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Nucleophilic substitution reactions at a dicoordinated sulfur compound take place through a bimolecular mechanism 1,2 as well as a tricoordinated sulfur compound. [3][4][5] These reactions are well known to proceed through a stepwise mechanism with a hypervalent sulfur species(sulfuranide) as an intermediate or through a single step with synchronous bond formation and breaking (S N 2 type mechanism) as shown in Scheme 1.The tool of criterion for the mechanism of nucleophilic substitution reactions has been most frequently used Bronsted and Hammett eq. For example, a break or curvature in Bronsted plot has often been observed for the aminolysis of ester with good leaving group. 6,7 Nonlinear free energy relationships have been often interperated as a change of a rate determining step for a stepwise mechanism, while a linear Bronsted plot suggests no change in mechanism.The studies on nucleophilic substitution reactions of a dicoordinated sulfur compound are very rare in comparison with those of a tricoordinated or tetracoordinated sulfur compounds. The authors have performed the kinetic studies on the reaction of 4-nitrobenzenesulfenyl chloride with substituted (X)benzylamines in DMSO at 25 o C to gain further information into the aminolysis mechanism of a dicoordinated sulfur compound. Results and DiscussionThe reaction of 4-nitrobenzenesulfenyl chloride with benzylamines in DMSO obeyed pseudo-first order kinetics under large excess amine concentration. Pseudo-first-order rate constant (k obsd ) was obtained from the slope of the plot of ln(λ−λ t ) vs time and listed in Table 1.The k obsd value increases with increasing concentration of amine, but it shows the upward curvature at higher concentration of amine as shown in Figure 1. Therefore, the k obsd can be given by Eq. (1), where k o is the solvolytic rate constant, and k 2 , k 3 are the second order and the third order rate constants with X-benzylamine, respectively. When the reactions take place as described in Eq. (1), involving the term of general base catalysis, the plot of(2), should be linear, and the expected linear plot was obtained as seen in Figure 2. • ■ Scheme 1
Nucleophilic substitution reactions at a dicoordinated sulfur compound take place through a bimolecular mechanism 1,2 as well as a tricoordinated sulfur compound. [3][4][5] These reactions are well known to proceed through a stepwise mechanism with a hypervalent sulfur species(sulfuranide) as an intermediate or through a single step with synchronous bond formation and breaking (S N 2 type mechanism) as shown in Scheme 1.The tool of criterion for the mechanism of nucleophilic substitution reactions has been most frequently used Bronsted and Hammett eq. For example, a break or curvature in Bronsted plot has often been observed for the aminolysis of ester with good leaving group. 6,7 Nonlinear free energy relationships have been often interperated as a change of a rate determining step for a stepwise mechanism, while a linear Bronsted plot suggests no change in mechanism.The studies on nucleophilic substitution reactions of a dicoordinated sulfur compound are very rare in comparison with those of a tricoordinated or tetracoordinated sulfur compounds. The authors have performed the kinetic studies on the reaction of 4-nitrobenzenesulfenyl chloride with substituted (X)benzylamines in DMSO at 25 o C to gain further information into the aminolysis mechanism of a dicoordinated sulfur compound. Results and DiscussionThe reaction of 4-nitrobenzenesulfenyl chloride with benzylamines in DMSO obeyed pseudo-first order kinetics under large excess amine concentration. Pseudo-first-order rate constant (k obsd ) was obtained from the slope of the plot of ln(λ−λ t ) vs time and listed in Table 1.The k obsd value increases with increasing concentration of amine, but it shows the upward curvature at higher concentration of amine as shown in Figure 1. Therefore, the k obsd can be given by Eq. (1), where k o is the solvolytic rate constant, and k 2 , k 3 are the second order and the third order rate constants with X-benzylamine, respectively. When the reactions take place as described in Eq. (1), involving the term of general base catalysis, the plot of(2), should be linear, and the expected linear plot was obtained as seen in Figure 2. • ■ Scheme 1
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