O extrato diclorometano do caule de Raputia praetermissa levou ao isolamento de quatro compostos novos, 4-desóxi-raputindol C (1), raputimonoindol A-B (2, 3) e hexadecanil 2-hidróxi-4-metóxi-cinnamato (5), juntamente com os alcalóides 5-(4-metóxi-metilfuran-2-il)-1H-indol (raputimonoindol C), furoquinolinos maculosidine, robustine, evolitrine e dictamnine. O estudo do extrato hexano levou ao isolamento de N-metil-4-metóxi-quinolin-2(1H)-ona, skimmianina, cicloartenona, sitosterol, stigmasterol e sitostenona. Os alcalóides antranílicos isolados indicam que o gênero possui afinidade química relevante com aqueles da tribo Cusparieae, mas difere de Neoraputia devido à ausência de alcalóides prenilindois neste último, cujas espécies foram anteriormente incluídas em Raputia.

The dichloromethane extract from the stems of Raputia praetermissa afforded four new compounds, 4-deoxyraputindole C (1), raputimonoindoleA-B (2, 3), and hexadecanyl 2-hydroxy-4-methoxy-cinnamate (5), besides the alkaloids 5-(4-methoxymethylfuran-2-yl)-1H-indole (raputimonoindole C), furoquinolines maculosidine, robustine, evolitrine and dictamnine. The hexane extract yielded N-methyl-4-methoxyquinolin-2(1H)-one, skimmianine, cycloartenone, sitosterol, stigmasterol and sitostenone. The anthranilate alkaloid content indicates that the genus is strongly related to those included in Cusparieae tribe, but differs from Neoraputia by the absence of prenylindole alkaloids in the late, whose species have previously been placed in Raputia.

Onze alcalóides acridônicos isolados de Swinglea glutinosa(Bl.) Merr. foram avaliados para suas atividades in vitrocontra linhagens de Plasmodium falciparumsensíveis a cloroquina 3D7, Trypanosoma brucei rhodesienseSTIB9000 e Leishmania donovaniL82. Ensaios com células KB foram também executados com o objetivo de se determinar o grau de toxicidade das substâncias ativas contra os parasitas. Nove dos compostos apresentaram IC50 entre 0,3 e 11,6 µM contra P. falciparum. Em contraste, um pequeno número de compostos mostrou atividade significativa contra T. brucei rhodesiensee nenhum apresentou atividade contra L. donovani. Entre os alcalóides três tiveram IC50 < 1,0 µM contra P. falciparum, enquanto que contra T. b. rhodesiensecinco mostraram IC50 < 10 µM. A caracterização dos alcalóides, 1,3,5-triidróxi-4-metóxi-10-metil-2,8bis(3-metilbut-2-enil)acridin-9(10H)-ona (1), 2,3-diidro-4,9-diidróxi-2-(2-hidróxipropan-2-il)11-metóxi-10-metilfuro[3,2-b]acridin-5(10H)-ona (2) e 3,4-diidro-3,5,8-triidróxi-6-metóxi-2,2,7trimetil-2H-pirano[2,3-a]acridin-12(7H)-ona (3), é aqui discutida. Discute-se também a relação estrutura-atividade para todos os compostos ensaiados. O isolamento e dados espectrais para os alcalóides 1-3estão sendo aqui descritos pela primeira vez, embora em trabalho anterior tenham sido relatadas as suas atividades citotóxicas.

Eleven acridone alkaloids isolated from Swinglea glutinosa(Bl.) Merr. were examined for in vitroactivity against chloroquine-sensitive Plasmodium falciparum3D7, Trypanosoma brucei rhodesienseSTIB900 and Leishmania donovaniL82. An assay with KB cells was developed in order to compare in vitrotoxicity of alkaloids with the selective action on the parasites. Nine of the compounds had IC50 values ranging from 0.3 to 11.6 µM against P. falciparum. In contrast, a small number of compounds showed significant activity against T. brucei rhodesienseand none had activity against L. donovani. Among the alkaloids three had IC50 < 1.0 µM against P. falciparum, whereas against T. b. rhodesiensefive had IC50 < 10 µM. The characterization of the acridone alkaloids, 1,3,5-trihydroxy-4-methoxy-10-methyl-2,8-bis(3-methylbut-2-enyl)acridin-9(10H)-one (1), 2,3-dihydro-4,9-dihydroxy-2-(2-hydroxypropan-2-yl)-11-methoxy-10-methylfuro[3,2-b] acridin-5(10H)-one (2) and 3,4-dihydro-3,5,8-trihydroxy-6-methoxy-2,2,7-trimethyl-2Hpyrano[2,3-a]acridin-12(7H)-one (3), is discussed, as well as the structure-activity relationship of all compounds assayed. Isolation and spectral data of alkaloids 1-3are described for the first time although their citotoxicities to cancer cells have been described before.

