New alkylamides from pericarps of Zanthoxylum bungeanum

Two new unsaturated alkylamides(2E,7E,9E)-N-(2-hydroxy-2-methylpropyl)-6,11-dioxo-2,7,9-dodecatrienamide(1) and (2E,6E,8E)-N-(2-hydroxy-2-methylpropyl)-10-oxo-2,6,8-decatrienamide(2) together with six known compounds(3-8) have been isolated from the pericarps of Zanthoxylum bungeanum.Their structures were elucidated on the basis of extensive spectroscopic analysis,including MS,IR,1D and 2D NMR experiments.     

Alpha-glucosidase inhibitory constituents from Cuscuta reflexa

Two new compounds, 7'-(3',4'-dihydroxyphenyl)-N-[(4-methoxyphenyl)ethyl]propenamide (4), and 7'-(4'-hydroxy,3'-methoxyphenyl)-N-[(4-butylphenyl)ethyl]propenamide (5) have been isolated from Cuscuta reflexa along with five known compounds, 6,7-dimethoxy-2H-1-benzopyran-2-one (1), 3-(3,4-dihydroxyphenyl)-2-propen-1-ethanoate (2), 6,7,8-trimethoxy-2H-1-benzopyran-2-one (3), 3-(4-O-beta-D-glucopyranoside-3,5-dimethoxyphenyl)-2-propen-1-ol (6), 2-(3-hydroxy-4-methoxyphenyl)-3,5-dihydroxy-7-O-beta-D-glucopyranoside-4H-1-benzopyrane-4-one (7), reported for the first time from this species. Structures of these compounds were determined by spectral analysis. These compounds showed strong inhibitory activity against alpha-glucosidase.     

Amides from the stem of Capsicum annuum

7'-(4'-hydroxyphenyl)-N-[(4-methoxyphenyl)ethyl]propenamide (1), 7'-(3',4'-dihydroxyphenyl)-N-[(4-methoxyphenyl)ethyl]propenamide (2), N-p-trans-coumaroyltyramine (3), N-trans-caffeoyltyramine (4), beta-sitostenone (5), ferulic acid (6), hydroferulic acid (7), 5-hydroxy-3,4-dimethoxycinnamic acid (8), veratic acid (9), vanillic acid (10), isovanillic acid (11), syringic acid (12), (+)-syringaresinol (13), and pheophorbide a (14) were isolated from the stems of Capsicum annuum (Solanaceae). Among them, 1 is a new amide compound. The structures of these compounds were characterized and identified by spectral analyses.     

Synthesis, structure, and biological activity of ferrocenyl carbohydrate conjugates

Seven ferrocenyl carbohydrate conjugates were synthesized. Coupling reactions of monosaccharide derivatives with ferrocene carbonyl chloride produced {6-N-(methyl 2,3,4-tri-O-acetyl-6-amino-6-deoxy-alpha-D-glucopyranoside)}-1-ferrocene carboxamide (3), {1-O-(2,3,4,6-tetra-O-benzyl-D-glucopyranose)}-1-ferrocene carboxylate (4), and {6-O-(1,2,3,4-tetra-O-acetyl-beta-D-glucopyranose)}-1-ferrocene carboxylate (5). Similarly, 1,1'-bis(carbonyl chloride)ferrocene was coupled with the appropriate sugars to produce the disubstituted analogues bis{6-N-(methyl 2,3,4-tri-O-acetyl-6-amino-6-deoxy-alpha-D-glucopyranoside)}-1,1'-ferrocene carboxamide (8), bis{1-O-(2,3,4,6-tetra-O-benzyl-D-glucopyranose)}-1,1'-ferrocene carboxylate (9), and bis{6-O-(1,2,3,4-tetra-O-acetyl-beta-D-glucopyranose)}-1,1'-ferrocene carboxylate (10). {6-N-(Methyl-6-amino-6-deoxy-alpha-D-glucopyranoside)}-1-ferrocene carboxamide monohydrate (12) was synthesized via amide coupling of an activated ferrocenyl ester with the corresponding carbohydrate. All compounds were characterized by elemental analysis, 1H NMR spectroscopy, and mass spectrometry. X-ray crystallography confirmed the solid-state structure of three ferrocenyl carbohydrate conjugates: 2-N-(1,3,4,6-tetra-O-acetyl-2-amino-2-deoxy-D-glucopyranose)-1-ferrocene carboxamide (1), 1-S-(2,3,4,6-tetra-O-acetyl-1-deoxy-1-thio-D-glucopyranose)-1-ferrocene carboxylate (2), and 12. The above compounds, along with bis{2-N-(1,3,4,6-tetra-O-acetyl-2-amino-2-deoxy-D-glucopyranose)}-1,1'-ferrocene carboxamide (6), bis{1-S-(2,3,4,6-tetra-O-acetyl-1-deoxy-1-thio-D-glucopyranose)}-1,1'-ferrocene carboxylate (7), and 2-N-(2-amino-2-deoxy-D-glucopyranose)-1-ferrocene carboxamide (11) were examined for cytotoxicity in cell lines (L1210 and HTB-129) and for antimalarial activity in Plasmodium falciparum strains (D10, 3D7, and K1, a chloroquine-resistant strain). In general, the compounds were nontoxic in the human cell line tested (HTB-129), and compounds 4, 7, and 9 showed moderate antimalarial activity in one or more of the P. falciparum strains.     

