Synthesis of 4,4′-Bis[4-(2,5-dioxo-2,5-dihydro-1H-pyrroll-1-yl)-phenylcarbonylamino]-3,3′-dichlorodiphenylmethane and 1,4-Bis{2-[4-(2,5-dioxo-2,5-dihydro-1H-pyrrol-1-yl)-phenylcarbonyloxy]ethoxy}benzene

Russian Journal of Organic Chemistry - 4,4′-Bis[4-(2,5-dioxo-2,5-dihydro-1H-pyrrol-1-yl)phenylcarbonylamino]-3,3′-dichlorodiphenylme-thane has been obtained by the reaction of...     

Ultrasound-Mediated Synthesis of 3,4-Dihydropyrimidin-2-(1H)-Ones (or Thiones) with NaHSO4·H2O

Abstract

A fast and efficient Biginelli synthesis of 3,4-dihydropyrimidin-2-(1H)-ones (or thiones) by the reaction of aromatic aldehydes, β-dicarbonyls, and urea/thiourea using NaHSO₄·H₂O/ultrasound system is presented. The reactions were carried out in refluxing n-hexane/CH₃CN (2.5:0.5 mL) to afford the products in excellent yields.     

2,4-Bis{[6-(2,2-dimethylpropyl)-3-ethyl-1,3-benzothiazol-2(3H)-yl­idene]methyl}cyclobutenediylium-1,3-­diolate

The title compound, C₃₄H₄₀N₂O₂S₂, adopts a trans conformation. The four conjugated Csp²—Csp² single and double bonds of the polymethinic moiety, which bridges both heterocyclic end groups and the central four-membered ring, display nearly equal bond lengths. The mol­ecule is nearly planar, with interplanar angles between the benzo­thia­zole end groups and the central four-membered ring of 6.9 (1) and 7.7 (1)°; the angle between the heterocyclic systems is 1.8 (1)°. The crystal packing involves π-stacking effects, with intermolecular C⃛C distances varying from 3.755 (3) to 3.991 (3) Å.     

Highly ordered thin films of 5,5'-bis(3'-fluoro-biphenyl-4-yl)-2,2' : 5',2'-terthiophene with two meso-phases

The growth process and phase state of 5,5'-bis(3'-fluoro-biphenyl-4-yl)-2,2'?:?5',2'- terthiophene (m-F2BP3T) thin films were investigated by atomic force microscopy (AFM), in-plane and out-of-plane X-ray diffraction (XRD), and selected area electron diffraction (SAED). Two meso-phases (thin film phases) of m-F2BP3T films on SiO(2) surface were obtained in the early stages. The m-F2BP3T films initially exhibited two-dimensional (2D) layers (≤4 ML) followed by three-dimensional (3D) island growth. The film structure evolved two thin film phases in the first four layers and the bulk phase was formed from the fifth layer, which occurred concomitantly with the change of the growth mode. Moreover, the variation of weak epitaxy growth behavior of ZnPc from 2D to 3D growth further reflects that the phase state of the first three layers is different from that of the fourth layer, in spite of ZnPc crystals showing just one orientation corresponding to commensurate epitaxy. The novel phase behavior is closely related to the synergistic effects of the outstanding soft matter properties, limited elasticity of organic molecules, and strain originating from the SiO(2) substrate. This study investigates novel phase behavior in organic thin films and provides significant insight into the mechanism of the phase transition.     

