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Bulletin of the Korean Chemical Society (BKCS)

ISSN 0253-2964(Print)
ISSN 1229-5949(Online)
Volume 35, Number 8
BKCSDE 35(8)
August 20, 2014 

The α-Effect in SNAr Reaction of 1-Fluoro-2,4-dinitrobenzene with Hydrazine: Ground-State Destabilization versus Transition-State Stabilization
Hyo-Jin Cho, Ik-Hwan Um*
The α-Effect, Hydrazine, SNAr reaction, H-bonding interaction, Brønsted-type plot
A kinetic study is reported on SNAr reaction of 1-fluoro-2,4-dinitrobenzene with a series of primary amines including hydrazine in H2O at 25.0 oC. The plots of kobsd vs. [amine] are linear and pass through the origin, indicating that general-base catalysis by a second amine molecule is absent. The Brønsted-type plot exhibits an excellent linear correlation with βnuc = 0.46 when hydrazine is excluded from the correlation. The reaction has been suggested to proceed through a stepwise mechanism, in which expulsion of the leaving group occurs after the rate-determining step (RDS). Hydrazine is ca. 10 times more reactive than similarly basic glycylglycine (i.e., the α-effect). A five-membered cyclic intermediate has been suggested for the reaction with hydrazine, in which intramolecular H-bonding interactions would facilitate expulsion of the leaving group. However, the enhanced leaving-group ability is not responsible for the α-effect shown by hydrazine because expulsion of the leaving group occurs after RDS. Destabilization of the ground-state of hydrazine through the electronic repulsion between the nonbonding electron pairs is responsible for the α-effect found in the current SNAr reaction.
2371 - 2374
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