A new anthraquinone from Galium verum L

A new anthraquinone (4) and three known anthraquinones (1-3) were isolated from Galium verum L. Their structures were identified as 1,3-dihydroxy-2-methylanthraquinone (1), physcion (2), 2-hydroxy-1,3-dimethoxyanthraquinone (3), 2,5-dihydroxy-1,3-dimethoxyanthraquinone (4) by means of chemical and spectroscopic analysis. Compound 2 was isolated from the genus Galium for the first time. In addition, compound 4 was assayed for antimicrobial activity in vitro.     

Identification of a new naphthalene and its derivatives from the bulb of eleutherine americana with inhibitory activity on lipopolysaccharide-induced nitric oxide production

A new naphthoquinone, (-)-3-[2-(acetyloxy)propyl]-2-hydroxy-8-methoxy-1,4-naphthoquinone (1) was isolated from the bulb of Eleutherine americana MERR. et HEYNE (Iridaceae) together with two known compounds, eleutherinol (6) and 1,5-dihydroxy-3-methylanthraquinone (7) which were found in this species for the first time. The other known compounds, (-)-isoeleutherin (2), (+)-eleutherin (3), (-)-hongconin (4), and (+)-dihydroeleutherinol (5) which were reported previously from this species, were also isolated in the present study. Compounds 2-6 exhibited potent inhibitory activity on nitric oxide production in RAW 264.7 lipopolysaccharide-activated mouse macrophage cells with IC(50) values of 7.7, 11.4, 19.8, 21.7, and 34.4 microM, respectively, whereas the other two compounds, 1 and 7, were inactive. The structure of compound 1 was elucidated by spectroscopic data analysis including 1D and 2D NMR experiments.     

Antiangiogenic polyketides from Peperomia dindygulensis Miq

Two new polyketides: 2Z-(heptadec-12-enyl)-4-hydroxy-3,4,7,8-tetrahydro-2H-chromen-5(6H)-one (1) and 2-(heptadec-12-enyl)-5-hydroxy-5,6,7,8-tetrahydrochromen- 4-one (2), together with eleven known compounds: 4-hydroxy-2-[(3,4-methylenedioxy- phenyl)tridecanoyl] cyclohexane-1,3-dione (3), oleiferinone (4), 4-hydroxy-2-[(3,4- methylenedioxyphenyl)undecanoyl]cyclohexane-1,3-dione (5), 4-hydroxy-2-[(11-phenyl- undecanoyl)cyclohexane-1,3-dione (6), proctorione C (7), surinone C (8), 5-hydroxy- 7,8,4'-trimethoxyflavone (9), 5-hydroxy-7,8,3',4'-tetramethoxyflavone (10), 5-hydroxy- 7,3',4'-trimethoxyflavone (11), 5,8-dihydroxy-7,3',4'-trimethoxyflavone (12) and cepharanone B (13) were isolated from the whole plant of Peperomia dindygulensis Miq. Their structures were elucidated by spectroscopic methods, including 2D-NMR techniques. Compounds 2, 3, 5 and 8 inhibited human umbilical vein endothelial cell (HUVEC) proliferation and compounds 5 and 8 sharply suppressed HUVEC tube formation.     

A one-pot reaction of (chlorocarbonyl) phenyl ketene with β-ketoamides and thiochromen-2-one

Readily available (chlorocarbonyl)phenyl ketene and a varied set of β-ketoamides were reacted in a one-step procedure to produce 2-pyrone derivatives. β-Ketoamide derivatives are versatile intermediates for the synthesis of heterocyclic compounds. For instance, 1-morpholino-3-phenyl-1,3-propanedione, 1-phenyl-3-piperidino-1,3-propanedione, 1-phenyl-3-pyrrolidino-1,3-propanedione, 1-piperidino-1,3-butanedione, 1-morpholino-2-phenyl ethanone were used in these reactions to produce 2-pyrone derivatives. In addition, the preparation of 4-hydroxy-3-phenylthiochromeno[4,3-b]pyran-2,5-dione derivatives and 4-hydroxy-7-methyl-3-phenyl pyrano[3,2-c]chromeno-2,5-dione were described. For the synthesis of these compounds 4-hydroxy-2H-thiochromen-2-ones and 4-hydroxy-8-methyl-2H-chromen-2-one were reacted with (chlorocarbonyl)phenyl ketene and the final products were isolated in good yields.     