Pilocarpus riedelianus was studied in order to obtain compounds with activity against fungi and bacteria. The dichloromethane extract, the most active one, was chromatographed yielding hexane and dichloromethane fractions. Six known sesquiterpenes, alpha-calacorene, beta-calacorene, gamma-calacorene, cadalene, sesquichamaenol and 1-hydroxy-1,3,5-bisabolatrien-10-one were identified in the hexane fractions. The identification of these compound was done by NMR and GC/MS analyses. The hexane fraction from the dichloromethane extract showed activity against several fungi and bacteria.

Droplet counter-current chromatography, rotation locular counter-current chromatography and high-speed counter-current chromatography were applied to the preparative separation of the alkaloid ricinine from the dichloromethane extracts of Ricinus communis leaves. The solvent system used was composed of dichloromethane-methanol-water (93:35:72 v/v/v) and all techniques led to the isolation of large amounts of the alkaloid. The best result was obtained through HSCCC, since the ricinine yield was respectively 50% and 30% higher than when using RLCCC or DCCC.

O estudo da fração acetato de etila do extrato metanólico das folhas de Almeidea rubra A. St.-Hil. (Rutaceae) permitiu o isolamento de duas substâncias inéditas: 4-metoxi-6-[2-(metilamino)fenil]-2H-piran-2-ona e acetato de rel-(7R,8R)-8-[(E)-3-hidroxi-3-metil-1-butenil]-4,8-dimetoxi-5,6,7,8 -tetraidrofuro[2,3-b]quinolin-7-ila; e dos alcalóides arborinina, N-metil-1-hidroxi-3-metoxiacridona, esquimianina, cocusagina, isodutaduprina, isoesquimianina e isococusagina. Através da análise dos dados espectroscópicos foram estabelecidas as estruturas químicas das substâncias isoladas sendo que para os alcalóides inéditos tais dados são descritos pela primeira vez. Além disso, os ensaios bilógicos sobre as formas tripomastigotas do Trypanosoma cruzi das substâncias isoladas mostraram que elas possuem atividade tripanocida moderada.

The investigation of the ethyl acetate fraction of methanol extract from leaves of Almeidea rubra A. St.-Hil. (Rutaceae) afforded two new compounds 4-methoxy-6-[2-(methylamino)phenyl]-2H-pyran-2-one and rel-(7R,8R)-8-[(E)-3-hydroxy-3-methyl-1-butenyl]-4,8-dimethoxy-5,6,7,8 -tetrahydrofuro[2,3-b]quinoline-7-yl acetate, along with the known compounds arborinine, N-methyl-1-hydroxy-3-methoxyacridone, skimmianine, kokusagine, isodutaduprine, isoskimmianine, and isokokusagine. Their structures were established based on their spectral data, and for the new compounds these data are described herein. Additionally, these compounds were assayed on the tripomastigote forms of Trypanosoma cruzi showing moderate trypanocidal activity.

