Capsaicinoids from hot pepper (Capsicum annuum L.) and their phytotoxic effect on seedling growth of lettuce (Lactuca sativa L.)

Abstract

One new capsaicinoid, N-vanillyl-4E,6E-dien-8-methylnonanamide (4), along with nine known capsaicinoids, capsaicin (1), dihydrocapsaicin (2), N-vanillyloctanamide (3), nordihydrocapsaicin (5), N-vanillyldecanamide (6), homocapsaicin (7), N-vanillyl-4,8-dimethylnonanamide (8), homodihydrocapsaicin II (9), and homodihydrocapsaicin I (10) were isolated from the fruits of Capsicum annuum using semi-preparative high-performance liquid chromatography. The structural characterizations of the isolated compounds were elucidated by spectroscopic data and comparison with the literatures. Bioassays showed that the isolated capsaicinoids significantly reduced the radical length of Lactuca sativa seedling, this inhibition being dose-dependent.     

Pseudolycorine N-oxide,a new N-oxide from Narcissus tazetta

Abstract

A new N-oxide, Pseudolycorine N-oxide (1) was characterised along with eleven known alkaloids homolycorine (2), O-methylmaritidine (3), 8-O-demethylhomolycorine (4), homolycorine N-oxide (5), lycorine (6), narciclasine (7), pseudolycorine (8), ungeremine (9), 8-O-demethylmaritidine (10), zefbetaine (11) and lycorine N-oxide (12), from Narcissus tazetta. Their structures were established on the basis of spectroscopic data analysis. The extract, fractions and isolated compounds were screened for in vitro cytotoxicity against two human cancer cell lines, human cervical cancer (SiHa) and human epidermoid carcinoma (KB) cells. The study demonstrated the cytotoxic potential of extract and its chloroform and n-butanol fractions. Further, the results revealed the bioactive potential of narciclasine, pseudolycorine and homolycorine alkaloids. However, new N-oxide (1) was not active against these cell lines.     

Activity of some platinum(II/IV) complexes with edda-type ligands against human adenocarcinoma HeLa cells

Cisplatin analogues, cis-dichloro(ethylenediamine-N,N′-di-3-propanoic acid)platinum(II) (1) and cis-iodo(ethylenediamine-N,N′-di-3-propanoic acid)platinum(II) (2), as well as trans-dichloro-(ethylenediamine-N,N′-di-3-propanoato)platinum(IV) (3), trans-dibromo(ethylenediamine -N,N′-di-3-propanoato)platinum(IV) (4), trans-dichloro(propylenediamine-N,N′-diacetato)-platinum(IV) (5) and trans-dibromo(propylenediamine-N,N′-diacetato)platinum(IV) (6), -([Pt(H₂eddp)Cl₂], [Pt(Heddp)I], trans-[Pt(eddp)Cl₂], trans-[Pt(eddp)Br₂], trans-[Pt(pdda)Cl₂] and trans-[Pt(pdda)Br₂], respectively) were used to assess antitumor selectivity against human adenocarcinoma HeLa cells. The results show that different oxidation states of platinum, different halide ligands, chelating aminocarboxylato and diamine backbones have similar effects with edda-type ligands and activity is lower than for cisplatin.     

Two new Lycopodium alkaloids from Phlegmariurus phlegmaria (L.) Holub

Two new Lycopodium alkaloids, 4β-hydroxynankakurine B (1) and Δ^13,N,N_α-methylphlegmarine-N_β-oxide (2), together with three known analogues, lycoposerramine E (3), nankakurine B (4) and lobscurinol (5), were isolated from Phlegmariurus phlegmaria. Their structures were established by mass spectrometry and 1D and 2D NMR techniques.     

An isoindole alkaloid from Portulaca oleracea L.

A novel isoindole alkaloid named oleraisoindole (1), together with six known compounds, 7′-ethoxy-trans-feruloyltyramine (2), N-trans-feruloyltyramine (3), N-trans-feruloyl-3-methoxytyramine (4), N-trans-p-coumaroyltyramine (5) aurantiamide (6) and ferulic acid methyl ester (7) were isolated from Portulaca oleracea L. Compounds 2 and 7 were isolated for the first time from this plant. Compound 1 was identified using spectroscopic methods including HR-ESI-TOF-MS, 1D-NMR, 2D-NMR. It was tested in a nitric oxide (NO) inhibition assay and was shown to inhibit NO production in RAW 264.7 cells induced by LPS.     

