1
0
Tetrahedron
+
1
419, 1370, 1252, 1179, 1111, 1033, 1019
A
. H
C
R
C
M
E
S
P
(ES
T
E
):D MAN2H
U
, A
S
r-H
C
R
),
I
7
P
.3
T
2 (d, J = 7.65 Hz, 1H, Ar-H), 2.45 (s, 3H, Me)
+
13
calcd. for C H ClNO [M+H] 296.0842; found 296.0845.
ppm. C NMR (125 MHz, CDCl ): δ 161.23, 152.82, 152.54,
18
15
3
1
42.53, 141.84, 138.53, 137.01, 131.04, 129.45, 128.57,
4
.3.18. 2-(4-Methoxyphenyl)-5-nitropyridine (2.18): Yellow
-1
o
125.95, 122.16, 121.46, 21.44 ppm. IR (KBr, cm ): 3058,
2994, 2225, 1954, 1578, 1557, 1436, 1400, 1230. HRMS
solid, (169 mg, 98%), mp 118-120 C, Rf (10% EtOAc/
Hexane) 0.27; H NMR (500 MHz, CDCl ): δ 9.44 (d, J = 2.75
Hz, 1H, Ar-H), 8.46 (dd, J = 8.85 Hz, 2.75 Hz, 1H, Ar-H), 8.06
1
3
+
+
(ES ): calcd. for C H N [M+H] 195.0922; found 195.0920.
13 11 2
2
7
(d, J = 8.85 Hz, 2H, Ar-H), 7.82 (d, J = 8.85 Hz, 1H, Ar-H),
4.3.24. 2-(4-Methoxyphenyl)-5-methylpyridine (2.28) : Yellow
solid, (101 mg, 68%), mp 46-47 C, R (10% EtOAc/Hexane)
0.28; H NMR (500 MHz, CDCl ): δ 8.47 (s, 1H, Ar-H), 7.91
13
o
7
.02 (d, J = 9.15 Hz, 2H, Ar-H), 3.88 (s, 3H, OMe) ppm.
C
f
1
NMR (125 MHz, CDCl ): δ 162.04, 162.0, 145.26, 142.23,
3
3
1
31.81, 129.54, 129.28, 118.94, 114.51, 55.47 ppm. IR (KBr,
(d, J = 8.85 Hz, 2H, Ar-H), 7.56 (d, J = 7.9 Hz, 1H, Ar-H),
7.52-7.50 (m, 1H, Ar-H), 6.98 (d, J = 8.85 Hz, 2H, Ar-H), 3.85
(s, 3H, OMe), 2.34 (s, 3H, Me) ppm. C NMR (125 MHz,
-
1
cm ): 3074, 2962, 2840, 1597, 1518, 1437, 1288, 1176, 1050.
HRMS (ES ): calcd. for C H N O [M] 230.0691; found
+
+
13
12
10
2
3
2
30.0699.
CDCl ): δ 160.18, 154.36, 149.70, 137.42, 131.78, 130.85,
3
-
1
1
27.91, 119.37, 114.06, 55.33, 18.10 ppm. IR (KBr, cm ):
4
.3.19. 2-(4-Ethoxyphenyl)-5-nitropyridine (2.21): Yellow
o
2921, 1608, 1514, 1477, 1306, 1273, 1173, 1025, 1046, 820.
solid, (168 mg, 92%), mp 124-127 C, Rf (10% EtOAc/
Hexane) 0.25; H NMR (500 MHz, CDCl ): δ 9.44 (d, J = 2.45
Hz, 1H, Ar-H), 8.47 (dd, J = 8.55 Hz, 2.45 Hz, 1H, Ar-H), 8.05
+
+
1
HRMS (ES ): calcd. for C13
00.1072.
H14NO [M+H] 200.1075; found
3
2
(
7
d, J = 8.85 Hz, 2H, Ar-H), 7.82 (d, J = 8.85 Hz, 1H, Ar-H),
4.3.25. 3-Chloro-2-(4-methylphenyl)pyridine (2.29): Colorless
liquid, (149 mg, 97%), Rf (10% EtOAc/Hexane) 0.28; H
1
.01 (d, J = 9.15 Hz, 2H, Ar-H), 4.11 (q, J = 7.05 Hz, 2H,
13
CH ), 1.45 (t, J = 6.75 Hz, 3H, CH ) ppm. C NMR (125
NMR (500 MHz, CDCl ): δ 8.58 (dd, J = 4.6 Hz, 1.25 Hz, 1H,
2
3
3
MHz, CDCl ): δ 162.06, 161.45, 145.26, 142.19, 131.79,
Ar-H), 7.78 (dd, J = 8.25 Hz, 1.5 Hz, 1H, Ar-H), 7.63 (d, J =
3
1
29.34, 129.27, 118.90, 114.98, 63.70, 14.72 ppm. IR (KBr,
8.25 Hz, 2H, Ar-H), 7.27 (d, J = 7.95 Hz, 2H, Ar-H), 7.19 (dd,
-
1
13
cm ): 2977, 1598, 1572, 1504, 1458, 1423, 1391, 1342, 1307,
1
calcd. for C H N O [M] 244.0848; found 244.0842.
