Organometallics
Article
1H), 7.17 (s, Ar−H, 1H), 7.13−7.05 (m, Ar−H, 2H), 3.71 (s, CH3,
3H). 13C NMR (101 MHz, CDCl3) δ 139.1, 130.4, 129.0, 127.6, 126.7,
126.2, 126.0, 32.6.
1,2-Dimethyl-5-(thiophen-2-yl)-1H-imidazole (4l).36 1H NMR
(400 MHz, CDCl3) δ 7.31 (dd, J = 5.2, 1.2 Hz, Ar−H, 1H), 7.07
(dd, J = 5.2, 3.6 Hz, Ar−H, 1H), 7.02−6.99 (m, Ar−H, 2H), 3.54 (s,
CH3, 3H), 2.41 (s, CH3, 3H). 13C NMR (101 MHz, CDCl3) δ 146.2,
131.3, 127.4, 127.1, 126.2, 125.7, 124.6, 31.1, 13.6.
1-Methyl-5-(5-methylthiophen-2-yl)-1H-imidazole (3m). 1H
NMR (400 MHz, CDCl3) δ 7.52 (s, Ar−H, 1H), 7.15 (s, Ar−H,
1H), 6.86 (d, J = 3.5 Hz, Ar−H, 1H), 6.77−6.72 (m, Ar−H, 1H), 3.69
(s, CH3, 3H), 2.51 (s, CH3, 3H). 13C NMR (101 MHz, CDCl3) δ
140.6, 138.8, 128.5, 127.9, 126.9, 126.1, 125.6, 32.4, 15.1. ESI-MS m/z:
178.2, [3m]+ (C9H10N2S+, calcd 178.1).
1,2-Dimethyl-5-(5-methylthiophen-2-yl)-1H-imidazole (4m). 1H
NMR (400 MHz, CDCl3) δ 6.96 (s, Ar−H, 1H), 6.81 (d, J = 3.5 Hz,
Ar−H, 1H), 6.75−6.72 (m, Ar−H, 1H), 3.54 (s, N−CH3, 3H), 2.50
(s, CH3, 3H), 2.42 (s, CH3, 3H). 13C NMR (101 MHz, CDCl3) δ
146.0, 140.6, 128.9, 126.8, 126.7, 126.4, 125.6, 31.1, 15.2, 13.6. ESI-MS
m/z: 192.1, [4m]+ (C10H12N2S+, calcd 192.1).
3-(1-Methyl-1H-imidazol-5-yl)pyridine (3n).42 1H NMR (400
MHz, CDCl3) δ 8.68 (dd, J = 2.2, 0.7 Hz, Ar−H, 1H), 8.62 (dd, J
= 4.9, 1.6 Hz, Ar−H, 1H), 7.75−7.69 (m, Ar−H, 1H), 7.58 (s, Ar−H,
1H), 7.41−7.35 (m, Ar−H, 1H), 7.18 (s, Ar−H, 1H), 3.69 (s, CH3,
3H). 13C NMR (101 MHz, CDCl3) δ 148.7, 139.7, 135.3, 129.7, 128.8,
125.7, 123.4, 123.3, 32.4.
3-(1,2-Dimethyl-1H-imidazol-5-yl)pyridine (4n).5f 1H NMR (400
MHz, CDCl3) δ 8.63 (dd, J = 2.2, 0.8 Hz, Ar−H, 1H), 8.59 (dd, J =
4.9, 1.6 Hz, Ar−H, 1H), 7.69−7.64 (m, Ar−H, 1H), 7.39−7.33 (m,
Ar−H, 1H), 7.01 (s, Ar−H, 1H), 3.53 (s, CH3, 3H), 2.46 (s, CH3,
3H). 13C NMR (101 MHz, CDCl3) δ 149.0, 148.7, 146.9, 135.6, 129.9,
126.7, 126.5, 123.4, 31.3, 13.5.