Syntheses and structures of cobalt(II), nickel(II), and copper(II) complexes with N,N,N′,N′-tetraalkylpyridine-2,6-dicarboxamides (O-daap) containing nitrate as the counter ion

Reactions of M(NO₃)₂?·?xH₂O [M?=?Co(II), Ni(II), and Cu(II)] with N,N,N′,N′-tetraalkylpyridine-2,6-dicarboxamides(O-daap) in CH₃CN yield [Co(O-dmap)(NO₃)₂] (1), [Co(O-deap)(NO₃)₂] (2), [Co(O-dpap)(NO₃)₂] (3), [Ni(O-dmap)(H₂O)₃](NO₃)₂] (4), [Ni(O-deap)(H₂O)₂(NO₃)](NO₃)] (5), [Cu(O-deap)(NO₃)₂] (6), and [Cu(O-dpap)(NO₃)₂] (7). X-ray crystal structures of 1, 2, 4, 5, and 7 reveal that O-daap ligands coordinate tridentate to each metal, O–N–O, with nitrate playing a vital role in molecular and crystal structures of all the complexes. The coordination geometry in the two Co(II) complexes, 1 and 2, is approximately pentagonal bipyramidal with nitrate bonded in a slightly unsymmetrical bidentate chelating mode. [Ni(dmap)(H₂O)₃](NO₃)₂ (4) and [Ni(deap)(H₂O)₂(NO₃)](NO₃) (5) exhibit octahedral geometry, the former containing uncoordinated nitrate while the latter has one nitrate coordinated unidentate and the other nitrate outside the coordination sphere. The Cu(II) in [Cu(dpap)(NO₃)₂] (7) occupies a distorted square pyramidal geometry and is linked to two unidentate nitrates, although one nitrate is also involved in a weak interaction with the metal through its other oxygen. IR spectra and other physical studies are consistent with their crystal structural data. O-dmap?=?N,N,N′,N′-tetramethylpyridine-2,6-dicarboxamides; O-deap?=?N,N,N′,N′-tetraethylpyridine-2,6-dicarboxamides; and O-dpap?=?N,N,N′,N′-tetraisopropylpyridine-2,6-dicarboxamides.     

Two new monoterpenoid indole alkaloids from Alstonia rostrata

Two new indole alkaloids, winphyllines A (1) and B (4), along with four known alkaloids, N_b-demethylechitamine (2), 17-O-acetylnorechitamine (3), 12-methoxyechitamidine (5), and N(4)-demethylastogustine (6), were isolated from the methanol extract of the twigs of Alstonia rostrata. The structures of 1 and 4 were elucidated by means of HRMS and NMR spectroscopic methods. The in vitro cytotoxic activity of the isolated alkaloids against several human cancer cell lines was evaluated.     

Secondary metabolites isolated from the fungus <Emphasis Type="Italic">Biscogniauxia cylindrospora</Emphasis> BCRC 33717

One new dihydroisocoumarin, (3S)-5-hydroxy-8-O-methylmellein (1), as well as nine known compounds, 5-formylmellein (2), mellein-5-carboxylic acid (3), 5-hydroxymethylmellein (4), 3β-hydroxystigmast-5- en-7-one (5), N-trans-feruloyltyramine (6), N-cis-feruloyltyramine (7), vanillic acid (8), methyl paraben (9), and syringaldehyde (10), were isolated from the n-BuOH-soluble fraction of the 70% EtOH extract of rice fermented with the endophytic fungus Biscogniauxia cylindrospora (BCRC 33717). Their structures were elucidated by 1D and 2D NMR spectroscopy together with HR-ESI-MS analysis and comparison of the spectroscopic data with those reported for structurally related compounds.     

Mixed-ligand complexes of iron(II), iron(III), copper(II), and cobalt(II) with pyrazolonic and 2,2′-bipyridine ligands

New mixed-ligand complexes, [M₂(BAMP)(bipy)₂][MCl₄]₂, M=Co⁺²(1), Cu⁺²(2), [M₂(TAMEN)(bipy)₂][MCl₄]₂, M=Fe⁺²(3), Co²⁺(4), and [Fe₂(TAMEN)(bipy)₂][FeCl₆]₂ (5), where BAMP and TAMEN stand for the Mannich bases N,N′-bis(antipyryl-4-methylene)-piperazine and N,N′-tetra(antipyryl-4-methylene)-1,2-ethane-diamine, respectively, have been obtained and characterized by elemental analyses, conductometric and magnetic susceptibility measurements at room temperature, mass spectrometry, UV-Vis, infrared, and mass spectroscopy, and ¹H NMR spectra for the ligands.     

