Zur Kenntnis der β‐halogen‐substituierten Fettsäuren und der β‐Lactone

The Stereochemistry and Mechanism of the Transformation of Cinnamic Acid Dibromide to β-Bromostyrene1

“…Influence of Substituents upon Rate and Product Composition.-Mechanisms (1), (2) and (3) demand that the rate of decarboxylative elimination be first order in the concentration of the anion of the /3-halo acid (neglecting salt effects27). This was true of the cases studied by Johansson87 and Hagman, 23 Olson and Miller38 and Lane and Heine.39…”

“…Ogata40 and co-workers have published kinetic data for a considerable number of additional /3-halo acids; their first-order rate constants fall appreciably with time, in part, at least, since they failed to keep their solutions at constant pH. Since the formation of olefin from the salts of ß-halo acids proceeds simultaneously with formation of /3-hydroxy acid or /3-lactone, 23,41 it is of interest to consider the effect of substituents upon both reaction rate and product composition. From the above cited kinetic work, the following conclusions may be drawn.…”

Solvolytic Displacement Reactions At Saturated Carbon Atoms

“…In the hydrolysis of chlorosuccinate ion Holmberg (339,340,341) (382,383) was able to isolate the p-lactone intermediates of the solvolyses of p-bromocarboxylate salts. By analogy with a set of related reactions, the formation of the p-lactone should be considered as a displacement reaction accompanied by complete inversion of configuration.…”

The Reaction between Bromosuccinate Ion and Thiosulfate Ion

“…As long ago as 1912 Holmberg (3) and Johansson (7) showed that bromosuccinate ion reacted in neutral solution to form a /3-lactone, (8) showed that the formation of lactones is probably a common reaction for beta-substituted acids and is often concealed only by the high reactivity of such lactones. It was to avoid this lactone formation that Olson and Long, in the work mentioned above, maintained a high hydrogen-ion concentration.…”

“…Step 1, the production of the lactone from the bromosuccinate, has been extensively investigated by Johansson (7,8) and by Holmberg (5). Johansson followed the rate of production of the lactone by titrating the bromide ion with silver nitrate solution.…”