2-Methyl-5-(1-methyl-1H-imidazol-5-yl)pyridine (3o). 1H NMR
(400 MHz, CDCl3) δ 8.49 (d, J = 1.5 Hz, Ar−H, 1H), 7.62−7.46 (m,
Ar−H, 2H), 7.19 (d, J = 8.0 Hz, Ar−H, 1H), 7.07 (s, Ar−H, 1H), 3.62
(s, CH3, 3H), 2.55 (s, CH3, 3H). 13C NMR (101 MHz, CDCl3) δ
157.9, 148.2, 139.5, 136.0, 130.0, 128.5, 123.1, 122.8, 32.4, 24.1. ESI-
5-(1,2-Dimethyl-1H-imidazol-5-yl)-2-methylpyridine (4o). 1H
NMR (400 MHz, CDCl3) δ 8.46 (d, J = 2.0 Hz, Ar−H, 1H), 7.51
(dd, J = 8.0, 2.3 Hz, Ar−H, 1H), 7.18 (d, J = 8.0 Hz, Ar−H, 1H), 6.93
(s, Ar−H, 1H), 3.47 (s, CH3, 3H), 2.55 (s, CH3, 3H), 2.40 (s, CH3,
3H). 13C NMR (101 MHz, CDCl3) δ 157.6, 148.4, 146.5, 136.1, 130.0,
126.5, 123.6, 123.0, 31.2, 24.1, 13.6. ESI-MS m/z: 187.3, [4o]+
+
MS m/z: 173.3, [3o]+ (C10H11N3 , calcd 173.1).
2-Chloro-5-(1-methyl-1H-imidazol-5-yl)pyridine (3p).30 1H NMR
(400 MHz, CDCl3) δ 8.33 (dd, J = 2.5, 0.6 Hz, Ar−H, 1H), 7.61 (dd, J
= 8.3, 2.5 Hz, Ar−H, 1H), 7.50 (s, Ar−H, 1H), 7.33 (dd, J = 8.3, 0.7
Hz, Ar−H, 1H), 7.07 (d, J = 1.0 Hz, Ar−H, 1H), 3.61 (s, CH3, 3H).
13C NMR (101 MHz, CDCl3) δ 150.5, 148.3, 140.0, 138.0, 129.0
128.5, 124.6, 124.1, 32.4.
+
(C11H13N3 , calcd 187.1).
2-Chloro-5-(1,2-dimethyl-1H-imidazol-5-yl)pyridine (4p). 1H
NMR (400 MHz, CDCl3) δ 8.36 (d, J = 2.3 Hz, Ar−H, 1H), 7.61
(dd, J = 8.2, 2.5 Hz, Ar−H, 1H), 7.37 (d, J = 8.2 Hz, Ar−H, 1H), 6.99
(s, Ar−H, 1H), 3.50 (s, CH3, 3H), 2.43 (s, CH3, 3H). 13C NMR (101
MHz, CDCl3) δ 150.5, 148.6, 147.3, 138.2, 128.7, 127.3, 125.6, 124.2,
5-(1-Methyl-1H-imidazol-5-yl)pyrimidine (3q).40 1H NMR (400
MHz, CDCl3) δ 9.17 (s, Ar−H, 1H), 8.78 (s, Ar−H, 2H), 7.59 (s, Ar−
H, 1H), 7.23 (s, CH3, 1H), 3.70 (s, CH3, 3H). 13C NMR (101 MHz,
CDCl3) δ 157.5, 155.3, 140.6, 129.9, 126.4, 124.4, 32.6.
+
31.3, 13.6. ESI-MS m/z: 207.2, [4p]+ (C10H10ClN3 , calcd 207.1).
5-(1,2-Dimethyl-1H-imidazol-5-yl)pyrimidine (4q).40 1H NMR
(400 MHz, CDCl3) δ 9.17 (s, Ar−H, 1H), 8.75 (s, Ar−H, 2H),
7.08 (s, Ar−H, 1H), 3.56 (s, CH3, 3H), 2.46 (s, CH3, 3H). 13C NMR
(101 MHz, CDCl3) δ 157.4, 155.5, 148.0, 128.0, 126.4, 125.1, 31.5
13.7.
4-(1-Methyl-1H-imidazol-5-yl)isoquinoline (3r).43 1H NMR (400
MHz, CDCl3) δ 9.30 (s, Ar−H, 1H), 8.47 (s, Ar−H, 1H), 8.06 (d, J =
8.0 Hz, Ar−H, 1H), 7.77−7.63 (m, Ar−H, 4H), 7.21 (s, Ar−H, 1H),
3.47 (s, CH3, 3H). 13C NMR (101 MHz, CDCl3) δ 153.3, 144.4,
139.2, 135.3, 131.3, 130.4, 128.3, 128.0, 127.7, 124.4, 121.0, 32.1.
