Convenient Modular Syntheses of Fluorous Secondary Phosphines and Selected Derivatives
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Reactions of the fluorous primary phosphines Rfn(CH 2)2PH2 [Rfn = (CF2) n-1CF3; n = 6, 8, 10] and Rfn′CH=CH 2 [(n′ = 6, 8, 10) (1:1; THF, reflux) in the presence of AIBN give the title compounds [Rfn (CH2)2][R fn′(CH2)2]PH [n/n′ = 6/6 (4, 55%), 8/8 (5, 58%), 10/10 (6, 53%), 8/6 (7, 52%), 10/8 (8, 51%)] as low-melting white solids on up to 10-g scales. The chiral tertiary phosphine [R f6(CH2)2][Rf8(CH2) 2][Rf10 (CH2)2]P (9) is similarly prepared from 7 and Rf10 CH=CH2 in the presence of VAZO (neat, 100°C; 67%). The reaction of 5 and THF·BH3 yields the phosphine borane 5·BH3 (95%). Additions of triphosgene [(CCl3O)2CO] to 5 or Rf8(CH2) 2PH2 give [Rf8(CH2) 2]2PCl or Rf8(CH2) 2PCl2, which are characterized in situ. The CF 3C6F11/toluene partition coefficients of 4-9 increase with the number and lengths of the Rfn segments. © 2005 Wiley-VCH Verlag GmbH & Co. KGaA.
author list (cited authors)
Emnet, C., Tuba, R., & Gladysz, J. A.