Phytochemical and chemotaxonomic study on Ficus tsiangii Merr. ex Corner

Thirty-four compounds, including ten coumarins (1–10), thirteen flavonoids (11–23), three triterpenoid, one lignanoid (24), seven triterpenes (25–31) and three other compounds (32–34), were isolated from the stems of Ficus tsiangii Merr. ex Corner (F. tsiangii). Their structures were identified as xanthyletin (1), coumarin (2), umbelliferone (3), isoangenomalin (4), dihydroxanthyletin (5), scopoletin (6), nodakenetin (7), 6,7-dihydroxy-coumarin (8), 4'-O-β- glucopyranosyl-3'-hydroxy-nodakenetin (9), 6-carboxy-umbelliferone (10), 5,7,4'-trimethoxy- 3'-hydroxy-aurone (11), apigenin (12), naringenin (13), genistein (14), luteolin (15), prunetin (16), chrysoeriol (17), 5,6,7,-trihydroxy-4'-methoxy-flavone (18), eriodictyol (19), isocarthamidin (20), 5,7,2',4'-tetrahydroxyflavone (21), taxifolin (22), dihydro-kaempferol (23), syringeresinol (24), taraxerol (25), taraxerone (26), lupeolacetate (27), 3-acetoxy-12- oleanene-11-ketone (28), 3-acetoxy-lup-12,20(29)-diene (29), oleanic acid (30), ursolic acid (31), 3,4,5-trimethoxy phenyl-1-O-glucopyranoside (32), 8'-hydroxyabscisic acid glucoside (33) and adenosine (34). Among them, all compounds except 3, 14, 17, 25, 26, 30, 33 were isolated from the plant for the first time, and compounds 1, 4, 5, 8–11, 16, 18, 20, 23, 24, 32, 34 were firstly reported from the genus Ficus. The chemotaxonomic significance of these compounds was summarized as follows.     

New steroid and other compounds from non-polar extracts of Clusia burle-marxii and their chemotaxonomic significance

Phytochemical investigation of the non-polar extract of Clusia burle-marxii led to the identification of a new steroid (1), along with friedelinol (2), β-sitosterol (3), friedelin (4), stigmast-5-en-3β,7β-diol (5), stigmast-5-en-3β,7α-diol (6), stigmasterol (7), sitostenone (8), betulinic acid (9), butyrospermol (10), euphol (11), betulin aldehyde (12), 2,2-dimethyl-5-hydroxy-7-phenyl-chromane (13), 6-deoxyisojacareubin (14), padiaxanthone (15) and betulonic acid (16). This is the first report of the identification of compounds 5, 6 and 10 in the family, the first report of compounds 14 and 15 in the genus, and the first report of compounds 2, 3, 7, 8, 12, 16 in the species. Chemotaxonomic significance of these compounds is described herein.     

Phytochemical investigation on the roots of Juglans mandshurica and their chemotaxonomic significance

Phytochemical research of the roots of Juglans mandshurica Maxim. (Juglandaceae) verified 37 secondary metabolites, including thirteen diarylheptanoids (1–13), five naphthoquinones (14–18), five tetralones (19–23), three lignans (24–26), three phenols (27–29), two anthraquinones (30–31), two triterpenoids (32–33), two secoiridoids (34–35), one naphthalenyl glycoside (36), and one flavonoid (37). The chemical structures of these constituents were elucidated by NMR spectroscopy and compared with data from the literature. This is the first confirmation of the presence of ten compounds (6, 12, 16, 18, 24–26, 30, 32–33) isolated from the family Juglandaceae, two compounds (1 and 8) from the genus Juglans, and four compounds (27, 31, 34–35) from J. mandshurica. The isolation and chemotaxonomic significance of the metabolites from the roots of J. mandshurica were described in this study.     

