S2
Metal Chloride Hydrates as Lewis Acid Catalysts in Multicomponent Synthesis
J. Braz. Chem. Soc.
-
1
nmax/cm 1541, 1523, 1348, 777, 699; GS-MS (IE, 70 eV)
(dd, 1H, J 2.9 and 1.5 Hz), 7.68 (dd, 1H, J 4.8 and
1.1 Hz), 7.62 (dd, 1H, J 5.5 and 2.9 Hz), 6.80-7.50 (m, 8H),
+
m/z (%) 341 (M , 100.0), 311 (47.8), 295 (21.1), 165 (42.6),
9 (22.0), 77 (13.2), 63 (3.3), 43 (2.2).
13
8
3.75 (s, 3H), 3.79 (s, 3H); C NMR (100 MHz, DMSO-d )
6
d 148.3, 143.4, 137.7, 134.7, 131.8, 131.2, 130.6, 130.4,
2
-(2-Nitrophenyl)-4,5-diphenyl-1H-imidazole (8h):
129.2, 128.7, 128.4, 128.3, 128.1, 127.1, 126.8, 122.6,
119.4; IR (Nujol) nmax/cm 3391, 1655, 1600, 1573, 1508,
o
5
1
-1
solid; mp 224-225 C; H NMR (300 MHz, DMSO-d6)
d 12.98 (sl, 1H, NH), 8.00 (d, 1H, J 7.6 Hz), 7.93 (d, 1H,
J 8.2 Hz), 7.79 (t, 1H, J 7.6 Hz), 7.64 (t, 1H, J 7.6 Hz),
1259, 1163, 842, 832; GC-MS (IE, 70 eV) m/z (%) 362
+
(M , 100.0), 347 (28.4), 275 (4.1), 181 (5.7).
7
.35-7.60 (m, 8H), 7.31 (t, 1H, J 7.0 Hz), 7.23 (t, 1H,
1
3
J 7.0 Hz); C NMR (75 MHz, DMSO-d ) d 148.2, 140.9,
4,5-Bis(4-fluorophenyl)-2-phenyl-1H-imidazole (8m):
6
o
8 1
1
1
37.4, 134.6, 132.0, 130.5, 129.7, 129.4, 128.7, 128.6,
28.2, 128.1, 127.9, 126.9, 126.6, 123.9,123.3; IR (Nujol)
solid; mp 255-257 C; H NMR (400 MHz, DMSO-d6)
d 12.67 (br s, 1H, NH), 8.07 (dd, 2H, J 8.4 and 1.1 Hz),
7.50-7.60 (m, 4H), 7.48 (t, 2H, J 7.5 Hz), 7.38 (t, 1H,
J 7.3 Hz), 7.29 (t, 2H, J 8.8 Hz), 7.14 (t, 2H, J 8.8 Hz);
-1
nmax/cm 1601, 1524, 1502, 1364, 724, 694; GC-MS (IE,
+
7
1
7
0 eV) m/z (%) 341 (M , 59.7), 311 (100.0), 207 (15.0),
65 (40.1), 147 (14.2), 135 (21.3), 104 (79.0), 89 (46.3),
7 (25.6), 63 (13.8), 51 (11.4).
13
1
C NMR (100 MHz, DMSO-d ) d 161.5 (d, J 245.7 Hz),
160.9 (d, J 243.4 Hz), 145.4, 136.1, 131.4 (d, J 3.1 Hz),
30.4 (d, J 8.4 Hz), 130.1, 128.7 (d, J 7.6 Hz), 128.5,
CF CF
128.1, 128.0, 127.2 (d, J 3.1 Hz), 126.9, 125.0, 115.5
CF
(d, J 21.4 Hz), 114.9 (d, J 21.4 Hz); IR (Nujol)
CF CF
nmax/cm 1606, 1590, 1537, 1514, 1595, 1226, 1156, 835;
GC-MS (IE, 70 eV) m/z (%) 332 (M , 100.0), 201 (44.1),
89 (9.6), 77 (3.0), 63 (4.6), 51 (2.2), 39 (2.0).
6
CF
4
1
CF
CF
3
3
1
4
2
-(Furan-2-yl)-4,5-diphenyl-1H-imidazole (8i): solid;
o
1
2
2
mp 229-230 C; H NMR (300 MHz, DMSO-d ) d 12.85
6
6
-1
(
br s, 1H, NH), 7.81 (d, 1H, J 1.6 Hz), 7.36-7.75 (m, 10H),
+
6
.98 (d, 1H, J 3.4 Hz), 6.65 (dd, 1H, J 3.4 and 1.8 Hz);
1
3
C NMR (75 MHz, DMSO-d ) d 148.3, 145.7,143.1,
6
1
38.6, 138.0, 129.6, 128.5, 128.3, 127.7, 111.9, 107,5; IR
-1
(Nujol) nmax/cm 1602, 1500, 764, 696; GC-MS (IE, 70 eV)
4-[4,5-Bis(4-fluorophenyl)-1H-imidazol-2-yl)]
+
o
1
m/z (%) 286 (M , 100.0), 257 (9.4), 165 (22.0), 143 (6.1),
benzonitrile (8n): solid; mp 272-274 C; H NMR
1
28 (8.6), 89 (3.7), 77 (9.0), 63 (2.8), 51 (12.1).
