Beilstein Journal of Organic Chemistry 2009, 5, No. 51.
aliphatic), 1514 (C=C aromatic), 1251 (C-O aromatic). UV–vis aliphatic), 22.65, 25.95, 29.08, 29.32, 29.37, 29.55, 29.59,
(CH2Cl2): λmax (ε, L·mol−1·cm−1) = 240 nm (24000). Elemental 29.61, 29.64, 31.89 (CH2 aliphatic), 36.81 (N-CH3), 68.65
analysis for C22H35IN2O·1/4H2O, Calcd: C, 55.64; H, 7.53; N, (O-CH2), 115. 91 (CH phenyl), 121.60 (CH imidazolium),
5.90%. Found: C, 55.78; H, 7.48; N, 5.34%.
123.70 (CH phenyl), 124.33 (CH imidazolium), 127.21 (N-C
phenyl), 134.42 (CH imidazolium), 160.51 (C-O-CH2 phenyl).
νmax/cm−1 2921 and 2850 (C-H aliphatic), 1516 (C=C
aromatic), 1255 (C-O aromatic), 826 cm−1 (PF6−). UV–vis
General procedure for metathesis in
water–anion exchange
A mixture of 1a dissolved in dichloromethane (4 mL) and a (CH2Cl2): λmax (ε, L·mol−1·cm−1) = 249 nm (11700). Elemental
mixture of the corresponding salts dissolved in water (3 mL) analysis for C22H35F6N2OP·1/7H2O, Calcd: C 53.81, H 7.24, N
were stirred together for 140 h. The organic layer was separ- 5.70%. Found: C 53.77, H 7.31, N 5.51%.
ated off, washed with water and dried over calcium chloride.
1-[4-(Dodecyloxy)phenyl]-3-methyl-1H-
Crystallization with dichloromethane and diethyl ether gave the
corresponding imidazolium salt.
imidazol-3-ium trifluoromethanesulfonate (1d)
Following the general procedure using 1a (0.730 g, 1.55 mmol)
and sodium trifluoromethanesulfonate (0.616 g, 3.51 mmol)
provided 1d with a yield of 46% (0.349 g, 0.71 mmol).
1-[4-(Dodecyloxy)phenyl]-3-methyl-1H-
imidazol-3-ium tetrafluoroborate (1b)
Following the general procedure using 1a (0.797 g, 1.69 mmol)
and sodium tetrafluoroborate (0.511 g, 4.56 mmol) provided 1b 1H NMR (300 MHz, CDCl3): δ = 0.89 (t, 3H, J = 6.8Hz, CH3
with a yield of 72% (0.525 g, 1.22 mmol).
aliphatic chain), 1.28 (broad s, 16H, CH2 aliphatic chain),
1.41–1.46 (m, 2H, O-CH2-CH2-CH2), 1.76–1.83 (m, 2H,
1H NMR (300 MHz, CDCl3): δ = 0.86 (t, 3H, J = 6.3 Hz, CH3 O-CH2-CH2), 3.99 (t, 2H, J = 6.6 Hz, O-CH2), 4.10 (s, 3H,
aliphatic chain), 1.28 (broad s, 16H, CH2 aliphatic chain), N-CH3), 7.02 and 7.51 (AA′ and BB′, 2 × 2H, J = 8.8 Hz, CH
1.41–1.46 (m, 2H, O-CH2-CH2-CH2), 1.75–1.84 (m, 2H, phenyl), 7.49 (broad s, 2H, N-CH-CH-N), 9.41 (broad s, 1H,
O-CH2-CH2), 3.98 (t, 2H, J = 6.3 Hz, O-CH2), 4.11 (s, 3H, N-CH-N). 13C NMR (75 MHz, CDCl3): δ = 13.96 (CH3
N-CH3), 7.02 and 7.53 (AA′ and BB′, 2 × 2H, J = 9.0 Hz, CH aliphatic), 22.54, 25.85, 28.97, 29.21, 29.26, 29.44, 29.48,
phenyl), 7.48 (broad s, 2H, N-CH-CH-N), 9.37 (broad s, 1H, 29.51, 29.53, 31.78 (CH2 aliphatique), 36.52 (N-CH3), 68.54
