Smith, Hilton A.; Hunt, Paul P. published the artcile< Kinetics of the esterification of the cyclohexanedicarboxylic acids with diphenyldiazomethane>, Category: esters-buliding-blocks, the main research area is .
The rates of esterification of 1,2-, 1,3-, and 1,4-cyclohexanedicarboxylic acids (I) and their monomethyl esters (II) in absolute EtOH with diphenyldiazomethane (III) were determined at 15, 25, 35, and 45° by using a spectrophotometer to determine the extent of reaction. The rate constants are a combination of the rates of reaction of III with the acids or monomethyl ester and the EtOH (acid, average rate constants in l./mole min. at 15, 25, 35, 45°, Εa × 10-4 cal./mole) cis-1,2-, 0.264, 0.696, 1.72, 3.79, 1.63; trans-1,2-, 0.362, 0.889, 2.14, 4.71, 1.56; cis-1,3-, 0.278, 0.730, 1.78, 3.96, 1.62; trans-1,3-, 0.207, 0.525, 1.28, 2.90, 1.62; cis-1,4-, 0.210, 0.541, 1.33, 2.90, 1.59; trans-1,4-, 0.260, 0.678, 1.62, 3.56, 1.58 (monomethyl ester, average rate constants in l./mole min. at 15, 25, 35, 45°, Εa × 10-4 cal./mole) cis-1,2-, 0.158, 0.405, 0.984, 2.21, 1.61; trans-1,2-, 0.228, 0.567, 1.38, 2.99, 1.58; cis-1,3-, 0.150, 0.376, 0.926, 2.11, 1.61; trans-1,3-, 0.115, 0.297, 0.712, 1.63, 1.60; cis-1,4-, 0.117, 0.294, 0.717, 1.61, 1.61; trans-1,4-, 0.137, 0.337, 0.829, 1.87, 1.59. The rate constants for the reaction of III with I or II show a total variation of less than 2, whereas the acid- and base-catalyzed esterifications of I have a total variation of about 20, indicating the relatively minor importance of steric considerations in the reaction of III with I and II. The presence of the Me group does not materially increase the steric hindrance to reaction with III. The large rates for the cis- and trans-1,2-acids and monoesters indicate that the electron-sink properties of the carboxyl or ester group are more important than the steric effects. The acid group is more reactive in II than in I. The cis-1,3 and trans-1,4 compounds behave similarly, as do the trans-1,3 and the cis-1,4 compounds
Journal of the American Chemical Society published new progress about Activation energy. 112-63-0 belongs to class esters-buliding-blocks, and the molecular formula is C19H34O2, Category: esters-buliding-blocks.
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