Kinetics of hydrolysis of aromatic bicycling disulfonyl dichlorides

Abstract

PRZEMYS~AW SANECIU and EDWARD ROKASZEWSKI. Can. J. Chem. 66, 3056 (1988). Hydrolysis of 16 compounds C102S-Ar-B-Ar-S02C1 (B, bridge) in 20% H20, 8 0 8 v/v CH3C02H, 0.5 mol dmp3 CH3C02Na at 298.15 K has been investigated by a polarographic method. From plots of the hydrolysis, pseudo-first-order rate kl k2 constants for two consecutive reactions A -+ AI -+A2 have been computed and the influence of -SO2C1 groups, bridges B, and SO3-groups on the reactivity of -S02C1 groups has been discussed. The ratio of rate constants k2/k, ranges from 0.45 to 30, depending on the structure. Log (kl/(2kH)) correlated linearly with u-g:&HS and log (k,/kl) correlated linearly with ApK for the analogous diamine series H2N-Ar-B-Ar-NH2.PRZEMYSLAW SANECKI et EDWARD ROKASZEWSKI. Can. J. Chem. 66, 3056 (1988). Optrant i 298,15 K, en solution dans un mClange 20:80 (v/v) de H20/CH3C02H contenant 0,5 mol dm-) de CH3C02Na, et faisant appe1.i une mCthode polarographique, on a Ctudit I'hydrolyse de 16 composts du type C102S-S-Ar-B-Ar-S02C1 (pont, B). A partir des courbes d'hydrolyses, on a calculC les constantes de pseudo-premier ordre des deux rtactions kl k2 consCcutives A -+ Al -+ A2; on discute de l'influence des groupements -S02C1, des ponts B ainsi que des groupements SO3-sur la rkactivitt des groupements -S02CI. Selon la structure, les rapports des constantes de vitesse kz/kl varient de 0,45 i 30. On a Ctabli une corrklation lintaire entre le log (kl/2kH) et le u.g:&HS ainsi qu'entre le log (k2/kl) et le ApK de la skrie des diamines analogues H2N-Ar-B-Ar-NH2.[Traduit par la revue]

Numerical Modeling of ECE‐ECE and Parallel EE‐EE Mechanisms in Cyclic Voltammetry. Reduction of 1,4‐Benzenedisulfonyl Difluoride and 1,4‐Naphthalenedisulfonyl Difluoride

“…Its mechanism, typical for acid halides, was for the first time recognized for À SO 2 Cl [15], and later on for À SO 2 F group [38]. For the 1,3-benzenedisulfonyl fluoride investigated previously two irreversible two-electron peaks has been observed, each of them has corresponded to complete two-electron reduction of only one À SO 2 F group [12].…”

“…In addition, the obtained kinetic data indicated ( Fig. 2 and 4) that the "second" rate constant k 2 , k 4 , ... is determined with less accuracy as compared to the "first" k 1 , k 3 ... what is repeatedly met in both chemical and electrochemical kinetics (see, e.g., [31] and [45] with the literature referred therein).…”

Chemoselective Reactions of Functionalized Sulfonyl Halides

“…Thus, methyl(trifluoromethyl)dioxirane (TFDO) was tolerated as an oxidant for the double bond epoxidation [314] or tertiary benzylic C−H hydroxylation [315] (Scheme 46, A ). Other benzylic C−H bond oxidants compatible with the SO 2 Cl moiety include CrO 3 , [287] KMnO 4 [316] or SeO 2 [317] (Scheme 46, B ). Additional notable examples tolerating the sulfonyl chloride moiety include oxidation of sulfur‐ or selenium‐containing groups with H 2 O 2 , [318,319] Br 2 , [320,321] or even F 2 [185] (Scheme 46, C ), as well as reaction of triazole derivative 34 with N 2 O 4 (Scheme 46, D ) [307] …”