Building Blocks for Novel Oligoazulenes
FULL PAPER
Pentamer 30: Compounds 4b and 28 afforded 30 as black crystals
Dimer 34, Trimer 38 and Tetramer 39: Compounds 37 and 31 af-
forded a mixture of 34, 38 and 39, which were separated by column
(26%), m.p. Ͼ 270 °C. FT-IR (KBr): ν = 2959 cm–1, 2887 (C–H),
˜
1575, 1459, 1403, 1361, 1239, 863. 1H NMR (300 MHz, CDCl3, chromatography on alumina (BII-III) with CH2Cl2/n-hexane (1:3).
25 °C): δ = 1.50 [s, 18 H, C(CH3)3], 1.52 [s, 18 H, C(CH3)3], 1.53
Dimer 34: Brown needles (68%), m.p. 175–177 °C. FT-IR (KBr): ν
˜
3
[s, 9 H, C(CH3)3], 7.32 (d, JH,H = 4.0 Hz, 2 H, 3ЈЈ-H), 7.42 (dd,
= 2960 cm–1, 2924, 2856 (C–H), 2132 (CϵC), 1560, 854, 835. 1H
NMR (300 MHz, CDCl3, 25 °C): δ = 0.33 [s, 9 H, Si(CH3)3], 1.47
3JH,H = 10.3, 1.4 Hz, 2 H, 5ЈЈ-H), 7.53–7.59 (m, 8 H, 5-, 5Ј-, 7-,
3
7Ј-, 7ЈЈ-H), 8.03 (d, JH,H = 4.0 Hz, 2 H, 2ЈЈ-H), 8.20 (s, 2 H, 2Ј-
[s, 18 H, C(CH3)3], 7.48–7.53 (m, 4 H, 5-, 5Ј-, 7-, 7Ј-H), 8.03, 8.05
3
H), 8.23 (s, 1 H, 2-H), 8.29 (d, JH,H = 10.3 Hz, 2 H, 4ЈЈ-H), 8.65–
3
(2 s, each 1 H, 2-, 2Ј- H), 8.14, 8.50, 8.56, 8.57 (4 d, JH,H
=
8.73 (m, 8 H, 4-, 4Ј-, 8-, 8Ј-, 8ЈЈ-H) ppm. 13C NMR (75.40 MHz,
CDCl3, 25 °C): δ = 32.0, 32.0 [C(CH3)3], 39.1, 39.3 [C(CH3)3], 89.6,
89.9, 89.9, 90.9 (CϵC), 111.1, 111.2, 111.3, 111.7, 117.7, 122.8,
123.2, 124.2, 135.8, 136.5, 136.8, 138.7, 139.9, 140.2, 140.4, 140.5,
140.6, 140.7, 163.6, 165.1 (CAz) ppm. UV/Vis (dichloromethane):
λmax (log ε) = 294 nm (5.03), 313 (5.01), 329 (5.01), 409 (4.87), 625
(3.44). MS (FD): m/z (%) = 1008 (100) [M+], 505 (5). C78H72
(1009.4): calcd. C 92.81, H 7.19; found C 92.23, H 7.81.
10.6 Hz, each 1 H, 4-, 4Ј-, 8-, 8Ј-H), ppm. 13C NMR (75.40 MHz,
CDCl3, 25 °C): δ = 0.5 [Si(CH3)3], 31.9 [C(CH3)3], 39.0 [C(CH3)3],
88.8, 90.1, 98.5, 100.9 (CϵC), 73.8, 110.0, 110.6, 112.8, 123.1,
123.5, 124.0, 135.4, 136.1, 136.2, 138.5, 139.5, 140.2, 141.0, 141.5,
144.6, 164.1, 164.3 (CAz) ppm. UV/Vis (dichloromethane): λmax (log
ε) = 249 nm (4.62), 288 (4.79), 307 (4.76), 323 (4.70), 333 (4.68),
422 (4.31), 435 (4.31), 460 (4.31), 626 (3.08). MS (FD): m/z (%) =
612 (3) [M+], 78 (35). C35H37ISi (612.7): calcd. C 68.62, H 6.09;
found C 68.74, H 6.07.
