PAPER
Synthesis of Alkyl and Fluoroalkyl Chains Containing Thioether-Phosphines
4105
129.7 (s, C4), 129.1 (s, C4¢), 128. 9 (d, 3JC-P = 6.9 Hz, C3¢), 127.6
Hz, C3), 129.6 (s, C4), 128.3 (s, C5), 104–124 (m, C9–C16), 31.2
2
(s, C5), 104–124 (m, C9–C16), 31.4 (t, JC-F = 22.2 Hz, C7), 26.0
(t, 2JC-F = 22.0 Hz, C8), 26.6 (m, C7).
(m, C8).
19F NMR (282 MHz, THF-d8): d = –127.2 (m, 6 F, F9), –123.9 (m,
6 F, F10), –123.7 (m, 6 F, F11), –122.8 (m, 18 F, F12–F14), –114.9
(m, 6 F, F15), –82.1 (m, 9 F, F16).
31P NMR (121 MHz, THF-d8): d = –24.1 (s).
19F NMR (282 MHz, CDCl3): d = –126.6 (m, 2 F, F9), –123.8 (m, 2
F, F10), –123.20 (m, 2 F, F11), –122.4 (m, 6 F, F12–F14), –114.2
(q, 3JF-F = 14.2 Hz, 2 F, F15), –81.2 (t, 3JF-F = 10.7 Hz, 3 F, F16).
31P NMR (121 MHz, CDCl3): d = –12.9 (s).
HRMS (FAB): m/z [M – H]+ calcd for C48H24F51PS3: 1697.7900;
HRMS (IE): m/z [M] calcd for C28H18F17PS: 740.0600; found:
found: 1697.9900.
740.0614.
Tris{2-[(1H,1H,2H,2H-perfluorohexyl)sulfanyl]phenyl}phos-
phine (7)
Compound 7, the solid was purified by five consecutive recrystalli-
zations (EtOH–hexane) causing low yield for the isolated com-
pound; white solid: yield: 470 mg (63%); mp 41–42 °C.
[2-(Decylsulfanyl)phenyl]diphenylphosphine (6)
Creamy oil; yield: 1.39 g (95%).
IR (film): 3051, 2923, 2852, 1571, 1477, 1433, 743, 695, 501 cm–1.
3
1H NMR (300 MHz, CDCl3): d = 7.39 (ddd, JH3-H4 = 7.7 Hz,
IR(KBr): 3048, 2963, 1445, 1355, 1222, 1133, 748, 692, 528 cm–1.
4JH3-H5 = 1.2 Hz, 4JH3-P = 4.2 Hz, 1 H, H3), 7.31 (td, 3JH4-H5 = 7.5 Hz,
4JH4-H6 = 1.5 Hz, 1 H, H4), 7.30 (m, 10 H, H2¢–H4¢), 7.06 (td,
3JH5-H6 = 7.7 Hz, 1 H, H5), 6.76 (ddd, 3JH6-P = 3.7 Hz, 1 H, H6), 2.86
3
1H NMR (300 MHz, THF-d8): d = 7.63 (ddd, JH3-H4 = 7.8 Hz,
4JH3-P = 4.2 Hz, 4JH3-H5 = 1.2 Hz, 3 H, H3), 7.39 (td, 3JH4-H5 = 7.8 Hz,
4JH4-H6 = 1.5 Hz, 3 H, H4), 7.20 (td, 3JH5-H6 = 7.8 Hz, 3 H, H5), 6.69
(ddd, 3JH6-P = 2.5 Hz, 3 H, H6), 3.20 (AA¢BB¢XX¢YY¢, 2JA-A¢ = 19.9
2
3
3
(AA¢BB¢CC¢DD¢, JA-A¢ = 13.9 Hz, JA-B = 3.5 Hz, JA-B¢ = 7.5 Hz,
4JA-C = –0.5 Hz, 4JA-C¢ = –0.4 Hz, 5JA-D = –0.8 Hz, 5JA-D¢ = –0.8 Hz,
