P. J. Dyson et al.
FULL PAPER
1
Data for 6: Yield: 95%; m.p. 1058C; 1H NMR: d=8.77 (s, 1H), 7.45 (s,
2H), 4.17 (t, 3J(H,H)=7.1 Hz, 2H), 2.38 (t, 3J(H,H)=7.1 Hz, 2H),
2.08 ppm (m, 2H); 13C NMR: d=179.7, 139.0, 126.6, 125.2, 51.5, 38.5,
33.2, 27.7 ppm; IR: n˜ =3404, 3107, 2956, 2762, 2640, 2563, 2509, 2453,
Data for 16a: Yield: >99%; colorless liquid; m.p. À588C; H NMR: d=
8.63 (s, 1H), 7.42(s, 1H), 7.37 (s, 1H), 4.19 (t, 3J(H,H)=7.1 Hz, 2H),
3.82(s, 3H), 2.38 (t, 3J(H,H)=7.1 Hz, 2H), 2.11 ppm (m, 2H); 13C NMR:
d=179.7, 139.0, 126.7, 125.2, 51.4, 38.6, 33.1, 27.7 ppm; IR: n˜ =3161,
3120, 2947, 1734, 1576, 1421, 1168, 1055 cmÀ1; ESI-MS: 169 [cation]+; ele-
mental analysis calcd (%) for C8H13BF4N2O2: C 37.53, H 5.12, N 10.94;
found: C 37.61, H 5.17, N 10.99.
1702, 1558, 1463, 1410, 1268, 1193, 1157, 1063 cmÀ1
; ESI-MS: 169
[MÀCl]+; elemental analysis calcd (%) for C8H13ClN2O2: C 46.95, H
6.40, N 13.69; found: C 47.01, H 6.42, N 13.65.
Data for 16b: Yield: 99%; colorless liquid; m.p. À618C; 1H NMR: d=
Data for 7: Yield: 97%; m.p. 2608C (decomp); 1H NMR: d=8.84 (s,
1H), 7.47 (s, 2H), 5.06 ppm (s, 4H); 13C NMR: d=172.7, 141.1, 126.4,
52.1 ppm; IR: n˜ =3141, 3112, 2898, 2583, 2493, 1730, 1565, 1404,
1163 cmÀ1; ESI-MS: 185 [MÀCl]+; elemental analysis calcd (%) for
C7H9ClN2O4: C 38.11, H 4.11, N 12.70; found: C 38.23, H 4.14, N 12.65.
Data for 8: Yield: 96%; colorless solid; m.p. 1728C; 1H NMR: d=8.77
(s, 1H), 7.45 (s, 2H), 4.17 (t, 3J(H,H)=7.1 Hz, 4H), 2.38 (t, 3J(H,H)=
7.1 Hz, 4H), 2.08 ppm (m, 4H); 13C NMR: d=179.7, 138.5, 125.5, 51.6,
33.2, 27.6 ppm; IR: n˜ =3421, 3104, 2920, 2581, 2512, 1710, 1558, 1461,
1433, 1406, 1374, 1263, 1181, 1153, 1063 cmÀ1; ESI-MS: 241 [MÀCl]+; ele-
mental analysis calcd (%) for C11H17ClN2O4: C 47.75, H 6.19, N 10.12;
found C 47.81, H 6.22, N 10.05.
8.63 (s, 1H), 7.40 (s, 1H), 7.35 (s, 1H), 4.16 (t, 3J(H,H)=7.1 Hz, 2H),
3.80 (s, 3H), 2.37 (t, J(H,H)=7.1 Hz, 2H), 2.07 ppm (m, 2H); 13C NMR:
3
d=179.7, 139.0 126.6, 125.2, 120.9–124.1 (m, CF3), 51.4, 38.6, 33.10,
27.6 ppm; IR: n˜ =3484, 3156, 3117, 2962, 1722, 1575, 1416, 1249, 1224,
1157, 1027 cmÀ1; ESI-MS: 169 [cation]+; elemental analysis calcd (%) for
C9H13F3N2O5S: C 33.96, H 4.12, N 8.80; found: C 34.06, H 4.15, N 8.83.
Data for 17a: Yield: >97%; colorless solid; m.p. 2108C (decomp);
1H NMR: d=8.83 (s, 1H), 7.55 (s, 2H), 5.15 ppm (s, 4H); 13C NMR: d=
172.7, 141.2, 126.5, 53.0 ppm; IR: n˜ =3164, 3132, 2974, 1736, 1571, 1403,
1176, 1005 cmÀ1; ESI-MS: 185 [cation]+; elemental analysis calcd (%) for
C7H9BF4N2O4: C 30.91, H 3.34, N 10.30; found: C 31.03, H 3.39, N 10.25.
