An investigation by the NMR method of the structure of the alkaloid sophorine fromSophora alopecuroides

A new base — sophorine, with mp 59–60°C, [α] _D ²³ -18.9° (c 0.98; ethanol) — has been isolated from the epigeal part of the plantSophora alopecuroides L. Its IR spectrum and the nature of its mass spectrometric composition have permitted sophorine to be assigned to the quinolizidine alkaloids. The¹³C NMR spectrum has shown the presence of 19 carbon atoms. The analysis of several of the carbon signals has confirmed the results of IR and mass spectroscopy. Additional details of the structure of sophorine have been obtained from its PMR spectrum.     

Alkaloids ofAconitum coreanum. I. Structure of acorine

Two C₂₀-diterpene alkaloids have been isolated from the epigeal part ofAconitum coreanum (Levl.) Rapaics: the known 14-hydroxy-2-isobutyrylhetesine (I) (Guan-Fu base Z) and a new one — acorine (II), C₂₂H₂₉NO₅, mp 214–215°C (from acetone), _D ²⁰ +9° (c 0.01; methanol), for which the structure of 2-acetyl-14-hydroxy-hetesine has been established. Details of the IR, mass, and¹³C NMR spectrum of (I) and (II) and of the PMR spectrum of (II) are given.Institute of the Chemisry of Plant Substances of the Uzbek Academy of Sciences, Tashkent. All Union Scientific-Research Institute of Medicinal Plants. Translated from Khimiya Prirodnykh Soedenenii, No. 5, pp. 690–692, September–October, 1987.     

Phytoecdysteroids of plants of the genusSilene X. Sileneoside E — 2-Deoxy-α-ecdysone 3-O-β-D-glucopyranoside — FromSilene brahuica

A new ecdysteroid has been isolated from the epigeal organs ofSilene brahuica Boiss. — 2-deoxy--ecdysone 3-O--D-glucopyranoside (I), C₃₃H₅₄O₁₀, mp 195–196°C, [] _D ²⁰ + 44.4° (methanol). The enzymatic hydrolysis of (I) led to 2-deoxy--ecdysone. Details of the IR, UV, mass, and¹H and¹³C NMR spectra of all the compounds are given.Institute of the Chemistry of Plant Substances, Academy of Sciences of the Uzbek SSR, Tashkent. Translated from Khimiya Prirodnykh Soedinenii, No. 3, pp. 323–326, May–June, 1986.     

Obtusinin — A new coumarin fromHaplophyllum obtusifolium

The epigeal part ofHaplophyllum obtusifolium collected in Ustyurt has yielded -sitosterol, isofraxetin, and a new coumarin — obtusinin — with the composition C₁₅H₁₈O₆, mp 135–137°C (methanol), [] _D ²⁰ +140.9° (c 0.44; chloroform). The structure of obtusinin has been established on the basis of the results of a study of UV, IR, PMR, and mass spectra and also of some chemical transformations (hydrolysis, acetylation).Institute of the Chemistry of Plant Substances, Academy of Sciences of the Uzbek SSR, Tashkent. Combined Institute of Natural Sciences of the Karakalpak Branch, Academy of Sciences of the Uzbek SSR, Nukus. Translated from Khimiya Prirodnykh Soedinenii, No. 3, pp. 328–330, May–June, 1980.     

Structures of daurosides A and B — New acylated coumarin glycosides fromHaplophyllum dauricum

From the roots and epigeal parts ofHaplophyllum dauricum (L.) G. Don., new acylated courmarin glycosides have been isolated: dauroside A, C₂₃H₂₈O₁₃, mp 145–147°C (ethanol), [] _D ²² – 72.7° (methanol), and dauroside B, C₃₀H₃₂O₁₄, mp 145–150°C (methanol) [] _D ²² 0° (pyridine). Their structures have been established on the basis of chemical transformations and IR, UV, mass,¹H NMR and¹³C NMR spectra.Institute of the Chemistry of Plant Substances, Academy of Sciences of the Uzbek SSR, Tashkent. Translated from Khimiya Prirodnykh Soedinenii, No. 2, pp. 142–147, March–April, 1983.     

