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J. Org. Chem. 1998, 63, 6302-6308
Additions of PH3 to Monosubstituted Alkenes of the Formula H2CdCH(CH2)x(CF2)yCF3: Convenient, Multigram Syntheses of a Family of Partially Fluorinated Trialkylphosphines with Modulated Electronic Properties and Fluorous Phase Affinities Luke J. Alvey, Drew Rutherford, Jerrick J. J. Juliette, and J. A. Gladysz*,† Department of Chemistry, University of Utah, Salt Lake City, Utah 84112 Received April 14, 1998
Reactions of PH3 and commercially available H2CdCHRf (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 H2CdCHCH2Rf8 (7) and H2CdCHCH2CH2Rf8 (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 Bu3SnCH2CHdCH2 and IRf8 (hν, CH2Cl2, 81%) or ICH2Rf8 (VAZO, refluxing CF3C6H5, 56%). The reaction of 1 and H2O2 gives OdP(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 >99.7:99.7:99.7:99.7:99.7:724) 1072 (M+, 100), 1053 (M+ - F, 70), 1003 (M+ - CF3, 2), 953 (M+ - CF2CF3, 2), 903 (M+ - (CF2)2CF3, 5), 853 (M+ - (CF2)3CF3, 4), 803 (M+ - (CF2)4CF3, 2), 753 (M+ - (CF2)5CF3, 1), 739 (M+ - CH2(CF2)5CF3, 15), 725 (M+ - (CH2)2(CF2)5CF3, 2). P(CH2CH2(CF2)7CF3)3 (2). A bomb was charged with H2CdCH(CF2)7CF3 (10.02 g, 22.46 mmol), AIBN (0.270 g, 1.64 mmol, 7 mol %), and PH3 (75 psi, ca. 5.9 mmol)14,29 in a procedure analogous to that for 1. After 16 h, the bomb was vented, purged, opened, and analyzed by 31P NMR16c as before. Then CF3C6H5 (20 mL), VAZO (0.225 g, 0.921 mmol), and H2CdCH(CF2)7CF3 (1.00 g, 2.24 mmol) were added. The slightly yellow mixture was kept in a Schlenk flask at 90 °C for 24 h. The solvent was removed by oil pump vacuum to give a white solid. Then CF3C6F11 (20 mL) and toluene (20 mL) were added. The layers were separated. Volatiles were removed from the CF3C6F11 layer by oil pump vacuum. The light yellow solid was dissolved in CF3C6H5 (ca. 50 mL) and toluene (ca. 40 mL) was added. The sample was cooled to -20 °C. A tan solid precipitated, which was collected by filtration, distilled (175 °C, 5 × 10-5 mmHg, bulb-to-bulb), and dissolved in CF3C6H5 (10 mL). The solution was filtered through a silica gel column (2 × 10 cm), which was rinsed with CF3C6H5 (100 mL). The solvent was removed by oil pump vacuum to give 2 as a white solid (7.88 g, 5.74 mmol, 70% based upon total alkene), mp 47-48 °C (capillary), 47.5 °C (DSC).30 Anal. Calcd for C30H12F51P: C, 26.25; H, 0.88. Found: C, 26.28; H, 0.93. 1H NMR (δ, CF C F ) 1.67 (m, 6H), 2.16 (m, 6H); 13C{1H} 3 6 11 NMR (δ, CF3C6F11, partial) 16.5 (d, 1JPC ) 17 Hz), 27.6 (dt, 2J 2 31 1 PC ) 21 Hz, JCF ) 24 Hz); P{ H} NMR (δ, CF3C6F11) -25.4 (s). MS (EI, direct inlet probe, m/z >924) 1372 (M+, 100), 1353 (M+ - F, 70), 1303 (M+ - CF3, 2), 1253 (M+ - CF2CF3, 3), 1203 (M+ - (CF2)2CF3, 5), 1153 (M+ - (CF2)3CF3, 3), 1103 (M+ - (CF2)4CF3, 2), 1053 (M+ - (CF2)5CF3, 1), 1003 (M+ - (CF2)6CF3, 4), 953 (M+ - (CF2)7CF3, 6), 939 (M+ - CH2(CF2)7CF3, 15), 926 (M+ - (CH2)2(CF2)7CF3 + H, 9), 925 (M+ - (CH2)2(CF2)7CF3, 1). (29) The approximate initial amount of PH3 was calculated as follows. The alkene volume (6.90 g ÷ 1.52 g/mL ) 4.54 mL in the preparation of 1) and the stirring bar volume (0.4 mL) were subtracted from the autoclave volume (30 mL), and the difference utilized in the inert gas equation, n ) PV/RT (T ) 298 K; 75 psi gauge reading ) 5.1 atm above ambient pressure, or 6.1 atm total). (30) For the graphical method used to obtain the melting point, see Cammenga, H. K.; Epple, M. Angew. Chem., Int. Ed. Engl. 1995, 34, 1171; Angew. Chem. 1995, 107, 1284.
