Synthesis of sulfur-containing vicinal aminoalcohols on the basis of N-(oxiran-2-ylmethyl)amines

The reaction of (methanediyldibenzene-4,1-diyl)dimethanethiol, (oxydibenzene-4,1-diyl)dimethanethiol, biphenyl-4,4′-diyldimethanethiol with 1-(oxiran-2-ylmethyl)piperidine and N-(oxiran-2-ylmethyl)-N-ethylaniline afforded the corresponding sulfur-containing vicinal aminoalcohols resulting from the opening of the oxirane ring in keeping with Krasusky rule.     

Synthesis and thermal properties of rigid oxa-bridged-containing dimers and tetramers

Several symmetrical, linear dimers and some star-like tetramers were prepared using easily accessible oxa-bridged derivatives as central rigid cores. In order to produce new liquid crystalline materials various mesogenic/promesogenic groups, containing biphenyl-4,4′-diol, 4,4′-(diazene-1,2-diyl)diphenol and cholesterol sub-moieties, were connected through oxy-ethylene linkers via an ester linkage, in the end-on fashion. Their thermal behaviour and mesomorphic properties were investigated by differential scanning calorimetry (DSC), polarized optical microscope (POM), and variable temperature small-angle X-ray diffraction (XRD) methods. While essentially all the biphenyl-4,4′-diol- and 4,4′-(diazene-1,2-diyl)-based dimeric derivatives exhibited smectic liquid crystalline mesophases, the nature of which are mesogenic groups dependent, none of the cholesterol-containing compounds and tetramers were mesomorphic.     

The solvent extraction and spectrophotometric determination of vanadium (V) with 4-(2-thiazolylazo)resorcinol and tetrazolium salts

The formation and extraction of ion-associate complexes between the vanadium(V)-4-(2-thiazolylazo)resorcinol (TAR) anionic chelate and the cations of some mono-and ditetrazolium salts {3-(4,5-dimethyl-2-thiazol)-2,5-diphenyl-2H-tetrazolium bromide (Thiazolyl blue, MTT), 3-(2-naphtyl)-2,5-diphenyl-2H-tetrazolium chloride (Tetrazolium violet), 2-(4-iodophenyl)-3-(4-nitrophenyl)-5-phenyl-2H-tetrazolium chloride (Iodonitrotetrazolium chloride), 3,3′-[3,3′-dimetoxy(1,1′-biphenyl)-4,4′-diyl]-bis[2,5-diphenyl-2H-tetrazolium] chloride (Tetrazolium blue chloride) and 3,3′-(3,3′-dimetoxy-4,4′-biphenylene)bis[2-(4-nitrophenyl)-5-phenyl-2H-tetrazolium chloride] (Nitro blue tetrazolium chloride)} have been studied. The optimum extraction conditions have been found. The composition of the V-TAR-monotetrazolium and V-TAR-ditetrazolium complexes extracted into chloroform has been determined to be 1:2:3 and 2:4:3 respectively. The extraction, distribution and association constants, and the recovery factors have been calculated. The relationship between the molecular weight of tetrazolium cations, and the association constants of their complexes has been discussed. The special behavior of the tetrazolium cations, containing-NO₂ groups has been noticed. The effects of foreign ions and reagents on the extraction of vanadium with TAR and the best tetrazolium salt-MTT have been studied. A sensitive, selective, simple and fast method for the determination of vanadium has been developed.      