(400 MHz, DMSO-d ) d 12.98 (br s, 1H, NH), 8.23 (d, 2H,
6
J 8.3 Hz), 7.93 (d, 2H, J 8.3 Hz), 7.55 (d, 2H, J 8.8 Hz),
1
3
4
,5-Diphenyl-2-(thiophen-2-yl)-1H-imidazole (8j):
7.54 (d, 2H, J 8.8 Hz), 7.00-7.40 (m, 4H); C NMR
o
1 1
solid; mp 255-256 C; H NMR (300 MHz, DMSO-d6)
d 12.79 (br s, 1H, NH), 7.69 (d, 1H, J 3.5 Hz), 7.25-7.51
m, 11H), 7.15 (dd, 1H, J 4.7 and 3.5 Hz); C NMR (75
MHz, DMSO-d ) d 124.1, 126.2, 126.5, 127.0, 127.8,
28.1, 128.6, 130.8, 133.9, 134.7, 136.6, 141.5; IR (Nujol)
nmax/cm 1594, 1493, 765, 695; GC-MS (IE, 70 eV)
m/z (%) 304 (6.77), 302 (M , 100.0), 165 (39.7), 151 (8.7),
5 (7.4), 89 (5.8), 77 (6.3), 69 (6.5), 63 (4.1), 51 (4.3).
(100 MHz, DMSO-d ) d 143.5, 134.0, 132.6, 128.7, 128.0,
125.4, 125.1, 118.6, 110.0; IR (Nujol) nmax/cm 2229, 1608,
1516, 1497, 1223, 1161, 847, 837; GC-MS (IE, 70 eV)
m/z(%)357(M , 100.0), 201(42.5), 107(13.3);HRMS(ESI,
6
-1
13
(
+
6
+
1
w/H ) calcd. 358.11522, found 358.11503.
-
1
+
4,5-Bis(4-fluorophenyl)-2-(furan-2-yl)-1H-imidazole
(8o): solid; mp 223-225 C; H NMR (400 MHz, DMSO-d )
o
1
9
6
d 12.81 (br s, 1H, NH), 7.79 (dd, 1H, J 1.8 and 0.7 Hz),
7.42-7.58 (m, 4H), 7.27 (t, 2H, J 9.0 Hz), 7.14 (t, 2H,
J 9.0 Hz), 6.96 (dd, 1H, J 3.3 and 0.7 Hz), 6.64 (dd, 1H,
4
,5-Diphenyl-2-(thiophen-3-yl)-1H-imidazole (8k):
o
1
solid; mp 257-259 C; H NMR (300 MHz, DMSO-d ) d
2.63 (br s, 1H, NH), 8.04 (dd, 1H, J 2.9 and 1.3), 7.71
dd, 1H, J 5.0 and 1.2 Hz), 7.65 (dd, 1H, J 5.0 and 2.9
Hz), 7.31-7.53 (m, 10H); C NMR (75 MHz, DMSO-d )
d 142.7, 132.5, 128.4, 127.7,127.0, 125.9, 121.8; IR
Nujol) nmax/cm 1593, 1493, 765, 697; GC-MS (IE, 70 eV)
m/z (%) 304 (6.64), 302 (M , 100.0), 165 (46.6), 151 (8.9),
9 (10.3), 77 (6.5), 63 (5.2), 51 (4.2); HRMS (ESI, w/H )
6
1
3
1
(
J 3.3 and 1.8 Hz); C NMR (100 MHz, DMSO-d ) d
6
1
1
161.6 (d, J 244.1 Hz), 161.0 (d, J 241.9 Hz), 145.5,
CF CF
13
3
143.0, 138.4, 136.8, 136.0, 130.4 (d, J 8.4 Hz), 128.9 (d,
JCF 8.4 Hz), 127.0 (d, J 3.1 Hz), 126.3, 115.6 (d,
JCF 22.1 Hz), 115.0 (d, J 21.4 Hz), 111.7, 107.4;
IR (Nujol) nmax/cm 1606, 1529, 1514, 1496, 1228, 1158,
836, 738; GC-MS (IE, 70 eV) m/z (%) 322 (M , 100.0),
293 (11.8), 201 (18.8), 107 (3.9); HRMS (ESI, w/H ) calcd.
6
CF
3
4
CF
-1
2
2
(
CF
+
-1
+
+
8
+
calcd. 303.09505, found 303.09518.
3
23.09905, found 323.09912.
4
,5-Bis(4-methoxyphenyl)-2-(thiophen-3-yl)-
o
7 1
1
H-imidazole (8l): solid; mp 199-201 C; H NMR
4,5-Bis(4-fluorophenyl)- 2-(thiophen-3-yl)-
1H-imidazole (8p): solid; mp 255-256 C; H NMR
o
1
(
400 MHz, DMSO-d ) d 12.35 (br s, 1H, NH), 7.97
6