Secondary metabolites from Corispermum mongolicum Iljin and their chemotaxonomic significance

A phytochemical investigation of the whole plant of Corispermum mongolicum Iljin (Chenopodiaceae) led to the isolation of thirty-eight compounds, including thirteen phenylpropanoids (1–13), six megastigmane-type norsesquiterpenoids (14–19), eight sterols (20–27), two flavonoid glycosides (28, 29), one alkaloid (30), two aromatic glycosides (31, 32), one aliphatic glycoside (33), one triterpenoid (34), one diterpenoid (35), two cerebrosides (36, 37) and one monogalactosyldiacyl glycerol (38). The chemical structures of these compounds were elucidated on the basis of spectral data and by comparisons of spectroscopic data with reported values in the literature. Twenty-eight compounds (1, 2, 4–16, 19, 20, 23–27, 30, 32–35, 37) were first found in the family Chenopodiaceae. The chemotaxonomic significance of these compounds is discussed.     

Chemical constituents from the fruits of Rhus typhina L. and their chemotaxonomic significance

This work describes the isolation and characterization of twenty-nine compounds from the fruits of Rhus typhina L., including eleven flavonoids (1–11), eleven phenols (12–22), two pentacyclic triterpenes (23–24), two organic acids (25–26), one lumichrome (27), one courmarin (28) and one pyrimidine (29) on the basis of their spectroscopic data. Compounds apigenin (1), daidzein (4), orobol (5), 3′, 5, 5′, 7-tetrahydroxyflavanone (6), naringenin (7), butein (8), (-)-catechin (9), quercetin-3-O-α-L-(3″-O-galloyl)-rhamnoside (11), 2-hydroxybenzoic acid (13), 4-hydroxybenzaldehyde (14), vanillin (15), methyl 3,4-dihydroxybenzoate (16), 3,5-dihydroxybenzamide (18), tyrosol (19), caffeic acid (20), 3-(2,4,6-trihydroxyphenyl)-1-(4-hydroxyphenyl)-propan-1-one (21), phlorizin (22), friedelin (23), oleanolic acid (24), 4,4-dimethyl-heptanedioic acid (25), anthranilic acid (26), lumichrome (27), scoparone (28) and uracil (29) have not been recorded before in this plant. This is the first report on the occurrence of compounds 4–7, 9, 11, 13–14, 16, 18–21, 25–29 from the genus Rhus. Moreover, the chemotaxonomic significance of these isolated compounds was also summarized.     

Chemical constituents of the Piper crocatum leaves and their chemotaxonomic significance

Chemical study of Piper crocatum leaves has led to isolation of a new megastigmane glucoside isomer (18), along with 23 known compounds including fifteen phenolic compounds (1–15), two monoterpenes (16 and 17), three sesquiterpenes (19–21), a phenolic amide glycoside (22), a neolignan (23), and a flavonoid C-glycoside (24). Structures of these compounds were identified via spectroscopic methods and compared with those reported in the literature. Seven compounds (7, 11, 13, 14, 17, 20, and 24) from the P. crocatum species and 17 others (1–6, 8–10, 12, 15–16, 18–19, and 21–23) from the Piper genus and Piperaceae family were isolated and reported for the first time. Furthermore, this study discusses chemotaxonomic relations between P. crocatum and other Piper species.     

Chemical constituents of Leucas zeylanica and their chemotaxonomic significance

Chemical study of the whole plant of Leucas zeylanica (L.) B. Br. has led to isolation of a new norditerpenoid isomer (1), along with 29 known compounds, including one norditerpenoid (2), three flavonoid glycosides (3–5), six flavonoids (6–11), two phytosterols (12–13), two phenylpropanoids (14, 19), two phthalate esters (15, 16), two phenolic compounds (17, 18), five terpenoids (20–24), one aliphatic glycoside (25), one nucleobase (26), one amino acid (27), two alkaloids (28–29), and one cytochalasin (30). The structures of these compounds were identified using NMR spectroscopic methods and comparing them with those previously reported. Twelve compounds (6, 15, 17–20, 22, 23, 26–29) were isolated for the first time from Leucas zeylanica and ten others (2, 4, 5, 7, 14, 16, 21, 24, 25, 30) from the Leucas genus. This study also discusses the chemotaxonomic relationships between Leucas zeylanica and other species of Leucas.     