Two new homoisoflavonoids from Caesalpinia pulcherrima

Two new homoisoflavonoids, (E)-7-methoxy-3-(4'-methoxybenzylidene)chroman-4-one (1) and (E)-7-hydroxy-3-(3',4',5'-trimethoxybenzylidene)chroman-4-one (5), along with three known homoisoflavonoids (Z)-7-hydroxy-3-(4'-methoxybenzylidene)chroman-4-one (isobon ducellin) (2), (E)-7-hydroxy-3-(4'-methoxybenzylidene)chroman-4-one (bonducellin) (3) and (E)-7-hydroxy-3-(2',4'-dimethoxybenzylidene)chroman-4-one (4) were isolated from the whole plant of Caesalpinia pulcherrima. The structures of these new compounds were elucidated by electron impact mass spectrometry (EI-MS) and 1D and 2D-NMR spectral studies. Antimicrobial activity of the new compounds was evaluated.     

Structure elucidation and NMR assignments for two amide alkaloids from a Mangrove endophytic Fungus (No. ZZF-22)

The structure elucidations and complete (1)H and (13)C NMR assignments are reported for two new natural products: 3-benzylidene-8,8a-dihydroxy-2-methyl-hexahydro-pyrrolo[1,2-a]pyrazine-1,4-dione(1) and 4-hydroxy-6-(hydroxy-phenyl-methyl)-N-(3-methyl-butyryl)-nicotinamide (2). Both of these secondary metabolites were isolated from the fermentation medium of a Mangrove endophytic fungus. High resolution electron impact mass spectrometry (HREIMS), FT-IR Spectroscopy and NMR experiments including gCOSY, gHMQC, gHMBC and NOE were used for determination of the structures and assignments of the amide alkaloids.     

Synthesis of novel 6-(substituted amino)-4-(4-ethoxyphenyl)-1-phenyl-2(1H)-pyridinones via azo coupling

Abstract  

6-(Substituted amino)-4-(4-ethoxyphenyl)-1-phenyl-2(1H)-pyridinones were prepared from β-aryl glutaconic acid, which, on fusion with aniline, results in 4-(4-ethoxyphenyl)-1-phenylpyridine-2,6(1H,5H)-dione. This, on further treatment with phosphorus oxychloride gave 6-chloro-4-(4-ethoxyphenyl)-1-phenyl-2(1H)-pyridinone, and further treatment with secondary amines yielded 6-(substituted amino)-4-(4-ethoxyphenyl)-1-phenyl-2(1H)-pyridinones. These were subjected to azo coupling with different aryldiazonium chlorides furnishing two isomers, which were separated by column chromatography. All compounds were characterized by elemental analysis, and use of IR and NMR spectral data, and were evaluated for antimicrobial activity.     

5-氟尿嘧啶修饰卟啉的合成及抗肿瘤活性

合成了一种5-氟尿嘧啶修饰的自由卟啉(5-[2-(5-氟尿嘧啶-3-基)乙氧基苯基]-10,15,20-三(4-甲氧基苯基)卟啉)及其2种金属卟啉配合物:5-[2-(5-氟尿嘧啶-3-基)乙氧基苯基]-10,15,20-三(4-甲氧基苯基)锰卟啉和5-[2-(5-氟尿嘧啶-3-基)乙氧基苯基]-10,15,20-三(4-甲氧基苯基)锌卟啉。 通过紫外可见光谱(UV-Vis)、红外光谱(IR)和核磁共振谱氢谱(¹H NMR)对目标化合物进行了结构表征。 用噻唑蓝法(MTT法)测定了自由卟啉、锰卟啉及锌卟啉分别对肺腺癌细胞株A549、肝癌细胞株Bel7402和人结肠癌细胞株HCT-8的抑制活性。 其中,锰卟啉对人结肠癌细胞株HCT-8的半抑制浓度为IC₅₀为17.8 mg/L,具有一定的细胞毒作用。     