A new lactam alkaloid from Portulaca oleracea L. and its cytotoxity

A new lactam alkaloid named oleraciamide D (1), indentified as (5R)-4-(3-methoxy-4-hydroxyphenyl)-5-(4-hydroxyphenyl)-5,6-dihydropyridin-2(1H)-one, together with five known compounds, indole-3-aldehyde (2), portulacatone (3), N-trans-feruloyloctopamine (4), N-trans-feruloyl-3′-O-methyldopamine (5) and N-trans-feruloyltyramine (6) were isolated from Potulaca oleracea L. Among them, indole-3-aldehyde (2) was isolated from the medicine for the first time. The structure of the new alkaloid was elucidated via UHPLC-ESI-Q-TOF/MS, 1D NMR and 2D NMR. The five known compounds were established by comparing the ¹H-NMR and ¹³C NMR with the reported literature. Oleraciamide D (1) showed cytotoxicity against SH-SY5Y cells when concentration at 50 uM by CCK-8 method.     

Synthesis and characterization of 2-hydroxy-pyridine modified Group 4 alkoxides

The reaction of Group 4 metal alkoxides ([M(OR)₄]) with the potentially bidentate ligand, 2-hydroxy-pyridine (2-HO-(NC₅H₄) or H-PyO), led to the isolation of a family of compounds. The products isolated from the reaction of [M(OR)₄] [where M = Ti, Zr, or Hf; OR = OPrⁱ (OCH(CH₃)₂), OBu^t (OC(CH₃)₃), or ONep (OCH₂C(CH₃)₃] under a variety of stoichiometries with H-PyO were identified by single crystal X-ray diffraction as [(OPrⁱ)₂(PyO-κ²(O,N))Ti(μ-OPrⁱ)]₂ (1), [(ONep)₂Ti(μ(O)-PyO-κ²(O,N))₂(μ-ONep)Ti(ONep)₃] (2), [(ONep)₂Ti(μ(O)-PyO-κ²(O,N))(η¹(N),μ(O)-PyO)(μ-O)Ti(ONep)₂]₂ (2a), [H][(PyO-κ²(O,N))(η¹(O)-PyO)Ti(ONep)₃] (3), [(OR)₂Zr(μ(O)-PyO-κ²(O,N))₂(μ-OR)Zr(OR)₃] (OR = OBu^t (4), ONep (5)), [(OR)₂Zr(μ(O,N)-PyO-κ²(O,N))₂(μ(O,N)-PyO)Zr(OR)₃] (OR = OBu^t (6), ONep (7)), [[(OBu^t)₂Zr(μ(O)-PyO-(κ²(N,O))(μ(O,N)-PyO)₂Zr(OBu^t)](μ₃-O)]₂ (6a), [[(ONep)(PyO-κ²(N,O))Zr(μ(O,N)-PyO-κ²(N,O))₂(μ(O)-PyO-κ²(N,O))Zr(ONep)](μ₃-O)]₂ (7a), [(OBu^t)(PyO-κ²(O,N))Zr(μ(O)-PyO-κ²(O,N))₂((μ(O,N)-PyO)Zr(OBu^t)₃] (8), [(OBu^t)₂Hf(μ(O)-PyO-κ²(N,O))₂(μ-OBu^t)Hf(OBu^t)₃] (9), [(OR)₂ M(μ(O)-PyO-κ²(N,O))₂(μ(O,N)-PyO)M(OR)₃] (OR = OBu^t (10), ONep (11)), and [(ONep)₃Hf(μ-ONep)(η¹(N),μ(O)-PyO)]₂Hf(ONep)₂ (12)·tol. The structural diversity of the binding modes of the PyO led to a number of novel structure types in comparison to other pyridine alkoxy derivatives. The majority of compounds adopt a dinuclear arrangement (1, 2, 4–11) but oxo-based tetra- (2a and 7a), tri- (12), and monomers (3) were observed as well. Compounds 1–12 were further characterized using a variety of analytical techniques including Fourier Transform Infrared Spectroscopy, elemental analysis, and multinuclear NMR spectroscopy.     

