2790
S. Achelle et al. / Tetrahedron 64 (2008) 2783e2791
4.6.17. 2,4,6-Tris-phenylethynylpyrimidine (24)
methylcyclohexane/ethyl acetate 293 mg (45%) of 27 as
1
Cross-coupling reaction of 2,4,6-trichloropyrimidine
(91 mg, 0.50 mmol) with potassium phenylethynyltrifluorobo-
rate (520 mg, 2.50 mmol), PdCl2(dppf)$CH2Cl2 (108 mg,
0.13 mmol) according to the general procedure E gave after
purification by column chromatography (silica gel, eluent pe-
troleum ether/ethyl acetate (9:1)) 140 mg (74%) of 24 as
a beige solid. Mp 246e247 ꢁC. H NMR (CDCl3): d 3.88 (s,
18H, 6ꢃOCH3), 3.89 (s, 9H, 3ꢃOCH3), 6.88 (s, 6H, HPh),
7.52 (s, 1H, H5). 13C (CDCl3): d 56.6, 61.4, 85.6, 87.8, 92.3,
97.5, 110.3, 111.3, 115.6, 117.9, 123.7, 141.1, 142.4, 153.4
(2C), 153.6 (2C). IR: 2217, 1578, 1563, 1504, 1472, 1238,
1123 cmꢀ1. Anal. Calcd for C37H34N2O9 (650.67): C, 68.30;
H, 5.27; N, 4.31. Found: C, 68.66; H, 5.44; N, 3.99.
1
a brown solid. Mp 181e183 ꢁC. H NMR (CDCl3): d 7.42
(m, 9H, HPh), 7.56 (s, 1H, H5), 7.65 (dd, J1¼7.5 Hz,
J2¼1.9 Hz, 4H, HPh), 7.71 (dd, J1¼7.5 Hz, J2¼1.9 Hz, 2H,
HPh). 13C (CDCl3): d 86.7, 88.2, 89.0, 95.7, 121.3, 121.6,
124.2, 128.8, 129.0, 130.2, 130.6, 132.9, 133.2, 151.9,
154.0. IR: 2216, 1557, 1495, 1362, 755, 690 cmꢀ1. Anal.
Calcd for C28H16N2 (380.13): C, 88.40; H, 4.24; N, 7.36.
Found: C, 88.35; H, 4.31; N, 7.26.
References and notes
1. (a) Burroughes, J. H.; Bradley, D. D. C.; Brown, A. R.; Marks, R. N.;
Mackay, K.; Friend, R. H.; Burns, P. L.; Holmes, A. B. Nature 1990,
347, 539; (b) Handbook of Conducting Polymers, 2nd ed.; Skotheim,
T. A., Ed.; Dekker: New York, NY, 1997; (c) Conjugated Conducting
Polymers; Kies, H., Ed.; Springer: Berlin, 1992; Vol. 102; (d) Conjugated
Polymers; Bredas, J. L., Sylbey, R., Eds.; Kluwer: Dordrecht, The
Netherlands, 1991; (e) Roncali, J. Chem. Rev. 1992, 92, 711; (f)
Gustafsson, G.; Cao, Y.; Treacy, G. M.; Klavetter, F.; Colaneri, N.; Heeger,
A. J. Nature 1992, 357, 477; (g) Hide, F.; Diaz-Garcia, M. A.; Schwartz,
B. J.; Heeger, A. J. Acc. Chem. Res. 1997, 30, 430; (h) Kraft, A.;
Grimsdale, A. C.; Holmes, A. B. Angew. Chem., Int. Ed. 1998, 37, 402;
(i) Bernius, M. T.; Inbasekaran, M.; O’Brien, J.; Wu, W. S. Adv. Mater.
