Article
Organometallics, Vol. 29, No. 22, 2010 5969
(m, 1H, H-6), 4.46 (m, 2H, H-5,60), 4.14 (s, 3H, NCH3), 3.52
(s, 3H, OCH3). 13C NMR (300 MHz, CDCl3): δ 166.22, 165.77,
165.52 (CO), 138.94 (NCN), 134.16, 133.62, 133.34, 130.20,
129.92, 129.59, 128.78, 128.69, 128.50, 128.34, 127.94 (Ph),
123.80, 123.25 (CHdCH), 97.22 (C-1), 71.27 (H-2), 69.77 (H-4),
69.67 (H-3), 66.64 (H-5), 56.79 (H-6), 49.58 (OCH3), 37.40
(NCH3). IR (KBr): 3157 (vw), 3036 (vw), 2942 (vw), 2843 (vw),
1728 (s), 1600 (vw), 1582 (vw), 1562 (vw), 1492 (vw), 1451 (w),
1316 (m), 1282 (s), 1262 (s), 1196 (vw), 1174 (w), 1103 (m), 1095
(m), 1070 (w), 1046 (vw), 1025 (vw), 1000 (vw), 972 (vw), 915
(vw), 854 (vw), 803 (vw), 750 (vw), 709 (s), 686 (w), 667 (vw), 617
(vw), 598 (vw), 505 (vw), 475 (vw) cm-1. Anal. Calcd for
C32H33IN2O9: C, 53.64; H, 4.64; N, 3.91. Found: C, 53.60; H,
4.82; N, 3.93. MS (MALDI-TOF): m/z calcd for C32H31N2O8
([M - I]þ) 571.21, found 571.13.
Preparation of [Ag(C1mbgim)2]I (7). A 700.0 mg (1.0 mmol)
amount of 4, 115.0 mg (0.5 mmol) of Ag2O, and 5.0 mL of
dichloromethane were added into a 50 mL flask. The flask was
covered with aluminum foil and stirred for 3 h. Celite was used
to remove the gray precipitate of AgI. Solvent was removed
from the resulting light yellow filtrate, and a 680.0 mg (0.49
1
mmol, 98.3% yield) amount of white solids was obtained. H
NMR (300 MHz, CDCl3): δ 7.95-7.19 (m, 15H, o-Ph), 7.10 (s,
1H, CHdCH), 6.92 (s, 1H, CHdCH), 6.06 (t, J = 9.2 Hz, 1H,
H-3), 5.29 (t, J = 9.9 Hz, 1H, H-4), 5.19 (m, 2H, H-1,2), 4.47 (m,
2H, H-6,60), 4.24 (m, 1H, H-5), 3.79 (s, 3H, NCH3), 3.25 (s, 3H,
OCH3). 13C NMR (300 MHz, CDCl3): δ 184.08 (NCN), 165.81,
165.64, 165.60 (CdO), 133.63, 133.50, 133.16, 129.95, 129.94,
129.64, 129.05, 128.88, 128.62, 128.53, 128.46, 128.27 (Ph),
122.47, 122.23 (CHdCH), 96.78 (C-1), 71.82 (C-2), 70.38 (C-4),
70.19 (C-3), 66.84 (C-5), 56.24 (C-6), 52.09 (OCH3), 39.60
(NCH3). IR (KBr): 3423 (vw), 3165 (vw), 3134 (vw), 3063 (w),
3949 (w), 2905 (w), 2841 (vw), 1821 (vw), 1726 (s), 1600 (s), 1559
(s), 1491 (vw), 1452 (m), 1379 (s), 1334 (vw), 1315 (w), 1276 (s),
1262 (s), 1197 (vw), 1178 (w), 1161 (vw), 1107 (m), 1069 (w), 1026
(m), 976 (vw), 936 (vw), 913 (w), 855 (w), 840 (w), 803 (vw), 746
Preparation of 1-Ethyl-3-(methyl 2,3,4-tri-O-benzoyl-6-deoxy-
r-D-glucopyrano-6-yl)imidazolium Bromide (5, C2mbgimHBr).
