Anti-inflammatory activities of the chemical constituents isolated from Trametes versicolor

Twenty-seven compounds including nine triterpenoids (1–9), eight sterols (10–17), two ribonucleotides (18, 19), four phenols (20–23), three glycosides (24–26), and one furan (27) were isolated from the fruiting bodies of Trametes versicolor (L.) Lloyd. This study is the first confirmation of the presence of the 11 compounds (3, 5, 6, 8, 18, 20, 21, 23–25, and 27) isolated from the Polyporaceae family, with six of these (2 and 12–16) from the genus Trametes. Compounds 3, 4, 10, 11, 16 and 17 were found to significantly inhibit the production of NO, TNF-α and IL-6 in a dose-dependent manner.     

A new 9,10-dihydrophenanthrene from Dendrobium moniliforme

A new 9,10-dihydrophenanthrene,1,5-dihydroxy-3,4,7-trimethoxy-9,10-dihydrophenanthrene (1) was isolated and identified from the whole plants of Dendrobium moniliforme, as well as 24 known compounds including hircinol (2), (2R^*,3S^*)-3-hydroxymethyl-9-methoxy-2-(4′-hydroxy-3′,5′-dimethoxyphenyl)-2,3,6,7-tetrahydro-phenanthro[4,3-b]furan-5,11-diol (3), diospyrosin (4), aloifol I (5), moscatilin (6), 3,4′-dihydroxy-3′,4,5-trimethoxybibenzyl (7), gigantol (8), 3,3′-dihydroxy-4,5-dimethoxybibenzyl (9), longicornuol A (10), N-trans-cinnamoyltyramine (11), paprazine (12), N-trans-feruloyl 3′-O-methyldopamine (13), moupinamide (14), dihydroconiferyl dihydro-p-coumarate (15), dihydrosinapyl dihydro-p-coumarate (16), 3-isopropyl-5-acetoxycyclohexene-2-one-1 (17), p-hydroxybenzaldehyde (18), vanillin (19), p-hydroxyphenylpropionic acid (20), vanillic acid (21), protocatechuic acid (22), (+)-syringaresinol (23), β-sitosterol (24) and daucosterol (25). Compounds 3, 4, 13, 16, 17 and 20 were isolated from the Dendrobium genus for the first time, and compounds 2, 5, 7, 9–12, 14, 15, 18, 21 and 22 were originally obtained from D. moniliforme.     

Polymerizations of methyl methacrylate and rac-lactide by zinc(II) precatalyst containing N-substituted 2-iminomethylpyridine and 2-iminomethylquinoline

The reaction of [ZnCl₂] with N-cyclopentyl-1-(quinolin-2-yl)methanimine (L_A), N-cyclohexyl-1-(quinolin-2-yl)methanimine (L_B), N-cyclohexyl-1-(pyridin-2-yl)methanimine (L_C), 2,6-diethyl-N-(pyridin-2-ylmethylene)aniline (L_D), N-cyclopentyl-1-(pyridin-2-yl)methanimine (L_E), and N-phenyl-(pyridin-2-yl)methanimine (L_F) in ethanol produced the bidentate [(NN′)ZnCl₂] complexes, [L_AZnCl₂], [L_BZnCl₂], [L_CZnCl₂], [L_DZnCl₂], [L_EZnCl₂] and [L_FZnCl₂], respectively. The molecular structures revealed that the zinc in [L_nZnCl₂] (L_n = L_A ? L_D) showed a distorted tetrahedral geometry involving two nitrogens of N,N’-bidentate ligands and two chloride ligands. Most of these initiators were effective for polymerization of methyl methacrylate (MMA) and polymerization of rac-lactide (rac-LA). [L_CZnCl₂] (with N-cyclohexyl substituted at imine-pyridine moiety) exhibited the highest catalytic activity for MMA polymerization in the presence of modified methylaluminoxane (MMAO) with an activity of 3.33 × 10⁴ g PMMA/mol·Zn·h at 60 °C, giving moderate syndiotactic poly methyl methacrylate (PMMA) with high molecular weight (9.62 × 10⁵ g/mol). The dimethyl derivatives [L_nZnMe₂] (L_n = L_A ? L_F), generated in situ, polymerized rac-LA with moderate activity and yielded a polylactide (PLA) with good number-average molecular weights and narrower polydispersity indices (PDIs). [L_AZnMe₂] effectively initiates the ring-opening polymerization (ROP) of rac-LA to attain heterotactic PLA (P_r = 0.91).     