J. Org. Chem., Vol. 63, No. 18, 1998 6307 P(CH2CH2(CF2)9CF3)3 (3). A bomb was charged with H2CdCH(CF2)9CF3 (6.04 g, 11.1 mmol), AIBN (0.200 g, 1.22 mmol, 11 mol %), and PH3 (75 psi, ca. 6.5 mmol)14,29 in a procedure analogous to that for 1. After 12 h, the bomb was repressurized to 75 psi (ca 4.0 mmol). After an additional 12 h, the bomb was vented, purged, opened, and analyzed by 31P NMR16d as before. Then CF3C6H5 (5 mL), VAZO (0.10 g, 0.41 mmol), and H2CdCH(CF2)9CF3 (0.262 g, 0.480 mmol) were added. The mixture was kept in a Schlenk flask at 90 °C for 2 h. The solvent was removed by oil pump vacuum and the residue continuously extracted with benzene in a Soxhlet apparatus. After 24 h, 3 was collected from the thimble as a white solid and dried by oil pump vacuum (4.05 g, 2.42 mmol, 63% based upon total alkene), mp 102-103 °C (capillary), 100.8 °C (DSC).30 Anal. Calcd for C36H12F63P: C, 25.84; H, 0.72. Found: C, 25.64; H, 0.78. 1 H NMR (δ, CF3C6F11) 1.67 (m, 6H), 2.13 (m, 6H); 13C{1H} NMR (δ, CF3C6F11, partial) 16.4 (m), 27.4 (m); 31P{1H} NMR (δ, CF3C6F11) -25.5 (s). MS (EI, direct inlet probe, m/z >1224) 1672 (M+, 100), 1653 (M+ - F, 84), 1603 (M+ - CF3, 2), 1553 (M+ - CF2CF3, 4), 1503 (M+ - (CF2)2CF3, 7), 1453 (M+ - (CF2)3CF3, 7), 1403 (M+ - (CF2)4CF3, 7), 1353 (M+ - (CF2)5CF3, 5), 1303 (M+ - (CF2)6CF3, 3), 1253 (M+ - (CF2)7CF3, 2), 1203 (M+ - (CF2)8CF3, 6), 1153 (M+ - (CF2)9CF3, 10), 1139 (M+ CH2(CF2)9CF3, 23), 1126 (M+ - (CH2)2(CF2)9CF3 + H, 15), 1125 (M+ - (CH2)2(CF2)9CF3, 3). OdP(CH2CH2(CF2)5CF3)3 (6). A 1 dram vial was charged with 1 (0.773 g, 0.721 mmol), CF3C6H5 (2 mL), and aqueous H2O2 (0.5 mL, 30% w/w, ca. 4 mmol). The mixture was shaken vigorously (2 min) and allowed to settle (15 min). A 31P NMR spectrum of the lower CF3C6H5 layer showed 6 and a byproduct (δ 43.5, 53.1; 98:2). Water (2 mL) was added, and the layers were separated (aerobic workup). The aqueous layer was washed with CF3C6H5 (2 mL). The CF3C6H5 layers were combined and dried over MgSO4. The solution was concentrated (ca. 0.5 mL) and stored at -20 °C. After 24 h, the resulting white powder was collected by filtration and dried by oil pump vacuum to give 6 (0.689 g, 0.633 mmol, 88%), mp 52-56 °C (capillary), 53.5 °C (DSC).30 Anal. Calcd for C24H12F39PO: C, 26.48; H, 1.11. Found: C, 26.61; H, 1.05. 1H NMR (δ, CF C F ) 2.13 (m, 6H), 2.45 (m, 6H); 13C{1H} 3 6 11 NMR (δ, CF3C6F11, partial) 19.3 (d, 1JPC ) 68 Hz), 24.2 (t, 2JCF ) 24 Hz, w1/2 ) 8 Hz, and 2JPC < 4 Hz); 31P{1H} NMR (δ, CF3C6F11) 41.2 (s). MS (FAB, m/z) 1089 (M+ + 1, 100). Reduction of 6. A Schlenk flask was charged with 6 (0.452 g, 0.415 mmol), CF3C6H5 (5 mL), HSiCl3 (2.30 g, 17.0 mmol), and N2 gas, sealed, and placed in a 48 °C oil bath. After 4 h, a 31P NMR spectrum showed 6 to be 90% consumed. After an additional 1 h, volatiles were removed by oil pump vacuum, and CF3C6F11 (5 mL) and toluene (5 mL) were added to the colorless oily residue. The layers were