Chemical constituents of the roots of Scorzonera divaricata and their chemotaxonomic significance

The phytochemical study of the roots of Scorzonera divaricata Turcz led to the isolation of 27 compounds, including eight sterols (1–8), one lignan (9), two cumarins (10, 11), five phenylpropanoids (12–16), six benzene derivatives (17–22), methyl-β-D-fructofuranoside (23), monolinolein (24), and three aliphatic acids (25–27). The structures of isolated compounds were identified using NMR and ESI-MS spectroscopic methods and comparing them with those previously reported. Except for β-daucosterol (8), scopoletin (10) and caffeic acid (16) from S. divaricata, this is the first report of the other 24 compounds from S. divaricata. Among them, eleven compounds (2–6, 11, 17, 19, 20, 23, 25) were reported from genus Scorzonera for first time, suggesting that they could be used to distinguish S. divaricata from the other species of Scorzonera. Furthermore, the chemotaxonomic significance of isolated compounds from S. divaricata has also been discussed.     

Chemical constituents from Dictamnus dasycarpus Turcz.

Fifteen compounds (1–15) were isolated from Dictamnus dasycarpus Turcz. The structures of all compounds were elucidated on the basis of spectroscopic data. Their structures were identified as dictamnine (1), skimmianine (2), haplopine (3), γ-fagarine (4), dasycarine (5), glycolone (6), 8,9-dimethoxygeibalansine (7), 7,8-dimethoxymyrtopsine (8), 8-methoxyflindersine (9), 3-formylindole (10), kihadanin A (11), fraxinellone (12), β-sitosterol (13), radicol (14), and magnolol (15). Among them, compounds 10 and 15 were isolated for the first time in the genus Dictamnus and this is the first report of the presence of compound 14 in the Dictamni dasycarpus Turcz.     

Cytotoxic withanolides from the aerial parts of Tubocapsicum anomalum

Ten new withanolides (1–10) and three artificial withanolides (11–13) were isolated from the aerial parts of Tubocapsicum anomalum, together with five known analogues (14–18). Their structures were determined on the basis of extensive spectroscopic and chemical methods. They include seven acnistin–type (1–4, 11, 14 and 15), three withajardin–type (5–7), and eight normal–type (8–10, 12, 13 and 16–18) withanolides. Of normal–type withanolides, a chemical conversion from the 16α,17α–epoxywithanolide (16) to Δ^13,14–16α–hydroxywithanolide (18) was achieved by Wagner–Meerwein rearrangement. All isolates were evaluated for their cytotoxicity against four human tumor cell lines (HCT–116, HepG2, MCF–7 and A375). Among them, compounds 1–3, 6–8, 14, 16–18 showed cytotoxic activity with IC₅₀ values of 0.24–8.71 μM.     

A new methoxylated flavone from Lonicera hypoglauca and its chemotaxonomic significance

Phytochemical investigation of the stems and leaves of Lonicera hypoglauca Miq. led to the isolation of one novel methoxylated flavone, acunminatin (7,2′,4′-trihydroxyl-5,5′- methoxyflavone) (1), and fourteen known compounds (2–15), including six flavonoids (mearnsetin 2, kaempferol 3, acacetin 4, 5,7,3′,4′-tetramethoxyflavone 5, tricin 6, and 5,7,3′,4′,5′-pentamethoxyflavone 7), two coumarins (umbelliferone 8 and scopoletin 9), two phenylpropanoids (trans-ferulic acid 10 and chlorogenic acid 11), two iridoid glycosides (loganin 12 and sweroside 13), and two triterpenoids (uvaol 14 and ursolic acid 15). The structures of the compounds were identified by spectroscopic analysis and by comparing their spectral data with those reported in the literature. Five of these compounds (1, 2, 4, 5, and 7) were isolated from the L. genus for the first time, and compounds 6–8 and 14–15 were isolated for the first time from L. hypoglauca. The chemotaxonomic significance of the isolated compounds in the L. genus and the Caprifoliaceae family are discussed herein.     