Electrospray mass spectrometric studies of a potential antitumor drug and its analogous platinum(II) and platinum(IV) complexes with the ethylenediamine-N,N′-di-3-propanoato ligand and its dibutyl ester

Abstract  The electrospray mass spectrometric (ESI–MS) behavior of the complexes trans-dichloro(ethylenediamine-N,N′-di-3-propionato)platinum(IV), trans-dibromo(ethylenediamine-N,N′-di-3-propionato)platinum(IV), dichloro(ethylenediamine-N,N′-di-3-propionic acid)platinum(II), tetrachloro(O,O′-di-n-butyl-ethylenediamine-N,N′-di-3-propanoate)platinum(IV), chlorotribromo(O,O′-di-n-butyl-ethylenediamine-N,N′-di-3-propanoate)platinum(IV), and dichloro(O,O′-di-n-butyl-ethylenediamine-N,N′-di-3-propanoate)platinum(II), with the formulae trans-[PtCl₂(eddp)] (1), trans-[PtBr₂(eddp)] (2), [PtCl₂(H₂eddp)] (3), [PtCl₄(Bu₂eddp)] (4), [PtBr₃Cl(Bu₂eddp)] (5), and [PtCl₂(Bu₂eddp)]·H₂O (6), is reported. The deprotonated molecular ions or halide adducts are usually observed. ESI–MS data demonstrate the usefulness of the method for efficient characterization of metal complexes in solution. Graphical Abstract        

Synthesis,crystal structure,and antibacterial activity of mononuclear nickel(II) and cobalt(III) Schiff-base complexes

Four new mononuclear complexes, [Ni(L¹)(NCS)₂] (1), [Ni(L²)(NCS)₂] (2), [Co(L¹)(N₃)₂]ClO₄ (3), and [Co(L²)(N₃)₂]ClO₄ (4), where L¹ and L² are N,N′-bis[(pyridin-2-yl)methylidene]butane-1,4-diamine and N,N′-bis[(pyridin-2-yl)benzylidene]butane-1,4-diamine, respectively, have been prepared. The syntheses have been achieved by reaction of the respective metal perchlorate with the tetradentate Schiff bases, L¹ and L², in presence of thiocyanate (for 1 and 2) or azide (for 3 and 4). The complexes have been characterized by microanalytical, spectroscopic, single crystal X-ray diffraction and other physicochemical studies. Structural studies reveal that 1–4 are distorted octahedral geometries. The antibacterial activity of all the complexes and their constituent Schiff bases have been tested against Gram-positive and Gram-negative bacteria.     

Inhibition effect of phenyl compounds from the Oryza sativa roots on melanin production in murine B16-F10 melanoma cells

Five phenyl compounds, vanillin (1), methyl trans-ferulate (2), trans-p-coumaric acid methyl ester (3), N-benzoyltryptamine (4), and N-(trans-cinnamoyl)tryptamine (5), were isolated from the roots of Oryza sativa L. and identified on the basis of spectroscopic data. Compounds 3 and 5 showed strong inhibition effect on melanin production in murine B16-F10 melanoma cells and tyrosinase activity. Also, the quantitative analysis of the compounds was carried out using LC/MS/MS experiment. Compounds 3 and 5 could be used as skin-whitening agents.     

Zinc(II) complexes of 2-pyridine-derived N (4)- p -tolyl thiosemicarbazones: study of in vitro antibacterial activity

Reaction of N(4)-p-tolyl-2-formylpyridine thiosemicarbazone (H2Fo4pT), N(4)-p-tolyl-2-acetylpyridine thiosemicarbazone (H2Ac4pT), and N(4)-p-tolyl-2-benzoylpyridine thiosemicarbazone (H2Bz4pT) with ZnCl₂ gave [Zn(H2Fo4pT)Cl₂] (1), [Zn(H2Ac4pT)Cl₂] (2), and [Zn(H2Bz4pT)Cl₂] (3). In the first two complexes a tridentate N_py–N–S thiosemicarbazone binds to the zinc while in the latter N–S coordination occurs. Upon coordination the antibacterial activity against Salmonella typhimurium increases in 1 and 3.     

SYNTHESES AND SOME PROPERTIES OF SULFOXIDES,SULFILIMINES, AMINOSULFONIUM SALTS AND SULFOXIMINES CONTAINING PYRIDINE NUCLEI

