Notes
J . Org. Chem., Vol. 66, No. 5, 2001 1913
matography or by HPLC method. In the case of inseparable
product mixtures, product ratios were calculated by 1H NMR
method.
4-[(4-Nitr oph en yl)eth yn yl]-1,1′-biph en yl (1e). Eluent, hex-
ane/EtOAc ) 4/1; yellow solid; mp 184-185 °C; 1H NMR δ 7.27-
7.42 (m, 3 H), 7.50-7.56 (m, 2 H), 7.56 (s, 4 H), 7.61 (t, 2 H, J
) 8 Hz), 8.15 (t, 2 H, J ) 8 Hz); 13C NMR δ 88.2, 94.7, 120.9,
123.7, 127.0, 127.2, 127.9, 128.9, 130.3, 132.2, 132.3, 140.0, 142.0,
146.9; MS (EI, m/z) 299 (M+, 100). Anal. Calcd for C20H13NO2:
C, 80.25; H, 4.38; N, 4.68. Found: C, 79.69; H, 4.77; N, 4.54.
1-Nitr o-4-(p h en yleth yn yl)ben zen e (1f).15 Eluent, hexane/
EtOAc ) 8/1; yellow solid; mp 111-113 °C (lit.15 118-120 °C);
1H NMR δ 7.35-7.45 (m, 3 H), 7.50-7.58 (m, 2 H), 7.66 (t, 2 H,
J ) 8 Hz), 8.22 (t, 2 H, J ) 8 Hz); 13C NMR δ 87.5, 94.7, 122.0,
123.6, 128.5, 129.2, 130.2, 131.8, 132.2, 146.9; MS (EI, m/z) 223
(M+, 100).
1,4-Di(ph en yleth yn yl)ben zen e (1g).19 Eluent, hexane; white
solid; mp 178-180 °C (lit.19 180-181 °C); 1H NMR δ 7.30-7.40
(m, 6 H), 7.45-7.60 (m, 4 H), 7.52 (s, 4 H); 13C NMR δ 89.1,
91.2, 123.0, 123.1, 128.4, 128.45, 131.5, 131.6; MS (EI, m/z) 278
(M+, 100).
Gen er a l P r oced u r e for th e Son oga sh ir a Cou p lin g Be-
t w een Acet ylen ic Alcoh ol 5 a n d Ar yl Br om id e 7 Un d er
P h a se Tr a n sfer Con d ition s (P T Meth od ). A degassed mix-
ture of aryl bromide (3.0 mmol), acetylenic alcohol 5 (3.0 mmol
per bromine atom), copper(I) iodide (0.3 mmol), palladium(II)
dichlorobistriphenylphosphine (0.3 mmol), and tetrabutylam-
monium iodide (0.3 mmol) in a heterogeneous mixture of toluene
(5.0 mL) and aqueous sodium hydroxide (5 M, 2.0 mL) was
placed in a sealed tube under nitrogen. The mixture was heated
at 80 °C for 24 h and then cooled to room temperature. The
solution was filtered over a pad of silica gel, and the filtrate was
concentrated under reduced pressure. The residue was chro-
matographed on silica gel, eluting with the appropriate solvent
to give the various products.
1,4-Dip h en yl-1,3-bu ta d iyn e (4a ).14 Eluent, hexane; white
1
solid; mp 85-86 °C (lit.14 85-86 °C); H NMR δ 7.26-7.35 (m,
4(4′-Br om op h en yl)tola n (8).20 (See footnote e in Table 1.)
Eluent, hexane; pale yellow solid; mp 196-200 °C (dec); 1H NMR
δ 7.32-7.40 (m, 4 H), 7.47 (d, 2 H, J ) 9 Hz), 7.51-7.63 (m, 8
H); MS (EI, m/z) 332/334 (M+, 35).
6 H), 7.45-7.50 (m, 4 H); 13C NMR δ 73.9, 81.6, 121.8, 128.5,
129.2, 132.5; MS (EI, m/z) 202 (M+, 20).
1-(P h en ylet h yn yl)n a p h t h a len e (1a ).15 Eluent, hexane;
1
colorless oil; H NMR δ 7.35-7.70 (m, 8 H), 7.78 (d, 1 H, J ) 8
4,4′-Bis(p h en yleth yn yl)bip h en yl (1h ).21 Eluent, hexane;
Hz), 7.89 (t, 2 H, J ) 8 Hz), 8.46 (d, 1 H, J ) 8 Hz); MS (EI,
1
pale yellow solid; mp 250-251 °C (dec) (lit.21 252-254 °C); H
m/z) 228 (M+, 17).
