Enantioselective synthesis of aziridines using asymmetric transfer hydrogenation as a precursor for chiral derivatives used as bonding agent for rocket solid propellants

A rapid, expedient and enantioselective method for the synthesis of beta-hydroxy amines and monosubstituted aziridines in up to 99% e.e., via asymmetric transfer hydrogenation of a-amino ketones and cyclisation through treatment with tosyl chloride and base, is described. (1R,2R)-N-(para-toluenesulfonyl)-1,2-ethylenediamine with formic acid has been utilised as a ligand for the Ruthenium (II) catalysed enantioselective transfer hydrogenation of the ketones.The chiral 2-methyl aziridine, which is a potentially more efficient bonding agent for Rocket Solid Propellant has been successfully achieved.

Constituintes químicos de Ottonia corcovadensis Miq. da floresta Amazônica: atribuição dos deslocamentos químicos dos átomos de hidrogênio e carbono

In an ethanolic extract of leaves of Ottonia corcovadensis (Piperaceae) were identified sixteen terpenoids of essential oil and the three flavonoids 3',4',5,5',7-pentamethoxyflavone (1), 3',4',5,7-tetramethoxyflavone (2) and 5-hydroxy-3',4',5',7-tetramethoxyflavone (3) and cafeic acid (4). Two amides (5 and 6) were isolated from an ethanolic extract of the roots. The structures were established by spectral analysis, meanly NMR (1D and 2D) and mass spectra. Extensive NMR analysis was also used to complete ¹H and 13C chemical shift assignments of the flavonoids and amides. The components of the essential oil were identified by computer library search, retention indices and visual interpretation of mass spectra.

Constituintes químicos voláteis e não-voláteis de Cochlospermum vitifolium (Willdenow) Sprengel

The essential oils from leaves, root bark and root wood of Cochlospermum vitifolium were investigated for the first time. The oils were obtained by hydrodistillation and analyzed by GC/MS. The main volatile constituents were beta-caryophyllene (8.2 - 46.5%), beta-bisabolene (11.5 - 29.3%), gamma-muurolene (28.4%), alpha-humulene (26.0%), 1-hydroxy-3-hexadecanone (16.2 - 19.5%) and beta-pinene (10.6%). Phytochemical analysis of the root bark and root wood extracts yielded excelsin, pinoresinol, narigenin, aromadendrin, galic acid and a triacylbenzene, along with beta-sitosterol and stigmasterol and their D-glucosides. The structures of all compounds were determined by analyses of the spectroscopic data (NMR and MS), and comparison with the literature.

Estudo fitoquímico e avaliação alelopática de Memora peregrina - "ciganinha" - Bignoniaceae, uma espécie invasora de pastagens em Mato Grosso do Sul

Memora peregrina (local name: 'ciganinha' - Bignoniaceae) is a weed that often invades pastures in the Brazilian state of Mato Grosso do Sul. From its leaves and subterranean parts, the following compounds were isolated: allantoin (20.7 w/w in subterranean parts), the iridoid 6beta-hydroxyipolamiide, hyperin, 3'-O-methylhyperin, 4-hydroxy-N-methylproline, beta-sitosterol, alpha-amirin and beta-amirin, and lupeol. Allantoin exhibited an activity of inducing germination in seeds of Lactuca sativa used as a biological model, and the iridoid showed moderate activity in the larval development of Anagasta kuehniella. These results, associated with this plant's behavior, are suggestive of the occurrence of adaptive and competitive strategies in relation to other plant species.

