PAPER
Synthesis of Si(OR) -Functionalised Imidazolium Salts
625
3
1
3
C NMR (50.32 MHz, CDCl ): d = 136.1 (NCHN), 123.6 (CHCH),
(3) Le Boulaire, V.; Grée, R. Chem. Commun. 2000, 2195.
(4) Laali, K. K.; Gettwert, V. J. J. Fluorine Chem. 2001, 107,
31.
3
1
(
21.9 (CHCH), 51.3 (NCH ), 50.4 (OCH ), 36.7 (NCH ), 23.7
CH CH CH ), 5.5 (SiCH ).
2
3
3
2 2 2 2
+
+
(5) Song, C. E.; Shim, W. H.; Roh, E. J.; Lee, S.-G.; Choi, J. H.
Chem. Commun. 2001, 1122.
MS (ESI ): m/z = 245 ([M – I] , 100%).
–
–
MS (ESI ): m/z = 499 ([M + I] , 100%).
(
6) (a) Song, C. E.; Shim, W. H.; Roh, E. J.; Choi, J. H. Chem.
Commun. 2000, 1695. (b) Stark, A.; MacLean, B. L.; Singer,
R. D. J. Chem. Soc., Dalton Trans. 1999, 63.
7) Earle, M. J.; McCormac, P. B.; Seddon, K. R. Chem.
Commun. 1998, 2245.
8) Wheeler, C.; West, K. N.; Liotta, C. L.; Eckert, C. A. Chem.
Commun. 2001, 887.
9) Gordon, C. M.; McCluskey, A. Chem. Commun. 1999, 1431.
+
HRMS (CI): m/z calcd for C H N O Si ([M – I] ): 245.1321;
found: 245.1323.
1
0
21
2
3
(
(
(
1
-(4-Acetylphenyl)-3-(3-propyltrimethoxysilane)imidazolium
Iodide (6c)
-Iodopropyltrimethoxysilane (1.00 mL, 5.11 mmol) was added to
a solution of 4¢-(imidazol-1-yl)acetophenone (2c; 0.951 g, 5.11
mmol) in toluene (10 mL). The reaction mixture was heated at
00 °C (external temperature) with exclusion of light for 18 h. The
mixture was allowed to cool to r.t. and the supernatant solution was
removed with a pipette. The resultant solid was washed with toluene
3 × 10 mL) and dried in vacuo. The product was obtained as a co-
lourless solid (1.871 g, 77%).
3
(
(
10) Kabalka, G. W.; Malladi, R. R. Chem. Commun. 2000, 2191.
11) (a) Dubreuil, J. F.; Bazureau, J. P. Tetrahedron Lett. 2000,
1
41, 7351. (b) Peng, J.; Deng, Y. New J. Chem. 2001, 25, 639.
(
(
(
(
12) Brasse, C. C.; Englert, U.; Salzer, A.; Waffenschmidt, H.;
Wasserscheid, P. Organometallics 2000, 19, 3818.
13) Mizushima, E.; Hayashi, T.; Tanaka, M. Green Chem. 2001,
(
3
, 76.
14) Ross, J.; Chen, W.; Xu, L.; Xiao, J. Organometallics 2001,
0, 138.
15) (a) Mathews, C. J.; Smith, P. J.; Welton, T. Chem. Commun.
000, 1249. (b) Sirieix, J.; Oßberger, M.; Betzemeier, B.;
1
H NMR (200.13 MHz, CDCl ): d = 10.86 (br s, 1 H, NCHN), 8.16
3
(
AA¢BB¢ spin system, dm, 2 Harom, JA,B = 8.8 Hz) and 8.03 (dm, 2
2
Harom, J = 8.8 Hz), 7.84 (dd, 1 H, J = 1.8 Hz, NCH), 7.62 (dd, 1
AB
H, J = 1.8 Hz, NCH), 4.59 (t, 2 H, J = 7.31 Hz, NCH ), 3.58 (s, 9 H,
OCH ), 2.65 (s, 3 H, CH ), 2.14 (m, 2 H, CH CH CH ), 0.72 (m,
H, SiCH2).
2
2
3
2
1
3
3
2
2
2
Knochel, P. Synlett 2000, 1613.
(
16) Xu, L.; Chen, W.; Xiao, J. Organometallics 2000, 19, 1123.
