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DOI: 10.1055/s-2006-941563
Ethynyl[2.2]paracyclophanes as Building Blocks for Extended π-Systems
Publication History
Publication Date:
22 May 2006 (online)
Abstract
Novel extended aromatic π-electron systems, the hydrocarbons 4, 5, 8, 11, and 13 are readily available by coupling reactions from the recently described ethynyl[2.2]paracyclophanes.
Key words
cyclophanes - acetylenes - coupling reactions - extended π-systems
- 1
Bondarenko L.Dix I.Hinrichs H.Hopf H. Synthesis 2004, 2751 ; and references quoted therein - 2
Minuti L.Taticchi A.Marrocchi A.Landi S.Gacs-Baitz E. Tetrahedron Lett. 2005, 46: 5735 - 3
Leung M.Viswanath MB.Chou P.-T.Pu S.-C.Lin H.-C.Jin B.-Y. J. Org. Chem. 2005, 70: 3560 - 5
Wityak J.Chan JB. Synth. Commun. 1991, 21: 977 - 8 For the preparation of mixed-valence compounds from a derivative of 11d, see:
Amthor S.Lambert C. J. Phys. Chem. A 2006, 110: 1177
References and Notes
Analytical Data.
Compound 4: 1H NMR (400.1 MHz, CDCl3): δ = 2.85-2.92 (m, 1 H, 2-H), 2.95-3.15 (m, 5 H, 1-, 9-, 10-H), 3.22-3.29 (m, 1 H, 1-H), 3.63-3.70 (m, 1 H, 2-H), 6.47-6.49 (m, 2 H, 8-, 12-H), 6.50-6.54 (m, 3 H, 7-, 13-, 16-H), 6.58 (d, 4
J = 1.67 Hz, 1 H, 5-H), 7.01-7.04 (dd, 4
J = 1.74 Hz, 3
J = 7.78 Hz, 1 H, 15-H), 7.35-7.41 (m, 3 H, 21-, 22-, 23-H), 7.57-7.60 (m, 2 H, 20-, 24-H). 13C NMR (100.6 MHz, CDCl3): δ = 142.44 (s, C-3), 139.68, 139.48 (s, C-6, -14), 139.34 (s, C-11), 136.98 (d, C-5), 133.85 (d, C-8), 133.28 (d, C-13), 132.74 (d, C-7), 132.71 (d, C-16), 132.42 (d, C-12), 131.43 (d, C-20, -24), 130.04 (d, C-15), 128.40 (d, C-21,
-23), 128.07 (d, C-22), 124.83 (s, C-4), 123.85 (s, C-19), 92.81 (s, C-18), 89.72 (s, C-17), 35.45 (t, C-10), 35.11 (t, C-9), 34.53 (t, C-2), 34.31 (t, C-1). IR (KBr): 3010 (w), 2923 (s), 1894 (m), 1598 (m), 1493 (s), 799 (m), 757 (vs), 692 (s) cm-1. UV (MeCN): λmax (lg ε) = 200 (4.69), 226 (4.36, sh), 298 (4.25) nm. MS (70 eV): m/z (%) = 308 (39) [M+], 204 (100), 104(23). Anal. Calcd for C24H20 (308.42): C, 90.46; H, 6.38. Found: C, 90.46; H, 6.29.
Compound 5: 1H NMR (400.1 MHz, CDCl3): δ = 2.94-2.99 (m, 2 H, 2-, 2′-H), 3.01-3.20 (m, 10 H, 1-, 9-, 10-, 1′-, 9′-, 10′-H), 3.27-3.34 (m, 2 H, 1-, 1′-H), 3.68-3.75 (m, 2 H, 2-, 2′-H), 6.50-6.59 (m, 10 H, 7-, 8-, 12-, 13-, 16-, 7′-, 8′-, 12′-, 13′-, 16′-H), 6.64 (d, 4
J = 1.41 Hz, 2 H, 5-, 5′-H), 7.07-7.10 (dd, 4
J = 1.73 Hz, 3
J = 7.78 Hz, 2 H, 15-, 15′-H). 13C NMR (100.6 MHz, CDCl3): δ = 141.93 (s, C-3, -3′), 139.76 (s, C-6, -6′), 139.40 (s, C-11, -14, -11′, -14′), 137.07 (d, C-5, -5′), 133.84 (d, C-8, -8′), 133.29 (d, C-13, -13′), 132.71, 132.46 (d, C-12, -16, -12′, -16′), 132.61 (d, C-7, -7′), 130.16 (d, C-15, -15′), 125.35 (s, C-4, -4′), 92.88 (s, C-17, -17′), 35.56 (t, C-10, -10′), 35.11 (t, C-9, -9′), 34.61, 34.60 (t, C-1, -2, -1′, -2′). IR (KBr): 3009 (w), 2927 (vs), 2194 (vw), 1636 (m), 1629 (m), 1625 (m), 1619 (m), 1500 (m), 1414 (m), 899 (m), 718 (m). cm-1. UV (MeCN): λmax (lg ε) = 198 (4.72), 220 (4.49, sh), 316 (4.09) nm. MS (70 eV): m/z (%) = 438 (74) [M+], 333 (26), 319 (19), 229 (100), 215 (52), 104 (72). Anal. Calcd for C34H30 (438.61): C, 89.46; H, 6.69. Found: C, 89.48; H, 7.04
Analytical Data for Compound 11d.
