Phytochemistry (v.54, #8)

Index (vii-viii).

Insecticidal rocaglamide derivatives from Aglaia spectabilis (Meliaceae) by C Schneider; F.I Bohnenstengel; B.W Nugroho; V Wray; L Witte; P.D Hung; L.C Kiet; P Proksch (731-736).
Bark of Aglaia spectabilis collected on the island of Phu Quoc (Vietnam) yielded 11 insecticidal cyclopentatetrahydrobenzofurans of the rocaglamide type including four new natural products. Structure elucidation of the new compounds is described. All rocaglamide derivatives isolated exhibited strong insecticidal activity towards neonate larvae of the polyphagous pest insect Spodoptera littoralis when incorporated into an artificial diet. LC50 values varied from 0.8 to 80 ppm. The most active compounds isolated, methylrocaglate and C-3′ hydroxylmethylrocaglate, were similar with regard to their insecticidal activity to the well-known natural insecticide azadirachtin.
Keywords: Aglaia spectabilis; Meliaceae; Benzofurans; Rocaglamide derivatives; Structure elucidation; Natural insecticides; Spodoptera littoralis;

A geranylated chalcone with 5α-reductase inhibitory properties from Artocarpus incisus by Kuniyoshi Shimizu; Ryuichiro Kondo; Kokki Sakai; Supanida Buabarn; Uraiwan Dilokkunanant (737-739).
A geranylated chalcone was isolated from leaves of Artocarpus incisus and it showed potent 5α-reductase inhibitory activity.
Keywords: Artocarpus incisus; Moraceae; 5α-Reductase inhibitor; Geranylated chalcone; 3′-Geranyl-2′,3,4,4′-tetrahydroxychalcone;

Saikosaponins from roots of Bupleurum gibraltaricum and Bupleurum spinosum by Alejandro F. Barrero; Ali Haı̈dour; Ahmed Sedqui; Ahmed Ibn Mansour; Ignacio Rodrı́guez-Garcı́a; Antonio López; M. Muñoz-Dorado (741-745).
Two new saikosaponins have been identified in the butanolic fraction of the ethanol extract of the roots of Bupleurum spinosum: 3β,16α,23,28-tetrahydroxyoleana-11,13(18)-dien-30-oic acid 3-O-β-D-glucopyranosyl-(1→2)-β-D-glucopyranosyl-(1→3)-β-D-fucopyranoside, and 3β,16α,23,28,30-pentahydroxyoleana-11,13(18)-diene 3-O-β-D-glucopyranosyl-(1→2)-β-D-glucopyranosyl-(1→3)-β-D-fucopyranoside. 3β,16β,23-trihydroxy-13,28-epoxyolean-11-ene 3-O-β-D-glucopyranosyl-(1→2)-β-D-glucopyranosyl-(1→3)-β-D-fucopyranoside was also isolated, and this structure agreed with the one proposed for bupleuroside I, but their spectroscopic data have not been described until now. From the same fraction of the roots of Bupleurum gibraltaricum, the known compound buddlejasaponin IV has been isolated as the predominant component (90%). Structures were elucidated using spectroscopic analysis, specially 2D-NMR experiments.
Keywords: Bupleurum spinosum; Bupleurum gibraltaricum; Umbelliferae; Saikosaponins; Bupleuroside I;

Volatile constituents of wood-rotting basidiomycetes by Joachim Rösecke; Martin Pietsch; Wilfried A. König (747-750).
Phytochemical investigation of the hydrodistillation products of the basidiomycetes Fomitopsis pinicola, Piptoporus betulinus, Gloeophyllum odoratum and Trametes suaveolens led to the identification of numerous mono- and sesquiterpenes as well as many aliphatic alcohols, aldehydes and ketones and some aromatic compounds. In addition, some diterpenes were identified as constituents of Fomitopsis pinicola. The absolute configuration of some terpenes was determined.
Keywords: Piptoporus betulinus; Fomitopsis pinicola; Gloeophyllum odoratum; Trametes suaveolens; Basidiomycete; Volatile metabolites; Sesquiterpene; Fungal terpenoids;

Triterpene saponins and iridoid glucosides from Galium rivale by Salvatore de Rosa; Carmine Iodice; Maya Mitova; Nedjalka Handjieva; Simeon Popov; Mincho Anchev (751-756).
Three new glycosides of the oleanene-type triterpenes, rivalosides C–E (13), along with three known triterpene saponins, momordin IIb (4) and rivalosides A–B (56), and five known iridoid glucosides: monotropein, scandoside, deacetylasperulosidic acid, geniposidic acid and asperulosidic acid, were isolated from aerial parts of Galium rivale. The structures of the new compounds were elucidated by spectral methods and chemical means as 2α-acetoxy-3α,19α-dihydroxy-olean-12-en-28-oic acid 28-O-β-D-glucopyranosyl-(1 → 6)-β-D-glucopyranoside, 2α,3α,19α-trihydroxy-olean-12-en-28-oic acid 28-O-β-D-glucopyranosyl-(1 → 6)-β-D-glucopyranoside and 3-O-β-D-glucuronopyranosyl-24-hydroxy-olean-12-en-28-oic acid 28-O-β-D-glucopyranoside, for rivalosides C–E, respectively. The taxonomic significance of the rivalosides in G. rivale was discussed.
Keywords: Galium rivale; Rubiaceae; Rivalosides C–E; Triterpene saponin; Iridoid glycoside;

