14503-42-5Relevant academic research and scientific papers
Using 11C/14C incoming group and secondary α-deuterium KIEs to determine how a change in leaving group alters the structure of the transition state of the S(N)2 reactions between m-chlorobenzyl para- substituted benzenesulfonates and cyanide ion
Westaway, Kenneth C.,Fang, Yao-Ren,Persson, Jonas,Matsson, Olle
, p. 3340 - 3344 (2007/10/03)
The 11C/14C incoming group and secondary α-deuterium KIEs and Hammett ρ value found by changing the substituent in the leaving group of the S(N)2 reactions between meta-chlorobenzyl para-substituted benzenesulfonates and cyanide ion in 0.5% aqueous acetonitrile at 0 °C suggest that these reactions occur via an unsymmetrical, product-like transition state. Changing to a better leaving group leads to a transition state with a slightly shorter nucleophile-α-carbon bond and a longer α- carbon-leaving group bond. The changes in transition state structure are consistent with the Bond Strength Hypothesis.
Rate and Product Analytical Study of the Solvolysis of 3-Chlorobenzyl Arenesulfonates in Aqueous 2,2,2-Trifluoroethanol
Gordon, Isobel M.,Maskill, H.
, p. 1951 - 1954 (2007/10/02)
The rates of solvolysis of 3-chlorobenzyl 4-methyl-, 4-methoxy-, and 4-bromo-benzenesulfonates at different temperatures in 1:1 (v/v) 2,2,2-trifluoroethanol-water have been measured and the activation parameters determined.Qualitatively, the rate constants show the expected dependence upon the substituent in the benzenesulfonate leaving group, and the toluenesulfonate is 42 times less reactive (at 25 deg C) than benzyl toluenesulfonate itself.In the product analytical study, the ratio of the 3-chlorobenzyl alcohol to the 3-chlorobenzyl trifluoroethyl ether was determined in each of the three cases, and shown to be independent of the nature of the nucleofuge.Introduction of the 3-chloro substituent into the electrophile, however, causes the selectivity for water as opposed to trifluoroethanol to be increased by ca. 50percent.The results are discussed in terms of a substitution reaction which is concerted but not synchronous, a solvent-induced, largely uncoupled SN2 mechanism.