A study of the chemical composition of the essential oil ofLedum palustre

Eight substances have been isolated by preparative chromatography on silica gel from the essential oil ofLedum palustre L., collected in the Kostroma oblast in August. Six of them have been described previously for this essential oil (myrcene, palustrol, ledol, allocaromadendrene, 6-methyl-2-methyleneocta-5,7-dien-3-ol, and cyclocolorenone) and two are new substances not described in the literature: a colorless liquid with a pleasant smell having the composition C₁₀H₁₄O₂, mp 108–111°C/4 mm Hg, n _D ²⁰ 1.4925, d ₂₀ ²⁰ 1.002, []_D±0°C, which has been called lepalol, and a colorless liquid with a pleasant smell having the composition C₁₀H₁₂O, bp 91–93°C/4 mm Hg, n _D ²⁰ 1.5175, d ₂₀ ²⁰ 0.9444, []_D±0°C, which have been proposed for lepalin and lepalol on the basis of their IR, UV, and NMR spectra. The physical constants of all the substances isolated and the characteristics of their IR, NMR, and mass spectra are given.All-Union Scientific-Research Institute of Medicinal Plants, Moscow. Translated from Khimiya Prirodnykh Soedinenii, No. 3, pp. 322–325, May–June, 1979.     

13,14-Dehydrosophoridine fromSophora alopecuroides

Summary A new alkaloid, C₁₅H₂₂ON₂, with mp 84–85°C [] _D ²⁰ + 77.9° (c 0.56; ethanol) has been isolated fromSophora alopecuroides L. On the basis of UV, IR, PMR, and mass spectral characteristics and the hydrogenation reaction, its most probable structure has been determined as 13,14-dehydrosophoridine.V. I. Lenin Tashkent State University. Translated from Khimiya Prirodnykh Soedinenii, No. 2, pp. 231–233, March–April, 1978.     

Dissociation constants of the ampholyte glycine in 50 mass % methanol-water from 5 to 55°C,with related thermodynamic quantities

The two thermodynamic dissociation constants of glycine at 11 temperatures from 5 to 55°C in 50 mass % methanol-water mixed solvent have been determined from precise emf measurements with hydrogen-silver bromide electrodes in cells without liquid junction. The first acidic dissociation constant (K ₁)for the process HG⁺H⁺+G^± is expressed as a function ofT(^oK) by the equation pK ₁ = 2043.5/T – 9.6504 + 0.019308T. At 25°C, pK ₁is 2.961 in the mixed solvent, as compared with 2.350 in water, with H°=1497 cal-mole^–1, G°=4038 cal-mole^–1, S°=–8.52 cal-°K^–1-mole^–1, and C _p ^o =–53 cal-°K^–1-mole^–1. The second acidic dissociation constant (K ₂)for the process G^±H⁺+G^– over the temperature range studied is given by the equation pK ₂ = 3627.1/T – 7.2371 + 0.015587T. At 25°C, pK ₂is 9.578 in MeOH–H₂O as compared with 9.780 in water, whereas H° is 10,257 cal-mole^–1, G° is 13,063 cal-mole^–1, S° is –9.41 cal-°K^–1-mole^–1, and C _p ^o is –43 cal-°K^–1-mole^–1. The protonated glycine becomes weaker in 50 mass % methanol-water, whereas the second dissociation process becomes stronger despite the lower dielectric constant of the mixed solvent (=56.3 at 25°C).     

Acetylsevedine fromKorolkowia sewerzowii

The epigeal part ofKorolkowia sewerzowii Regl. has yielded a new alkaloid — acetylsevedine with mp 189°C (with foaming), []_D –36.6°, C₂₉H₄₇NO₄. On the basis of the IR, PMR, and mass spectra of acetylsevedine, of the products of its transformation, and also a passage to the known alkaloid sevedine, the structure of 6-acetoxy-3, 14-dihydroxycevanine has been established for acetylsevedine.Institute of the Chemistry of Plant Substances, Academy of Sciences of the Uzbek SSR, Tashkent. Translated from Khimiya Prirodnykh Soedinenii, No. 3, pp. 352–353, May–June, 1986.     

Ionization constants of aqueous ammonia from 25 to 250°C and to 2000 bar

The ionization constant of ammonia has been determined by conductivity measurements and found to vary from 1.77×10^–5 at 25°C to 1.3×10^–6mol-kg^–1 at 250°C. The pressure effect to 2000 bar has been measured and the ratio K₂₀₀₀/K₁ is 6.8 at 25°C and 11 at 250°C. The standard molar volume change for the ionization at 1 bar, V ₁ ^o , changes from –28.8 at 25°C to –67 cm³-mol^–1 at 250°C.     

