Hydrolysis of phosphoranes containing a perfluoropinacolyl ring

• Published in: Canadian journal of chemistry 1983-10, Vol.61 (10), p.2264-2267
• Main Authors: Janzen, Alexander F, Lemire, Alberta E, Marat, Ronald Kirk, Queen, Alan
• Format: Article
• Language: English
• Subjects: Chemistry; Exact sciences and technology; Kinetics and mechanisms; Organic chemistry; Reactivity and mechanisms
• ISSN: 0008-4042; 1480-3291
• DOI: 10.1139/v83-392

The hydrolysis of phosphoranes Ph 2 P(pfp)Cl, Ph 2 P(pfp)OR, PhP(pfp)(OR) 2 , and (RO) 3 P(pfp), containing a perfluoropinacolyl (pfp) ring, occurs under neutral, basic, or acidic conditions and leads to the formation of acyclic perfluoropinacolyl products, i.e. R 2 P(O)OC(CF 3 ) 2 C(CF 3 ) 2 OH, as determined by 1 H, 19 F, 31 P, 13 C nmr and ir studies. In the presence of a base, all trifluoromethyl groups in Ph 2 P(O)OC(CF 3 ) 2 C(CF 3 ) 2 OH are equilibrated, as verified by 19 F and 13 C nmr; and from the variable temperature 19 F nmr line-shape analysis the activation parameters for this exchange process were found to be: Ea = 36.0 ± 3 kJ mol −1 , ΔH ≠  = 33.5 ± 3 kJ mol −1 , ΔS ≠  = −86 ± 8 J K −1  mol −1 , . The reactions of phosphoranes with HF were briefly investigated.