Trimer 32: Compounds 6b and 31 afforded 32 as green crystals
(43%), m.p. Ͼ 270 °C. FT-IR (KBr): ν = 2960 cm–1, 2928, 2856
˜
Trimer 38: Black crystals (13%), m.p. Ͼ 270 °C. FT-IR (KBr): ν =
˜
(C–H), 2138 (CϵC), 1576, 1359, 1247, 1096, 840, 759. 1H NMR
(300 MHz, CDCl3, 25 °C): δ = 0.36 [s, 18 H, Si(CH3)3], 1.49 [s, 18
2960 cm–1, 2866 (C–H), 2132 (CϵC), 1576, 1560, 1456, 1400, 840.
1H NMR (300 MHz, CDCl3, 25 °C): δ = 0.33 [s, 9 H, Si(CH3)3],
1.48 [s, 18 H, C(CH3)3], 1.49 [s, 9 H, C(CH3)3], 7.48–7.55 (m, 6 H,
5-, 5Ј-, 5ЈЈ-, 7-, 7Ј-, 7ЈЈ-H), 8.06, 8.08, 8.15 (3 s, each 1 H, 2-, 2Ј-,
2ЈЈ-H), 8.16–8.64 (m, 6 H, 4-, 4Ј-, 4ЈЈ-, 8-, 8Ј-, 8ЈЈ-H) ppm. 13C
NMR (75.40 MHz, CDCl3, 25 °C): δ = 0.5 [Si(CH3)3], 31.9
[C(CH3)3], 39.0 [C(CH3)3], 88.9, 89.3, 89.4, 90.2, 98.5, 100.9
(CϵC), 73.9, 109.9, 110.7, 110.9, 111.0, 112.9, 123.1, 123.5, 123.7,
124.0, 135.4, 136.1, 136.2, 136.3, 138.5, 139.5, 140.2, 140.3, 140.4,
140.5, 141.0, 141.4, 144.7, 164.1, 164.3 (CAz) ppm. UV/Vis (dichlo-
romethane): λmax (log ε) = 248 nm (4.71), 297 (4.90), 325 (4.84),
330 (4.84) sh, 420 (4.54), 455 (4.48) sh, 631 (3.22). MS (FD): m/z
(%) = 818 (100) [M+]. C51H51ISi (819.0): calcd. C 74.80, H 6.28;
found C 75.20, H 6.54.
H, C(CH3)3], 1.50 [s, 9 H, C(CH3)3], 7.48–7.56 (m, 6 H, 5-, 5Ј-,
3
7-, 7Ј-H), 8.09 (s, 2 H, 2Ј-H), 8.19 (s, 1 H, 2-H), 8.48 (d, JH,H
=
3
10.6 Hz, 2 H, 4Ј-H), 8.61 (d, JH,H = 10.7 Hz, 2 H, 8Ј-H), 8.64 (d,
3JH,H = 10.5 Hz, 2 H, 4-, 8-H) ppm. 13C NMR (75.40 MHz,
CDCl3, 25 °C): δ = 0.5 [Si(CH3)3], 31.9 [C(CH3)3], 39.0 [C(CH3)3],
89.4, 98.5, 101.0 (CϵC), 110.0, 110.8, 111.1, 123.6, 124.0, 136.1,
136.2, 136.3, 140.3, 140.5, 141.0, 141.5, 164.3 (CAz) ppm. UV/Vis
(dichloromethane): λmax (log ε) = 250 nm (4.79), 301 (5.02), 333
(4.94), 420 (4.56), 457 (4.48), 631 (3.26). MS (FD): m/z (%) = 788
(100) [M+], 394 (9). C56H60Si2 (789.3): calcd. C 85.22, H 7.66;
found C 85.27, H 7.72.
