Sodium acetate catalyzed tandem Knoevenagel–Michael multicomponent reaction of aldehydes, 2-pyrazolin-5-ones,and cyano-functionalized C–H acids: Facile and efficient way to 3-(5-hydroxypyrazol-4-yl)-3-aryl-propionitriles

Sodium acetate catalyzed multicomponent reaction of aryl aldehydes, 2-pyrazolin-5-ones, and malononitrile or alkyl cyanoacetates in alcohols results in the formation of substituted 3-(5-hydroxy-3-methylpyrazol-4-yl)-3-arylpropionitriles in 80–99% yields. The developed efficient catalytic approach to the substituted 3-(5-hydroxy-3-methylpyrazol-4-yl)-3-arylpropionitriles – the promising compounds for human cardiovascular diseases therapy and different biomedical applications – is beneficial from the viewpoint of diversity-oriented large-scale processes and represents facile, efficient and environmentally benign synthetic concept for multicomponent reactions strategy.     

Synthesis and Crystal Structure of 2（1-Phenyl-3-methyl-5-chloro-1H-pyrazol-4-yl）-3-（1-naphthoylamido）-4-thiazolidinone

1INTRODUCTIONManypyrazolederivativeshavebeenreportedtoshowvariousbiologicalactivitiestobeusedasbactericide[1],fungicide[2],herbicide[3],insecticide[4]andvirucide[5]agents.Inaddition,4-thiazolidinoneplaysavitalroleowingtoitswiderangeofbiologi-calactivities…     

Synthesis and Crystal Structure of Trans-4-[ （5-（ 2,4-Dichlorophenoxy）-3-methyl-1-phenyl-1H-pyrazol-4-yl）methyleneamino]-1,5-dimethyl-2-phenyl-l,2-dihydropyrazol-3-one

The title compound trans-4-[（5-（2,4-dichlorophenoxy）-3-methyl- 1-phenyl-1H-pyrazol-4-yl）methyleneamino]- 1,5-dimethyl-2-phenyl-1,2-dihydropyrazol-3-one 3 （C28H23Cl2N5O2, Mr = 532.41） has been synthesized and its crystal structure was determined by single-crystal X-ray diffraction analysis. It crystallizes in triclinic, space group P1- with a = 8.9438（4）, b = 11.6065（5）, c = 14.2215（6）A, α = 112.566（1）, β = 92.324（2）, γ = 102.91（1）°, V= 1315.65（10） A^3, Z = 2, Dc = 1.344 g/cm^3,μ（MoKa） = 0.282 mm^-1, λ = 0.71073 A, F（000） = 552, the final R = 0.0587 and wR = 0.1578 for 5071 observed reflections （I 〉 2σ（I））. X-ray analysis reveals that the product is a thermodynamically stable trans isomer. Intra- and intermolecular C（ 12）-H（12）…O（1） and C（28）-H（28）...O（1）# 1 hydrogen bonds were observed in the title compound.     

Synthesis of 4-（2-Phenylhydrazono）-l-（4-phenylthiazol-2-yl）- 1H-pyrazol-5（4H）-one Compounds and Characterization of Their Affinities to Anti-apoptotic Bcl-2 Family Proteins

Organic compounds containing the thiazol-2-yl-lH-pyrazol-5（4H）-one moiety are known to be associated with versatile pharmacological applications. In this study, we describe the methods for preparing 4-（2-phenylhydrazono）- l-（4-phenylthiazol-2-yl）-1H-pyrazol-5（4H）-one compounds. A set of 26 compounds were synthesized with overall yields ranging between 37%-92%. They were tested in a fluorescence polarization-based binding assay against three anti-apoptotic Bcl-2 family proteins, including Bcl-xL, Bcl-2, and Mcl-1. Our results indicate that this class of compounds are not effective inhibitors of these anti-apoptotic Bcl-2 family proteins. Their apoptosis-inducing ef- fects are possibly due to BAX activation as suggested by Gavathiotis et al. in their recent study. However, other possibilities should not be ignored. In addition, a crystal structure obtained by us reveals that the exocyclic double bond in the molecular structure of this class of compounds is in the （Z）-configuration.     

