Infrared spectrum of benzene in bromine and carbon tetrachloride solutions

The benzene—bromine complex at room temperature has been re-studied by infrared with bromine in excess of benzene. Solutions of 0.225 M benzene in bromine—carbon tetrachloride mixtures were studied. Under this condition, the spectral changes of measurable benzene absorption bands were observed more clearly than previously. The out-of-plane vibrations of benzene were observed to shift to higher frequencies. The equilibrium constant was found to be 0.11 ? mole^?1. The accord with the equilibrium constant derived from benzene rich systems supports the concept of a specific interaction. A C_6V symmetry is favoured for the geometry of the complex.     

Unperturbed dimensions of poly(ethylene oxide)

The intrinsic viscosities of fractions of poly(ethylene oxide) in the molecular weight range 1.5 × 10³ to 10⁶ have been measured at 25°C in benzene, carbon tetrachloride, and acetone; at 35°C in 0.45M aqueous potassium sulfate; and at 50°C in methyl isobutyl ketone and diethylene glycol diethyl ether. The latter three are practically theta solvents. The value of (r₀² /M)^1/2 for poly(ethylene oxide) is calculated to be 0.84 Å from the molecular weights of the high molecular weight fractions, and their intrinsic viscosities in the theta solvents and acetone. Erroneous values result if the usual methods of determination are applied to the data obtained for the low molecular weight (<10⁴) fractions or to the intrinsic viscosities in the very good solvents, benzene and carbon tetrachloride.     

Sorption of organic vapors by polystyrene

Activity coefficients of benzene, toluene, cyclohexane, carbon tetrachloride, chloroform, and dichloromethane in binary solutions with polystyrene at 23.5°C have been determined using a piezo-electric sorption apparatus. The investigated solvent concentration ranges were 15 to 39 wt % for benzene, 14 to 29 wt % for toluene, 15 to 28 wt % for cyclohexane, 26 to 38 wt % for carbon tetrachloride, 24 to 46 wt % for chloroform, and 21 to 41 wt % for dichloromethane. The polystyrene (weight-averaged) molecular weights were 1.1 × 10⁵ and 6.0 × 10⁵ g/gmole. The weight-fraction activity coefficients (Ω₁ = a₁/w₁) of cyclohexane, toluene, and carbon tetrachloride in polystyrene solutions determined in this work agree within experimental error with previously published values determined by measurement of vapor pressure lowering and vapor absorption by thin films. We find disagreement, at low solvent concentrations, between our results for benzene and chloroform and previously published results. We have analyzed our results using Flory's version of corresponding-states polymer solution theory. The theory can account, qualitatively, for the cyclohexane and carbon tetrachloride results. It cannot account for the toluene, benzene, dichloromethane, or chloroform results.     

Effects of 60Co gamma rays on poly[bis(p-tolylamino)Phosphazene]

The behaviour of poly-[bis(p-tolylamino)phosphazene] under ⁶⁰Co gamma irradiation was investigated in chloroform, carbon tetrachloride, benzene, toluene and tetrahydrofuran. Viscosity, average molecular weights and spectral changes were used to follow the degradation. The degradation mechanism was interpreted in terms of a combined interaction of the polymer molecule with dissolved oxygen and radiolysis products of the solvent.     

Thermodynamics and kinetics of complexation of iron(III) ion by picolinic and dipicolinic acids

The complexation reactions of iron(III) with 2-pyridine carboxylic acia (picolinic acid) and 2,6-pyridine dicarboxylic acid (dipicolinic acid) in aqueous solutions have been studied by spectrophotometric and stopped flow techniques. Equilibrium constants were determined for the 1 : 1 complexes at temperatures between 25 and 80°C. The values obtained are: Picolinic Acid (HL): Fe³⁺+ H₂L⁺? FeHL³⁺+H+(K₁ = 2.8,ΔH = 2 kcal mole^?1 at 25°C, μ = 2.67 M) Dipicolinic Acid (H₂D): Fe³⁺+H₂D? FeD⁺+2H⁺(K₁K_1A= 227 M, ΔH = 3.4 kcal mole^?1 at 25°C,μ = 1.0 M). The rate constants for the formation of these complexes are also given. The results are used to evaluate the effects of these two acids upon the rate of dissolution of iron(III) from its oxides.     

