175167-66-5Relevant articles and documents
The reaction of secondary phosphines and di-1-adamantylphosphine oxide with trifluoroacetic anhydride and hexafluoroacetone
Goerlich, Jens R.,Plack, Volker,Schmutzler, Reinhard
, p. 29 - 35 (2007/10/03)
While the secondary phosphines (1-Ad)2PH (1) (1-Ad=adamantyl) and Trt(Ph)PH (2) (Trt=triphenylmethyl) reacted readily with trifluoroacetic anhydride (TFAA) to give the trifluoroacetylphosphines 7 and 8. (1-Ad)2P(:O)H (6) could not be converted into the corresponding trifluoroacetylphosphine oxide 10 by treatment with TFAA. Compound 10 was observed by 19F and 31P NMR spectroscopy in the reaction of (1-Ad)2PC(:O)CF3 (7) with (H2N)2C(:O)·H2O2. Two pathways were observed for the reaction of 1 with excess hexafluoroacetone (HFA), starting from the primary HFA adduct (1-Ad)2PC(CF3)2OH (13). Oxidation of 13 led to the tertiary phosphine oxide 14 which was also available from (1-Ad)2P(:O)H (6) and HFA. Isomerization of 13 gave (1-Ad)2POCH(CF3)2 (15) whose oxidation with excess HFA furnished the phosphorane 16. Hydrolysis of 16 led to the phosphinic ester 17. As is known for Ph2PH (3), Ph(C6F5)PH (4) reacted with HFA to give the α-hydroxyphosphine 19. No reaction was observed when Trt(Ph)PH (2) and (C6F5)2PH (5) were treated with HFA.
