4050
M. Debdab et al.
PAPER
1-(2-{[(tert-Butoxycarbonyl)amino]acetoxy}ethyl)-3-methyl-
imidazolium Hexafluorophosphate (7bh)
The procedure used was as described for 7ah, but 4dh (1.2 g, 4.3
mmol) was used instead of 4ch.
Pale brown oil; yield: 1.2 g (76%).
1H NMR (200 MHz, acetone-d6): d = 9.06 (s, 1 H), 8.21 (s, 1 H),
7.81 (s, 1 H), 7.70 (s, 1 H), 7.64 (br s, 1 H), 4.70 (t, J = 4.4 Hz, 2 H),
4.58 (t, J = 4.5 Hz, 2 H), 4.07 (s, 3 H), 4.02 (d, J = 6.1 Hz, 2 H).
White powder; yield: 1.7 g (92%); mp 70 °C.
13C NMR (50 MHz, acetone-d6): d = 170.0, 162.7, 138.0, 124.7,
1H NMR (200 MHz, acetone-d6): d = 9.13 (s, 1 H), 7.85 (s, 1 H),
7.76 (s, 1 H), 6.46 (br s, 1 H), 4.70 (t, J = 4.7 Hz, 2 H), 4.61 (t,
J = 4.7 Hz, 2 H), 4.11 (s, 3 H), 3.86 (d, J = 6.2 Hz, 2 H), 1.41 (s, 9
H).
13C NMR (50 MHz, acetone-d6): d = 170.8, 157.0, 138.0, 124.7,
123.8, 79.5, 63.2, 49.5, 42.7, 36.7, 28.5.
123.7, 63.5, 49.4, 40.3, 36.6.
HRMS-FAB: m/z calcd for C9H14N3O3: 212.1035; found: 212.1036.
1-{2-[(Formylamino)acetoxy]ethyl}-2,3-dimethylimidazolium
Tetrafluoroborate (8at)
The procedure used was as described for 7ah, but 4ct (0.98 g, 4.3
mmol) was used instead of 4ch, 6 (0.46 g, 4.5 mmol) was used in-
stead of 5, and washing was with EtOAc (3 × 50 mL).
HRMS-FAB: m/z calcd for C26H44N6O8F6P [2C+, PF6 ]+:
713.28625; found: 713.2862.
–
White powder; yield: 1.1 g (80%); mp 54 °C.
1-(2-{[(tert-Butoxycarbonyl)amino]acetoxy}ethyl)-2,3-dimeth-
ylimidazolium Tetrafluoroborate (7at)
The procedure used was as described for 7ah, but 4ct (0.98 g, 4.3
1H NMR (200 MHz, DMSO-d6): d = 8.44 (br s, 1 H), 8.08 (s, 1 H),
7.64 (s, 1 H) 7.63 (s, 1 H), 4.41 (s, 4 H), 3.86 (d, J = 6.0 Hz, 2 H),
3.75 (s, 3 H), 2.63 (s, 3 H).
13C NMR (50 MHz, DMSO-d6): d = 169.3, 161.9, 145.1, 122.5,
121.3, 62.8, 46.6, 39.4, 34.8, 9.3.
mmol) was used instead of 4ch.
White powder; yield: 1.5 g (90%); mp 128 °C.
1H NMR (200 MHz, acetone-d6): d = 7.68 (d, J = 2.0 Hz, 1 H), 7.63
(d, J = 1.9 Hz, 1 H), 6.36 (br s, 1 H), 4.63 (t, J = 4.5 Hz, 2 H), 4.55
(t, J = 4.5 Hz, 2 H), 3.95 (s, 3 H), 3.81 (d, J = 6.2 Hz, 2 H), 2.82 (s,
3 H), 1.41 (s, 9 H).
13C NMR (50 MHz, acetone-d6): d = 170.8, 156.9, 146.5, 123.5,
122.2, 79.4, 63.5, 47.9, 42.7, 35.5, 28.5, 9.8.
HRMS-FAB: m/z calcd for C10H16N3O3: 226.1192; found:
226.1188.
1-{2-[(Formylamino)acetoxy]ethyl}-3-methylimidazolium
Tetrafluoroborate (8bt)
The procedure used is as described for 7ah, but 4dt (0.92 g, 4.3
mmol) was used instead of 4ch, 6 (0.46 g, 4.5 mmol) was used in-
stead of 5, and washing was with EtOAc (3 × 50 mL).
HRMS-FAB: m/z calcd for C14H24N3O4: 298.17668; found:
298.1771.
Pale brown oil; yield: 1.2 g (96%).