Chemical constituents from Agrimonia pilosa Ledeb. and their chemotaxonomic significance

Phytochemical investigation of the ethanol extract from the whole plant of Agrimonia pilosa led to the isolation of 31 compounds, including 16 flavonoids (1–16), 5 triterpenes (17–21), 1 isocoumarin (22), 5 phenolic acids (23–27), 1 ceramide (28), 2 agrimols (29–30) and 1 fatty acid (31). Their structures were determined by various spectroscopic analyses. Compounds 5, 7 and 20 were firstly isolated from the genus Agrimonia, and compounds 6, 10–11, 15, 26, 28 and 31 were isolated from the family Rosaceae for the first time. Moreover, the chemotaxonomic significance of these compounds was summarised.     

NOVEL N,S-SUBSTITUTED DIENES BY THE REACTION OF 2-NITROTHIOSUBSTITUTED HALODIENES AND PRIMARY AMINES

Mono(thio)substituted 1a–c gave compounds 3a–c and 5a with o-toluidin (2) and m-toluidin (4) in ether. Compounds 9a–c and 11a, b were obtained from the reaction of compounds 1a–c with p-fluorophenylamine (8) and p-fluorobenzylamine (10). Compounds 7a and 15c were obtained from the reaction of 1a and 1c with p-phenylendiamine (6) and o-phenylendiamine (14). Compound 13c was synthesized from the reaction of compound 1c with benzidine (2).     

Selective Benzoylation of 1-(β-D-Xylopyranosyl)-3,5-dimethylpyrazole

Abstract

Selective benzoylation of l-(β-d-xylopyranosyl)-3,5-dimethylpyrazole (1) has been performed to give 2,3,4-tri- (2), 3,4-di- (3), 2,4-di- (4), 3- (5) and 4-benzoate (6). The O-acetyl derivatives of compounds 3 and 4 (7, 8), di-O-acetyl of 5 and 6 (9, 10) and O-methanesulphonyl of 3 and 4 (11, 12) have been obtained. The relative reactivity of the hydroxyl groups of 1 was HO-4 ≥ HO-3 ? HO-2. The analysis of ¹ H NMR and ¹³C NMR spectra of 1-12 is presented.     

Chemical constituents and biological activities from branches of Colubrina asiatica

Sixteen compounds were isolated from a Thai medicinal plant, Colubrina asiatica. The isolated compounds were elucidated on the basis of spectroscopic methods (IR, 1D and 2D NMR) as six triterpene acids (1–6), five steroids (7–11), one benzoic acid derivative (12), two peptides (13 and 14), one sesquiterpenoid (15) and one jujubogenin (16). Compounds 3 and 10 showed antimalarial activity against Plasmodium falciparum. Compound 5 showed antimycobacterial activity. Moreover, compounds 3, 5, 6, 10 and 14 exhibited weak cytotoxicity against cancer cell lines. Compounds 1–15 have been isolated for the first time from this plant.     

Synthesis and Biological Activities of Novel 1,4-Bridged Bis-1,2,4-Triazoles,Bis-1,3,4-Thiadiazoles and Bis-1,3,4-Oxadiazoles

Abstract

The terephthalic acid hydrazide(1) reacted with phenyl/benzyl isothiocyanate2a,bto yield the corresponding bis-thiosemicarbazides4a,b,viaacid hydrolysis of the intermediate 3whereas cyclization of4gave the bis-1,2,4-triazoles 5,6and bis-1,3,4-thiadiazoles7,8. Similarly, compound 1reacted with phenyl isocyanate9to give the bis-semicarbazide10, which was cyclized to the bis-oxadiazole 11and/or bis-1,2,4-triazole12in POCl_ti3and NaOH respectively.     

A new coumarin from the roots of Micromelum minutum

A new coumarin, minutuminolate (1), together with eleven known coumarins (2–12), was isolated from the roots of Micromelum minutum. The structures of these compounds were established on the basis of their 1D and 2D NMR spectroscopic data. Compounds 2, 5, 10, 11 and 12 showed cytotoxicity against KB cell line. In addition, compounds 2, 3, 4, 7, 11 and 12 also showed weak cytotoxicity against NCI-H187 cell line.     