Investigations on 2,3′-Biquinolyl. 16. The Regioselectivity of Reduction of 1-Alkyl-3-(2-quinolyl)quinolinium and 1,1′-Dialkyl-3,3′-di(2-quinolyl)-1,1′,4,4′-biquinolyl Iodides Using Metallic Zinc,Lithium and Potassium

The reaction of 1-alkyl-3-(2-quinolyl)quinolinium iodides with excess zinc in THF gives a diastereomeric mixture of 1,1′-dialkyl-3,3′-di(2-quinolyl)-1,1′,4,4′-tetrahydro-4,4′-biquinolyls. An excess of lithium in THF gives a mixture of 1′,2′-dihydro-2,3′-biquinolyl and 1′-alkyl-1′, 4′-dihydro-2,3′-biquinolyl with the former predominating. The reduction by lithium in THF of 1,1′-dialkyl-3,3′-di(2-quinolyl)-1,1′,4,4′-tetrahydro-4,4′-biquinolyls leads to analogous products. Reduction of 1-alkyl-3-(2-quinolyl)quinolinium iodides by metallic potassium gives 1-alkyl-1′,4′-dihydro-2,3′-biquinolyls. __________ Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 8, pp. 1208–1212, August, 2005.     

Design of postmetallocene catalytic systems of aryliminetype for olefins polymerization: XIII. Synthesis of tetradentate bis(2-hydroxy-1-naphthaldimine) ligands and their complexes with titanium(IV) dichloride

Reactions of 2-hydroxy-1-naphthaldehyde with 1,4-diaminobutane, 1,6-diaminohexane, 4,4′-methylenedianiline and its alkyl- and cycloalkyl-sybstituted derivatives, with 4,4′-sulfonyldianiline, 2,2′- and 4,4′-oxydianiline, 4,4′-(1,4-phenylenebisoxy)dianiline, 4,4′-[propane-2,2-diylbis(1,4-phenylenebisoxy)]dianiline, and p-terphenyl-4,4″-diamine afforded a series of the corresponding diimines that at treating with TiCl₂(OPr-i)₂ formed mono- and binuclear complexes of titanium(IV) dichloride with tetradentate ligands LTiCl₂ and L₂(TiCl₂)₂.     

Synthesis of azoles from 3,3′-[(4-alkoxyphenyl)imino]bis(propanoic acid hydrazides)

Abstract  

Reaction of 3,3′-[(4-alkoxyphenyl)imino]bis(propanoic acid hydrazides) with CS₂ in alkaline solution and subsequent acidification gave 5,5′-[[(4-alkoxyphenyl)imino]diethane-2,1-diyl]bis(1,3,4-oxadiazole-2(3H)-thiones). The same dihydrazides on reaction with phenyl isocyanates or phenyl isothiocyanates were converted to bis[N′-(phenylaminocarbonyl)propanoic acid hydrazides] and bis[N′-(phenylaminocarbonothioyl)propanoic acid hydrazides], which underwent cyclization in alkaline medium to produce 5,5′-[[(4-alkoxyphenyl)imino]diethane-2,1-diyl]bis(4-phenyl-2,4-dihydro-3H-1,2,4-triazol-3-ones) and their 3-thio analogues, whereas in sulfuric acid or POCl₃ 5,5′-[[(4-alkoxyphenyl)imino]diethane-2,1-diyl]bis(N-phenyl-1,3,4-oxadiazol-2-amines) and 5,5′-[[(4-alkoxyphenyl)imino]diethane-2,1-diyl]bis(N-phenyl-1,3,4-thiadiazol-2-amines) were obtained.     

Enzymatic catalysis of 2,6-dimethoxyphenol by laccases and products characterization in organic solutions

2,6-Dimethoxyphenol (DMP) as a substrate was widely used in determination of laccase activity. It is surprising, however, that its catalyzed oxidation products have not been completely determined until now. Studies were thus conducted on Rhus laccase (RL) and immobilized Rhus laccase (IRL)-catalyzed oxidation reactions of 2,6-dimethoxyphenol in water-organic solvent systems. These reactions pro- ceeded well in water-(im)miscible organic solvent systems pre-saturated with water. Only one product, 3,3′,5,5′-tetramethoxy-1,1′biphenyl-4,4′-diol (TMBP), was produced by RL catalysis, and it was thor- oughly characterized by FT-IR, NMR, GC-MS, etc. A simple enzymatic mechanism of this reaction is proposed.     