Tansition metal complexes with 2-(1-(carboxymethyl)-2-methyl-1H-benzimidazol-3-ium-3-yl)acetate (HL): Synthesis and crystal structure of [Co(L)2(H2O)4] · 6H2O and [Cu(L)2(H2O)2] · 4H2O

Transition metal complexes of 2-(1-(carboxymethyl)-2-methyl-1H-benzimidazol-3-ium-3-yl)acetate (HL), namely [Co(L)₂(H₂O)₄] · 6H₂O (I) and [Cu(L)₂(H₂O)₂] · 4H₂O (II), have been synthesized by a hydrothermal procedure and characterized by X-ray crystallography, CIF files CCDC nos. 1007524 (I), 1007525 (II). Both I and II are mononuclear molecules. In I, the Co²⁺ ion is in octahedral coordiantion environment and surrounded by four O atoms from water molecules and two carboxylate O atoms of two deprotonated ligand (L^?) occupied six culmination. While in II, the Cu²⁺ ion is located in a square-planar geometry, bounded to two aqua O atoms and two carboxylate O atoms from L^?.     

Differentiation of Constitutional Isomer of 2,2a,3,4-Tetrahydro- 4-methyl-2a-phenyl-2-(thiophen-2-yl)-1H-azeto[2,1-d][1,5] benzothiazepin-1-one-5-oxide and Fragmentations of 2,3-Dihydro- 2,4-diphenyl-1,5-benzothiazepine-1-oxide/-1,1-dioxide

Introduction Mostimportantantibioticspossessarepresen- tativestructureofaβ-lactamfusedfive-orsix- memberedheterocyclicringcontainingnitrogenand sulfuratoms.Forinstance,theeffectiveantibi- otics,penicillin,penamandpenem,havefusedthi- azolidine-β-lactam,andtheeffectiveantibiotics, cephalosporinandcephem,arefuseddihydroth- iazine-β-lactams[1].Recently,someβ-lactam derivativeshavealsobeenrecognizedasthein- hibitorsofhumanleukocytaseelastase[2]andserine protease[3].Thesynthesisofbicyclicβ-lact…     

Crystal Structure of CH(3,5-Me2-4-EtPz)2W(CO)3SnPh3·0.25C6H6 (Pz = Pyrazol-1-yl)

The reaction of triphenylstannyl-bis(3,5-dimethyl-4-ethylpyrazol-1-yl)methane with W(CO)5THF yields the title compound (C37.5H39.5N4O3SnW, Mr = 896.79) which is of triclinic,space group P1 with a = 9.755(3), b = 13.696(4), c = 14.359(5) A, α = 96.202(7), β= 93.313(6), γ=94.845(6)°, V = 1896(1) A3, Z = 2, Dc = 1.571 g/cm3, λ(MoKα) = 0.71073 A, μ= 3.728 mm-1,F(000) = 881, R = 0.0491 and wR = 0.0856 for 4242 observed reflections (I≥2σ(I)). The crystalstructural analysis indicates that bis(3,5-dimethyl-4-ethylpyrazol-1-yl)methide acts as a tridentate monoanionic K3-[N,C,N] chelating ligand, and four-membered metallacycles are found in this heterodinuclear complex.     

Synthesis of new pyrido[2′,3′:3,4]pyrazolo[5,1-c]-[1,2,4]triazin-4(6H)-one derivatives

Russian Chemical Bulletin - New pyrido[2′,3′:3,4]pyrazolo[5,1-c][1,2,4]triazin-4(6H)-one derivatives were synthesized from accessible 1,2,4-triazine and pyrazolo[5,1-c][1,2,4]triazine...     

A new convenient four-component synthesis of 6-amino-2H, 4H-pyrano[2,3-c]pyrazole-5-carbonitriles and one-pot synthesis of 6 ′-amino-5-cyano-1,2-dihydrospiro-[(3H)-indole-3,4 ′-(4 ′H)-pyrano[2,3-c]pyrazol]-2-ones

A new convenient method for the synthesis of 6-amino-2H,4H-pyrano[2,3-c]pyrazole-5-carbonitriles, namely, four-component condensation of carbonyl compounds (aromatic aldehydes, heterocyclic ketones), malononitrile, β-keto esters, and hydrazine hydrate in ethanol in the presence of triethylamine as a catalyst, which occurs selectively, is developed. One-pot two-step modification of this method is proposed for the synthesis of spiro[(3 H)-indole-3,4 ′-(4′H)-pyrano[2,3-c]pyrazol]-2-ones.     

