Cardiac glycosides ofAcokanthera venenata

Six cardenolides have been isolated from the leaves ofAcokanthera venenata G. Don: AV-1, mp 252–255°C, [] _D ²⁰ +39.4° (MeOH); AV-2, mp 199–208°C, [] _D ²⁰ -59.3° (MeOH); AV-3, mp 269–275°C/300–304°C, [] _D ²¹ –69.8° (MeOH); AV-4, mp 279–289°C; AV-5, mp 222–225°, [] _D ²⁰ -64.3° (MeOH); and AV-6, mp 193–196°C [] _D ²⁰ –23.8° (MeOH — CHCl₃). AV-5 has been identified as acovenoside A. AV-3 is a new cardiac glycoside: it is 1-acetoxy-3-(4-O--D-glucosyl-3-O-methyl--L-talomethylosyloxy)-14-hydroxy-5, 14-card-20(22)-enolide (glucoacovenoside B).Khar'kov State Pharmaceutical Institute. All-Union Scientific Research Institute of Drug, Chemistry and Technology, Khar'kov. Translated from Khimiya Prirodnykh Soedinenii, No. 3, pp. 372–376, May–June, 1987.     

Preparation of 21-aldehydes of Δ17(20)-steroids

A method is described for the synthesis of 17(20)-unsaturated 21-aldehydes by the oxidation of 17-hydroxy-17-vinylsteroids with pyridine chlorochromate. The following compounds were obtained in the course of the investigation: 3-hydroxy-trans-pregna-5,17-dien-21-al acetate, mp 177–178°C (MeOH); trans-pregna-5,17(20)-diene-3,21-diol 3-acetate (I), mp 150–153°C (MeOH); the 21-acetate of (I), with mp 130–133°C (ether-hexane); 3-oxo-trans-pregna-4,17(20)-dien-21-al, with mp 130–132°C (MeOH); and 3-oxo-trans-pregna-4,17(20)-dien-21-cic acid, C₂₁H₂₈O₃, mp 261–263°C. The IR and NMR spectra of the substances obtained are given.All-Union Scientific-Research Institute of Pharmaceutical Chemistry, Moscow. Translated from Khimiya Prirodnykh Soedinenii, No. 3, pp. 340–342, May–June, 1979.     

Triterpene glycosides ofAstragalus and their genins. XII. Askendoside B fromAstragalus taschkendicus

On the basis of chemical transformations and with the aid of physicochemical characteristics it has been established that a new glycoside of the cycloartane series — askendoside B (I) — isolated from the roots ofAstragalus taschkendicus Bge., is 20S,24R-epoxycycloartane-3,6,16,25-tetraol 3-0-[0--L-arabinopyranosyl-(1 2)-(3-0-acetyl--D-xylopyranoside)] 6-0--D-xylopyranoside, C₄₇H₇₆O₁₈, mp 215–218°C, [] _D ²⁰ –45.5° (c 1.1; pyridine). The acid hydrolysis of (I) yielded cyclosiversigenin (II) with mp 239–241°C, [] _D ²⁰ +54.5° (c 1.2; MeOH), and cyclosiversigenin 3-0--D-xylopyranoside (III) with mp 262–264°C, [] _D ²⁰ +41° (c 0.4; MeOH). The periodate oxidation of glycoside (I) followed by acid hydrolysis likewise led to (II) and to D-xylose. The alkaline hydrolysis of (I) yielded askendoside D (IV), with mp 235–236°C, [] _D ²³ –8.5° (c 1.0; pyridine). The Smith degradation of (I) led to (III). The IR and PMR spectra of (I) 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. 457–460, July–August, 1983.     

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.     

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) [] _D ²⁰ +56.4±2° (c 0.0; methanol); II — C₃₀H₄₈O₇, mp 227–229° (ethyl acetate-methanol), [] _D ²⁰ +60.1±2° (c 1.3; methanol); III — C₂₉H₄₈O₇, mp, 241–242° (ethyl acetate-methanol), [] _D ²⁰ +30±2° (c 0.1; dioxane). The structure of (III) was established on the basis of spectral characteristics as 2, 3, 14, 20R, 22R, 23-5-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.Institute of the Chemistry of Plant Substances of the Uzbek SSR Academy of Sciences, Tashkent. Translated from Khimiya Prirodnykh Soedinenii, No. 5, pp. 681–684, September–October, 1987.     

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.     

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 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-3,22-30-triol, C₃₁H₅₀O₅, mp 169–171°C (hexane-acetone), [] ₅₄₆ ²⁰ –11.06° (c 4.52; pyridine); and 2 — (21S, 22S, 23R)-21-methoxy-21,23-epoxycycloart-24-ene-3,22,30-triol, C₃₁H₅₀O₅, mp 190–193°C (hexane-acetone), [] ₅₄₆ ²⁰ +106.6° (c 0.3; pyridine). The results of¹H and¹³C NMR spectroscopy and of mass spectrometry for the new compounds are given.Irkutsk Institute of Organic Chemistry, Siberian Division of the USSR Academy of Sciences. Translated from Khimiya Prirodnykh Soedinenii, No. 4, pp. 510–516, July–August, 1989.     

