The Photoisomerization Behavior of the (4-Hydroxycinnamoyl)-spermidines

The photoisomerization behavior of three mono[(E)-3-(4-hydroxyphenyl)prop-2-enoyl]spermidines, 1, 2 , and 3 , and three bis[(E)-3-(4-hydroxyphenyl)prop-2-enoyl]spermidines, 4, 5 , and 6 , are investigated. The synthetic product (E)- 1 could be almost quantitatively (> 96%) converted into its isomer (Z)- 1 under UV light irradiation. In the cases of (E)- 2 and (E)- 3 , a mixture of (E)/(Z) ca. 1:2 was obtained, when the same conditions were applied. The comparison of their UV spectra provides the possible explanation for these different behaviors. Furthermore, it was noticed that the (Z) → (E) isomerization of the C?C bond took place during the purification by reverse-phase high-performance liquid chromatography (RP-HPLC), and the (E)/(Z)-mixture is thus inseparable. The same feature could be observed during the isolation of the (Z,Z)-N,N′-bis[3-(4-hydroxyphenyl)prop-2-enoyl]-spermidines, (Z,Z)- 4 , (Z,Z)- 5 , and (Z,Z)- 6 . Nevertheless, the fractions of (Z,Z)- 5 and (Z,Z)- 6 were in almost pure state collected, and their ¹-NMR spectra are presented.     

Electrospray-Ionization Mass Spectrometry. Part III. Acid-Catalyzed Isomerization of N,N′-Bis[(E)-3-(4-hydroxyphenyl)prop-2-enoyl]spermidines by the Zip Reaction

The electrospray tandem mass spectra (ESI-MS/MS) of the three N,N′-bis[(E)-3-(4-hydroxyphenyl)prop-2-enoyl]spermidines 1–3 displayed the same fragment-ion signals. These isomers could not be differentiated by ESI-MS/MS, since their fragmentation patterns are similar. (E,E)-N-(3-[¹⁵N]Aminopropyl)-3,3′-bis(4- hydroxyphenyl)-N,N′-(butane-1,4-diyl)bis[prop-2-enamide] ([¹⁵N(1)])-( 1 ) was synthesized in order to get further information about the fragmentation mechanisms. The comparison of the ESI-MS/MS of 1 and [¹⁵N(1)]- 1 revealed a transamidation, the Zip reaction, under mass-spectral conditions of the [ 1 + H]⁺ ions. Because of this reaction, the three isomers 1–3 could not be distinguished.     

Electrospray-Ionization Mass Spectrometry. Part 2. Neighboring-Group Participation in the Mass-Spectral Decomposition of 4-Hydroxycinnamoyl-spermidines

The three mono substituted N-[(E)-3-(4-hydroxyphenyl)prop-2-enoyl]spermidines 1–3 have been studied by positive-ion electrospray-ionization tandem mass spectrometry (ESI-MS/MS). Because of the neighboring-group participation, the MS/MS of [ 1 + H]⁺ and [ 2 + H]⁺ are essentially similar, while compound 3 can be easily distinguished from 1 and 2 because of the characteristic ions at m/z 218. However, with the source collision-induced dissociation (source-CID) MS/MS technique, the compounds 1 and 2 can be unambiguously distinguished by the signal of the pyrrolidinium ion (m/z 72) from their daughter ion (m/z 275). The source-CID MS/MS of the labeled compound N-(4-aminobutyl)-N-(3-aminopropyl)-N-[3-(4- hydroxyphenyl)prop-2-en[¹⁵N]amide] ([¹⁵N(4)]- 2 ) provide more information on the decomposition mechanisms and proved the occurrence of a partial transamidation reaction 2→1 during the measurement.     

Allgemeiner Zugang zu Polyaminen mit Ethan-1,2-diamin-Einheiten: Synthese von nicht natürlich vorkommenden homologen und isomeren N1,4-Di(4-cumaroyl)sperminen

█tl="American"█The synthesis of the three N,N′-di(4-coumaroyl)tetramines, i.e., of (E,E)-N-{3-[(2-aminoethyl)amino]propyl}-3,3′-bis(4-hydroxyphenyl)-N,N′-(ethane-1,2-diyl)bis[prop-2-enamide] ( 1a ), (E,E)-N-{4-[(2-aminoethyl)amino]butyl}-3,3′-bis(4-hydroxyphenyl)-N,N′-(ethane-1,2-diyl)bis[prop-2-enamide] ( 1b ), and (E,E)-N-{6-[(2-aminoethyl)amino]hexyl}-3,3′-bis(4-hydroxyphenyl)-N,N′-(ethane-1,2-diyl)bis[prop-2-enamide] ( 1c ), is described. It proceeds through stepwise construction of the symmetric polyamine backbone including protection and deprotection steps of the amino functions. Their behavior on TLC in comparison with that of 1,4-di(4-coumaroyl)spermine (=(E,E)-N-{4-[(3-aminopropyl)amino]butyl}-3,3′-bis(4-hydroxyphenyl)-N,N′-(propane-1,3-diyl)bis[prop-2-enamide]; 2 ) is discussed.     

