H. Clavier et al. / Journal of Organometallic Chemistry 690 (2005) 3585–3599
3597
126.5, 127.7, 128.5, 132.4, 133.7, 153.6. HRMS (EI)
calcd for C14H19OBr: 282.0619, found: 282.0610.
1.70-1.90 (m, 23H, PCy3), 2.40 (m, 5H, CH2 and
PCy3), 2.90 (m, 4H, CH2 and PCy3), 4.01 (s, 3H,
CH3), 4.50 (t, J(H,H) = 7.0 Hz, 2H, CH2), 5.37 (sept,
J(H,H) = 7.7 Hz, 1H, CH), 7.28 (d, J(H,H) = 7.9 Hz,
1H, CHar), 7.62 (d, J(H,H) = 8.6 Hz, 1H, CHar), 7.68
(m, 2H, 2CH), 7.81 (m, 1H, CHar), 9.00 (s, 1H, CH),
17.39 (d, J(H,H) = 4.9 Hz, 1H, Ru = CH). 13C NMR
(100 MHz, (CD3)2CO): d (ppm): 22.1, 22.4, 26.4 (3C),
27.9 (d, J(C,P) = 9.9 Hz, 6C), 28.7 (6C), 29.5, 31.2,
33.6 (d, J(C,P) = 21.2 Hz, 3C), 36.1, 46.8, 69.9, 113.6,
122.4 (2C), 124.3, 131.4, 137.2, 137.5, 143.3, 146.9. 19F
NMR (376 MHz, (CD3)2CO): d (ppm): À72.9 (d,
J(F,P) = 708.0 Hz, 6F, PF6). 31P NMR (162 MHz,
(CD3)2CO): d (ppm): À143.0 (sept, J(P,F) = 708 Hz,
1P, PF6), 60.3 (s, 1P, PCy3). HRMS (FAB) calcd for
C+: C35H56N2OCl2PRu: 723.2551, found: 723.2556. Ele-
mental analysis calcd for C35H56N2OF6Cl2P2Ru: C,
48.39; H, 6.50; N, 3.22; found: C, 48.14; H, 6.57; N,
3.37.
4.2.7. 1-[3-(4-Isopropoxy-3-vinyl-phenyl)-propyl]-3-
methyl-3H-imidazol-1-ium hexafluorophosphate (7)
A 10 ml round bottomed flask equipped with a
condenser was charged with 4-(3-bromo-propyl)-1-iso-
propoxy-2-vinyl-benzene 13 (1.1 g, 3.9 mmol), methyl-
imidazole (623 lL, 7.8 mmol, 2 equiv) and dry toluene
(3.9 ml). The mixture was stirred overnight at 100 ꢁC
then the solvent was evaporated off. The residue was dis-
solved in distilled water (30 ml). Hexafluorophosphoric
acid (10 ml, 60% in water) was slowly added dropwise.
After 10 min stirring, dichloromethane and brine were
added. The organic phase was washed with brine until
to reach a neutral pH, dried over magnesium sulfate, fil-
trated and concentrated. A purification by silica gel
chromatography using dichloromethane/acetone (3/1)
as the eluent afforded the desired product as a colorless
oil (1.47 g, 3.41 mmol, 87% (two steps)). 1H NMR
(400 MHz, (CD3)2CO): d (ppm): 1.29 (d, J(H,H) =
6.1 Hz, 6H, 2CH3), 2.09 (tt, J(H,H) = 7.4 Hz, 2H,
CH2), 2.56 (t, J(H,H) = 7.4 Hz, 2H, CH2), 3.77 (s, 3H,
CH3), 4.09 (t, J(H,H) = 7.2 Hz, 2H, CH2), 4.46 (sept,
J(H,H) = 6.0 Hz, 1H, CH), 5.19 (d, J(H,H) = 11.4 Hz,
1H, CH2), 5.75 (d, J(H,H) = 17.8 Hz, 1H, CH2), 6.78
(d, J(H,H) = 8.4 Hz, 1H, CHar), 6.98 (m, 2H, CH and
CHar), 7.17 (m, 2H, 2CH), 7.25 (m, 1H, CHar), 8.28 (s,
1H, CH). 13C NMR (100 MHz, (CD3)2CO): d (ppm):
21.1 (2C), 30.3, 30.4, 35.0, 48.5, 70.0, 113.2, 113.6,
121.0 (2C), 122.5, 125.1, 126.6, 127.7, 130.9, 134.6,
152.6. 19F NMR (376 MHz, (CD3)2CO): d (ppm):
À72.3 (d, J(F,P) = 712.8 Hz, 6F, PF6). 31P NMR (162
MHz, (CD3)2CO): d (ppm): À143.1 (sept, J(P,F) =
712.8 Hz, 1P, PF6). HRMS (FAB) calcd for C+:
C18H25N2O: 285.1967, found: 285.1957.
