Carbon-13 kinetic isotope effects in the decarbonylation of lactic acid of natural isotopic composition in phosphoric acid medium

The 13C kinetic isotope effect fractionation in the decarbonylation of lactic acid (LA) of natural isotopic composition by concentrated phosphoric acids (PA) and by 85% H3PO4 has been studied in the temperature interval of 60-150 deg C. The values of the 13C(1) isotope effects in the decarbonylation of lactic acid in 100% H3PO4, in pyrophosphoric acid and in more concentrated phosphoric acids are intermediate between the values calculated assuming that the C(1)-OH bond is broken in the rate-controlling step of dehydration and those calculated for rupture of the carbon-carbon bond in the transition state. In the temperature interval of 90-130 deg C the experimental 13C fractionation factors determined in concentrated PA approach quite closely the 13C fractionation corresponding to C(2)-C(1) bond scission. The 13C(1) kinetic isotope effects in the decarbonylation of LA in 85% orthophosphoric acid in the temperature range of 110-150 deg C coincide with the 13C isotope effects calculated assuming that the frequency corresponding to the C(1)-OH vibration is lost in the transition state of decarbonylation. A change of the mechanism of decarbonylation of LA in going from concentrated PA medium to 85% H3PO4 has been suggested. A possible secondary 18O and a primary18O kinetic isotope effect in decarbonylation of lactic acid in phosphoric acids media have been discussed, too. (author) 21 refs.; 3 tabs