The structure of feterin — A new terpenoid coumarin fromFerula teterrima

Summary From the roots ofFerula teterrima Kar. et Kir. a new terpenoid coumarin — feterin — has been isolated with the formula C₂₆H₃₂O₆, mp 155–158°C, [] _D ^2° -52.02° (chloroform), M⁺ 440, the structure and relative configuration of which have been established with the aid of the INDOR method and on the basis of a study of the PMR spectra in the presence of the paramagnetic shift reagent Eu(DMP)₃.All-Union Scientific-Research Institute of Medicinal Plants, Moscow. Translated from Khimiya Prirodnykh Soedinenii, No. 3, pp. 318–322, May–June, 1978.     

Coumarins fromPhlojodicarpus sibiricus

Phlojodicarpin [8-(2,3-epoxy-1-hydroxy-3-methylbutyl)-7-methoxycoumarin, C₁₅H₁₆O₅, mp 143–145°C, [] _D ²⁵ -37.5°], and isophlojodicarpin [8-(1,2-epoxy-3-hydroxy-3-methylbutyl)-7-methoxycoumarin, C₁₅H₁₆O₅, mp 132–134°C, [] _D ²⁵ -102.5°] have been isolated from the epigeal part ofPhlojodicarpus sibiricus. The results of the IR, UV, PMR, and mass spectrometry of these compounds 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. 47–49, January–February, 1981.     

Structure of severidinine

A new alkaloid, severidinine, with mp 145–147°C []_D –50.2°, C₁₉H₄₅NO₆, has been isolated from the epigeal part ofKoralkowia sewerzowii Regel. On the basis of the IR, PMR, and mass spectra of severidinine and its transformation products, and also passage to the known alkaloids severidine, the structure of 3-acetylseveridine has been established for severidinine.Institute of the Chemistry of Plant Substances, Academy of Sciences of the Uzbek SSR, Tashkent. Translated from Khimiya Prirodnykh Soedinenii, No. 4, pp. 488–490, July–August, 1983.     

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.     

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.     

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.     

Synthesis,crystal structure and magnetic properties of a two-dimensional mixed-valence assembly [Fe(salen)]2[Fe(CN)5NO]

A cyanide-bridged Fe^III–Fe^II mixed-valence assembly, [Fe^III(salen)]₂[Fe^II(CN)₅NO] [salen = N,N-ethylenebis(salicylideneiminato)dianion], prepared by slow diffusion of an aqueous solution of Na₂[Fe(CN)₅NO] · 2H₂O and a MeOH solution of [Fe(salen)NO₃] in an H tube, has been characterized by X-ray structure analysis, i.r. spectra and magnetic measurements. The product assumes a two-dimensional network structure consisting of pillow-like octanuclear [—Fe^II—CN—Fe^III—NC—]₄ units with dimensions: Fe^II—C = 1.942(7) Å, C—N = 1.139(9) Å, Fe^III—N = 2.173(6) Å, Fe^II—C—N = 178.0(6)°, Fe^III—N—C = 163.4(6)°. The Fe^II—N—O bond angle is linear (180.0°). The variable temperature magnetic susceptibility, measured in the 4.8–300 K range, indicates the presence of a weak intralayer antiferromagnetic interaction and gives an Fe^III–Fe^III exchange integral of –0.033 cm^–1.     

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.     

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.     

Reactivity of the carbocation generated in the photolysis of 1,2,2,4,6-pentamethyl-1,2-dihydroquinoline toward azide ion

The reaction of the azide ion with the carbocation generated in the photolysis of 1,2,2,4,6-pentamethyl-1,2-dihydroquinoline in methanol was studied by pulse (conventional and laser) and steady-state photolysis techniques. The adduct of the azide ion was characterized by ¹H NMR spectrum. Experimental results were interpreted taking into account a competition between the addition of methanol and azide ion to the carbocation. The rate constants for the reaction of the azide ion with the carbocation (k _Az) were measured at 2—48 °C in a wide range of [N₃ ^–]₀ concentrations from 2·10^–7 to 0.1 mol L^–1 at different ionic strengths () of the solution. The resulting k _Az values are more than an order of magnitude lower than those for diffusional-controlled reactions and vary from 3.2·10⁸ ( = 0) to 4.5·10⁶ L mol^–1 s^–1 ( = 0.8 mol L^–1) in the presence of NaClO₄ (18 °C). The activation energy of addition of the azide ion to the carbocation is 21 kJ mol^–1, which is by 12 kJ mol^–1 lower than the activation energy of the reaction of the carbocation with methanol. The features of the reaction under study are discussed from the viewpoint of the structures of carbocations generated in the photolysis of dihydroquinolines.