Abstract
Hydrolysis reactions of N-aryliminotriphenylphosphoranes (I) at varying pH have been investigated kinetically. The reactions produced aniline derivatives and triphenylphosphine oxide as the products. The reactions are first-order, and the Hammett ρ values are −0.29 and −0.63 at pH 3.0 and 8.0, respectively. The reaction rate increased linearly with acetate ion concentration at [AcO−] < 0.05 M and approached a limiting value at higher base concentration. The plot of logk t versus pH shows that there are two different regions in the rate profile; one part in which logk t increases with hydronium ion concentration and the other where k t is a constant regardless of pH. On the basis of these results, a plausible hydrolysis mechanism is proposed. At pH < 8.0, the reaction proceeds by protonation of the iminophosphorane nitrogen atom, followed by the addition of a water molecule. At pH > 8.0, the proton transfer from water to α-nitrogen of the iminophosphorane becomes the rate limiting step.
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From Kinetika i Kataliz, Vol. 46, No. 1, 2005, pp. 26–34.
Original English Text Copyright © 2005 by Pyun, Lee, Kim.
This article was submitted by the authors in English.
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Pyun, SY., Lee, YH. & Kim, TR. Mechanism of the hydrolysis of N-aryliminotriphenylphosphoranes. Kinet Catal 46, 21–28 (2005). https://doi.org/10.1007/s10975-005-0031-x
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DOI: https://doi.org/10.1007/s10975-005-0031-x