Aromatische Spirane, 23. Mitt.: Darstellung von unsymmetrisch substituierten Dimethyl-2,2′-Spirobiindan-1,1′-dionen

Summary Both spirodiketones7 and8 were obtained as a mixture (56:44) by treatment of dicarbonic acid5 with polyphosphoric acid (PPA).5 was accessible from dimethylester3, synthesized byretro-Claisen reaction between1 and2. In the same way,30 was obtainedvia 27. The preparation of the pure spiro compounds7 and8, resp., was achieved by aldol reaction between9 and10 or9 and16, resp. Short treatment of the resulting compounds11 and17 with diazomethane yielded the methylbenzoates12 and18. Prolonged reaction (several hours) gave the pyrazole compounds14 and19, resp., which were also obtained (several days) from phthalides14 and20. The latter were formed from the benzylidene compounds11 and17, resp., by heating.11 and17 (after hydrogenation to15a and21a) were cyclized either withPPA or thermically to the spiro compounds7 and8. The main product20 was cyclized thermically to8 after reduction with zinc to a mixture of21a and8 (20:75).

     

Synthesis and Antibacterial Activity of Some New S-Triazole Derivatives

Abstract

Alkylation of 4-anilino-5-phenyl-4H-1,2,4-triazole-3-thiol (1) with some halo compounds yielded the corresponding sulfides 2a–f. Some sulfides 2e,f were cyclized to give triazolothiadiazines 3 and 4. Triazolothiadiazoles 5 and 6 were prepared through the reaction of compound 1 with carbon disulfide or ethyl orthoformate, respectively. Treatment of compound 1 with ethyl chloroformate or phenyl isothiocyanate yielded triazolo-thiadiazole and triazole 9 and 10, respectively. Reaction of compound 1 with Lawesson's reagent gave triazolothiadiazaphosphole derivative 11. Also, compound 1 underwent cyclocondensation reactions with some bidentate reagents to give triazolothiazines 4, 12, and 13. Triazolo-thiazepines and triaziepine 14–16 were synthesized via the reaction of compound 1 with β-ketoesters or ethyl cyanoacetate. Tricyclic systems 19 and 20 were prepared through the reaction of compound 4 with the appropriate reagent. Some synthesized compounds were tested for antibacterial activity.

Supplemental materials are available for this article. Go to the publisher's online edition of Phosphorus, Sulfur, and Silicon and the Related Elements to view the free supplemental file.     

Synthesis of canthine/erythrinane alkaloid analogs

The pentacyclic lactams9,11, and14 were prepared using a thermal condensation of tryptamine with symmetrical oxodiesters3 and4 as the key step. The formation of the ring E in the tetracyclic compounds5,6,8,10,12, and13 is strongly dependent on the ring size.

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Synthese von Analoga der Canthin/Erythrina Alkaloide (Kurze Mitteilung)

Zusammenfassung Die pentacyclischen Verbindungen9,11 und14 wurden durch thermische Kondensation von Tryptamin mit symmetrischen Oxodiestern3 und4 als wichtigster Reaktionsstufe dargestellt. Die Bildung des Ringes E in den tetracyclischen Verbindungen5,6,8,10,12 und13 ist stark von der Ringgröße abhängig.

     

Acetoacetanilides in Heterocyclic Synthesis,Part 1: An Expeditious Synthesis of Thienopyridines and Other Fused Derivatives

3-Oxo-N-{4-[(pyrimidin-2-ylamino)sulfonyl]phenyl}butanamide 1 reacts with arylidinecyanothioacetamide in refluxing ethanolic TEA to give the pyridinethione 2 rather than thiopyrane 4. Compound 2 reacts with α-haloketones to give the s-alkylated derivatives 7a–e. Compound 7a–e undergoes cyclization into thieno[2,3-b]pyridine derivatives 8a–e. The saponification of 8a gives the amino acid 9, which affords 10 when refluxed in Ac₂O. The treatment of 10 with NH₄OAc/AcOH gives 11. Compound II is also obtained when 8e is refluxed in Ac₂O. The reaction of 8a with hydrazine hydrate gives 12 and with formamide gives 13. Compound 13 also is obtained from the reaction of 8e with triethylorthoformate. The acetylation of 8a with Ac₂O gives the amide derivative 14, which, on treatment with aromatic amines, affords 15a–c. Compounds 15a–c are cyclized with H₂SO₄ to 16a–c. Compound 16 is obtained also from the acetylation of compound 8c, d by Ac₂O. Reactions of compound 8e with CS₂ in refluxing dioxane afford 17. The diazotization and self-coupling of 8e give the pyridothienotriazine 18. Finally, the chloronation of compound 13 with POCl₃ affords the chloride derivative 19.     

