Dihydrocinnamic Acid Derivatives Research Articles

Identification and quantification of novel cranberry-derived plasma and urinary (poly)phenols

Cranberries are a rich source of (poly)phenols, in particular proanthocyanidins, anthocyanins, flavonols, and phenolic acids. However, little is known about their bioavailability in humans. We investigated the absorption, metabolism, and excretion of cranberry (poly)phenols in plasma and urine of healthy young men after consumption of a cranberry juice (787 mg (poly)phenols). A total of 60 cranberry-derived phenolic metabolites were identified using UPLC-Q-TOF-MS analysis with authentic standards. These included sulfates of pyrogallol, valerolactone, benzoic acids, phenylacetic acids, glucuronides of flavonols, as well as sulfates and glucuronides of cinnamic acids. The most abundant plasma metabolites were small phenolic compounds, in particular hippuric acid, catechol-O-sulfate, 2,3-dihydroxybenzoic acid, phenylacetic acid, isoferulic acid, 4-methylcatechol-O-sulfate, α-hydroxyhippuric acid, ferulic acid 4-O-sulfate, benzoic acid, 4-hydroxyphenyl acetic acid, dihydrocaffeic acid 3-O-sulfate, and vanillic acid-4-O-sulfate. Some benzoic acids, cinnamic acids, and flavonol metabolites appeared in plasma early, at 1–2 h post-consumption. Others such as phenylacetic acids, benzaldehydes, pyrogallols, catechols, hippuric and dihydrocinnamic acid derivatives appear in plasma later (Tmax 4–22 h). The 24 h urinary recovery with respect to the amount of (poly)phenols consumed was 6.2%. Our extensive description of the bioavailability of cranberry (poly)phenols lays important groundwork necessary to start understanding the fate of these compounds in humans.

CHEMICAL STUDY OFHortia superba(Rutaceae) AND INVESTIGATION OF THE ANTIMYCOBACTERIAL ACTIVITY OF CRUDE EXTRACTS AND CONSTITUENTS ISOLATED FROMHortiaSPECIES

In this paper, the chemical study of Hortia superba and antimycobacterial potential of Hortia species were investigated. Crude extracts and limonoids, alkaloids, dihydrocinnamic acid derivatives and coumarins isolated from Hortia superba, Hortia oreadica and Hortia brasiliana were evaluated against Mycobacterium tuberculosis H37Rv, Mycobacterium kansasii and Mycobacterium avium. The results obtained demonstrated an inhibitory effect of the dichloromethane extract of leaves of H. oreadica (MIC 31.25 µg mL-1), indolequinazoline (15.62 µg mL-1) and furoquinoline (31.25 µg mL-1) alkaloids, and dihydrocinnamic acid derivatives (62.50 µg mL-1), on the growth of M. tuberculosis. These results are promising in relation to the search for biologically active natural products and could be useful in the development of effective new drugs against mycobacteria.

Dihydrocinnamic acid derivatives from Hortia species and their chemotaxonomic value in the Rutaceae

Phytochemical studies of Hortia brasiliana and Hortia oreadica (Rutaceae) have led to the identification of three novel dihydrocinnamic acids: 5-methoxy-2,2-dimethyl-2H-1-benzopyran-8-propanoic acid, 5,6-dimethoxy-2,2-dimethyl-2H-1-benzopyran-8-propanoic acid and erythro-2-hydroxy-4-methoxy-3-(1,2,3-trihydroxy-3-methylbutyl)benzenepropanoic acid from H. brasiliana and the second compound and six known dihydrocinnamic acids from H. oreadica. Engler included Hortia as the single Neotropical genus in the Toddalioideae subtribe Toddaliinae. However, the range of dihydrocinnamic acid derivatives found in H. brasiliana and H. oreadica show that they contain similar compounds to other species of Hortia and clearly point to their phytochemical affinities with other Rutoideae species.

Determination of the antibacterial activity of crude extracts and compounds isolated from Hortia oreadica (Rutaceae) against oral pathogens

Extracts from Hortia oreadica afforded four dihydrocinnamic acid derivatives, isolated from the n-hexane extract, as well as limonoid guyanin and the furoquinoline alkaloid dictamnine, both isolated from the dichloromethane extract. The extracts and the isolated compounds were tested against some oral pathogens, so as to investigate their antibacterial activity. The results showed that the n-hexane extract and the compound dictamnine are the most active against the selected microorganisms.

