Lactones ofFerula gigantea

The following substances have been isolated from an acetone extract ofFerula gigantea B. Fedtsch.: a coumarin — umbelliferone, C₉H₆O₂, mp 230–233°C; and sesquiterpene lactones — talassin A, C₂₅H₃₀O₇, mp 188–191°C; malaphyllinin, C₂₄H₂₄O₇, mp 231–235°C; malaphyll, C₂₉H₃₂O₉, mp 212–213°C; and malaphyllin, C₂₆H₂₈O₉, mp 216–218°C. Structures have been proposed for three new sesquiterpene lactones on the basis of an analysis of their spectral characteristics.All-Union Scientific-Research Institute of Medicinal Plants, Moscow. M. V. Lomonosov Moscow State University, Botanical Garden, Moscow. Translated from Khimiya Prirodnykh Soedinenii, No. 4, pp. 490–495, July–August, 1979.     

Coumarins ofHapolophyllum obtusifolium. Structures of two new coumarin glycosides

Two coumarin glycosides have been isolated from an aqueous ethanolic extract of the epigeal part ofHaplophyllum obtusifolium: (I) — C₁₆H₁₆O₁₀, mp 164–166°C, [α]_D ?52.4° (dimethylformamide); and (II) — C₂₆H₂₆O₁₂, mp 206–208°C, [α]_D ?110.5° (pyridine). It has been established on the basis of chemical transformations and spectral characteristics that (I) has the structure of fraxetin 7-O-β-D-glucopyranoside and (II) that of scopoletin 7-O-(6′-O-feruloyl-β-D-glucopyranoside).     

Flavonoids of inflorescences of Calendula officinalis

By column chromatography on polyamide sorbent, the inflorescences of pot marigold calendula have yielded eight substances of flavonoid nature: two aglycons — quercetin (C₁₅H₁₀O₇, mp 309–311°C) and isorhamnetin (C₁₆H₁₂O₇, mp 314–316°C); six glycosides, of which three have been identified as isoquercetin (C₂₁H₂₀O₁₂, [α] _D ²⁰ ?36° in methanol, mp 218–220°C), isorhamnetin 3-O-β-D-glucoside (C₂₂H₂₂O₁₂, [α] _D ²⁰ ?59° in dimethylformamide, mp 193–195°C), narcissin (C₂₈H₃₂O₁₆, [α] _D ²¹ ?28° in dimethylformamide, mp 180–182°C), and three substances that have proved to be new and have been called calendoflaside (C₂₈H₃₂O₁₅, [α] _D ²¹ ?85° in methanol, mp 192–195°C; calendoflavoside (C₂₈H₃₂O₁₆, [α] _D ²⁰ ?106° in methanol, mp 189–192°C), and calendoflavobioside (c₂₇H₃₀O₁₆, [α] _D ²⁰ ?105° in methanol, mp 194–197°C).     

A new component ofArtemesia hanseniana

A sesquiterpene lactone with mp 97–99°C, C₁₅H₂₀O₃, identified as deoxy-ψ-santonin, has been isolated from the epigeal part ofArtemisia hanseniana var.phylostachus.     

Comparative characterization of the coumarin composition ofSeseli campestre growing in Moldavia and in the Caucasus

The results are given of the identification of (?)-trans-khellactone and its 4′-methyl ether and (?)-3′(S), 4′(S)-trans-3′-senecioyloxy-4′-angeloyloxy-3′,4′-dihydroseselin and of the establishment of the structure of three new khellactone derivatives — campestrol (VII), C₁₉H₂₂O₆, [α] _D ²⁰ + 32° (c 7.8; chloroform), campestrinol (X), C₂₄H₂₆O₇, mp 116–118°C, and campestrinoside (I), C₂₀H₂₄O₁₀, mp 172–173°C, [α]_D ?272.5° (c 4.7; ethanol). It has been shown on the basis of chemical and spectral characteristics that campesol, earlier described as a new substance, is a mixture of two isomeric compounds — 4′-hydroxy-3′-senecioyloxy-3′,4′-dihydroseselin and 3′-angeloyloxy-4′-hydroxy-3′,4′-dihydroseselin.     