separated. The solvent was removed from the CF3C6F11 layer by oil pump vacuum to give a colorless oil (0.430 g) that was distilled (100 °C, 8 × 10-5 mmHg, bulb-to-bulb) to give 0.383 g of a colorless liquid. A 31P NMR spectrum showed a mixture of 1 (96%), 6 (1%), PH(CH2CH2Rf6)2 (2%),16b and two unidentified species (δ 103.4, 29.2; 1%, 1%). The liquid was dissolved in CF3C6H5. The solution was filtered through a silica gel plug (2 × 1 cm), which was rinsed with CF3C6H5. The solvent was removed from the filtrate by oil pump vacuum to give 1 as a colorless liquid (0.377 g, 0.352 mmol, 85%, >97% purity by 31P NMR). H2CdCHCH2(CF2)7CF3 (7).21 A Schlenk flask was charged with ICF2(CF2)6CF3 (18.722 g, 34.291 mmol), Bu3SnCH2CHd CH2 (17.0 mL, 54.8 mmol), and CH2Cl2 (20 mL). The solution was photolyzed (Rayonet model RMA-400; R.P.R. 2537 Å lamps). After 1 h, CH2Cl2 (20 mL) was added (aerobic workup). The biphasic mixture was extracted with CF3C6F11 (2 × 10 mL). The solvent was removed from the extracts by rotary evaporation and the residue distilled (77-80 °C, 20 mmHg) to give 7 as a colorless liquid (12.825 g, 27.872 mmol, 81%). Anal. Calcd for C11H5F17: C, 28.71; H, 1.10. Found: C, 28.71; H, 1.16. 1H NMR (δ, CDCl ) 5.81 (ddt, 3J 3 HH ) 17, 11, 7 Hz), 5.35 (dm, 3JHH ) 11 Hz), 5.33 (dm, 3JHH ) 17 Hz), 2.85 (dtm, 3JHH ) 7 Hz, 3JHF ) 18 Hz); 13C NMR (δ, CDCl3, partial) 125.4 (d,
6308 J. Org. Chem., Vol. 63, No. 18, 1998 1 1 CH ) 158 Hz), 122.6 (t, JCH ) 160 Hz), 36.1 (td, JCH ) 130 Hz, 2JCF ) 22 Hz); 19F NMR (δ, CDCl3) -81.5 (t, JFF ) 8 Hz, CF3), -113.8 (pseudopentet, 2F), -122.4 (m, 6F), -123.3 (m, 2F), -123.6 (m, 2F), -126.8 (m, 2F). IR (cm-1, CHCl3) νCdC 1649 m. P(CH2CH2CH2(CF2)7CF3)3 (4). A bomb was charged with 7 (5.021 g, 10.91 mmol), AIBN (0.183 g, 1.14 mmol, 10 mol %), and PH3 (100 psi; pressure maintained throughout reaction)14 in a procedure similar to that for 1. After 4 h, the bomb was vented, purged, opened, and analyzed by 31P NMR16e as before. Then VAZO (0.027 g, 0.11 mmol) and 7 (1.020 g, 2.217 mmol) were added. The mixture was stirred at 100 °C for 12 h and dissolved in CF3C6H5 (10 mL). The solution was filtered through a silica gel column (2 × 6 cm), which was rinsed with CF3C6H5 (60 mL). The filtrate was concentrated by oil pump vacuum (20 mL) and cooled to 10 °C. A white powder formed, which was collected on a frit. The filtrate was concentrated to 10 mL and cooled to 10 °C. A second crop of white powder formed, which was similarly collected, combined with the first, and dried by oil pump vacuum to give 4 (4.544 g, 3.213 mmol, 73% based upon total alkene), mp 71.5-72.5 °C (capillary), 67.1 °C (DSC).30 Anal. Calcd for C33H18F51P: C, 28.02; H, 1.28. Found: C, 28.16; H, 1.31. 