O estudo da fração acetato de etila do extrato metanólico das folhas de Almeidea rubra А. St.-Hil. (Rutaceae) permitiu o isolamento de duas substâncias inéditas: 4-metoxi-6-[2-(metilamino)fenil]-2H-piran-2-ona e acetato de rel-(7R,8R)-8-[(E)-3-hidroxi-3-metil-1-butenil]-4,8-dimetoxi-5,6,7,8-tetraidrofuro[2,3-b]quinolin-7-ila; e dos alcalóides arborinina, N-metil-1-hidroxi-3-metoxiacridona, esquimianina, cocusagina, isodutaduprina, isoesquimianina e isococusagina. Através da análise dos dados espectroscópicos foram estabelecidas as estruturas químicas das substâncias isoladas sendo que para os alcalóides inéditos tais dados são descritos pela primeira vez. Além disso, os ensaios bilógicos sobre as formas tripomastigotas do Trypanosoma cruzi das substâncias isoladas mostraram que elas possuem atividade tripanocida moderada.

The investigation of the ethyl acetate fraction of methanol extract from leaves of Almeidea rubra A. St.-Hil. (Rutaceae) afforded two new compounds 4-methoxy-6-[2-(methylamino)phenyl]-2H-pyran-2-oneand rel-(7R,8R)-8-[(E)-3-hydroxy-3-methyl-1-butenyl]-4,8-dimethoxy-5,6,7,8-tetrahydrofuro[2,3-b]quinoline-7-yl acetate, along with the known compounds arborinine, N-methyl-1-hydroxy-3-methoxyacridone, skimmianine, kokusagine, isodutaduprine, isoskimmianine, and isokokusagine. Their structures were established based on their spectral data, and for the new compounds these data are described herein. Additionally, these compounds were assayed on the tripomastigote forms of Trypanosoma cruzi showing moderate trypanocidal activity.

O estudo de Trattinnickia burserifolia levou ao isolamento dos triterpenos conhecidos ursanos alfa-amirenona, alfa-amirina, 3-epi-alfa-amirina, 3alfa,16beta-diidroxiurs-12-eno; oleananos beta-amirenona, beta-amirina, 3-epi-beta-amirina, 3alfa,16beta-diidroxiolean-12-eno; tirucalanos ácidos 3alfa-hidroxitirucal-8,24-dien-21-óico, 3alfa-hidroxitirucal-7,24-dien-21-óico, e 3-oxotirucal-8,24-dien-21-óico; damaranos dammarenediol-II e 3alfa,20(S)-diidroxidamar-24-eno. Além desses foram ainda isolados o monoterpeno novo 2(S*)-fenilacetoxi-4(R*)-p-menta-1(7),5-dieno, e os triterpenos novos 3beta-fenilacetoxiurs-12-eno, 3beta-fenilacetoxiolean-12-eno e 3beta,16beta,11alfa-triidroxiurs-12-eno. Os triterpenos de T. burserifolia, T. rhoifolia e Dacryodes foram analisados em mistura. Os espectros de RMN 13C mostraram que os principais triterpenos eram alfa-amirina e beta-amirina em T. burserifolia; alfa-amirina, beta-amirina, 3-epi-alfa-amirina, 3-epi-beta-amirina, lupenona, ácidos 3alfa-hidroxitirucal-8,24-dien-21-óico e 3alfa-hidroxitirucal-7,24-dien-21-óico em T. rhoifolia; alfa-amirina, beta-amirina, lupeol, tirucalol, sitosterol e estigmasterol em D. hopkinsii. A quimiossistemática da tribo Protieae é discutida.

Trattinnickia burserifolia has yielded the known ursanes, alpha-amyrenone, alpha-amyrin, 3-epi-alpha-amyrin, 3alpha,16beta-dihydroxyurs-12-ene, the oleananes beta-amyrenone, beta-amyrin, 3-epi-beta-amyrin, 3alpha,16beta-dihydroxyolean-12-ene, the tirucallane acids 3alpha-hydroxytirucall-8,24-dien-21-oic, 3alpha-hydroxytirucall-7,24-dien-21-oic and 3-oxotirucall-8,24-dien-21-oic, the dammaranes dammarenediol-II and 3alpha,20(S)-dihydroxydammar-24-ene. Besides it was isolated the new monoterpene 2(S*)-phenylacetoxy-4(R*)-p-mentha-1(7),5-diene and, the new triterpenes 3beta-phenylacetoxyurs-12-ene, 3beta-phenylacetoxyolean-12-ene and 3beta,16beta,11alpha-trihydroxyurs-12-ene. The triterpenes from T. burserifolia, T. rhoifolia and Dacryodes were analyzed in mixture. Their 13C NMR spectra showed that the major triterpenes were in T. burserifolia alpha-amyrin and beta-amyrin; in T. rhoifolia alpha-amyrin, beta-amyrin, 3-epi-alpha-amyrin, 3-epi-beta-amyrin, and lupenone; in T. rhoifolia alpha-amyrin, beta-amyrin, 3-epi-alpha-amyrin, 3-epi-beta-amyrin, 3alpha-hydroxytirucall-8,24-dien-21-oic acid and 3alpha-hydroxytirucall-7,24-dien-21-oic acid; in D. hopkinsii alpha-amyrin, beta-amyrin, lupeol, tirucallol, sitosterol and stigmasterol. Aspects of chemosystematic of the tribe Protieae are discussed.