2000, 12, 1737; (j) Ho, P. K. H.; Kim, J. S.; Burroughes, J. H.; Becker,
H.; Li, S. F. Y.; Brown, T. M.; Cacialli, F.; Friend, R. H. Nature 2000,
4.6.18. 2,4,6-Tris-(4-methoxyphenylethynyl)pyrimidine (25)
Cross-coupling reaction of 2,4,6-trichloropyrimidine
(183 mg, 1.00 mmol) with potassium 4-methoxy-phenylethy-
nyltrifluoroborate (1.14 g, 5.00 mmol), PdCl2(dppf)$CH2Cl2
(215 mg, 0.27 mmol) according to the general procedure E
gave after purification by column chromatography (silica
gel, eluent petroleum ether/ethyl acetate (9:1)) 164 mg
(35%) of 25 as a beige solid. Mp 202e203 ꢁC. 1H NMR
(CDCl3): d 3.86 (s, 9H, 3ꢃOCH3), 6.94e6.89 (m, 6H, HPh),
7.44 (s, 1H, H5), 7.58 (d, J¼9.0 Hz, 4H, HPh), 7.60 (d,
J¼9.0 Hz, 2H, HPh). 13C (CDCl3): d 55.8, 86.3, 87.6, 89.3,
90.5, 113.4, 113.7, 114.7, 123.4 (2C), 134.7 (2C), 151.9,
154.1, 161.2 (2C). IR: 2209, 1605, 1555, 1511, 1295, 1253,
1179, 827 cmꢀ1. Anal. Calcd for C31H22N2O3 (470.52): C,
79.13; H, 4.71; N, 5.95. Found: C, 79.44; H, 4.93; N, 5.73.
404, 481; (k) Gross, M.; Muller, D. C.; Nothofer, H.-G.; Scherf, U.; Neher,
¨
¨
D.; Brauchle, C.; Meerholz, K. Nature 2000, 405, 661; (l) Kulkarni, A. P.;
Tonzola, C. J.; Babel; Jenekhe, S. A. Chem. Mater. 2004, 16, 4556; (m)
Hughes, G.; Bryce, M. R. J. Mater. Chem. 2005, 15, 94.
2. (a) Billard, J.; Dubois, J. C.; Nguyen, H. T.; Zann, A. Nouv. J. Chim. 1978,
2, 535; (b) Chang, J. Y.; Baik, J. H.; Lee, C. B.; Han, M. J. J. Am. Chem.
Soc. 1997, 119, 3197; (c) Nori, T.; Sekine, J.; Watanabe, T.; Furukawa, T.;
Takezoe, H. J. Mater. Chem. 1996, 6, 1231; (d) Walba, D. M.; Korblova,
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3. (a) Zhang, W.-B.; Jin, W.-H.; Zhou, X.-H.; Pei, J. Tetrahedron 2007, 63,
´
2907; (b) Dıez-Barra, E.; Garcıa-Martınez, J. C.; Merino, S.; del Rey, R.;
´
´
4.6.19. 2,4,6-Tris-(4-N,N-dimethylamino-phenylethynyl)-
pyrimidine (26)
´
´
´
´
Rodrıguez-Lopez, J.; Sanchez-Verdu, P.; Tejeda, J. J. Org. Chem. 2001,
66, 5664; (c) Yamaguchi, Y.; Kobayashi, S.; Wakamiya, T.; Matsubara,
Y.; Yoshida, Z.-i. Angew. Chem., Int. Ed. 2005, 44, 7040.
Cross-coupling reaction of 2,4,6-trichloropyrimidine
(183 mg, 1 mmol) with potassium 4-N,N-dimethylaminophe-
nylethynyltrifluoroborate (1.25 g, 5 mmol), PdCl2(dppf)$
CH2Cl2 (215 mg, 0.27 mmol) according to the general proce-
dure C gave after purification by column chromatography
(silica gel, eluent petroleum ether/ethyl acetate (7:3)) 259 mg
(51%) 26 as a brown solid. Mp 245e247 ꢁC. 1H NMR
(CDCl3): d 3.02 (s, 18H, 3ꢃN(CH3)2), 6.64 (d, J¼9.0 Hz, 6H,
HPh), 7.32 (s, 1H, H5), 7.47 (d, J¼9.0 Hz, 4H, HPh), 7.49 (d,
J¼9.0 Hz, 2H, HPh). 13C (CDCl3): d 40.4, 86.2, 87.6, 91.0,
100.1, 107.0, 108.6, 111.9, 112.0, 122.8, 134.4, 134.6, 151.7,
4. (a) Schull, G.; Douillard, L.; Fiorini-Debuisschert, C.; Charra, F.;
Mathevet, F.; Kreher, D.; Attias, A. J. Nano Lett. 2006, 6, 1360; (b) Schull,
G.; Douillard, L.; Fiorini-Debuisschert, C.; Charra, F.; Mathevet, F.;
Kreher, D.; Attias, A. J. Adv. Mater. 2006, 18, 1954.