Isolation of secondary metabolites from Hortia oreadica (Rutaceae) leaves through high-speed counter-current chromatography

High-speed counter-current chromatography (HSCCC) with a two-phase solvent system (hexane–ethanol–acetonitrile–water 10:8:1:1, v/v) was applied to examine the leaves of Hortia oreadica, which afforded the known limonoid guyanin ( 1), the alkaloids rutaecarpin ( 2) and dictamnine ( 6), the dihydrocinnamic acid derivatives methyl 5,7-dimethoxy-2,2-dimethyl-2 H-1-benzopyran-6-propanoate ( 3), 5,8-dimethoxy-2,2-dimethyl-2 H-1-benzopyran-6-propanoic acid ( 4), together with the new E-3,4-dimethoxy-α(3-hydroxy-4-carbomethoxyphenyl)cinnamic acid ( 5). The recovery of compounds 1–6 was determined by comparison with LC-atmospheric pressure chemical ionization MS/MS data: 66.2%, 93.1%, 102.5%, 101.2%, 99.0% and 84.9%, respectively. Compound 3 showed IC 50 of 23.6 μM against Plasmodium falciparum and 15.6 μM against Trypanosoma brucei rhodesienses and was not toxic to KB cells (IC 50 > 100 μM).

Chemical Constituents of the Aquatic Plant Schoenoplectus lacustris: Evaluation of Phytotoxic Effects on the Green Alga Selenastrum capricornutum

Forty-nine secondary metabolites were isolated from aqueous and alcoholic extracts of the aquatic plant Shoenoplectus lacustris. All compounds were characterized based on spectroscopic data. Eleven free and glycosylated low-molecular polyphenols, 17 cinnamic acid and dihydrocinnamic acid derivatives, 11 flavonoids, and 10 C13 nor-isoprenoids were identified. The structure of the new compound, 1-benzoyl-glycerol-2-alpha-L-arabinopyranoside, was elucidated by 2D NMR experiments (COSY, HSQC, HMBC, NOESY). To evaluate potential phytotoxic effects, all compounds were tested on the green alga Selenastrum capricornutum, a unicellular organism commonly used in tests of toxicity as a bioindicator of eutrophic sites. The most active compound was (-)-catechin, showing an inhibition similar to that of the algaecide CuSO4.

Divergence of secondary metabolism in cell suspension cultures and differentiated plants of Piper cernuum and P. crassinervium

The secondary metabolism in the leaves of P. cernuum produces cinnamic and dihydrocinnamic acid derivatives and the lignan cubebin. In case of P. crassinervium flavonoids and prenylated hydroquinones were characterized as major compounds. The cell cultures showed the production of the phenylethylamines dopamine and tyramine in P. cernuum, while in case of P. crassinervium four alkamides were isolated as major compounds, including the new 2,3,4-trimethoxy-N-methyl-aristolactam and 3-hydroxy-2-methoxy-N-methyl-aristolactam.

Composição química de Baccharis dracunculifolia, fonte botânica das própolis dos estados de São Paulo e Minas Gerais

A própolis é uma substância resinosa coletada pelas abelhas de diversas partes das plantas. Sua composição depende da época, vegetação e local de coleta. Análises fitoquímicas de própolis produzidas de Baccharis dracunculioflia (alecrim-do-campo) por abelhas Apis mellifera africanizada nos estados de São Paulo e Minas Gerais foram feitas por espectrofotometria na região U.V.-Visível, CCDAE-FR, CLAE-FR e CG-EM. Uma característica dos compostos fenólicos das própolis analisadas e da espécie vegetal de B. dracunculiofolia foi a alta proporção de artepilin C e outros derivados do ácido cinâmico. Com base nas evidências fitoquímicas, B. dracunculifolia foi identificada como a principal fonte vegetal das própolis produzidas nos estados de São Paulo e Minas Gerais.