Synthesis and Biological Activities of 4-Arylmethylidene-1-aryl-2-（selenomorpholin-4-yl） -2-imidazolin-5-one

In a search for novel agrochemical with high activity and low toxicity, a series of substituted 4,5-dihydro-imidazol-5-one containing selenomorpholine group were synthesized by a three-step synthetic route starting from 2-azido-3-aryl-acrylic acid ethyl ester. The structures of title compounds were confirmed by ^1H NMR, IR, mass spectroscopy and elemental analysis. The preliminary bioassay against GibbereUa zeae, Fusarium oxysporum, Pellicularia sasakii, Physalospora piricola and Cercospora beticola indicated that most title compounds displayed fungicidal activity at the concentration of 50 ppm and compounds 41,4n, 40 were found to have particularly high activities against Physalospora piricola. A further in vivo test showed that compounds 41, 4n and 4o possessed better fungicidal activity against Physalospora piricola at a concentration of 100 ppm than Carbendazim. To our knowledge, this is first report that 4,5-dihy-dro-imidazol-5-one containing selenomorpholine group display fungicidal activity against Physalospora piricola.     

Synthesis and Antibacterial Activities of 4-Amino-3-(1-aryl-5-methyl-1,2,3-triazol-4-yl)-5-mercapto-1,2,4-triazoles/2-Amino-5-(1-aryl-5-methyl-1,2,3-triazol-4-yl)-1,3,4-thiadiazoles and Their Derivatives

ＩｎｔｒｏｄｕｃｔｉｏｎＳｃｈｉｆｆｂａｓｅｓ ,ａｍｉｄｅｓ ,ｉｍｉｄａｚｏｌｏ[2 ,1 ｂ] 1,3,4 ｔｈｉａｄｉａｚｏｌｅｓ,ａｎｄ 7Ｈ ｓ ｔｒｉａｚｏｌｏ[3,4 ｂ] 1,3,4 ｔｈｉａｄｉ ａｚｉｎｅｓｃｏｎｔａｉｎｉｎｇｈｅｔｅｒｏｃｙｃｌｅｓｈａｖｅｂｅｅｎａｔｔｒａｃｔｉｎｇｍｕｃｈａｔｔｅｎｔｉｏｎａｓｐｏｔｅｎｔｉａｌａｎｔｉｆｕｎｇａｌａｇｅｎｔｓ .1 51,2 ,3 ｔｒｉａ ｚｏｌｅ ,6 7ｍｅｒｃａｐｔｏ 1,2 ,4 ｔｒｉａｚｏｌｅ ,81,3,4 ｔｈｉａｄｉａｚｏｌｅ9 10ａｎｄｔｈｅｉｒｒｅｌａｔｅｄｃｏ…     

Utility of 2-(5-methyl-1-phenyl-1H-pyrazol-4-yl)-2-oxo-N′-phenylaceto-hydrazonoyl bromide as precursor for synthesis of new functionalized heterocycles

2-(5-Methyl-1-phenyl-1H-pyrazol-4-yl)-2-oxo-N′-phenylaceto-hydrazonoyl bromide was synthesized and used as precursor for synthesis of some new 1,3,4-thiadiazoles, pyrrolo[3,4-c]pyrazoles, and 1,2,4-triazolo[4,3-a]pyrimidines. The mechanisms that account for formation of products were discussed. Also, the structures of all the newly synthesized products were confirmed based on elemental analysis, spectral data and by alternative methods.     

A Comparative Study of the Solvent Extraction of the Trivalent Elements of the Lanthanoid Series with Thenoyltrifluoroacetone and 4-Benzoyl-3-methyl-1-phenyl-2-pyrazolin-5-one Using Diphenylsulphoxide as Synergistic Agent

Solvent extraction of the trivalent lanthanoids (except Pm) with mixtures of a chelating extractant, either 1-(2-thienyl)-4,4,4-trifluoro-1,3-butanedione (thenoyltrifluoro-acetone, HTTA) or 4-benzoyl-3-methyl-1-phenyl-2-pyrazolin-5-one (HP) and diphenylsulphoxide (S), from chloride solutions has been studied in C₆H₆. It was found that, in the presence of a diphenylsulfoxide, the lanthanoids were extracted as Ln(TTA)₃⋅S and LnP₃⋅S. The extraction data have been analyzed by a graphical method taking into account aqueous phase speciation and the plausible complex extracted into the organic phase. On the basis of the experimental data, values of the equilibrium constants have been calculated. Positive values of the synergistic coefficients show that all lanthanoids are extracted synergistically upon the addition of compound S to the chelating extractant. The separation of the lanthanoids with synergistic mixtures was, in most cases, a little higher than those obtained using HTTA or HP alone.     

