40088-76-4Relevant academic research and scientific papers
The Kinetics and Mechanism of the Thallium(III) Ion-promoted Hydrolysis of Thiolurethanes in Aqueous Solution. A Metal Ion-promoted Elimination
Satchell, Derek P. N.,Satchell, Rosemary S.,Wassef, Wasfy N.
, p. 1199 - 1202 (2007/10/02)
The hydrolysis of thiolurethanes R1C6H4NHCOSC6H4R2 (1), in dilute aqueous perchloric acid, under conditions where the spontaneous hydrolysis is negligible, is promoted by Ti3+ ions.The organic products are the corresponding anilinium ion and the thalium salt of the thiophenol.The effects of substituent changes (R1,R2) of changes in +>, temperature, ionic strength, and of replacement of the NH proton by Me, are all compatible with hydrolysis occurring by elimination-addition mechanisms via the isocyanate as a reactive intermediate; thalium ion-promoted E1 cb and E2 routes are implicated.In effect the elimination-addition type of mechanism which is important for these esters at higher pH has been made available at low pH by complexation with Tl3+ ions.With the thiolurethanes RC6H4NHCOSEt, (2) which are less susceptible to the spontaneous and base-catalysed elimination-addition mechanisms of hydrolysis than are thiolurethanes (1), the presence of Tl3+ ions can also lead to promoted hydrolysis via elimination, but an AAc1-like route (with Tl3+ taking the role of H+) seems to be available to the N-Me derivatives.
