The amidic unit is of fundamental importance in biological systems and to organic chemistry. Of primary concern to living systems are the acyl-transfer reactions of amides, not the least of which is the transfer to H20,

A study of the hydrolysis of formamide is reported with the aims of isolating the water reaction for hydrolysis from the acid and base hydrolysis terms and determining the solvent deuterium kinetic isotope effect (dkie) on base-catalyzed hydrolysis. Respective activation parameters (ΔH‡ and ΔS‡) of (17.0 ± 0.4) kcal mol–1 and (–18.8 ± 1.3) cal mol–1 K–1 for the acid reaction and (17.9 ± 0.2) kcal mol–1 and (–11.1 ± 0.5) cal mol–1 K–1 for the base reaction were determined from Eyring plots of the second-order rate constants over the range of 27–120°C. Kinetic studies at the minima of the pH/rate profiles in the pH range from 5.6 to 6.2 in MES buffers at 56°C, and in the pH range of 4.25–6.87 in acetate and phosphate buffers at 120°C are reported. At 56°C the available data fit the expression k56obs = 0.00303[H3O+] + 0.032[HO–] + (3.6 ± 0.1) × 10–9, while at 120°C the data fit k120obs = (0.15 ± 0.02)[H3O+] + (3.20 ± 0.24)[HO–] + (1.09 ± 0.29) × 10–6. Preliminary experimental estimates of Ea (ln A) of 22.5 kcal mol–1 (15.03) for the water rate constant (kw) are calculated from an Arrhenius plot of the 56 and 120°C data giving an estimated kw of 1.1 × 10–10 s–1 (t1/2 = 199 years) at 25°C. Solvent dkie values of kOH/kOD = 1.15 and 0.77 ± 0.06 were determined at [OL–] = 0.075 and 1.47 M, respectively. The inverse value is determined under conditions where the the first step of the reaction dominates and is analyzed in terms of a rate-limiting attack of OL–.Key words: formamide, activation parameters, water reaction, acid and base hydrolysis, solvent kinetic isotope effect.

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A theory for stabilization of carbonium ions or other cations, by delocalization of neighboring bonds, is described. Such delocalization is available without changing the reactant geometry and is termed "vertical stabilization." The stabilizing influence is contrasted to the bridged-ion theory of neighboring group participation, in which the neighboring group moves toward the reaction center as the transition state is approached, and to frangomeric acceleration, in which the neighboring group moves away from the reaction center as the transition state is approached. The effects of structural changes on the magnitude of (vertical) -conjugation are discussed. In addition, further evidence is offered against significant effects of C-H hyperconjugation on bond lengths. Delocalization of bonds was first discussed in detail by Mulliken6 in his treatment of carbon-hydrogen hyperconjugation as an explanation of certain properties (1) Supported by the Air Force Office of Scientific Research, Grants AFOSR-69-1639 and AFOSR-69-1639A.(2) The effects ofconjugation on singlet neutral molecules, on free radicals, and on carbanions will be considered in subsequent papers.(3) The major part of these ideas was presented at the 155th National Meeting of the American Chemical Society, San Francisco, Calif., April 1968, p 39. Previous discussions ofconjugation in cations are found in ref 4a-g.(4) (a) W.