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  • Organic Chemistry  (4)
  • Physical Chemistry  (3)
  • Wiley-Blackwell  (7)
  • 1985-1989  (7)
  • 1
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    Helvetica Chimica Acta 68 (1985), S. 840-845 
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Nature and Stability of Some Metallic Complexes of Dinucleating Cryptands in Solution III. The Monocycle [22]-Py2N4The nature and stability of complexes formed by a new 22-membered monocycle L = [22]-Py2N4 with the cations Mn+ = Cu2+, Co2+, Ni2+, Zn2+, Cd2+, Pb2+, and Ag+ have been determined in aqueous solutions (0.01M NaClO4, 25°) by pH-metry and also, for the copper system, by UV-absorption spectrophotometry. The stepwise protonation constants of the four amine functions of L were 9.1, 8.3, 7.1 and 3.7 logarithms units, respectively. No evidence was found for the protonation of the two pyridine nitrogen atoms. Mononuclear complexes MLn+ were identified in all systems investigated, but the dinuclear species M2L2n+ were only found with Cu2+ and Ag+. The logarithms of the overall stability constants for the copper and silver complexes are CuL2+, 12.9; Cu2L4+, 18.6; Agl+, 6.3; Ag2L2+, 10.9, respectively. Mononuclear hydroxy species MLOH(n-1)+ were identified in all systems except those of copper and silver. No dinuclear hydroxy complexes were detected. The complexing properties of L are compared to those of the large and less rigid bis-dien.
    Additional Material: 3 Ill.
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  • 2
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Nature and Stability of Some Metallic Complexes of Dinucleating Cryptands in Solution. I. A Polyazapolyoxa Cylindrical Macrotricycle and its Monocyclic SubunitpH-metry and UV spectrophotometry were used to study the complexing properties of the cylindrical macrotricycle, 1,7,13,19-tetraaza-4,16-dioxa-10,22,27,32-tetraoxatricyclo[17.5.5.5]tetratriacontane (1) and of its constitutive monocyclic subunit, 1,7-diaza-4,10-dioxacyclododecane (2) with some transition and heavy metal cations (Cu2+, Co2+, Ni2+, Zn2+, Cd2+, Pb2+, Ag+), in aqueous medium 0.1M Et4NClO4, at 25°. The protonation constants of the ligands as well as the nature and the stabilities of the complexes formed in the pH-regions studied were determined. The tricycle 1 only formed dinuclear M2L complexes with Cu2+, Zn2+, and Ag+, accompanied in the latter case by a protonated mononuclear MLH species, and with Cu2+ and Zn2+ at high pH-values by dinuclear hydroxo complexes. Only mononuclear complexes were evidenced with the other cations, ML being accompanied either by protonated or hydroxy mononuclear species. The mononuclear complexes of 1, when they existed, were more stable than the corresponding complexes of 2, except for cobalt which formed complexes of comparable stability with both ligands. In the other cases (Cd2+, Pb2+, Ag+), the stability differences between the complexes of 1 and 2 increased with the size of the cation.
    Additional Material: 3 Ill.
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  • 3
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 21 (1989), S. 51-61 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: We have carried out a kinetic study of the 4-pyridinecarboxaldehyde plus n-hexylamine system, at 25°C, in water-dioxan mixtures (0-60% v/v) and in the pH range pKa + 1.5 〉 pH 〉 pKa - 1.5, where pKa is the pK value of the conjugate acid of the amine. The results obtained could be interpreted in terms of a rate constant for Schiff's base hydrolysis and a rate constant for the reaction between the nonprotonated n-hexylamine and the nonhydrated form of 4-pyridinecarboxaldehyde. Both constants decrease sharply as the dioxan content of the solvent increases, in a manner consistent with Marshall's model [J. Phys. Chem., 74, 346 (1970)]. It is suggested that the transition state of the rate-limiting step (carbinolamine dehydration) is highly solvated by water molecules and has a high separation of charges.
    Additional Material: 5 Ill.