Glycosylation of 4‐Aryl‐1‐thioxo[1,2,4] triazolo[4,3‐a] quinazolin‐5(4H)‐one

Reaction of 4‐aryl‐1‐thioxo [1,2,4] triazolo [4,3‐a] quinazolin‐5 (4H)‐ones (2a,b) with acetylated glycosyl bromides 3a–c under alkaline conditions afforded the corresponding S‐glycoside derivatives 4, 5 and N‐glycoside derivatives 6, 7. Oxidation of S‐glycosyl derivatives 4, 5 with m‐chloroperbenzoic acid yielded the corresponding sulphones 8, 9, whereas the N‐glycosyl derivatives 6, 7 yielded 1‐oxo derivatives 10, 11. However their O‐deacetylation with sodium methoxide in methanol caused cleavage of the S‐glycosyl residue and gave N ²‐glycosylated analogues 12, 13, 14 and 15.     

Reaction of CH acids with 2-arylidenecycloalkanones: Synthesis of β-keto acid anilide derivatives of naphthalene,indene, fluorene,and phenanthrene

Summary 2-Arylidene-cyclohexanone1, -cyclopentanone2, -1-indanone3 and-1-tetralone4 react with acetoacetanilide5 yielding 2-oxo-4-aryl-3-carboxylic acid anilides derivatives of naphthalene7, indene8, fluorene9 and phenanthrene10. Reaction of1 and3 with benzoylacetanilide6 yields the corresponding Michael adducts11 and12.

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Reaktion von CH-Säuren mit 2-Arylidencycloalkanonen. Synthese von -Ketosäureanilid-Derivaten von Naphthalin, Inden, Fluoren und Phenanthren

Zusammenfassung 2-Arylidencyclohexanone1, -cyclopentanone2, -1-indanone3 und -1-tetralone4 reagieren mit Acetoacetanilid5 unter Bildung von 2-Oxo-4-aryl-3-carbonsäureanilid-Derivaten von Naphthalin7, Inden8, Fluoren9 und Phenanthren10. Die Reaktion von1 und3 mit Benzoylacetanilid6 ergibt die entsprechenden Michael-Addukte11 und12.

     

REAKTIONEN DES PYRIDINIUM-FLUOR-DITHIOPHOSPHORSÄURE-BETAINS

Abstract

Pyridinium-fluor-dithiophosphorsäure-betain (1) reagiert mit Hydrazin unter Bildung von Pyridinium-hydrazin-bis(fluor-dithiophosphate) (3), mit Phenylhydrazin unter Bildung von Pyridinium-phenylhydrazido-fluordithiophosphat (5). 3 und 5 können mit Methyljodid in die entsprechenden S-Methylester 7 und 8 überführt werden. Die Umsetzung der Titelverbindung 1 mit H₂S führt zu Pyridinium-difluor-pentathiodiphosphat (9). Das primäre Hydrolyseprodukt von 1 ist nicht stabil. Mercaptane und 1 reagieren zu den Pyridiniumsalzen der Fluor-trithiophosphorsäure-monoester (10), die durch Umsetzung mit Methyljodid in die Fluor-trithiophosphorsäure-diester (12) umgewandelt werden können. Die Reaktion von Phenyl-t-butyl-phosphan mit 1 hat eine P–P-Verknüpfung zur Folge. Reaktionsprodukt ist Pyridinium-phenyl-t-butyl-phosphido-fluor-dithiophosphat (13).