Anthraquinones and anthraquinols fromMorinda lucida: The biogenetic significance of oruwal and oruwalol

Two novel anthraquinols-oruwal and oruwalol; ten anthraquinones: damnacanthal, nor-damnacanthal, soranjidiol, alizarin-1-methyl ether, rubiadin, rubiadin-1-methyl ether, 2-methylanthraquinone, anthraquinone-2-aldehyde, 1-hydroxy-2-methylanthraquinone, 1-methoxy-2-methylanthraquinone; and hexacosanoic acid were obtained from the stem ofMorinda lucida. The structure of oruwal was confirmed as 9,10-dimethoxyanthracene-2-aldehyde by synthesis, while oruwalol was characterized as 5- or 8-hydroxy-9,1O-dimethoxyanthracene-2-aldehyde from analytical and spectroscopic evidence. The biogenetic significance of the co-occurrence of the anthraquinones, oruwal and oruwalol is discussed.     

Two neolignan glucosides and antihistamine release activities from Bidens parviflora WILLD

Two new neolignan glucosides, bidenlignasides A (1) and B (2), were isolated from the whole plant of Bidens parviflora WILLD. The structures of the two new compounds 1 and 2 established to be 3-hydroxy-1-(4-hydroxy-3-methoxyphenyl)-3-[5E-(3-hydroxypropenyl)-3-methoxy-2-O-beta-D-glucosyl)phenyl] propan-1-one and 3-{3-[1,3-dihydroxy-3-(4-hydroxy-3-methoxyphenyl)propyl]-4-hydroxy-5-methoxyphenyl}-allyl-O-beta-D-glucuside, respectively, on the basis of spectral and chemical evidence. Compounds 1 and 2 were found to inhibit histamine release from peritoneal exudate mast cells induced by antigen-antibody reaction.     

Monodictyquinone A: a new antimicrobial anthraquinone from a sea urchin-derived fungus Monodictys sp

A new antimicrobial anthraquinone, 1,8-dihydroxy-2-methoxy-6-methylanthraquinone, monodictyquinone A (1), was isolated from a culture of a marine-derived fungus of the genus Monodictys which was isolated from the sea urchin, Anthocidaris crassispina, along with three known compounds, pachybasin (2), chrysophanol (3), and emodin (4).     

One new anthraquinone from marine Streptomyces sp. FX-58

One new anthraquinone, 1,8-dihydroxy-2-ethyl-3-methylanthraquinone (1), together with two known compounds octadecanoic acid (2) and cholest-4-en-3-one (3) was isolated from marine actinomycete Streptomyces sp. FX-58. The structure of 1 was elucidated on the basis of spectroscopic methods, especially, the 2D-NMR spectral analysis. The cytotoxic activities of 1 were evaluated in vitro.     

Tetrahedral intermediates 3: The kinetics and mechanism of the breakdown of some hemiorthoesters

The kinetics of the breakdown of hemiorthoesters generated from dialkoxyalkyl acetates or ketene acetals have been investigated. The following compounds were studied: dimethyl hemiorthoformate (1b), diethyl hemiorthoformate (2b), 2-hydroxy-1,3-dioxolane (3b), 2-hydroxy-4,4,5,5-tetramethyl-1, 3-dioxolane, (4b), 2-hydroxy-2-methyl-1,3-dioxolane (5b),and 2-hydroxy-2,4,4,5,5-pentamethyl-1,3-dioxolane (6b).The whole series was studied in aqueous acetonitrile (c_H2O= 8.33 M); 4b, 5b, and 6b were studied in aqueous acetonitrile (c_H2O = 2.22 M) and 4b and 6b in water. Complete pc_H-rate or pH-rate profiles were obtained for each reaction. The mechanisms of the hydronium-ion, hydroxide-ion and “water” catalysed reactions are discussed and compared to those for the breakdown of hemiacetals and the hydrolysis of orthoesters.     