Synthesis and Crystal Structure of 4-（4-Chlorophenyl）-6-methyl-5-methoxy-caronyl-3,4-dihydropyrimidin-2（H）-one

1 INTRODUCTION Biginelli reaction is a three-component condensa-tion of ethyl acetoacetate, benzaldehyde and urea forthe synthesis of 3,4-dihydropyrimidin-2(1H)-ones(Scheme 1). The reaction can be carried out in aone-pot fashion in alcohol solution in t…     

Catalyst free Michael addition of 3-methyl-2-pyrazolin-5-one to β-nitrostyrenes ‘on water’: a green protocol for facile synthesis of 4-(1-aryl-2-nitroethyl)-3-methyl-1H-pyrazol-5-ol

A highly efficient and green protocol has been developed for the synthesis of 4-(1-aryl-2-nitroethyl)-3-methyl-1H-pyrazol-5-ol via Michael addition of 3-methyl-2-pyrazolin-5-one with β-nitrostyrenes under catalyst free conditions on aqueous medium. A series of 4-(1-aryl-2-nitroethyl)-3-methyl-1H-pyrazol-5-ols have been synthesized with good to excellent yield. C-alkylated product was observed exclusively with 3-methyl-2-pyrazolin-5-one without formation of N-alkylated product.     

L-Proline catalyzed one-pot multi-component synthesis of 2-（1,3-diphenyl-1H-pyrazol-4-yl）quinazolin-4（3H）-one derivatives and their biological studies

A new series of quinazolin-4（3H）-one derivatives containing a（1 3-diphenyl-1H-pyrazol-4-yl） core with substituents at the 2-position and aromatic or heteroaromatic substituents at the 3-position were synthesized using an L-proline catalyzed one-pot multi-component reaction approach.All the synthesized compounds were characterized and screened for their antimicrobial,antifungal and anti-tubercular activities.     

Synthesis of 5-Substituted-3-[(2’R,4’R)-4’-Hydroxy-2’-hydroxymethyltetrahydrofuran-4’-yl]-1,2,4-oxadiazoles and Their Epimers

The syntheses of 5-substituted-3-[( 2' R, 4' R)-4 ' -hydroxy-2 ' -hydroxymethyltetra-hydrofuran-4' -yl]D-1 ,2, 4-oxadiazoles and their epimers were accomplished with the aid of th construction of 1,2, 4-oxadiazoles by condensation of O-acylated cyanohydrins with hydroxylamine via intramolecular transacylation and subsequent cyclization.     

Synthesis,Crystal Structure and Biological Activity of N-tert-butyl-N-(4-methyl-1,2,3-thiadiazole)-5-yl-N’-(4-methyl-1,2,3-thiadiazole)-5-formyl-N’-3,5-dichloropyridin-2-yl-diacylhydrazine

The title compound N-tert-butyl-N-(4-methyl-1,2,3-thiadiazole)-5-yl-N'-(4-me-thyl-1,2,3-thiadiazole)-5-formyl-N'-3,5-dichloropyrid-2-yl-diacylhydrazines (C18H17Cl2N7O3S2, Mr = 514.41) has been synthesized by the reaction of N-tert-butyl-N'-3,6-dichloropyridine-2-formyl hydrazine with 4-methyl-1,2,3-thiadiazole-5-carbonyl chloride and triethylamine, and its structure was characterized by 1H NMR, HR MS, and single-crystal X-ray diffraction. The crystal of the title compound belongs to monoclinic, space group C2/c with a = 27.726(8), b = 11.045(3), c = 14.507(4), β = 96.758(4)°, Z = 8, V = 4412(2) 3, Dc = 1.549 g/cm3, μ = 0.521 mm-1, F(000) = 2112, R = 0.0405 and wR = 0.1153. X-ray analysis indicates that all rings are non-planar in this molecule. The bioassay results indicate that both the title compound and the positive control RH-5992 have weak fungicide activities, while the title compound has good insecticidal activity against Plutella xylostella L. and no insecticidal activity against Culex pipiens pallens.     

