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  • Electronic Resource  (3)
  • Polymer and Materials Science  (2)
  • Kinetics  (1)
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  • Electronic Resource  (3)
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  • 1
    Electronic Resource
    Electronic Resource
    Springer
    Monatshefte für Chemie 124 (1993), S. 1149-1156 
    ISSN: 1434-4475
    Keywords: Aroyl azide ; 4-Toluoyl azide ; Alcoholysis ; Aminolysis ; “Nucleophilic catalysis” ; Kinetics ; Steric effects
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Zusammenfassung Primäre Amine reagieren in nicht-nucleophilen Lösungsmitteln mit 4-Toluoyl-azid in einer einheitlichen Reaktion 2. Ordnung, die durch die Größe des Amins und die Lösungsmittel-Polarität beeinflußt wird. Das ändert sich in Gegenwart von Alkoholen, wo auch die Bildung von 4-Toluylsäureestern beobachtet wird. Diese Konkurrenzreaktion wird durch den „kleinsten“ Alkohol (Methanol) und/oder die relativ größeren Amine (Cylohexylamin bzw. 3-Pentylamin) besonders stark begünstigt. Verglichen mit der einfachen Alkoholyse von 4-Toluoylazid wird eine enorme Beschleunigung der Esterbildung, proportional zur Konzentration des nucleophilen Amins, beobachtet. Der Reaktionsmechanismus wird mit besonderer Berücksichtigung sterischer Effekte bei der Konkurrenz von Nucleophilen um das Aroylazid diskutiert.
    Notes: Summary Primary amines2[R:n-butyl(2a), cyclohexyl (2b), 3-pentyl (2c)] react with 4-toluoyl azide1 in non-nucleophilic solvents in a clear second order reaction, which is strongly dependent on the size of the amine2 and the solvent polarity (k 2 [Acetonitril; 25 °C]: 15.51 (2a), 0.83 (2b) and 0.19 (2c) 1/mol·min; ΔH#=22.1 kJ/mol, ΔS#=−170.5 J/mol·K [2b in Acetonitril]). Drastic changes occur in the presence of nucleophilic solvents. With nucleophilic amines2 added to these in the solutions a concurrent reaction with alcohols4 [R: methyl (4a), ethyl (4b),n-butyl (4c)] yielding 4-toluoyl ester5 is observed. This is especially dominating with the “smallest” alcohol methanol (4a) and/or effectively promoted by “bulky” amines (2b, 2c; up to 99%5a). Compared with the pure alcoholysis a huge acceleration of the ester formation, proportional to the cencentration of the nucleophilic amine2, is observed. The reaction mechanism is discussed with special emphasis on steric effects in the competition of nucleophiles for the aroyl azide1.
    Type of Medium: Electronic Resource
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  • 2
    Electronic Resource
    Electronic Resource
    New York, NY [u.a.] : Wiley-Blackwell
    Journal of Applied Polymer Science 55 (1995), S. 1495-1505 
    ISSN: 0021-8995
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: The photoreactive amphiphile p-(stearyl amido) benzoyl azide (SABAz) was synthesized and grafted onto surface of thin polyacrylonitrile (PAN) films by irradiation with UV light. Two different techniques were applied, namely, Langmuir-Blodgett (LB) deposition and casting from solution. A high degree of order and a hydrophobic surface were established by reflection-absorption FT-IR spectroscopy (RA-IR) and contact angle measurements. The stability against treatment with water, tetrahydrofuran, and chloroform was tested. A considerable amount of amphiphilic molecules remains on the surface also after treatment with chloroform. RA-IR spectra taken from photomodified PAN films prepared by both techniques are almost identical after chloroform treatment, indicating a similar coupling mechanism. © 1995 John Wiley & Sons, Inc.
    Additional Material: 7 Ill.
    Type of Medium: Electronic Resource
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  • 3
    Electronic Resource
    Electronic Resource
    New York, NY [u.a.] : Wiley-Blackwell
    Journal of Applied Polymer Science 60 (1996), S. 1147-1161 
    ISSN: 0021-8995
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: Chemical reactions toward acyl azide activated polyacrylonitrile (PAN) and conditions for membrane surface modifications are described. Ultrafiltration (UF) membranes were prepared from PAN homopolymer and copolymer with methyl acrylate. Besides hydrazide formation and nitrosation, a new method to introduce acyl azide groups into carboxyl modified PAN, using azido transfer with diphenyl phosphoryl azide, was developed. Chemical conversions were characterized, especially with Fourier transform infrared spectroscopy. The heterogeneous modifications are not chemically selective due to side reactions and/or incomplete conversion. The pore structure is altered predominately via modified polymer swelling causing changed UF fluxes and selectivities. However, for the modification via PAN reaction with hydroxyl amine, acid hydrolysis, and azido transfer, the initial membrane separations performance is qualitatively preserved. Using the acyl azide ḿethod, amylo-glucosidase (AG) (EC 3.2.1.3) was immobilized onto the modified PAN UF membranes, enabling hydrolysis of starch or maltose to glucose. Enzyme activity was assayed depending on previous chemical modification (azide content) and immobilization (pH) conditions as well as hydrolysis parameters (substrate, conversion during diffusion or UF). The best results (up to 600 mU/cm2 at 40°C and pH 5.0) were obtained after modification of PAN membranes via carboxyl creation and azido transfer. AG convalently bound to PAN is not influenced much in its catalytic properties (Km = 3.48 and 3.1 mmol/L for free and bound AG, respectively, with maltose at 40°C and pH 5.0). Under UF conditions, AG effective activity can be improved by the convective flow through the membrane. UF selectivity for the polymer starch determines effective substrate concentrations in the membrane, thus affecting observed activities and product purities in the filtrate. © 1996 John Wiley & Sons, Inc.
    Additional Material: 10 Ill.
    Type of Medium: Electronic Resource
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