254. Reaction kinetics and the Walden inversion. Part III. Homogeneous hydrolysis and alcoholysis of α-bromopropionic acid, its ester and anion

Solvolytic Displacement Reactions At Saturated Carbon Atoms

“…Three separate studies have shown that the rate of the first-order solvolysis of a-bromopropionate ion increases slightly with increasing ionic strength (141,297,549). The only study which led to the contrary result (167) has been demonstrated to have been incorrectly interpreted (297).…”

“…The methanolysis of methyl a-bromopropionate is accompanied by complete inversion of configuration (167). By analogy with other neighboring groups, if participation were to occur in this system, a retention of configuration would be expected .…”

“…The reaction of a-bromopropionate ion with methoxide ion follows second-order kinetics and yields a-methoxypropionate ion with inversion of configuration (167). The methanolysis of the salt itself in weakly basic solutions follows first-order kinetics and yields a-methoxypropionate ion with retention of configuration (167).…”

Absence of SN1 Involvement in the Solvolysis of Secondary Alkyl Compounds

“…Their conclusions rely on results reported in other papers in this series and on prior papers, particularly Hughes et al (5) and Cowdrey et al (6). These papers discussed the results of a number of their studies dealing with nucleophilic substitution and elimination at saturated carbons, and constituted much of their evidence for the mechanisms by which these transformations took place.…”

Kinetics of the Alkaline Solvolysis of Trichloroacetate Ion in Water-Ethanol Solutions

“…BROOKS and DAWSON 3 studied the progressive elimination of bromine in the aqueous hydrolysis of sodium bromoacetate and concluded that the course of reaction is approximately unimolecular. The reaction of a-bromopropionate ion with methoxide ion follows secondorder kinetics and yields a-methoxy-propionate with inversion of configuration 4 .…”