Current time in Korea 11:34 Apr 19 (Fri) Year 2024 KCS KCS Publications
KCS Publications
My Journal  Log In  Register
HOME > Search > Browsing(BKCS) > Archives

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 
 
Title
 The α-Effect in SNAr Reaction of 1-Fluoro-2,4-dinitrobenzene with Hydrazine: Ground-State Destabilization versus Transition-State Stabilization
Author
 Hyo-Jin Cho, Ik-Hwan Um*
Keywords
 The α-Effect, Hydrazine, SNAr reaction, H-bonding interaction, Brønsted-type plot
Abstract
 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.
Page
 2371 - 2374
Full Text
 PDF

How to access to the WOL for The Bulletin of the Korean Chemical Society ?

The Bulletin of the Korean Chemical Society will be co-published with Wiley-VCH from 2015 towards. The online version of the Journal will thus be available on Wiley Online Library, Wiley(-VCH)'s global online platform.

KCS members can get a free online access to the Bulletin of the Korean Chemical Society in WOL.

Close