J = 8.25 Hz, 4.55 Hz, 1H, Ar-H), 2.41 (s, 3H, Me) ppm.
C
+
255, 1181, 1152, 1116, 1152, 1116, 1050. HRMS (ES ):
NMR (125 MHz, CDCl ): δ 156.55, 147.50, 138.78, 138.04,
3
+
135.30, 130.07, 129.21, 128.73, 122.77, 21.36 ppm. IR (neat,
13
12
2
3
-
1
25
cm ): 3039, 2921, 2863, 1907, 1615, 1571, 1553, 1423, 1130,
4
.3.20. 2-(3-Methoxyphenyl)-5-nitropyridine (2.22) : Yellow
+
+
o
1028, 1016. HRMS (ES ): calcd. for C12
H11ClN [M+H]
solid, (145 mg, 84%), mp 96-99 C, R (10% EtOAc/Hexane)
0
f
1
204.0580; found 204.0583.
.29; H NMR (500 MHz, CDCl ): δ 9.48 (d, J = 2.55 Hz, 1H,
3
2
8
Ar-H), 8.51 (dd, J = 8.85 Hz, 2.85 Hz, 1H, Ar-H), 7.89 (d, J =
.9 Hz, 1H, Ar-H), 7.67 (s, 1H, Ar-H), 7.62 (d, J = 7.7 Hz, 1H,
Ar-H), 7.43 (t, J = 8.0 Hz, 1H, Ar-H), 7.06 (dd, J = 8.3 Hz, 2.0
4.3.26. 3-Chloro-2-(4-methoxyphenyl)pyridine (2.30) : White
o
8
solid, (152 mg, 92%), mp 45-47 C, R (10% EtOAc/Hexane)
f
1
0.22; H NMR (500 MHz, CDCl ): δ 8.56 (dd, J = 4.55 Hz, 1.4
3
13
Hz, 1H, Ar-H), 3.90 (s, 3H, OMe) ppm. C NMR (125 MHz,
CDCl ): δ 162.19, 160.23, 145.16, 142.89, 138.41, 131.89,
Hz, 1H, Ar-H), 7.76 (dd, J = 8.0 Hz, 1.45 Hz, 1H, Ar-H), 7.71
(d, J = 8.9 Hz, 2H, Ar-H), 7.17 (dd, J = 8.05 Hz, 4.6 Hz, 1H,
3
1
30.10, 120.20, 119.95, 116.88, 112.79, 55.45 ppm. IR (KBr,
Ar-H), 6.99 (d, J = 8.85 Hz, 2H, Ar-H), 3.86 (s, 3H, OMe)
-
1
13
cm ): 3075, 2967, 2841, 1597, 1581, 1518, 1461, 1450, 1437,
1
2
ppm. C NMR (125 MHz, CDCl ): δ 160.05, 156.11, 147.49,
3
+
+
351, 1289, 1176. HRMS (ES ): calcd. for C H N O [M]
138.11, 130.80, 130.62, 129.91, 122.54, 113.42, 55.31 ppm. IR
12
10
2
3
-
1
30.0691; found 230.0697.
(KBr, cm ): 3061, 2936, 2841, 1609, 1570, 1514, 1461, 1431,
+
26
1305, 1181, 1028, 1111. HRMS (ES ): calcd. for C12
[M+H] 220.0529; found 220.0525.
H11ClNO
4
.3.21. 2-(4-Chlorophenyl)-5-nitropyridine (2.23) : Yellow
+
o
solid, (121 mg, 69%), mp 153-155 C, Rf
EtOAc/Hexane) 0.42; H NMR (500 MHz, CDCl ): δ 9.47 (d, J
(10%
1
28
4.3.27.