1H NMR (δ, CF C F ) 1.46-1.38 (m, 6H), 1.83-1.69 (m, 3 6 11 6H), 2.23-2.03 (m, 6H); 13C NMR (δ, CF3C6F11, partial) 32.4 (ttd, 1JCH ) 131 Hz, 2JCF ) 22 Hz, 3JCP ) 12 Hz), 27.3 (td, 1J 2 1 1 CH ) 126 Hz, JCP ) 15 Hz), 17.1 (td, JCH ) 129 Hz, JCP ) 17 Hz); 31P{1H} NMR (δ, CF3C6F11) -34.8 (s). CF3SO2OCH2(CF2)7CF3 (8).22 A round-bottom flask was charged with HOCH2(CF2)7CF3 (22.472 g, 49.927 mmol), pyridine (4.80 mL, 59.3 mmol), and CHCl3 (100 mL) and placed in a 0 °C bath. Then (CF3SO2)2O (10.0 mL, 59.4 mmol) was added dropwise with stirring over 30 min. The bath was removed. After 12 h, solvent was removed by rotary evaporation (aerobic workup). The white residue was dissolved in ether (250 mL). The solution was washed with cold water (100 mL) and dried over MgSO4. The solvent was removed under vacuum (10 mmHg) to give 8 as a white powder (27.103 g, 46.556 mmol, 93%) mp 33.5 °C (DSC).30 Anal. Calcd for C10H2F20O3S: C, 20.63; H, 0.35. Found: C, 20.86; H, 0.42. 1H NMR (δ, CDCl ) 4.82 (t, 3J 13C (δ, CDCl , 3 HF ) 12 Hz); 3 partial) 68.3 (tt, 1JCH ) 157 Hz, 2JCF ) 28 Hz); 19F (δ, CDCl3) -74.5 (t, JFF ) 12 Hz, CF3), -81.3 (m, 2F), -120.2 (m, 2F), -122.3 (m, 6F), -123.3 (m, 2F), -126.6 (m, 2F). ICH2(CF2)7CF3 (9). A round-bottom flask was charged with 8 (27.103 g, 46.556 mmol), KI (15.495 g, 93.342 mmol), and ethylene glycol (270 mL) and fitted with a condenser. The mixture was refluxed for 12 h and cooled. Water was added (270 mL; aerobic workup). The mixture was extracted with ether (2 × 150 mL). The extracts were washed with aqueous Na2S2O3 (100 mL, 0.10 M) and dried over MgSO4. The solvent was removed under vacuum (10 mmHg) to give 9 as a white powder (24.324 g, 43.437 mmol, 93%), mp 37.2 °C (DSC).30 Anal. Calcd for C9H2F17I: C, 19.30; H, 0.36. Found: C, 19.28; H, 0.42. 1H NMR (δ, CDCl ) 3.64 (t, 3J 13C NMR (δ, 3 HF ) 17 Hz); CDCl3, partial) -4.1 (tt, 1JCH ) 151 Hz, 2JCF ) 26 Hz); 19F NMR (δ, CDCl3) -81.3 (t, JFF ) 12 Hz, CF3), -107.4 (pseudopentet, 2F), -121.9 (m, 2F), -122.2 (m, 2F), -122.3 (m, 4F), -123.2 (m, 2F), -126.6 (m, 2F). H2CdCHCH2CH2(CF2)7CF3 (10).23 A Schlenk flask was charged with 9 (10.075 g, 17.991 mmol), Bu3SnCH2CHdCH2 (8.40 mL, 27.1 mmol), VAZO (0.4327 g, 1.771 mmol, 10 mol %), and CF3C6H5 (50 mL) and fitted with a condenser. The solution was refluxed for 6 h. The solvent was removed by rotary evaporation, and CH2Cl2 (100 mL) was added. The biphasic mixture was extracted with CF3C6F11 (2 × 20 mL). The solvent was removed from the extracts by rotary evapora1J
Alvey et al. tion. The residue was distilled (74-75 °C, 15 mmHg) to give 10 as an analytically impure colorless liquid (4.783 g, 10.09 mmol, 56%). Anal. Calcd for C12H7F17: C, 30.40; H, 1.49. Found: C, 31.32; H, 1.61. 