Ethyl orthocarbonate, hydrolysis

If the hydrolysis of methyl orthobenzoate in weakly acidic solution is carried out in the presence of various amounts of added nucleophiles, such as hydroxylamine or semicarbazide, a considerable fraction of the orthoester is transformed to the product of the reaction with the amine rather than to methyl benzoate, while the rate coefficient remains unchanged [183]. Similarly, the rate of hydrolysis of ethyl orthocarbonate in aqueous cacodylic acid buffer is the same in the presence of 0.04 M NaC104 and of 0.04 M Nal [192]. Thus, nucleophilic catalysis is absent even under conditions when general acid catalysis is effective. 

There are two instances in which the value of kD/kH depends upon the conditions under which a reaction is carried out. In the acid-catalyzed hydrolysis of ethyl orthocarbonate Wynne-Jones (110) finds fcD/fcH > 1 for catalysis by hydrogen ions, but kD/kK < 1 for catalysis by acetic acid. 

The hydrolysis reactions of acetals, ketals, and orthoesters are catalyzed by acids but not by bases. It has been found that these three groups of substrates are hydrolyzed via a common general mechanism — involving similar types of intermediates — though the rate-determining step may vary from case to case. In the hydrolyses of ethyl orthoacetate, orthopropionate, and orthocarbonate, general acid catalysis was unambiguously established for the first time by Bronsted and Wynne-Jones [158]. 

The A2 mechanism can be excluded with certainty for the hydrolyses of all orthoesters discussed. This is done on the basis of the determined volume of activation, AF = +2.4 cm3 (Table 1) for ethyl orthoformate [32], on the basis of the strongly increased rate in comparison to orthoformate (no steric hindrance) for orthoacetate and orthopropionate, and on the basis of the results of experiments with added nucleophiles for orthobenzoate [183] and orthocarbonate [192]. The observed AS values (Table 12) are in agreement with these conclusions. Consequently, the mechanism of orthoester hydrolysis must be either A1 or A-SE2, or possibly a concerted process with proton transfer and carbonium ion formation in the same step. 

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