Phytoecdysteroids ofRhaponticum carthamoides

From the roots with rhizomes of the plantRhaponticum carthamoides Willd) Iljin Compositae), in addition to integristerone A, ecdysterone, polypodin B, 2-deoxyecdysterone, and 24(28)-dehydromakisterone A, we have isolated the new compounds ecdysteron3–2,3-monoacetonide (I), ecdysterone 20,22-monoacetonide (II)) and rhapisterone (III): I — C₃₀H₄₈O₇, mp 232–233° (ethyl acetate-methanol) [α] _D ²⁰ +56.4±2° (c 0.0; methanol); II — C₃₀H₄₈O₇, mp 227–229° (ethyl acetate-methanol), [α] _D ²⁰ +60.1±2° (c 1.3; methanol); III — C₂₉H₄₈O₇, mp, 241–242° (ethyl acetate-methanol), [α] _D ²⁰ +30±2° (c 0.1; dioxane). The structure of (III) was established on the basis of spectral characteristics as 2β, 3β, 14α, 20R, 22R, 23ζ-5β-stigmast-7-en-6-one. Details of the PMR, mass, and IR spectra of all the compounds and of the CD of rhapisterone are given.     

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

A new genin — cycloorbigenin (I), C₃₀H₄₈O₅, mp 217–219°C, [α] _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 16β,23:16α,24-diepoxy-23(R),24(S)cycloartane-3β,7β,25-triol. The acetylation of (I) with acetic anhydride in pyridine yielded its diacetate (II), C₃₄H₅₂O₇, mp 148–150°C, [α] _D ²⁰ +32.6° (c 0.92; methanol) and its triacetate (III), C₃₆H₅₄O₈, mp 137–139°C, [α] _D ²⁰ +75° (c 0.4; methanol). The Jones oxidation of (I) led to a diketone (IV), C₃₀H₄₄O₅, mp 155–158°C, [α] _D ²⁰ -73° (c 0.63; methanol). Details of the PMR, IR, and mass spectra are given for all the compounds.     

Triterpene glycosides of Thalictrum squarrosum. III. Structures of squarrogenins 1 and 2

Two genins — squarrogenin 1 and squarrogenin 2 — have been isolated from nodding meadow rue by the hydrolysis of squarrosides A1 and A2. The compounds are epimeric at C-21 and have the following structures: 1 — (21R, 22S, 23R)-21-methoxy-21,23-epoxycycloart-24-ene-3β,22β-30-triol, C₃₁H₅₀O₅, mp 169–171°C (hexane-acetone), [α] ₅₄₆ ²⁰ ?11.06° (c 4.52; pyridine); and 2 — (21S, 22S, 23R)-21-methoxy-21,23-epoxycycloart-24-ene-3β,22β,30-triol, C₃₁H₅₀O₅, mp 190–193°C (hexane-acetone), [α] ₅₄₆ ²⁰ +106.6° (c 0.3; pyridine). The results of¹H and¹³C NMR spectroscopy and of mass spectrometry for the new compounds are given.     

Withasteroids ofPhysalis. VII. 14α-Hydroxyixocarpanolide and 24,25-expoxywithanolide D

Two new withasteroid have been isolated fromPhysalis angulata L. — 14α-hydroxyixocarpanolide and 24,25-epoxywithanolide D. 14α-hydroxyixocarpanolide — C₂₈H₄₀O₇, mp 245–250°C (from methanol), [α] _D ²⁰ +29±2° (chloroform). 24,25-Epoxywithanolide D — C₂₈H₃₈O₇, mp 257–261°C (from methanol, [α] _D ²⁰ +23±2° (chloroform). On the basis of its UV, IR, CD, mass, and¹H and¹³C NMR spectra the structure of 5α,14α,20R-trihydroxy-1-oxo-6α,7α-epoxy-22R-2itha-2-enolide is suggested for 14α-hydroxyixocarpanolide. On the basis of spectral characteristics and the preparation of 4β-acetoxy and 4-oxo derivatives of 24,25-epoxywithanolide D, the structure of 4β,20R-dihydroxy-1-oxo-5β,6β;24S,25S-diepoxy-22R-witha-2-enolide is proposed for it.     

Structure and stereochemistry of lapidin

The roots ofFerula lapidosa Eug.Korov. have yielded lapidin, C₂₀H₃₀O₄, mp 80–81°C (hexane), [α]D²⁰ +166° (c 1.5; chloroform) — an ester of a new carotane alcohol lapidol and angelic acid. A structure and absolute configuration has been suggested for it on the basis of chemical transformations and spectral characteristics.     

Structure of ergolide

The epigeal part ofErigeron khorassanicus Boiss. has yielded a new sesquiterpene lactone of the pseudoguaiane type — ergolide C₁₇H₂₂O₅, mp 179–180°C (ethanol) [α] _D ²⁰ +123° (c 4.88; ethanol). On the basis of chemical transformations and spectral characteristics, its structure and configuration have been established as 6-acetoxy-4-oxo-1,7αH,6,8,10βH-pseudoguai-11(13)-en-8,12-olide.     