5. (a) Terenziani, F.; Le Droumaguet, C.; Katan, C.; Mongin, O.; Blanchard-
Desce, M. ChemPhysChem 2007, 8, 723; (b) Cho, B. R.; Lee, S. J.; Lee,
S. H.; Son, K. H.; Kim, Y. H.; Doo, J.-Y.; Lee, G. J.; Kang, T. I.; Lee,
Y. K.; Cho, M.; Jeon, S.-J. Chem. Mater. 2001, 13, 1438; (c) Lee, H.;
An, S.-Y.; Cho, M. J. Phys. Chem. B 1999, 103, 4992; (d) Brasselet, S.;
Cherioux, F.; Audebert, P.; Zyss, J. Chem. Mater. 1999, 11, 1915.
6. (a) Attias, A.-J.; Cavalli, C.; Bloch, B.; Guillou, N.; Noel, C. Chem.
¨
Mater. 1999, 11, 2057; (b) Lemaıtre, N.; Attias, A.-J.; Ledoux, I.; Zyss,
ˆ
152.3, 153.6, 161.5. IR: 2181, 1606, 1550, 1367, 1115 cmꢀ1
.
J. Chem. Mater. 2001, 13, 1420; (c) Attias, A.-J.; Cavalli, C.; Donnio,
ˆ
Anal. Calcd for C34H31N5 (509.26): C, 80.13; H, 6.13; N,
13.74. Found: C, 79.84; H, 5.93; N, 13.94.
B.; Guillon, D.; Hapiot, P.; Malthete, J. Chem. Mater. 2002, 14, 375.
7. (a) Meier, H.; Holst, H. C.; Oehlhof, A. Eur. J. Org. Chem. 2003, 4173;
(b) Meier, H.; Karpuk, E.; Holst, H. C. Eur. J. Org. Chem. 2006, 2609;
(c) Pieterse, K.; Lauritsen, A.; Schenning, A. P. H. J.; Vekemans,
A. J. M.; Meijer, E. W. Chem.dEur. J. 2003, 9, 5597; (d) Lee, S. J.;
Chang, J. Y. Tetrahedron Lett. 2003, 44, 7493; (e) Lee, H.; Kim, D.;
Lee, H.-K.; Qiu, W.; Oh, N.-K.; Zin, W.-C.; Kim, K. Tetrahedron Lett.
2004, 45, 1019; (f) Lee, C. J.; Lee, S. J.; Chang, J. Y. Tetrahedron Lett.
2002, 43, 3863; (g) Park, G.; Cho, B. R. J. Phys. Org. Chem. 2004, 17,
169.
4.6.20. 2,4,6-Tris-(3,4,5-trimethoxyphenylethynyl)-
pyrimidine (27)
Cross-coupling reaction of 2,4,6-trichloropyrimidine
(183 mg, 1.0 mmol) with potassium phenylethynyltrifluorobo-
rate (1.62 g, 5.4 mmol), PdCl2(dppf)$CH2Cl2 (216 mg,
0.26 mmol) according to the general procedure E gave after
purification by column chromatography (silica gel, eluent hep-
tane/ethyl acetate (5:5)) and recrystallization in a mixture of
8. Cristiano, R.; Westphal, E.; Bechtold, I. H.; Bortoluzzi, A. J.; Gallardo, H.
Tetrahedron 2007, 63, 2851.
9. Jaung, J.-Y. Dyes Pigments 2006, 71, 245.