´
J. G. Rodrıguez, J. L. Tejedor
FULL PAPER
for 15 h. Flash chromatography on silica gel, eluting with hexane/
compound 10 (50 mg, 0.08 mmol), compound 11 (207 mg,
ethyl acetate (2:1), gave 6 as a yellow solid. M.p. 221Ϫ223 °C, 0.32 mmol), and freshly distilled triethylamine (40 mL) was stirred
550 mg (90%) yield. IR (KBr pellet): ν˜ ϭ 3474, 2931, 2226, 2198, for 40 h at 65 °C. Flash chromatography on silica gel, eluting with
1
2126, 1409, 838, 787 cmϪ1. H NMR: δ ϭ 1.65 (s, 6 H), 2.91 (s, 6 hexane/dichloromethane (1:2), gave 13 as a yellow solid. M.p.
H), 7.15 (d, J ϭ 7.7 Hz, 1 H), 7.62Ϫ7.43 (m, 8 H), 7.67 (s, 4 H),
208Ϫ209 °C, 128 mg (74%) yield. UV/Vis (CH2Cl2): λmax (ε) ϭ 239
7.77 (d, J ϭ 7.3 Hz, 1 H), 7.82 (d, J ϭ 7.3 Hz, 1 H), 7.84 (d, J ϭ nm (209830 mϪ1·cmϪ1), 268 s (115630), 293 s (82976), 367 (210700).
1
6.9 Hz, 1 H), 8.14 (d, J ϭ 8.1 Hz, 1 H), 8.29 (d, J ϭ 8.5 Hz, 1 H),
IR (KBr pellet): ν˜ ϭ 2226, 2208, 1460, 834, 794 cmϪ1. H NMR:
8.45 (d, J ϭ 8.1 Hz, 1 H), 8.48 (d, J ϭ 8.1 Hz, 1 H) ppm. 13C
δ ϭ 2.91 (s, 18 H), 7.15 (d, J ϭ 7.7 Hz, 3 H), 7.67 (s, 24 H),
NMR: δ ϭ 31.48, 45.37, 65.71, 81.88, 89.08, 89.18, 90.22, 93.76, 7.78Ϫ7.45 (m, 24 H), 7.85 (d, J ϭ 7.2 Hz, 12 H), 8.14 (d, J ϭ
94.35, 94.57, 95.77, 114.64, 120.90 (2 C), 121.23 (2 C), 121.129,
122.88, 123.02, 123.10, 123.69, 124.47, 125.39, 126.25 (2 C), 126.81,
127.17, 127.23, 128.65, 130.55, 131.13 (2 C), 131.33, 131.66 (2 C),
8.4 Hz, 3 H), 8.28 (d, J ϭ 8.7 Hz, 3 H), 8.40 (d, J ϭ 8.4 Hz, 6 H),
8.52 (d, J ϭ 8.7 Hz, 6 H) ppm. 13C NMR: δ ϭ 45.35, 88.97, 90.25
(2 C), 91.73 (2 C), 92.90 (2 C), 93.71 (2 C), 94.74, 114.65, 120.37,
131.72, 133.11 (2 C), 134.68, 151.44 ppm. C45H33NO (603.26): 120.87 (2 C), 121.46 (4 C), 122.88 (4 C), 124.44, 125.36, 126.22 (4
calcd. C 89.52, H 5.51, N 2.32; found C 89.34, H 5.75, N 2.49.
C), 126.50 (2 C), 126.81, 127.95 (2 C), 128.76, 131.22 (5 C), 131.66
(4 C), 132.14, 133.03 (2 C), 134.64 (2 C), 139.28, 151.41 ppm. MS
(FAB): m/z (%) ϭ 2157.7 (100) [Mϩ]. C168H99N3 (2157.78): calcd.
C 93.43, H 4.62, N 1.95; found C 93.35, H 4.80, N 1.70.
