Month 2017
Deoxygenation of Amine N-oxides
0
N,N -Bis(pyridin-2-yl)ethane-1,2-diamine [17] (3).
Dark
CDCl ): δ7.26 (d, 2H, J = 7.20 Hz), δ7.63 (dd, 1H,
J = 7.5, 7.5 Hz); Ms (EI) m/z = 148 (M ).
3
ꢀ
1
+
brown solid; Mp: 134–136°C; IR (KBr, ν cm ): 3229,
905, 2867, 1605, 1572, 1527, 1437, 1331, 1148, 767;
H NMR (300 MHz, CDCl ): δ3.57 (s, 4H), δ6.39 (d,
H, J = 8.49 Hz), δ6.56 (app t, 2H, J = 6.6 Hz), δ7.38
app t, 2H, J = 8.68 Hz), δ8.07 (d, 2H, J = 4.15 Hz);
Methyl isonicotinate [23] (11).
(Neat, ν cm ): 3054, 2888, 1738, 1296, 1109, 758; H
Colorless liquid; IR
2
ꢀ
1
1
1
3
NMR (300 MHz, CDCl ): δ3.92 (s, 3H), δ7.86 (d, 2H,
2
(
3
13
J = 6.45 Hz), δ8.78 (d, 2H, J = 6.32 Hz); Ms (EI) m/
C
+
NMR (75.47 MHz, CDCl ): δ 42.2, 107.7, 113.2, 137.6,
z = 137 (M ).
3
+
2-Chloroisonicotinonitrile [24] (12).
White solid; Mp:
1
48.0, 158.7; Ms (EI) m/z: 214 (M ).
ꢀ
1
0
N,N -Dimethyl-N-(pyridin-2-yl)ethane-1,2-diamine (4).
70–72°C; IR (KBr, ν cm ): 3086, 2468, 2240, 1547,
ꢀ
1
1
1
381, 1217, 886, 847; H NMR (300 MHz, CDCl3):
Pale brown liquid; IR (Neat, ν cm ): 3413, 2926, 1599,
500, 1426, 772; H NMR (300 MHz, CDCl ): δ2.73 (s,
H), δ3.05 (s, 3H), δ3.23 (m, 2H), δ3.82 (m, 2H), δ6.60
d, 1H, J = 8.79 Hz), δ6.69 (app t, 1H, J = 6.83 Hz),
δ7.55 (app t, 1H, J = 8.79 Hz), δ8.13 (d, 1H,
J = 3.90 Hz); C NMR (75.47 MHz, CDCl ): δ 33.1,
7.4, 47.5, 47.9, 106.3, 112.6, 137.7, 147.2, 158.2. Ms
ESI) m/z: 166 (M+H) ; Anal. Calcd for C H N : C,
1
1
3
(
δ7.48 (dd, 1H, J = 2.10, 7.50 Hz), δ7.64 (d, 1H,
J = 2.10 Hz), δ8.56 (d, 1H, J = 7.50 Hz); Ms (EI) m/
3
+
z = 138 (M ).
2
-Pyridine carboxaldehyde [25] (13). Yellow liquid; IR
ꢀ
1
1
3
(Neat, ν cm ): 3092, 2876, 1725, 1582, 1281, 1006, 758;
H NMR (300 MHz, CDCl ): δ7.71–7.48 (m, 1H), δ7.94
3
1
3
(
6
2
3
+
(dd, 2H, J = 18.3, 7.1 Hz), δ8.82 (s, 1H), δ10.09 (s, 1H);
9 15 3
1
3
C NMR (CDCl , 75.47 MHz): δ 121.23, 127.50, 136.75,
5.42; H, 9.15; N, 25.43. Found: C, 65.29; H, 9.11, N,
5.25.
3
+
1
49.82, 152.40, 192.94; Ms (EI) m/z = 107 (M ).
0
0
Isoquinoline [26] (14). Pale yellow liquid; IR (Neat, ν
N,N -Dimethyl-N,N -bis(pyridin-2-yl)ethane-1,2-diamine
Pale brown solid; Mp: 128–132°C; IR (KBr, ν
ꢀ
1
(
5).
cm ): 3065, 1628, 1586, 1500, 1381, 1260, 940, 864;
ꢀ
1
1
H NMR (300 MHz, CDCl ): δ7.73–7.52 (m, 3H), δ7.81
cm ): 3427, 2923, 1602, 1501, 1425, 1323, 985, 770;
H NMR (300 MHz, CDCl ): δ3.03 (s, 6H), δ3.76 (s,
H), δ6.48–6.54 (m, 4H), δ7.40 (app t, 2H, J = 8.87 Hz),
δ8.16 (d, 2H, J = 5.85 Hz); C NMR (75.47 MHz,
3
1
(d, J = 8.2 Hz, 1H), δ7.96 (d, J = 8.2 Hz, 1H), δ8.52 (d,
3
13
4
J = 5.8 Hz, 1H), δ9.25 (s, 1H); C NMR (75.47 MHz,
1
3
CDCl ): δ 120.48, 126.47, 127.26, 127.64, 127.68,
3
CDCl ): δ 37.2, 48.1, 105.9, 111.6, 137.5, 147.9, 158.2;
130.37, 135.79, 142.96, 152.51.