NMR δ 7.33-7.40 (m, 6 H), 7.53-7.59 (m, 4 H), 7.61 (s, 8 H);
3-Nitr o-1-(p h en yleth yn yl)ben zen e (1b).16 Eluent, hexane/
MS (EI, m/z) 354 (M+, 7).
1
EtOAc ) 20/1; yellow solid; mp 68-70 °C (lit.16 56-57 °C); H
4,4′-Bis(p h en yleth yn yl)d ip h en yleth yn e (1i). Eluent, hex-
NMR δ 7.24-7.30 (m, 3 H), 7.40 (t, 1 H, J ) 8 Hz), 7.40-7.47
(m, 2 H), 7.70 (d, 1 H, J ) 8 Hz), 8.05 (d, 1 H, J ) 8 Hz), 8.25
(s, 1 H); 13C NMR δ 86.8, 91.9, 122.1, 122.8, 125.1, 126.3, 128.5,
129.0, 129.3, 131.7, 137.2, 148.1; MS (EI, m/z) 223 (M+, 100).
4-(P h en yleth yn yl)-1,1′-bip h en yl (1c).17 Eluent, hexane;
white solid; mp 162-163 °C (lit.17 165-167 °C); 1H NMR δ 7.31-
7.38 (m, 3 H), 7.49 (t, 2 H, J ) 7 Hz), 7.54-7.65 (m, 8 H); 13C
NMR δ 89.3, 90.0, 122.1, 123.3, 127.0, 127.6, 128.2, 128.3, 128.8,
131.6, 132.0, 140.3, 140.9; MS (EI, m/z) 254 (M+, 18).
1
ane; pale yellow solid; mp 259-260 °C (dec); H NMR δ 7.31-
7.40 (m, 6 H), 7.48-7.60 (m, 4 H), 7.52 (s, 8 H); MS (EI, m/z)
378 (M+, 32); HRMS (EI) 378.1386 (C30H18 requires 378.1408).
1,3,5-Tr is(p h en yleth yn yl)ben zen e (1j).22 Eluent, hexane;
white solid; mp 141-142 °C (lit.22 144-145 °C); 1H NMR δ 7.32-
7.40 (m, 9 H), 7.50-7.58 (m, 6 H), 7.66 (s, 3 H); 13C NMR δ 87.8,
90.5, 122.7, 124.0, 128.4, 128.6, 131.6, 134.0; MS (EI, m/z) 378
(M+, 100).
4-(P h en yleth yn yl)ben zop h en on e (1d ).18 Eluent, hexane/
1
Ack n ow led gm en t. We thank the Research Grants
Council, HKSAR, for the financial support (CUHK4203/
97P).
EtOAc ) 10/1; yellow solid; mp 109-111 °C; H NMR δ 7.35-
7.40 (m, 3 H), 7.45-7.65 (m, 7 H), 7.78-7.84 (m, 4 H); 13C NMR
δ 88.7, 92.5, 122.7, 127.6, 128.4, 128.5, 128.8, 130.0, 130.1, 131.4,
131.8, 132.6, 136.7, 137.4, 196.0; MS (EI, m/z) 282 (M+, 12).
J O001538Q
(14) Crisp, G. T.; Flynn, B. L. J . Org. Chem. 1993, 58, 6614.
(15) Okuro, K.; Furuune, M.; Enna, M.; Miura, M.; Nomura, M. J .
Org. Chem. 1993, 58, 4716.
(16) Colvin, E. W.; Hamill, B. J . J . Chem. Soc., Perkin Trans. 1 1977,
869.
(19) Nguyen, P.; Yuan, Z.; Agocs, L.; Lesley, G.; Marder, T. B. Inorg.
Chim. Acta 1994, 220, 289.
(20) Ku¨bel, C.; Chen, S.-L.; Mu¨llen, K. Macromolecules 1998, 31,
6014.
(17) Uno, H.; Sakamoto, K.; Suzuki, H. Bull. Chem. Soc. J pn. 1992,
65, 218.
(18) Fu¨rstner, A.; Seidel, G. Tetrahedron 1995, 51, 11165.
(21) Aitken, R. A.; Drysdale, M. J .; Hill, L.; Lumbard, K. W.;
MacCallum, J . R.; Seth, S. Tetrahedron 1999, 55, 11039.
(22) J ones, K. M.; Keller, T. M. Polymer 1995, 36, 187.