Abstract
The acetolysis of trans-1,2-diphenyl-2-phenylthiol[1-13C]vinyl tosylate (2-OTs-1-13C) under anhydrous conditions (HOAc–Ac2O–NaOAc) gave trans-1,2-diphenyl-2-phenylthio[1,2-13C]vinyl acetate (2-OAc-1,2-13C) as product. The label was scrambled equally over C-1 and C-2 and there was no detectable amount of cis-product. These results are consistent with the involvement of an intermediate sulfur-bridged thiirenium ion in the reaction. Soivolysis of 2-OTs-1-13C in 70% HOAc – 30% H2O containing 3 equiv. of NaOAc gave 1,2-diphenyl-2-phenylthio[1,2-13C]ethanone (α-phenyl-α-(phenylthio)acetophenone) (5-1,2-13C) and 1,2-diphenyl[1,2-13C]ethanone (desoxybenzoin) (6-1,2-13C) as major and minor products, respectively. The 13C-label in both of these ketones was again equally distributed over C-1 and C-2. Further studies with unlabeled 2-OTs showed that its soivolysis in aqueous HOAc gave, besides ketones 5 and 6, some benzil and diphenyl disulfide. It was also found that 6, benzil, and diphenyl disulfide were derived from the initial product 5. A possible mechanism for these conversions is proposed.
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