4-(1-Methyl-1H-imidazol-5-yl)quinolone (3s). 1H NMR (400
MHz, CDCl3) δ 8.98 (d, J = 4.4 Hz, Ar−H, 1H), 8.19 (d, J = 8.4
Hz, Ar−H, 1H), 7.82−7.74 (m, Ar−H, 2H), 7.69 (s, Ar−H, 1H),
7.60−7.54 (m, Ar−H, 1H), 7.34 (d, J = 4.4 Hz, Ar−H, 1H), 7.26 (s,
Ar−H, 1H), 3.52 (s, CH3, 3H). 13C NMR (101 MHz, CDCl3) δ 149.8,
148.6, 139.7, 136.0, 130.6, 130.0, 129.9, 128.6, 127.4, 127.4, 125.4,
4-(1,2-dimethyl-1H-imidazol-5-yl)isoquinoline (4r).40 1H NMR
(400 MHz, CDCl3) δ 9.27 (s, Ar−H, 1H), 8.44 (s, Ar−H, 1H),
8.08−7.98 (m, Ar−H, 1H), 7.73−7.60 (m, Ar−H, 3H), 7.06 (s, Ar−H,
1H), 3.30 (s, CH3, 3H), 2.49 (s, CH3, 3H). 13C NMR (101 MHz,
CDCl3) δ 153.0, 144.4, 135.3, 131.1, 130.8, 128.7, 128.2, 128.2, 128.0,
127.6, 124.5, 121.8, 31.1, 13.6.
1
4-(1,2-Dimethyl-1H-imidazol-5-yl)quinolone (4s). H NMR (400
+
122.5, 32.4. ESI-MS. m/z: 209.3, [3s]+ (C13H11N3 , calcd 209.1).
MHz, CDCl3) δ 8.95 (d, J = 4.4 Hz, Ar−H, 1H), 8.17 (d, J = 8.4 Hz,
Ar−H, 1H), 7.83 (d, J = 8.4 Hz, Ar−H, 1H), 7.79−7.72 (m, Ar−H,
1H), 7.59−7.51 (m, Ar−H, 1H), 7.30 (d, J = 4.4 Hz, Ar−H, 1H), 7.11
(s, Ar−H, 1H), 3.38 (s, CH3, 3H), 2.52 (s, CH3, 3H). 13C NMR (101
MHz, CDCl3) δ 149.8, 148.6, 147.0, 136.6, 130.0, 129.8, 128.6, 128.5,
127.3, 127.2, 125.5, 122.3, 31.5, 13.7. ESI-MS m/z: 223.3, [4s]+
3-(1-Methyl-1H-imidazol-5-yl)quinolone (3t).36 1H NMR (400
MHz, CDCl3) δ 8.95 (d, J = 2.3 Hz, Ar−H, 1H), 8.15−8.08 (m, Ar−
H, 2H), 7.83 (dd, J = 8.1, 1.3 Hz, Ar−H, 1H), 7.76−7.69 (m, Ar−H,
1H), 7.62−7.55 (m, Ar−H, 2H), 7.25 (d, J = 0.8 Hz, Ar−H, 1H), 3.73
(s, CH3, 3H). 13C NMR (101 MHz, CDCl3) δ 150.0, 147.2, 139.9,
134.3, 129.9, 129.4, 129.2, 127.8, 127.5, 127.3, 123.0, 120.0, 32.6.
1,2-Dimethyl-5-(4-nitrophenyl)-1H-imidazole (4e).36 1H NMR
(400 MHz, CDCl3) δ 8.29 (d, J = 8.9 Hz, Ar−H, 2H), 7.53 (d, J =
8.9 Hz, Ar−H, 2H), 7.12 (s, Ar−H, 1H), 3.61 (s, CH3, 3H), 2.48 (s,
CH3, 3H). 13C NMR (101 MHz, CDCl3) δ 148.0, 146.4, 136.9, 131.4,
128.2, 128.0, 124.0, 31.7, 13.6.
+
(C14H13N3 , calcd 223.1).