Synthesis of new functionally substituted hetarylcarbamates from methyl {4-[(2<Emphasis Type="Italic">E</Emphasis>)-3-(4-methoxyphenyl)-prop-2-enoyl]phenyl}carbamate

Three-component condensation of methyl {4-[(2E)-3-(4-methoxyphenyl)prop-2-enoyl]phenyl}- carbamate with ninhydrin and L-proline in methanol–water (10: 1) afforded methyl {4-[1,3-dioxo-1′- (4-methoxyphenyl)-1,1′,2′,3,5′,6′,7′,7a′-octahydrospiro[indene-2,3′-pyrrolizin]-2′-ylcarbonyl]phenyl}carbamate. Heating of methyl {4-[(2E)-3-(4-methoxyphenyl)prop-2-enoyl]phenyl}carbamate with isatin and benzylamine in methanol gave methyl {4-[4′-(4-methoxyphenyl)-2-oxo-5′-phenyl-1,2-dihydrospiro[indole-3,2′-pyrrolidin]-3′-ylcarbonyl]phenyl}carbamate. The condensation of methyl {4-[(2E)-3-(4-methoxyphenyl)prop-2- enoyl]phenyl}carbamate with sarcosine and 11H-indeno[1,2-b]quinoxalin-11-one generated in situ from ninhydrin and o-phenylenediamine in boiling ethanol led to the formation of methyl {4-[4′-(4-methoxyphenyl)-1′-methyl-11,11a-dihydro-5aH-spiro[benzo[b]phenazine-6,2′-pyrrolidin]-3′-ylcarbonyl]phenyl}carbamate.     

On-Line Coupling of High-Performance Liquid Chromatography to Atmospheric Pressure Chemical Ionization Mass Spectrometry (HPLC/APCI-MS and MS/MS). The Pollen Analysis of Hippeastrum x hortorum (Amaryllidaceae)

A H₂O/MeOH extract of the pollen of Hippeastrum x hortorum (Amaryllidaceae) was analyzed. A mixture of different compounds (at the most 84) was found, namely the geometrically ((E,E), (E,Z), (Z,E), and (Z,Z) and structurally isomeric N,N′-dicoumaroyl (=N,N′-bis[3-(4-hydroxyphenyl)prop-2-enoyl]), N,N′-diferuloyl (=N,N′-bis[3-(4-hydroxy-3-methoxyphenyl)prop-2-enoyl]), N,N′-disinapoyl (=N,N′-bis[3-(4-hydroxy-3,5-dimethoxyphenyl)prop-2-enoyl]), N-coumaroyl-N′-feruloyl, and N-feruloyl-N′-sinapoyl derivatives of spermidine (=4-azaoctane-1,8-diamine=N-(3-aminopropyl)butane-1,4-diamine). Their structures were proven by using on-line-coupled high-performance liquid chromatography and atmospheric-pressure chemical-ionization mass spectrometry (HPLC-UV(DAD)/APCI-MS and MS/MS), UV-induced (E)⇌(Z) photoisomerization, and catalytic hydrogenation, as well by comparing their spectra and chromatographic behavior with those of synthetic standards. According to the physicochemical properties of these natural compounds, a proposed biological function is discussed.     

