4
4
3
4
3
4
7
.4, NCH
2
), 7.37 (1H, t, J 1.8, NCHCHN), 7.56 (1H, t, J 1.8,
tt, J 7.8, J 1.2, CHCHCH) and 9.46 (2H, dd, J 6.7, J 1.2,
CHNCH).
NCHCHN) and 9.97 (1H, s, NCHN)
N-Octyl-N,N,N-triethylammonium
bromide,[OctNEt
3
]Br.
1
-Decyl-3-methylimidazolium bromide, [DecMim]Br. N-
3
3
Triethylamine (12 cm , 8.71 g, 0.086 mol), 1-bromooctane
Methylimidazole (10 cm , 10.30 g, 0.125 mol), 1-bromodecane
29 cm , 77.14 g, 0.140 mol) and ethyl acetate (40 cm ) were
heated under reflux for 28 h in an atmosphere of argon. The
biphasic system obtained was separated and the upper organic
phase discharged. The bottom product phase was washed with
ethylacetate (3 ¥ 40 cm ), and dried under vacuum (0.01 mbar)
at 50 C to give 1-decyl-3-methylimidazolium bromide (33.74 g,
9%) as a colourless viscous liquid. d
3H, t, J 6.7, NC
3
3
3
3
(12 cm , 13.41 g, 0.069 mol) and acetonitrile (25 cm ) were
heated under reflux for 18 h in an atmosphere of argon. The
(
◦
mixture obtained was cooled to 0 C and ethyl acetate was
added in portions until precipitation of a white solid. The
cold suspension was filtered, the solid collected, washed with
3
3
◦
ethyl acetate (3 ¥ 30 cm ) and dried under vacuum (0.01 mbar)
to give N-octyl-N,N,N-triethylammonium bromide (15.12 g,
8
(
H
(300 MHz, CDCl
), 0.99–1.22 (14H, m, CH ), 1.75 (2H,
), 3.97 (3H, s, NCH ), 4.16 (2H, t, J
3
) 0.69
3
3
74%) as a white solid. d
6.8, NC ), 1.21–1.44 (19H, m, CH
1.70 (2H, quintet, J 7.1, NCH2CH2), 3.24–32.27 (2H, m,
H
(300MHz; CDCl
3
) 0.87 (3H, t, J
7
H
14CH
3
2
3
3
7
H
14CH
3
2
and NCH
2
CH ),
3
quintet, J 7.2 NCH
.4, NCH
NCHCHN) and 10.08 (1H, s, NCHN)
2
CH
2
3
3
4
4
7
2
), 7.40 (1H, t, J 1.8, NCHCHN), 7.59 (1H, t, J 1.8,
3
NCH
2
C
7
H
15) and 3.52 (6H, q, J 7.3, NCH
2
CH ); m/z (ESI)
3
2
14 (M+, 100%).
1
-Octyl-3-methylimidazolium chloride, [OctMim]Cl. N-
3
Methylimidazole (40 cm , 41.2 g, 0.502 mol), 1-chlorooctane
103 cm , 89.52 g, 0.602 mol) and ethyl acetate (100 cm ) were
Acknowledgements
3
3
(
We thank Sasol Technology (UK) Ltd for partial funding of a
studentship (SLD).
heated under reflux for 5 days in an atmosphere of argon. The
biphasic system obtained was separated and the upper organic
phase discharged. The bottom product phase was washed with
3
ethyl acetate (3 ¥ 50 cm ), and dried under vacuum (0.01 mbar)
Notes and references
◦
at 50 C to give 1-octyl-3-methylimidazolium chloride (63.0 g,
1
P. Anastas, and J. Warner, Green Chemistry: Theory and practice,
Oxford University Press, USA, 1998.
5
4%) as a pale yellow liquid. d
H
(300 MHz, CDCl
), 1.12 (10H, m, CH ), 1.75 (2H, quintet, J
), 3.97 (3H, s, NCH ), 4.18 (2H, t, J 7.7, NCH
.39 (1H, t, J 1.7, NCHCHN), 7.63 (1H, t, J 1.7, NCHCHN)
3
) 0.69 (3H, t,
3
3
J 6.8, NC
7
H
14CH
3
2
2 For different methods of catalyst recycling, see (a) D. J. Cole-
Hamilton, Science, 2003, 299, 1702; (b) Catalyst Separation, Recovery
and Recycling: Chemistry and Process Design, ed. D. J. Cole-Hamilton
and R. P. Tooze, Springer, Dordrecht, 2005.
3 For review, see Aqueous-Phase Organometallic Catalysis, ed.
B. Cornils and W. A. Herrmann, Wiley-VCH, Weinheim, 2nd edn,
3
7.3 NCH
2
CH
2
3
2
),
3
3
7
and 10.42 (1H, s, NCHN).
2
004.
1
-Octyl-3-methylimidazolium trifluoroacetate, [OctMim]TfA.
4
5
H.-W. Bohnen and B. Cornils, Adv. Catal., 2002, 47, 1.
B. Cornils, Org. Process Res. Dev., 1998, 2, 121.
6 (a) A. Buhling, P. C. J. Kamer and P. W. N. M. van Leeuwen, J. Mol.
Catal. A: Chem., 1995, 98, 69; (b) A. Buhling, J. W. Elgersma, P. C. J.
