Synthesis,structure, and complexing ability of fluoroalkyl-containing 2,2′-(biphenyl-4,4′-diyldihydrazono)bis(1,3-dicarbonyl) compounds

New fluoroalkyl-containing 2,2′-(biphenyl-4,4′-diyldihydrazono)bis(1,3-diketones) and 2,2′-(biphenyl-4,4′-diyldihydrazono)bis(3-oxopropionates) were synthesized by azo coupling of the corresponding 1,3-dicarbonyl compounds with biphenyl-4,4′-bis(diazonium) dichloride. Complexing ability of the obtained bis-hydrazones was studied, and new coordination compounds of the general formula M₂L₂ [where M = Ni(II), Cu(II); L = fluoroalkyl-containing 2,2′-(biphenyl-4,4′-diyldihydrazono)bis(1,3-diketone)] were obtained.     

Synthesis,Characterization, and in vitro Antibacterial Evaluation of Barbituric Acid Derivatives

Russian Journal of Organic Chemistry - A series of 5,5′-(arylmethylene)bis[1,3-dimethyl-6-(methylamino)pyrimidine-2,4(1H,3H)-diones] have been synthesized by 2: 1 condensation of...     

Synthesis of polyurethanes containing nucleic acid base derivatives as grafted pendants and their precursor amino functionalized polyurethane

A new route to polyurethanes containing nucleic acid base derivatives as grafted pendants have been established. The method is based on the grafting of 2-(thymin-1-yl)propionic acid (TPA) or 2-(adenin-9-yl)propionic acid (APA) onto amino functionalized polyurethane, poly[2-amino-2-methyl-1,3-propylene methylene bis(4-phenyl carbamate)] (PU-NH₂, IX ) at the primary amino group by the N-hydroxy compound of active ester technique. Two novel polymer models of polynucleic acid—poly[2-(2′-(thymin-1′-yl) propionamido)-2-methyl-1,3-propylene methylene bis(4-phenylcarbamate)] (PU–NHT, X ) and poly[2-(2′-(adenin-9′-yl)propionamido)-2-methyl-1,3-propylene methylene bis(4-phenylcarbamate)] (PU–NHA-40, XI )—were obtained. The amino functional polyurethane was prepared by the following three step reactions; (1) Selective N-protection of N-benzyloxycarbonyloxy-5-norbornene-2,3-dicarbonimide (CbzONB) with 2-amino-2-methyl-1,3-propanediol gave the N-protecting diol monomer 2-benzyloxycarbonylamino-2-methyl-1,3-propanediol (CbzAMP); (2) N-Protecting polurethane poly(2-benzyloxycarbonylamino-2-methyl-methyl-1,3) propylene methylene bis(4-phenylcarbamate) (PU–NHCbz, VIII ) was obtained by the polyaddition of 4,4′-diphenyl-methane diisocyanate (MDI) with CbzAMP. (3) Deprotection of PU–NHCbz produced amino polyurethane PU-NH₂. Prior to polymer synthesis, the amidation of APA with 3-aminoheptane or diethylamine were carried out as a model reaction study and the related monomer model compounds were prepared by the same methods.     

Synthesis,characterization, optical and anti-bacterial properties of benzothiazole Schiff bases and their lanthanide (III) complexes

Two new Schiff base ligands comprising benzothiazole derivatives, namely (N,N′,E,N,N′E)-N,N′-(1,3-phenylenebis(methanylylidene))bis(5-nitrobenzo[d]thiazoL2-amine (L1) and (N,N′,E,N,N′E)-N,N′-(1,3-phenylene-bis(methanylylidene))bis(5-methylthiazo-L2-amine (L2), have been synthesized and thoroughly characterized using FTIR, ¹H NMR, mass UV/vis and fluorescence spectral techniques. Further, L1 and L2 lead to the formation of lanthanide complexes 1–6 with Ce(III), Nd(III), and Pr(III) ions in 1:2 (metal:ligand) stoichiometry. UV/vis spectra of L1, L2 and 1–6 exhibit characteristic ligand centered absorptions in the range of 230–350 nm. Besides, both ligands and complexes show significant emissions and good anti-bacterial activity against pathogenic bacteria. Ligands and complexes display anti-bacterial activity against bacteria Staphylococcus aureus (S. aureus) (MTCC 1144) causing skin infection and food poisoning and pimple-causing bacteria propionic bacteria acnes (P. acnes) (MTCC 1951).     