1H NMR (400.1 MHz, CDCl3): δ = 2.89-2.96 (m, 2 H, 2-, 10-H), 2.99-3.06 (m, 2 H, 1-, 9-H), 3.12-3.28 (m, 2 H, 1-, 9-H), 3.57-3.64 (m, 2 H, 2-, 10-H), 6.49 (d, 3
J = 7.90 Hz, 2 H, 8-, 16-H), 6.62 (d, 4
J = 1.79 Hz, 2 H, 5-, 13-H), 7.03-7.06 (dd, 4
J = 1.83 Hz, 3
J = 7.91 Hz, 2 H, 7-, 15-H), 7.34-7.41 (m, 6 H, 23-, 24-, 25-, 33-, 34-, 35-H), 7.57-7.60 (m, 4 H, 22-, 26-, 32-, 36-H). 13C NMR (100.6 MHz, CDCl3): δ = 143.69 (s, C-3, -11), 139.69 (s, C-6, -14), 138.12 (d, C-5, -13), 133.36 (d, C-8, -16), 132.41 (d, C-22, -26, -32, -36), 131.40 (d, C-7, -15), 129.13 (d, C-24, -34), 128.43 (d, C-23, -25, -33, -35), 123.17 (s, C-4, -12), 121.88 (s, C-21, -31), 82.13 (s, C-20, -30), 81.78 (s, C-17, -27), 74.23 (s, C-18, -19, -28, -29), 33.96 (t, C-2, -10), 33.87 (t, C-1, -9). IR (KBr): 3035 (w), 2929 (m), 2211 (w), 2141 (w), 1440 (m), 753 (vs), 685 (s) cm-1. UV (MeCN): λmax (lg ε) = 208 (4.84), 228 (4.75, sh), 248 (4.64), 302 (4.59), 322 (4.65), 344 (4.54) nm. MS (70 eV): m/z (%) = 456 (73) [M+], 441 (10), 426 (5), 228 (100). HRMS: m/z calcd for C36H24 (456.59): 456.188; found: 456.187 ± 2 ppm. Anal. Calcd for C36H24 (456.59): C, 93.07; H, 5.24. Found: C, 92.97; H, 5.22.
Analytical Data for Compound 13.
1H NMR (400.1 MHz, CDCl3): δ = 2.93-3.01 (m, 4 H, 9-, 10-, 9′-, 10′-H), 3.09-3.16 (m, 4 H, 9-, 10-, 9′-, 10′-H), 3.18-3.24 (m, 4 H, 1-, 2-, 1′-, 2′-H), 3.55-3.65 (m, 4 H, 1-, 2-, 1′-, 2′-H), 6.54-6.56 (dd, 4
J = 1.77 Hz, 3
J = 7.95 Hz, 2 H, 7-, 7′-H), 6.57-6.60 (m, 2 H, 13-, 13′-H), 6.67 (d, 4
J = 1.44 Hz, 2 H, 16-, 16′-H), 6.71 (br s, 2 H, 5-, 5′-H), 6.77-7.08 (m, 4 H, 8-, 13-, 8′-, 13′-H), 7.35-7.42 (m, 6 H, 23-, 24-, 25-, 23′-, 24′-, 25′-H), 7.58-7.61 (m, 4 H, 22-, 26-, 22′-, 26′-H). 13C NMR (100.6 MHz, CDCl3): δ = 143.95 (s, C-14, -14′), 143.83 (s, C-3, -3′), 139.70 (s, C-6, -11, -6′, -11′), 137.46 (d, C-16, -16′), 137.35 (d, C-5, -5′), 133.19 (d, C-12, -12′), 133.11 (d, C-7, -7′), 132.42 (d, C-22, -26, -22′, -26′), 131.08 (d, C-8, -13, -8′, -13′), 129.13 (d, C-24, -24′), 128.42 (d, C-23, -25, -23′, -25′), 124.02 (s, C-4, -4′), 123.89 (s, C-15, -15′), 121.86 (s, C-21, -21′), 82.30, 82.26 (s, C-17, -20, -17′, -20′), 81.62 (s, C-27, -27′), 77.53, 74.23 (s, C-18, -19, -28, -18′, -19′, -28′), 34.82 (t, C-9, -10, -9′, -10′), 33.11 (t, C-1, -2, -1′, -2′). IR (KBr): 3039 (vw), 2927 (s), 2208 (w), 2136 (w), 1489 (m), 1441 (m), 755 (vs), 723 (s), 688 (s) cm-1. UV (MeCN): λmax (lg ε) = 204 (4.99), 222 (4.99), 260 (4.66, sh), 270 (4.54, sh), 306 (4.56, sh), 324 (4.72), 344 (4.70), 363 (4.46, sh) nm. MS (70 eV): m/z (%) = 710 (6) [M+], 481 (9), 254 (35), 228 (100).