Phytochemical examination of solvent extracts of the wood-rotting fungi Daedalea quercina and Daedaleopsis confragosa var. tricolor led to the isolation of five new triterpene derivatives and some known fungal constituents. All structures were identified by one- and two-dimensional NMR spectroscopy and mass spectrometry. From Daedalea quercina, the new natural products 16-O-acetylpolyporenic acid C, 16α-acetoxy-24-methylene-3-oxolanost-8-en-21-oic acid, (+)-24-methylene-3,23-dioxolanost-8-en-26-oic acid, (+)-3β,12β-dihydroxy-24-methyl-23-oxolanost-8-en-26-oic acid and 12β,23-epoxy-3α,23-dihydroxy-24-methyllanost-8-en-26-oic acid could be isolated. From Daedaleopsis confragosa var. tricolor, the compounds 3α-carboxyacetoxyquercinic acid, 3α-carboxyacetoxy-24-methylene-23-oxolanost-8-en-26-oic acid and 5α,8α-epidioxyergosta-6,22-dien-3β-ol were identified. These are the first described triterpene derivatives isolated from this fungus.
Keywords: Daedalea quercina; Daedaleopsis confragosa var. tricolor; Polyporaceae; Basidiomycete; Triterpene derivatives;

Sesquiterpenoids and phenolics from Crepis mollis by Wanda Kisiel; Klaudia Zielińska; Swati P Joshi (763-766).
From the roots of Crepis mollis, one new and two known guaianolides were isolated together with eight known guaianolide glycosides, one known germacranolide glycoside and two known phenylpropanoids. The structure and relative configuration of the new compound were established as 9α-hydroxy-4β, 15, 11β, 13-tetrahydro-dehydrozaluzanin C by spectral methods.
Keywords: Crepis mollis; Asteraceae; Lactuceae; Sesquiterpene lactones; Phenylpropanoids; Glycosides;

Diterpenoids from the roots of Croton macrostachys by Modest C. Kapingu; Dominique Guillaume; Zakaria H. Mbwambo; Mainen J. Moshi; Febronia C. Uliso; Rogasian L.A. Mahunnah (767-770).
Three novel diterpenoids have been isolated from the roots of Croton macrostachys. The structure and stereochemistry of the compounds have been unambiguously settled as neoclerodan-5,10-en-19,6β;20,12-diolide, 3α,19-dihydroxytrachylobane, and 3α,18,19-trihydroxytrachylobane from detailed spectroscopic evidence.
Keywords: Croton macrostachys; Euphorbiaceae; Diterpenoid; Neoclerodan-5,10-en-19,6β;20,12-diolide; 3α,19-Dihydroxytrachylobane; 3α,18,19-Trihydroxytrachylobane;

Labdane diterpenes from Otostegia fruticosa by Nawal M Al-Musayeib; Fawkeya A Abbas; M.Shamim Ahmad; Jaber S Mossa; Farouk S El-Feraly (771-775).
The new labdane diterpenes otostegin A (2), otostegin B (6) and 15-epi-otostegin B (7) were isolated from the aerial parts of Otostegia fruticosa, besides the previously known labdanes preleoheterin (1), leoheterin (3), leopersin C and 15-epi-leopersin C (4, 5), ballonigrin (9) and vulgarol (11), along with the iridoid glucoside 8-O-acetylharpagide (10). The structure elucidation of all the isolated compounds was based on their spectral data and chemical derivatization.
Keywords: Otostegia fruticosa; Labdane diterpenes; Otostegin; Harpagide; Ballonigrin; Vulgarol;

Highly oxidized cuparene-type sesquiterpenes from a mycelial culture of Flammulina velutipes by Noemia Kazue Ishikawa; Keiko Yamaji; Satoshi Tahara; Yukiharu Fukushi; Kunihide Takahashi (777-782).
Cuparene-type sesquiterpenes were isolated from a culture broth of Flammulina velutipes (Curt.:Fr.) Sing. Using spectroscopic methods (HR-MS, 1H and 13C NMR, and 2D NMR, spectroscopy), their structures were determined to be 2,3,4,5-tetrahydro-2,7-dihydroxy-5,8,10,10-tetramethyl-2,5-methano-1-benzoxepin and 5-methyl-2-(3-oxo-1,2,2-trimethylcyclopentyl)benzoquinone. Both showed antimicrobial activity against Cladosporium herbarum and Bacillus subtilis.
Keywords: Flammulina velutipes; Tricolomataceae; Basidiomycota; Enokitake; Antimicrobial activity; Sesquiterpenoid; Cuparene-type; Enokipodin A; Enokipodin B;

Minor sulfated saikosaponins from the aerial parts of Bupleurum rigidum L. by Sandra Sánchez-Contreras; Ana Marı́a Dı́az-Lanza; Carmen Bartolomé; Manuel Bernabé (783-789).
Five new sulfated saikosaponins (Sandrosaponins II–VI) were isolated as minor components from the aerial parts of Bupleurum rigidum L. Their structures have been established by 1D and 2D-NMR techniques, FABMS, and chemical methods.
Keywords: Bupleurum rigidum; Umbelliferae; Saponins; Saikosaponins;

Chromatographic separation of ethanolic root extracts of Taraxacum laevigatum and Taraxacum disseminatum afforded a total of eight germacrane- and eudesmane-type sesquiterpenoids, including new compounds, 1β,3β,6α-trihydroxy-4α(15)-dihydrocostic acid methyl ester and its 1-O-β-glucopyranoside. Their structures were established by spectroscopic analyses. In addition, the structure of 4α(15),11β(13)-tetrahydroridentin B-1-O-β-glucopyranoside was elucidated by extensive NMR studies.
Keywords: Taraxacum laevigatum; Taraxacum disseminatum; Asteraceae; Lactuceae; Sesquiterpenoids; Germacranolides; Eudesmanolides; Costic acid derivatives; Glycosides;