Reactions of Elemental Phosphorus and Phosphine with Electrophiles in Superbasic Systems: XV. Phosphorylation of Allyl Halides with Elemental Phosphorus

Elemental phosphorus (red or white) reacts with allyl chloride and allyl bromide in a two-phase system aqueous KOH-organic solvent to form tertiary symmetrical and mixed phosphine oxides among which tris(prop-2-enyl)-, bis(prop-2-enyl)[(E)-prop-1-enyl]-, bis(prop-2-enyl)[(Z)-prop-1-enyl]-, (prop-2-enyl)[(E)-prop-1-enyl][(Z)-prop-1-enyl]-, bis[(E)-prop-1-enyl](prop-2-enyl)-, bis[(Z)-prop-1-enyl](prop-2-enyl)-, tris-[(E)-prop-1-enyl]-, and bis[(E)-prop-1-enyl][(Z)-prop-1-enyl]phosphine oxides were identified. The conditions (room temperature, 60% aqueous KOH-dioxane) allowing preparation from white phosphorus and allyl bromide of tris(prop-2-enyl)- and bis(prop-2-enyl)[(E)-prop-1-enyl]phosphine oxides as major products in the total yield of up to 96% were found.     

Hepatoprotective phenylethanoid glycosides from Cirsium setosum

Two new phenylethanoid glycosides, namely β-D-glucopyranoside, 1″-O-(7S)-7-(3-methoxyl-4-hydroxyphenyl)-7-methoxyethyl-3″-α-L-rhamnopyranosyl-4″-[(8E)-7-(3-methoxyl-4-hydroxyphenyl)-8-propenoate] (1) and β-D-glucopyranoside, 1″-O-(7S)-7-(3-methoxyl-4-hydroxyphenyl)-7-methoxyethyl-3″-α-L-rhamnopyranosyl-4″-[(8E)-7-(4-hydroxyphenyl)-8-propenoate] (2), together with six phenylethanoid glycosides were isolated from Cirsium setosum. Their structures were elucidated by their spectroscopic data and references. Compounds 2, 4, 5, 7 and 8 (10 μM) exhibited moderate hepatoprotective activities. Compounds (3–8) were obtained from this plant for the first time.     

Crystal structures,Hirshfeld analysis,and energy framework analysis of two differently 3′-substituted 4-methylchalcones: 3′-(N=CHC6H4-p-CH3)-4-methylchalcone and 3′-(NHCOCH3)-4-methylchalcone

Two crystal structures of chalcones, or 1,3-diarylprop-2-en-1-ones, are presented; both contain a p-methyl substitution on the 3-Ring, but differ with respect to the m-substitution on the 1-Ring. Their systematic names are (2E)-3-(4-methylphenyl)-1-(3-{[(4-methylphenyl)methylidene]amino}phenyl)prop-2-en-1-one (C₂₄H₂₁NO) and N-{3-[(2E)-3-(4-methylphenyl)prop-2-enoyl]phenyl}acetamide (C₁₈H₁₇NO₂), which are abbreviated as 3′-(N=CHC₆H₄-p-CH₃)-4-methylchalcone and 3′-(NHCOCH₃)-4-methylchalcone, respectively. Both chalcones represent the first reported acetamide-substituted and imino-substituted chalcone crystal structures, adding to the robust library of chalcone structures within the Cambridge Structural Database. The crystal structure of 3′-(N=CHC₆H₄-p-CH₃)-4-methylchalcone exhibits close contacts between the enone O atom and the substituent arene ring, in addition to C…C interactions between the substituent arene rings. The structure of 3′-(NHCOCH₃)-4-methylchalcone exhibits a unique interaction between the enone O atom and the 1-Ring substituent, contributing to its antiparallel crystal packing. In addition, both structures exhibit π-stacking, which occurs between the 1-Ring and R-Ring for 3′-(N=CHC₆H₄-p-CH₃)-4-methylchalcone, and between the 1-Ring and 3-Ring for 3′-(NHCOCH₃)-4-methylchalcone.     

Microwave-assisted synthesis of 1-{2-[(1-benzyl-1<Emphasis Type="Italic">H</Emphasis>-1,2,3-triazol-4-yl)methoxy]phenyl}-3-(3-aryl-1-phenyl-1<Emphasis Type="Italic">H</Emphasis>-pyrazol-4-yl)prop-2-en-1-ones and their antimicrobial activity

A series of new (E)-1-{2-[(1-benzyl-1H-1,2,3-triazol-4-yl)methoxy]phenyl}-3-(3-aryl-1-phenyl-1H-pyrazol-4-yl)prop-2-en-1-ones (3a–3i) has been synthesized via copper-catalyzed 1,3-dipolar azide-alkyne cycloaddition reaction (CuAAC) of benzyl azide with substituted (E)-3-(3-aryl-1-phenyl-1H-pyrazol-4-yl)-1-[2-(prop-2-ynyloxy)phenyl]prop-2-en-1-ones (2a–2i). The synthesized compounds have been characterized by their IR, ^lH, ¹³C NMR spectra, and mass spectroscopy data. All the compounds have been screened for antimicrobial activity.     