New diarylheptanoids from Alnus japonica and their antioxidative activity

In the course of research on the bioactive constituents of woody plants in the Cyugoku area of Japan, a methanol extract of the leaves of Alnus japonica were found to have strong antioxidative activity. Ethyl acetate soluble and n-buthanol soluble fractions of the methanol extract had a potent antioxidative effect. Both fractions were purified by silica gel column chromatography and HPLC using an ODS column to give four new diarylheptanoids along with known diarylheptanoids and flavonoids. These new compounds were elucidated to be 7-(3,4-dihydroxyphenyl)-5-hydroxy-1-(4-hydroxyphenyl)-3-heptanone-5-O-beta-D-xylopyranoside (1), 1-(3,4-dihydroxyphenyl)-5-hydroxy-7-(4-hydroxyphenyl)-3-heptanone-5-O-beta-D-xylopyranoside (2), 1,7-bis-(3,4-dihydroxyphenyl)-5-hydroxy-3-heptanone-5-O-[2-(2-methylbutenoyl)]-beta-D-xylopyranoside (3) and 1,7-bis-(3,4-dihydroxyphenyl)-5-methoxy-3-heptanone (4) using spectral methods and especially 1H-, 13C-NMR and 2D-NMR measurements. The isolated compounds including their main constituent, oregonin (5), were tested for antioxidative activity. Some of these compounds having two catechol structures showed potent antioxidative activity. Compounds having one catechol structure showed moderate antioxidative activity, but a peracetate of 5 having no catechol structure exhibited no antioxidative activity. Thus the catechol structure of the diarylheptanoids is indispensable for antioxidative activity.     

DNA binding,cleavage, catalytic,magnetic active; 2,2–bipyridyl based d-f hetero binuclear Gd(III), Cu(II) complexes and their Electrochemical,fluorescence studies

Several 2,2-bipyridyl-based d-f heterobinuclear [GdCuL1-5(bpy)2(NO3)2] complexes are present, where (Ligand 1) (9E)-N¹-(2-Hydroxy-5-methylbenzylidene)–N²-((E)-2-(2-hydroxy-5-methyl benzylideneamino)ethyl)ethane-1,2-diamine. (Ligand 2) N¹,N¹-bis((E)-2-(2-hydroxy-5-methylbenzylideneamino)ethyl)ethane-1,2-diamine. (Ligand 3) (9E)-N¹-(2-((E)-2-(2-hydroxy-5-methylbenzylideneamino)ethylamino)ethyl)–N²-(2-hydroxy-5-methylbenzylidene)ethane-1,2-diamine. (Ligand 4) (9E)-N¹-(2-((E)-3-(2-hydroxy-5- methylbenzylideneamino) propylamino) ethyl)–N³-(2-hydroxy-5-methylbenzylidene)propane-1,3-diamine and (Ligand 5) (9E)-N-(2-hydroxy-5-methylbenzylidene)-3-(4-((E)-3-(2-hydroxy-5-methylbenzylideneamino)propyl)piperazin-1-yl)propan-1-amine. These compounds were described using spectroscopy and the elemental analysis method. Researches were conducted into the luminous, Genetic code, catalytic, magnetism, and breaking attributes of the [GdCuL1-5(bpy)2(NO3)2] complexes. In DMF with 0.1 M tetra-n-butylammonium perchlorate, the binuclear [GdCuL1-5(bpy)2(NO3)2] network complexes exhibit two one electron irreversible reduction events. VSM was used to calculate the complexes' magnetic susceptibility. There is ferromagnetic coupling in the [GdCuL1-5(bpy)2(NO3)2] complexes. The [GdCuL1-5(bpy)2(NO3)2] complexes' excited state lifetimes lengthen in the following order: [GdCuL5(bpy)₂] [GdCuL1(bpy)2(NO3)2] [GdCuL3(bpy)2(NO3)2] [GdCuL4(bpy)2] and [GdCuL2(bpy)2(NO3)2]. The binuclear [GdCuL1-5(bpy)2(NO3)2] complexes' inceptive rate of progress for oxidizing 1,2-benzenediol to cyclohexa-3,5-diene-1,2-dione are longer chains with higher activity. Both the [GdCuL5(bpy)2(NO3)2] and [GdCuL4(bpy)2(NO3)2] complexes have strong DNA genetic code properties in the calf genus thymus. The complexes exhibit considerable singlet oxygen-mediated oxidative rift of circular recombinant plasmid pBR322 cloning vector in the existence of 2-sulfanylethanol.     