Synthesis,Reactions, and Antiviral Activity of 1-(1H-Pyrazolo[3,4-b]pyridin-5-yl)ethanone and Pyrido[2′,3′:3,4]pyrazolo[5,1-c][1,2,4]triazine Derivatives

1-(3-Amino-6-methyl-4-pyridin-3-yl-1H-pyrazolo[3,4-b]pyridin-5-yl)ethanone (3) was obtained in very pure state and used as a good starting material for the present study. It diazotized to give the corresponding diazonium salt 9 and also reacted with phenyl isothiocyanate to give the corresponding thiourea derivative 4. Compound 4 was used for the preparation of thiazole derivatives 5–8 via the reaction with active halogen-containing compounds. On the other hand, compound 9 coupled with several active –CH₂- containing compounds to afford the corresponding triazine derivatives 10–17. Considering the data from IR, ¹ H NMR, mass spectra, and elemental analyses, the chemical structures of the newly synthesized heterocyclic compounds were elucidated. Cytotoxicity, anti-HSV1, and anti-HAV-MBB activity were evaluated for the newly synthesized heterocyclic compounds.     

C—H…Cl Hydrogen Bond and π-π Interaction Based Two 3D Supramolecular Architectures of Cu(II) and Co(II) Complexes with Chiral 1,2-Bis(benzimidazol-2-yl) ethane Ligand Containing 2D Grids

合成了两个新的配合物CuLCl₂•2EtOH(1) 和CoLCl₂ (2) [L是( S , S )－1,2－二N－甲基苯并咪唑－1,2－二甲氧基－乙烷],并通过单晶X衍射确定它们的结构。配合物1中,L作为三齿[N, N, O]配体,而配合物2 中,L作为二齿[N, N]配体。这两个配合物共同的结构特点都是通过分子内氢键形成2维的格子结构,然后通过分子间的C－H···Cl型氢键和π–π堆积作用形成3维结构。     

Synthesis and Crystal Structure of a Heterotrinuclear Compound [PdCu2(tdt)((μ-dppm)2(MeCN)4]-(ClO4)2·2/3H2O (tdt = 3,4-Toluenedithiolate,dppm = Bis(diphenylphosphino)methane)

The heterotrinuclear compound [PdCu2(tdt)((-dppm)2(MeCN)4](ClO4)2(2/3H2O 1 (tdt = 3,4-toluenedithiolate, dppm = bis(diphenylphosphino)methane) has been prepared and characterized by X-ray structural analysis. Compound 1 crystallizes in trigonal system, space group R3c with a = b = 34.4275(3), c = 32.6700(5) (A), V = 33534.4(7) (A)3, Mr = 1527.21, Z = 18, Dc = 1.361 g/cm3, F(000) = 13974, μ(MoKα) = 1.069 mm-1, the final R = 0.0703 and wR = 0.1389 for 8375 observed reflections with I>2σ(I). The dithiolate tdt displays a chelating and bridging coordination mode, which chelates a PdII and bridges two Cu Ⅰ atoms. The PdⅡ center is located in an approximate square-planar environment with S2P2 donors, and each CuⅠ center exhibits a tetrahedral geometry.     

Synthesis and mononuclear complexes of the bis-bidentate ligand 2,5-di(2-pyridyl)-1,3,4-thiadiazole (dptd): spin crossover in [Fe(II)(dptd)2(NCSe)2] and [Fe(II)(dptd)2(NCBH3)2]·H2O