Saponins from Lonicera bournei by Ting Xiang; Yasuhiro Tezuka; Li-Jun Wu; Arjun H. Banskota; Shigetoshi Kadota (795-799).
The lupane-triterpene glycosides, bourneioside A and bourneioside B, and two known saponins were isolated from Lonicera bournei Hemsl. The structures of bourneioside A and B were elucidated as 3-O-β-D-glucopyranosyl-23-hydroxy-lup-20(29)-en-28-oic acid-28-O-β-D-glucopyranosyl ester and 3-O-β-D-glucopyranosyl-23-hydroxy-lup-20(29)-en-28-oic acid-28-O-[β-D-glucopyranosyl-(1→6)-β-D-glucopyranosyl] ester, respectively, on the basis of spectral data and chemical evidence.
Keywords: Lonicera bournei Hemsl.; Caprifoliaceae; Bourneioside A; Bourneioside B;

Tirucallane triterpenoids from Dysoxylum hainanense by Xiao-Dong Luo; Shao-Hua Wu; Yun-Bao Ma; Da-Gang Wu (801-805).
Four tirucallane derivatives, 3β,22S-dihydroxy-tirucalla-7,24-dien-23-one, 22,23-epoxy-tirucalla-7-ene-3β,24,25-triol, 3β,25-dihydroxy-tirucalla-7,23-diene, 23,26-dihydroxy-tirucalla-7,24-dien-3-one, together with two known triterpenoids, 24,25-epoxy-3β,23-dihydroxy-7-tirucallene, tirucalla-7,24-diene-3β,23-diol, were isolated from Dysoxylum hainanense. Their structures were elucidated on the basis of spectroscopic evidence.
Keywords: Dysoxylum hainanense; Meliaceae; Tirucallanes; 3β,22S-Dihydroxy-tirucalla-7,24-dien-23-one; 22,23-Epoxy-tirucalla-7-ene-3β,24,25-triol; 3β,25-Dihydroxy-tirucalla-7,23-diene; 23,26-Dihydroxy-tirucalla-7,24-dien-3-one;

Iridoids from Caryopteris x clandonensis by Sébastien Hannedouche; Edouard Stanislas; Claude Moulis; Isabelle Fourasté (807-809).
In continuation of our phytochemical studies on Caryopteris x clandonensis (Lamiaceae), three further iridoids were isolated from the methanolic extract of the stems. Their structures were established by 1D and 2D NMR and MS analysis as a C-6 epimer of 8-O-acetylharpagide (6-epi-8-O-acetylharpagide), a derivative of harpagide which contained the unusual feature of a 3′,4′ seco-glycopyranosyl moiety (clandonoside II) and a methyl cetal of 8-O-acetylharpagide aglucone hydrate named clandonensine.
Keywords: Caryopteris x clandonensis; Lamiaceae; Verbenaceae; Iridoids; Seco-glycoside; 6-epi-8-O-acetylharpagide; Clandonoside II; Clandonensine; 8-O-acetylharpagide;

Sesquiterpene lactone and friedelane derivative from Drypetes molunduana by J Wandji; J.D Wansi; V Fuendjiep; E Dagne; D.A Mulholland; F Tillequin; Z.T Fomum; B.L Sondengam; B.C Nkeh; D Njamen (811-815).
A new sesquiterpene lactone, drypemolundein A and a new friedelane derivative, drypemolundein B, along with seven known compounds have been isolated from the whole stems of Drypetes molunduana Pax and Hoffm. Their structures were established on the basis of one- and two-dimensional NMR, homo- and hetero-nuclear spectroscopic evidence.
Keywords: Drypetes molunduana; Euphorbiaceae; Stems; Drypemolundeins A and B; Sesquiterpene lactone; Friedelane; Triterpenoids; Lignan;

Triterpenoid saponins from Ardisia mamillata by J. Huang; Y. Ogihara; H. Zhang; N. Shimizu; T. Takeda (817-822).
Two saponins were isolated from the roots of Ardisia mamillata HANCE. Their structures were established on the basis of MALDI-TOFMS, 1H, 13C NMR and 2D NMR (COSY, HOHAHA, HETCOR, HMBC and ROESY) spectra, and on chemical evidence, to be ardisimamilloside A, 3-O-{α-L-rhamnopyranosyl-(1→2)-β-D-glucopyranosyl-(1→4)-[β-D-glucopyranosyl-(1→2)]-α-L-arabinopyranosyl}-3β, 16α,28α-trihydroxy-13β,28-epoxy-oleanan-30-al; and ardisimamilloside B, 3-O-{α-L-rhamnopyranosyl-(1→2)-β-D-glucopyranosyl-(1→4)-[β-D-glucopyranosyl-(1→2)]-α-L-arabinopyranosyl}-3β-hydroxy-13β,28-epoxy-oleanan-16-oxo-30-al.
Keywords: Ardisia mamillata; Myrsinaceae; Triterpenoid saponin; Ardisimamilloside A; Ardisimamilloside B;

Two oleanane triterpenoids from Gordonia ceylanica and their conversions to taraxarane triterpenoids by H.M.T.B. Herath; P.S. Athukoralage; Joanne F. Jamie (823-827).
Chemical investigation of the hot hexane extract of the stem bark of Gordonia ceylanica afforded two new oleanane triterpenoids, 3β-acetoxy-11α,13β-dihydroxyolean-12-one (1) and 3β,11α-diacetoxy-13β-hydroxyolean-12-one (2). The attempted acid hydrolysis of these two compounds resulted the dehydration and subsequent methyl group migration to afford the taraxarane triterpenoids 3β,11α-dihydroxytaraxer-14-en-12-one (4) and 3β-hydroxy-11α-acetoxytaraxer-14-en-12-one (5), respectively. These taraxaranes have not been previously reported.
Keywords: Gordonia ceylanica; Theaceae; Triterpenoids; Oleanane; Taraxarane;

