Chlorination. I. Physical evidence for polar effects in the products of the chlorination of cyclohexanecarboxylic acid

Kinetics of the acid-catalyzed .alpha.-bromination of aliphatic acids

“…Since 4b and 4c are less stable than 4a, the path via 4a is favored, thus exerting little steric hindrance. A bromide ion attack on 4 gives -bromoacyl bromide (5). Lower aliphatic acids show less reactivity than that expected from Taft's equation;19 this tendency is remarkable with acetic acid.…”

“…+ HC1 + H2S04 (5) RR'C=C=0 4-Br2 -X RR'CBrCOBr (6) RR'CBrCOBr + CH3OH -RR'CBrC02CH3 + HBr (7) Step 5 for formation of ketene is irreversible or at least shifts greatly to the right side and this reaction competes with other reactions of aliphatic acids such as the formation of RR'-CH(OH)2+, RR'CHCO+, RR'C(S03H)C02H, RR'CHCOO-LCISO^H^c m I Figure 1. Correlation between concentration of chlorosulfonic acid and rate constant (A0bsd) for bromination of isobutyric acid at 60 °C.…”