A 2.30 g (4.1 mmol) amount of 2, 10.0 mL of THF, and 5.0 mL
(86.5 mmol) of bromoethane were added into a 50 mL flask, and
the mixture was heated to reflux for 2 h. The solution was cooled
to room temperature, and white solids precipitated. The white
solids were collected, washed with diethyl ether, and dried under
a dynamic pump. A 2.78 g amount (100% yield) of white solids
was obtained. 1H NMR (300 MHz, CDCl3): δ 10.21 (s, 1H,
NCHN), 7.98-7.22 (m, 15H, Ph), 7.63 (s, 1H, CHdCH), 7.39
(s, 1H, CHdCH), 7.65 (d, J = 1.7 Hz, 1H, CHdCH), 6.15 (t, J =
9.9 Hz, 1H, H-3), 5.22 (m, 2H, H-1,4), 5.12 (dd, J= 3.6, 10.5 Hz,
1H, H-2), 4.83 (d, J = 10.0 Hz, 1H, H-6), 4.45 (m, 4H, NCH2-,
H-5,60), 3.48 (s, 3H, OCH3), 1.65 (t, J = 7.7 Hz, 3H, NCH2-
CH3). 13C NMR (300 MHz, CDCl3): δ 166.02, 165.64, 165.50
(CdO), 138.01 (NCN), 133.94, 133.56, 133.30, 130.11, 129.83,
129.51, 128.55, 128.44, 128.71, 128.61, 128.55, 128.44, 128.30,
128.03 (Ph), 123.33, 122.27 (CHdCH), 97.03 (C-1), 71.34 (C-4),
71.27 (C-2), 69.82 (C-3), 66.87 (C-5), 56.33 (C-6), 49.40 (OCH3),
45.47 (NCH2), 15.62 (NCH2CH3). IR (KBr): 3149 (vw), 3065 (vw),
2943 (vw), 2844 (vw), 1729 (s), 1601 (vw), 1583 (vw), 1566 (vw),
1451 (vw), 1316 (w), 1282 (s), 1263 (s), 1193 (vw), 1170 (w), 1108
(w), 1094 (w), 1070 (vw), 1042 (vw), 1026 (vw), 973 (vw), 932 (vw),
915 (vw), 854 (vw), 804 (vw), 755 (vw), 708 (m), 686 (vw), 616 (vw),
514 (vw) cm-1. Anal. Calcd for C33H35BrN2O9: C, 57.99; H, 5.16;
N, 4.10. Found: C, 58.12; H, 5.30; N, 4.01. MS (MALDI-TOF):
m/z calcd for C33H33N2O8 ([M - Br]þ) 585.22, found 585.18.
Preparation of 1-Butyl-3-(methyl 2,3,4-tri-O-benzoyl-6-deoxy-
r-D-glucopyrano-6-yl)imidazolium Bromide (6, C4mbgimHBr).
A procedure similar to that described for the preparation of 4
was used. The reaction of 2 (1.11 g, 2.0 mmol) with bromobu-
tane (5.0 mL, 46.5 mmol) afforded 1.30 g (94% yield) of white
solids of 6. 1H NMR (300 MHz, CDCl3): δ 10.30 (s, 1H,
NCHN), 7.98-7.25 (m, 15H, Ph), 7.61 (s, 1H, CHdCH), 7.42
(s, 1H, CHdCH), 6.16 (t, J = 10.6 Hz, 1H, H-3), 5.23 (d, J = 8.6
Hz 1H, H-4), 5.17 (d, J = 3.5 Hz, 1H, H-1), 5.10 (dd, J = 3.3,
10.2 Hz, 1H, H-2), 4.94 (m, 1H, H-6), 4.39 (m, 4H, NCH2,
H-5,60), 3.48 (s, 3H, OCH3), 1.90 (m, 2H, NCH2CH2-), 1.36 (m,
2H, NCH2CH2CH2-), 0.92 (t, 3H, J = 7.1 Hz, NCH2CH2-
CH2CH3). 13C NMR (300 MHz, CDCl3): δ 166.11, 165.72,
165.49 (CO), 138.58 (NCHN), 134.03, 133.59, 133.31, 130.16,
129.88, 129.55, 128.75, 128.62, 128.31, 127.99 (Ph), 123.38,
122.09 (CHdCH), 97.07 (C-1), 71.35 (C-2), 69.79 (C-3,4),
66.76 (C-5), 56.40 (C-6), 50.03 (OCH3), 49.32 (NCH2-), 32.05
(NCH2CH2-), 19.46 (NCH2CH2CH2-), 13.50 (NCH2CH2-
CH2CH3). IR (KBr): 3426 (m), 3133 (vw), 3162 (vw), 3065
(vw), 2959 (m), 2936 (m), 2874 (vw), 2842 (vw), 1728 (s), 1601
(w), 1583 (w), 1562 (vw), 1513 (vw), 1492 (w), 1451 (m), 1371
(vw), 1337 (vw), 1317 (vw), 1280 (s), 1262 (s), 1194 (w), 1172 (m),
1107 (m), 1096 (m), 1070 (w), 1043 (vw), 1026 (w), 972 (vw), 944
(vw), 915 (vw), 855 (vw), 804 (vw), 755 (w), 711 (m), 686 (vw),
(w), 711 (s), 688 (m), 617 (vw), 560 (vw), 529 (vw), 497 (vw) cm-1
.
MS (MALDI-TOF): m/z calcd for C64H60N4O16Ag ([M - I]þ)
1249.95, found 1249.31.