Tetranortriterpenoids and Dihydrocinnamic Acid Derivatives from Hortia colombiana

A novel tetranortriterpenoid and two dihydrocinnamic acid derivatives were obtained from the wood of Hortia colombiana. Their structures were elucidated by detailed NMR investigations and the relative configurations established by Difference NOE experiments. In addition, alloxanthoxyletin, nerolidol, epoxynerolidol, three known dihydrocinnamic acid derivatives and two amides were isolated. Detailed analysis of NMR data of Hortiolide A, whose structure was previosly established by X ray, are also provided.

A polar effects controlled enantioselective 1,2-chlorine atom migration via a chlorine-bridged radical intermediate.

An enantioselective 1,2-chlorine atom migration was observed in the tributyltin hydride reduction of various dihalogenated dihydrocinnamic acid derivatives. It is proposed that the reduction involves the formation of a chlorine-bridged radical intermediate, followed by hydrogen atom transfer to either the beta- or the alpha-carbon. The product distribution is affected by electron-withdrawing groups in that hydrogen atom transfer to the proximate carbon is favored. Presumably, this is due to the transition state of the hydrogen delivery step being electron rich, due to the relatively electropositive tin radical. These results demonstrate a 1,2-chlorine atom migration reaction governed by polar effects.

Prenylated Coumarins, Chalcone and New Cinnamic Acid and Dihydrocinnamic Acid Derivatives from Brosimum gaudichaudii

Three new natural cinnamic acid and dihydrocinnamic acid derivatives were isolated from the roots of Brosimum gaudichaudii, in addition to fourteen known substances (ten coumarins, one chalcone, b-sitosterol, 3b-O-b-D-glucopyranosylsitosterol and b-amyrin). The structures were established by spectral data, including analysis of 2D-NMR experiments and mass spectra. All aromatic compounds have 4-hydroxy-3-prenylcinnamic acid as a common precursor. The new substances are derived from a precursor of the coumarins, which through an O-methylation lost its ability to form the lactone ring.

Coumarins and dihydrocinnamic acid derivatives from Micromelum falcatum

Besides the known coumarins microminutinin and 6-methoxymicrominutinin, the new dihydrocinnamic acid derivatives 3,4-dihydro-1,2- secomicrominutinin, 3,4-dihydro-1,2- secomicrominutinin methylester and 3,4-dihydro-1,2- secomicrominutinin-9- O-glucoside as well as the new 8-prenylated coumarin microfalcatin isovalerate were isolated from the leaves of Micromelum falcatum (Rutaceae). The structures were elucidated by mass and NMR spectroscopy. The relative configuration of microfalcatin isovalerate was established as 1′,2′- threo by analysis of the NOE effects of its acetonide.

3,4,8-Trimethoxy-2-quinolone: A New Alkaloid from Eriostemon gardneri

A new alkaloid, 3,4,8-trimethoxy-2quinolone (l), and six known com- pounds including TWO pyranocoumarins, avicennol and cis-avicennol, two dihydrocinnamic acid derivatives, eriostemoic acid and eriostoic acid, and two flavonoid glycosides, hesperidin and diosmin, have been isolated from the aerial parts of Eriostemon gardneri. Eriostemon gardneri P.G. Wilson (Rutaceae), an undershrub found near the south coast from Cheyne Bay east to beyond Esperance, and north towards Lake King in Western Australia, is one of eighteen species placed in Eriostemon sect. Nigrostipulae (1-3). As part of our phy- tochemical survey on the genus Eriosremon (Pb), we wish to report on the major secondary metabolites found in a sample of the aerial parts of Eriostemon gardnwi. Seven compounds were isolated and characterized as 3,4,8-trimethoxy-2- quinolone El), avicennol (7,8), cis-

New coumarin and dihydrocinnamic acid derivatives from two malaysian populations of Micromelum minutum

Three novel compounds, two compounds and a dihydrocinnamic acid, have been isolated from two collections of Micromelum minutum and identified by means of NMR spectroscopy. A sample collected from Pahang gave the typical coumarin micromelin and a new dihydrocinnamic acid derivative of micromelin which was identified as 1,2- seco-dihydromicromelin. The second sample, collected from Kelantan, gave two new tetracyclic coumarins, microminutinin and 6-methoxymicrominutinin, which possess a fused bifurano system that appears to be derived by cyclization of a 7-oxygenated-8-(1,2-dimethyl)propylcoumarin precursor. The structure of microminutinin is revised from that proposed in a previous paper.