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.     

Triterpene glycosides and their genins fromThalictrum foetidum. V. Structure of cyclofoetoside B

A new glycoside (cyclofoetoside B) (I) has been isolated from the epigeal part of the plantThalictrum foetidum L. (Ranunculaceae). On the basis of chemical transformations and with the aid of physicochemical characteristics it has been established that cyclofoetoside B is 24S-cycloartane-3, 16, 24, 25, 29-pentaol 3-O--L-arabinopyranoside 16-O-[O--L-rhamnopyranoside-(1 6)--D-glucopyranoside], C₄₇-H₈₀O₁₇, mp 194–197°C (methanol); [] _D ²⁴ +15.7 ± 2° (c 0.88; pyridine). The enzymatic hydrolysis of (I) has yielded cyclofoetigenin B (III), 24S-cycloartane-3,16,24,25,29-pentaol 16-O--D-glucopyranoside, (IV), C₃₆H₆₂O₁₀, mp 223–225°C (acetone), [] _D ²⁴ +37 ± 2° (c 0.97; methanol) and 24S-cycloartane-3,16,24,25,29-pentaol 16-O-[O--L-rhamnopyranosyl-(1 6)--D-glucopyranoside, C₄₂H₇₂O₁₄, mp 229–231°C (methanol), [] _D ³⁰ +41 ± 2° (c 0.7; methanol). Details of the IR and¹H and¹³C NMR spectra of the compounds are given.Irkutsk Institute of Organic Chemistry, Academy of Sciences of the USSR. Institute of the Chemistry of Plant Substances, Academy of Sciences of the Uzbek SSR, Trashkent. Translated from Khimiya Prirodnykh Soedinenii, No. 3, pp. 341–345, May–June, 1986.     

Phytoecdysones ofSilene praemixta. II. Premixisterone

The structure of premixisterone (I) — a new ecdysteroid fromS. praemixta M. Pop. (Caryophyllaceae) — has been established. Compound (I) has the composition C₂₇H₄₄O₅, mp 110–112°C (from C₂H₅OH + H₂O), [] _D ²⁴ 0 ± 4° (c 0.85; MeOH), 202 nm (log 3.35), _max ^KBr 3415 cm^–1 (OH), 1710 cm^–1 (C=0), and does not contain the ⁷-6-keto grouping that is characteristic of natural ecdysteroids. The acetylation of (I) with (CH₃CO)₂ in Py gave the amorphous 3,22-diacetylpremixisterone (II), C₂₁H₄₈O₇. Compound (I) has the structure of 3,14,22R,25-tetrahydroxy-5-cholest-8-en-6-one. 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. 6, pp. 797–799, November–December, 1979.     

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.     

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.     

Glycosylation of triterpenoids of the dammarane series I. 20(S),24(R)-epoxydammarane-3α-12β,25-triol 25-O-β-D-glucopyranoside

The glycosylation of 3,12-diacetoxy-20(S),24(R)-epoxydammaran-25-ol with -acetobromoglucose under the conditions of Helferich's modification and with D-glucose tert-butyl orthoacetate under the conditions of the orthoester method gives a high yield (60–64%) of the hexacetate of the -D-glucoside at the tertiary hydroxy group of 20(S),24(R)-epoxydammarane-3,12,25-triol (III) with mp 207–209°C (ethanol), [] _D ²⁰ -20.9 (c 1.0, CHCl₃). Saponification with 10% KOH in methanol gives the free 20(S),24(R)-epoxydammarane-3,12,25-triol 25-O--D-glucoside (V) (yield 90%) with mp 275–279°C (methanol), [] _D ²⁰ +11.4° (c, 1.0, C₅H₅). The results of IR and¹H and¹³C NMR spectroscopy and of elementary analysis are given.Pacific Ocean Institute of Bioorganic Chemistry of the Far Eastern Scientific Center, Academy of Sciences of the USSR, Vladivostok. Translated from Khimiya Prirodnykh Soedinenii, No. 2, pp. 205–208, March–April, 1980.     

