Kinetics and Mechanism of the Aminolysis of Phenylacetyl Chlorides in Acetonitrile

Title
Kinetics and Mechanism of the Aminolysis of Phenylacetyl Chlorides in Acetonitrile
Authors
Lee, H.W; Lee, J.W.
Keywords
NUCLEOPHILIC-SUBSTITUTION REACTIONS, CROSS-INTERACTION CONSTANTS
Issue Date
1998-01-26
Publisher
Bulletin of the Korean Chemical Society
Abstract
The aminolysis reactions of phenylacetyl chlorides with anilines and N,N-dimethylanilines (DMAs) in acetonitrile at -15.0 degrees C are investigated. The magnitude of rho(X)(=-2.8 similar to-2.9) and rho(Y) (=0.9 similar to 1.3, after correcting for the fall-off), and the negative sign of rho(X)(=-0.12) for the reactions with anilines suggest an associative S(N)2 mechanism. For the reactions with DMAs, the magnitude of these Hammett coefficients increases so that tighter bond making in the transition state (TS) is predicted. A nonlinear Hammett plots obtained for the DMAs with an electron acceptor substituent is interpreted to result from a more advanced degree of leaving group departure to assist closer approach of the bulky DMA in the TS. The normal secondary kinetic isotope effects (k(H)/k(D)>1.0) involving deuterated anilines suggest partial deprotonation by hydrogen bonding to the departing chloride ion.
URI
http://dspace.inha.ac.kr/handle/10505/20161
ISSN
0253-2964
Appears in Collections:
College of Natural Science(자연과학대학) > Chemistry (화학) > Journal Papers, Reports(화학 논문, 보고서)
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