Synthesis,characterization, and immobilization of nickel(II) tetradentate Schiff-base complexes on clay as heterogeneous catalysts for the oxidation of cyclooctene

Nickel(II) tetradentate Schiff-base complexes of N,N′-(bis(pyridin-2-yl)formylidene)ethane-1,2-diamine (L1), N,N′-(bis(pyridin-2-yl)formylidene)cyclohexane-1,2-diamine (L2), N,N′-(bis(pyridin-2-yl)formylidene)benzene-1,2-diamine (L3), N,N′-(bis(pyridin-2-yl)formylidene)meso-stilben-1,2-diamine (L4), and N,N′-(bis(pyridin-2-yl)formylidene)propane-1,3-diamine (L5) were synthesized, characterized, and immobilized on sodium montmorillonite. The complexes were characterized by IR spectroscopy, diffuse reflectance spectra (DRS), and atomic absorption spectroscopy (AAS). IR and DRS data of the heterogeneous catalysts show that the Ni(II) complexes were physically entrapped within the sodium montmorillonite clay. The supported complexes show good catalytic activity for the epoxidation of cyclooctene using tert-butylhydroperoxide (TBHP) as oxygen source in acetonitrile. The Ni-catalyzed oxidation proceeds with 62.3% selectivity for epoxidation with 69% conversion for supported [Ni(L5)].     

Strontium- und Barium-bis[N,N′ -bis(trimethylsilyl)benzamidinate] aus der Additionsreaktion der Erdalkalimetall-bis[bis(trimethylsilyl)amide] mit Benzonitril

Strontium and Barium Bis[N,N′-bis(trimethylsilyl)benzamidinates] from the Addition Reaction of the Alkaline Earth Metal Bis[bis(trimethylsilyl)amides] and Benzonitrile The reaction of strontium bis[bis trimethylsilyl)amide] with benzonitrile yields strontium bis[N,N′- bis(trimethylsilyl)benzamidinate] · 2THF, which crystallizes in the orthorhombic space group Pbcn (a = 1845.4(3); b = 131 1,3(2); c = 1838,(3) pm; Z = 4). During the similar reaction of barium bis[bis(trimethylsilyl)amide] with benzonitrile the benzonitrile adduct barium bis[N,N′-bis(trimethylsilyl)benzamidinate] · 2 THF · benzonitrile is formed. After the addition of diphenylacetylene to the strontium di(benzamidinate) in diglyme a clathrate of the composition strontium bis[N,N′-bis(trimethylsilyl)benzamidinate] · diglyme · diphenylacetylene could be isolated; the spectroscopic data as well as the X-ray structure (monoclinic, C2/c, a = 1492.2(2); b = 1539.1(2); c = 2337.8(3)pm; Z = 4) confirm the isolated appearance of the acetylene molecule without interaction to the metal center in solution and in the solid state, respectively.     

Synthesis,Structural Characterization,Molecular Docking,Thermal Studies,and Antimicrobial Activity of Ni(II) Binuclear Complexes

Russian Journal of General Chemistry - A new hexadentate ligand, 3,3′-{(1E,1′E)-[(4-chloro-1,2-phenylene)bis(azaneylylidene)]bis(methaneylylidene)}bis(2-hydroxybenzoic acid) (H4L) was...     