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, [α] _D ²² ? 17.5° (c 1; ethanol). Reduction with LiAlH₄ has yielded a diol C₂₂H₃₈O₅, mp 165–166°C [α] _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, [α] _D ²⁰ ?3.9° (c 1; ethanol). The synthesis of lagohirsidin from lagochilin has been effected.     

A study of the coumarins ofHaplophyllum obtusifolium. The structure of obtusidin and of obtusiprenin

The epigeal part ofHaplophyllum obtusifolium Ledeb has yielded scopoletin and the following new coumarins: obtusidin, C₁₅H₁₆O₅, mp 165–167°C, and obtusiprenin, C₁₅H₁₆O₅, mp 139–140°C. It has been established on the basis of chemical and spectral characteristics that obtusidin has the structure of 3-(1′-1′-dimethylallyl)-7,8-dihydroxy-6-methoxycoumarin, and obtusipernin that of 5-(3′,3′-dimethylallyl)-7,8-dihydroxy-6-methoxycoumarin.     

A sesquiterpene lactone fromAcroptilon repens

A new sesquiterpene lactone has been isolated from the epigeal part ofAcroptilon repens, with the composition C₁₉H₂₂O₆, mp 199–201°C, M⁺ 346, and it has been called acroptin (I). The treatment of (I) with acetic anhydride in pyridine gave a diacetate (II). The structure of (I) has been confirmed by the NMR spectra of (I) and (II). Details of the IR and NMR spectra of (I) and (II) are presented.     

Terpenoid coumarins ofFerula kokanica

From an alcoholic extract of the roots ofFerula kokanica Rgl. et Schmalh., collected in the region of the village of Oman-kutan (Samarkand Province), have been isolated polyanthinin, mogoltadone, gummosin, kellerin, feshurin, and umbelliferone, and two new coumarins: deacetylkellerin, C₂₄H₃₂O₅, M⁺ 400, mp 134–136°C, [α] _D ²² +52° (c 0.1, ethanol), and kokanidin, C₂₆H₃₄O₆, M⁺ 442, mp 189–191°C, [α] _D ¹⁸ ?30° (c 1.0; ethanol). The structure of deacetylkellerin has been established on the basis of the results of a study of UV, IR, PMR, and mass spectra. The structure and configuration of kokanidin have been established on the basis of spectral characteristics and also conversion into conferol acetate and feshurin.     

A new terpenoid coumarin fromFerula kopetdaghensis

From the roots ofFerula kopetdaghensis Eug. Kor. have been isolated nevskin and isosamarcandin and a new terpenoid coumarin kopeolone, C₂₄H₃₀O₅, M⁺ 398, mp 125–126°C, [α]_D ¹⁸ +70° (c 0.1, ethanol). On the basis of UV, IR, PMR, and mass spectrometry, and also of transformation into farnesiferols B and C, the configurations of kopeolone, kopeolin, kopeoside, fekrol, kopetdaghin, and fekolin have been established. The configuration of farnesiferol C suggested previously has been confirmed.     

Shonachalin B — A new eudesmanolide fromArtemisia fragans

The results are given of an investigation of a new eudesmanolide fromArtemisia fragans Willd., shonachalin B, with the composition C₁₅H₂₂O₄, mp 127–129°C.     

Subhirsine — A new alkaloid from the roots ofConvolvulus subhirsutus

The roots ofConvolvulus subhirsutus collected on the territory of the Chimkent Province (Kazakh SSR) have yielded a new dimeric alkaloid of the tropane series — subhirsine with mp 190–191°C, composition C₃₃N₄₀O₉N₂. Its structure has been established.     

Compactin — A new orobol bioside fromGenista compacta

From the epigeal part ofGenista compacta has been isolated the new isoflavone bioside compactin — C₂₇H₃₀O₁₆, mol. wt 610, mp 206–208°C, [α] _D ²⁰ + 35.8° — for which on the baseos chemical transformations and spectral characteristics the structure of 7-[O-β-D-glucopyranosyl-(1 → 2)-β-D-glucopyransyloxy]-3′,4′,5-trihydroxyisoflavone, or orobol 7-O-β-sophoroside, has been established.     

Structure of valivine

The total chloroform-extracted material from the epigeal part ofFritillaria valujevii Regel has yielded a new base — valivine, with mp 256–258°C, [α]_D -48°, C₂₈·H₄₇NO₃ (I). The structure and configuration of valivine have been established on the basis of a study of its IR, NMR, and mass spectra and those of its transformation products.