Cinnamic acid bridges between cell wall polymers in wheat and phalaris internodes

A method has been devised for the quantitative determination of cinnamic acids participating in ester—ether bridges between cell wall polymers based on the different reactivities of free carboxylic acids and their esters towards borohydride reductants and the different susceptibilities of cinnamic acid ester and benzyl ether linkages to alkaline treatments. Lignin—polysaccharide containing fractions extracted with dioxane—H 2O from cell walls of wheat ( Triticum aestivum) and phalaris ( Phalaris aquatica) internodes are hydrogenated using a Pd/C catalyst at room temperature to convert cinnamic acids to their corresponding dihydrocinnamic acids. The sample is subsequently reduced with LiBH 4 in ether—toluene to convert ester-linked dihydrocinnamates to their corresponding alcohols, hydrolysed with 4 M NaOH at 170°, and the dihydrocinnamic acid derivatives released from their etherified forms determined by GC. Using model compounds it was shown that these reactions proceeded quantitatively. The results indicate that all of the etherified ferulic acid in the dioxane—H 2O-soluble fractions of walls of wheat and phalaris internodes is also ester-linked. It has been calculated that there are nine to 10 ferulic acid ester—ether bridges for every 100 C 6—C 6 lignin monomers. p-Coumaric acid is not involved in ester-ether bridges.

Alkaloids, flavonols and coumarins from Drummondita hassellii and C. calida

The aerial parts of both Drummondita hassellii and D. calida have yielded a number of simple furoquinoline alkaloids and polymethoxylated flavonols. Of the latter 3,5,6,7,8,4′-hexamethoxyflavonol (auranetin-5-methyl ether) and 3,5,7,8,4′-pentamethoxyflavonol (flindulatin-5-methyl ether), both isolated from D. calida, appear to be novel. In addition both species produced dihydrocinnamic acid derivatives, including the previously unrecorded trans-avicennic acid [6-(3-methylbut-1-( E)-3-dienyl)-5, 7-dimethoxy-2,2-dimethylbenzopyran-8-propanoic acid]. Finally, three novel coumarins were isolated from D. hassellii and identified as 6,7-di(3,3-dimethylallyloxy)-5-methoxycoumarin, 6,7-di-(3,3-dimethylallyloxy)-5-hydroxycoumarin and 7-(3,3-dimethylallyloxy)-6-hydroxy-5-methoxycoumarin. No coumarins were detected in D. calida. The systematic value of these findings is briefly discussed.

Induced formation of dihydrophenanthrenes and bibenzyl synthase upon destruction of orchid mycorrhiza

Increasing amounts of 1,7-dihydroxy-5-methoxy-9,10-dihydrophenanthrene and 3,3′-dihydroxy-5,4′-dimethoxybibenzyl were formed in rhizomes of the orchid Epipactis palustris after wounding. The induced formation of these compounds depended on wounding and the extent of fungal infection present within the rhizome. In a similar way, the activity of a bibenzyl synthase converting m-hydroxyphenylpropionyl-CoA and malonyl-CoA into 3,5,3′-trihydroxybibenzyl was induced. The enzyme exhibits molecular properties which indicate its relation to stilbene syntheses but shows catalytic activities which prove its substrate preference of dihydrocinnamic acid derivatives to cinnamic acid derivatives.

Structural confirmation of dihydrocinnamic acids from Adiscanthus fusciflorus by 13C NMR

In the wood of Adiscanthus fusciflorus six known alkaloids 4-methoxy-2-quinolone, 1-methyl-4-methoxy-2-quinolone, dictamine, skimmianine, γ-fagarine and N-methylflindersine and two new dihydrocinnamic acids 3-[2′,6′-dimethoxy-6″,6″-dimethylpyrano(2″,3″:4′, 3′)phenyl]-propionic acid and its methyl ester were identified. The structures of the dihydrocinnamic acid derivatives were confirmed by 13C NMR.