3-Chloro-2-(3-methoxyphenyl)pyridine
(2.31) :
3
=
2.75 Hz, 1H, Ar-H), 8.52 (dd, J = 8.85 Hz, 2.75 Hz, 1H, Ar-
Colorless liquid, (112 mg, 68%), Rf (10% EtOAc/Hexane)
1
H), 8.04 (d, J = 8.55 Hz, 2H, Ar-H), 7.88 (d, J = 8.85 Hz, 1H,
Ar-H), 7.49 (d, J = 8.85 Hz, 2H, Ar-H) ppm. C NMR (125
MHz, CDCl ): δ 161.14, 145.30, 142.94, 137.31, 135.40,
0.27; H NMR (500 MHz, CDCl ): δ 8.59 (d, J = 4.9 Hz, 1H,
3
13
Ar-H), 7.79 (d, J = 7.95 Hz, 1H, Ar-H), 7.37 (t, J = 7.90 Hz,
1H, Ar-H), 7.30 (d, J = 7.6 Hz, 1H, Ar-H), 7.24-7.21 (m, 2H,
3
-
1
13
1
1
32.07, 129.37, 128.92, 119.81 ppm. IR (KBr, cm ): 3094,
598, 1511, 1578, 1459, 1410, 1343, 1289, 1261, 1093. HRMS
Ar-H), 6.99-6.97 (m, 1H), 3.85 (s, 3H, OMe) ppm. C NMR
(125 MHz, CDCl ): δ 159.26, 156.40, 147.48, 139.42, 138.12,
3
+
+
(ES ): calcd. for C H ClN O [M] 234.0196; found 234.0194.
130.18, 129.07, 123.12, 121.76, 114.85, 114.58, 55.33 ppm. IR
11
7
2
2
-
1
(
neat, cm ): 3046, 2937, 2834, 1601, 1582, 1570, 1455, 1432,
4
.3.22. 2-(4-Fluorophenyl)-5-nitropyridine (2.24): Yellow
+
o
1320, 1300, 1235, 1179, 1028. HRMS (ES ): calcd. for
C H11ClNO [M+H] 220.0529; found 220.0528.
12
solid, (119 mg, 73%), mp 124-127 C, Rf (10% EtOAc/
Hexane) 0.40; H NMR (500 MHz, CDCl ): δ 9.47 (d, J = 2.6
+
1
3
Hz, 1H, Ar-H), 8.52 (dd, J = 8.85 Hz, 2.55 Hz, 1H, Ar-H),
4.3.28. 3-Chloro-2-(3,4-dimethoxyphenyl)pyridine (2.32):
o
8
7
1
1
2
1
.11-8.08 (m, 2H, Ar-H), 7.86 (d, J = 8.55 Hz, 1H, Ar-H),
White solid, (149 mg, 79%), mp 84-85 C, Rf (10%
13
1
.22-7.19 (m, 2H, Ar-H) ppm. C NMR (125 MHz, CDCl ): δ
EtOAc/Hexane) 0.12; H NMR (500 MHz, CDCl ): δ 8.57 (d, J
3
3
1
64.59 (d, J = 149.56 Hz), 161.28, 145.26, 142.76, 133.19,
= 4.6 Hz, 1H, Ar-H), 7.78 (d, J = 7.9 Hz, 1H, Ar-H), 7.37 (d, J
= 8.55 Hz, 1H, Ar-H), 7.30 (s, 1H, Ar-H), 7.19 (dd, J = 8.25
C-F
3
2
32.02, 129.24 (d, J = 8.4 Hz ), 119.65, 116.21 (d, J
=
C-F
C-F
-
1
2.78 Hz) ppm. IR (KBr, cm ): 3060, 1904, 1603, 1576, 1588,
Hz, 4.9 Hz, 1H, Ar-H), 6.95 (d, J = 8.25 Hz, 1H, Ar-H), 3.93
+
13
510, 1467, 1347, 1230. HRMS (ES ): calcd. for C H FN O
(s, 6H, OMe) ppm. C NMR (125 MHz, CDCl ): δ 156.0,
11
7
2
2
3
+
[
M] 218.0492; found 218.0494.
149.6, 148.5, 147.38, 143.85, 138.27, 130.62, 129.97, 122.64,
-
1
1
22.32, 112.57, 110.40, 55.92 ppm. IR (KBr, cm ): 2999,
4
.3.23. 2-(3-Methylphenyl)-3-cyanopyridine (2.26): Yellow
o
2934, 2835, 1604, 1570, 1519, 1463, 1428, 1270, 1227, 1173,
solid, (132 mg, 91%), mp 78-80 C, R (10% EtOAc/Hexane)
0
+
+
f
1
1027. HRMS (ES ): calcd. for C13
H13ClNO
2
[M+H] 250.0635;
.36; H NMR (500 MHz, CDCl ): δ 8.87 (d, J = 4.6 Hz, 1H,
3
found 250.0638.
Ar-H), 8.61 (d, J = 4.9 Hz, 1H, Ar-H), 8.07 (d, J = 6.1 Hz, 1H,
Ar-H), 8.0 (d, J = 8.25 Hz, 1H, Ar-H), 7.72 (d, J = 5.15 Hz,