Pyridinium-fluoro-dithiophosphoric betaine (1) reacts with hydrazine to give pyridinium hydrazine bis(fluoro-dithiophosphate) (3), with phenylhydrazine to give pyridinium phenylhydrazido fluoro-dithiophosphate (5). 3 and 5 can be converted into the corresponding S-methyl esters 7 and 8 by methyl iodide. Reaction of the title compound 1 with H₂S yields pyridinium difluoro pentathiodiphosphate (9). The primary hydrolysis product of 1 is not stable. Mercaptanes and 1 yield pyridinium salts of fluoro trithiophosphoric monoesters (10) which by reaction with methyl iodide can be converted into fluoro trithiophosphoric diesters (12). The reaction of phenyl t-butyl phosphane with 1 results in the formation of a P–P bond. Reaction product is pyridinium phenyl t-butyl phosphido fluoro dithiophosphate (13).     

Electronic states of XC<Subscript>3</Subscript>H<Subscript>3</Subscript>Si five-membered rings (X = CH,N, P,and As)

Stable configurations of XC₃H₃Si five-membered rings, 1 _X and 2 _X (X = CH, N, P, and As) in the singlet and triplet states are found at B3LYP/6-311++G** level of theory. All the singlet states of 1 _X and 2 _X have lower potential energy than the triplet state. The ΔG _s−t differences between the singlet and triplet states of 1 _X and 2 _X changes at the B3LYP/6-311++G** level in the order (in kcal/mol): 1 _N (−17.56) > 1 _CH (−15.26) > 1 _P (−4.96) > 1 _As (−3.45) and 2 _CH (−15.26) > 2 _N (−9.21) > 2 _P (−7.39) > 2 _As (−6.15), respectively.     

CHLOROSULFONATION OF 9-ARYLOCTAHYDROXANTHEN-1,8-DIONES

The 9-aryloctahydroxanthen-1,8-diones (3, 4– 24) were prepared by reaction of cyclohexan-1,3-dione (1) with selected arylaldehydes. The xanthendiones (4– 9, 11, 12, 18, 21, 22) were successfully reacted with chlorosulfonic acid, and the crude sulfonyl chlorides were converted into 15 sulfonamides (26– 40) for screening as potential pesticides. Attempted chlorosulfonation of the xanthendiones (13– 17) was unsuccessful. α-Methylcinnamaldehyde was reacted with cyclohexandione (1) to yield the corresponding xanthendione derivative (23). On the other hand, with o-methoxycinnamaldehyde an impure product formed and the p-methoxy isomer afforded the corresponding 2-arylpyran (25). The NMR spectral data of the compounds are briefly discussed.     

Novel Syntheses and Reactions of Polynuclear Heterocyclic Derivatives Derived From Thioxopyridopyrimidine,With a New Ring System

Pyridopyrimidine derivatives 2 reacted with hydrazonoylchloride derivatives and yielded triazolopyridopyrimidines 6a–f. Compound 4b reacted with aliphatic acids and afforded triazolo-pyridopyrimidines 7a,b, and the reaction with carbon disulfide afforded 10-mercapto-triazolopyridopyrimidine (10). Moreover, the reaction of 4b with β -ketoesters afforded 10-pyrazolyl-pyridopyrimidines derivatives 11, 13, 14, and 15. Compound 4b reacted with nitrous acid to give tetrazolopyridopyrimidine 16, which reduced to 10-amino-derivative 17. On the other hand, the reaction of 4b with aromatic aldehydes afforded arylidines derivatives 18a–c, which were later cyclized to triazolo-pyridopyrimidines deivatives 19a–c. Finally, 4b reacted with α-haloketones to give triazines derivativrs 20, with new ring systems.     

New cytotoxic and anti-inflammatory compounds isolated from Morus alba L.

Six Diels–Alder adducts (1–6) and nine prenylated flavanones (7–15) were isolated from the root bark of Morus alba L. Among them, soroceal B (1) and sanggenol Q (7) were new compounds. Their structures were elucidated on the basis of extensive spectroscopic methods, including 1D and 2D NMR techniques. Compounds 1–3, 9, 10, 12, 13 and 15 exhibited cytotoxic activity against five human tumour lines and compound 2 inhibited significantly selective cytotoxic activities towards HL-60 and AGS cells with IC₅₀ of 3.4 and 3.6 μM. Compounds 3, 5, 9 and 12 exhibited moderate inhibitory activity against nitric oxide production in LPS-activated RAW264.7.