Data for 17b: Yield: >96%; colorless solid; m.p. 1408C (decomp);
1H NMR: d=8.71 (s, 1H), 7.33 (s, 2H), 4.92ppm (s, 4H); 13C NMR: d=
172.2, 141.1, 126.3, 120.9–124.1 (m, CF3), 52.7 ppm; IR: n˜ =3165, 2990,
1743, 1663, 1423, 1175 cmÀ1; ESI-MS: 185 [cation]+; elemental analysis
calcd (%) for C8H9F3N2O7S: C 28.75, H 2.71, N 8.83; found: C 28.83, H
2.79, N 8.85.
Synthesis of 9–12: In a typical procedure, a mixture of 5 (0.010 mol) and
triethylamine (0.011 mol) in dichloromethane (20 mL) was stirred at RT
for 24 h under an inert atmosphere of dry nitrogen. The solid was filtered
and washed with dichloromethane (315 mL) to give the product.
Data for 9: Yield: 97%; colorless solid; m.p. 2708C (decomp); 1H NMR:
d=8.61 (s, 1H), 7.34 (s, 1H), 7.32(s, 1H), 4.71 (s, 2H), 3.82ppm (s, 3H);
13C NMR: d=175.3, 139.8, 126.3, 126.1, 54.8, 38.6 ppm; IR: n˜ =3186,
3148, 3096, 3061, 2994, 2953, 2866, 2242, 1692, 1624, 1567, 1376, 1310,
1294, 1188, 1119, 1034 cmÀ1; ESI-MS: 141 [M+H]+; elemental analysis
calcd (%) for C6H8N2O2: C 51.42, H 5.75, N 19.99; found: C 51.51, H
5.81, N 20.01.
1
Data for 18a: Yield: >99%; colorless liquid; m.p. À578C; H NMR: d=
8.74 (s, 1H), 7.43 (s, 2H), 4.16 (t, 3J(H,H)=7.1 Hz, 4H), 2.34 (t,
3J(H,H)=7.1 Hz, 4H), 2.07 ppm (m, 4H); 13C NMR: d=179.8, 138.5,
125.5, 51.6, 33.2, 27.6 ppm; IR: n˜ =3153, 2943, 1712, 1566, 1417, 1161,
1061 cmÀ1; ESI-MS: 241 [cation]+; elemental analysis calcd (%) for
C11H17BF4N2O4 (%): C 40.27, H 5.22, N 8.54; found: C 40.41, H 5.28, N
8.55.
Data for 10: Yield: 98%; colorless solid; m.p. 958C; 1H NMR: d=8.64
(s, 1H), 7.40 (s, 1H), 7.34 (s, 1H), 4.14 (t, 3J(H,H)=7.1 Hz, 2H), 3.79 (s,
3H), 2.22 (t, 3J(H,H)=7.1 Hz, 2H), 2.06 ppm (m, 2H); 13C NMR: d=
182.0, 139.0, 126.6, 125.2, 51.7, 38.6, 35.0, 28.4 ppm; IR: n˜ =3367, 3089,
1
Data for 18b: Yield: >99%; colorless liquid; m.p. À608C; H NMR: d=
8.76 (s, 1H), 7.44 (s, 2H), 4.16 (t, 3J(H,H)=7.1 Hz, 4H), 2.36 (t,
3J(H,H)=7.1 Hz, 4H), 2.07 ppm (m, 4H); 13C NMR: d=179.8, 138.5,
125.5, 120.9–124.1 (m, CF3), 51.6, 33.1, 27.55 ppm; IR: n˜ =3147, 1710,
1565, 1412, 1241, 1223, 1155, 1027 cmÀ1; ESI-MS: 241 [cation]+; elemen-
tal analysis calcd (%) for C12H17F3N2O7S: C 36.92, H 4.39, N 7.18; found:
C 37.01, H 4.43, N 7.20.
3066, 2962, 2849, 1659, 1564, 1471, 1397, 1176 cmÀ1
; ESI-MS: 337
[MÀCl]+; elemental analysis calcd (%) for C16H25ClN4O4: C 51.54, H
6.76, N 15.03; found: C 51.61, H 6.82, N 15.25.
Data for 11: Yield: 97%; colorless solid; m.p. 2908C (decomp);
1H NMR: d=8.84 (s, 1H), 7.50 (s, 2H), 4.98 ppm (s, 4H); 13C NMR: d=
174.0, 140.7, 126.4, 54.2 ppm; IR: n˜ =3145, 3111, 2960, 1666, 1613, 1562,
1334, 1163; ESI-MS: 185 [M+H]+; elemental analysis calcd (%) for
C7H8N2O4: C 45.66, H 4.38, N 15.21; found: C 45.73, H 4.40, N 15.18.
