89243-78-7Relevant articles and documents
Phosphorylated Enols, Lactones, and Alcohols as Reaction Products of Bifunctional Acylphosphanes and their Oxides
Lindner, Ekkehard,Kern, Herbert
, p. 355 - 365 (2007/10/02)
Bifunctional acylphosphanes of the type Ph2P-C(O)-n-C(O)-PPh2 (2a-i) are obtained from the acid chlorides ClC(O)-n-C(O)Cl (1a-i) and (CH3)3Si-PPh2. 2d (n=2) and 1c, e-i (n=1, 3-6) can be transformed with molecular oxygen and by reaction with CH3OPPh2, respectively to the phosphane oxides Ph2(O)P-C(O)-n-CO-P(O)Ph2 (3c-i), 3a, b are not accessible.With a medium chain length the unstable phosphane oxides prefer, as it could be shown with the example of 3f, intramolecular cyclization, in the course of which intermediary formed 4f is changed into the unsaturated lactone 5f under separation of HP(O)Ph2.With a chain length of n = 4-6 one obtains the bifunctional tetraphosphorylated alcohols 6g-i either by oxidation of 2g,h in the simultaneous presence of HP(O)Ph2 or by reaction of 3h, i with HP(O)Ph2.In solution results decomposition of 6g-i to give the oxides 3g-i and HP(O)Ph2, which is dependent of electronic and steric factors.This could be proved with the example of the mono- and bifunctional alcohols 9 an 7i, respectively.The hydrolysis of 3c yields the enol 11c.