1-(Dimethylamino)-5-{[4-({5-[(4-ethynyl-1-phenyl)ethynyl]-1-naph-
thyl}ethynyl)-1-phenyl]ethynyl}naphthalene (7): Following the gen-
eral method used for the synthesis of 3, a mixture of compound
6 (600 mg, 1.0 mmol), dry toluene (150 mL), and finely powdered
1,3,5-Tris{1-(3-hydroxy-3-methyl-1-butyn)-5-naphthylethynyl}-
sodium hydroxide (4 mg, 0.10 mmol) was stirred for 6 h and then benzene (9): Following the general method used for the synthesis
filtered. The residual solid was purified by silica gel column chro-
matography, eluting with hexane/dichloromethane (1:1), to give 7
as a yellow solid. M.p. 180Ϫ181 °C, 543 mg (100%) yield. UV/Vis
of 4, a mixture of dichlorobis(triphenylphosphane)palladium(ii)
(141 mg, 0.20 mmol), cuprous iodide (3.8 mg, 0.02 mmol), 1,3,5-
triethynylbenzene (190 mg, 0.67 mmol), 4-(5-iodo-1-naphthyl)-2-
(CH2Cl2): λmax (ε) ϭ 245 nm (45498 mϪ1·cmϪ1), 271 (27404), 293 methyl-3-butyn-2-ol (1.3 g, 12.06 mmol), and freshly distilled tri-
(22705), 364 (47600). IR (KBr pellet): ν˜ ϭ 3301, 2924, 2212, 2107,
1405, 836, 792 cmϪ1 1H NMR: δ ϭ 2.91 (s, 6 H), 3.21 (s, 1 H),
7.15 (d, J ϭ 7.2 Hz, 1 H), 7.63Ϫ7.45 (m, 8 H), 7.67 (s, 4 H), 7.78
ethylamine (40 mL) was stirred for 48 h. Flash chromatography on
silica gel, eluting with hexane/ethyl acetate (1:1), gave 9 as a dark
amber oil, 431 mg (83%) yield. IR (film): ν˜ ϭ 3387, 1400, 956, 786
.
(d, J ϭ 7.2 Hz, 1 H), 7.83 (d, J ϭ 7.5 Hz, 1 H), 7.84 (d, J ϭ 6.9 Hz, cmϪ1. 1H NMR: δ ϭ 1.77 (s, 18 H), 7.43 (dd, J ϭ 8.2, J ϭ 7.0 Hz,
1 H), 8.15 (d, J ϭ 8.7 Hz, 1 H), 8.29 (d, J ϭ 8.1 Hz, 1 H), 8.45 (d,
6 H), 7.64 (d, J ϭ 7.0 Hz, 3 H), 7.70 (d, J ϭ 7.0 Hz, 3 H), 7.79 (s,
J ϭ 9.3 Hz, 1 H), 8.48 (d, J ϭ 8.4 Hz, 1 H) ppm. 13C NMR: δ ϭ 3 H), 8.22 (d, J ϭ 8.2 Hz, 3 H), 8.34 (d, J ϭ 8.2 Hz, 3 H) ppm.
45.36, 79.06, 83.24, 89.15, 89.28, 90.17, 93.72, 94.15, 94.57, 114.64,
120.88 (2 C), 121.12 (2 C), 121.27, 122.15, 122.98, 123.64, 124.43,
13C NMR: δ ϭ 31.48, 65.67, 79.95, 88.74, 92.92, 99.24, 120.65,
120.75, 124.09, 125.89, 125.99, 126.66, 127.07, 130.88, 131.03,
125.36, 126.25 (2 C), 126.81, 127.12, 127.28, 128.76, 130.51, 131.14, 132.82, 132.95, 134.03 ppm. C57H42O3 (774.31): calcd. C 88.34, H
131.52 (2 C), 131.62 (2 C), 132.16, 133.09 (2 C), 134.65, 151.41
ppm. MS (70 eV): m/z (%) ϭ 545 (100) [Mϩ], 544 (6), 273 (20).
C42H27N (545.21): calcd. C 92.45, H 4.99, N 2.57; found C 92.24,
H 5.28, N 2.80.
5.46; found C 88.56, H 5.70.
1,3,5-Tris{1-ethynyl-5-naphthyethynyl}benzene (10): Following the
general method used for the synthesis of 3, a mixture of 9 (150 mg,
0.19 mmol), dry toluene (40 mL), and finely powdered sodium hy-
droxide (1 mg, 0.02 mmol) was stirred for 20 h and then filtered.