Taxane diterpenoids from Taxus yunnanensis and Taxus cuspidata by Qing-Wen Shi; Takayuki Oritani; Hiromasa Kiyota; Ding Zhao (829-834).
Chemical examination of the seeds of the Chinese yew, Taxus yunnanensis Cheng et L. K. Fu and the Japanese yew, Taxus cuspidata Sieb et Zucc, resulted in the isolation of four taxane diterpenoids. The structures of these taxoids were established as (12α)-2α-acetoxy-5α,9α,10β-trihydroxy-3,11-cyclotax-4(20)-en-13-one; 2α,7β,13α-triacetoxy-5α,9α-dihydroxy-2(3→20)abeotaxa-4(20),11-dien-10-one; 9α,10β-diacetoxy-5α-cinnamoyloxytaxa-4(20),11-dien-13α-ol and the known 2α,7β,9α,10β,13-pentaacetoxy-taxa-4(20),12-diene-5α,11β-diol on the basis of spectral analysis.
Keywords: Taxus yunnanensis Cheng et L. K. Fu; Taxus cuspidata Sieb et Zucc; Taxaceae; Seeds; Taxoids; Taxane diterpenoid;

Euphane triterpenoid and lipid constituents from Butea monosperma by Mamta Mishra; Yogendra N. Shukla; Sushil Kumar (835-838).
Besides stigmasterol, stigmasterol-ßD-glucopyranoside and nonacosanoic acid, two new compounds isolated from the stems of Butea monosperma have been characterised as 3α-hydroxyeuph-25-ene and 2,14-dihydroxy-11,12-dimethyl-8-oxo-octadec-11-enylcyclohexane by spectral data and chemical studies.
Keywords: Butea monosperma; Fabaceae; 3α-Hydroxyeuph-25-ene; Lipids; Steroids;

Neutral taxoids from Taxus cuspidata as modulators of multidrug-resistant tumor cells by Katsuhiko Kosugi; Jun-ichi Sakai; Shujun Zhang; Yusuke Watanabe; Hirofumi Sasaki; Toshio Suzuki; Hisahiro Hagiwara; Naonori Hirata; Katutoshi Hirose; Masayoshi Ando; Akihiro Tomida; Takashi Tsuruo (839-845).
Two taxoids, taxinine NN-7 (1) and 3,11-cyclotaxinine NN-2 (2), were isolated from the neutral fraction of the EtOAc extract of a mixture of needles and young stems of Taxus cuspidata. The structures were determined by spectroscopic analysis. Both compounds showed some activity as modulators of multidrug-resistant tumor cells.
Keywords: Taxus cuspidata; Taxaceae; Taxinine NN-7; Cyclotaxinine NN-2; Modulators of multidrug-resistant tumor cells;

Diterpene glucosides from Pieris formosa by Li-Quan Wang; Shao-Nong Chen; Kin-Fai Cheng; Can-Jun Li; Guo-Wei Qin (847-852).
Five diterpene glucosides, pierisformosides B–F were isolated from Pieris formosa D. Don (Ericaceae). Their structures were elucidated on the basis of spectral analysis, including 1 H – 1 H COSY, 13 C – 1 H COSY, HMBC and NOESY experiments.
Keywords: Pieris formosa; Ericaceae; Diterpene glucosides; Pierisformosides B–F; Structure elucidation;

Triterpenoid saponins from Fagonia cretica by S.M.Abdel Khalik; Toshio Miyase; Hanan A. El-Ashaal; F.R. Melek (853-859).
Four new triterpenoid saponins were isolated and identified from the aerial parts of Fagonia cretica. They were characterized as 3-O-[β-D-glucopyranosyl (1→2)-α-L-arabinopyranosyl] hederagenin 28-O-β-D-glucopyranosyl ester, 3-O-[β-D-glucopyranosyl (1→2)-α-L-arabinopyranosyl] oleanolic acid 28-O-[β-D-glucopyranosyl (1→6)-β-D-glucopyranosyl] ester, 3-O-[β-D-glucopyranosyl (1→2)-α-L-arabinopyranosyl] 27-hydroxy oleanolic acid 28-O-[β-D-glucopyranosyl (1→6)-β-D-glucopyranosyl] ester and 3β-O-[β-D-glucopyranosyl (1→2)-α-L-arabinopyranosyl] olean-12-en-27-al-28-oic acid 28-O-[β-D-glucopyranosyl (1→6)-β-D-glucopyranosyl] ester. The structures of the saponins were assigned by spectral analyses (FABMS, 1H, 13C NMR, 1H–1H COSY, TOCSY, HMQC and HMBC spectra) and NOE experiments. To the best of our knowledge the genin 3β hydroxy olean-12-en-27-al-28-oic acid is new.
Keywords: Fagonia cretica; Zygophyllaceae; Triterpenoid saponins;