Synthesis and antiproliferative activity of combretastatin derivatives with adamantane fragment

Russian Chemical Bulletin - The work describes the synthesis of 2-adamantyl 7-[(2-{[(2E)-3-(3-hydroxy-4-methoxyphenyl)-2-(3,4,5-trimethoxyphenyl)prop-2-enoyl]amino}ethyl)amino]-7-oxoheptanoate and...     

Microwave assisted synthesis of substituted (<Emphasis Type="Italic">Z</Emphasis>)-2-{[1-phenyl-3-(thiophen-2-yl)-1<Emphasis Type="Italic">H</Emphasis>-pyrazol- 4-yl]methylene}benzofuran-3(2<Emphasis Type="Italic">H</Emphasis>)-ones and their antimicrobial activity

Aurones, pyrazole and thiophene scaffolds are known for their potential antimicrobial activity. Herein, we have synthesized hybrid compounds containing three substituted (Z)-2-{[1-phenyl-3-(thiophen-2-yl)- 1H-pyrazol-4-yl]methylene}benzofuran-3(2H)-ones that had been produced from substituted (E)-1-(2-hydroxyphenyl)- 3-[1-phenyl-3-(thiophen-2-yl)-1H-pyrazol-4-yl]prop-2-en-1-ones in high yields. All synthesized compounds were tested in vitro for their antimicrobial activity. Several of those demonstrated promising activity against some fungal and bacterial strains.     

Synthesis of (E)- and (Z)-3(5)-(2-hydroxyphenyl)-4-styrylpyrazoles

Abstract  

An efficient synthesis method for the preparation of a series of new (Z)- and (E)-3(5)-(2-hydroxyphenyl)-4-styrylpyrazoles was developed. The reaction of (Z)- and (E)-3-styrylchromones with hydrazine hydrate afforded the corresponding (Z)- and (E)-3(5)-(2-hydroxyphenyl)-4-styrylpyrazoles, except for nitro derivatives, where both (Z)- and (E)-4′-nitro-3-styrylchromones afforded (E)-3(5)-(2-hydroxyphenyl)-4-(4-nitrostyryl)pyrazoles. The reaction mechanism for these transformations is discussed and the stereochemistries of all products were established by NMR experiments.     

Stereoselective synthesis of 2-substituted 6-[1-(2,6-difluorophenyl)ethyl]-5-methylpyrimidin-4(3<Emphasis Type="Italic">H</Emphasis>)-ones

A procedure has been proposed for the synthesis of 2-(cyclopentylsulfanyl)-6-[(1R)-1-(2,6-difluorophenyl) ethyl]-5-methylpyrimidin-4(3H)-one through intermediate (3R)-4,4-dimethyl-2-oxotetrahydrofuran-3-yl (2R)-2-(2,6-difluorophenyl)propanoate which was obtained from prochiral 2-(2,6-difluorophenyl)prop-1-en-1-one generated in situ. The proposed procedure may be regarded as stereoselective route to 6-[(1R)-1-(2,6- difluorophenyl)ethyl]-5-methylpyrimidin-4(3H)-one derivatives.     

Uncommon secondary metabolites from Etlingera pavieana rhizomes

From the rhizomes of Etlingera pavieana (Pierre ex Gagnep.) R.M. Sm., four phenylpropens, (E)-3-(4-methoxyphenyl)prop-2-en-1-amine (1), (E)-4-methoxycinamaldehyde (2), (E)-4-methoxycinamic acid (3) and (E)-1-methoxy-4-(3-methoxyprop-1-enyl)benzene (4), together with two other compounds, (E)-((E)-3-(4-methoxyphenyl)allyl)3-(4-hydroxyphenyl)acrylate (5) and 4-methoxybenzoic acid (6) were isolated. This is the first report on the presence of all compounds in Etlingera. Compounds 1 and 5 have been previously synthesised, but this is the first report of their isolation from a natural source. Compound 5 exhibited weak activity against Mycobacterium tuberculosis with MIC 50.00 μg/mL and cytotoxic activity against the KB, MCF7 and NCI-H187 cells with IC₅₀ values of 25.11, 20.16 and 34.83 μg/mL, respectively.     