Synthesis and Pharmacological Evaluation of Some Novel Imidazo[2,1-b][1,3,4]thiadiazole Derivatives

Synthesis of bis‐1,3‐{6′‐arylimidazo[2,1‐b][1,3,4]thiadiazol‐2‐yl}‐1,2,2‐trimethylcyclopentane ( 3 ), bis‐1,3‐{thiadiazolo[2′,3′:2,1]imidazo[4,5‐b]quinoxalinyl}‐1,2,2‐trimethylcyclopentane ( 5 ) has been achieved by the reaction of bis‐(5′‐amino‐1′,3′,4′‐thiadiazolyl)‐1,2,2‐trimethylcyclopentane with α‐haloketones, 2,3‐dichloroquinoxaline respectively. Bromination of compound 3 furnished bis‐1,3‐{5′‐bromo‐6′‐arylimidazo[2,1‐b][1,3,4]thiadiazol‐2‐yl}‐1,2,2‐trimethylcyclopentane ( 4 ). The structural assignment of these compounds was supported by IR, ¹H NMR and elemental analysis data. The antimicrobial, anti‐inflammatory and antifungal activities of some of the compounds have also been evaluated.     

The water-soluble indolium-based fluorescence probes for detection of the extreme acidity or extreme alkalinity

In this work, 3,3′-(((1E,1′E)-(H,12H-5,11-methanodibenzo[b,f][1,5]diazocine-2,8-diyl)bis(ethene-2,1-diyl))bis(1,1-dimethyl-1H-benzo[e]indole-3-ium-2,3-diyl))bis(propane-1-sulfonate) (1), 3,3’-(((1E,1′E)-(6H,12H-5,11-methanodibenzo[b,f][1,5]diazocine-2,8-diyl)bis(ethene-2,1-diyl))bis(3,3-dimethyl-3H-indole-1-ium-2,1-diyl))bis(propane-1-sulfonate) (2), 2,2’-((1E,1′E)-(6H,12H-5,11-methanodibenzo[b,f][1,5]diazocine-2,8-diyl)bis(ethene-2,1-diyl))bis(1,3,3-trimethyl-3H-indol-1-ium) iodide (3) and 2,2’-((1E,1′E)-(6H,12H-5,11-methanodibenzo[b,f][1,5]diazocine-2,8-diyl)bis(ethene-2,1-diyl))bis(1,1,3-trimethyl-1H-benzo[e]indol-3-ium) iodide (4) were designed and synthesized by ethylene bridging of the N-substituted indolium salts and the Tröger’s Base (TB) framework. The probes exhibited a longer absorption and emission wavelength and the emission wavelength of them in dichloromethane (DCM) was more than 600 nm, performed a red fluorescence. All of the probes could work on the extreme acidic and the extreme alkaline environments and showed a good liner response in the working pH range. Especially, 2 and 4 were soluble in water and manifested a good pH sensing in a water system. Also, ¹H NMR analysis illustrated how these dyes worked as the pH-sensitive fluorescence probes. In addition, they performed excellent reversibility, high selectivity and good photostability.     

Synthesis of linear polyquaternary salts derived from 4,4′-Bipyridine

1,1″-(1,3-Propanediyl)bis-4,4′-bipyridinium dibromide is converted to 1,1″-(1,3-propanediyl)bis[1′-(3-hydroxypropyl)-4,4′-bipyridinium] tetrabromide by reaction with 1,3-dibromopropane in hot aqueous dimethylformamide. The tetraquaternary salt participates in a dequaternization and coupling reaction on treatment with hot aqueous hydrobromic acid to afford an octaquaternary salt, which is readily converted to decaquaternary and dodecaquaternary derivatives. The 1,4-butanediyl analogue participates in a similar sequence of reactions.     

“Seems Bad Turns Good” – traces of precursor in dicationic ionic liquid lead to analytical application

Research on Chemical Intermediates - We explored a geminal dicationic ionic liquid (DCIL), 1′-(propane-1,3-diyl)bis(4-aminopyridin-1-ium) dibromide, [C3(Amp)2][Br]2, as a fluorescent probe...     