Triterpenoidal constituents from Eucalyptus camaldulensis var. obtusa leaves by Bina S Siddiqui; Ishrat Sultana; Sabira Begum (861-865).
An investigation on the constituents of the fresh, uncrushed leaves of Eucalyptus camaldulensis var. obtusa has led to the isolation of the triterpenoid amirinic acid and four known triterpenoids ursolic acid lactone, betulinic acid, oleanolic acid and ursolic acid. Amirinic acid transformed into amirolide in deuterated chloroform at room temperature. The new products were characterized by exhaustive spectroscopic studies as 2α,3β,7β-trihydroxy-11α-methoxyurs-12-en-28-oic acid and 2α,3β,7β-trihydroxyurs-11-en-28,13β-olide.
Keywords: Eucalyptus camaldulensis var. obtusa; Myrtaceae; Triterpenoids; Amirinic acid; Amirolide;

The ubiquitous glycolipid 1,2-dilinolenoyl-3-galactopyranosylglycerol and a new protolimonoid glucoside, named prieurianoside, were isolated from the leaves of Trichilia prieuriana. The structure of the latter was established, by spectroscopic techniques, as 12β,21-diacetoxy-29-β-D-glucopyranosyloxy-23ξ-hydroxytirucalla-7,24-dien-3-one.
Keywords: Trichilia prieuriana; Meliaceae; Protolimonoid glucoside; Prieurianoside; Monogalactosyl diglyceride;

A stilbene and dihydrochalcones with radical scavenging activities from Loiseleuria procumbens by Muriel Cuendet; Olivier Potterat; Aline Salvi; Bernard Testa; Kurt Hostettmann (871-874).
A new dihydrochalcone, 6″-acetylphloridzosid, was isolated from the whole plant of Loiseleuria procumbens (L.) Desv. and identified as 2′-O-(6″-O-acetylglucopyranosyl)-4,4′,6′-trihydroxydihydrochalcone by spectroscopic methods. In addition, one stilbene and three other dihydrochalcones were identified as (E)-piceid, phloretin (2′,4,4′,6′-tetrahydroxydihydrochalcone), phloridzosid (2′-O-glucopyranosyl-4,4′,6′-trihydroxydihydrochalcone) and asebotin (2′-O-glucopyranosyl-4′-methoxy-4,6′-dihydroxydihydrochalcone), respectively. Some of these compounds showed scavenging properties towards the 2,2-diphenyl-1-picrylhydrazyl radical and antioxidant properties in a test with lysozyme.
Keywords: Loiseleuria procumbens; Ericaceae; Radical scavenging activity; Stilbene; Dihydrochalcone; E-piceid; Phloretol; Phloridzosid; Asebotin; 6″-Acetylphloridzosid;

Stilbene dimers from the lianas of Gnetum hainanense by Kai-Sheng Huang; Ying-Hong Wang; Rong-Li Li; Mao Lin (875-881).
Five stilbene dimers, gnetuhainins F–J, were isolated together with gnetulin, rhapontigenin, isorhapontigenin and gnetol from the lianas of Gnetum hainanense C. Y. Cheng. Their structures and stereochemistry have been established on the basis of spectral evidence, especially 2D NMR spectroscopic techniques.
Keywords: Gnetum hainanense; Gnetaceae; Oligostilbenes; Gnetuhainins F–J; Structural elucidation;

Benzophenone glycosides from Gnidia involucrata by Julien Ferrari; Christian Terreaux; Sevsen Sahpaz; Jerome D. Msonthi; Jean-Luc Wolfender; Kurt Hostettmann (883-889).
Six compounds have been isolated from the methanol extract of the aerial parts of Gnidia involucrata (Thymelaeaceae). They were identified as 2,3,4′,5,6-pentahydroxybenzophenone-4-C-glucoside and 2,4′,6-trihydroxy-4-methoxybenzophenone-2-O-glucoside, together with mangiferin, kaempferol-3-O-glucoside, yuankanin and manniflavanone by chemical and spectroscopic means. The structures of three additional C-glycosyl flavones — vitexin, isovitexin and isoorientin — were determined on-line by LC/UV/APCI-MS n analysis of the crude extract.
Keywords: Gnidia involucrata; Thymelaeaceae; Benzophenone glycosides; Biflavanone; Yuankanin; Mangiferin; Manniflavanone; Flavonoid C-glycosides;

Minor phenolics from Crinum bulbispermum bulbs by M.A. Ramadan; M.S. Kamel; K. Ohtani; R. Kasai; K. Yamasaki (891-896).
From the bulbs of Crinum bulbispermum Milne, four new minor compounds were isolated viz. 4-hydroxy-2′,4′-dimethoxy-dihydrochalcone (1), 4,5-methylenedioxy-4′-hydroxy-2-aldehyde[1,1′-biphenyl] (4), hippacine (6), and 4′-hydroxy-7-methoxy-flavan-3-ol (7). In addition, four known compounds were isolated and identified as 2(S),3′,4′-dihydroxy-7-methoxy flavan (2), isolarrien (3), isoliquiritigenin (5) and liquiritigenin (8).The structures of the isolated compounds were established by spectral evidence.
Keywords: Crinum bulbispermum; Amaryllidaceae; Flavans; Flavanones; Chalcones; Dihydrochalcones; Pyrrolophenanthridone alkaloid;

The reported isolation of cis-epoxyconiferyl alcohol must be incorrect, based upon comparison of the reported Nuclear Magnetic Resonance (NMR) spectral data for the isolate with those for synthesized coniferyl and cinnamyl alcohol epoxide derivatives. Attempts to prepare cis- and trans-coniferyl alcohols were unsuccessful, although their acetate derivatives could be synthesized. The NMR spectral data for a synthetic sample of pinoresinol were in excellent agreement with those for the purported isolate.
Keywords: Fraxinus oxycarpa; Oleaceae; Pinoresinol; Epoxyconiferyl alcohol;