DEEP CATALYTIC OXIDATION OF BENZENE IN THE PRESENCE OF SEVERAL VOLATILE ORGANIC COMPOUNDS ON METAL OXIDES AND Pt/Al2O3 CATALYSTS

Oxidation of benzene into CO₂ in air has been studied in the temperature range of 300-673 K on supported metal oxides and on 0.7% Pt/Al₂O₃, in the absence and in the presence of several Volatile Organic Compounds (VOCs). On the metal oxides, the deep oxidation of benzene is strongly inhibited in presence of VOCs and O-containing VOCs lead to more toxic VOCs (i.e: acetaldehyde).     

The Extractive-Spectrophotometric Determination of Iron(III) As a Mixed-Ligand Complex with N-Hydroxy-N,N′DI-p-Tolyl-p-Toluamidine and Thiocyanate

The extractive-photometric determination or iron(III) as a mixed-ligand complex with N -hydroxy-N, N′ -di-p -tolyl-p -toluamidine (HDTTA) and thiocyanate is described. The orange-red Waterinsoluble 1:1:2 (metal: HDTTA: SCN^?) ternary complex formed in 0.1–0.6 M hydrochloric acid solutions is quantitatively extractable into benzene. The wavelength of maximum absorption, molar absorptivity and sensitivity of the colour system are 460nm, 12000 l. mole^?1 cm^?1 and 0.0046 μg Fe/cm ²respectively. The influence or foreign ions on the determination of iron has been studied. This method has also been applied to determine the iron content of several alloys.     

Spectroscopic studies of the electron donor-acceptor interactions of aromatic hydrocarbons with tetrachlorophthalic anhydride

Electron donor-acceptor (EDA) interactions of tetrachlorophthalic anhydride (TCPA) with benzene,p-xylene, mesitylene, fluorene,t-stilbene and pyrene have been investigated by spectroscopic technique. The spectroscopic and thermodynamic parameters of the complexes formed are reported. The enthalpies of formation range between 0.2 to 5.0 kcal mole⁻¹. Among all the donors studied, pyrene appears to be the strongest electron donor towards tetrachlorophthalic anhydride.     

NANOSECOND IRRADIATION STUDIES OF BIOLOGICAL MOLECULES-I. COENZYME Q 6 (UBIQUINONE-30)

Abstract— The coenzyme ubiquinone, an isoprenoid benzoquinone present in the electron-transport chain of mitochondria, has been studied using nanosecond laser flash photolysis and pulse radiolysis. The hitherto undetected triplet excited state of the coenzyme has been identified and some of the physico-chemical properties determined. These measurements may assist the understanding in molecular terms of the degradative action of light upon biological materials, photophosphorylation and the possible initiation of biological electron transport via quinone light absorption. Laser photolysis of ubiquinone in cyclohexane and pulse radiolysis of ubiquinone in benzene results in the formation of a transient absorption with maximum around 440 nm and a half-life of 650 nsec in cyclohexane and 450 nsec in benzene. Energy transfer sensitisation of the β-carotene triplet absorption by ubiquinone in cyclohexane at a rate consistent with the life-time of the 440 nm transient absorption, yields strong evidence that this transient species is triplet ubiquinone. The triplet reacts with oxygen with a rate constant of 2 × 10^--⁹ mole^-1 sec^-1. Photolysis studies of ubiquinone in ethanol and isopropanol and addition of ethanol to ubiquinone in cyclohexane show that little ubisemiquinone is formed by reaction of the triplet with alcohols. Electron spin resonance studies support this conclusion, and also show that some ubisemiquinone is however formed on photolysis of solutions of ubiquinone in methylcyclohexane. Energy transfer experiments in the presence of various triplet energy donors and acceptors suggest that the triplet energy of ubiquinone lies between 176 and 123 W mole^-1, and that the triplet extinction coefficient at 440 nrn is 19 ,000 mole^-1 cm^-1 in cyclohexane and 13 ,000 mole^-1 cm^-1 in benzene (at 430 nm). The singlet to triplet crossover efficiency for ubiquinone in cyclohexane was estimated to be 0.04. The low triplet energy level, crossover efficiency and abnormal type of reaction with alcohols are reflections of the profound influence of the isoprenoid chain upon excited states of this quinone.     