4.2.9. Ionic liquid-supported catalyst (9)
In a Schlenk flask, 1-[3-(4-isopropoxy-3-vinyl-phe-
nyl)-propyl]-3-methyl-3H-imidazol-1-ium hexafluoro-
phosphate 7 (159 mg, 0.37 mmol) was diluted in dry
dichloromethane (37 ml). Copper (I) chloride (73 mg,
0.74 mmol) and Grubbsꢀ catalyst 3 (494 mg, 0.6 mmol,
1.5 equiv) were introduced. The resulting solution was
degassed three times (vacuum/argon) and stirred for
30 h at reflux. The solvent was evaporated under vac-
uum, the residue was dissolved in dry acetone (10 ml)
and the insoluble materials were removed by filtration
and washed with acetone (2 · 5 ml). The filtrate was
evaporated under vacuum and then solubilised in the
minimum amount of dichloromethane. The same
amount of toluene was added and the solution was
cooled at À10 ꢁC over 10 h. The resulting green crystals
were filtered and washed with cold toluene and dried un-
der vacuum to afford a green powder (228 mg, 90%). 1H
4.2.8. Ionic liquid-supported catalyst (8)
In a Schlenk apparatus were introduced copper (I)
chloride (49 mg, 0.5 mmol, 1.25 equiv) and Grubbs cat-
alyst 2 (494 mg, 0.6 mmol, 1.5 equiv). Three degassing
(vacuum/argon) were performed and the 1-[3-(4-Iso-
propoxy-3-vinyl-phenyl)-propyl]-3-methyl-3H-imidazol-
1-ium hexafluorophosphate 7 (172 mg, 0.4 mmol) in
solution in dry dichloromethane (8 ml) was syringed
into the reaction mixture. The resulting solution was
again degassed three times and stirred for 3 h at room
temperature. The solvent was evaporated off under vac-
uum, the residue was dissolved in dry acetone (8 ml).
The excess of 2 was removed by filtration and washed
with acetone (8 ml). After concentration, the catalyst
was precipitated in a 1/1 pentane/dichloromethane mix-
ture (8 ml), filtrated, washed with the same mixture
(8 ml) and dried under vacuum to afford a brown solid
(270 mg, 0.31 mmol, 78%). 1H NMR (400 MHz,
(CD3)2CO): d (ppm): 1.30 (m, 11H, 2CH3 and PCy3),
NMR (400 MHz, CD2Cl2):
d
J(H,H) = 1.7 Hz, 6H, 2CH3),
(ppm): 1.19 (d,
2.15 (quint,
J(H,H) = 6.8 Hz, 2H, CH2), 2.41 (s, 18H, 6CH3), 2.76
(t, J(H,H) = 6.8 Hz, 2H, CH2), 3.67 (s, 3H, CH3), 4.13
(m, 6H, 3CH2), 4.81 (sept, J(H,H) = 6.2 Hz, 1H, CH),
6.59 (d, J(H,H) = 1.7 Hz, 1H, CHar), 6.74 (d,
J(H,H) = 8.5 Hz, 1H, CHar), 7.07 (s, 3H, 3CHar), 7.17
(m, 2H, 2CH), 7.38 (dd, J(H,H) = 1.7 and 8.5 Hz, 1H,
CHar), 8.25 (s, 1H, CH), 16.45 (s, 1H, Ru = CH). 13C
NMR (100 MHz, CD2Cl2): d (ppm): 21.1 (6C), 21.4
(2C), 30.8, 31.6, 36.8, 50.3, 51.8 (2C), 75.6, 113.3,
121.4, 121.9, 124.0, 125.5, 128.4 (4C), 129.2 (2C), 129.5
(4C), 133.8, 136.5, 139.1, 145.2 (2C), 150.8, 210.2,
295.2 (q, J(C,Ru) = 27.2 Hz, 1C). 19F NMR
(376 MHz,
CD2Cl2):
d
(ppm):
À72.8
(d,
J(F,P) = 711 Hz, 6F, PF6). 31P NMR (162 MHz,
CD2Cl2): d (ppm): À143.1 (sept, J(P,F) = 711 Hz, 1P,
PF6). HRMS (FAB) calcd for C+: 749.2327, found: