Additions of PH3 to Monosubstituted Alkenes of the Formula H2CCH(CH2)x(CF2)yCF3: Convenient, Multigram Syntheses of a Family of Partially Fluorinated Trialkylphosphines with Modulated Electronic Properties and Fluorous Phase Affinities
- 1 September 1998
- journal article
- research article
- Published by American Chemical Society (ACS) in The Journal of Organic Chemistry
- Vol. 63 (18) , 6302-6308
- https://doi.org/10.1021/jo980692y
Abstract
Reactions of PH3 and commercially available H2CCHRf (Rf6/8/10 = (CF2)5CF3/(CF2)7CF3/(CF2)9CF3) give, in two-stage processes conducted with free radical initiators (AIBN, VAZO; 80−90 °C), the phosphines P(CH2CH2Rf)3 (1−3; 63−75%). Analogous reactions with H2CCHCH2Rf8 (7) and H2CCHCH2CH2Rf8 (10) give P(CH2CH2CH2Rf8)3 (4, 73%) and P(CH2CH2CH2CH2Rf8)3 (5, 66%), in which the phosphorus is increasingly insulated from the electronegative Rf moiety. The alkenes 7 and 10 are prepared from Bu3SnCH2CHCH2 and IRf8 (hν, CH2Cl2, 81%) or ICH2Rf8 (VAZO, refluxing CF3C6H5, 56%). The reaction of 1 and H2O2 gives OP(CH2CH2Rf6)3 (6, 88%), which can be reduced with HSiCl3 to 1. Partition coefficients (CF3C6F11/toluene, 27 °C) range from 98.8:1.2 (1, 4) through 98.9:1.1 (5) to >99.7:f segments is evident.Keywords
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