A simple and convenient protocol for the synthesis of the ligand 2,5-di(2-pyridyl)-1,3,4-thiadiazole (dptd) has been developed. Five new 2?:?1-type iron(II), cobalt(II), nickel(II) and copper(II) complexes have been prepared and structurally characterised, all of which feature the mononuclear trans-(N',N(1))(2) coordination mode. Spin crossover behaviour has been found for [Fe(II)(dptd)(2)(NCSe)(2)] (2) and [Fe(II)(dptd)(2)(NCBH(3))(2)]·H(2)O (3·H(2)O) with T(1/2) = 192 and 285 K, respectively, reflecting the increasing ligand field strength of the respective co-ligands and showing that the [Fe(II)(dptd)(2)L(2)] unit is suitable for the investigation of the co-ligand field effects on T(1/2). In addition, the 3?:?1-type low-spin complexes [Fe(II)(dptd)(3)]{B(CN)(4)}(2)·3MeOH (4·3MeOH) and [Fe(II)(dptd)(3)](OTf)(2)·1.25DCM·0.5H(2)O (5·1.25DCM·0.5H(2)O) have been studied by X-ray diffraction and have been found to exist exclusively as the mer or fac stereoisomer, respectively, in the solid state. In MeCN-d(3) solution the latter two complexes, as well as [Fe(II)(dptd)(3)](ClO(4))(2)·H(2)O (6·H(2)O), show counterion-independent stereoisomerisation, each yielding a ca. 3?:?1 mixture of mer and fac stereoisomers as identified by (1)H NMR spectroscopy.     

Domino reactions in the synthesis of benzothieno[2,3-c]pyridines. New one-pot method of preparing 2-([1]benzothieno-[2,3-c]pyridin-1-yl)benzoic acids and 8,13b-dihydro[1]benzothieno[2',3':3,4]pyrido-[2,1-a]isoindol-5(7?H)-ones

A series of previously unknown 2-([1]benzothieno[2,3-c]pyridin-1-yl)benzoic acids and 8,13b-dihydro-[1]benzothieno[2',3':3,4]pyrido[2,1-a]isoindol-5(7 H)-ones has been synthesized using domino reactions, taking place at the cyclization of 2-[3-oxo-4-(phenylsulfanyl)butyl]-1,3-isoindolinediones in polyphosphoric acid.     

Formation of N,N′-Di(5-alkoxycarbonyl-5-methyl-2-oxo-1-phenyl-2,5-dihydro-1H-pyrrol-3-yl)-N,N′-diphenyloxalylamides in the synthesis of alkyl 4-methyl-2,3,6-trioxo-1,5-diphenyl-1,2,3,4,5,6-hexahydropyrrolo[3,4-b]pyrrole-4-carboxylates

Russian Journal of Organic Chemistry -     

Spectral and thermochemical properties of the [Na(H2O)4] [EuL4]·0.775CH2Cl2 complex,HL = 1,3-bis(1,3-dimethyl-1H-pyrazol-4-yl)-1,3-propanedione

Reaction of Eu(NO₃)₃·6H₂O with 1,3-bis(1,3-dimethyl-1H-pyrazol-4-yl)-1,3-propanedione (HL) in the presence of NaOH affords the complex compound [Na(H₂O)₄] [EuL₄]·0.775CH₂Cl₂ (I). The spectral (UV, IR, ¹H NMR spectroscopy), and thermo-luminescent (TG-DSC-MS) properties of the complex I, as well as its fragmentation at the laser desorption ionization (LDI-MS) were studied.     

ZrOCl2 · 8H2O: An Efficient,Ecofriendly, and Recyclable Catalyst for Ultrasound-Accelerated,One-Pot,Solvent-Free Synthesis of 8-Aryl-7,8-dihydro-[1,3]dioxolo[4,5-g]quinolin-6-(5H)-one and 4-Aryl-3,4-dihydroquinolin-2(1 H)-one Derivatives

A convenient, one-pot, solvent-free reaction of amines, aromatic aldehydes, and Meldrum's acid to form 8-aryl-7,8-dihydro-[1,3]dioxolo[4,5-g]quinolin-6-(5H)-one and 4-aryl-3,4-dihydroquinolin-2-(1H)-one in the presence of 10 mol% ZrOCl₂.8H₂O under ultrasonic irradiation is described. This new protocol offers several advantages including low catalyst loading, clean reaction, easy workup, use of recyclable and ecofriendly catalyst, short reaction times, good yields, and solvent-free conditions.

