofSilphium perfoliatum has a yielded a new triterpene glycoside, silphioside C — C₅₀H₈₀O₁₉, mp 207–210°C (from aqueous methanol), []_D ²⁵ +19.3 ± 2°C (c 0.88; methanol). On the basis of acid hydrolysis, mild alkaline saponification, and the results of GLC and of IR, mass, and¹H and¹³C spectroscopy the structure of silphioside C had been established as 28--D-glucopyranosyl 3-O-[O--D-glucopyranosyl-(12)-(6-O-acetyl--D-glucopyranosyl)oleanolate.Institute of the Chemistry of Plant Substances, Academy of Sciences of the Uzbek SSR, Tashkent. Pyatigorsk Pharmaceutical Institute. Translated from Khimiya Prirodnykh Soedinenii. No. 4, pp. 519–522, July–August, 1985.     

Cardiac glycosides of Erysimum contractum

The cardenolide composition ofErysimum contractum Somm. et Lew. familyBrassicaceae (Cruciferae) has been investigated. The seeds of this plant have yielded strophanthidin, erysimin, erysimoside, erycordin, and new cardiac glycoside which has been called nigrescigenin digitoxoside. It has mp 141–145°C, []_D ²⁰+16.0±2° (c 0.75; methanol), C₂₉H₄₂O₁₀. On the basis of chemical transformations and spectral investigations it has been established that the new glycoside is 3--D-digitoxopyranosyloxy-5,11,14-trihydroxy-19-oxo-5,14-card-20(22)-enolide. The total content of cardiac glycosides in the seeds of this plant amounted to 3.2%, including 1.26% of erysimoside.All-Union Scientific-Research Institute of the Chemistry and Technology of Drugs, Kharkov. G. S. Skovroda Kharkov State Pedagogic Institute. Translated from Khimiya Prirodnykh Soedinenii, No. 1, pp. 58–62, January–February, 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.     

Culcitoside C1 from the starfishCulcita novaeguineae andLinckia guildingi

By repeated chromatography on Polikhrom-1, silica gel, and Florisil, ethanolic extracts of two species of starfish,Culcita novaeguineae andLinckia guildingi, have yielded the new steroid glycoside culcitoside C₁ (I): 5-cholestan-3,4,6,8,15,24-hexaol 24-O-[2,4-di-O-methyl--D-xylopyranosyl-(12)--L-arabinofuranoside], C₃₉H₆₈O₁₄, mp 245–248°C, []_D -35.8°, c 0.6; methanol). Its structure was shown by the results of acid hydrolysis, acetylation and methylation, and¹H and¹³C NMR spectroscopy.Pacific Ocean Institute of Bioorganic Chemistry, Far Eastern Scientific Center, Academy of Sciences of the USSR, Vladivostok. Translated from Khimiya Prirodnykh Soedinenii, No. 6, pp. 801–804, November–December, 1985.     

Stoichiometry and kinetics of the oxidation of hydroxylammonium ion by 12-tungstocobaltate(III) anion in aqueous solution

Summary The stoichiometry and kinetics of the oxidation of hydroxylammonium ion by the 12-tungstocobaltate(III) anion has been studied in hydrochloric acid medium. The ratio of mols of oxidant consumed per mol of hydroxylammonium ion is 11 and the evolution of nitrogen is confirmed. In the 0.1–1.0 mol dm^–3 [H⁺] region, the oxidation is acid-independent and obeys the empirical rate law: –d[oxidant]/dt=k[oxidant] [reductant] where k=(3.51±0.18)×10^–4 mol^–1dm³s^–1 at 22.4±0.1C and I=2.0 mol dm^–3 (NaCl). Possible reaction steps and mechanism are suggested.     

