1998
DOI: 10.1021/jo971398t
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Sodium N-Chlorobenzenesulfonamide as a Selective Oxidant for Hexosamines in Alkaline Medium:  A Kinetic and Mechanistic Study

Abstract: Oxidation of D-mannosamine (1), D-glucosamine (2), and D-galctosamine (3) by sodium N-chlorobenzenesulfonamide or chloramine-B (CAB) at 313 K is followed by a shortening of carbon chain and obeys the rate law, rate = k[CAB][sugar][HO(-)](x)(), where x is less than unity. The products are arabinonic acid, ribonic acid, and erythronic acid for 1 and 2 with smaller amounts of glyceric and hexonic acids, while lyxonic and threonic acids are predominant in the oxidation of 3 with smaller amounts of glyceric and hex… Show more

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Cited by 126 publications
(72 citation statements)
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“…A vant Hoff's plot was made for the Scheme 1. variation of K 2 with temperature [i.e., log K 2 versus 1/T (r > 0.9985, S 0.036)] and the values of the enthalpy of reaction, DH , entropy of reaction, DS, and free energy of reaction, DG, were calculated as 58.1 ± 2.6 kJ mol À1 , 253 ± 12 J K À1 mol À1 and À19.4 ± 1.0 kJ mol À1 , respectively. A comparison of the latter values with those obtained for the slow step of the reaction shows that these values mainly refer to the rate limiting step, supporting the fact that the reaction before the rate determining step are fairly slow and involves high activation energy [31].…”
Section: Discussionsupporting
confidence: 53%
“…A vant Hoff's plot was made for the Scheme 1. variation of K 2 with temperature [i.e., log K 2 versus 1/T (r > 0.9985, S 0.036)] and the values of the enthalpy of reaction, DH , entropy of reaction, DS, and free energy of reaction, DG, were calculated as 58.1 ± 2.6 kJ mol À1 , 253 ± 12 J K À1 mol À1 and À19.4 ± 1.0 kJ mol À1 , respectively. A comparison of the latter values with those obtained for the slow step of the reaction shows that these values mainly refer to the rate limiting step, supporting the fact that the reaction before the rate determining step are fairly slow and involves high activation energy [31].…”
Section: Discussionsupporting
confidence: 53%
“…A comparison of the later values (from K2) with those obtained for the slow step of the reaction shows that these values mainly refer to the rate-limiting step, supporting the fact that the reaction before rate determining step is fairly fast and involves low activation energy. 27 The negative value of indicate that the complex (C) is more ordered than the reactant. 28 A detailed mechanistic explanation is given in Scheme 2.…”
Section: Discussionmentioning
confidence: 99%
“…This leads to the formation of compacted intermediate complex and such activated complex is more ordered than the reactants due to loss of degree of freedom [28]. The experimental values of H ≠ and S ≠ were both favorable for electron-transfer process [29]. Again, the positive values of H ≠ and G ≠ indicate endothermic formation of the intermediate and its non-spontaneity, respectively.…”
Section: Discussionmentioning
confidence: 99%