Benzofused tricycles based on 2-quinoxalinol

This paper describes our recent efforts to synthesize novel compound scaffolds integrating 2-quinoxalinol with privileged structures of 1,3-dihydro-benzoimidazol-2-one, 1,3-dihydro-benzoimidazole-2-thione, 3-hydroxy-1H-quinoxalin-2-one, 2H-benzo[1,4]oxazin-3-ol, 2H-benzo[1,4]thiazin-3-ol, and 1,3,4,5-tetrahydro-benzo[1,4]diazepin-2-one, respectively. Eight novel benzofused tricycles and their substituent diversity points were developed. These include pyrazino[2,3-g]quinoxaline-2,8-diol (I), 3-hydroxy-6,8,9,10-tetrahydro-1,4,6,10-tetraaza-cyclohepta[b]naphthalen-7-one (II), 6-hydroxy-4H-1-oxa-4,5,8-triaza-anthracen-3-one (III), 6-hydroxy-4H-1-thia-4,5,8-triaza-anthracen-3-one (IV), 6-hydroxy-1,1-dioxo-1,4-dihydro-2H-1lambda(6)-thia-4,5,8-triaza-anthracen-3-one (V), 6-hydroxy-1,3-dihydro-imidazo[4,5-g]quinoxalin-2-one (VI), 6-hydroxy-1,3-dihydro-imidazo[4,5-g]quinoxaline-2-thione (VII), and 7-hydroxy-1,4-dihydro-pyrazino[2,3-g]quinoxaline-2,3-dione (VIII). This strategy of integrating two benzofused privileged structures into one molecule may provide a greater chance for the discovery of novel lead compounds.     

Synthesis of 2-aryl-4-hydroxy-5-thio substituted 1,3-thiazin-6-ones via sulfenylation of 2-aryl-4-hydroxy-[1,3]thiazin-6-ones with sulfenyl chlorides

A series of 2-aryl-4-hydroxy-5-thio substituted 1,3-thiazin-6-ones were synthesized for human immunodeficiency virus-1 protease inhibition. These compounds were synthesized by the treatment of 4-hydroxy-5-thio substituted-1,3-thiazin-6-ones with the corresponding sulfenyl chlorides. The products were obtained in good isolated yields, inspite of the presence of bulkyl substitutents at the ortho position of phenyl sulfenyl chloride portion.     

Iridoids and anthraquinones from the Malaysian medicinal plant,Saprosma scortechinii (Rubiaceae)

A further investigation of the leaves and stems of Saprosma scortechinii afforded 13 compounds, of which 10 are new compounds. These were elucidated as the bis-iridoid glucosides, saprosmosides G (1) and H (2), the iridoid glucoside, 6-O-epi-acetylscandoside (3), and the anthraquinones, 1-methoxy-3-hydroxy-2-carbomethoxy-9,10-anthraquinone (4), 1-methoxy-3-hydroxy-2-carbomethoxy-9,10-anthraquinone 3-O-beta-primeveroside (5), 1,3-dihydroxy-2-carbomethoxy-9,10-anthraquinone 3-O-beta-primeveroside (6), 1,3,6-trihydroxy-2-methoxymethyl-9,10-anthraquinone (7), 1-methoxy-3,6-dihydroxy-2-hydroxymethyl-9,10-anthraquinone (8), 1,3,6-trihydroxy-2-hydroxymethyl-9,10-anthraquinone 3-O-beta-primeveroside (9), and 3,6-dihydroxy-2-hydroxymethyl-9,10-anthraquinone (10). Structure assignments for all compounds were established by means of mass and NMR spectroscopies, chemical methods, and comparison with published data. The new anthraquinones were derivatives of munjistin and lucidin.     