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  • 4
    ISSN: 0170-2041
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Heteroaromatische nucleophile Substitutionsreaktionen durch Phasen-Transfer-Katalyse- Synthese von neuen Alkoxypyridazin-3(2H)-onenDie Synthese von einigen 4- und 5-alkoxysubstituierten Pyridazin-3(2H)-onen mit hypotensiver und β-blockierender Wirkung durch Phasen-Transfer-Katalyse aus Halogenpyridazin-3(2H)-onen wird beschrieben. Der nucleophile Austausch verläuft recht glatt in der 5-Stellung aber viel langsamer in der 4-Stellung. Im Falle von 4,5-Dihalogenpyridazin-3(2H)-onen ergibt die Phasen-Transfer-Katalyse eine hohe Regioselektivität für die Substitution in 5-Stellung.
    Notes: The synthesis of several 4- and 5-alkoxy-substituted pyridazin-3(2H)-ones with hypotensive and β-blocking activities by phase-transfer catalysis (PTC) starting from halopyridazin-3(2H)-ones is described. The nucleophilic displacement reaction proceeds easily at the 5-position and remarkably slower at the 4-position. In the case of 4,5-dihalopyridazin-3(2H)-ones the PTC methods provide a high regioselectivity towards substitution in 5-position.
    Additional Material: 2 Tab.
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  • 5
    ISSN: 0170-2041
    Keywords: H1-Antihistaminic ; Piperazines ; Phase-transfer catalysis ; Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Potentielle H1-Antihistaminica: Synthese von 4-[(2,3-Dihydro-2-oxo-1H-benzimidazol-1-yl)alkoxycarbonyl]-1-(diphenylmethyl)piperazinen durch selektive Phasen-Transfer-katalysierte Monoalkoxycarbonylierung von α,ω-DichloralkanenDie Synthese einer Reihe von neuen 4-[(2,3-Dihydro-2-oxo-1H-benzimidazol-1-yl)alkoxycarbonyl]-1-(diphenylmethyl)piperazinen 2 durch Phasen-Transfer-katalysierte Monoalkoxycarbonylierung von α,ω-Dichloralkanen wird beschrieben. Die Piperazine 2 ähneln Oxatomid1) (1) und sind potentielle H1-Antihistaminica. Ferner wurde eine Untersuchung zur regioselektiven Synthese von substituierten 1,3-Dihydro-1-isopropenyl-2H-benzimidazol-2-onen (5) durchgeführt.
    Notes: The synthesis of a series of new 4-[(2,3-Dihydro-2-oxo-1H-benzimidazol-1-yl)alkoxycarbonyl]-1-(diphenylmethyl)piperazines 2 by phase-transfer catalysed monoalkoxycarbonylation of α,ω-dichloroalkanes is described. Compounds 2 are related to oxatomide1) (1) and are potential histamine-H1 antagonists. A study on the regioselective preparation of substituted 1,3-dihydro-1-isopropenyl-2H-benzimidazol-2-ones (5) was also carried out.
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  • 6
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 18 (1986), S. 1249-1258 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The decomposition reactions of N-bromodiethanolamine, N-bromoethylethanolamine, and N-bromomethylethanolamine in aqueous solution have been studied kinetically under various experimental conditions. The results support a proposed reaction mechanism in which the rate controlling step is assumed to be the formation of an imine which is then hydrolyzed to the final decomposition products.
    Additional Material: 1 Ill.
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  • 7
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 20 (1988), S. 397-409 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The chlorinations of dimethylamine, diethylamine, methylethanolamine, ethylethanolamine and diethanolamine by N-chlorosuccinimide have been found to be equilibrium reactions of order one with respect to both N-chlorosuccinimide and amine in the forward direction and of order one with respect to succinimide and the resulting N-chloramine in the other. These results are explained by postulating a mechanism in which the rate controlling step consists in direct exchange of positive chlorine between the N-chlorosuccinimide and the amine.
    Additional Material: 5 Ill.
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