Data for 12: Yield: 99%; colorless solid; m.p. 1768C; 1H NMR: d=8.72
(s, 1H), 7.40 (s, 2H), 4.12 (t, 3J(H,H)=7.1 Hz, 4H), 2.21 (t, 3J(H,H)=
7.1 Hz, 4H), 2.01 ppm (m, 4H); 13C NMR: d=181.9, 138.4, 125.4, 51.8,
34.9, 28.3 ppm; IR: n˜ =3386, 3100, 2953, 1708, 1558, 1409, 1176,
Acknowledgements
We thank the EPFL and Swiss National Science Foundation for financial
support.
1020 cmÀ1 ESI-MS: 241 [M+H]+; elemental analysis calcd (%) for
;
C11H16N2O4: C 54.99, H 6.71, N 11.66; found: C 55.06, H 6.76, N 11.65.
[1] For leading reviews see: a) K. R. Seddon, J. Chem. Technol. Bio-
technol. 1997, 68, 351; b) T. Welton, Chem. Rev. 1999, 99, 2 071; c) P.
Wasserscheid, W. Keim, Angew. Chem. 2000, 112, 3926; Angew.
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Today 2002, 74, 157; g) J. Dupont, R. F. de Souza, P. A. Z. Suarez,
Chem. Rev. 2002, 102, 3667.
Protonation of zwitterions: On a 0.01 mol scale, addition of HBF4/
HSO3CF3 to 9 (1:1 molar ratio) at RT under an inert atmosphere of dry
nitrogen gave 15a/15b; similarly 17a/17b and 18a/18b were obtained by
adding HBF4/HSO3CF3 to the zwitterions 11 and 12. In all cases, the solid
salts became oils after addition of HBF4/HSO3CF3; 15a/15b and 17a/17b
changed back to solid again after two days at RT. The acids 16a/16b
were obtained by anion exchange from 6 and NaBF4/AgSO3CF3 accord-
ing to the literature method.[27, 28]
[2] Imidazolium salts and variations leading to functionalized ionic liq-
uids: J. H. Davis, Jr., in Ionic Liquids in Synthesis (Eds.: P. Was-
serscheid, T. Welton), Wiley-VCH, Weinheim, 2003, Chapter 2,
p. 33.
[3] W. A. Herrmann, C. Kꢁcher, L. J. Goossen, G. R. J. Artus, Chem.
Eur. J. 1996, 2, 1627.
[4] K.-M. Lee, Y.-T.-Y. Lee, J. B. Lin, J. Mater. Chem. 2003, 13, 1079.
[5] L. C. Branco, J. N. Rosa, J. J. Moura Ramos, C. A. M. Alfons, Chem.
Eur. J. 2002, 8, 3671.
[6] a) D. J. Brauer, K. Kottsieper, C. Liek, O. Stelzer, H. Waffenschmidt,
P. Wasserscheid, J. Organomet. Chem. 2001, 630, 177; b) R. P. J.
Bronger, M. S. Silva, P. C. J. Kamer, P. W. N. M. van Leeuwen,
Chem. Commun. 2002, 3044.
1
Data for 15a: Yield: 98%; colorless solid; m.p. 1388C; H NMR: d=8.66
(s, 1H), 7.37 (s, 1H), 7.36 (s, 1H), 5.00 (s, 2H), 3.81 ppm (s, 3H);
13C NMR: d=173.2, 140.2, 126.4, 126.3, 53.0, 38.7 ppm; IR: n˜ =3132,
3106, 2970, 2901, 1723, 1628, 1570, 1420, 1365, 1242, 1163, 1150 cmÀ1
;
ESI-MS: 141 [cation]+; elemental analysis calcd (%) for C6H9BF4N2O2:
C 31.61, H 3.98, N 12.29; found: C 31.71, H 4.01, N 12.32.
Data for 15b: Yield: 99%; colorless solid; m.p. 688C; 1H NMR: d=8.65
(s, 1H), 7.38 (s, 1H), 7.37 (s, 1H), 5.00 (s, 2H), 3.82ppm (s, 3H);
13C NMR: d=173.0, 140.2, 126.3, 120.9–124.1 (m, CF3), 52.8, 38.7 ppm;
IR: n˜ =3306, 3171, 2987, 2901, 1751, 1579, 1403, 1173, 1034 cmÀ1; ESI-
MS: 141 [cation]+; elemental analysis calcd (%) for C7H9F3N2O5S: C
28.97, H 3.13, N 9.65; found: C 29.01, H 3.16, N 9.62.
4892
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Chem. Eur. J. 2004, 10, 4886 – 4893