Structural confirmation of regioisomers of Lopinavir impurities using MS and gradient COSY (1H and 13C NMR assignment of Lopinavir impurities)

We report the complete (1)H and (13)C NMR assignment of impurities of six Lopinavir (2S)-N-[(2S, 4S, 5S)-5-{[2-(2,6-dimethylphenoxy)acetyl]amino}-4-hydroxy-1,6-diphenyl hexan-2-yl]-3-methyl-2-(2-oxo-1,3-diazinan-1-yl)butan- amide. Two of the impurities are regioisomers and GCOSY used to differentiate the two structures. The spectral assignments for all six impurities were achieved by concerted application of one and two-dimensional NMR techniques ((1)H NMR, (13)C NMR, DEPT, GCOSY, GHSQC and GHMBC).     

Synthesis of Schiff bases by condensation of hetarylcarboxaldehydes withp-phenetidine

Summary Treatment of quinolinecarboxaldehydes and their derivatives withp-ethoxyaniline yields in a one-step reaction a series of new Schiff bases in 47–73% yield. The products [quinoline-2-, 6-methylquinoline-2-, quinoline-4-, quinoline-8-, and acridine-9-N-(p-ethoxyphenyl)formimidoyl], have been fully characterized.

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Synthese von Schiffschen Basen durch Kondensation von Hetarylaldehyden mitp-Phenetidin

Zusammenfassung Umsetzung von Chinolinaldehyden und deren Derivaten mitp-Ethoxyanilin liefert in einer Einstufenreaktion neue Schiffsche Basen in 47–73%iger Ausbeute. Alle Produkte [Chinolin-2-, 6-Methylchinolin-2-, Chinolin-4-, Chinolin-8- und Acridin-9-N-(p-ethoxyphenyl)formimidoyl] wurden voll charakterisiert.

     

New insecticidal amides from petroleum ether extract of dried Piper nigrum L. whole fruits

The petroleum ether extract of dried ground whole fruits of Piper nigrum L. afforded 20 compounds (1-20) including two new insecticidal amides named as pipnoohine (1), and pipyahyine (2), seven reported for the first time from this plant (12, 13, 15-17, 19, 20), and eleven known compounds (3-11, 14, 18). The structure of 1 has been elucidated as (2E,4E,12Z)-N-(4-methylpentyl)octadeca-2,4,12-trienamide and that of 2 as (2E,4E,11E)-12-(benzo[1,3]dioxol-5-yl)-N-(3-methylbutyl)dodeca-2,4,11-trien-amide through extensive ID-, 2D-NMR spectral studies and chemical reactions. The known compounds have been identified through comparison of their spectral data with those reported in literature. 1 and 2 exhibited toxicity at 35.0 and 30.0 ppm respectively against fourth instar larvae of Aedes aegypti L. by WHO method.     

Asymmetric syntheses of the homalium alkaloids (-)-(s,s)-homaline and (-)-(r,r)-hopromine

The highly diastereoselective conjugate additions of the novel lithium amide reagents lithium (R)-N-(3-chloropropyl)-N-(α-methylbenzyl)amide and lithium (R)-N-(3-chloropropyl)-N-(α-methyl-p-methoxybenzyl)amide to α,β-unsaturated esters were used as the key steps in syntheses of the homalium alkaloids (-)-(S,S)-homaline and (-)-(R,R)-hopromine. The asymmetric synthesis of (-)-(S,S)-homaline was achieved in 8 steps and 18% overall yield, and the asymmetric synthesis of (-)-(R,R)-hopromine was achieved in 9 steps and 23% overall yield, from commercially available starting materials in each case. These syntheses therefore represent by far the most efficient total asymmetric syntheses of these alkaloids reported to date. A sample of the (4'R,4'S)-epimer of hopromine was also produced using this approach, which provided the first unambiguous confirmation of its absolute configuration and therefore that of natural (-)-(R,R)-hopromine.     

