J.L. Oliveira et al. / Tetrahedron 68 (2012) 2383e2390
2389
(100 MHz, CDCl3):
d
155.4, 151.1, 139.8, 125.0, 120.0. MS, m/z (rela-
4.8. Typical purification for the 2,6-dichloropyridineD2-
bromo-6-methylpyridine coupling reaction
tive intensity) 226 (47), 224 (Mþ, 75), 191 (32), 190 (12), 189 (100),
153 (37), 126 (14).
The evaporated crude product was distilled in a bulb to bulb
distillation apparatus (Kugelrohr) at 7 mmHg. The bipyridine
mixture was distilled at 156e190 ꢃC and separated from the ter-
pyridine mixture, distilled at 210e250 ꢃC. The terpyridine mixture
4.5.2. 60,600-Dichloro-2,20:6,200-terpyridine (19). Mp: 251e254 ꢃC.
ATR-FTIR (neat, cmꢀ1): 1573, 1553, 1466, 1421, 1367, 1299, 1267,
1157, 1090, 1069, 989, 908, 872, 802, 789, 710, 662, 631. 1H NMR
(400 MHz, CDCl3):
d
8.50 (dd, J¼7.2 and 7.8 Hz, 4H), 7.96 (t, J¼7.8 Hz,
was purified by flash chromatography on silica (35e70 mm) (pre-
1H), 7.82 (t, J¼7.3 Hz, 2H), 7.37 (d, J¼7.8 Hz, 2H). 13C NMR (100 MHz,
viously washed with (1%) triethylamine in CHCl3/hexane (8:2)), and
eluted with a mixture of CHCl3/hexane (8:2). The product 21 was
obtained as a white solid, and the same procedure was applied
two times to the remaining terpyridine mixture to obtain 130 mg,
10% yield.
CDCl3) d 156.6, 153.9, 151.0, 139.5, 138.2, 124.4, 121.9, 119.5. MS, m/z
(relative intensity): 304 (10), 303 (61), 302 (Mþ, 21), 301 (100), 268
(36), 267 (18), 266 (94), 230 (16). HRMS m/z (ERþ) calcd for
C15H10N3Cl2 (MþH)þ 302.0252, found 302.0263.
4.8.1. 60,600-Dimethyl-2,20:6,200-terpyridine (21). Mp: 169e170 ꢃC
(lit.:24 170e171 ꢃC); FTIR (KBr, cmꢀ1) 1571, 1438, 1077, 778, 635.
4.6. Typical purification for the 2,6-dibromopyridine
coupling reaction
1H NMR (400 MHz, CDCl3):
d
8.42 (d, J¼7.6 Hz, 2H), 8.25 (t,
J¼8.0 Hz, 2H), 7.91 (d, J¼7.6 Hz, 1H), 7.71 (d, J¼7.6 Hz, 1H), 7.15 (d,
The evaporated crude product was purified by flash chroma-
J¼7.2 Hz, 1H), 2.63 (s, 6H). 13C NMR (100 MHz, CDCl3):
d 157.8,
tography on silica (35e70
mm) (previously washed with (1%) trie-
155.7, 155.6, 137.7, 137.0, 123.3, 120.8, 118.2, 24.6. MS, m/z (relative
intensity): 261 (100), 246 (35), 219 (11), 169 (10), 130 (16), 117
(11), 92 (08).
thylamine/pentane), eluted with a gradient mixture of solvents
(pentane/CH2Cl2 50/50e100% CH2Cl2). Product 18 (885 mg, 56%
yield) and 20 (65 mg, 10% yield) were obtained.
Acknowledgements
4.6.1. 6,60-Dibromo-2,20-bipyridine (18). Mp: 227e236 ꢃC (lit.:23
221e223 ꢃC). ATR-FTIR (neat, cmꢀ1) 1570, 1533, 1407, 1375, 1260,
1152, 1116,1069, 984, 781, 725, 703, 623. 1H NMR (400 MHz, CDCl3):
The authors thank CNPq and CAPES/COFECUB (Proc. 532/06)
exchange program for financial support.
d
8.37 (d, J¼8.7 Hz, 2H), 7.67 (t, J¼8.2 Hz, 2H), 7.50 (d, J¼7.8 Hz, 2H).
13C NMR (100 MHz, CDCl3):
d 155.7, 142.0, 139.4, 128.9, 120.3. MS,
m/z (relative intensity): 316 (48), 315 (15), 314 (Mþ, 100), 312 (52),
Supplementary data
253 (21), 251 (20), 235 (46), 233 (52), 154 (37), 153 (40), 126 (19).
Supplementary data associated with this article can be found, in
4.6.2. 60,600-Dibromo-2,20:6,200-terpyridine (20). Mp: 260e262 ꢃC.
ATR-FTIR (neat, cmꢀ1): 1580, 1566, 1547, 1463, 1416, 1365, 1297,
1265, 1155, 1121, 1064, 985, 909, 859, 799, 786, 762, 691, 654, 627.
References and notes
1H NMR (400 MHz, CDCl3):
d
8.54 (d, J¼8.1 Hz, 2H), 7.67 (d, J¼8.1 Hz,
2H), 7.95 (t, J¼7.8 Hz, 1H), 7.71 (t, J¼7.4 Hz, 2H), 7.52 (d, J¼7.4 Hz,
2H). 13C NMR (100 MHz, CDCl3):
157.3, 154.0, 141.8, 139.4, 138.4,
1. Kaes, C.; Katz, A.; Housseini, M. W. Chem. Rev. 2000, 100, 3553e3590.
ꢁ
ꢁ ꢁ
2. Cannes, C.; Labbe, E.; Durandetti, M.; Devaud, M.; Nedelec, J.-Y. J. Electroanal.
Chem. 1996, 412, 85e93.
d
128.3, 122.2, 120.0. MS, m/z (relative intensity): 393 (31), 392 (13),
391 (Mþ, 74), 389 (47), 313 (14), 312 (89), 311 (17), 310 (100), 231
(21), 230 (44), 203 (15), 126 (11).
