The Alcoholysis of Some Aromatic Sulphonyl Chlorides.

Vinylogous nucleophilic catalysis. Tertiary amine promoted hydrolysis of 1-alkene-1-sulfonyl chlorides

“…Products and kinetics At pH 4.0 (pH-stat) 1 gave the expected ethenesulfonic acid (4) in 90% yield, along with a 10% yield of a second product identified as 2-hydroxyethanesulfonic acid (5). At pH 10.5 and 10.8 there seemed to be slightly more 5 (15% and 13%, as the salt).…”

“…Most previous reports (19)(20)(21)(22) described essentially synthetic investigations of 1, including a valuable study (21) of the formation of betaines by reaction with tertiary amines in glacial acetic acid and certain other media. Two kinetic studies have been reported (8b, 23); the former concluded that the cation CH2=CHSO2' was 'Complete set of tables giving observed first-order rate constants, product composition, and reaction conditions (5 -" k , and k, , are the exper~mental first-and second-order rate constants for reactlon wlth H 2 0 and OH-, respect~vely, kls and klc are calculated from kl = kls + klc and kls/klc = the ratlo of 4 to 5 (or of 6 to 7) In the product at pH 4 0, slmllarly k,,,,, and k,,,,, are from bH = k,,,,,, + k,,,,, and k,oHls/k,oHlc = the ratlo of 4 to 5 (or of 6 to 7) In the product at pH 10 5 to 12.7 (see d~s c u s s~o n In text) 0 1 M aqueous KC1 (plus 0 2% 1.2-d~methoxyethane) for 1 and 3, 0 05 M KC1 for CaHsS02CI and p-MeC6H4SO2C1 ' Values of k, for 1 at other temperatures are 8 86 X 10-'at I 0, 5 14 X lo-' at 17 3, 2 91 X W ' a t 35 0 , 7 18 X 10-'at 45 0, and 3 47 x lo-' s-I at 60 0°C (see also Table S1); these, after conversion to second-order rate constants (by dlvldlng by 55 5 M ) , gave AH' = 17 5 t 2 kcal mol-' and AS' = -21 t 8 cal K-' mol-I (maxlmum errors as estimated by Wlberg's method (24)) "At I 0°C kt for 3 IS 8 1 x 10-ss-l, AH' = 17.5 f 3 kcal mol-I and AS' = -21 f 10 cal K-' mol-I (also from second-order rate constants). …”

“…5 The small amount of 2-hydroxyethanesulfonic acid (5) formed by reaction of 1 at both high and low pH points to the hydroxysulfene (15) as an intermediate as indicated in Scheme 2; 15 is presumably formed in acidic medium by attack of water, with attack of hydroxide ion becoming important above pH -9. Postulation of the intermediacy of 15 raises the possibility that at least some of the ethenesulfonic acid (4) may arise from 15 (as shown by the broken arrow in Scheme 2); this, of course, would be a form of vinylogous nucleophilic catalysis.…”

Reaction Kinetics

“…They point out, for unimolecular solvolyses, the trend of activation entropy with molal volume, with the halogen ionizing, and with the solvent composition ; and, for bimolecular displacements, the trend with number and size of sub stituents, and with the nature of the incoming and outgoing halogen. The importance of the entropy of activation can also be noted in Tommila's data on the solvolysis of alkyl tosylates (216) and aryl sulfonyl chlorides (217).…”

Sulfonyl Chloride Kinetics. Part II. Solvolysis of a Series of Benzenesulfonyl Chlorides: An Unexpected Heat Capacity Variation

“…Nucleophilic displacement from a tetrahedral sulfur has been treated generally as analogous to the corresponding displacement from carbon and the same terminology based on similar mechanistic distinctions has tended to be used (4)(5)(6)(7)(8)(9)(10)(11)(12)(13). T o the degree that the activation processes are similar, such a comparison is valid but in this and in the following paper we attempt to identify and evaluate the source of differences.…”