92495-13-1Relevant articles and documents
Synthesis of electron-withdrawing butane- and arene-sulfonylamino phosphines and use in rhodium-catalyzed hydroformylation
Magee, Matthew P.,Li, Huan-Qiu,Morgan, Oma,Hersh, William H.
, p. 387 - 394 (2007/10/03)
Reaction of RSO2N(H)CH2CH2N(H)SO2R [R = Bu (1), 4-nitrobenzene (7), 1-naphthalene (9a), 2-naphthalene (9b)] with PhPCl2 or EtPCl2 gives monodentate phosphorus compounds 2 and 3 (R = Bu, PhP and EtP), and 8 (R = 4-nitrobenzene, PhP), and with Ph2PCl gives the corresponding bidentate phosphine ligands Ph2PN(SO2R)CH2CH2N(SO2R)P Ph2 [R = Bu (10), 4-nitrobenzene (11), 1- and 2-naphthalene (12a,b)]; similar reactions of N,N′-(1-butanesulfonyl)-2,2′-diaminobiphenyl (4) give monodentate 5 (PhP) and 6 (EtP) and N,N′-bis(diphenylphosphino)-N,N′-(1-butanesulfonyl)-2,2′-diami nobiphenyl (16). A monodentate analogue of 10 was also prepared, Ph2PN(Et)SO2Bu (14). Diphosphorus compounds with two butanesulfonylamino groups on phosphorus were also prepared from 1 and Cl2P(CH2)nPCl2 (n = 2, 4) to give 19 and 20. Details of the 13C NMR false AA′X systems are reported for 19 and 20. Rhodium-catalyzed hydroformylation reactions were run at 60 and 80 °C, at CO/H2 pressures from 4-11 atm, and in THF, toluene, CH2Cl2, and dioxane. Results show that the highest ratios of linear (n) to branched (iso) aldehydes were obtained with arenesulfonamides (n:iso > 10) while the bidentate alkanesulfonamide 10 gave a lower n:iso ratio of 7.2 but the highest rate [k1 = 1.98 h-1, turnover frequency = 1130 mol aldehyde (mol Rh)-1 h-1] in THF at 80 °C. Both the rate and n:iso ratio for 10 were found to increase with decreasing CO/H2 pressure in THF and in toluene, although the rate change was small for toluene. Both the rate and n:iso ratio for 10 also increased in CH2Cl2, but this was found not to be due to lower CO/H2 concentrations in solution, on the basis of solubility measurements in THF and CH2Cl2.