3
4
4
3
3
4
4
3JA¢-B = 7.2 Hz, JA¢-B¢ = 6.4 Hz, JA¢-C = 0.7 Hz, JA-C¢ = 0.7 Hz,
Hz, JA-B = 5.8 Hz, JA-B¢ = 10.7 Hz, JA-X = –0.2 Hz, JA-X¢ = –0.6
5JA¢-D = –1.2 Hz, 5JA¢-D¢ = –1.3 Hz, 2 H, H7), 1.56 (AA¢BB¢CC¢DD¢,
Hz, 5JA-Y = –0.9 Hz, JA-Y¢ = –5.0 Hz, JA¢-B = 12.9 Hz, JA¢-B¢ = 1.7
5
3
3
3
4
4
4
4
5
5
2JB-B¢ = –13.3 Hz, JB-C = 8.4 Hz, JB-C¢ = 8.1 Hz, JB-D = –5.3 Hz,
Hz, JA¢-X = 1.7 Hz, JA-X¢ = –1.9 Hz, JA¢-Y = –0.2 Hz, JA¢-Y¢ = 7.6
4JB-D¢ = –1.6 Hz, JB¢-C = 6.4 Hz, JB¢-C¢ = 6.4 Hz, JB¢-D = 2.6 Hz,
Hz, 2 H, H7), 2.46 (AA¢BB¢XX¢YY¢, 2JB-B¢ = –14.9 Hz, 3JB-X = 13.8
3
4
4
4
4
4
3
4JB¢-D¢ = 0.4 Hz, 2 H, H8), 1.23 (m, 14 H, H9–H15), 0.88 (t, 3JH-H
=
Hz, JB-X¢ = 14.6 Hz, JB-Y = 0.0 Hz, JB-Y¢ = 2.1 Hz, JB¢-X = 20.8
Hz, 4JB¢-X¢ = 20.4 Hz, 4JB¢-Y = 3.7 Hz, 4JB¢-Y¢ = –4.9 Hz, 2 H, H8).
6.7 Hz, 3 H, H16).
1
1
13C NMR (77.5 MHz, CDCl3): d = 142.5 (d, JC-P = 9.9 Hz, C1),
138.8 (d, JC-P = 27.4 Hz, C2), 136.9 (d, 1JC-P = 10.7 Hz, C1¢), 134.1
(d, 2JC-P = 20.2 Hz, C2¢), 133.5 (s, C6), 129.4 (d, 2JC-P = 3.5 Hz, C3),
129.2 (s, C4), 128.9 (s, C4¢), 128.6 (d, 3JC-P = 7.3 Hz, C3¢), 126.1 (s,
13C NMR (77.5 MHz, THF-d8): d = 142.4 (d, JC-P = 9.7 Hz, C1),
2
4
140.4 (d, JC-P = 29.7 Hz, C2), 135.2 (s, C6), 134.0 (d, JC-P = 2.9
Hz, C3), 130.8 (s, C4), 129.4 (s, C5), 125–106 (m, C9–C12), 32.3
(t, 2JC-F = 22.6 Hz, C8), 27.4 (m, C7).
19F NMR (282 MHz, THF-d8): d = –127.1 (m, 6 F, F9), –125.1 (m,
6 F, F10), –115.3 (m, 6 F, F11), –82.4 (m, 9 F, F12).
4
C5), 35.1 (d, JC-P = 6.5 Hz, C7), 29.3 (s, C9), 29.1 (s, C8), 29.1,
29.4, 29.6, 29.7, and 32.0 (s, C10–C14), 22.8 (s, C15), 14.2 (s, C16).
31P NMR (121 MHz, CDCl3): d = –13.6 (s).
31P NMR (121 MHz, THF-d8): d = –23.6 (s).
HRMS (IE): m/z [M] calcd for C28H35PS: 434.2200; found:
HRMS (FAB): m/z [M – H]+ calcd for C36H23F27PS3: 1097.0300;
434.2212.
found: 1097.0419.
Tris{2-[(1H,1H,2H,2H-perfluorodecyl)sulfanyl]phenyl}phos-
phine (8); Typical Procedure for 7 and 8
Partition Coefficient Determination
A round-bottom flask was charged with the desired compound
(0.024 mmol) and perfluoromethylcyclohexane (5 mL) was added.
