In:
Chemistry – A European Journal, Wiley, Vol. 20, No. 25 ( 2014-06-16), p. 7736-7745
Abstract:
A new efficient synthesis of functionalized perfluoroalkyl fluorophosphates by oxidative addition of Me 2 NCH 2 F to the electron‐deficient phosphanes (C 2 F 5 ) n PF 3− n ( n =0–3) is reported. The initially formed zwitterionic, hexacoordinated phosphates [(C 2 F 5 ) n F 5− n P(CH 2 NMe 2 −CH 2 NMe 2 )] are converted into the corresponding phosphonium salts [(Me 3 PCH 2 NMe 2 ] + [(C 2 F 5 ) n F 5− n P(CH 2 NMe 2 )] − by treatment with PMe 3 . In addition [(C 2 F 5 ) 3 F 2 P(CH 2 NMe 2 CH 2 NMe 2 )] can undergo a 1,3‐methyl shift from the internal to the terminal nitrogen—a structural characterization was achieved from the CF 3 analogue. Reaction of [(C 2 F 5 ) 3 F 2 P(CH 2 NMeCH 2 NMe 3 )] and PMe 3 gave rise to the formation of the zwitterionic phosphonium phosphate [(C 2 F 5 ) 3 F 2 P(CH 2 NMeCH 2 PMe 3 )], which was fully characterized by X‐ray diffraction analysis. Moreover, an efficient one‐pot synthesis of Cs + [(C 2 F 5 ) 3 F 2 P(CH 2 NMe 2 )] − was pursued. This salt turned out to be a useful nucleophile in several alkylation reactions.
Type of Medium:
Online Resource
ISSN:
0947-6539
,
1521-3765
DOI:
10.1002/chem.201402421
Language:
English
Publisher:
Wiley
Publication Date:
2014
detail.hit.zdb_id:
1478547-X
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