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  • Organic Chemistry  (6)
  • Physics  (1)
  • Wiley-Blackwell  (7)
  • American Chemical Society
  • Macmillian Magazines Ltd.
  • 1970-1974  (7)
  • 1940-1944
  • 1971  (7)
Collection
Publisher
  • Wiley-Blackwell  (7)
  • American Chemical Society
  • Macmillian Magazines Ltd.
Years
  • 1970-1974  (7)
  • 1940-1944
Year
  • 1
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science Part A-2: Polymer Physics 9 (1971), S. 1553-1577 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: As is well known, the chemical potentials of polymer and solvent in solution and, hence, the Flory-Huggins interaction parameter χ can be determined from scattered light intensities from dilute and concentrated solutions of the polymer in the solvent concerned. Preferably, measurements should be performed at temperatures as low as possible, provided the temperature exceeds the cloudpoint for the concentration used. It is shown that the lower the temperature and, consequently the higher the scattered light intensity, the better is the accuracy of the parameters obtained. At each temperature the scattered light intensity shows a maximum at some concentration. Below the theta temperature the ratio of scattered light intensity and concentrations also shows a maximum at some concentration. The values and the concentrations of these maxima for various temperatures enable the maximum of the spinodal to be determined. The spinodal itself can be determined by an extrapolation procedure of the reciprocal scattered light intensities. Measurements have been performed with three narrow-distribution polystyrene samples in cyclohexane. On the basis of the results, χ, and its dependence on concentration, temperature, and molecular weight can be determined to high accuracy.
    Additional Material: 13 Ill.
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  • 2
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    Helvetica Chimica Acta 54 (1971), S. 1361-1369 
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The interaction between Cu2+ and the terdentate ligands N-picolinoyl-ethylenediamine, glycine-2-pyridylmethylamide, Nα-(2-pyridylmethyl)-glycinamide and Nα-(2-pyridylmethyl)-glycine-ethylamide, respectively, has been studied by spectrophotometry and potentiometry. At high pH values the ionised amide group undergoes complex formation and the resulting chelates have similar structures and stabilities. In slightly acidic solution however, each ligand gives rise to a different species. These facts are explained by assuming that the neutral amide group coordinates through its carbonyl oxygen atom. The stability constant and the absorption spectrum of each complex have been calculated by computer programmes.
    Additional Material: 4 Ill.
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  • 3
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The complex formation between CuII and the title compound (tet a) is studied by spectrophotometry and pH-stat techniques. Between pH 4 and 5,5 the reaction proceeds in two steps, the first giving a blue intermediate, Cu(teta)2+ (blue), exhibiting a broad absorption band at 620 nm. Titration with NaOH and the absorption spectrum suggest that, in the intermediate, CuII is coordinated to only two amino groups of the ligand. Both steps are slow compared to other complex formation reactions of CuII. The rate of the first step, in which Cu(tet a)2+ (blue) is formed, is given by v1 = k1 · [Cu2+] [(tet a) H2+2]/[H+] with k1 = 2,7 · 10-6 s-1 at 40° and I = 0,1. In the second step the last two nitrogens of the quadridentate ligand are bound to CuII, giving the mauve end product. The rate of this step is given by v2 = k2 · [Cu(tet a)OH+ (blue)] [OH-] with k2 = 1,2 · 103 M-1 s-1 at 50° and I = 0,5.
    Additional Material: 3 Ill.
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  • 4
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    Helvetica Chimica Acta 54 (1971), S. 625-632 
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The kinetics of a two proton transfer between a blue octahedral and a yellow square planar nickel(II) complex with N, N′-diglycylethylenediamine (I, n = 1) resp. N, N′-diglycyl-1, 3-diaminopropane (I, n = 2) have been studied by spectrophotometry and pH-stat technique. The structure of these complexes and the mechanism of their interconversion are discussed and their reactions are compared with the analogous reactions of the copper(II)-N, N′-diglycyl-1, 3-diamino-propane complexes [1].
    Additional Material: 3 Ill.
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  • 5
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    Helvetica Chimica Acta 54 (1971), S. 1531-1543 
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The tetrahydroxyadipic acids and one trihydroxyadipic acid have been methylated, using methyl iodide and silver oxide in the presence of dimethylformamide.In addition to Δ2-di- or tri-methoxyadipic esters and the products expected for a double E2 elimination, cis-trans α, α'-dimethoxymuconic ester was frequently the principal product. The proposed theoretical interpretations involve as intermediates either a silver complex or a lactonic compound. A few preferential conformations, based on NMR. data, are proposed.
    Additional Material: 1 Ill.
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  • 6
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: All-cis cyclitols derived from cyclopentane have been prepared in two ways: (i) by LiAlH4 reduction of all-cis epoxypolyos; (ii) by dimethyl sulfoxide treatment, in the presence of sodium hydrogencarbonate, of brominated derivatives containing a neighbouring benzoyloxy group; under these conditions, the halogen is replaced by a cis-oriented hydroxyl group. Thus all-cis cyclopentane-tetrol and -pentol have been prepared; their configuration has been confirmed by NMR. spectroscopy.
    Additional Material: 1 Ill.
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  • 7
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: In aqueous solution N, N′-bis-(4-(5)-imidazolylmethyl)-ethylenediamine-cobalt (II) (CoIMEN2+) takes up molecular oxygen giving μ-dioxygen-μ-hydroxo-bis-[N, N′-bis-(4-(5)-imidazolylmethyl)-ethylenediamine]-dicobalt (II). (Co IMEN)2 O2 (OH)3+ is exceptionally stable against irreversible autoxydation to CoIII species. Its absorption spectrum is very similar to that of the known analogous complex (CoTRIEN)2 O2 (OH)3+.The kinetics of formation and dissociation of (CoIMEN)2O2(OH)3+ are studied by spectrophotometry and with an oxygen specific electrode. The rate of the forward reaction is described by vf = [CoIMEN2+]2 · [O2] · (k1 + k2 · [OH-]) with k1 = 9 · 104 M-2 s-1 and k2 = 1 · 1012M-3 S-1, at 25° and I = 0,2. A mechanism including hydroxylated as well as nonhydroxylated intermediates is proposed. Dissociation is preceeded by protonation of the oxygen adduct. At pH 1-2 the rate of dissociation is independent of [H+] and follows first order kinetics: vD = k3 · [(CoIMEN)2O2(OH)3+] with k3 = 2.15 · 10-2 S-1.
    Additional Material: 2 Ill.
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