ISSN:
0025-116X
Schlagwort(e):
Chemistry
;
Polymer and Materials Science
Quelle:
Wiley InterScience Backfile Collection 1832-2000
Thema:
Chemie und Pharmazie
,
Physik
Notizen:
The rate constants of the reaction of 1-azabicyclo[4.2.0]octane (1) with different alkyl esters or halides were measured using 1H NMR and UV spectroscopy as well as conductometric methods. The reactivities of the alkylating agents were found to decrease with increasing nucleophilicity of the derived anions (CF3SO⊖3 〉 I⊖ 〉 Br⊖ 〉 picryl⊖ 〉 Cl⊖). Reactivities of all ethyl derivatives, except ethyl chloride, are higher than the reactivity of the 1-alkyl-1-azoniabicyclo[4.2.0]octane cation (2), which means that for these compounds the rate constant of initiation is higher than that of propagation. The reactions proceed much slower in methanol than in nitrobenzene due to the strong donor-acceptor interactions between methanol and 1. Attempts to observe covalent active centers directly by NMR spectroscopy in the polymerization mixture or to detect them kinetically, were unsuccessfull. The reactivity of ethyl triflate, modelling the hypothetical active center, was found to be 2.104 times higher than the reactivity of ions 2. This is ascribed to the high strength of the bond in the cation 2, not sufficiently compensated by the strain of the four-membered ring.
Zusätzliches Material:
6 Ill.
Materialart:
Digitale Medien
URL:
http://dx.doi.org/10.1002/macp.1984.021850105