Kamer, and P. W. N. M. van Leeuwen, J. Mol. Catal. A: Chem., 1997,
1
-Octyl-3-methylimidazolium chloride (7.48 g, 0.032 mol) in
solution in water (25 cm ) was added to a suspension of silver
trifluoroacetate (7.42 g, 0.034 mol) in water (25 cm ) and the
mixture was stirrer overnight. The silver chloride precipitate
was removed by filtration and the aqueous phase was extracted
with dichloromethane (4 ¥ 25 cm ). The organic phases were
combined and washed with small portions of water (10 cm )
until silver nitrate test on the washings gave no precipitate. The
solvent was evaporated, and further drying under vacuum (0.01
mbar) gave 1-octyl-3-methylimidazolium trifluoroacetate (3.2 g,
3
3
1
16, 297; (c) M. Karlsson, M. Johansson and C. Andersson, J. Chem.
Soc., Dalton Trans., 1999, 4187.
3
7 (a) Z. Jin, X. Zheng and B. Fell, J. Mol. Catal. A: Chem., 1997, 116,
55; (b) F. Wen, H. B o¨ nnemann, J. Jiang, D. Lu, Y. Wang and Z. Jin,
Appl. Organomet. Chem., 2005, 19, 81; (c) H. Azoui, K. Baczko, S.
Cassel and C. Larpent, Green Chem., 2008, 10, 1197.
8 (a) A. Andreetta, G. Barberis and G. Gregorio, Chim. Ind., 1978, 60,
8
3
87; (b) S. L. Desset and D. J. Cole-Hamilton, Angew. Chem., Int.
Ed., 2009, 48, 1472.
3
1%) as a colourless liquid. d
H
(400 MHz, CDCl
), 1.27 (10H, m, CH ), 1.88 (2H, quintet, J
), 4.04 (3H, s, NCH ), 4.24 (2H, t, J 7.4, NCH
.27 (1H, t, J 1.7, NCHCHN), 7.33 (1H, t, J 1.7, NCHCHN)
3
) 0.81 (3H, t,
9
M. E. Davis, Transition to heterogeneous techniques (SAPC
and variations), in Aqueous Phase Organometallic Catalysis, ed.
B. Cornils and W. A. Herrmann, Wiley-VCH, Weinheim, 2nd edn,
2004.
3
3
J 6.9, NC
7
H
14CH
3
2
3
7
7
.2 NCH
2
CH
2
3
2
),
4
4
1
1
0 I. T. Horvath, Catal. Lett., 1990, 6, 43.
and 10.36 (1H, s, NCHN).
1 K.-D. Wiese, O. M o¨ ller, G. Protzmann and M. Trocha, Catal. Today,
2
003, 79–80, 97–103.
3
12 (a) P. Purwanto and H. Delmas, Catal. Today, 1995, 24, 135; (b) H.
Ding, B. E. Hanson, T. Bartik and B. Bartik, Organometallics, 1994,
N-Octylpyridinium bromide, [OctPyr]Br. Pyridine (10 cm ,
.78 g, 0.124 mol), 1-bromooctane (24 cm , 26.83 g, 0.139 mol)
and ethyl acetate (30 cm ) were stirred under reflux for 14 h
in an atmosphere of argon. The biphasic system obtained was
separated and the upper organic phase discharged. The bottom
product phase was washed with ethyl acetate (3 ¥ 30 cm ),
and dried under vacuum (0.01 mbar) at 50 C to give N-
octylpyridinium bromide (26.1 g, 77%) as a colourless liquid.
3
9
1
3, 3761.
3
1
3 (a) E. Monflier, G. Fremy, Y. Castanet and A. Mortreux, Angew.
Chem., Int. Ed. Engl., 1995, 34, 2269; (b) S. Tilloy, F. Bertoux, A.
Mortreux and E. Monflier, Catal. Today, 1999, 48, 245; (c) L. Leclerc,
F. Hapiot, S. Tilloy, K. Ramkisoening, J. N. H. Reek, P. W. N. M.
vanLeeuwen and E. Monflier, Organometallics, 2005, 24, 2070; (d) D.
Kirschner, T. Green, F. Hapiot, S. Tilloy, L. Leclercq, H. Bricout and
E. Monflier, Adv. Synth. Catal., 2006, 348, 379; (e) E. Karakhanov,
T. Buchneva, A. Maximov and M. Zavertyaeva, J. Mol. Catal. A:
Chem., 2002, 184, 11.
3
◦
3
d
1
(
H
(300 MHz, CDCl
3
) 0.66 (3H, t, J 6.8, NC
7
H
14CH
3
), 0.96–
CH ), 4.83
), 8.04 (2H, t, J 7.2, CHCHCH), 8.42 (1H,
3
.26 (10H, m, CH
2H, t, J 7.5, NCH
2
), 1.89 (2H, quintet, J 7.3 NCH
2
2
1
4 (a) H. Chen, Y. Li, J. Chen, P. Cheng, Y.-E. He and X. Li, J. Mol.
Catal. A: Chem., 1999, 149, 1; (b) L. Wang, H. Chen, Y.-E. He,
3
3
2
6
36 | Green Chem., 2009, 11, 630–637
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