Nosso interesse quimiotaxonômico sobre Neoraputia nos estimulou a examinar N. paraensis, visando a busca de alcalóides. As frações foram monitoradas via RMN ¹H e ESI-EM/EM e foram analisadas somente aquelas cujos espectros apresentavam características de alcalóides do ácido antranílico e flavonóides não isolados anteriormente. Foram isolados do caule os alcalóides flindersina, skimmianina, 8-metoxiflindersina e dictamnina; das folhas os flavonóides 3',4',7,8-tetrametoxi-5,6-(2",2"-dimetilpirano)-flavona, 3',4',5,7,8-pentametoxiflavona, 5-hidroxi-3',4',6,7-tetrametoxiflavona, 3',4'-metilenodioxi-5,6,7-trimetoxiflavona e 5-hidroxi-3',4'-metilenodioxi-6,7-dimetoxiflavona,. Os alcalóides do ácido antranílico não foram encontrados em dez anos. Vários flavonóides isolados de N. paraensis, N. magnifica, Murraya paniculata, enxerto de Citrus sinensis (Rutaceae) e Lonchocarpus montanus (Leguminosae) foram testados frente a gliceraldeído-3-fosfato desidrogenase de Trypanosoma cruzi, visando verificar seus potenciais em inibir a atividade da enzima. Os flavonóides polimetoxilados e um isoflavonóide foram os mais ativos.

Our taxonomic interest in the Neoraputia stimulated an investigation of N. paraensis searching for alkaloids. Fractions were monitored by ¹H NMR and ESI-MS/MS and only those which showed features of anthranilate alkaloids and flavonoids absent in the previous investigations were examined. Stems afforded the alkaloids flindersine, skimmianine, 8-methoxyflindersine and dictamnine; leaves yielded 3',4',7,8-tetramethoxy-5,6-(2",2"-dimethylpyrano)-flavone, 3',4',5,7,8-pentamethoxyflavone, 5-hydroxy-3',4',6,7-tetramethoxyflavone, 3',4'-methylenedioxy-5,6,7-trimethoxyflavone and 5-hydroxy-3',4'-methylenedioxy-6,7-dimethoxyflavone. The alkaloids have remained undiscovered for 10 years. A number of flavonoids isolated from N. paraensis, N. magnifica, Murraya paniculata, Citrus sinensis graft (Rutaceae), Lonchocarpus montanus (Leguminosae) were evaluated for their ability to inhibit the enzymatic activity of the protein glyceraldehyde-3-phosphate dehydrogenase from Trypanosoma cruzi. Highly oxygenated flavones and isoflavone were the most actives.

Seeds Citrus oils (C. sinensis, C. limon and C. reticulata) extraction with hexane in a soxhlet apparatus and through supercritical fluid (CO2) were done. Besides triglycerides, the oils obtained with hexane comprised volatile compounds such as terpenes and fatty alcohols, esters, and aldehydes. However, the oils obtained by extraction with supercritical fluid presented only triglycerides. These results indicate that the extraction using supercritical fluid presents better selectivity. The activity of the oils on the development of the ant symbiotic fungus, Leucoagaricus gongylophorus, showed week activity and the topic insecticide assay showed better activity for the tangerine seed oil.