Investigations on 2,3′-biquinoline series. 19. Regioselectivity of the reaction of 1,1′-dialkyl-3,3′-di(2-quinolyl)-1,1′,4,4′-tetrahydro-4,4′-biquinolines with organomagnesium and organolithium compounds

1,1′-Dialkyl-3,3′-di(2-quinolyl)-1,1′,4,4′-tetrahydro-4,4′-biquinolines react with organolithium and organo-magnesium compounds to form 1′-alkyl-2′-R-1′,2′-dihydro-2,3′-biquinolines. __________ Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 2, 224–226, February, 2006.     

Spectrophotometric determination of basicities of substituted acetylbiphenyls and biphenyl carboxylic acids

The basicities of several 2′-, 3′-, and 4′-substituted 4-acetylbiphenyls and biphenyl-4-carboxylic acids have been determined spectrophotometrically in sulphuric acid media at 30°C. The pK_BH ⁺ of 3′- and 4′-substituted compounds are correlated by the Hammett equation. The 4′-methoxy group deviates considerably in the Hammett plot. This is attributed to its conjugative interaction with the carbonyl or carboxyl group aided by protonation. Good correlation exists between pK_BH ⁺ and σ⁺. The basicities of 2′-substituted 4-acetylbiphenyls and biphenyl-4-carboxylic acids reaffirm the existence of π-electron steric effect of 2′substituents.     

Reactions of 2-phenyl-4,4-bis(trifluoromethyl)-4,5-dihydro-1,3,2-benzodioxaphosphepin-5-one with phenanthrenequinone and dibenzoyl

Reactions of 2-phenyl-4,4-bis(trifluoromethyl)-4,5-dihydro-1,3,2-benzodioxaphosphepin-5-one with 9,10-phenanthrenequinone and dibenzoyl gave hydrolytically unstable spirophosphoranes with five- and seven-membered rings, 2-phenyl-4,4-bis(trifluoromethyl)-4,5-dihydrospiro[[1,3,2]benzodioxaphosphepine-2,2′-phenanthro[9,10-d][1,3,2]dioxaphosphol]-5-one and 2,4′,5′-triphenyl-4,4-bis(trifluoromethyl)-4,5-dihydrospiro[[1,3,2]benzodioxaphosphepine-2,2′-[1,3,2]dioxaphosphol]-5-one. The structure of the first of these was proved by X-ray analysis.     

Synthesis and studies of homopolyamides based on 2,4-bis(6-chlorocarbonyl-2-naphthyloxy)-6-(4-methyl-1-piperazinyl)-s-triazine

Abstract  

Ten homopolyamides have been synthesized by polycondensation of the monomer 2,4-bis(6-chlorocarbonyl-2-naphthyloxy)-6-(4-methyl-1-piperazinyl)-s-triazine and different diamines such as 4,4′-biphenyldiamine, 4,4′-diaminobenzanilide, 4,4′-diaminodiphenylmethane, 4,4′-diaminodiphenyl sulfone, 4,4′-diaminodiphenyl sulfonamide, 2,4-diaminotoluene, o-phenylenediamine, m-phenylenediamine, p-phenylenediamine, and ethylenediamine. All polyamides were characterized by solubility, density, viscosity measurements, IR, NMR spectroscopy, and thermogravimetric analysis. The products were found to possess high thermal stability.     

A new synthesis of 1,3-difunctionalized 2-sulfonamidopropane derivatives via regioselective ring opening reactions of 2-(bromomethyl)-1-sulfonylaziridines by substituted arylsulfonamides

The novel functionalized N,N′-[2-(arylsulfonamido)propane-1,3-diyl]bis(N-allylarylsulfonamide) and N,N′-[2-(methylsulfonamido)propane-1,3-diyl]bis(N-benzylarylsulfonamide) derivatives have been prepared from 2-(bromomethyl)-1-sulfonylaziridines for the first time using substituted arylsulfonamides in the presence of sodium methoxide under catalyst-free condition in good yields.     