Dihydroflavonols from Lannea coromandelica by Md. Tofazzal Islam; Satoshi Tahara (901-907).
The dihydroflavonols, (2R,3S)-(+)-3′,5-dihydroxy-4′,7-dimethoxydihydroflavonol and (2R,3R)-(+)-4′,5,7-trimethoxydihydroflavonol were isolated from the stem bark of Lannea coromandelica, along with the known (2R,3R)-(+)-4′,7-di-O-methyldihydroquercetin, (2R,3R)-(+)-4′,7-di-O-methyldihydrokaempferol and (2R,3R)-(+)-4′-O-methyldihydroquercetin. All five compounds were isolated for the first time from the genus Lannea; furthermore, (2R,3S)-(+)-3′,5-dihydroxy-4′,7-dimethoxydihydroflavonol, was a rare cis-type isomer. The structures of all compounds were elucidated by spectroscopic methods including 2D NMR and CD analysis.
Keywords: Lannea coromandelica L. (Anacardiaceae); cis-type Dihydroflavonol, (2R,3S)-(+)-3′,5-dihydroxy-4′,7-dimethoxydihydroflavonol; (2R,3R)-(+)-4′,5,7-trimethoxydihydroflavonol; Isolation; Structure elucidation;

Lignans from Mosla scabra by Qi Wang; Christian Terreaux; Andrew Marston; Ren-Xiang Tan; Kurt Hostettmann (909-912).
Two new cyclobutane-type lignans, named moslolignans A and B, together with two known ones, andamanicin and magnosalin, were isolated from the whole plant of Mosla scabra. Their structures were established as 1β,2β,3α,4α-1,2-dimethyl-3-(3-methoxy-4,5-methylene-dioxyphenyl)-4-(2,4,5-trimethoxyphenyl)-cyclobutane and 1β,2β,3α,4α-1,2-dimethyl-3-(2,5-dimethoxy-3,4-methylenedioxyphenyl)-4-(2,4,5-trimethoxyphenyl)-cyclobutane by spectroscopic methods. This is the first report of naturally-occurring cyclobutane-type lignans with asymmetrical substitutions.
Keywords: Mosla scabra; Lamiaceae; Cyclobutane-type lignan; Moslolignan A; Moslolignan B; Andamanicin; Magnosalin;

Acylated delphinidin 3-rutinoside-5-glucosides in the flowers of Petunia reitzii by Fumi Tatsuzawa; Toshio Ando; Norio Saito; Takeshi Kanaya; Hisashi Kokubun; Yuko Tsunashima; Hitoshi Watanabe; Goro Hashimoto; Ritsuko Hara; Hiroko Seki (913-917).
Two acylated anthocyanins were isolated from selected individuals of Petunia reitzii, and identified to be delphinidin 3-O-[6-O-(4-O-(4-O-(6-O-(trans-caffeoyl)-β-D-glucopyranosyl)-trans-p-coumaroyl)-α-L-rhamnopyranosyl)-β-D-glucopyranoside]-5-O-[β-D-glucopyranoside] and delphinidin 3-O-[6-O-(4-O-(4-O-(β-D-glucopyranosyl)-trans-p-coumaroyl)-α-L-rhamnopyranosyl)-β-D-glucopyranoside]-5-O-[β-D-glucopyranoside]. Nine known anthocyanins were also identified.
Keywords: Petunia reitzii; Solanaceae; Acylated anthocyanins; Delphinidin 3-rutinoside-5-glucoside; Caffeic acid; p-Coumaric acid; Flower colour;

Anthocyanins in callus induced from purple storage root of Ipomoea batatas L. by Norihiko Terahara; Izabela Konczak-Islam; Makoto Nakatani; Osamu Yamakawa; Yukihiro Goda; Toshio Honda (919-922).
Two anthocyanins were isolated from the highly pigmented callus derived from the storage root of purple sweet potato (Ipomoea batatas L.) cultivar ‘Ayamurasaki’. One was identified as cyanidin 3-O-sophoroside-5-O-glucoside, and the other as cyanidin 3-O-(2-O-(6-O-(E)-p-coumaroyl-β-D-glucopyranosyl)-β-D-glucopyranoside)-5-O-β-D-glucopyranoside, by chemical and spectroscopic analysis.
Keywords: Ipomoea batatas L.; Convolvulaceae; Purple callus; Acylated anthocyanins; Cyanidin 3-p-coumaroylsophoroside-5-glucoside; Natural food colorant; Antioxidative activity;

Phenylpropanoid glycosides from Scrophularia ningpoensis by Yi-Ming Li; Shan-Hao Jiang; Wen-Yun Gao; Da-Yuan Zhu (923-925).
Three phenylpropanoid glycosides named ningposides A (3-O-acetyl-2-O-feruloyl-α-L-rhamnopyranose), B (4-O-acetyl-2-O-feruloyl-α-L-rhamnopyranose) and C (3-O-acetyl-2-O-p-hydroxycinnamoyl-α-L-rhamnopyranose) along with the known compounds sibirioside A, cistanoside D, angoroside C, acteoside, decaffeoylacteoside and cistanoside F were obtained from the roots of Scrophularia ningpoensis.
Keywords: Scrophularia ningpoensis; Scrophulariaceae; Phenylpropanoid; Glycoside; Ningposides A, B, C;

