Kinetic Carbon Isotope Effects in the Decarbonylation of Lactic Acid of Natural Isotopic Composition and of [1-14C] Lactic Acid

Studies of carbon-13 and carbon-14 kinetic isotope effects (K. I. E.) in the decarbonylation of lactic acid (L. A.) in sulphuric acid and in phosphoric acids media have been summarized and compared with earlier studies of ¹⁴C and ¹³C K. I. E. in the decarbonylation of formic and oxalic acids in concentrated sulphuric acid. Supplementary data concerning the decarbonylation of L. A. in sulphuric acid diluted with water and in pyrophosphoric acid are presented and discussed. The observed temperature dependences of ¹³C and ¹⁴C K. I. E. in concentrated H₂SO₄ and in concentrated phosphoric acids media have been rationalized by invoking a change of the mechanism of decarbonylation of L. A. in concentrated sulphuric and phosphoric acids with temperature. Preliminary calculational results concerning ¹³C and ^1??C K. I. E. in decarbonylation processes are also presented. In H₂SO₄ diluted with water and in H₃PO₄ diluted with water the temperature dependence of ¹³C and ¹⁴C K. I. E. is normal and well reproduced by one frequency approximation. In concentrated sulphuric acid and in concentrated phosphoric acids besides the C—OH bond rupture the rupture of a C—C bond had to be considered also to reproduce the observed ¹³C K. I. E. in selected temperature regions.