Naphthoquinonedioxime derivatives as analytical reagents for the spectrophotometric determination of nickel

Seven naphthoquinonedioxime compounds, including five new compounds. were synthesized and their reactions with nickel, cobalt and iron(II) ions were examined. The metal chelates of these dioximes absorb in the visible region, and the molar absorptivities of the complexes are about 1 · 10⁴ 1 mole^-1 cm^-1 in

aqueous solution. The chelates can be extracted into chloroloform with zephiramine. and the molar absorptivities of the nickel chelates are about 2 · 10⁴ 1 mole^-1 cm^-1. Of the dioximes examined. 1,2-naphthoquinonedioxime-6-sulfonic acid shows the highest sensitivity for nickel; the molar absorptivity of the nickel complex extracted into chloroform with zephiramine is 2.19 · 10⁴ I mole^-1 cm^-1 at 468 nm.     

Rate of complex formation for poly-n-vinyl carbazole and n-ethyl carbazole with various electron acceptors

The rates of complex formation for poly-N-vinyl carbazole and its saturated monomer analogue, N-ethyl carbazole, with various electron acceptors (chloranil, trinitrobenzene and picric acid) have been investigated. In mole ratios 1:1, the complex forming reactions in chloroform proceed rapidly, as measured by a “stopped flow” method; the rate constants are of the order of 10³ 1. mole^?1 sec^?1. The rate constants are smaller than those of the complexes with tetracyanoethylene as acceptor and decrease with decreasing electron affinity of the acceptor. The rate constants also depend on the molecular weight of the donor.     

Effect of solvent upon competitive liquid-liquid extraction of alkali metal cations by isomeric dibenzo-16-crown-5-oxyacetic acids

The selectivity and efficiency of competitive liquid-liquid extraction of alkali metal cations into organic solvents containingsym-(octyl)dibenzo-16-crown-5-oxyacetic acid (2) andsym-bis[4(5)-tert-butylbenzo]-16-crown-5-oxyacetic acid (3) have been determined. Solvents examined include: dichloromethane, chloroform, carbon tetrachloride, 1,2-dichloroethane, 1,1,1-trichloroethane, benzene, toluene,p-xylene, chlorobenzene, 1,2-dichlorobenzene, and 1,2,3,4-tetrahydronaphthalene. The Na⁺/K⁺ and Na⁺/Li⁺ extraction ratios are highest in chloroform. The extraction selectivity is found to correlate with the diluent parameter (DP) of the organic solvent.This paper is dedicated to the memory of the late Dr C. J. Pedersen.     

Molecular-weight distribution and structural transformation in water-soluble complexes of poly(acrylic acid) and bovine serum albumin

Interaction of polyacrylic acid (PAA) with bovine serum albumin (BSA) at different pH values and in a wide range of mixing molar ratios, γ = n_BSA/n_PAA, of components was investigated by size-exclusion high performance liquid chromatography with on-line refractive index, UV, light scattering and viscometer detectors. The results revealed the formation of stable water-soluble polymer-protein complexes at pH 5.0. For the soluble complexes thus formed, the number of the bound BSA molecules with one PAA molecule was expressed by a Langmuir-type equation as a function of the amount of excess BSA existing free in the solution. At saturation, one BSA molecule is bound to about 48 acrylic acid residues.The γ-dependencies of molecular properties and structural parameters (molecular weights, molecular-weight distribution, radius of gyration, and the Mark-Houwink equation constants) of aqueous solutions of polycomplex particles have been studied. It has been concluded from these results that the complex molecule is formed by the molecular association-dissociation processes between particles depending on protein molecules in mixtures. We assume that side-by-side association of BSA-PAA complex particles took place at γ ? 5. At γ > 5, dissociation of the aggregates occurred by the including certain protein molecules into composition and by the compactization of polycomplex particles.     

