J = 7.7 Hz), 4.04 (1H, m), 3.60 (2H, d, J = 6.5 Hz), 1.84 (2H,
pseudo-quint, J = 7.5 Hz), 1.29 (2H, pseudo-sext, J = 7.5 Hz),
1-(2,3-Dihydroxypropyl)-3-octyl-1H-imidazolium bromide (8)
([GLYOCTIM]Br)
1
3
0
.89 ppm (3H, t, J = 7.5 Hz). C-NMR (67.5, D
2
O): 135.9 (CH),
), 51.8 (CH ), 49.4
) ppm.
A mixture of 3-(1H-imidazol-1-yl)propane-1,2-diol (1) (14.20 g,
1
23.0 (CH), 122.3 (CH), 69.8 (CH), 62.4 (CH
), 31.2 (CH ), 18.7 (CH ), 12.6 (CH
2
2
1
00 mmol) and 1-bromooctane (26.1 mL, 28.97 g, 150 mmol)
(
CH
2
2
2
3
◦
was stirred at 80 C for 69 h. The crude reaction mixture
was washed with Et
heated at 75 C and stirred under vacuum (0.1 bar) for 24 h.
2
O (8 ¥ 20 mL), THF (3 ¥ 20 mL) and
◦
3
-Butyl-1-(2,3-dihydroxypropyl)-1H-imidazolium bromide (5)
[
GLYBIM]Br)
[GLYOCTIM]Br (8) (30.90 g, 92%) was obtained as a pale yellow
1
oil. IR (neat): 3305 (OH). (OH H-NMR (250 MHz, D
2
O): 8.90
A mixture of 3-(1H-imidazol-1-yl)propane-1,2-diol (1) (14.20 g,
1
was stirred at 40 C for 70 h. The top layer of the biphasic crude
reaction mixture, which contained unreacted starting material,
was decanted and the bottom layer was washed with Et
(
1H, s), 7.57 (2H, s), 4.37 (1H, dd, J = 14 Hz, J = 2.7 Hz),
00 mmol) and 1-bromobutane (16.1 mL, 20.56 g, 150 mmol)
◦
4.22 (1H, dd, J = 14 Hz, J = 7.7 Hz), 4.07 (1H, m) 3.62 (2H,
d, J = 5.7), 1.87 (2H, m), 1.26 (12H, m), 0,80 ppm (3H, m).
1
3
C-NMR (67.5, D O): 136.0 (CH), 123.2 (CH), 122.3 (CH),
2
2
O (6 ¥
◦
69.8 (CH), 62.4 (CH
2
), 51.9 (CH
2
), 49.7 (CH
2
), 31.3 (CH
2
), 29.4
), 13.6
2
2
5 mL), heated at 70 C and stirred under vacuum (0.1 bar) for
4 h. [GLYBIM]Br (5) (26.08 g, 93%) was obtained as a pale
(CH
CH
2
), 28.5 (CH
) ppm.
2
), 28.4 (CH ), 25.6 (CH
2
2
), 22.2 (CH
2
(
3
1
orange oil. IR (neat): 3295 (OH). H-NMR (250 MHz, D
2
O):
8
2
.85 (1H, s), 7.55 (2H, br s), 4.41 (1H, dd, J = 14 Hz, J =
.9 Hz), 4.21 (2H, dd, J = 14 Hz, J = 6.7 Hz), 4.10 (1H, m), 3.63
1
-(2,3-dihydroxypropyl)-3-octyl-1H-imidazolium
(
2H, d, J = 5.5 Hz), 1.87 (2H, pseudo-quint, J = 7.0 Hz), 1.30
bis(trifluoromethanesulfonyl)imide (9) ([GLYOCTIM][NTf
2
])
(
2H, pseudo-sext, J = 7.0 Hz), 0.92 ppm (3H, t, J = 7.0 Hz).
1
3
A mixture of [GLYOCTIM]Br (8) (6.82 g, 20.35 mmol) and
lithium bis(trifluoromethanesulfonyl)imide (5.86 g, 20.35 mmol)
in 35 mL of H
biphasic colorless mixture was allowed to cool to room tem-
perature and stirred for 22 h. The crude reaction mixture was
diluted with H O and acetone, and the solvents were removed in
C-NMR (67.5, D
9.9 (CH), 62.5 (CH
CH ), 12.7 (CH ) ppm.
2
O): 135.9 (CH), 123.0 (CH), 122.4 (CH),
6
(
2
), 51.8 (CH
2
), 49.5 (CH
2
), 31.3 (CH ), 18.8
2
◦
2
O were stirred at 70 C for 1 h. The resulting
2
3
3
-Butyl-1-(2,3-dihydroxypropyl)-1H-imidazolium
2
methanesulfonate (6) ([GLYBIM][OMs])
vacuo. The resulting yellow oil was diluted with acetone, filtered
and concentrated, and this operation was repeated twice. The
A mixture of 3-(1H-imidazol-1-yl)propane-1,2-diol (1) (15.08 g,
resulting crude product was then washed with H
and then heated at 80 C and stirred under vacuum (0.1 bar)
2
O (6 ¥ 20 mL)
6
6 mmol) and butyl methanesulfonate (15.08 g, 99 mmol) was
◦
◦
stirred at 80 C for 70 h. The crude reaction mixture was washed
with Et
◦
for 4 h. [GLYOCTIM][NTf ] (9) (9.41 g, 92%) was obtained as
O (5 ¥ 15 mL), THF (6 ¥ 20 mL), heated at 50 C and
2
2
1
a pale yellow oil. IR (neat): 3520 (OH). H-NMR (250 MHz,
stirred under vacuum (0.1 bar) for 24 h. [GLYBIM][OMs] (6)
CDCl
3-96 (3H, m, ABM system), 3.66–3.50 (2H, AB system), 1.83
2H, m), 1.25 (12H, br s), 0.86 ppm (3H, t, J = 6.4 Hz).