Supplemental materials are available for this article. Go to the publisher's online edition of Synthetic Communications® to view the free supplemental file.     

Weak but strong: role of weak C–H···X (X=O,N) hydrogen bonds in organization of crystals of (1S,2S,3S,4R,5R,8S)-diethyl 2,4-dicyano-3-(furan-2-yl)-8-morpholino-6-oxobicyclo[3.2.1]octane-2,4-dicarboxylate

Structural Chemistry - An X-ray diffraction study of (1S,2S,3S,4R,5R,8S)-diethyl 2,4-dicyano-3-(furan-2-yl)-8-morpholino-6-oxobicyclo[3.2.1]octane-2,4-dicarboxylate reveals the absence of strong...     

Large 1,3,5-triazine-based ligands coordinating transition metal ions: syntheses and structures of the ligands and the ball shaped nanometer-scaled Co complex [Co(2,4-R-6-R′-1,3,5-triazine)2](Br1.7(OH)0.3) · 4.8H2O {R = bis(2-diphenylmethylene) hydrazinyl; R′ = piperidin-1-yl}

Two new, large 1,3,5-triazine-based ligands with only N-donor functions were synthesized as well as the Co(II) salt [Co(DHPTBenz)₂](Br_1.7(OH)_0.3) · 4.8H₂O (DHPTBenz = 2,4-bis-(2-diphenylmethylene)-hydrazinyl-6-piperidin-1-yl-1,3,5-triazine). Single crystal X-ray structures of the Co(II) complex, DHPTBenz, and 2,4-dichloro-6-(piperidin-1-yl)-1,3,5-triazine (DCPT) have been determined. The last compound was used as starting material for the tridentate DHPTBenz ligand. Spectroscopic data of the ligand and the starting materials are reported. The Co(II) ion in the complex is distorted octahedrally coordinated by six N atoms of two DHPTBenz ligands. One N atom of the triazine ring of each ligand bonds axially with short distances of 1.953(3) Å and 1.954(3) Å, respectively, whereas two of the hydrazine-N atoms of two ligands form the equatorial plane with an average Co–N bond distance of 2.313 Å. The complex cation has a slightly elongated, nanometer-scaled ball shape with the longest diameter of 1.82 nm.     

Five-membered 2,3-dioxo heterocycles: LX. Reaction of 3-aroyl-1H-pyrrolo[2,1-c][1,4]benzoxazine-1,2,4-triones with cyclic enehydrazino ketones. Crystalline and molecular structure of N-[3′-benzoyl-4′-hydroxy-1′-(2-hydroxyphenyl)-6, 6-dimethyl-2,4,5′-trioxo-1′,4,5,5′,6,7-hexahydrospiro[indole-3,2′-pyrrol]-1(2H)-yl]-3-nitrobenzamide

3-Aroyl-1H-pyrrolo[2,1-c][1,4]benzoxazine-1,2,4-triones react with N′-(5,5-dimethyl-3-oxocyclohex-1-en-1-yl)benzohydrazides to give the corresponding N-[3′-aroyl-4′-hydroxy-1′-(2-hydroxyphenyl)-6,6-dimethyl-2,4,5′-trioxo-1′,4,5,5′,6,7-hexahydrospiro[indole-3,2′-pyrrol]-1(2H)-yl]benzamides. The molecular and crystalline structure of one of the products, N-[3′-benzoyl-4′-hydroxy-1′-(2-hydroxyphenyl)-6,6-dimethyl-2,4,5′-trioxo-1′,4,5,5′,6,7-hexahydrospiro[indole-3,2′-pyrrol]-1(2H)-yl]-3-nitrobenzamide, was determined by X-ray analysis.