N-CH-N). 13C NMR (75 MHz, CDCl3): δ = 14.07 (CH3 (O-CH2), 115. 84 (CH phenyl), 120.49 (q, J = 318.18 Hz,
aliphatic), 22.65, 25.95, 29.08, 29.32, 29.37, 29.55, 29.59, CF3SO3−), 121.36 (CH imidazolium), 123.33 (CH phenyl),
29.61, 29.64, 31.89 (CH2 aliphatic), 36.81 (N-CH3), 68.65 124.44 (CH imidazolium), 127.15 (N-C phenyl), 134.95 (CH
(O-CH2), 115. 96 (CH phenyl), 121.34 (CH imidazolium), imidazolium), 160.36 (C-O-CH2 phenyl). νmax/cm−1 3119 (C-H
123.59 (CH phenyl), 124.50 (CH imidazolium), 127.24 (N-C aromatic), 2915 and 2849 (C-H aliphatic), 1520 (C=C
phenyl), 134.97 (CH imidazolium), 160.47 (C-O-CH2 phenyl). aromatic), 1269 and 1028 (CF3SO3−). UV–vis (CH2Cl2): λmax
νmax/cm−1 2917 and 2849 (C-H aliphatic), 1514 (C=C (ε, L·mol−1·cm−1) = 256 nm (10100). Elemental analysis for
aromatic), 1249 (C-O aromatic), 1024 (BF4−). UV–vis C22H35F3N2O4S, Cacld: C 56.08, H 7.16, N 6.59%. Found: C
(CH2Cl2): λmax (ε, L·mol−1·cm−1) = 255 nm (10500). Elemental 55.84, H 6.86, N 5.40%.
analysis for C22H35BF4N2O·3/4H2O, Calcd: C 59.53, H 8.29, N
1-[4-(Dodecyloxy)phenyl]-3-methyl-1H-
6.31%. Found: C 59.74, H 8.02, N 6.20%.
imidazol-3-ium bis(trifluoromethane) sulfon-
1-[4-(Dodecyloxy)phenyl]-3-methyl-1H-
amide (1e)
1a (0.101 g, 0.21 mmol) and lithium bis(trifluoromethane)-
sulfonamide (0.145 g, 0.51 mmol) were dissolved in water (3
mL) and stirred for 140 h. The precipitate was filtred and
washed. Crystallization (chloroform/cyclohexane) provided 1e
with a yield of 90% (0.121 g, 0.19 mmol).
imidazol-3-ium hexafluorophosphate (1c)
Following the general procedure using 1a (0.695 g, 1.48 mmol)
and potassium hexafluoroborate (0.518 g, 2.18 mmol) provided
1c with a yield of 84% (0.607 g, 1.24 mmol).
1H NMR (300 MHz, CDCl3): δ = 0.89 (t, 3H, J = 6.8 Hz, CH 3
aliphatic chain), 1.28 (broad s, 16H, CH2 aliphatic chain), 1H NMR (300 MHz, CDCl3): δ = 0.89 (t, 3H, J = 6.8 Hz, CH3
1.41–1.46 (m, 2H, O-CH2-CH2-CH2), 1.76–1.85 (m, 2H, aliphatic chain), 1.28 (broad s, 16H, CH2 aliphatic chain),
O-CH2-CH2), 3.98 (t, 2H, J = 6.6 Hz, O-CH2), 4.07 (s, 3H, 1.42–1.52 (m, 2H, O-CH2-CH2-CH2), 1.77–1.86 (m, 2H,
N-CH3), 7.02 and 7.48 (AA′ and BB′, 2 × 2H, J = 8.8 Hz, CH O-CH2-CH2), 4.01 (t, 2H, J = 6.6 Hz, O-CH2), 4.07 (s, 3H,
phenyl), 7.45 (broad s, 2H, N-CH-CH-N), 9.10 (broad s, 1H, N-CH3), 7.05 and 7.46 (AA′ and BB′, 2 × 2H, J = 8.8 Hz, CH
N-CH-N). 13C NMR (75 MHz, CDCl3): δ = 14.06 (CH3 phenyl), 7.43–7.49 (m, 2H, N-CH-CH-N), 8.98 (broad s, 1H,
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