Artenolide — A new disesquiterpenoid fromArtemisia absinthium

A new steroid glycoside — alliospiroside B (I) — has been isolated from the collective fruit ofAllium cepa L. On the basis of chemical transformations and with the aid of physicochemical measurements it has been established that compound (I) has the structure of (25S)spirost-5-ene-1,3-diol 1-O-[O--L-rhamnopyranosyl-(1 2)--D-galactopyranoside. Compound (I) C₃₉H₆₂O₃, mp 200–202°C (from ethanol). [] _D ²⁰ –110.9±2° (c 1.01; pyridine) was obtained by extracting the collective fruit ofA. cepa with ethanol folowed by the column chromatographic separation of the combined glycosides on silica gel. The acid hydrolysis of (I) gave (25S)-ruscogenin (II), C₂₇H₄₂O₄, mp 189–191°C, [] _D ²³ –104.1±2° (c 0.98; pyridine). The¹H and¹³C NMR spectra are given for both compounds and the IR spectrum for compound (I).Institute of the Chemistry of Plant Substances of the Uzbek SSR, Academy of Sciences, Tashkent. Translated from Khimiya Prirodnykh Soedinenii, No. 5, pp. 589–592, September–October, 1986.     

Cardiac glycosides of Cheiranthus allioni. XIII. Glucoerycordin

From plains erysimum (Cheiranthus allioni) Hort., (Erysimum asperum) a new cardiac glycoside has been isolated which has been called glucoerycordin. Its chemical structure has been established mainly by stepwise hydrolysis and the identification of the hydrolysis products. Glucoerycordin C₄₁H₆₄ O₁₉, mp 131–135°C, [] _D ²⁰ –22.2 ± 3° (c 0.65; methanol) is 3-[O--D-glucopyranosyl-(1 4)-O--D-glycopyranosyl-(1 4)-gulomethylopyranosyloxy]-14,19-dihydroxy-5, 14-card-20(22)-enolide.All-Union Scientific-Research Institute of Drug Chemistry and Technology, Khar'kov. Khar'kov State Pharmaceutical Institute. Translated from Khimiya Prirodnykh, No. 1, pp. 73–75, January–February, 1989.     

Oxygenation of Trimethylsilylallenes Readily Obtainable from Organoboranes. Syntheses of 1-Trimethylsilyl-1-alkyn-3-ones and 1-Trimethylsilyl-1-alkyn-3-ols

Abstract

Recently we have reported that the reaction of sodium methoxide with ate-complexes (1) readily prepared from trimethyl-silylpropargyl phenyl ether and organoboranes gives trimethyl-silylallenes (2) selectively (eq. 1).¹ In an attempt to find a new synthetic application of such silylallenes (2), the oxidation of 2 was examined. Although the usual oxidants such as m-chloro-perbenzoic acid were found to be unsuitable for the oxidation of the silylallenes, it was discovered that 2 was autoxidized at room temperature to propargylic hydroperoxide (3) (eq. 2). For example, the acidified starch-iodine test² strongly suggested the presence of the organic hydroperoxide in the reaction mixture obtained from 1,2-heptadienyltrimethylsilane (2, R=Bu) and oxygen. The hydroperoxide (3, R=Bu) was isolated in a 40% yield by distillation, 45–48 [ddot]C/0.1 mmHg. In the infrared spectrum, the OH stretching frequency appears at 3430 cm^?1 and the C°C at 2180 cm,^?1     

Triterpene glycosides of Hedera taurica. IV. Structure of hederosides A1, A2, D1, and D2 from the berries of Crimean ivy

New triterpene glycosides have been isolated from the berries of Crimean ivyHedera taurica Carr. (family Araliaceae) — hederoside A₁ (methyl ester of 3-O--D-glucopyranosylhederagenin) and hederoside D₁ 3-O-[O--D-glucopyranosyl]-(12)--D-glucopyranosyl]hederagenin and also the known glycosides 3-O--D-glucopyranosyloleanolic acid and 3-O-[O--D-glucopyranosyl-(12)--L-arabinopyranosyl]hederagenin. The structures of these compounds were established on the basis of the results of chemical methods and¹H and¹³C NMR spectroscopy.M. V. Frunze Simferopol' State University. Translated from Khimiya Prirodnykh Soedinenii, No. 2, pp. 228–230, March–April, 1990.