Investigation of the reaction of 2-aminotheophyllines with glycerol epichlorohydrin

Depending on the nature and amount of the base used, as well as the reaction time, the following compounds are formed in the reaction of 8-aminothiophyl-lines with glycerol epichlorohydrin in anhydrous propanol; 7-(2-hydroxy-3-chloro-1-propyl)-8-arylaminotheophylline, 1,3-bis(8-arylamino-7-theophyllinyl)-2-hydroxypropane, 7-(2,3-epoxy-1-propy1)-8-alkyl(aryl) aminothiophyllines or 9-alkyl(aryl)-7-hydroxy-1,3-dimethyl-6,7,8,9-tetrahydropyrimido [2,1-f]purine-2,4-(1H,3H)diones. The structures of the compounds were confirmed by alternative synthesis and by data from the IR spectra. The mass spectrum of one of the compounds is presented.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 8, pp. 1102–1105, August, 1981.     

天然产物1,3-二-(2-羟基-4-甲氧基苯基)丙烷和1,3-二-(2,4-二羟基苯基)丙烷的合成

1,3-二-(2-羟基-4-甲氧基苯基)丙烷(1)和1,3-二-(2,4-二羟基苯基)丙烷(2)是从菊叶薯蓣(Dioscorea composita Hemsl.)分离出来的天然产物, 以间苯二酚为起始原料, 分别经甲酰化和乙酰化得到2,4-二羟基苯甲醛和2,4-二羟基苯乙酮, 然后经选择性地甲基化、甲氧甲基化、羟醛缩合、还原、脱保护等步骤完成了上述两种天然产物的首次全合成. 产物通过¹H NMR, IR, MS进行了结构确证.     

Synthesis and Properties of 7-Acetyl-8-aryl-9-cyano-3-hydroxy-6-methyl-3,4-dihydro-2H,8H-pyrido[2,1-<Emphasis Type="Italic">b</Emphasis>][1,3]thiazines

7-Acetyl-8-aryl-2-(1-chloro-2-hydroxy-3-propyl)thio-9-cyano-6-methyl-1,4-dihydropyridines were obtained by treatment of 1,4-dihydropyridine-2(3H)-thiones with epichlorohydrin in the presence of sodium bicarbonate. When treated with NaOMe, these compounds are readily intramolecularly alkylated with formation of 7-acetyl-8-aryl-3-hydroxy-9-cyano-6-methyl-3,4-dihydro-2H,8H-pyrido[2,1-b]-[1,3]thiazines. We have studied amination of 2-(1-chloro-2-hydroxy-3-propyl)thio-1,4-dihydropyridines and acylation of 3-hydroxy-3,4-dihydro-2H,8H-pyrido[2,1-b][1,3]thiazines. __________ Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 9, pp. 1394–1399, September, 2005.     

A new diphenyl ether from Phoma sp. strain, SHZK-2

A new diphenyl ether methyl 2-(2-formyl-3-hydroxy-5-methylphenoxy)-5-hydroxy-3-methoxybenzoate (3), together with four known compounds, asterric acid (1), methyl asterrate (2), 9(Z),12(Z)-nonadecadienoic acid (4) and orsellinic acid (5), were isolated from the Phoma sp. strain SHZK-2, which was isolated from a polluted environment in southern China. The structures of these compounds were determined by spectroscopic methods. Cytotoxicities of compounds against HEPG2 cell and Raji cell lines were preliminarily evaluated by the MTT method.     

Anthraquinones from the roots of Prismatomeris malayana

A novel anthraquinone, 1,3-dihydroxy-5,6-dimethoxy-2-methoxymethyl-9,10-anthraquinone (9) and a new natural product, 2-hydroxymethyl-1-methoxy-9,10-anthraquinone (8) were isolated from the roots of Prismatomeris malayana together with seven known anthraquinones, tectoquinone (1), 1-hydroxy-2-methyl-9,10-anthraquinone (2), rubiadin (3), rubiadin-1-methyl ether (4), 1,3-dihydroxy-5,6-dimethoxy-2-methyl-9,10-anthraquinone (5), nordamnacanthal (6), and damnacanthal (7). Their structures were determined on the basis of spectroscopic data. Some of the anthraquinones were tested for anticancer, antifungal, and antimalarial activities.     