3
1
+
Phenazine [27] (15).
Pale brown solid; H NMR
Ms (EI) m/z: 242 (M ); Anal. Calcd for C H N : C,
9.39; H, 7.49; N, 23.12. Found: C, 69.31; H, 7.42, N,
1
4 18 4
(
4
CDCl , 300 MHz): δ7.77–7.79 (m, 4H), δ8.18–8.21 (m,
6
2
3
3
1
H); C NMR(CDCl , 75.47 MHz): δ 129.6, 130.4, 143.4.
3
3.03.
4
4
-Methyl morpholine [28] (16). Pale yellow liquid; IR
-(Piperidin-1-yl)pyridine [18] (6).
Mp: 78–80°C; IR (KBr, ν cm ): 3340, 2962, 2805,
605, 1520, 1430, 815; H NMR (300 MHz, CDCl ):
δ1.69 (m, 6H), δ3.50 (m, 4H), δ6.74 (d, 2H,
Pale yellow solid;
ꢀ
1
ꢀ
1
(Neat, ν cm ): 2962, 2893, 1454, 1338, 1202, 1071,
906, 864; H NMR (300 MHz, CDCl ): δ2.28 (s, 3H),
δ2.39 (s, 4H), δ3.90–3.59 (m, 4H);
(75.47 MHz, CDCl ): δ 46.47, 55.46, 66.45.
1
1
1
3
3
13
C
NMR
1
3
J = 5.80 Hz), δ8.25 (br, 2H); C NMR (75.47 MHz,
3
CDCl ): δ 24.0, 25.2, 47.3, 107.5, 146.2, 155.6; Ms (EI)
3
+
m/z = 162 (M ).
4
-Methoxypyridine [19] (7). Colorless liquid; IR (Neat, ν
Acknowledgment. The author expresses his thanks to SASTRA
University, Thanjavur, for the financial support (Prof. T. R.
Rajagopalan Grant).
ꢀ
1
1
cm ): 3345, 1606, 1453, 1328, 1064, 758; H NMR
(
(
1
300 MHz, CDCl ): δ3.88 (s, 3H), δ6.89 (br, 2H), δ8.54
3
13
br, 2H); C NMR (75.47 MHz, CDCl ): δ 55.3, 110.5,
3
+
49.9, 166.7; Ms (EI) m/z = 109 (M ).
REFERENCES AND NOTES
2
-Picolinic acid [20] (8). White solid; Mp: 138–140°C;
ꢀ
1
IR (KBr, ν cm ): 2915, 1718, 1587, 1450, 1351, 1295,
1
1
[1] Ochiai, E. In Aromatic Amine Oxides; Elsevier: Amsterdam,
1
087, 752; H NMR (300 MHz, DMSO-d ): δ7.66 (d,
1967, p. 184.
6
[2] Singh, B.; Lesher, G. Y.; Pennock, P. O. J Heterocycl Chem
H, J = 6.20 Hz), δ8.03–8.10 (m, 2H), δ8.75 (d, 1H,
1
1
990, 27, 1841.
+
J = 6.20 Hz), δ10.08 (s, 1H); Ms (EI) m/z: 123 (M ).
[3] Balicki, R.; Kaczmarek, L.; Malinowski, M. Synth Commun
Pyridin-2-ol [21] (9).
05°C; IR (KBr, ν cm ): 3260, 3096, 2933, 1639, 1608,
418, 1242, 1099, 981, 781; H NMR (300 MHz,
Pale yellow solid; Mp: 103–
989, 19, 897.
ꢀ
1
1
1
[4] Konwar, D.; Boruah, R. C.; Sandhu, J. S. Synthesis 1990, 337.
[5] (a) Aoyagi, Y.; Abe, T.; Ohta, A. Synthesis 1997, 891; (b)
Campeau, L.-C.; Stuart, D. R.; Leclerc, J.-P.; Laperle, M. B.; Villemure,
E.; Sun, H.-Y.; Lasserre, S.; Guimond, N.; Lecavallier, M.; Fagou, K. J
Am Chem Soc 2009, 131, 3291.
1
CDCl ): δ6.31 (app t, 1H, J = 6.42 Hz), δ6.63 (d, 1H,
J = 9.14 Hz), δ7.42 (d, 1H, J = 5.43 Hz), δ7.48 (app t,
1
3
+
[6] Kaczmarek, L.; Balicki, R.; Malinowski, M. J Prakt Chem
H, J = 8.65 Hz); Ms (EI) m/z = 95 (M ).
1990, 332, 423.
2
,6-Dichloro pyridine [22] (10).
Colorless solid; Mp:
[
[
7] Balicki, R. Synthesis 1989, 645.
8] Balicki, R.; Cybulski, M.; Maciejewski, G. Synth Commun
ꢀ
1
8
1
2–84°C; IR (KBr, ν cm ): 2941, 1563, 1481, 1408,
362, 1163, 1136, 993, 791; H NMR (300 MHz,
1
2003, 33, 4137.
Journal of Heterocyclic Chemistry
DOI 10.1002/jhet