1 H NMR (δ, CDCl3) 5.90-5.76 (m, 1 H), 5.17-5.05 (m, 2 H), 2.42-2.33 (m, 2 H), 2.27-2.07 (m, 2 H); 13C NMR (δ, CDCl3, partial) 135.7 (d, 1JCH ) 155 Hz), 116.5 (t, 1JCH ) 154 Hz), 30.7 (tt, 1JCH ) 129 Hz, 2JCF ) 22 Hz), 24.6 (tt, 1JCH ) 128 Hz, 3J 19F NMR (δ, CDCl ) -81.5 (J CF ) 4 Hz); 3 FF ) 9 Hz, CF3), -115.1 (pseudopentet, 2F), -122.3 (m, 2F), -122.5 (m, 4F), -123.3 (m, 2F), -124.1 (m, 2F), -126.7 (m, 2F). IR (cm-1, neat) νCdC 1647 m. P(CH2CH2CH2CH2(CF2)7CF3)3 (5). A bomb was charged with 10 (5.017 g, 10.58 mmol), AIBN (0.175 g, 1.06 mmol, 10 mol %), and PH3 (100 psi)14 in a procedure analogous to that for 4. After 4 h, the bomb was vented, purged, opened, and analyzed by 31P NMR16a,f as before. Then VAZO (0.209 g, 0.855 mmol) and 10 (0.781 g, 1.65 mmol) were added. The mixture was stirred at 100 °C for 12 h and dissolved in CF3C6H5 (10 mL). The solution was filtered through a silica gel column (2 × 6 cm), which was rinsed with CF3C6H5 (60 mL). The solvent was removed from the filtrate by oil pump vacuum. The residue was dissolved in toluene (50 mL), and the solution was cooled to 10 °C. A white powder formed, which was collected on a frit. The filtrate was concentrated to 10 mL and cooled to 10 °C. A second crop of white powder formed, which was similarly collected, combined with the first, and dried by oil pump vacuum to give 5 (3.905 g, 2.681 mmol, 66% based upon total alkene), mp 44.5-45.0 °C (capillary), 40.2 °C (DSC).30 Anal. Calcd for C36H24F51P: C, 29.69; H, 1.66. Found: C, 29.52; H, 1.66. 1H NMR (δ, CF C F ) 2.08-1.96 (m, 6H), 1.74-1.69 (m, 3 6 11 6H), 1.55-1.45 (m, 6H), 1.39-1.33 (m, 6H); 13C NMR (δ, CF3C6F11, partial) 30.9 (tt, 1JCH ) 129 Hz, 2JCF ) 22 Hz), 27.7, 25.9 (2 × td, 1JCH ) 125/125 Hz, 2JCP ) 15/16 Hz), 21.9 (td, 1J 1 31P{1H} NMR (δ, CF C F ) CH ) 129 Hz, JCP ) 11 Hz); 3 6 11 -32.8 (s). Partition Coefficients. The following procedure is representative. A 1 dram vial was charged with 1 (0.0390 g, 0.0364 mmol), CF3C6F11 (2.000 ( 0.015 mL), and toluene (2.000 ( 0.015 mL), capped with a mininert valve, vigorously shaken (2 min), and immersed (cap-level) in a 35 °C bath. After 12 h, the bath was removed. After 1 h (ambient temperature 24 °C), the vial was taken into a drybox (27 °C). After 1 h, 0.400 ( 0.005 mL aliquots of each layer were added to stock solutions of hexadecane in hexane (2.000 ( 0.015 mL, 0.00222 M; for 4 and 5, 0.0111 M eicosane in hexanes). GLC analysis showed 8.52 × 10-5 mmol and 7.11 × 10-3 mmol of 1 in the toluene and CF3C6F11 aliquots, for a 98.8(0.5):1.2(0.5) ratio (Table 1; 3-11 injections averaged for each run). The total amount of 1 calculated from these data (0.0386 g or 0.0360 mmol using a 2.000/0.400 volume multiplier) is in close agreement with that utilized.
Acknowledgment. We thank the NSF (CHE9401572) for support of this research, Mr. Lazslo Kiss for some exploratory reactions, Professor A. Rheingold (University of Delaware) for preliminary X-ray data, and Dr. Istva´n Horva´th (Exxon Corporate Research) for many helpful discussions. Supporting Information Available: Instrumental data and NMR spectra with resonance assignments (2 pages). This material is contained in libraries on microfiche, immediately follows this article in the microfilm version of the journal, and can be ordered from the ACS; see any current masthead page for ordering information. JO980692Y