A novel three-dimensional malonate-bridged complex {[Cu4(4,4′- bpy)8(mal)2(H2O)4](ClO4)2(H2O)4(CH3OH)2}n

A novel malonate-bridged copper (II) compound of formula {[Cu₄(4,4′-bpy)₈(mal)₂(H₂O)₄](ClO₄)₂(H₂O)₄(CH₃OH)₂}_n (4,4′-bpy = 4,4′-bipyridine; mal = malonate dianion) has been prepared and structurally characterized by X-ray crystallography. This compound exhibits a novel three-dimensional network being composed of Cu-4,4′-bipyridine layers which are pillared by malonate bridge ligands. The copper(II) ions has two different coordination environment.     

Synthesis and characterization of the [Cu(Cin2bda)2]ClO4 and [Cu(Ncin2bda)2]ClO4 complexes: Crystal structure of [Cu(Ncin2bda)2]ClO4

Two copper(I) complexes [Cu(Cin₂bda)₂]ClO₄ (I) and [Cu(Ncin₂bda)₂]ClO₄ (II) have been prepared by the reaction of the ligands N²,N²′-bis(3-phenylallylidene)biphenyl-2,2′-diamine (L¹) and N²,N²′-bis[3-(2-nitrophenyl)allylidene]biphenyl-2,2′-diamine (L²) and copper(I) salt. These compounds were characterized by CHN analyses, ¹H NMR, IR, and UV-Vis spectroscopy. The C=N stretching frequency in the copper(I) complexes shows a shift to a lower frequency relative to the free ligand due to the coordination of the nitrogen atoms. The crystal and molecular structure of II was determined by X-ray single-crystal crystallography. The coordination polyhedron about the copper(I) center in the complex is best described as a distorted tetrahedron. A quasireversible redox behavior was observed for complexes I and II. The article is published in the original.     

Recyclization of ethyl 1-alkyl-5-benzoyl-6-methylsulfanyl-2-oxo-1,2-dihydropyridine-3-carboxylates into Bicyclic <Emphasis Type="Italic">N</Emphasis>-alkyl-5-benzoyl-2-oxo-1,2-dihydropyridine-3-carboxamide derivatives by the action of nitrogen-containing 1,4- and 1,5-binucleophiles

Reactions of ethyl 1-alkyl-5-benzoyl-6-methylsulfanyl-2-oxo-1,2-dihydropyridine-3-carboxylates with nitrogen-containing 1,4- and 1,5-binucleophiles (o-phenylenediamine, o-aminobenzenethiol, ethane-1,2-diamine, and propane-1,3-diamine) involved recyclization, leading to the formation of fused N-alkyl-5-benzoyl- 2-oxo-1,2-dihydropyridine-3-carboxamides, diethyl 6,6′-oxybis(1-alkyl-5-benzoyl-2-oxo-1,2-dihydropyridine-3-carboxylates), and diethyl 6,6′-[ethane-1,2-diyl(or propane-1,3-diyl)diimino]bis(1-alkyl-5-benzoyl-2-oxo-1,2-dihydropyridine-3-carboxylates), depending on the reactant ratio. The sequence of formation of intermediate recyclization products was determined.     

Electrochromic properties of poly(alkoxy-terthiophenes): an experimental and theoretical investigation

Much effort has been made to synthesize novel compounds and enhance the optical properties of poly(terthiophenes). The electrochromic properties of poly(4,4′′-dimetoxy-3′-methyl-2′-5′,2′′-terthiophene) (PDMMT) and poly(4,4′′-dipentoxy-3′-methyl-2′-5′,2′′-terthiophene) (PDPMT) have been studied focusing on the differences in the alkoxy-group length. Theoretical calculations were employed to elucidate the structural and thermodynamic stability of the monomers and dimmers. The results showed that in this type of thiophenes large alkoxy chains assist positive charge dispersion through hyperconjugative effect. Thus, PDPMT is thermodynamically more stable than PDMMT in the oxidized state, leading to better electrochromic stability and optical memory.     