O trabalho descreve o isolamento de três novos sesquiterpenóides do extrato metanólico dos galhos de Trichilia claussenii: 14-hidroxielemol, germacra-10(14)-en-9,11,15-triol e germacra-3,10(14)-dien-9,11-diol-4-carbaldeído. Também foram isolados os sesquiterpenos beta-eudesmol, criptomeridiol e o triterpeno 22,25-diidroxi-9beta,19-ciclolanost-23-en-3-ona. Do extrato diclorometânico das folhas de T. lepidota foram isolados mistura de hidrocarbonetos (C29H60, C31H64 e C33H68), mistura dos sesquiterpenos epóxido de cariofileno e epóxido de humuleno, espatulenol e os esteróides 24-metileno-12beta-hidroxicolesterol, 24-metil-12beta-hidroxicolest-4-en-3-ona, 3-palmitato de 24-metil-12beta-hidroxicolest-5-eno, mistura de 24-metilenocolesterol, campesterol, estigmasterol e beta-sitosterol, além de alfa-tocoferol e fitol. O extrato metanólico forneceu a N-metil-4-hidroxiprolina. As estruturas das substâncias isoladas foram estabelecidas com base em dados espectroscópicos.

The methanol extract of stems of Trichilia claussenii yielded three new sesquiterpenoids: 14-hydroxyelemol, germacra-10(14)-en-9,11,15-triol and germacra-3,10(14)-dien-9,11-diol-4-carbaldehyde. Two known sesquiterpenoids beta-eudesmol, cryptomeridiol and the triterpenoid 22,25-dihydroxy-9beta,19-cyclolanost-23-en-3-one were also isolated. The dichloromethane extract from the leaves of T. lepidota afforded a mixture of hydrocarbons (C29H60, C31H64 and C33H68), a mixture of the sesquiterpenes caryophyllene and humulene epoxides, spathulenol, and a series of sterols: 24-methylene-12b-hydroxycholesterol, 24-methyl-12beta-hydroxycholest-4-en-3-one, 24-methylene-12beta-hydroxycholest-5-ene-3-palmitate; a mixture of 24-methylenecholesterol, campesterol, stigmasterol and beta-sitosterol; besides alpha-tocoferol and phytol. From the methanol extract it was isolated N-methyl-4-hydroxyproline. The structures of the isolated compounds were determined on the basis of spectroscopic analysis.

A investigação fitoquímica dos extratos de caules e folhas da espécie endêmica Raulinoa echinata Cowan, Rutaceae, levou ao isolamento de alcalóides furoquinolínicos (esquimianina, kokusaginina, maculina e flindersiamina) e quinolônicos (1-metil-2-n-nonil-4-quinolona, 2-n-nonil-4-quinolona e 2-fenil-1-metil-4-quinolona). Os alcalóides isolados mostraram atividade antifúngica contra Leucoagaricus gongylophorus, o fungo simbionte de formigas cortadeiras (Atta spp). Quando testados in vitro contra formas tripomastigotas de Trypanosoma cruzi, os alcalóides foram inativos ou parcialmente ativos. Neste trabalho descrevem-se o isolamento dos alcalóides, a elucidação estrutural dos alcalóides quinolônicos e a estrutura obtida por difração de raio-X da flindersiamina, juntamente com os resultados dos bioensaios realizados.

Phytochemical survey of stems and leaves extracts of the South Brazilian endemic plant Raulinoa echinata Cowan, Rutaceae, led to the isolation of known furoquinoline alkaloids: the widespread skimmianine; kokusaginine, maculine, flindersiamine, and also quinolone derivatives: 1-methyl-2-n-nonyl-4-quinolone, 2-n-nonyl-4-quinolone and 1-methyl-2-phenyl-4-quinolone. These alkaloids showed antifungal activity against Leucoagaricus gongylophorus; the symbiotic fungus of leaf-cutting ants (Atta sexdens). They were inactive or displayed weak inhibitory activity when assayed in vitro against trypomastigote forms of Trypanosoma cruzi. In this paper, the isolation, structure elucidation and bioactivity results of these compounds are reported together with the X-ray structure of flindersiamine.

