2
616
X.-F. Duan et al.
SHORT PAPER
2
-Phenyl-4-(p-methylphenyl)pyridine(1a)15
Acknowledgment
–
1
IR (KBr): 3028, 1594, 1541, 1470, 1383, 812, 775 cm .
The authors thank NHTRDP (863 Program No. 2002A A322403),
National Science Foundation of China (202 21101), Shanghai Sci.
Tech. Comm. (03QB14006), and Shanghai Nanotech Promotion
1
H NMR (CDCl ): d = 2.46 (s, 3 H), 7.34 (d, J = 8.0 Hz, 2 H), 7.45–
3
7
2
.55 (m, 4 H), 7.63 (d, J = 8.1 Hz, 2 H), 7.95 (s, 1 H), 8.09–8.09 (m,
H), 8.75 (d, J = 5.1 Hz, 1 H).
(
0216nm040) for financial support. The authors are also grateful to
1
3
C NMR (CDCl ): d = 21.7, 119.0, 120.5, 127.3, 127.5, 129.5,
Dr. Shuang Liu for revising this paper.
3
1
30.3, 135.9, 139.7, 149.8, 150.2, 158.3.
MS (EI): m/z (%) = 245 (100), 230 (52), 115 (50).
References
2
-(p-Methoxyphenyl)-4-(p-chlorophenyl)pyridine (1b)
(1) Quéguiner, G.; Marsais, F.; Snieckus, V.; Epsztajn, J. Adv.
Heterocycl. Chem. 1991, 52, 187.
(2) (a) Trawick, B. N.; Daniher, A. T.; Bashkin, J. K. Chem.
Rev. 1998, 98, 939. (b) Harriman, A.; Ziessel, R. Coord.
Chem. Rev. 1998, 171, 331. (c) Lehn, J. M. Supramolecular
Chemistry; VCH Verlasgesellschaft: Weinheim, 1995.
IR (KBr): 3023, 2960, 2838, 1597, 1541, 1496, 1377, 1251, 1180,
8
–1
43, 812 cm .
1
H NMR (CDCl ): d = 3.91 (s, 3 H), 7.04 (d, J = 8.8 Hz, 2 H), 7.39
dd, J = 1.5, 5.2 Hz, 1 H), 7.50 (d, J = 8.5 Hz, 2 H), 7.65 (d, J = 9.5
3
(
Hz, 2 H), 7.86 (s, 1 H), 8.05 (d, J = 8.8 Hz, 2 H), 8.73 (d, J = 5.2 Hz,
H).
(
3) (a) Fallaphour, R. A. Synthesis 2000, 1138; and references
cited therein. (b) Cargill Thompson, A. M. W. Coord. Chem.
Rev. 1997, 160, 1. (c) Kröhnke, F. Synthesis 1976, 1.
1
MS (EI): m/z (%) = 297 (32), 295 (100), 280 (15), 260 (5).
(
4) (a) Bonnet, V.; Mongin, F.; Trécourt, F.; Breton, G.;
Marsais, F.; Knochel, P.; Quéguiner, G. Synlett 2002, 1008;
and references cited therein. (b) Fallahpour, R. A. Synthesis
Anal. Calcd for C H ClNO: C, 73.10; H, 4.74; N, 4.74. Found: C,
1
8
14
7
2.79; H, 4.95; N, 4.28.
2
000, 1665. (c) Stanforth, S. P. Tetrahedron 1998, 54, 263.
Preparation of Bipyridines(2 and 3) Via One-Pot Disubstitu-
tions of 2-Bromo-4-iodo-pyridine Using ArMgBr and 2-
(
(
5) (a) Bouillon, A.; Lancelot, J.-C.; Collot, V.; Bovy, P. R.;
Rault, S. Tetrahedron 2002, 58, 4369; and references cited
therein. (b) Uzuki, A. J. Organomet. Chem. 1999, 576, 147.
PySnBu ; General Procedure
3
After 2-bromo-4-iodopyridine (200 mg, 0.7 mmol) was coupled
(
c) Miyaura, N.; Suzuki, A. Chem. Rev. 1995, 95, 2457.
6) (a) Loren, J. C.; Siegel, J. S. Angew. Chem. Int. Ed. 2001, 40,
54. (b) Hargreaves, S. L.; Pilkington, B. L.; Russel, S. E.;
Worthington, P. A. Tetrahedron Lett. 2000, 41, 1653.
c) Trécourt, F.; Gervais, B.; Mongin, O.; Le Gal, C.;
with p-MePhMgBr as described above, 2-PySnBu (0.84 mmol),
3
Pd(PPh ) (40 mg, 0.035 mmol) and DMF (10 mL) was added to the
3
4
7
mixture at r.t. under an Ar atmosphere. The resulted mixture was
heated to distill off THF and the reaction was kept at 120 °C for 60
(
h. The reaction was quenched with sat. aq NH Cl solution and ex-
4
Mongin, F.; Quéguiner, G. J. Org. Chem. 1998, 63, 2892;
and references cited therein.
tracted with CH Cl . A brown slurry was obtained, after the organic
2
2
layer was dried over anhyd Na SO , CH Cl was removed. The
2
4
2
2
(
7) (a) Ellison, D. K.; Iwamoto, R. T. Tetrahedron Lett. 1983,
crude product was purified by flash chromatography (petroleum–
24, 31. (b) Kociam, O.; Mortimer, R. J.; Beer, P. D. J. Chem.
