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• W4206501897 abstract "3-Thio-2-oxoalkanoic acids I, III and IV (AH3) undergo dissociation and form the carboxylate (AH2), the thiolate-carboxylate dianion (AH) and for I even a trianion (A), when AH acts as a C-acid. Formation of a carbanion-enolate was confirmed by following the dissociation of thioether II. Generally, the hydration decreases in the sequence AH3>AH2>AH. Similarly for the thioether II, the conjugate acid is more strongly hydrated than the carboxylate anion. In ester V the conjugate acid is also more strongly hydrated than the thiolate anion. Hydration of ester V is comparable to the hydration of the acid form H3A of I. Introduction of an isopropyl group in α-position in IV decreases the hydration similar to the replacement of the SH group by a SC2H5 grouping. In acidic solutions polarographic reduction of acid form AH3 occurs after pre-protonation of the carbonyl group, either by electron transfer to the carbonyl group followed by elimination of the sulfide anion or by hydrogenolytic cleavage of the C−S bond. At pH 3–6 the monoanion AH2 is furthermore protonated on the carboxyl group and then reduced as AH3. At pH 6–11 the monoanion AH2 is reduced, either at the CO group or with cleavage of the C−S bond. At pH 8–11 this monoanion is formed by a rapid protonation of the dianion AH. For the thioether II where such acid-base equilibrium involving the thiol form is impossible, the half-wave of wave i2A potential at pH>6 is pH-independent. In more alkaline media, base-catalyzed dehydration takes place, occurring via geminal diol anion. Changes in the rate of dehydration resulting from structural changes considerably affect the pH-dependences of polarographic waves, particularly of wave i1 at pH<6. Differences between the behavior of 3-thio-2-oxobutanoic acid (III) (see Fig. 6) and 3-thio-4-methyl-2-oxopentanoic acid (IV) (see Fig. 7) similarly as for those between 3-thio-2-oxopropanoic acid (I) (see Fig. 1) and its 3-ethylthioether (II) (see Fig. 3) are most strking. Whereas at the DME the competition between C=O reduction and C−S cleavage is governed by differences in the rates of establishment of the acid-base equilibria, yields of preparative reductions obtained with a stirred mercury pool electrode are given by the position of these equilibria in the bulk of the solution. At the pool electrode AH3 is predominantly reduced on the CO group, monoanion AH2 shows comparable reduction of both the CO group and cleavage of the C−S bond, whereas the dianion AH is predominantly reduced at the C−S bond." @default.
• W4206501897 created "2022-01-26" @default.
• W4206501897 creator A5058581826 @default.
• W4206501897 date "1983-01-10" @default.
• W4206501897 modified "2023-10-01" @default.
• W4206501897 title "Competitive reduction of the carbonyl group and of the C-S bond in 3-thio-2-oxoalkanoic acids and their derivatives at the dropping mercury and mercury pool electrodes" @default.
• W4206501897 doi "https://doi.org/10.1016/0368-1874(83)80018-5" @default.
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