Subsequently, cyclohexane (2.5 mL) was added to form a biphasic
system at r.t. The system was stirred at 60 °C in order to form a
monophasic system. The system was allowed to cool to r.t. forming
a biphasic system again. The two phases were separated and the sol-
vents were removed under reduced pressure each. The solids recov-
ered from each phase were dissolved in a deuterated solvent (THF-
d8, CDCl3) and dodecane (16.6 mL, 0.073 mmol) was added as in-
ternal standard. The samples obtained in each phase were analyzed
A 50-mL Schlenk tube was charged with NaH [60% in mineral oil,
65.80 mg, 1.64 mmol; previously washed with hexane (3 × 10 mL)]
under an inert atmosphere and THF (5 mL) was added. At 0 °C, a
soln of 1b (150 mg, 0.42 mmol) in THF (10 mL) was slowly added.
The mixture was stirred at r.t. for 2 h. Then a soln of 1H,1H,2H,2H-
perfluorodecyl iodide (828.70 mg, 1.38 mmol) in THF (5 mL) was
added and the mixture was stirred for 48 h. Then, the solvent was
evaporated and the crude was dissolved in CH2Cl2 and filtered, and
the solvent was evaporated. The solid obtained was recrystallized
(EtOH–hexane) and dried under vacuum for 18 h to give a white
solid; yield: 537 mg (85%); mp 125–127 °C.
1
separately by H NMR techniques. The amount of compound re-
tained in each phase was determined by comparison to the internal
standard.
IR(KBr): 3039, 1355, 1202, 1146, 748, 529 cm–1.
1H NMR (300 MHz, THF-d8): d = 7.65 (ddd, JH3-H4 = 7.8 Hz,
3
Reaction of [Rh(acac)(CO)2] with 3, 5, 7, or 8 under Biphasic
Conditions
4JH3-H5 = 1.2 Hz, 4JH3-P = 4.3 Hz, 3 H, H3), 7.39 (td, 3JH4-H5 = 7.3 Hz,
4JH4-H6 = 1.5 Hz, 4JH4-P = 0.2 Hz, 3 H, H4), 7.21 (td, 3JH5-H6 = 7.8 Hz,
Experiments with precursor [Rh(acac)(CO)2] and compounds 3, 5,
7, and 8 were performed using molar ratios [L]/[Rh] = 2 and 1.25.
We describe the procedure for molar ratio = 2. A Schlenk flask was
charged with 3, 5, 7, or 8 (0.025 mmol). Perfluoromethylcyclohex-
ane (5 mL) was added and the soln was stirred at 60 °C until the sol-
id was completely dissolved. Afterwards, [Rh(acac)(CO)2] (0.0125
mmol) was added under inert gas flow. After a few seconds the soln
or suspension turned yellow and cyclohexane (2.5 mL) was added
and a biphasic system was formed. The mixture was stirred at 60 °C
obtaining a homogeneous phase. The system was allowed to cool to
r.t. forming a biphasic system again. For compound 8 the fluorous
3
3
H, H5), 6.69 (ddd, JH6-P = 2.5 Hz,
3
H, H6), 3.20
(AA¢BB¢XX¢YY¢, 2JA-A¢ = 20.1 Hz, 3JA-B = 5.1 Hz, 3JA-B¢ = 10.6 Hz,
4JA-X = –1.3 Hz, JA-X¢ = –0.4 Hz, JA-Y = 0.5 Hz, JA-Y¢ = –5.0 Hz,
4
5
5
3JA¢-B = 13.1 Hz, JA¢-B¢ = 1.7 Hz, JA¢-X = 1.7 Hz, JA¢-X¢ = –1.3 Hz,
5JA¢-Y = –1.7 Hz, JA¢-Y¢ = 7.6 Hz, 6 H, H7), 2.47 (AA¢BB¢XX¢YY¢,
2JB-B¢ = –14.8 Hz, 3JB-X = 14.9 Hz, 3JB-X¢ = 15.9 Hz, 4JB-Y = –1.1 Hz,
3
4
4
4JB-Y¢ = 1.4 Hz, JB¢-X = 21.8 Hz JB¢-X¢ = 20.1 Hz, JB¢-Y = 4.1 Hz,
3
3
4
4JB¢-Y¢ = –4.9 Hz, 6 H, H8).
1
13C NMR (77.5 MHz, THF-d8): d = 141.5 (d, JC-P = 9.9 Hz, C1),
2
2
139.1 (d, JC-P = 31.9 Hz, C2), 133.9 (s, C6), 133.4 (d, JC-P = 2.7
Synthesis 2010, No. 23, 4101–4106 © Thieme Stuttgart · New York