Polymerizable Ester-Type Banana Liquid Crystals: A Comparative Study of Mesophase Behavior

Two families of ester-type banana monomers are presented, 1,3-phenylene bis{4-[4′-(10-undecenyloxy)benzoyloxy]benzoate}s and 1,3-phenylene bis{[4′-(10-undecenyloxy)]-1,1′-biphenyl-4-carboxylate}s, in which the nature of the substituents on the central phenyl ring and the side arms was varied. The mesophase behavior of the monomers, including B₂ and B₇ phases, was correlated with their chemical structure and was compared with that of analogous azomethine-type banana mesogens. It is also shown that the banana monomers can be incorporated into new architectures of liquid crystal polymers.     

Synthesis of 3,3′-(1,6-hexanediyl)bis-pyrimidine derivatives and 3,4-dithia[6.6](1.3)pyrimidinophane

Several 3,3′-(1,6-hexanediyl)bis[6-methyl-2,4(1H,3H)-pyrimidinedione] derivatives ( 4a, 4b , and 4c ) were synthesized from 1,6-(hexanediyl)bis[6-methyl-2H-1,3-oxazine-2,4(3H)-dione] (3) . Compound 4c was converted to 6, which reacted with thiourea giving thiuronium salt 7 . 3,3′-(1,6-Hexanediyl)bis [1-(2-mercaptoethyl)-6-methyl-2,4(1H,3H)-pyrimidinedione] (9) was obtained by the hydrolysis of 7 , and then 9 was oxidized to 12,22-dimethyl-3,4-dithia[6.6] (1.3)-1,2,3,4-tetrahydro-2,4-dioxopyrimidinophane (10) .     

Reaction of thiourea with formaldehyde and simplest aliphatic diamines

N,N′-Bis(hydroxymethyl)thiourea reacted with propane-1,3-diamine at a molar ratio of 2 : 1 to give 5,5′-propane-1,3-diylbis(1,3,5-triazinane-2-thione), whereas 1,3,5,7,11,13,15,17-octaazatricyclo[15.3.1.1^7,11]-docosane-4,14-dithione was obtained in the reaction with equimolar amounts of the reactants. Tricyclic product was also formed in the three-component condensation of thiourea with formaldehyde and propane-1,3-diamine at a ratio of 1 : 3 : 1. The reactions of N,N′-bis(hydroxymethyl)thiourea with ethane-1,2-diamine (2 : 1) and of thiourea with formaldehyde and butane-1,4-diamine (1 : 2 : 1) afforded 5,5′-(ethane-1,2-diyl)bis(1,3,5-triazinane-2-thione) and 5,5′-(butane-1,4-diyl)bis(1,3,5-triazinane-2-thione), respectively.     

Preparation of polyimides utilizing the Diels–Alder reaction,II: Bis[N-(butadienyl-2-methyl)] amino arylenes with bismaleimides

Four new bisdienes were prepared from 2-bromomethyl-1,3-butadiene and N,N-diethyl benzidine; bis[4-(N-ethyl) aminophenyl]-p-diisopropylbenzene, 1,4-diamino-2,3,5,6-tetramethylbenzene and α,α′ bis(4-amino-3,5-dimethyl phenyl)-p-diisopropyl benzene. Polyimides were synthesized by the Diels–Alder reaction of these bisdienes and bis(4-maleimidylphenyl)methane and bis(3-maleimidylphenyl) sulfone. The polymers were soluble in m -cresol, dimethyl sulfoxide and chlorinated hydrocarbon solvents. Moderate thermal stability was observed by thermogravimetric analysis in air and nitrogen.     

Metallkomplexe von cyclophanen : I. Darstellung und charakterisierung von μ-(1,3-propandithiolato(2−)-S,S′:S,S′)-bis(tricarbonyleisen)-(FeFe), einem dynamischen metallorganischen tricyclus

μ-(1,3-Propanedithiolato(2?) (S,S′:S,S′)) bis(tricarbonyliron) (FeFe) (A) has been prepared in 30% yield by reaction of 2,6,15,19-tetrathial[7,7]-paracyclophane with Fe(CO)₅. It is supposed that the 1,3-propanedithia unit takes an especially favourable conformative fixation in the tetrathiacyclophane. This “phane effect” should be responsible for the relatively high yield.     