Nesta comunicação estamos reportando as propriedades tóxicas dos extratos metanólicos das flores, pedúnculos, folhas, pecíolo e casca do tronco de Dimorphandra mollis sobre as operárias de Apis mellifera. Astilbina (3-beta-O-rhamnosideo de 5,7,3',4'-- tetraidroxi-2,3-diidroflavonol) isolada dos pedúnculos e flores como o seu principal componente, apresentou atividade inseticida sobre abelhas confinadas. Os resultados obtidos indicam que a astilbina reduz a sobrevivência média das abelhas tratadas.

In this communication we have evaluated the toxic properties of methanol extracts from flowers, peduncles, leaves, petioles and stem bark of Dimorphandra mollis to Apis mellifera workers. Astilbin (5,7,3',4'-tetrahydroxy--2,3-dihydroflavonol-3-beta-O-rhamnoside) has been isolated from peduncles and flowers of this plant in large amounts. Astilbin presented insecticidal activity against confined bees. The results suggest that astilbin reduces the average survival of treated bees.

Da casca do caule de Picramnia teapensis Tul. foram isolados dois novos benzoatos triterpênicos, o 3alfa,7beta-dibenzoato do ácido lup-20(29)-en-28-óico e o 7beta-benzoato do ácido 3alfa-hidroxi-lup-20(29)-en-28-óico. A elucidação estrutural desses compostos foi fundamentada na análise dos dados espectroscópicos. Outros compostos conhecidos, beta-sitosterol, estigmasterol, lupeol e epilupeol, foram identificados em mistura por CG-EM. Nenhum dos triterpenos benzoilados mostrou efeito inibitório no crescimento in-vitro do Leucoagaricus gongylophorus (Fisher), também citado como Leucocoprinus gongylophorus (Heim), syn Rozites gongylophora (Möller), o fungo simbionte cultivado pelas formigas cortadeiras de folhas Atta sexdens L.

Two new benzoic acid esters of triterpene alcohols [lup-20(29)-en-28-oic acid 3alpha,7beta-dibenzoate and 3alpha-hydroxy-lup-20(29)-en-28-oic acid 7beta-benzoate] were isolated from the stem bark of Picramnia teapensis Tul. The structures of these compounds were established on the basis of spectral analyses. Other known compounds, beta-sitosterol, estigmasterol, lupeol and epilupeol, were identified in mixture by GC-MS. The triterpene esters have not shown in-vitro inhibitory effect on the growth of Leucoagaricus gongylophorus (Fisher), referred also as Leucocoprinus gongylophorus (Heim), syn Rozites gongylophora (Möller), the symbiotic fungus cultivated by the leaf-cutting ant Atta sexdens L.

Os óleos essenciais de Toona ciliata, Cedrela odorata e C. fissilis foram analisados por CG-EM. Cedrela apresentou em maior percentagem sesquiterpenos formados a partir do precursor pirofosfato de cis- e trans-farnesila. Já Toona mostra uma tendência em produzir principalmente sesquiterpenos derivados do pirofosfato de trans-farnesila. Estes resultados confirmam que a classificação destes dois gêneros em uma mesma tribo, Cedreleae, continua problemática. As respostas em eletroantenogramas médios (EAGs) dos óleos essenciais de T. ciliata e C. odorata, em fêmeas de Hypsipyla grandella, foram significativamente maiores que aquelas obtidas em machos, sugerindo que as fêmeas utilizariam os odores destes óleos para a seleção da planta hospedeira (gêneros de Swietenioidea) e na escolha de locais para oviposição.

The essential oils of Toona ciliata, Cedrela odorata and C. fissilis have been analysed by GC-MS. Cedrela contains the main sesquiterpenes formed from the cis- and trans-farnesyl pyrophosphate. In contrast, Toona tend to produce mainly sesquiterpenes formed from the trans-precursor. These results show that the affiliation of Toona in the tribe Cedreleae together with Cedrela is still rather problematic. Mean electroantennogram responses (EAGs) to the essential oils from T. ciliata and C. odorata, in Hypsipyla grandella females were significantly greater than those obtained for males, suggesting that females would use attractant odours messages from the host-plant (genera of Swietenioideae) as search strategy behaviour for habitat location and oviposition.