Preparation of [Ag(C2mbgim)2]Br (8). A procedure similar to
that described for the preparation of 7 was used. The reaction of
5 (665.0 mg, 1.0 mmol) with Ag2O (115.0 mg, 0.5 mmol) afforded
1
660.0 mg (0.49 mmol, 97.1% yield) of 8. H NMR (300 MHz,
CDCl3): δ 8.02-7.19 (m, 15H, Ph), 7.18 (s, J = 1.6 Hz, 1H,
CHdCH), 7.04 (s, J = 1.6 Hz, 1H, CHdCH), 6.08 (t, J = 9.8 Hz,
1H, H-3), 5.35 (t, J = 9.7 Hz, 1H, H-4), 5.20 (dd, J = 3.7, 9.8 Hz,
1H, H-2), 5.16 (d, J = 3.7 Hz, 1H, H-1), 4.35 (m, 2H, H-5,6), 4.24
(m, 1H, H-60), 4.10 (q, J = 7.4 Hz, 2H, NCH2-), 3.20 (s, 3H,
OCH3), 1.38(t, J= 7.3 Hz, 3H, NCH2CH3). 13C NMR (300 MHz,
CDCl3): δ 172.49 (NCN), 165.80, 165.64, 165.59 (CdO), 133.83,
133.54, 133.21, 130.02, 129.92, 129.60, 128.98, 128.80, 128.71,
128.47, 128.29 (Ph), 122.59, 120.63 (CHdCH), 96.93 (C-1),
71.75 (C-2), 70.20 (H-4), 70.10 (H-3), 68.99 (H-5), 55.71
(OCH3), 52.23 (H-6), 47.09 (NCH2-), 17.04 (NCH2CH3). IR
(KBr): 3436 (w), 3164 (vw), 3068 (vw), 2939 (vw), 2841 (vw), 1726
(s), 1651 (vw), 1596 (m), 1551 (s), 1492 (vw), 1466 (vw), 1452 (w),
1399 (w), 1384 (w), 1333 (vw), 1315 (w), 1280 (s), 1262 (s), 1199
(vw), 1178 (w), 1095 (m), 1069 (m), 1045 (m), 1026 (m), 977 (w),
913 (vw), 855 (vw), 838 (vw), 803 (vw), 710 (s), 687 (w), 617 (vw),
562 (vw), 512 (vw) cm-1. MS (MALDI-TOF): m/z calcd for
C66H64N4O16Ag ([M - Br]þ) 1279.87, found 1279.34.
Preparation of [Ag(C4mbgim)2]Br (9). A procedure similar to
that described for the preparation of 7 was used. The reaction of
6 (700.0 mg, 1.0 mmol) with Ag2O (115.0 mg, 0.5 mmol)
1
afforded 668.0 mg (0.47 mmol, 94.6% yield) of 9. H NMR
(300 MHz, CDCl3): δ 8.02-7.19 (m, 15H, Ph), 7.13 (s, 1H,
CHdCH), 6.96 (s, 1H, CHdCH), 6.02 (t, J = 9.5 Hz, 1H, H-3),
5.31 (t, J = 10.4 Hz, 1H, H-4), 5.13 (m, 2H, H-1,2), 4.31 (m, 2H,
H-60,6), 4.19 (m, 1H, H-5), 4.01 (t, J = 7.1 Hz, 2H, NCH2), 3.15
(s, 3H, OCH3), 1.69 (m, 2H, NCH2CH2-), 1.23 (m, 2H,
NCH2CH2CH2-), 0.85 (t, J = 7.2 Hz, 3H, NCH2CH2CH2-
CH3). 13C NMR (300 MHz, CDCl3): δ 172.88 (NCN), 164.75,
164.64, 164.52 (CdO), 132.80, 132.48, 132.14, 129.03, 128.88,
128.58, 127.95, 127.76, 127.70, 127.42, 127.23, 126.17 (Ph),
121.54, 119.98 (CHdCH), 95.87 (C-1), 70.72 (C-2), 69.13 (C-
3,4), 68.01 (C-5), 54.59 (C-6), 51.21 (OCH3), 50.84 (NCH2), 32.37
(NCH2CH2-), 18.62 (NCH2CH2CH2-), 12.63 (NCH2CH2-
CH2CH3). IR (KBr): 3163 (vw), 3133 (vw), 3067 (vw), 2957
(w), 2935 (w), 2873 (vw), 1728 (s), 1652 (m), 1597 (m), 1584 (vw),
1552 (m), 1492 (vw), 1452 (m), 1400 (w), 1383 (w), 1315 (w), 1280
(s), 1262 (s), 1196 (vw), 1178 (w), 1094 (m), 1069 (m), 1045 (m),
1026 (m), 976 (vw), 937 (vw), 914 (vw), 855 (vw), 839 (vw), 803
(vw), 708 (s), 686 (m), 617 (vw), 563 (vw), 513 (vw), 473 (vw)
cm-1. MS (MALDI-TOF): m/z calcd for C70H72N4O16Ag
([M - Br]þ) 1332.43, found 1332.40.
641 (vw), 617 (vw), 599 (vw), 564 (vw), 515 (vw), 475 (vw) cm-1
.
Anal. Calcd for C35H37BrN2O8: C, 60.61; H, 5.38; N, 4.04.
Found: C, 60.50; H, 5.27; N, 4.05. MS (MALDI-TOF): m/z
calcd for C35H37N2O8 ([M - Br]þ) 613.25, found 613.21.