Kinetic analysis and mechanism of the hydrolytic degradation of squaramides and squaramic Acids

[eng] The hydrolytic degradation of squaramides and squaramic acids, the product of partial hydrolysis of squaramides, has been evaluated by UV spectroscopy at 37 °C in the pH range 3−10. Under these conditions, the compounds are kinetically stable over long time periods (>100 days). At pH >10, the hydrolysis of the squaramate anions shows first-order dependence on both squaramate and OH−. At the same temperature and [OH−], the hydrolysis of squaramides usually displays biphasic spectral changes (A → B → C kinetic model) with formation of squaramates as detectable reaction intermediates. The measured rates for the first step (k1 ≈ 10−4 M−1 s−1) are 2−3 orders of magnitude faster than those for the second step (k2 ≈ 10−6 M−1 s−1). Experiments at different temperatures provide activation parameters with values of ΔH⧧ ≈ 9−18 kcal mol−1 and ΔS⧧ ≈ −5 to −30 cal K−1 mol−1. DFT calculations show that the mechanism for the alkaline hydrolysis of squaramic acids is quite similar to that of amides