Polyfluoro-2,3-epoxyalkanes in reactions with thiourea and thiosemicarbazide

Reactions of polyfluoro-2,3-epoxyalkanes with thiourea and thiosemicarbazide afforded 2-amino-4-hydroxy-4,5-di(polyfluoroalkyl)-5-fluoro-l,3-thiazolines and 2-hydrazino-4-hydroxy-4,5-di(polyfluoroalkyl)-5-fluoro-l,3-thiazolines respectively. Unsymmetrical oxiranes furnish mixtures of regioisomeric heterocyclic compounds, and the epoxy cycle is predominantly cleaved from the side of bulkier fluoroalkyl group. The reactions of E-oxiranes are stereospecific and provide 1,3-thiazolines in the E-form. The structure of compounds obtained was confirmed by IR,¹⁹F,¹H, and¹³C NMR spectroscopy, by mass spectra and chemical transformations. E-isomers of 2-amino-4-hydroxy-4,5-bis(trifluoromethyl)-5-fluoro-l,3-thiazoline and 2-amino-5-heptafluoropropyl-4-hydroxy-4-trifluoromethyl-5-fluoro-1,3-thiazoline were subjected to X-ray diffraction analysis. The study was carried out under financial support of the Russian Foundation for Basic Research (grant no. 00-03-332767), and the Foundation for Support of the Leading Scientific Schools (grant no. 00-15-97390).     

红葱中的新化学成分

通过正相和反相硅胶柱色以及高效液相色谱,从红葱60%乙醇提取物中分离得到3个新化合物,利用物理化学和光谱学方法鉴定了其结构,分别为9,9'-二羟基-8,8'-二甲氧基-1,1'-二甲基-1H,1H-['4,4']双[萘并(2,3-c)呋喃]-3,3'-二酮(1),6,8-二羟基-3,4-二甲氧基-1-甲基-蒽醌-2-羧酸甲酯(2),2-乙酰基-3,6,8-三羟基-1-甲基蒽醌(3).这3个化合物均能不同程度地诱导稻瘟霉菌丝变形,其最小变形质量浓度(Mini-mummorphologicaldeformationmassconcentration,MMDC)分别为145.8,50.2和124.8μg/mL.利用MTT法测定了化合物抑制人类红白血细胞株K562细胞生长的活性,化合物2的IC₅₀为49.1μg/mL.     

Anti-stress constituents of Evolvulus alsinoides: an ayurvedic crude drug

Bioactivity-guided purification of n-BuOH soluble fraction from the ethanol extract of Evolvulus alsinoides resulted in the isolation of two new compounds, 2,3,4-trihydroxy-3-methylbutyl 3-[3-hydroxy-4-(2,3,4-trihydroxy-2-methylbutoxy)-phenyl]-2-propenoate (1) and 1,3-di-O-caffeoyl quinic acid methyl ester (2) along with six known compounds, caffeic acid (3), 6-methoxy-7-O-beta-glucopyranoside coumarin (4), 2-C-methyl erythritol (5), kaempferol-7-O-beta-glucopyranoside (6), kaempferol-3-O-beta-glucopyranoside (7) and quecetine-3-O-beta-glucopyranoside (8). The structure of new compounds 1 and 2 were elucidated by spectroscopic analysis, while known compounds were confirmed by direct comparison of their NMR data with those reported in literature. This is the first report of the presence of phenolic constituents in Evolvulus alsinoides. The isolated compounds 1-5 and 8 were screened for anti-stress activity in acute stress induced biochemical changes in adult male Sprague-Dawley rats. Stress exposure has resulted in significant increase of plasma glucose, adrenal gland weight, plasma creatine kinase (CK), and corticosterone levels. Compound 1 displayed most promising antistress effect by normalizing hyperglycemia, plasma corticosterone, CK and adrenal hypertrophy, while compounds 2 and 3 were also effective in normalizing most of these stress parameters, however compounds 4, 5 and 8 were ineffective in normalizing these parameters.