Pentamer 35: Compounds 33 and 31 afforded 35 as green crystals
(31%), m.p. Ͼ 270 °C. FT-IR (KBr): ν = 2960 cm–1, 2928, 2852
˜
Tetramer 39: Black crystals (6%), m.p. Ͼ 270 °C. FT-IR (KBr): ν
˜
1
= 2960 cm–1, 2870 (C–H), 2136 (CϵC), 1561, 858, 835. H NMR
(C–H), 2132 (CϵC), 1654, 1560, 1542, 1508, 1388, 1356, 1292,
1242, 852, 836. 1H NMR (300 MHz, CDCl3, 25 °C): δ = 0.34 [s, 18
H, Si(CH3)3], 1.49 [s, 18 H, C(CH3)3], 1.50 [s, 18 H, C(CH3)3], 1.51
[s, 9 H, C(CH3)3], 7.50–7.56 (m, 10 H, 5-, 5Ј-, 5ЈЈ-, 7-, 7Ј-, 7ЈЈ-H),
8.08 (s, 2 H, 2ЈЈ-H), 8.20 (s, 2 H, 2Ј-H), 8.22 (s, 1 H, 2-H), 8.47 (d,
3JH,H = 10.6 Hz, 2 H, 4ЈЈ-H), 8.59–8.66 (m, 8 H, 4-, 4Ј-, 8-, 8Ј-, 8ЈЈ-
H) ppm. 13C NMR (75.40 MHz, CDCl3, 25 °C): δ = 0.5 [Si(CH3)3],
31.9 [C(CH3)3], 39.0 [C(CH3)3], 89.4, 89.5, 98.5, 101.0 (CϵC),
109.9, 110.8, 111.0, 111.1, 123.6, 124.0, 136.0, 136.2, 136.3, 140.3,
140.5, 141.0, 141.5, 164.3 (CAz) ppm. UV/Vis (dichloromethane):
λmax (log ε) = 249 nm (4.95), 303 (5.18), 330 (5.10), 422 (4.83), 458
(4.75) sh, 636 (3.48). MS (FD): m/z (%) = 1200 (3) [M+], 600 (100).
C88H88Si2 (1201.8): calcd. C 87.95, H 7.38; found C 88.00, H 7.42.
(300 MHz, CDCl3, 25 °C): δ = 0.34 [s, 9 H, Si(CH3)3], 1.49 [s, 18
H, C(CH3)3], 1.51 [s, 18 H, C(CH3)3], 7.50–7.56 (m, 8 H, 5-, 5Ј-,
5ЈЈ-, 5ЈЈЈ-, 7-, 7Ј-, 7ЈЈ-, 7ЈЈЈ-H), 8.09 (s, 1 H, 2-H), 8.13 (s, 1 H, 2ЈЈЈ-
3
H), 8.16 (d, JH,H = 10.8 Hz, 1 H, 4-H), 8.19 (s, 2 H, 2Ј-, 2ЈЈ-H),
3
8.46 (d, JH,H = 10.6 Hz, 1 H, 4ЈЈЈ-H), 8.58–8.65 (m, 6 H, 4Ј-,
4ЈЈ-, 8-, 8Ј-, 8ЈЈ-, 8ЈЈЈ-H) ppm. 13C NMR (75.40 MHz, CDCl3,
25 °C): δ = 0.5 [Si(CH3)3], 31.9 [C(CH3)3], 39.0 [C(CH3)3], 89.0,
89.4, 89.5, 90.2, 98.5, 101.0 (CϵC), 73.8, 110.0, 110.8, 111.0, 111.1,
112.9, 123.1, 123.6, 123.9, 135.4, 136.0, 136.2, 138.5, 139.6, 140.3,
140.5, 141.0, 141.5, 144.7, 164.1, 164.3 (CAz) ppm. UV/Vis (dichlo-
romethane): λmax (log ε) = 247 nm (4.86), 299 (5.05), 330 (4.98) sh,
422 (4.74), 455 (4.66) sh, 633 (3.39). MS (FD): m/z (%) = 1024
(100) [M+], 513 (85), 79 (75). C67H65ISi (1025.2): calcd. C 78.49, H
6.39; found C 78.12, H 6.35.