Chemical constituents from Piper boehmeriifolium (Miq.) Wall. ex C. DC

The chemical investigation of whole plants Piper boehmeriifolium (Miq.) Wall. ex C. DC. led to the isolation of 22 compounds, including two lignans (1–2), sixteen amide alkaloids (3–18), one diterpene (19), two monoterpenes (20–21), and one phenylpropanoid (22). Their structures were elucidated by extensive spectroscopic analyses including NMR, MS, and by comparison with the literature. Compounds 1–2, 6–7, 11–12, 14, and 17–22 were firstly isolated from P. boehmeriifolium, while compounds 2, and 19–20 were isolated from Piper genus for the first time. The chemotaxonomic significance of these isolated compounds is discussed.     

Chemical constituents from the aerial sections of Ajania potaninii

Nineteen compounds were isolated from Ajania potaninii, including one sulfur paraffin (1), one monoterpene (6), one lactone (3), one aliphatic acid (15), two sterols (8 and 10), one triterpenes (13), one alkaloid (18), eleven flavonoids (2, 4, 5, 7, 9, 11, 12, 14, 16 and 17) and one cyclic amide (19). All of these compounds were obtained from A. potaninii for the first time. This is the first report of N-nonanemercaptan (1), 3-hydroxy-5-decanolide (3), cirsiliol (5), 1,2,4-trihydroxy-p-mentane (6), 6-methoxytricin (7), eriodictyol (11), pectolinarigenin (12), 3,3′-di-O-methylquercetin (14), tetradecanoic acid (15), lappaconitine (18) and 1,1′,1″,1‴,1‴'-tricontane lactam (19) from the genus Ajania. The occurrence of compounds 18 and 19 in A. potaninii warrants further study.     

Coumarins and other components of Daphne oleoides Schreb. subsp. oleoides from Majella National Park

The present study reports about the phytochemical analysis of a sample of Daphne oleoides Schreb. subsp. oleoides (family Thymelaeaceae) collected from the Majella National Park. Twenty components, belonging to different classes of natural products, have been identified by means of spectroscopic and spectrometric techniques: [monomeric (4), bis- (5, 7–10, 20) and trimeric coumarins (11), including aglycones and glycosides, coumarinolignoid (6); flavonoids (16–19); glycosidic furolignans (14, 15), glucosidic phenylpropanoids (12, 13), cyclic tetrapyrrole derivatives (2, 3), unsaturated triglyceride (1)]. Besides the chemosystematic markers of the genus (4–10, 12, 14–18, 20) several other components were identified for the first time in the species (17, 20) and/or in the Daphne genus (1–3, 13, 19). The observed composition was discussed from the chemotaxonomic standpoint and compared with those recognized from a Sardinian accession. It was observed a pronounced difference in the two metabolites patterns, most probably attributable to geographic isolation of the studied populations and, in some extent, also by the different environmental conditions, evidencing a possible tendency of D. oleoides to the infraspecific chemovariability. Considering the wide traditional uses of Daphne spp. in ethnomedicine of several countries, also the pharmacologic potential of the identified secondary metabolites is discussed.     

Phytochemical and chemotaxonomic study on the Lichen Lethariella cladonioides

The comprehensive phytochemical research of Lethariella cladonioides (Nyl.) Krog, (Parmeliaceae), a lichen in southwest China, resulted in isolation of eighteen compounds (1–18), including a new phenolic acid 3,5-dihydroxy-4-methylbenzaldehyde (1) and seventeen known compounds, nine phenolic acids (2–10), one dibenzofuran (11), two depsides (12 and 13), one alkane (14), one glucoside (15), two polyols (16 and 17), and one fatty acid (18). The structures of these compounds were assigned by detailed interpretations of spectroscopic data (1D and 2D NMR, HR-ESI-MS) and comparisons with the published data. Among them, 3,5-dihydroxy-4-methylbenzaldehyde (1) is a new one. (−)-hydroxypropan-2′,3′-diol-orsellinate (10) have not been reported from any species in the lichens. Compounds 6, 7, 9, 12, 14, 16 and 18 were firstly isolated from the genus Lethariella (Motyka) Krog. Compounds 2, 6, 7, 9, 10, 12, 14, 16 and 18 were reported from L. cladonioides firstly. The chemotaxonomic significance of these compounds was also discussed.     