C-NMR (67.5, CDCl ): 136.0 (CH), 123.2 (CH), 122.3 (CH),
9.8 (CH), 63.1 (CH ), 51.9 (CH ), 50.2 (CH ), 31.7 (CH ),
30.0 (CH ), 29.0 (CH ), 28.8 (CH ), 26.1 (CH ), 22.6 (CH ),
3
): 8.65 (1H, br s), 7.45 (1H, br s), 7.28 (1H, br s), 4.4–
(
(
26.08 g, 93%) was obtained as a pale yellow oil. IR (neat): 3338
1
OH). H-NMR (250 MHz, D
2
O): 8.79 (1H, s), 7.51 (2H, br s),
(
4
.37 (1H, dd, J = 14 Hz, J = 1.7 Hz), 4.20 (1H, dd, J = 14 Hz,
1
3
J = 7.7 Hz), 4.03 (1H, m), 3.59 (2H, d, 5.1 Hz), 2.78 (3H, s),
3
6
2
2
2
2
1
0
1
.84 (2H, pseudo-quint, J = 7.2), 1.30 (2H, pseudo-sext, J = 7.2),
.90 ppm (3H, t, J = 7.2). C-NMR (67.5, D O): 135.9 (CH),
23.0 (CH), 122.3 (CH), 69.8 (CH), 62.4 (CH ), 51.7 (CH ), 49.4
), 38.5 (CH ), 31.1 (CH ), 18.7 (CH ), 12.6 (CH ) ppm.
1
3
2
2
2
2
2
2
1
4.0 (CH ) ppm.
3
2
2
(
CH
2
3
2
2
3
3,3¢-Methylenebis(1-(2,3-dihydroxypropyl)-1H-imidazolium
1
-(2,3-Dihydroxypropyl)-3-octyl-1H-imidazolium chloride (7)
dibromide (10) ([MEBISGLYIM]Cl)
(
[GLYOCTIM]Cl)
A mixture of 3-(1H-imidazol-1-yl)propane-1,2-diol (1) (20 g,
A mixture of 3-(1H-imidazol-1-yl)propane-1,2-diol (1) (8.87 g,
141 mmol) and dibromomethane (50 mL, 124.75 g, 718 mmol)
was stirred at 80 C for 72 h. The top layer of the biphasic crude
reaction mixture, which contained unreacted starting material,
◦
6
2 mmol) and 1-chlorooctane (31.8 mL, 27.65 g, 186 mmol) was
◦
stirred at 95 C for 90 h. The top layer of the biphasic crude
reaction mixture, which contained unreacted starting material,
was decanted and the bottom layer was washed with Et
50 mL), THF (4 ¥ 50 mL), heated at 85 C and stirred under
vacuum (0.1 bar) for 24 h. [MEBISGLYIM]Cl (10) (30.90 g,
2
O (3 ¥
◦
was decanted and the bottom layer was washed with AcOEt (5 ¥
◦
2
0 mL), Et
2
O (6 ¥ 20 mL), heated at 100 C and stirred under
vacuum (0.1 bar) for 24 h. [GLYOCTIM]Cl (7) (15.51 g, 92%)
was obtained as a pale orange oil. IR (neat) 3279 (OH). H-
96%) was obtained as a pale yellow oil. IR (neat): 3306 (OH).
1
1
H-NMR (250 MHz, D O): 9.40 (2H, s), 7.89 (2H, s), 7.72
2
NMR (250 MHz, D
.40–4.26 (2H, m), 4.07 (1H, m) 3.61 (2H, d, J = 5 Hz), 1.87 (2H,
m), 1.26 (12H, m), 0,80 ppm (3H, m). C-NMR (67.5, D O):
2
O): 8.90 (1H, s), 7.58 (1H, s), 7.55 (1H, s),
(2H, s), 6.80 (2H, s), 4.51 (2H, dd, J = 14 Hz, J = 2.7 Hz),
4
4.31 (2H, dd, J = 14 Hz, J = 8 Hz), 4.13 (2H, m), 3.67 ppm
1
3
13
2
(4H, d, J = 5.5 Hz). C-NMR (67.5, D
2
O): 137.6 (CH), 124.5
1
5
2
36.0 (CH), 123.2 (CH), 122.3 (CH), 69.8 (CH), 62.4 (CH
1.9 (CH ), 49.7 (CH ), 31.3 (CH ), 29.4 (CH ), 28.6 (CH
8.4 (CH ), 25.6 (CH ), 22.2 (CH ), 13.6 (CH ) ppm.
2
),
),
(CH), 122.1 (CH), 69.6 (CH), 62.5 (CH
(CH ) ppm.
2
), 59.0 (CH ), 52.0
2
2
2
2
2
2
2
1
2
2
2
3
ILs 2–10 appeared pure at H NMR and ESI-MS analysis.
6
24 | Green Chem., 2009, 11, 622–629
This journal is © The Royal Society of Chemistry 2009