Tropane alkaloids from the leaves and stem bark of Erythroxylon alaternifolium and Erythroxylon rotundifolium by A.L. Payo-Hill; R.Sarduy Dominguez; M.O. Suarez; M. Batista-Baez; H.T.Velez Castro; L. Rastrelli; R. Aquino (927-932).
A novel 3α,6β,7β-triol tropane alkaloid esterified by two benzoyl residues was isolated from the leaves of the endemic cuban species, Erythroxylon alaternifolium. Another novel 3α,6α,7β-triol tropane alkaloid esterified by trimethoxycinnamoyl and trimethoxybenzoyl residues was isolated from the leaves and stem bark of a second endemic cuban species, Erythroxylon rotundifolium. Their structures were elucidated as 3α,7β-dibenzoyloxy-6β-hydroxy-tropane and 3α-(3,4,5-trimethoxy-cinnamoyloxy)-7β-(3,4,5-trimethoxybenzoyloxy)-6α-hydroxy-tropane by spectroscopic methods including 2D-NMR techniques.
Keywords: Erythroxylon alaternifolium; Erythroxylon rotundifolium; Erythroxylaceae; Leaves; Stem bark; Tropane alkaloids; 3α,7β-dibenzoyloxy-6β-hydroxy-tropane; Alaternifoline; 3α-(3,4,5-trimethoxy-cinnamoyloxy)-7β-(3,4,5-trimethoxybenzoyloxy)-6α-hydroxy-tropane; Erythrorotundine;

Structure revision of isoline (ruwenine), bisline and isolinecic acid by Lyndia Susag; Masood Parvez; Simon Mathenge; Michael H. Benn (933-935).
X-ray crystallography of bisline, and the chemical interconversion of bisline and isoline (ruwenine), revealed that the structures previously assigned to these alkaloids required revision; as did that of isolinecic acid.
Keywords: Bisline; Isoline; Ruwenine; Ruzorine; Isolinecic acid; Pyrrolizidine alkaloids; Senecio ruwenzoriensis; Asteraceae;

Caffeine: also a fungal metabolite by Amauri Bogo; Peter G. Mantle (937-939).
Caffeine has been found to occur as a fungal metabolite and to be the principal alkaloid in sclerotia of Claviceps sorghicola, a Japanese ergot pathogen of Sorghum spp.
Keywords: Claviceps sorghicola; Sclerotia; Alkaloid; Sorghum bicolor; Caffeine;

Indole alkaloids from a culture of the fungus Aporpium caryae by Laura M Levy; Gabriela M Cabrera; Jorge E Wright; Alicia M Seldes (941-943).
In a screening for antifungal metabolites, two indole compounds of mixed biogenesis, 1H-indole-3-carboxylic acid, 1-(1,1-dimethyl-2-propenyl) methyl ester and 1H-indole-3-carboxylic acid, 1-(2,3-dihydroxy-1,1-dimethylpropyl) methyl ester were isolated from a culture of the basidiomycete Aporpium caryae. The structural elucidation of these compounds was accomplished by spectroscopic methods.
Keywords: Aporpium caryae; Basidiomycete; Indole alkaloids;

Alkaloids from Crinum macowanii by J.J. Nair; A.K. Machocho; W.E. Campbell; R. Brun; F. Viladomat; C. Codina; J. Bastida (945-950).
Eleven alkaloids have been isolated from fresh bulbs of Crinum macowanii (Amaryllidaceae). Macowine is reported here for the first time. The structure and stereochemistry of this new alkaloid as well as of the known ones were determined by physical and spectroscopic methods.
Keywords: Crinum macowanii; Amaryllidaceae; Bulbs; Alkaloids; Macowine; Lycorine; Cherylline; Crinine; Krepowine; Powelline; Buphanidrine; Crinamidine; Undulatine; 1-Epideacetylbowdensine; 4a-Dehydroxycrinamabine;

Four steroidal alkaloids from the leaves of Buxus sempervirens by Fabrice Loru; Danièle Duval; André Aumelas; Fatima Akeb; Didier Guédon; Roger Guedj (951-957).
Four new steroidal alkaloids, N20-formylbuxaminol E [(20S)-16α-hydroxy-20-(formylamino)-3β-(dimethylamino)-9,10-seco-buxa-9(11),10(19)-diene] (1), O16-syringylbuxaminol E [(20S)-16α-syringoyl-3β-(dimethylamino)-20-(amino)-9,10-seco-buxa-9(11),10(19)-diene] (2), N20-acetylbuxamine G [(20S)-20-(acetylamino)-3β-(methylamino)-9,10-seco-buxa-9(11),10(19)-diene] (3) and N20-acetylbuxamine E [(20S)-20-(acetylamino)-3β-(dimethylamino)-9,10-seco-buxa-9(11),10(19)-diene] (4) were isolated from the leaves of Buxus sempervirens. Their structures were determined mainly on the basis of 2D NMR studies.
Keywords: Buxus sempervirens; Buxaceae; Boxwood; Steroidal alkaloids; N20-Formylbuxaminol E; O16-Syringylbuxaminol E; N20-Acetylbuxamine E; N20-Acetylbuxamine G;

Alkaloids from Isopyrum thalictroides L. by Ralitsa S Istatkova; Stefan A Philipov (959-964).
Three new bisbenzylisoquinoline alkaloids, isopyruthaldine, isopythaldine and isothalmidine, containing new type of bridges were isolated from roots and rhizomes of Isopyrum thalictroides. The known isoquinoline alkaloids, reticuline, isocorydine, columbamine and palmatine, obtained from the aerial parts, are new for the genus Isopyrum. All structures were elucidated by spectroscopic analysis.
Keywords: Isopyrum thalictroides; Ranunculaceae; Bisbenzylisoquinoline alkaloids; Isopyruthaldine; Isopythaldine; Isothalmidine;