Abstract

Several 2-pyridyl sulfides (1) (e.g., methyl (1a), ethyl (1b), isopropyl (1c), benzyl (1d), 1-phenylethyl (1e), l-menthyl (If) 2-pyridyl sulfides; and bis(2-pyridylthio)methane (1g), and methyl 2-(N-oxy-pyridyl) sulfide (1h) were prepared by the usual method. Sulfoxides (2) were prepared by oxidation of the corresponding sulfides with m-chloroperbenzoic acid in good yields. A few sulfoxides were found to work as phase-transfer catalysts for some typical nucleophilic reactions in nonpolar solvents such as benzene, and in two-phase systems such as benzene-water. S-2-Pyridyl-N-(p-toluenesulfonyl) sulfilimines (3) were prepared upon treatment of sulfides with Chloramine-T. Hydrolysis of N-(p-toluenesulfonyl)-2-pyridyl-o-tolylsulfilimine (3i) with conc. sulfuric acid gave the corresponding free sulfilimine in a moderate yield. S-2-Pyridyl sulfoximines (4) were not obtained by the general method from the sulfoxides and hydrazoic acid. Alkyl-2-pyridyl sulfoximines, however, were obtained by oxidation of the free sulfilimines derived from the corresponding aminosulfonium salts (5) prepared by reaction of the sulfides with mesitylene-sulfonylhydroxylamine (MSH). These free sulfilimines and sulfoximines thus prepared were found to give adducts with a few copper salts.     

Intramolecular cyclization of 1,3-diamino-2-hydroxypropan-N,N,N´,N´-tetrakis(methylphosphonic acid) upon phosphonomethylation of 1,3-diaminopropan-2-ol

Phosphonomethylation of 1,3-diaminopropan-2-ol affords the mixture of 1,3-diamino-2-hydroxypropan-N,N,N´,N´-tetrakis(methylphosphonic acid) (1) with its cyclic ether, viz., [(6-[bis(phosphonomethyl)amino]methyl-2-hydroxy-2-oxido-1,4,2-oxazaphosphinan-4-yl)methyl]phosphonic acid (2), but not 1, as assumed earlier.

     

Syntheses,characterization, and crystal structures of ruthenium(II)/(III) complexes with tridentate salicylaldiminato ligands

Treatment of [Ru(PPh₃)₃Cl₂] with one equivalent of tridentate Schiff base 2-[(2-dimethylamino-ethylimino)-methyl]-phenol (HL) in the presence of triethylamine afforded a ruthenium(III) complex [RuCl₃(κ²-N,N-NH₂CH₂CH₂NMe₂)(PPh₃)] as a result of decomposition of HL. Interaction of HL and one equivalent of [RuHCl(CO)(PPh₃)₃], [Ru(CO)₂Cl₂] or [Ru(tht)₄Cl₂] (tht = tetrahydrothiophene) under different conditions led to isolation of the corresponding ruthenium(II) complexes [RuCl(κ³-N,N,O-L)(CO)(PPh₃)] (2), [RuCl(κ³-N,N,O-L)(CO)₂] (3), and a ruthenium(III) complex [RuCl₂(κ³-N,N,O-L)(tht)] (4), respectively. Molecular structures of 1·CH₂Cl₂, 2·CH₂Cl₂, 3 and 4 have been determined by single-crystal X-ray diffraction.     

A New Lycopodine-type Alkaloid from Lycopodium japonicum

A new lycopodine-type alkaloid, 12β-hydroxy-acetylfawcettiine N-oxide (1), together with seven known analogues, acetyllycoposerramine M (2), lycopodine (3), lycoclavine (4), diphaladine A (5), lycoposerramine K (6), 11β-hydroxy-12-epilycodoline (7) and fawcettiine (8), were isolated from Lycopodium japonicum. Their structures were established by mass spectrometry and 1D and 2D NMR techniques. The isolated alkaloids were assayed for their inhibition activities against acetylcholinesterase, but no inhibitory activities for the compounds were detected.     

Studies on two cadmium(II) and two zinc(II) complexes of 4′-chloro-2,2′ : 6′,2″-terpyridine with 1 : 1 or 1 : 2 ratio of metal and ligand

The reaction between 4′-chloro-2,2′ : 6′,2″-terpyridine (tpyCl) with d¹⁰ transition-metal ions produced two cadmium(II) and two zinc(II) metal complexes, formulated as [Cd(tpyCl-κ ³ N,N′,N″)(NO₃-κ ² O,O′)(NO₃-κO)(H₂O-κO)] (1), [Cd(tpyCl-κ ³ N,N′,N″)₂](ClO₄)₂ (2), [Zn(tpyCl-κ ³ N,N′,N″)₂](ClO₄)₂ (3), and [Zn(tpyCl-κ ³ N,N′,N″)₂](BF₄)₂ (4). Supramolecular interactions include coordinative bonding, O–H ··· O, O–H ··· Cl, C–H ··· F, and C–H ··· Cl hydrogen bonding and π–π stacking, all of which play essential roles in forming different frameworks of 1–4.