Syntheses, structures, and properties of copper(II) complexes of bis(2-pyridylmethyl) derivatives of o-, m-, and p-phenylenediamine and aniline

Copper(II) complexes of the ligand 1,n-bis[bis(2-pyridylmethyl)amino]benzene with n = 2-4 (1,n-tpbd) and its mononuclear derivative bis(2-pyridylmethyl)aniline (phbpa) were synthesized and structurally characterized. Magnetic measurements and DFT calculations were performed on [CuCl2(phbpa)], [Cu2Cl4(1,3-tpbd)], [(Cu2Cl2(ClO4)(1,3-tpbd))Cl(Cu2Cl2(OH2)(1,3-tpbd))](ClO4)2, and [Cu2(OH2)2(S2O6)(1,3-tpbd)]S2O6, and the exchange-polarization mechanism was successfully demonstrated.     

Thermal analysis of 1,4‐di[n′‐(quinolyl)]buta‐1,3‐diynes,structure, and topo‐oligomerization: Polymerization of 3‐ethynylquinoline with the triethyl aluminum/vanadium 2,4‐pentanedionate catalyst system

Conjugated 1,4‐bis(n′‐quinolyl)‐1,3‐butadiynes were obtained through the oxidative dimerization of the corresponding n′‐ethynylquinolines catalyzed by cuprous chloride. Differential scanning calorimetry analysis of the 1,4‐bis[n′‐(quinolyl)]buta‐1,3‐diyne molecules produced evidence of a syn–anti rotational equilibrium around the 1,3‐diyne axis and an irreversible transformation into a thermopolymer. The topo‐oligomerization of 1,4‐bis[3′‐(quinolyl)]buta‐1,3‐diyne, which took place by irradiation with sunlight, was investigated with matrix‐assisted laser desorption/ionization time‐of‐flight mass spectrometry. Accurate X‐ray molecular structure and refinement analysis of 1,4‐bis[3′‐(quinolyl)]buta‐1,3‐diyne was conducted. The molecular crystalline packing consisted of parallel arrays of two groups of centrosymmetric molecules (antirotamer) in a herringbone assemblage in the solid state. The polymerization of 3‐ethynylquinoline was carried out with the AlEt₃/V(acac)₃ system to produce a mixture of 1,2,4‐ and 1,3,5‐tris(3′‐quinolyl)benzene cyclotrimers and a trans–cisoid polyene structure. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 6031–6040, 2004     

Regioselective Synthesis of 5‐(2‐Cyanoethyl)‐1,1′‐biphenyl‐2‐carboxylates by Formal [3+3] Cyclocondensations of 1,3‐Bis[(trimethylsilyl)oxy]buta‐ 1,3‐dienes

5‐(2‐Cyanoethyl)‐1,1′‐biphenyl‐2‐carboxylates were prepared by regioselective formal [3+3] cyclocondensations of 1,3‐bis[(trimethylsilyl)oxy]buta‐1,3‐dienes.     

Building libraries of skeletally diverse scaffolds from novel heterocyclic active methylene compound through multi-component reactions

Libraries of skeletally diverse potential bioactive polycyclic/spirocyclic heterocyclic compounds; 2-amino-7,9-dimethyl-5-oxo-4-aryl-4,5,6,7-tetrahydropyrano[2,3-d]pyrazolo[3,4-b]pyridine-3-carbonitrile, 2′-amino-7′,9′-dimethyl-2,5′-dioxo-6′,7′-dihydro-5′H-spiro[indoline-3,4′-pyrano[2,3-d]pyrazolo[3,4-b]pyridine]-3′-carbonitrile, and 5,5′-(arylmethylene)bis(4-hydroxy-1,3-dimethyl-1H-pyrazolo[3,4-b]pyridin-6(7H)-one) have been synthesized through a multi-component reaction using novel heterocyclic active methylene compound 4-hydroxy-1,3-dimethyl-1H-pyrazolo[3,4-b]pyridine-6(7H)-one as one of the building blocks. This protocol can be considered to be an efficient and eco-friendly strategy for diversity oriented synthesis.