EtOAc–Et N, 100:4:1).
3
Soc., Perkin Trans. 1 1990, 3203. (c) Kauffman, T.; Konig,
J.; Woltermann, A. Chem. Ber. 1976, 109, 3864.
4
-(p-Methylphenyl)-2,2¢-bipyridine (3)
–
1
(8) Talik, T. Rocz. Chem. 1957, 31, 569.
IR (KBr): 3004, 1599, 1582, 1542, 1457, 1385, 811, 793 cm .
(
9) (a) Rocca, P.; Cochennec, C.; Marsais, F.; Thomas-dit-
Dumont, L.; Mallet, M.; Godard, A.; Quéguiner, G. J. Org.
Chem. 1993, 58, 7832. (b) Mallet, M.; Quéguiner, G.
Tetrahedron 1986, 42, 2253. (c) Gribble, G. W.; Saulnier,
M. G. Tetrahedron Lett. 1980, 21, 4137.
(10) (a) Quéguiner, G. J. Heterocycl. Chem. 2000, 37, 615.
(b) Marsais, F.; Laperdrix, B.; Güngör, T.; Mallet, M.;
Quéguiner, G. J. Chem. Res., Synop. 1982, 278.
1
H NMR (CDCl ): d = 2.45 (s, 3 H), 7.32–7.37 (m, 3 H), 7.56 (dd,
3
J = 1.5, 5.0 Hz, 1 H), 7.71 (d, J = 8.0 Hz, 2 H), 7.87 (td, J = 1.5, 7.5
Hz, 1 H), 8.48 (dd, J = 0.5, 8.0 Hz, 1 H), 8.69–8.75 (m, 3 H).
1
3
C NMR (CDCl ): d = 21.7, 119.2, 121.7, 121.8, 124.2, 127.4,
3
1
30.2, 135.7, 137.4, 139.6, 149.6, 149.7, 156.6, 157.0.
+
+
MS (ESI): m/z (%) = 269.1 [M + Na ], 247.1 [M + H ].
Anal. Calcd for C H N : C, 82.93; H, 5.69; N, 11.38. Found: C,
17
14
2
(11) (a) Mallet, M.; Branger, G.; Marsais, F.; Quéguiner, G. J.
Organomet. Chem. 1990, 382, 319. (b) Mallet, M.;
Quéguiner, G. Tetrahedron 1985, 41, 3433.
8
3.22; H, 5.56; N, 11.20.
1
5
4
,4¢-Di(p-methylphenyl)-2,2¢-bipyridine(2)
(
(
(
12) Karig, G.; Spencer, J. A.; Gallagher, T. Org. Lett. 2001, 3,
35.
13) Li, X.-H. Dissertation; Beijing Normal University: China,
003.
1
Mp and H NMR data were in accordance with the literature.
8
Preparation of Bipyridines 2 Via One-Pot Disubstitutions of 2-
Bromo-4-iodopyridine Using ArMgBr and Homo-Coupling
After 2-bromo-4-iodopyridine (200 mg, 0.7 mmol) was coupled
with p-MePhMgBr as described above, N,N-diisopropylethyl amine
2
14) (a) Abarbri, M.; Thibonnet, J.; Bérillon, L.; Dehmel, F.;
Rottländer, M.; Knochel, P. J. Org. Chem. 2000, 65, 4618.
(
b) Trécourt, F.; Breton, G.; Mongin, F.; Quéguiner, G.
(
0.12 mL, 0.7 mmol), Pd(OAc) (7.87 mg, 0.035 mmol), Bu NBr
2
4
Tetrahedron 2000, 56, 1349.
(
112.7 mg, 0.35 mmol) and DMF (10 mL) were added. The mixture
(
15) Munoz, B.; Chen, C.; Mcdonald, I. A. Biotech. Bioeng.
was heated to distill off THF under an Ar atmosphere. When the
temperature reached 115 °C, i-PrOH (0.5 mL, 0.7 mmol) was add-
ed. After keeping the mixture at 115 °C for about 60 h, the reaction
was post-treated as above.
2000, 71, 78.
Synthesis 2004, No. 16, 2614–2616 © Thieme Stuttgart · New York