24837-73-8Relevant academic research and scientific papers
Structure-reactivity relationship of benzyl benzenesulfonates. Part 3. Prediction of reaction mechanism by the use of correlation interaction coefficients
Yoh, Soo-Dong,Cheong, Duk-Young
, p. 701 - 705 (1996)
Nucleophilic substitution reactions of (Z)-benzyl (X)-benzene sulfonates with (Y)-pyridines were investigated in acetone at 35 °C. The magnitudes of the Hammett reaction constants ρX, ρY and ρZ indicate that a stronger nucleophile leads a lesser degree of bond breaking and a better leaving group is accompanied by a lesser degree of bond formation. The magnitude of interaction term, ρlj can be used to determine the structure of the transition state (TS) for the SN reaction. In particular, the comparison of ρXZ with ρYZ and the sign of ρZ can predict that this reaction series proceed via dissociative SN2 process. This result also accords with the treatment of the MOFJ diagram. The sign of the product ρXZρYZ can predict the movement of the TS.
Quantitative approach to the Menschutkin reaction of benzylic systems
Yoh, Soo-Dong,Cheong, Duk-Young,Lee, Oh-Seuk
, p. 63 - 68 (2003)
The quaternization reactions of substituted (Z)-benzyl (X)-benzenesulfonates with substituted (Y)-pyridines were investigated in acetonitrile at 35 °C. The magnitudes of the Hammett reaction constants ρX, ρY and ρZ indicate that a stronger nucleophile leads to a lesser degree of bond breaking. In addition, a better leaving group is accompanied by a lesser degree of bond formation. Application of multi-Hammett interactions, |ρYZ| > |ρXY| >ρXZ|, predicts that these Menschutkin-type reactions are dissociative SN2 reactions. In particular, the reaction of strongly activated benzyl derivatives with tertiary amines in acetonitrile reveals a more advanced bond breaking like SN1 reactions. The predicted mechanism for the benzylation of pyridines with benzylic systems is evident from More O'Ferrall-Jencks diagram and the semi-empirical MO calculations with the AM1 method. Copyright