Fatty acid amides from freshwater green alga Rhizoclonium hieroglyphicum by Valery M. Dembitsky; Ilia Shkrob; Olga A. Rozentsvet (965-967).
Freshwater green algae Rhizoclonium hieroglyphicum growing in the Ural Mountains were examined for their fatty acid amides using capillary gas chromatography–mass spectrometry (GC–MS). Eight fatty acid amides were identified by GC–MS. (Z)-9-octadecenamide was found to be the major component (2.26%).
Keywords: Fatty amides; Green algae; Rhizoclonium hieroglyphicum;

Two novel triterpenoids have been isolated from the roots of Lantana camara L.: 3ß,19α dihydroxy ursan-28-oic acid and 21,22ß- epoxy-3ß-hydroxy olean-12-en-28-oic acid in its methyl ester form. Its leaves have yielded an essential oil which is rich in sesquiterpenes. Oleanolic acid, which is thought to be a hepatoprotective compound, was isolated from L. camara roots and converted into its 28 → 13ß lactone by a facile photo-oxidation reaction.
Keywords: Lantana camara; Weed; Verbenaceae; Roots; Triterpenoid; Leaves; Essential oil; Terpenes; Photo-oxidation; Oleanolic acid; Hepatoprotective;

Diarylheptanoids from Myrica arborea by Mathieu Tene; Hyppolite Kamdem Wabo; Pierre Kamnaing; Apollinaire Tsopmo; Pierre Tane; Johnson Foyere Ayafor; Olov Sterner (975-978).
Investigations of the stem and root bark of Myrica arborea (Myricaceae) have yielded two novel diarylheptanoids, myricarborin and 11-O-β-D-xylopyranosylmyricanol along with the known myricanol and 5-O-β-D-glucopyranosylmyricanol. The structures of the novel compounds were determined by spectroscopic methods.
Keywords: Myrica arborea; Myricaceae; Diarylheptanoids; Myricarborin; 11-O-β-D-xylopyranosylmyricanol; 5-O-β-D-glucopyranosylmyricanol;

Constituents of Chondria armata by Mangala B. Govenkar; Solimabi Wahidulla (979-981).
A novel long chain fatty ester, pentyl hentriacontanoate 1 and an orange red pigment, caulerpin 2 have been isolated and characterised from a red alga Chondria armata. The pigment caulerpin hitherto known to be a constituent of green algae of genus Caulerpa is being reported here for the first time from a red alga.
Keywords: Chondria armata; Rhodomelaceae; Pentyl hentriacontanoate; Caulerpin;

C21 steroidal glycosides from Hemidesmus indicus by Poonam Sigler; Rina Saksena; Desh Deepak; Anakshi Khare (983-987).
Two novel pregnane glycosides, denicunine (1) and heminine (4), have been isolated from the dried stem of Hemidesmus indicus R.Br. (family: Asclepiadaceae). Chemical transformations and spectroscopic evidence viz: 1 H and 13 C NMR spectroscopy and FABMS are consistent with the structures calogenin 3-O-3-O-methyl-β-D-fucopyranosyl-(1 → 4)-O-β-D-oleandropyranoside and calogenin 3-O-β-D-cymaropyranosyl-(1 → 4)-O-β-D-digitoxopyranoside, respectively.
Keywords: Hemidesmus indicus; Asclepiadaceae; Pregnane glycosides; Denicunine; Heminine; Calogenin; C21 steroids;

A 6-substituted-5,6-dihydro-2-pyrone from Cryptocarya strictifolia by Lia Dewi Juliawaty; Mariko Kitajima; Hiromitsu Takayama; Sjamsul Arifin Achmad; Norio Aimi (989-993).
The structure and absolute configuration of an α-pyrone isolated from Cryptocarya strictifolia was elucidated as 6R-(4′R,6′R-dihydroxy-8′-phenyloct-1′-enyl)-5,6-dihydro-2H-pyran-2-one. Pinocembrin and lysicamine were also isolated.
Keywords: Cryptocarya strictifolia; Lauraceae; 6-Substituted-5,6-dihydro-2-pyrone; Strictifolione; Absolute configuration; Pinocembrin; Lysicamine;

Fluorescence studies of ATP-diphosphohydrolase from Solanum tuberosum var. Desirée by V. Espinosa; A.M. Kettlun; A. Zanocco; E. Cardemil; M.A. Valenzuela (995-1001).
Chemical modification of potato apyrase suggests that tryptophan residues are close to the nucleotide binding site. K d values (± Ca2+) for the complexes of apyrase with the non-hydrolysable phosphonate adenine nucleotide analogues, adenosine 5′-(β,γ-methylene) triphosphate and adenosine 5′-(α,β-methylene) diphosphate, were obtained from quenching of the intrinsic enzyme fluorescence. Other fluorescent nucleotide analogues (2′(3′)-O-(2,4,6-trinitrophenyl) adenosine 5′-triphosphate, 2′(3′)-O-(2,4,6-trinitrophenyl) adenosine 5′-diphosphate, 1,N6-ethenoadenosine triphosphate and 1,N6-ethenoadenosine diphosphate) were hydrolysed by apyrase in the presence of Ca2+, indicating binding to the active site. The dissociation constants for the binding of these analogues were calculated from both the decrease of the protein (tryptophan) fluorescence and enhancement of the nucleotide fluorescence. Using the sensitised acceptor (nucleotide analogue) fluorescence method, energy transfer was observed between enzyme tryptophans and ethene-derivatives. These results support the view that tryptophan residues are present in the nucleotide-binding region of the protein, appropriately oriented to allow the energy transfer process to occur.
Keywords: Solanum tuberosum; Potato; Solanaceae; Intrinsic and extrinsic fluorescence; ATP-diphosphohydrolase; Apyrase;