The residual solid was purified by silica gel column chromatogra-
phy, eluting with hexane/dichloromethane (2:1), to give 10 as a
1,3,5-Tris{[5-({4-[(5-{dimethylamino}-1-naphthyl)ethynyl]-1-phen-
yl}ethynyl)-1-naphthyl]ethynyl}benzene (12): Following the general
method used for the synthesis of 4, a mixture of dichlorobis(tri-
phenylphosphane)palladium(ii) (76 mg, 0.11 mmol), cuprous iodide pale-yellow solid. M.p. Ͼ 300 °C (dark, dec.), 112 mg (100%) yield,
(2 mg, 0.01 mmol), compound 5 (240 mg, 0.54 mmol), 1,3,5-tri-
iodobenzene (80 mg, 0.18 mmol), and freshly distilled triethylamine
which shows very poor solubility in organic solvents. UV/Vis
(CH2Cl2): λmax (ε) ϭ 238 nm (190160 mϪ1·cmϪ1), 284 (30536), 340
(40 mL) was stirred for 48 h. Flash chromatography on silica gel, (1145708), 356 (112110). IR (KBr pellet): ν˜ ϭ 3288, 2210, 2102,
1
eluting with hexane/dichloromethane (1:2), gave 12 as an orange
967, 779 cmϪ1. H NMR (55 °C): δ ϭ 3.50 (s, 3 H), 7.58 (dd, J ϭ
solid. M.p. 205Ϫ208 °C, 203 mg (80%) yield. UV/Vis (CH2Cl2)) 8.1, J ϭ 7.2 Hz, 6 H), 7.82 (d, J ϭ 7.2 Hz, 3 H), 7.86 (d, J ϭ
λmax (ε) ϭ 241 nm (118900 mϪ1·cmϪ1), 266 s (60896), 289 s (48390) 6.9 Hz, 3 H), 7.91 (s, 3 H), 8.43 (d, J ϭ 8.1 Hz, 3 H), 8.50 (d, J ϭ
366 (102900). IR (KBr pellet): ν˜ ϭ 2939, 2207, 2131, 1405, 835,
7.8 Hz, 3 H) ppm. 13C NMR (55 °C): δ ϭ 81.62, 82.43, 88.87,
786 cmϪ1. 1H NMR: δ ϭ 2.92 (s, 18 H), 7.15 (d, J ϭ 6.6 Hz, 3 H), 93.11, 120.63, 121.06, 124.52, 126.20, 126.34, 127.42, 127.49,
7.78Ϫ7.41 (m, 12 H), 7.68 (s, 12 H), 7.77 (d, J ϭ 7.2 Hz, 3 H), 7.87 131.40, 131.96 (3 C), 134.32 ppm. MS (MALDI-TOF): m/z (%) ϭ
(d, J ϭ 6.6 Hz, 3 H), 7.89 (d, J ϭ 6.3 Hz, 3 H), 7.94 (s, 3 H), 8.15 600.0. C48H24 (600.19): calcd. C 95.97, H 4.03; found C 96.08, H
(d, J ϭ 8.1 Hz, 3 H), 8.29 (d, J ϭ 8.7 Hz, 3 H), 8.52 (d, J ϭ 8.1 Hz,
6 H) ppm. 13C NMR: δ ϭ 45.38, 88.80, 89.16, 90.23, 93.04, 93.76,
94.65, 114.65, 120.95, 121.36, 123.01, 123.70 (2 C), 124.30 (2 C),
124.46, 126.27, 126.40, 126.82, 128.58, 128.63, 128.72 (2 C), 130.53,
131.29 (2 C), 131.67 (2 C), 133.11 (2 C), 133.55, 134.86, 151.43
ppm. MS (FABϩ): m/z (%) ϭ 1407.5. C108H69N3 (1407.55): calcd.
C 92.08, H 4.94, N 2.98; found C 92.25, H 5.10, N 2.81.
4.32.
1-(Dimethylamino)-5-{[4-({5-[(4-iodo-1-phenyl)ethynyl]-1-naphthyl}-
ethynyl)-1-phenyl]ethynyl}naphthalene (11): Following the general
method used for the synthesis of 4, a mixture of dichlorobis(tri-
phenylphosphane)palladium(ii) (16 mg, 0.023 mmol), cuprous iod-
ide (0.4 mg, 0.002 mmol), compound 5 (100 mg, 0.23 mmol), 1,4-
diiodobenzene (303 mg, 0.92 mmol), and freshly distilled triethyl-
1,3,5-Tris({5-[(4-{[5-({4-[(5-{dimethylamino}-1-naphthyl)ethynyl]-1- amine (100 mL) was stirred for 15 h. Flash chromatography on sil-
phenyl}ethynyl)-1-naphthyl]ethynyl}-1-phenyl)ethynyl]-1-naphthyl}- ica gel, eluting with hexane/dichloromethane (1:1), gave 11 as a
ethynyl)benzene (13): Following the general method used for the
synthesis of 4, a mixture of dichlorobis(triphenylphosphane)pallad-
yellow solid. M.p. 203Ϫ204 °C, 135 mg (91%) yield. IR (KBr pel-
1
let): ν˜ ϭ 2924, 1405, 962, 837, 788 cmϪ1. H NMR: δ ϭ 2.91 (s, 6
ium(ii) (17 mg, 0.024 mmol), cuprous iodide (0.5 mg, 0.002 mmol), H), 7.15 (d, J ϭ 7.3 Hz, 1 H), 7.38 (d, J ϭ 8.5 Hz, 2 H), 7.85Ϫ7.46
Eur. J. Org. Chem. 2005, 360Ϫ367