Benzoquinonas, hidroquinonas e sesquiterpenos de Auxemma glazioviana

Two new compounds, 5 and 8, and an epimeric mixture 4a/4b were isolated from hardwood of Auxemma glazioviana. Their structures and relative configurations were determined by modern spectroscopic analysis to be rel-10alpha,11alpha-epoxy-11beta-ethoxy-8alpha- hydroxy-2-methoxy -8abeta-methyl-5,6,7,8,8a,9,10,10abeta-octahydro-1,4-anthracenedione (or rel-2R,2aR,5R,5aS ,10bS,10cS-2-ethoxy-5-hydroxy-8-methoxy-5a-methyl- 2a,3,4,5,5a,6,10b,10c-octahydro-2H-anthra[9,1-bc]furan-7,10-dione, 4a), rel-10alpha,11alpha- epoxy-11alpha-ethoxy-8alpha-hydroxy-2-methoxy-8abeta-methyl-5,6,7,8,8a,9,10,10abeta-octahydro- 1,4-anthracenedione (or rel-2S,2aR,5R,5aS ,10bS,10cS-2-ethoxy-5-hydroxy-8-methoxy- 5a-methyl-2a,3,4,5,5a,6,10b10c-octahydro-2H-anthra[9,1-bc]furan-7,10-dione, 4b), rel-10alpha,11alpha-epoxy-8alpha,11-dihydroxy-2-methoxy-8abeta-methyl-5,6,7,8,8a,9,10,10abeta- octahydro-1,4-anthracenedione (or rel-2S,2aR,5R,5aS ,10bS,10cS-2,5-dihydroxy-8- methoxy-5a-methyl-2a,3,4,5,5a,6,10b,10c-octahydro-2H-anthra[9,1-bc]furan-7,10 -dione, 5) and rel-10,11-epoxy-8abeta-methyl-1,4,5alpha,9alpha-tetrahydroxy-5,6,7,8,8a,9,10,10a- octahydro-8-anthracenone (or rel-2aS,5aS,6R,10bR ,10c5-2a,6,7,10-tetrahydroxy-5a-methyl-2a,3,4,5,5a,6,10b,10c-octahydro-2H-anthra [9,1-bc]-furan-5-one, 8). In addition, known compounds were also isolated.

Constituintes químicos da raiz e do talo da folha do açaí (Euterpe precatoria Mart., Arecaceae)

Phytochemical investigation of the hexane, ethyl acetate and methanolic extracts of roots and leaf stalks of Euterpe precatoria Mart. ("açaí"), afforded stigmast-4-en-6beta-ol-3-one (3); p-hydroxy benzoic acid (4); 3beta-O-D-glucopyranosyl-sitosterol (5); beta-sitosterol palmitate (6); mixtures of beta-sitosterol and stigmasterol (1 and 2), alpha-, beta-amirin and lupeol (7, 8 and 9), friedelin-3-one and 28-hydroxy-friedelin-3-one (10 and 11) and alpha-, beta-D-glucose (12, 13). Except for 1, 2 and 4, the other isolated constituents are described in the genus for the first time. Compounds 3 and 5 gave good results in the brine shrimp bioassay, which detects compounds with potential uses as antitumor agents, pesticides, etc..

Sesquiterpenos do caule de Pilocarpus riedelianus e atividades sobre microorganismos

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.

Triterpenóides pentacíclicos das folhas de Terminalia brasiliensis

Eleven oleanane, ursane and lupane-type triterpenes were isolated from the leaves of Terminalia brasiliensis Camb, daturadiol (3b,6beta-dihydroxy-olean-12-ene), 3beta-hydroxy-30-norlupan-20-one, lupenone, beta-amyrenone, alpha-amyrenone, lupeol, beta-amyrin, alpha-amyrin, betulin, erythrodiol and uvaol, in addition to squalene, sitosterol and alpha-tocopherol. The structures of these compounds were identified by ¹H and 13C NMR spectral analysis and comparison with literature data.

Constituintes químicos de Bombacopsis glabra (bombacaceae)

The chemical study of the barks of the stem and roots of Bombacopsis glabra (Bombacaceae) led to the isolation and identification of 5-hydroxy-3,7,4'-trimethoxyflavone (1), 5-hydroxy-3,6,7,4'-tetramethoxyflavone (2), the naphtoquinone isohemigossypolone (3), the ester triacontil p-coumarate (4) besides lupeol and a mixture of beta-sitosterol and stigmasterol. Their structures were elucidated by spectroscopic analysis, including IR, ¹H and 13C NMR and MS. All these compounds, except 3, were isolated for the first time in the family.