A chemical investigation ofAchillea nobilis

From the flower heads and leaves ofAchillea nobilis collected in the flowering phase close to Balytkykol, Egindybulak region, Karaganda Province, Kazakh SSR, by extraction with chloroform and chromatography of the combined substances on a column of silica gel we have isolated a new sesquiterpene lactone anobin C₁₅H₂₀O₅, mp 175.5–177.5°C and have identified for the first time estafiatin, C₁₅H₁₈O₃, mp 102–104°C []²⁰ –10.3° (chloroform); hanphyllin, C₁₅H₂₀O₃, mp 189°C (decomp), [] _D ²⁰ + 58.6° (c 0.39; chloroform), and 3,5-dihydroxy-6,7,8-trimethoxyflavone, C₁₈H₁₆O₇, mp 148–150°C. On the basis of chemical and spectral characteristics it has been established that anobin has the structure of 4,10-dihydroxy-2,3-epoxy-5,7(H),6(H)-guai-11(13)-en-6,12-olide. It has been established that estafiatin possesses a pronounced growth regulating activity.Deceased.Chemical and Metallurgical Institute, Academy of Sciences of the Kazakh SSR, Karaganda. Translated from Khimiya Prirodnykh Soedinenii, No. 5, pp. 603–607, September–October, 1984.     

Structure of a new chalcone ammothamnidin fromAmmothamnus lehmanni

A new chalcone ammothamnidin with the composition C₂₅H₂₈O₄, mp 112–114°C [] _D ²⁰ + 4.5° (methanol) has been isolated from the epigeal part and roots ofAmmothamnus lehmanni Bge. On the basis of chemical transformations and IR, UV,¹H and¹³C NMR, and mass spectra it has been shown that ammothamnidin has the structure of 2,2,4-trihydroxy-3-(2-isopropenyl-5-methylhex-4-enyl)chalcone.A. Navoi Samarkand State University. Institute of the Chemistry of Plant Substances, Academy of Sciences of the Uzbek SSSR, Tashkent. Translated from Khimiya Prirodnykh Soedinenii, No. 4, pp. 445–450, July–August, 1983.     

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.     

Products of the ozonolysis of epitorulosol

The structure of the products of the ozonization of epitorulosol [13S-labda-8(20),14-diene-13,19-diol] (I) has been established. Compound (I) (1 g) was ozonized at –30°C in 100 ml of absolute CH₃OH until saturation. The O₃ was driven off by nitrogen, 1 ml of (CH₃)₂S was added at –10°C, and the mixture was stirred for 1 h each at –10, 0, and 20°C and was worked up, and the product (1.13 g) was chromatographed on a column containing 45 g of silica gel. The following were eluted in the order of increasing polarity: 420 mg of 19-hydroxy-8,13;8,14-diepoxy-13S-15,20-bisnorlabdan-14-one (II), mp 141.5–142.5°C (from petroleum ether), [] _D ²³ –63° (c 3.1); 255 mg of 8,13;8,14-diepoxy-13S-15,20-bisnorlabdane-14,19-diol (III), characterized in the form of the diacetate (IV) with mp 100–107°C (from petroleum ether); and 117 mg of 19-hydroxy-14,15,20-trisnorlabdane-8,13-dione (V), mp 82–83°C [from petroleum ether-diethyl ether (1:1)], [] _D ²⁶ –40° (c 1.7). The same products but in different ratios were formed on the ozonization of (I) in CH₂Cl₂-Py or in hexane followed by decomposition of the ozonide by heating with H₂O. The []_D values were measured in CHCl₃. Details of the IR and PMR spectra are given.Institute of Chemistry, Academy of Sciences of the Moldavian SSR, Kishinev. Institute of Organic Chemistry, Siberian Branch of the USSR Academy of Sciences, Novosibirsk. Translated from Khimiya Prirodnykh Soedinenii, No. 4, pp. 524–527, July–August, 1987.     

The structure of the flavonoids from Rhodiola algida. II

Summary New flavonoid glycosides have been obtained from the roots ofRhodiola algida: rhodalgin (I), composition C₂₀H₁₈O₁₁, mp 239–240°C; acetylrhodalgin (II) C₂₂H₂₀O₁₂, mp 223–224°C; diacetylrhodalgin (III), C₂₄H₂₂O₁₃, mp 208–209°C; and triacetylrhodalgin (IV), C₂₆H₂₄O₁₄, mp 230–231°C.It has been established that they have the following structures: (I), 3,4,5,7,8-pentahydroxyflavone 8-O--L-arabinopyranoside; (II), 3,4,5,7,8-pentahydroxyflavone 8-O-(3-O-acetyl--L-arabinopyranoside; (III), 3,4,5,7,8-pentahydroxyflavone 8-O-(2,3-di-O-acetyl)--D-xylopyranoside; and (IV), 3,4,5,7,8-pentahydroxyflavone 8-O-(2,34-tri-O-acetyl)--D-xylopyranoside. The -L-arabinopyranose and -D-xylopyranose are present in these compounds in the C1 conformations.In the performance of this investigation, the authors consulted O. S. Chizhov, and M. B. Zoltarev (N. D. Zelinskii Institute of Organic Chemistry of the Academy of Sciences of the USSR) and V. I. Sheichenko (All-Union Institute of Medicinal plants).All-Union Scientific-Research Institute of Medicinal Plants. Translated from Khimiya Prirodnykh Soedinenii, No. 6, pp. 712–720. November–December, 1975.