H NMR (200.13 MHz, CD OD): d = 8.31–8.20 (m, 3 H, aromatic
and imidazolium protons), 7.97–7.88 (m, 3 H, aromatic and imida-
zolium protons), 4.37 (t, 2 H, NCH ), 3.59 (s, 9 H, 3 OCH ), 2.68 (s,
(17) (a) Brown, R. A.; Pollet, P.; McKoon, E.; Eckert, C. A.;
Liotta, C. L.; Jessop, P. G. J. Am. Chem. Soc. 2001, 123,
1254. (b) Chauvin, Y.; Mussmann, L.; Olivier, H. Angew.
Chem., Int. Ed. Engl. 1996, 34, 2698.
3
2
3
3
H, CH ), 2.11 (m, 2 H, CH CH CH ), 0.74 (m, 2 H, SiCH ).
3 2 2 2 2
1
3
(18) Zim, D.; De Souza, R. F.; Dupont, J.; Monteiro, A. L.
Tetrahedron Lett. 1998, 39, 7071.
C NMR (50.32 MHz, CDCl ): d = 196.3 (C=O), 138.1 (Carom),
3
1
(
2
37.3 (Carom), 135.6 (NCHN), 130.6 (CHarom), 123.4 (NCH), 122.1
CHarom), 120.5 (NCH), 52.4 (NCH ), 50.8 (OCH ), 26.8 (CH ),
4.1 (CH CH CH ), 5.9 (SiCH ).
2 2 2 2
(
(
19) Kubisa, P. Prog. Polym. Sci. 2004, 29, 3.
20) Sémeril, D.; Olivier-Bourbigou, H.; Bruneau, C.; Dixneuf,
P. H. Chem. Commun. 2002, 146.
2 3 3
+
+
MS (ESI ): m/z = 349 ([M – I] , 100%).
(
21) (a) Schöfer, S. H.; Kaftzik, N.; Wasserscheid, P.; Kragl, U.
Chem. Commun. 2001, 425. (b) Madeira Lau, R.; van
Rantwijk, F.; Seddon, K. R.; Sheldon, R. A. Org. Lett. 2000,
+
HRMS (CI): m/z calcd for C H N O Si ([M – I – H] ): 348.1505;
found: 348.1507.
1
7
24
2
4
2, 4189.
(
22) Reviews on NHCs: (a) Herrmann, W. A.; Köcher, C.
Acknowledgment
Angew. Chem., Int. Ed. Engl. 1997, 36, 2162.
(
b) Weskamp, T.; Böhm, V. P. W.; Herrmann, W. A. J.
We are grateful to the Deutsche Forschungsgemeinschaft for post-
doctoral funding (C.S.J.C) within the framework of the GRK 532
Organomet. Chem. 2000, 600, 12. (c) Jafarpour, L.; Nolan,
S. P. Adv. Organomet. Chem. 2000, 46, 181. (d) Herrmann,
W. A. Angew. Chem. Int. Ed. 2002, 41, 1290.
23) Hillier, A. C.; Grasa, G. A.; Viciu, M. S.; Man Lee, H.;
Yang, C.; Nolan, S. P. J. Organomet. Chem. 2002, 653, 69.
24) Çetinkaya, B.; Özdemir, I.; Bruneau, C.; Dixneuf, P. H. J.
Mol. Catal. A: Chem. 1997, 118, L1.
(European Network for the formation of PhDs ‘Physical methods
for the structural investigation of new materials’ and to Exeter Uni-
versity for PhD funding (C.S.J.C). The LCC is grateful to the Mini-
stère de la Recherche and the CNRS (Paris) for support. We also
thank Mathias Grober and Richard Graf (Saarbrücken) for running
Mass Spectrometry and High-Resolution Mass Spectrometry expe-
riments.
(
(
(
(
(
25) Çetinkaya, B.; Özdemir, I.; Dixneuf, P. H. J. Organomet.
Chem. 1997, 534, 153.
26) Poyatos, M.; Mas-Marzá, E.; Mata, J. A.; Sanaú, M.; Peris,
E. Eur. J. Inorg. Chem. 2003, 1215.
References
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(
(
b) Welton, T. Chem. Rev. 1999, 99, 2071.
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3
(
9, 3772. (d) Gordon, C. M. Appl. Catal., A 2001, 222, 101.
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(
3
Chem. 2002, 182-183, 419. (i) Dupont, J.; de Souza, R. F.;
Suarez, P. A. Z. Chem. Rev. 2002, 102, 3667.
(
2) Peng, J.; Deng, Y. Tetrahedron Lett. 2001, 42, 5917.
Synthesis 2005, No. 4, 622–626 © Thieme Stuttgart · New York