Heptamer 36: Compounds 33 and 34 afforded 36 as brownish-black
crystals (19%), m.p. Ͼ 270 °C. FT-IR (KBr): ν = 2960 cm–1, 2920,
˜
2862 (C–H), 2135 (CϵC), 1578, 1361, 1246, 854, 836. 1H NMR 6-tert-Butyl-1-[(6-tert-butylazulen-1-yl)ethynyl]-3-(trimethylsilyl-
(300 MHz, CDCl3, 25 °C): δ = 0.34 [s, 18 H, Si(CH3)3], 1.43 [s, 18
ethynyl)azulene (40): Compounds 3b and 31 afforded 40 as greenish
H, C(CH3)3], 1.50 [s, 18 H, C(CH3)3], 1.52 [s, 27 H, C(CH3)3], 7.49– blue crystals (91%), m.p. 177–179 °C. FT-IR (KBr): ν = 2960 cm–1
˜
7.57 (m, 14 H, 5-, 5Ј-, 5ЈЈ-, 5ЈЈЈ-, 7-, 7Ј-, 7ЈЈ-, 7ЈЈЈ-H), 8.08 (s, 2 H, (C–H), 2135 (CϵC), 1577, 1460, 1430, 1403, 1357, 1248, 1084, 994,
1
2ЈЈЈ-H), 8.20 (s, 2 H, 2ЈЈ-H), 8.22 (s, 2 H, 2Ј-H), 8.23 (s, 1 H, 2-H),
8.47 (d, JH,H = 10.6 Hz, 2 H, 4ЈЈЈ-H), 8.60–8.68 (m, 12 H, 4-,
919, 896, 840, 759, 682. H NMR (300 MHz, CDCl3, 25 °C): δ =
3
0.36 [s, 9 H, Si(CH3)3], 1.48 [s, 9 H, C(CH3)3], 1.49 [s, 9 H,
4Ј-, 4ЈЈ-, 8-, 8Ј-, 8ЈЈ-, 8ЈЈЈ-H) ppm. 13C NMR (75.40 MHz, CDCl3, C(CH3)3], 7.29 (d, JH,H = 4.0 Hz, 1 H, 3Ј-H), 7.38 (dd, JH,H
=
3
3
4
25 °C): δ = 0.5 [Si(CH3)3], 31.9, 32.0 [C(CH3)3], 39.0 [C(CH3)3], 10.3, JH,H = 1.7 Hz, 1 H, 5Ј-H), 7.44–7.54 (m, 3 H, 5-, 7-, 7Ј-H),
3
89.4, 89.6, 98.5, 101.0 (CϵC), 110.0, 110.8, 111.1, 111.2, 123.6,
123.9, 136.0, 136.2, 140.3, 140.5, 141.0, 141.5, 164.3 (CAz) ppm.
UV/Vis (dichloromethane): λmax (log ε) = 249 nm (5.08), 305 (5.30),
8.01 (d, JH,H = 4.0 Hz, 1 H, 2Ј-H), 8.08 (s, 1 H, 2-H), 8.23 (d,
3JH,H = 10.3 Hz, 1 H, 4Ј-H), 8.47 (d, JH,H = 10.6 Hz, 1 H, 4-H),
3
8.65 (m, 2 H, 8-, 8Ј-H) ppm. 13C NMR (75.40 MHz, CDCl3,
330 (5.24), 417 (5.00), 459 (4.91) sh, 640 (3.63). MS (FD): m/z (%) 25 °C): δ = 0.5 [Si(CH3)3], 31.9, 32.0 [C(CH3)3], 38.9, 39.0
= 1612 (100) [M+], 806 (20). C120H116Si2 (1614.4): calcd. C 89.28,
H 7.24; found C 89.07, H 7.32.
[C(CH3)3], 89.2, 90.2, 98.4, 101.1 (CϵC), 109.9, 111.0, 111.2, 117.4,
122.3, 122.6, 123.8, 135.5, 136.0, 136.3, 136.4, 136.6, 138.6, 139.7,
Eur. J. Org. Chem. 2006, 791–802
© 2006 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.eurjoc.org
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