13798-51-1Relevant articles and documents
Kinetics and mechanism of the aminolysis of cycloalkylmethyl arenesulfonates
Oh, Hyuck Keun,Song, Se Jeong,Jo, Dong-Soo,Lee, Ikchoon
, p. 91 - 96 (2007/10/03)
Nucleophilic substitution reactions of cycloalkylmethyl arenesulfonates (CmH2n-1 CH2OSO2C6H4Z) with anilines (XC6H4NH2) in methanol at 65.0 °C were studied. The reactivity order (n=4>6>7>5) reflects largely the order of steric effect of the ring size (SEs term) except for n=5, which exhibits the least reactivity. This reversal of the order for n=5 is considered to result from large rate retardation due to polar effect of the ρ*σ* term. Application of the Taft equation to the rate data for n=5 and 6 gives ρ=17·4 and 5=2·3 with correlation coefficient of 0·90. The σ* values for n=4 and 7 are estimated to be - 0·23 and - 0·11, respectively. The positive ρxz values of ca 0·3 are consistent with previous results for the reactions at primary reaction centers.
Bimolecular Nucleophilic Substitution (SN2) Reactions of Neopentyl Arenesulfonates with Anilines and Benzylamines in Methanol
Koh, Han Joong,Lee, Hai Whang,Lee, Ikchoon
, p. 253 - 258 (2007/10/02)
Bimolecular nucleophilic substitution (SN2) reactions of neopentyl arenesulfonates with anilines and benzylamines in methanol at 55.0 deg C are reported.The tightness of the transition state (TS) is similar to that for other typical SN2 processes at a primary alkyl carbon centre based on the magnitude of the cross-interaction constant ρxz (0.30) between the substituents in the nucleophile (X) and leaving group (Z).The TS variation is in accord with that predicted by the potential energy surface diagram, which in turn is consistent with the positive sign of ρxz; a later TS is obtained with a weaker nucleophile and nucleofuge.Taft's polar substituent constant, ?*, for the trimethylsilyl group is estimated to be -0.48 by using a factor of 1.875 for the fall-off of ?* from the tert-butyl to the neopentyl group and extrapolating from the experimental Taft plot.
Cross Interaction Constants As a Measure of Transition State structure. Part 7. Aminolysis of Alkyl Benzenesulphonates
Lee, Ikchoon,Choi, Young Hoon,Rhyu, Keun Woo,Shim, Chang Sub
, p. 1881 - 1886 (2007/10/02)
Kinetic studies of the reactions of methyl and ethyl benzenesulphonates with anilines and benzylamines in methanol and acetonitrile at 65.0 deg C have been reported.The magnitudes of cross-interaction constants between substituents in the nucleophile (X) and the leaving group (Z),ρxz and βxz, were found to be greater for the ethyl series which indicates a tighter transition state for ethyl rather than methyl derivatives.This unexpected trend has been rationalized by making the assumption that the small electron-donating polar effect, of the α-methyl substituent in the ethyl compounds, requires a tighter transition-state structure in addition to the major effect of steric repulsion on the activation barrier which is present in all SN2 reactions taking place at a carbon centre.