Chemical constituents from Artemisia argyi and their chemotaxonomic significance

Twelve compounds, including one monoterpene (1), two sesquiterpene lactones (2–3), six flavonoids (4–9), one phenolic glycoside (10), one chromone (11) and one phenolic acid (12), were isolated and identified from the leaves of Artemisia argyi. Compounds 1–2, 4 and 6–7 have not been recorded before in this plant. Compounds 3, 9 and 11 were isolated from the genus Artemisia for the first time. This paper is the first report on the presence of compound 10 in species of Asteraceae. In addition, the chemotaxonomic significance of these compounds was summarized.     

Phytochemical investigation of Eremostachys moluccelloides Bunge (Lamiaceae)

Phytochemical investigation of the aerial parts of Eremostachys moluccelloides Bunge led to the identification of a new diterpene, 2β,14-dihydroxy −11-formyl- 12-carboxy-13-des-isopropyl-13-hydroxymethyl-abieta-8,11,13- triene- 16(17)- lactone (1), along with the known compounds 12, 18-dicarboxy-14-hydroxy-13-des -isopropyl-13-hydroxymethyl- abieta-8,11,13-triene-16(17)-lactone (2), 5-hydroxy-3′,4′,7-trimethoxyflavone (3), 5-hydroxy-4’,7-dimethoxyflavone (4), luteolin-7-O-β-glucoside (5), verbascoside (6), luteolin 7-O-(6″-O-β-D-apiofuranosyl) -β-D-glucopyranoside (7), chlorogenic acid (8), echinacoside (9), apigenin-7-O-β-D-glucoside (10), p-coumaric acid (11), vanillic acid (12), apigenin-7-O-(6″-E-p-coumaroyl)-β-D-glucopyranoside (13), apigenin-7-O-(3″,6″-E-p-dicoumaroyl)-β-glucoside (14), lamalbide (15), 6β-hydroxy-7-epi-loganin (16), phloyoside II (17) The structures were elucidated on the basis of 1D and 2D NMR spectroscopy, UV, MS and by comparison with compounds previously reported in the literature. Compounds 1–4, 8, 9, 11, 12, 14 have not been reported previously from any species within the genus Eremostachys. Compounds 1–14, 17 were obtained from this species for the first time. The chemotaxonomic significance of the isolated compounds is discussed.     

Fatty acid derivatives and dammarane triterpenes from the glandular trichome exudates of Ibicella lutea and Proboscidea louisiana

Ibicella lutea and Proboscidea louisiana, both of the Martyniaceae family, are known for rich glandular trichomes on their leaves and stems. Chemical investigations of the glandular trichome exudates on leaves of the two plants furnished three types of secondary metabolites, glycosylated fatty acids, glycerides (2-O-(3,6-diacetyloxyfattyacyl)glycerols and 2-O-(3-acetyloxyfattyacyl)glycerols) and dammarane triterpenes. The glycosylated fatty acids from I. lutea were determined to be 6(S)-(6-O-acetyl-β-d-glucopyranosyloxy)-octadecanoic acid (1A), -eicosanoic acid (1B) and -docosanoic acid (1C), as well as their respective deacetyl congeners (2A, 2B and 2C), whereas P. louisiana furnished 8(S)-(6-O-acetyl-β-d-glucopyranosyloxy)-eicosanoic acid (3A) and -docosanoic acid (3B) and their respective deacetyl congeners (4A and 4B), together with 2B. Both plants contained 12 identical 2-O-[(3R,6S)-3,6-diacetyloxyfattyacyl]glycerols (5A-L), in which the fatty acyl moieties contained between 17 and 21 carbon atoms. The corresponding mono-acetyloxy compounds, 2-O-[(3R)-3-acetyloxyfattyacyl]glycerols (6A–L) were detected in both plants. Among these glycerides, ten compounds (5A, 5C, 5F, 5H, 5K, 6A, 6C, 6F, 6H and 6K) had iso-fattyacyl structures and four (5E, 5J, 6E and 6J) had anteiso-fattyacyl structures. A previously unknown dammarane triterpene, betulatriterpene C 3-acetate (7), was isolated together with three known dammarane triterpenes, 24-epi-polacandrin 1,3-diacetate (8), betulatriterpene C (9) and 24-epi-polacandrin 3-acetate (10) from I. lutea, whereas 12 dammarane triterpenes, named probosciderols A–L (12–23), and the known compound betulafolienetriol (11) were isolated from P. louisiana. The structures of these compounds were elucidated by spectroscopic analysis including 2D-NMR techniques and chemical transformations. The 6-O-acetylglucosyloxy-fatty acids 1A–C (42%) and the dammarane triterpenes 7–10 (31%) were the two most abundant constituents in the glandular trichome exudate of I. lutea, whereas the dammarane triterpenes 11–23 (47%) and the glucosyloxy-fatty acids (4A, 4B and 2B) (38%) were the most abundant constituents in the glandular trichome exudate of P. louisiana.     