3-(1,2-Dimethyl-1H-imidazol-5-yl)quinolone (4t).5g 1H NMR
(400 MHz, CDCl3) δ 8.92 (d, J = 2.2 Hz, Ar−H, 1H), 8.10 (dd, J
= 10.0, 5.4 Hz, Ar−H, 2H), 7.83 (d, J = 8.3 Hz, Ar−H, 1H), 7.75−7.65
(m, Ar−H, 1H), 7.63−7.52 (m, Ar−H, 1H), 7.11 (s, Ar−H, 1H), 3.59
(s, CH3, 3H), 2.47 (s, CH3, 3H). 13C NMR (101 MHz, CDCl3) δ
150.3, 147.1, 134.3, 130.2, 129.7, 129.2, 127.8, 127.6, 127.3, 127.3,
126.8, 123.8, 31.5, 13.7.
4-(1,2-Dimethyl-1H-imidazol-5-yl)benzaldehyde (4f).13a 1H NMR
(400 MHz, CDCl3) δ 9.98 (s, CHO, 1H), 7.95−7.82 (m, Ar−H, 2H),
7.50 (d, J = 8.2 Hz, Ar−H, 2H), 7.05 (s, Ar−H, 1H), 3.57 (s, CH3,
3H), 2.43 (s, CH3, 3H). 13C NMR (101 MHz, CDCl3) δ 191.5, 147.4,
136.3, 134.9, 132.3, 130.1, 128.1, 127.5, 31.7, 13.6.
5-(3,5-Bis(trifluoromethyl)phenyl)-1,2-dimethyl-1H-imidazole
(4u). 1H NMR (400 MHz, CDCl3) δ 7.83 (s, Ar−H, 1H), 7.78 (s, Ar−
H, 2H), 7.08 (s, Ar−H, 1H), 3.56 (s, CH3, 3H), 2.46 (s, CH3, 3H).
13C NMR (101 MHz, CDCl3) δ 147.6, 132.7, 132.4, 132.0, 131.7,
1,2-Dimethyl-5-(p-tolyl)-1H-imidazole (4j).40 1H NMR (400 MHz,
CDCl3) δ 7.23 (s, Ar−H, 4H), 6.91 (s, Ar−H, 1H), 3.49 (s, CH3, 3H),
2.43 (s, CH3, 3H), 2.38 (s, CH3, 3H). 13C NMR (101 MHz, CDCl3) δ
145.6, 137.5, 133.5, 129.3, 128.5, 127.6, 125.5, 31.2, 21.2, 13.7.
5-(1,2-Dimethyl-1H-imidazol-5-yl)-2-methoxypyridine (4k). 1H
NMR (400 MHz, CDCl3) δ 8.12 (dd, J = 2.4, 0.6 Hz, Ar−H, 1H),
7.51 (dd, J = 8.5, 2.5 Hz, Ar−H, 1H), 6.88 (s, Ar−H, 1H), 6.78 (dd, J
= 8.5, 0.7 Hz, Ar−H, 1H), 3.93 (s, OCH3, 3H), 3.45 (s, CH3, 3H),
2.41 (s, CH3, 3H). 13C NMR (101 MHz, CDCl3) δ 163.6, 146.5,
146.1, 139.0, 129.9, 125.9, 119.6, 110.8, 53.5, 31.0, 13.6. ESI-MS m/z:
203.3, [4k]+ (C11H13N3O+, calcd 203.1).
130.7, 128.0 (t, J = 5.1 Hz), 127.1 (q, J = 272.7 Hz), 121.1 (q, J = 4
+
Hz), 31.4, 13.7. ESI-MS m/z: 308.3, [4u]+ (C13H10F6N2 , calcd 308.1).
5-(1,2-Dimethyl-1H-imidazol-5-yl)-2-fluoropyridine (4v). 1H
NMR (400 MHz, CDCl3) δ 8.18 (d, J = 2.4 Hz, Ar−H, 1H), 7.78−
7.70 (m, Ar−H, 1H), 6.99 (dd, J = 8.4, 3.0 Hz, Ar−H, 1H), 6.95 (s,
Ar−H, 1H), 3.48 (s, CH3, 3H), 2.42 (s, CH3, 3H). 13C NMR (101
MHz, CDCl3) δ 164.1 (d, J = 240.7 Hz), 147.0, 146.9 (d, J = 3.9 Hz),
141.2 (d, J = 8.1 Hz), 128.7, 126.9, 124.6 (d, J = 4.7 Hz), 109.8 (d, J =
+
37.6 Hz), 31.2, 13.6. ESI-MS m/z: 191.2, [4v]+ (C10H10FN3 , calcd
191.1).
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Organometallics XXXX, XXX, XXX−XXX