1-(2-{[(tert-Butoxycarbonyl)amino]acetoxy}ethyl)-3-methyl-
imidazolium Tetrafluoroborate (7bt)
The procedure used was as described for 7ah, but 4dt (0.92 g, 4.3
1H NMR (200 MHz, acetone-d6): d = 9.04 (s, 1 H), 8.20 (s, 1 H),
7.81 (s, 1 H), 7.70 (s, 1 H), 7.61 (br s, 1 H), 4.65 (t, J = 4.6 Hz, 2 H),
4.55 (t, J = 4.4 Hz, 2 H), 4.05 (s, 3 H), 4.01 (d, J = 6.1 Hz, 2 H).
13C NMR (50 MHz, acetone-d6): d = 170.0, 162.7, 140.1, 124.7,
123.7, 63.7, 49.3, 40.3, 36.6.
mmol) was used instead of 4ch.
White powder; yield: 1.5 g (92%); mp 95 °C.
1H NMR (200 MHz, acetone-d6): d = 9.10 (s, 1 H), 7.83 (s, 1 H),
7.74 (s, 1 H), 6.41 (br s, 1 H), 4.67 (t, J = 4.7 Hz, 2 H), 4.59 (t,
J = 4.7 Hz, 2 H), 4.08 (s, 3 H), 3.85 (d, J = 6.2 Hz, 2 H), 1.40 (s, 9
H).
13C NMR (50 MHz, acetone-d6): d = 170.9, 156.9, 138.2, 124.7,
123.8, 79.4, 63.3, 49.5, 43.8, 36.6, 28.5.
HRMS-FAB: m/z calcd for C9H14N3O3: 212.10352; found:
212.1040.
1-[2-(Aminoacetoxy)ethyl]-2,3-dimethylimidazolium Hexafluo-
rophosphate (9ah)
A soln of 7ah (1.1 g, 2.5 mmol) in MeCN (5 mL) was successively
treated with MeOH (0.20 mL, 5.0 mmol) and AcCl (0.36 mL, 5.0
mmol). After 24 h at r.t., the solvent was removed under reduced
pressure. The residue was washed with EtOAc (2 × 10 mL) and
dried under reduced pressure for 10 h.
HRMS-FAB: m/z calcd for C13H22N3O4: 284.16103; found:
284.1613.
1-{2-[(Formylamino)acetoxy]ethyl}-2,3-dimethylimidazolium
Hexafluorophosphate (8ah)
Beige powder; yield: 0.67 g (78%); mp 130 °C.
The procedure used was as described for 7ah, but 6 (0.46 g, 4.5
mmol) was used instead of 5, and washing was with EtOAc (3 × 50
mL).
1H NMR (200 MHz, DMSO-d6): d = 8.54 (br s, 2 H), 7.73 (d,
J = 1.9 Hz, 1 H), 7.66 (d, J = 1.9 Hz, 1 H), 4.46 (s, 4 H), 3.79 (s, 2
H), 3.77 (s, 3 H), 2.61 (s, 3 H).
Beige powder; yield: 1.2 g (74%); mp 116 °C.
13C NMR (50 MHz, DMSO-d6): d = 167.2, 145.2, 122.6, 121.4,
1H NMR (200 MHz, DMSO-d6): d = 8.45 (br s, 1 H), 8.08 (s, 1 H),
7.64 (s, 1 H) 7.63 (s, 1 H), 4.40 (s, 4 H), 3.86 (d, J = 6.2 Hz, 2 H),
3.75 (s, 3 H), 2.60 (s, 3 H).
13C NMR (50 MHz, DMSO-d6): d = 169.3, 161.9, 145.2, 122.5,
121.3, 62.8, 46.5, 39.4, 34.8, 9.3.
63.7, 46.5, 39.8, 34.9, 9.6.
HRMS-FAB: m/z calcd for C9H16N3O2: 198.12425; found:
198.1245.
1-[2-(Aminoacetoxy)ethyl]-3-methylimidazolium Hexafluoro-
phosphate (9bh)
The procedure used was as described for 9ah, but 7bh (1.1 g, 2.5
mmol) was used instead of 7ah.
HRMS-FAB: m/z calcd for C10H16N3O3: 226.11917; found:
226.1188.
1-{2-[(Formylamino)acetoxy]ethyl}-3-methylimidazolium
Hexafluorophosphate (8bh)
The procedure used was as described for 7ah, but 4dh (1.2 g, 4.3
mmol) was used instead of 4ch, 6 (0.46 g, 4.5 mmol) was used in-
stead of 5, and washing was with EtOAc (3 × 50 mL).
Beige powder; yield: 0.51 g (62%); mp 153 °C.
1H NMR (200 MHz, DMSO-d6): d = 9.24 (s, 1 H), 8.25 (br s, 2 H),
7.81 (s, 1 H), 7.73 (s, 1 H), 4.49 (s, 4 H), 3.87 (s, 3 H), 3.80 (s, 2 H).
13C NMR (50 MHz, acetone-d6): d = 167.0, 137.3, 123.5, 122.6,
63.5, 47.8, 39.6, 35.8.
Synthesis 2006, No. 23, 4046–4052 © Thieme Stuttgart · New York