Constituintes químicos de Philodendron imbe Schott

The chemical composition of the ethanolic extract of the leaves and roots from Philodendron imbe Schott was investigated. The main constituents isolated the leaves were beta-sitosterol one polyprenoid hexaprenol, and 6beta-hydroxy-stigmast-4-en-3-one, a steroid, not yet reported in the Philodendron gender. A mixture of constituents, namely, ethyl myristoleate, alpha-bisabolol, ethyl isopalmitate, 3-octadecenyl-phenol and the major component ethyl palmitate, were isolated from the roots. Structure elucidation of these secondary metabolites was accomplished by spectrometric analysis, including 1D and 2D NMR experiments such as ¹H, ¹H and ¹H,13C-COSY.

Controle da biossíntese de poli-hidroxialcanoatos bacterianos através do fluxo de substratos

Manipulation of the flux of substrates was utilized to control the amount of 3-hydroxyvalerate and 3-hydroxy-4-pentenoate produced by Burkohlderia sp. The 3HV production rate was directly proportional to the propionic acid uptake rate with the last one completely directed to 3HV biosynthesis. The 3HPE production rate was inversely proportional to the sucrose uptake rate probably due to operation of the glyoxylate cycle.

Physicochemical composition of pure and adulterated royal jelly

The physicochemical composition of pure royal jelly as well as of some adulterated samples was analyzed by determining moisture, ash, lipids, nitrogen/proteins, carbohydrates, starch and 10- HDA (10-hydroxy-2-decenoic acid). The solubility in alkaline medium was used to detect the main frauds for adulterating royal jelly which comprise addition of yogurt, water, egg white, sweet condensed milk mixed with propolis, unripe banana and corn starch slurry.

Estatinas hipolipêmicas e novas tendências terapêuticas

Statins are the most used drugs for the treatment of hyperlipidemia in primary and secondary prevention, with the aim of decreasing the levels of plasmatic cholesterol- lipoproteins. Owing to their structural similarity to the substrate HMG-CoA (3-hydroxy-3-methylglutaryl-CoA), they inhibit the HMG-CoA reductase enzyme, disrupting the cholesterol biosynthesis. Currently, six therapeutic statins are available: lovastatin (Mevacor) and pravastatin (Pravachol), which are natural, sinvastatin (Zocor), a semi-synthetic derivative, and the totally synthetic statins, fluvastatin (Lescol), atorvastatin (Lipitor) and rosuvastatin (Crestor). Recent investigations have showed other important effects of statins, such as antineoplastic action and improvement in endothelial function.

Clerodane diterpenes from leaves of Casearia sylvestris Swartz

Ethanolic extracts of the leaves of Casearia sylvestris yielded a novel clerodane diterpene, 15-hydroxy-3-cleroden-2-one, together with the known diterpenes (-)-hardwickiic acid, reported for the first time from this species, and casearins B and G, previously isolated from C. sylvestris. The structures of all four compounds were determined by spectrometric analysis. The new clerodane diterpene and (-)-hardwickiic acid contain structural features that are completely different from the highly oxygenated casearins and casearvestrins isolated from C. sylvestris.

Antifungal derivatives from Piper mollicomum and P. lhotzkyanum (Piperaceae)

Bioguided fractionation of the extracts from leaves of Piper mollicomum and Piper lhotzkyanum against the fungi Cladosporium cladosporioides and C. sphaerospermum afforded seven bioactive compounds, four being chromenes: methyl 2,2-dimethyl-2H-chromene-6-carboxylate, methyl 8-hydroxy-2,2-dimethyl-2H-chromene-6-carboxylate, 2-methyl-2-[4'-methyl-3'-pentenyl]-2H-1-benzopyran-6-carboxylic acid, 2,2-dimethyl-2H-chromene-6-carboxylic acid, one a dihydrochalcone: 2',6'-dihydroxy-4'-methoxydihydrochalcone, and two flavanones: 7-methoxy-5,4'-dihydroxy-flavanone and 7,4'-dimethoxy-5-hydroxy-flavanone. The structures of the bioactive isolated derivatives were elucidated by interpretation of their NMR data [¹H and 13C (BBD, DEPT 135º)], and mass spectral data as well as by comparison with data described in the literature.