Hydroamination of Dihapto-Coordinated Benzene and Diene Complexes of Tungsten: Fundamental Studies and the Synthesis of γ-Lycorane

Reactions are described for complexes of the form WTp(NO)(PMe₃)(η²-arene) and various amines, where the arene is benzene or benzene with an electron-withdrawing substituent (CF₃, SO₂Ph, SO₂Me). The arene complex is first protonated to form an η²-arenium species, which then selectively adds the amine. The resulting η²-5-amino-1,3-cyclohexadiene complexes can then be subjected to the same sequence with a second nucleophile to form 3-aminocyclohexene complexes, where up to three stereocenters originate from the arene carbons. Alternatively, 1,3-cyclohexadiene complexes containing an ester group at the 5 position (also prepared from an arene) can be treated with acid followed by an amine to form trisubstituted 3-aminocyclohexenes. When the amine is primary, ring closure can occur to form a cis-fused bicyclic γ-lactam. Highly functionalized cyclohexenes can be liberated from the tungsten through oxidative decomplexation. The potential utility of this methodology is demonstrated in the synthesis of the alkaloid γ-lycorane. An enantioenriched synthesis of a lactam precursor to γ-lycorane is also described. This compound is prepared from an enantioenriched version of the tungsten benzene complex. Regio- and stereochemical assignments for the reported compounds are supported by detailed 2D-NMR analysis and 13 molecular structure determinations (SC-XRD).     

Charge Transfer Complex Role in the Formation of Chlorobenzene in the γ‐Irradiated Carbon Tetrachloride‐Benzene System

The formation of carbon tetrachloride‐benzene charge transfer complex was confirmed by UV and NMR spectrometric studies. A change in UV spectrum of benzene is observed upon addition of carbon tetrachloride. Whereas the appearance of new bands supports the formation of charge transfer complex. NMR study shows that, chemical shift of benzene pmr signal depends on the CCl₄‐C₆H₆ molar ratio. This observation is another criterion for the formation of benzene‐carbon tetrachloride charge transfer complex. Job's Continuous Variation method indicates that a 2:1 CCl₄‐C₆H₆ charge transfer complex (2:1 CTC) is formed. The association constants (K_2:1) of (2:1 CTC) was found to be 0.0197 M^?2. The maximum concentration of (2:1 CTC) was found to be in samples with 2:1 CCl₄‐C₆H₆ molar ratio (33% benzene mole). On the other hand the maximum yield of chlorobenzene was obtained, also, upon radiolysis of CCl₄‐C₆H₆ samples at a 2:1 molar ratio (33% benzene mole). Therefore, it could be concluded that (2:1 CTC) participates in the formation of chlorobenzene upon radiolysis of the benzene‐carbon tetrachloride system. This conclusion was supported by the dependence of the chlorobenzene yield of a γ‐irradiated carbon tetrachloride‐benzene system (2:1 molar ratio) on irradiation time according to a third order kinetic equation with a very good linearity (R² = 0.9977). Accordingly, the rate constant for the chlorobenzene formation under this condition was found to be ≈ 5.5 × 10^?7 L².mol^?2.h^?1. We propose a radiation chemical mechanism in which the 2:1 CTC plays a role in the formation of chlorobenzene.     

Miniemulsion polymerization initiated by L‐ascorbic acid and sulfonate/sulfate surfactants