Synthesis of 4′-[3-methyl-5-thioxo-1H-1,2,4-triazol-4(5H)-yl]-2′,5′-diphenyl-2′,4′-dihydro spiro[indolin-3,3′[1,2,4]triazol]-2-one derivatives

In this paper 1,3-dipolar cycloaddition reaction has been studied. An efficient synthesis of 4′-[3-methyl-5-thioxo-1H-1,2,4-triazol-4(5H)-yl]-2′,5′-diphenyl-2′,4′-dihydro spiro(indolin-3,3′[1,2,4]triazol)-2-one derivatives using triethylamine in MeCN at room temperature is reported. The structures of the obtained compounds were confirmed by means of elemental analysis, MS and spectral (IR, ¹H, and ¹³C NMR) methods.     

Synthesis and Crystal Structure of 4-Bromo-5-ethoxy-3-methyl-5- （naphthalen- 1-yl）- 1-tosyl- 1H-pyrrol-2（5H）- one

The title compound 4-bromo-5-ethoxy-3-methyl-5-(naphthalen-1-yl)-1-tosyl-1H- pyrrol-2(5H)-one 1 (C24H22BrNO4S, Mr = 500.40) has been synthesized and its crystal structure was determined by single-crystal X-ray diffraction analysis. It crystallizes in monoclinic, space group P21/n with a = 8.8562(15), b = 18.118(3), c = 14.055(2) , β = 99.855(3)o, V = 2221.9(6) 3, Z = 4, Dc = 1.496 g/cm3, μ = 1.975 mm-1, λ = 0.71073 , F(000) = 1024, R = 0.0607 and wR = 0.1371.     

Synthesis,Crystal Structure and Recognition Properties of 2-（5-（4-Chlorophenyl）-1-phenyl-4,5-dihydro-1H-pyrazol-3-yl）pyridine

The title compound 2-(5-(4-chlorophenyl)-1-phenyl-4,5-dihydro-1H-pyrazol-3-yl)- pyridine(C20H16ClN3, Mr = 333.81) has been synthesized and its crystal structure was determined by single-crystal X-ray diffraction. The crystal belongs to monoclinic, space group P21/n with a = 10.9925(12), b = 11.0378(12), c = 14.2751(18) , β = 98.074(11)°, V = 1714.9(3)3, Z = 4, Dc = 1.293 g/cm3, μ(MoKα) = 0.228 mm-1, F(000) = 696, the final R = 0.0521 and wR = 0.1349 for 3495 observed reflections with I 2σ(I). Intermolecular C–H...π interactions and π-π stacking interactions stabilize the crystal structure. The binding study by fluorescence spectroscope titration showed that the title compound can selectively recognize Fe3+ in THF solution with fluorescence quenching.     

Synthesis,Characterization and X-ray Crystal Structure of 4-Fluoro-N-（2-methyl-5-（（2-（p-tolyloxy）acetamido）- methyl）pyrimidin-4-yl）benzamide

A new crystal of 4-fluoro-N-(2-methyl-5-((2-(p-tolyloxy)acetamido)methyl)pyrimi- din-4-yl)benzamide has been prepared at room temperature and characterized by 1H NMR, 13C- NMR, IR, MS, elemental analysis and X-ray single-crystal determination. The compound crystallizes in monoclinic, space group P21 /c with a = 17.226(5), b = 13.934(4), c = 17.262(5), μ= 92.180(5)°, V = 4140(2) ?3, Dc = 1.311 g/cm3, Z = 8, F(000) = 1712 and ??= 0.095 mm-1. The molecular packing in the crystal is the result of N–H···O hydrogen bonds.     

A new route for the synthesis of substituted 5-amino-4-cyanoimidazol-2-ones – precursors for the preparation of 3,6,7,9-tetrahydro-8H-purin-8-ones derivatives

5-Alkyl(aryl)amino-4-cyanoimidazol-2-ones were obtained on the basis of 2-alkoxycarbonylamino-3,3-dichloroacrylonitriles. They were then used for the synthesis of derivatives of 3,6,7,9-tetrahydro-8H-purin-8-ones.