103249-38-3Relevant articles and documents
Additions of PH3 to Monosubstituted Alkenes of the Formula H2C=CH(CH2)x(CF2)yCF 3: Convenient, Multigram Syntheses of a Family of Partially Fluorinated Trialkylphosphines with Modulated Electronic Properties and Fluorous Phase Affinities
Alvey, Luke J.,Rutherford, Drew,Juliette, Jerrick J.J.,Gladysz
, p. 6302 - 6308 (1998)
Reactions of PH3 and commercially available H2C=CHRf(Rf6/8/10 = (CF2)5CF3/(CF2)7CF 3/(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 H2C=CHCH2Rf8 (7) and H2C=CHCH2CH2Rf8 (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 Bu3SnCH2CH=CH2 and IRf8 (hv, CH2Cl2, 81%) or ICH2Rf8 (VAZO, refluxing CF3C6H5, 56%). The reaction of 1 and H2O2 gives O=P(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.
PHOSPHONIUM IONIC LIQUIDS AND COATINGS MADE THEREFROM
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Page/Page column 25, (2009/09/05)
ABSTRACT The present invention provides phosphonium ionic liquids (11) and coatings made therefrom. Highly fluorinated phosphonium ionic liquids based on (11) having been produced exhibiting high thermal stabilities, low melting points and temperature dependent solvent miscibilities. These salts and derivatives of (11) have also been employed in the preparation of superhydrophobic surfaces, indicating that ionic liquids are not only new alternative solvents, but also viable functional materials. All derivatives of (11) form biphasic systems with common laboratory solvents of ranging polarity at room temperature. Based on the solvent miscibility experiments with water and the high fluorine loading, the PILs showed obvious evidence of being hydrophobic. Coatings made with these phosphonium ionic liquids (11), salts and derivatives thereof were superhydrophobic with water contact angles were measured and all of the surfaces were determined to be superhydrophobic with contact angles > 150°.
Molecular engineering in homogeneous catalysis: One-phase catalysis coupled with biphase catalyst separation. The fluorous-soluble HRh(CO){P[CH2CH2(CF2)5CF3]3}3 hydroformylation system
Horváth, István T.,Kiss, Gábor,Cook, Raymond A.,Bond, Jeffrey E.,Stevens, Paul A.,Rábai, József,Mozeleski, Edmund J.
, p. 3133 - 3143 (2007/10/03)
The hydroformylation of decene-1 was studied in the presence of the fluorous-soluble P[CH2-CH2(CF2)5CF3]3 modified rhodium catalyst at 100 °C and 1.1 MPa of CO/H2 (1:1) in a 50/50 vol % toluene/C6F11CF3 solvent mixture, which forms a homogeneous liquid phase at and above 100 °C. P[CH2CH2(CF2)5CF3]3 was selected on the basis of a semiempirical calculation of the electronic properties of P[(CH2)(x)(CF2)(y)CF3]3 (x = 0, y = 2, 4 and x = 0-5, y = 2) and prepared by the reaction of PH3 with CH2=CH(CF2)5CF3. The solution structure of HRh(CO){P[CH2CH2(CF2)5CF3]3}3 (1) in C6F11CF3 is similar to that of HRh(CO)(PPh3)3 (2) in toluene and HRh(CO){P(m-C6H4SO3Na)3}3 (3) in water. High-pressure NMR of 1 under 2.1-8.3 MPa of CO/H2 (1:1) revealed that 1 is in equilibrium with HRh(CO)2{P[CH2CH2(CF2)5CF3]3}2 (4). Kinetic studies show that the reaction is first order in both rhodium and decene-1. While the reaction is inhibited by P[CH2-CH2(CF2)5CF3]3, the normal/iso (n/i) ratio of the aldehyde increases with increasing phosphine concentration. The catalytic activity of the Rh/P[CH2CH2(CF2)5CF3]3 catalyst is similar to that of the nonfluorous analogue Rh/P[(CH2)7CH3]3 catalyst and is an order of magnitude lower than that of the Rh/PPh3 catalyst. Surprisingly, the n/i product selectivity of Rh/P[CH2CH2(CF2)5CF3]3 is closer to the selectivity of the Rh/PPh3 catalyst than that of the Rh/P[(CH2)7CH3]3 catalyst. The fluorous biphase catalyst recovery concept was tested in a semicontinuous hydroformylation of decene-1 with the Rh/P[CH2CH2(CF2)5CF3]3 catalyst. During 9 consecutive reaction/separation cycles, a total turnover of more than 35 000 was achieved with a loss of 1.18 ppm of Rh/mol of undecanals. The fluorous-soluble Rh/P[CH2CH2(CF2)5CF3]3 catalyst was also tested for the continuous hydroformylation of ethylene using the high-boiling fluorous solvent FC-70, which allows continuous removal of propanal at the reaction temperature of 110 °C. The long-term stability of the Rh/P[CH2CH2(CF2)5CF3]3 catalyst is better than that of the Rh/PPh3 catalyst. Thus, the Rh/P[CH2CH2(CF2)5CF3]3 catalyst is the first catalyst system which can be used for the hydroformylation of both low and high molecular weight olefins and provides facile catalyst separation for both low and high molecular weight aldehydes.
