| Abstract: | Organic Phosphorus Compounds. IX. Studies on the Mechanism of the Trichlorphone-DDVP Rearrangement The base-initiated rearrangement of 2,2,2-trichloro-1-hydroxy-ethanephosphonic acid dimethyl ester (Trichlorphone) 1 in deuterated media leads to deuterium-free O, O-dimethyl O-2,2-dichlorovinyl phosphate (DDVP) 3 . This result favours the course of reaction suggested by KHARASCH and BENGELSDORF (path A: rearrangement after deprotonation of the hydroxyl group) and rules out a mechanism via the enolphosphonate 5 as an intermediate DDVP-precursor (path B) as postulated later. In accordance with path A, C1-substituted Trichlorphone derivatives 12 can also be transformed to corresponding vinyl phosphates 13 . Crossing experiments prove the intramolecular character of the Trichlorphone-DDVP rearrangement. |
