60692-79-7Relevant articles and documents
The Formation of P-C Bonds Utilizing Organozinc Reagents for the Synthesis of Aryl- A nd Heteroaryl-Dichlorophosphines
Kirst, Christin,Tietze, Jonathan,Ebeling, Marian,Horndasch, Lukas,Karaghiosoff, Konstantin
, p. 17337 - 17343 (2021/11/18)
Aryl- A nd heteroaryl-dichlorophosphines are mildly and selectively made in a one-pot synthesis in moderate to good yields starting from the respective aryl bromides or five-membered heterocycles, following lithiation with nBuLi, transmetalation with ZnCl
Copolymerization of ethylene and methyl acrylate by cationic palladium catalysts that contain phosphine-diethyl phosphonate ancillary ligands
Contrella, Nathan D.,Sampson, Jessica R.,Jordan, Richard F.
supporting information, p. 3546 - 3555 (2014/08/05)
A series of benzo-linked phosphine-diethyl phosphonate (P-PO) and phosphine-bis(diethyl phosphonate) (P-(PO)2) ligands and the corresponding (P-PO)PdMe(2,6-lutidine)+ and (P-(PO) 2)PdMe(2,6-lutidine)+ complexes were synthesized. Cationic (P-PO)PdMe(2,6-lutidine)+ complexes are active for ethylene oligomerization/polymerization, with activities of 2 kg mol-1 h -1 for {κ2-1-PiPr2-2-P(O)(OEt) 2-5-Me-Ph}PdMe(2,6-lutidine)+ (3c), 125 kg mol -1 h-1 for {κ2-1-PPh2-2-P(O) (OEt)2-5-Me-Ph}PdMe(2,6-lutidine)+ (3a), and 1470 kg mol-1 h-1 for {κ2-1-P(2-OMe-Ph) 2-2-P(O)(OEt)2-Ph}PdMe(2,6-lutidine)+ (3b). The polyethylene is highly linear, with over 80% terminal unsaturation and low (230-1890 Da) molecular weight in all cases. 3b copolymerizes ethylene with methyl acrylate, exhibiting highly selective (95%) in-chain (rather than chain-end) acrylate incorporation. The P-(PO)2 catalyst {κ2-1-P(4-tBu-Ph)(2-P(O)(OEt)2-5-Me-Ph)- 2-P(O)(OEt)2-5-Me-Ph}PdMe(2,6-lutidine)+ (3d) is more active for ethylene homopolymerization (2640 kg mol-1 h -1), yielding linear, low-molecular-weight polymer (1280-1430 Da) with predominantly internal olefin placement. In ethylene/methyl acrylate copolymerization, 3d incorporates 2.6 mol % methyl acrylate, 60% of which is in-chain. Both 3b and 3d catalyze ethylene/acrylic acid copolymerization, albeit with low (-1 h-1) activities and acrylic acid incorporation up to 1.1 mol %.
Base-induced 1,3-sigmatropic rearrangement of mesitylphosphonium salts
Solomon, Sophia A.,Allen, Lucy K.,Dane, Sarah B. J.,Wright, Dominic S.
supporting information, p. 1615 - 1619 (2015/04/27)
Attempted synthesis of the ylide dianion [2,4,6-Me3C6H2P(CHR)3]2- (2,4,6-Me3C6H2 = mesityl, R = H or Me) by the reaction of mesitylphosphonium iodides [2,4,6-Me3C6H2PR3]+I- (R = Me, 1; R = Et, 2) with tBuLi at reflux does not result in the anticipated deprotonation of the phosphorus-bonded R groups. Instead, quantitative 1,3-sigmatropic rearrangement occurs to give new benzylic phosphonium salts [(3,5-Me2C6H3)CH2PR3]+I- (R = Me, 6; R = Et, 7), in which the phosphonium centre, the R3P group, is transferred to an ortho-CH3 group. In situ 31P NMR spectroscopic studies show that the reaction is base-activated and stoichiometric with respect to tBuLi. DFT calculations support the conclusion that the rearrangement is thermodynamically favourable in the gas phase and in THF and show that the rearrangement is enthalpically driven. Teaching an old dog new tricks: First synthesised in 1935, phosphonium salts [2,4,6-Me3C6H2PR3]+I- (2,4,6-Me3C6H2 = mesityl, R = Me or Et) exhibit an unexpected quantitative rearrangement in the presence of tBuLi, in which the phosphine group R3P is transferred to an ortho-CH3 position.