Reduction of (<Emphasis Type="Italic">E</Emphasis>)-3-aryl-2-(thiazol-2-yl)acrylonitriles with lithium aluminum hydride

Reduction of (E)-3-aryl-2-(4-arylthiazol-2-yl)acrylonitriles with lithium aluminum hydride in dry ether afforded (Z)-1-amino-3-aryl-2-(thiazol-2-yl)prop-1-ene derivatives in 15 to 40% yields. The structure of (Z)-1-amino-3-(2-chlorophenyl)-2-[4-(4-methylphenyl)thiazol-2-yl]prop-1-ene was confirmed by X-ray diffraction analysis. Dedicated to Academician N. K. Kochetkov on the occasion of his 90th birthday. __________ Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 5, pp. 1301–1303, May, 2005.     

New lipoxygenase and cholinesterase inhibitory sphingolipids from Carthamus oxyacantha

Two new sphingolipids: oxyacanthin A [(2S,3S,4R)-2-{[(2R,5E)-2-hydroxyoctadec-5-enoyl]amino}hexaeicosane-1,3,4-triol; 1] and B [(2S,3S,4R)-2-{[(2R,5E)-2-hydroxyoctadec-5-enoyl]amino}hexaeicosane-1,3,4-triol-1-O-β-D-glucopyranoside; 2], together with 1-octacosanol, β-sitosterol, β-sitosterol 3-O-β-D-glucopyranoside and luteolin 7-O-β-glucopyranoside were isolated from the methanolic extract of the whole plant of Carthamus oxyacantha. Their structures were elucidated using ¹H and ¹³C NMR spectra and 2D NMR analyses (HMQC, HMBC and COSY) in combination with mass spectrometry (EI-MS, HR-EI-MS, FAB-MS and HR-FAB-MS) experiments and in comparison with the literature data of the related compounds. Both the compounds 1 and 2 showed inhibitory potential against lipoxygenase (LOX) in a concentration-dependent manner with IC₅₀ values 83.3 ± 1.3 and 245.7 ± 1.1 µM, whereas compound 2 showed inhibition against enzymes acetylcholinesterase (AChE) and butyrylcholinesterase (BChE) with IC₅₀ values 65.3 ± 0.1 and 93.6 ± 0.1 µM, respectively.     

Product of the reaction of methyl (<Emphasis Type="Italic">Z</Emphasis>)-3-bromo-3-(4-methylbenzenesulfonyl) prop-2-enoate with acetylacetone

Methyl (Z)-3-bromo-3-(4-methylbenzenesulfonyl)prop-2-enoate reacted with acetylacetone in THF in the presence of sodium hydride (3 h, 50°C) to give methyl (E)-3-acetyl-2-[(4-methylbenzenesulfonyl)-methylidene]-4-oxopentanoate as the only product. According to the X-ray diffraction data, the crystalline product has enol structure.     

Synthesis of (<Emphasis Type="Italic">E</Emphasis>)- and (<Emphasis Type="Italic">Z</Emphasis>)-3(5)-(2-hydroxyphenyl)-4-styrylpyrazoles

Abstract  An efficient synthesis method for the preparation of a series of new (Z)- and (E)-3(5)-(2-hydroxyphenyl)-4-styrylpyrazoles was developed. The reaction of (Z)- and (E)-3-styrylchromones with hydrazine hydrate afforded the corresponding (Z)- and (E)-3(5)-(2-hydroxyphenyl)-4-styrylpyrazoles, except for nitro derivatives, where both (Z)- and (E)-4′-nitro-3-styrylchromones afforded (E)-3(5)-(2-hydroxyphenyl)-4-(4-nitrostyryl)pyrazoles. The reaction mechanism for these transformations is discussed and the stereochemistries of all products were established by NMR experiments. Graphical abstract        

Cyclopropanation of methyl (2<Emphasis Type="Italic">E</Emphasis>)-3-[(1<Emphasis Type="Italic">R</Emphasis>,6<Emphasis Type="Italic">S</Emphasis>)-7,7-dimethyl-2-oxo-3-oxabicyclo[4.1.0]hept-4-en-4-yl]prop-2-enoate with dichlorocarbene and diazomethane

Cyclopropanation of methyl (2E)-3-[(1R,6S)-7,7-dimethyl-2-oxo-3-oxabicyclo[4.1.0]hept-4-en-4-yl]prop-2-enoate with dichlorocarbene occurred at the endocyclic double bond, while its reaction with diazomethane in the presence of Pd(acac)₂ involved the exocyclic double bond. The resulting lactones reacted with sodium methoxide in methanol via opening of one cyclopropane fragment.