Phenolic constituents from the roots of Rosa laevigata (Rosaceae)

Chemical investigation of the root of Rosa laevigata led to the isolation of sixteen phenolic compounds, including seven flavonoids (1–7), five condensed tannins (8–12), two stilbenes (13 and 14) and two benzoic acid derivatives (15 and 16). Their structures were identified as (+)-catechin (1), (+)-gallocatechin (2), (2R, 3S, 4S)-cis- leucocyanidin (3), (2R, 3S, 4S)-cis-leucofisetinidin (4), (2S, 3R, 4R)-cis- leucofisetinidin (5), dehydrodicatechin A (6), phloridzin (7), procyanidin B3 (8), fisetinidol-(4α, 8)-catechin (9), guibourtinidol- (4α, 8)-catechin (10), ent- isetinidol -(4α, 6)-catechin (11), fisetinidol-(4β, 8)-catechin (12), (Z)-3-methoxy-5-hydroxy- stilbene (13), (Z)-piceid (14), gallic acid (15) and 4-hydroxybenzoic acid- 4-O-β-D-glucopyranoside (16). Among them, compounds 3–7, 9–14, and 16 were isolated from R. laevigata for the first time, and compounds 3–7, 9, 10, 12–14 and 16 were reported for the first time from the genus Rosa. The chemotaxonomic significance of these compounds was summarized.     

Chemical constituents isolated from Clusia criuva subsp. Criuva and their chemophenetics significance

Clusia criuva belongs to the Clusiaceae family and it is endemic to the rupestrian fields in Chapada Diamantina National Park (Brazil). Phytochemical investigation of C. criuva trunks led to the isolation of five triterpenoids [winchic acid (1), betulinic acid (2), lupeol (3), friedelin (4), and friedelinol (5)], four steroids [lanosterol (6), stigmasterol (7), β-sitosterol (8), and sitostenone (9)], seven polyprenylated benzophenone derivatives [propolone A (10), propolone B (11), propolone C (12), propolone D (13), sampsonione B (14), hyperisampsin E (15), and hyperisampsin F (16)], four xanthones [neriifolone C (17), 6-deoxyisojacareubin (18), osajaxanthone F (19), and brasilixanthone B (20)], two biphenyls [aucuparina (21) and 2,2-dimethyl-5-hydroxy-7-phenylchromene (22)], and two tocotrienol derivatives [2Z- and 2E-δ-tocotrienoloic acids (23 and 24)]. Compounds 1, 11, 12, 15, and 16 were isolated for the first time in the Clusiaceae family, compounds 17, 19 and 21 were isolated for the first time in the genus Clusia, whereas 2–10, 13, 14, 18, 20, 22–24 were isolated for the first time in Clusia criuva. Compounds 1, 2, 11, 12, 13 and 15 showed potent in vitro cytotoxic activity against GL-15 glioblastoma-derived human cell line. Chemophenetics significance of these compounds is described herein.