Styrene miniemulsions that were stabilized by common anionic surfactants (sodium dodecyl benzene sulfonate, sodium dodecyl sulfate, and disulfonated alkyl diphenyl oxide sodium salt) polymerized at 25 °C in the presence of L ‐ascorbic acid without the addition of a free‐radical initiator. The polymerizations exhibited high rates and molecular weights, with conversions greater than 70% achieved in less than 1 h and weight‐average molecular weights greater than 1 × 10⁶ g/mol. Polymers did not form in the absence of L ‐ascorbic acid. Although the final conversion was only slightly independent on the L ‐ascorbic acid concentration, it was dependent on the surfactant concentration. The rate and final conversion were also strongly dependent on the surfactant type. Moreover, it was possible to initiate polymerizations with a monomer‐soluble derivative of L ‐ascorbic acid (L ‐ascorbic acid 6‐palmitate), although the rates were dramatically reduced compared with those when water‐soluble L ‐ascorbic acid was used. High yields and high‐molecular‐weight polymers were also produced with butyl acrylate and methyl methacrylate with L ‐ascorbic acid in the presence of sodium dodecyl benzene sulfonate. The initiation was attributed to an interaction between the surfactant and L ‐ascorbic acid, which formed a redox initiation system that generated radicals capable of adding monomer. These results are of particular significance for redox‐initiated emulsion/miniemulsion polymerizations with L ‐ascorbic acid as the reducing agent and with sulfate or sulfonate surfactants. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 69–80, 2007     

Direct Resolution of Secondary Tert-Butylphenylphosphine Oxide

Abstract

Secondary phosphine oxides constitute an important class of organophosphorus compounds and are higly useful as versatile phosphinoylating agents and as ligands ^[1,2] They are however not readily available in the optically active form.^[3–5] We wish to demonstrate that P-chiral secondary teri-butylphenylphosphine oxide (I) can be promptly resolved into enantiomers by means of its diastereoisomeric complexes with L-O,O-dibenzoyltanaric acid (L-DBTA) Dissolution of equimolar amounts of racemic I and L-DBTA in the 4 I benzene acetone mixture yields crystalline II complex containing exclusively the R-enantiomer of the starting phosphine oxide The complexed S-enantiomer is obtained from the mother liquor by crystallization from benzene The enantiomers of I are freed from their L-DBTA complexes by simple washing with aqueous NaOH Both enantiomers of 1 of very high optical purity are thus obtained from a single batch These enantiomers have subsequently been tested for their configurational stability in selected synthetic applications.     

Gas phase ion molecule reactions of organometallic compounds; protonation of selected η6-arenetricarbonylchromium complexes and η6-cycloheptatriene complexes of the Group VI metals with various Brønsted acid reagent ions

η⁶-Arenetricarbonylchromium(0) complexes, (with the η⁶-arene = benzene, toluene, methylbenzoate and acetophenone) and η⁶-cycloheptatrienetricarbonyl complexes of chromium(0), molybdenum(0) and tungsten(0) undergo reactions in the gas phase with the Brønsted acid reagent ions H₃⁺, CH₅⁺, t-C₄H₉⁺, (NH₃)_nH⁺ which depend on the Brønsted acid strengths of these ions and also on the basicity of the metal complexes. Processes which involve either metal or ligand proton attachment, as well as charge exchange, electrophillic addition and rearrangement reactions have been identified. Some comparisons are drawn between these gas phase observations and the solutions phase behaviour of these compounds.     

Complex formation of cetirizine drug with bivalent transition metal(II) ions in the presence of alanine: synthesis,characterization, equilibrium studies,and biological activity studies

Mononuclear cobalt(II), nickel(II), and copper(II) complexes of cetirizine·2HCl (CTZ = 2-[2-[4-[(4-chlorophenyl)phenyl methyl]piperazine-1-yl]-ethoxy]acetic acid) in the presence of alanine (Ala) as a representative example of amino acids were synthesized and elucidated by different physical techniques. All complexes have been characterized with the help of elemental analyses, molecular weights, molar conductance values, magnetic moments, and spectroscopic data. The measured molar conductance values in DMSO indicate that the complexes are nonelectrolytes. Quantum chemical calculations were performed with semi-empirical method to find the optimum geometry of complexes. The metal–oxygen bond length in the synthesized complexes obeys the order M–OH₂ > M–O_CTZ > M–O_Ala. Formation equilibria of the ternary complexes have been investigated. Ternary complexes are formed by a simultaneous mechanism. Stoichiometry and stability constants for the complexes formed are reported. The concentration distributions of various species formed in solution were also evaluated as a function of pH. CTZ and its metal chelates have been screened for their antimicrobial activities against some selected types of gram-positive (G⁺) and gram-negative (G^?) bacteria. They were more active against (G⁺) than (G^?) bacteria.