Iridium(I)-Catalyzed Asymmetric Intermolecular Hydroarylation of Norbornene with Benzamide

 Starting from the dinuclear chloro-bridged Ir(I) complexes [IrCl(PP)]₂ (PP = (R)-(6,6′-dimethylbiphenyl-2,2′-diyl)-1,1′-bis-(diphenylphosphine), (R)-(6,6′-dimethoxy-biphenyl-2,2′-diyl)-1,1′-bis-(diphenylphosphine), and (R)-1-((S)-2-(diphenylphosphino-ferrocenyl))-ethyldicyclohexylphosphine), a new class of cyclopentadienyl Ir(I) complexes containing a chiral bisphosphine ([IrCp(PP)]) was prepared and characterized. These new complexes are suited precatalysts for the direct hydroarylation of norbornene with benzamide. 2-(exo-Norbornyl)-benzamide is formed with an enantiomeric excess of up to 94% by the use of 1 mol% iridium, albeit in low yield.     

Hydrothermal synthesis and crystal structure of [Ni(Bptc)<Subscript>2</Subscript>(Bimb)<Subscript>2</Subscript>(H<Subscript>2</Subscript>O)<Subscript>2</Subscript>]

In the compound [Ni(Bptc)₂(Bimb)₂(H₂O)₂] (I), where H₄Bptc is 3,3′,4,4′-biphenyltetracarboxylic acid; Bimb is 4,4′-bis(1-imidazolyl)biphenyl), Ni(II) has a distorted octahedral coordination geometry, which was bonded with two N atoms from two Bimb ligands, two O atoms from two H₂Bptc²⁻ ligands and two water O atoms. The crystal structure of compound I is stabilized by the π-π-stacking and hydrogen bonds interaction.     

Syntheses and structures of copper(II) and nickel(II) complexes with <Emphasis Type="Italic">N</Emphasis>,<Emphasis Type="Italic">N</Emphasis>′-(4,4′-bithiazole-2,2′-diyl)diacetimidamide ligands: in vitro cytotoxicities and DNA-binding properties

Two complexes of general formula, [M(DABTA)]NO₃ [M = Cu^II (1) or Ni^II (2), DABTA = N,N′-(4,4′-bithiazole-2,2′-diyl)diacetimidamide], have been synthesized and characterized by elemental analyses, molar conductivity measurements, IR and electronic spectra studies and single-crystal X-ray diffraction. The crystal structures show that the two complexes have similar molecular structures in which each metal atom has a square-planar coordination environment. Hydrogen bonding interactions link each complex into a 2-D infinite network. The DNA-binding properties and cytotoxicities of the complexes were investigated. The results suggest that the two complexes can interact with DNA by intercalation, with binding affinities following the order of 1 > 2, which is consistent with their in vitro cytotoxicities.     

Mechanistic studies in the attempted synthesis of 5,5-dimethyl-2-isopropylidene-1,3-cyclohexanedione

In contrast to the corresponding cyclopentanedione derivative, 5,5-dimethyl-2-isopropyl-2-phenylsulfinyl-1,3-cyclohexanedione (3) does not undergo the expected cis-elimination of phenylsulfenic acid on warming in CH₂Cl₂ to afford the title compound 1, but instead gives an equimolar mixture of 5,5-dimethyl-2-(1 ′-isopropyl-4′,4′-dimethyl-2′,6′-dioxocyclohexyl)-2-isopropyl-1, 3-cyclohexanedione (9) and S-phenyl benzenethiosulfonate (10). These products result from dimerization of the 4,4-dimethyl-1-isopropyl-2,6-dioxocyclohexylradical (7) andthephenylsulfinyl radical (8), respectively. Diploma Thesis, University of Hamburg, 1990.