โ Scribed by A. Iliceto; A. Fava; U. Mazzucato
No coin nor oath required. For personal study only.
THIOCYANIC acid esters have long been known to undergo thermal isomerization to give the corresponding isothiocyanic acid esters. Although the isomerization reaction is believed to be quite general and is frequently used as a synthetic route to isothiocyanates, little is known about its nature and mechanism. We wish to report here a number of observations which may have considerable mechanistic significance.
In all cases recorded in the literature,' drastic tempe rature conditions are required to obtain isomerization; this
๐ SIMILAR VOLUMES
The mechanism of isomerization of allyl thiocyanate to allyl isothiocyanate has been investigated both experimentally and theoretically. The kinetic study indicates that the reaction is unimolecular and is not ionic. The entropy of activation suggests strongly that the mechanism involves a cyclic tr
Aryl and alkyl thiocyanates are known to isomerize to isothiocyanates through an ionization path '. For the benzyl derivative the reaction does not take place in mild conditions (unless electrophilic catalysts lb or an ionic thiocyanate are present: in this last case a direct nucleophilic displaceme