1154
Kasák, Brath, Krascsenicsová-Poláková, Kicková, Moldovan, Putala:
7.32 ddd, 2 H, J = 1.6, 7.5, 8.2 (Ar-H); 7.32 d, 4 H, 3J = 3.6 (Ar-H); 7.03 ddd, 2 H, J = 1.0, 4.9,
7.5 (Ar-H); 6.32 d, 2 H, 3J = 7.91 (Ar-H). 13C NMR (75 MHz, CDCl3): 149.8, 143.5, 141.0,
135.9, 133.4, 132.7, 128.5, 128.3, 128.2, 127.6, 127.2, 127.1, 126.9, 122.5, 121.1, 92.8, 89.3.
GC-MS-FAB, m/z (%): 455 (100) [M• + – 1], 378 (62), 226 (26). For C34H20N2 (456.5) calcu-
lated: 89.45% C, 4.42% H, 6.14% N; foun d: 89.73% C, 4.50% H, 5.85% N. (RS)-7: m .p.
241–244 °C (ch loroform –h exan es).
2,2′-Bis(3-pyridyleth yn yl)-1,1′-bin aph th alen e (8)
A dried Sch len k flask con tain in g a stirrin g bar, capped with a rubber septum , was
flam e-dried un der vacuum , filled with argon an d cooled to room tem perature. Th e flask was
ch arged with 15 (100 m g, 0.33 m m ol), 3-brom opyridin e (128 m g, 0.825 m m ol), CuI (3.3 m g,
0.0165 m m ol) an d [Pd(PPh 3)4] (18.1 m g, 0.0165 m m ol), evacuated again an d filled with ar-
gon . Toluen e (4.5 m l) an d Et3N (1.7 m l) were successively in jected in to th e flask. Th e dark
brown reaction m ixture was h eated to 80 °C for 2 h . After coolin g, water (3 m l) was added,
th e m ixture was poured in to 10% aqueous NH4Cl an d extracted th ree tim es with eth yl ace-
tate (10-m l portion s). Com bin ed organ ic fraction s were dried over Na2SO4. After filtration
an d evaporation th e solven t, th e residue was ch rom atograph ed on silica gel (h exan es–eth yl
acetate, gradien t from 2:1 to 1:1). (RS)- or (R)-8 (177 m g, 85%) as an off-wh ite solid was ob-
tain ed.
(R)-2,2′-Bis(3-pyridylethynyl)-1,1′-binaphthalene (8). M.p. 191–193 °C, [α ]2D1 –2.9 (c 1, ch loro-
form ), RF 0.10 (eth yl acetate–h exan es, 1:1). UV-VIS (MeOH (log ε)): 226 (6.59), 268 (6.78),
316 (6.32). IR (ch loroform ): 2275 m , 2095 m , 1595 m , 1530 m , 1470 m , 1420 m , 920 m , 800 s,
695 s, 650 w. 1H NMR (300 MHz, CDCl3): 8.33 d, 2 H, J = 3.1 (py-H); 8.01 d, 2 H, 3J = 8.7
(Ar-H); 7.98 d, 2 H, J = 9.56 (Ar-H); 7.88 s, 2 H (py-H); 7.78 d, 2 H, 3J = 8.7 (Ar-H); 7.52 ddd,
2 H, J = 2.5, 5.5, 10.4 (Ar-H); 7.32–7.39 m , 4 H (Ar-H); 7.01–7.11 m , 4 H (Ar-H). 13C NMR
(75 MHz, CDCl3): 152.2, 148.3, 140.8, 138.1, 133.4, 132.7, 128.5, 128.3, 128.1, 127.2, 127.1,
126.8, 123.0, 122.95, 121.2, 92.6, 90.3. GC-MS-FAB: 456 (100) [M• +], 377 (18), 226 (16). For
C
34H20N2 (456.5) calculated: 89.45% C, 4.42% H, 6.14% N; foun d: 89.64% C, 4.56% H,
5.83% N. (RS)-8: m .p. 223–225 °C (ch loroform –h exan es).
2,2′-Bis(4-pyridyleth yn yl)-1,1′-bin aph th alen e (9)
A dried Sch len k flask con tain in g a stirrin g bar, capped with a rubber septum , was flam e-
dried un der vacuum , filled with argon an d cooled to room tem perature. Th e flask was
ch arged with 15 (200 m g, 0.66 m m ol), 4-brom opyridin e (256 m g, 1.65 m m ol), CuI (6.3 m g,
0.033 m m ol) an d [Pd(PPh 3)4] (36 m g, 0.033 m m ol), evacuated again an d filled with argon .
Toluen e (6 m l) an d Et3N (2 m l) were successively in jected in to th e flask. Th e dark brown re-
action m ixture was h eated to 80 °C for 2 h . After coolin g, water (3 m l) was added, th e m ix-
ture was poured in to 10% aqueous NH4Cl an d extracted th ree tim es with eth yl acetate
(10-m l portion s). Com bin ed organ ic fraction s were dried over an h ydrous Na2SO4. After
filtration an d evaporation of th e solven t, th e residue was ch rom atograph ed on silica gel
(h exan es–eth yl acetate, 2:1). (RS)- or (R)-9 (141 m g, 47%) as an off-wh ite solid was obtain ed.
Th e product decom poses with in several h ours even at –30 °C un der argon atm osph ere.
(R)-2,2′-Bis(4-pyridylethynyl)-1,1′-binaphthalene (9). M.p. 240–244 °C, [α ]2D1 –5.0 (c 0.85, ch loro-
form ), RF 0.06 (eth yl acetate–h exan es, 1:1). UV-VIS (MeOH (log ε)): 228 (5.60), 280 (5.64),
324 (5.48). IR (ch loroform ): 2260 m , 2100 m , 1580 s, 1500 m , 1470 m , 1410 m , 985 m , 910 m ,
805 s, 680 s, 650 m . 1H NMR (300 MHz, CDCl3): 8.34 d, 4 H, 3J = 4.4 (py-H); 8.03 d, 2 H, 3J =
8.5 (Ar-H); 8.00 d, 2 H, 3J = 8.2 (Ar-H); 7.78 d, 2 H, 3J = 8.5 (Ar-H); 7.51–7.58 m , 2 H (Ar-H);
Collect. Czech. Chem. Commun. 2007, Vol. 72, No. 8, pp. 1139–1157