Synthesis of potential biologically active 1,2-benzothiazin-3-yl-quinazolin-4(3H)-ones

A series of potential biologically active 2-(4-hydroxy-1,1-dioxido-2H-1,2-benzothiazin-3-yl)quinazolin-4(3H)-ones was synthesized in a straight forward manner by condensation of respective 4-hydroxy-1,2-benzothiazine-1,1-dioxides with anthranilamide followed by simple and high throughput cyclization of N-[2-(aminocarbonyl)phenyl]-4-hydroxy-1,2-benzothiazine-3-carboxamide-1,1-dioxides. All the synthesized compounds were subjected to preliminary evaluation for their biological activity against Gram positive and Gram negative bacteria. Some of the assayed compounds showed marked activity against Bacillus subtilis.     

Cinnamyl derivatives: synthesis and factor Xa (FXa) inhibitory activities

To develop a potent and oral anticoagulant, a series of compounds with cinnamyl moiety was synthesized and their factor Xa (FXa) inhibitory activities were examined. As a result, some cinnamyl derivatives showed potent FXa inhibitory activities in vitro. Among them, compounds with substituent at the 3-position on the central benzene ring represented by (N-{4-[1-(acetimidoyl)piperidin-4-yloxy]-3-chlorophenyl}-N-[(E)-3-(3-amidinophenyl)-2-propenyl]sulfamoyl)acetic acid dihydrochloride (45b) and (N-{4-[1-(acetimidoyl)piperidin-4-yloxy]-3-carbamoylphenyl}-N-[(E)-3-(3-amidinophenyl)-2-propenyl]sulfamoyl)acetic acid dihydrochloride (45j) exhibited potent FXa inhibitory activities with IC(50) values of less than 10 nM in vitro. These compounds also showed potent anticoagulant activities both in vitro and ex vivo. Furthermore, these compounds exhibited no lethal toxicity (30 mg/kg, i.v.).     

Synthesis and anti-inflammatory activity of some benzofuran and benzopyran-4-one derivatives

New series of furosalicylic acids 3a-c, furosalicylanilides 6a-n, furobenzoxazines 8a-f, 1-benzofuran-3-arylprop-2-en-1-ones 12a,b, 6-(aryl-3-oxoprop-1-enyl)-4H-chromen-4-ones 16a-c and 6-[6-aryl-2-thioxo-2,5-dihydropyrimidin-4-yl]-4H-chromen-4-ones 17a-c were synthesized. Anti-inflammatory activity evaluation was performed using carrageenan-induced paw edema model in rats and prostaglandin E(2) (PGE(2)) synthesis inhibition activity. Some of the tested compounds revealed comparable activity with less ulcerogenic effect than Diclofenac at a dose 100 mg/kg. All the synthesized compounds were docked on the active site of cyclooxygenase-2 (COX-2) enzyme and most of them showed good interactions with the amino acids of the active site comparable to the interactions exhibited by Diclofenac.     

Synthesis of Tetrahydro-1H,7H-benzo[ij]quinolizine-1,7-dione Derivatives

Tetrahydro-1H,7H-benzo[ij]quinolizine-1,7-diones have been obtained by the cyclization of N-alkoxyphenyl-N-(2-carboxyethyl)--alanines. Fission of the ester bond occurs on cyclization of N-(4-ethoxyphenyl)-N-(2-carboxyethyl)--alanine, but the cyclization of the 3,4-dialkoxyphenyl derivative leads to the formation of 9-alkoxy-8-hydroxy-2,3,5,7-tetrahydro-1H,7H-benzo[ij]quinolizine-1,7-diones. The corresponding dioximes and diphenylhydrazones were obtained.     

Microbial metabolism. Part 7 : Curcumin

Microbial metabolism of the cancer chemopreventive agent, curcumin [(1E,6E)-1,7-bis(4-hydroxy-3-methoxyphenyl)hepta-1,6-diene-3,5-dione] (1) with Pichia anomala (ATCC 20170) yielded four major metabolites, 5-hydroxy-1,7-bis(4-hydroxy-3-methoxyphenyl)heptan-3-one (2), 5-hydroxy-7-(4-hydroxy-3-methoxyphenyl)-1-(4-hydroxyphenyl)heptan-3-one (3), 1,7-bis(4-hydroxy-3-methoxyphenyl)heptan-3,5-diol (4), 5-hydroxy-1,7-bis(4-hydroxyphenyl)heptane-3-one (5) and two minor products, 1-(4-hydroxy-3-methoxyphenyl)-7-(4-hydroxyphenyl)heptane-3,5-diol (6) and 1,7-bis(4-hydroxyphenyl)heptane-3,5-diol (7). The structures of compounds 2-5 were established on the basis of spectroscopic data. Compounds 6 and 7 were assigned tentative structures.