ꢁ
ꢁ ꢁ
3. Cannes, C.; Condon, S.; Durandetti, M.; Perichon, J.; Nedelec, J.-Y. J. Org. Chem.
2000, 65, 4575e4583.
4. (a) Donnici, C. L.; De Oliveira, I. M.; Temba, E. S. C.; De Castro, M. C. R. Quim.
Nova 2002, 25, 668e675; (b) Chelucci, G.; Thummel, R. P. Chem. Rev. 2002, 102,
3129e3170.
5. (a) Jolly, P. W.; Wilke, G. The Organic Chemistry of Nickel; Academic: New York,
NY, 1975; Vol. 2; p 246; (b) Jolly, P. W. In Nickel Catalysed Coupling of Organic
Halides and Related Reactions; Wilkinson, G., Ed.; Pergamon: Oxford, UK, 1982;
Vol. 8; p 713.
4.7. Procedure for 2,6-dichloropyridineD2-bromo-6-
methylpyridine preparative coupling reaction
6. Ullman, F.; Bielecki, J. Chem. Ber. 1901, 34, 2174e2185.
7. Semmelhack, M. F.; Helquist, P. M.; Gorzynski, J. D. J. Am. Chem. Soc. 1972, 94,
9234e9236.
To an undivided electrochemical cell, fitted by a zinc rod as the
anode and surrounded by a nickel foam as the cathode, were added
DMF (50 mL), 0.1 M NaI, and 1,2-dibromoethane (2.5 mmol, 215 mL).
The mixture was electrolyzed under argon at a constant current
intensity of 0.2 A at room temperature for 20 min. Then the current
was stopped, and [Ni(bpy)]Br2 complex21 (2.6 mmol, 562 mg), 2,6-
dichloropyridine (5 mmol, 0.74 g), and 2-bromo-6-methylpyridine
(10 mmol, 1.72 g) were sequentially added. The solution was elec-
trolyzed at 0.1 A and room temperature until the starting material
was totally consumed (8 h).
8. Semmelhack, M. F.; Helquist, P.; Jones, L. D.; Keller, L.; Mendelson, L.; Ryono, L. S.;
Smith, J. G.; Stauffer, R. D. J. Am. Chem. Soc. 1981, 103, 6460e6471.
9. Iyoda, M.; Otsuka, H.; Sato, K.; Nisato, N.; Oda, M. Bull. Chem. Soc. Jpn. 1990, 63,
80e87.
ꢁ
ꢁ
ꢁ
10. (a) Nedelec, J. Y.; Perichon, J.; Troupel, M. Top. Curr. Chem. 1997, 141e173;
(b) Budnikova, Y. G.; Kargin, Y. G. Russ. J. Gen. Chem. 2000, 70, 116e120;
(c) Yakhvarov, D. G.; Samieva, E. G.; Tazeev, D. I.; Budnikova, Yu. G. Russ. Chem.
Bull. Int. Ed. 2002, 51, 796e804.
11. Cassol, T. M.; Demnitz, F. W. J.; Navarro, M.; De Neves, E. A. Tetrahedron Lett.
2000, 41, 8203e8206.
12. De Franc¸ a, K. W. R.; Navarro, M.; Leonel, E.; Durandetti, M.; Nedelec, J.-Y. J. Org.
Chem. 2002, 67, 1838e1842.
ꢁ
ꢁ ꢁ
ꢁ
13. De Franc¸ a, K. W. R.; Oliveira, J. L.; Tupolevck, F.; Silva, A. P.; Navarro, M.; Leonel,
4.7.1. Workup. The reaction mixture was poured into a round-
bottomed flask and solvents were removed under low pressure to
dryness. A saturated tetrasodium EDTA solution (50 mL) and
6.5 mol Lꢀ1 NH4OH solution (50 mL) were added to the crude oil,
and the mixture was stirred over night with chloroform (100 mL).
The organic layer was separated from the mixture and the aqueous
solution was washed with chloroform (3ꢂ30 mL). The combined
organic layers were dried over Na2SO4, filtered, and evaporated
under vacuum.
ꢁ
ꢁ
E.; Nedelec, J.-Y. J. Org. Chem. 2005, 70, 10778e10781.
14. Amatore, C.; Jutand, A. Organometallics 1988, 7, 2203e2214.
ꢁ
15. (a) Meyer, G.; Troupel, M.; Perichon, J. J. Organomet. Chem. 1990, 393, 137e142;
ꢁ
ꢁ ꢁ
(b) Sengmany, S.; Leonel, E.; Polissaint, F.; Nedelec, J.-Y.; Pipelier, M.;
Thobie-Gautier, C.; Dubreuil, D. J. Org. Chem. 2007, 72, 5631e5636.
ꢁ
ꢁ
ꢁ
16. (a) Gosmini, C.; Rollin, Y.; Nedelec, J.-Y.; Perichon, J. J. Org. Chem. 2000, 65,
ꢁ
6024e6026; (b) Conan, A.; Sibille, S.; Perichon, J. J. Org. Chem. 1991, 56,
2018e2024; (c) Mellah, M.; Labbe, E.; Nedelec, J.-Y.; Perichon, J. New J. Chem.
ꢁ
ꢁ
ꢁ
ꢁ
2001, 25, 318e321.
17. Zembayashi, M.; Tamao, K.; Yoshida, J.; Kumada, M. Tetrahedron Lett. 1977, 18,
4089e4091.