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DOI: 10.1055/s-2006-939730
Synthesis and Spectroscopic Properties of a Novel Bis-spirocalixarene
Publication History
Publication Date:
22 May 2006 (online)
Abstract
A convenient synthesis of the first spiro-bound calix[4]arene containing fluorenyl moieties at the para-position is presented. Dynamic NMR effects of the spiro-calixarene 4 are in accord with a preferred partial-cone conformation.
Key words
calixarenes - oxidation - spiro compounds - ligands - iron
- 1
Mitschke U.Bäuerle P. J. Mater. Chem. 2000, 10: 1471 ; and references cited herein -
2a
Gutsche CD. Calixarenes The Royal Society of Chemistry; Cambridge: 1989. -
2b
Calixarenes: A Versatile Class of Macrocyclic Compounds
Vicens J.Böhmer V. Kluwer; Dordrecht: 1991. -
2c
Gutsche CD. Calixarenes Revisited The Royal Society of Chemistry; Cambridge: 1998. -
2d
Calixarenes 2001
Asfari Z.Böhmer V.Harrowfield J.Vicens J. Kluwer; Dordrecht: 2001. - 3 Compound 1 was synthesized according to a method previously described:
Dyker G.Mastalerz M.Merz K. Eur. J. Org. Chem. 2003, 4355 - Suzuki-type cross-couplings with calix[4]arenes were previously described by:
-
4a
Xu B.Miao Y.-J.Swager TM. J. Org. Chem. 1998, 63: 8561 -
4b
Larsen M.Krebs FC.Harrit N.Jørgensen M. J. Chem. Soc., Perkin Trans. 2 1999, 1749 -
4c
Wong MS.Xia PF.Lo PK.Sun XH.Wong WY.Shuang S. J. Org. Chem. 2006, 71: 940 - 5 O-Alkylated halocalixarenes gave yields > 83% in the reaction with 2-biphenylboronic acid:
Mastalerz M. PhD Thesis Bochum; Germany: 2005. - 6 For a review on related oxidative arylation reactions see:
Waldvogel SR.Mirk D. In Handbook of C-H Transformations Wiley-VCH; Weinheim: 2005. p.251-261 - 7
Jaime C.de Mendoza J.Prados P.Nieto PM.Sãnchez C. J. Org. Chem. 1991, 56: 3372 - 8
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Douadi T.Cariou M.Simonet J. Tetrahedron 1996, 52: 4449 - For other examples of spiro-annulated products from calix[4]arenes, see:
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Litwak AM.Biali SE. J. Org. Chem. 1992, 57: 1943 -
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Georghiou PE.Ashram M.Clase HJ.Brisdon JN. J. Org. Chem. 1998, 63: 1819
References and Notes
Calixarene 2: To a solution of calixarene 1 (300 mg, 0.52 mmol) in 2-butanone (20 mL) NBS (1.135 g, 6.34 mmol) was added and the mixture was stirred for 20 h at r.t. An aq solution of Na2S2O3 (20%, 20 mL) was added and the mix-ture was stirred for 20 min before the layers were separated. The organic layer was washed with H2O (2 × 25 mL) and brine (25 mL), then dried over MgSO4. The solvents were removed on a rotary evaporator to give 430 mg of an orange colored residue. After flash chromatography (PE-EtOAc, 2:1; R
f
0.26) and subsequent drying in vacuo (100 °C, 1 mbar), calixarene 2 was isolated as a colorless solid; yield: 230 mg (60%).
Mp 174 °C. IR (KBr): 3448, 3059, 2929, 1594, 1573, 1469, 1456, 1428, 1285, 1264, 1236, 1189, 1141, 1098, 1071, 990, 962, 914, 880, 858, 805, 776, 735 cm-1. 1H NMR (400.1 MHz, CDCl3): δ = 3.39 (d, J = 14.0 Hz, 4 H), 3.96 (d, J = 13.5 Hz, 4 H), 6.95 (t, J = 7.5 Hz, 2 H), 7.01 (d, J = 7.0 Hz, 4 H), 7.09 (m, 4 H), 7.14 (s, 4 H), 7.85 (t, J = 6.8 Hz, 2 H, Py-4-H), 8.25 (d, J = 3.5 Hz, 2 H, Py-6-H). 13C NMR (100.6 MHz, CDCl3): δ = 32.24 (t), 110.67 (d), 111.14 (s), 118.71 (d), 126.54 (d), 129.49 (d), 130.13 (d), 131.18 (s), 132.77 (s), 140.03 (d, Py-C-4), 147.32 (s), 147.81 (d, Py-C-6), 152.12 (s), 162.92 (s, Py-C-2). MS (FAB): m/z (%) = 737 (26)[M + H+]. UV/Vis (CH3CN): λmax (log ε) = 218 (4.6), 268 (3.9), 290 (sh, 3.7) nm. Anal. Calcd for C38H28Br2N2O4·H2O (754.48): C, 60.49; H, 4.01; N, 3.71. Found: C, 60.76; H, 3.79; N, 3.60.
Calixarene 3: To a solution of bromocalixarene 2 (220 mg, 0.30 mmol) and 2-biphenylboronic acid (225 mg, 1.136 mmol) in THF (10 mL) an aq solution of K2CO3 (2 N, 10 mL) and Pd(PPh3)4 (115 mg, 99 µmol) were added and the mixture was stirred at 120 °C under argon in a screw-capped flask for 20 h. The organic layer was washed with brine (25 mL) and dried over MgSO4. THF was removed on a rotary evaporator to give 500 mg of a brown solid. After flash-chromatography (PE-EtOAc, 4:1; R
f
0.16) and subsequent drying in vacuo, calixarene 3 was isolated as a colorless solid; yield: 120 mg (46%).
Mp 145-160 °C. IR (KBr): 3448, 3050, 2925, 1593, 1468, 1457, 1428, 1320, 1280, 1237, 1183, 1142, 1083, 919, 876, 804, 762, 747, 701 cm-1. 1H NMR (400.1 MHz, CDCl3): δ = 3.15 (d, J = 13.9 Hz, 4 H), 3.97 (d, J = 13.9 Hz, 4 H), 6.51 (d, J = 7.6 Hz, 4 H), 6.71 (s, 2 H), 6.77 (t, J = 7.6 Hz, 2 H), 6.86, (s, 4 H), 7.00 (ddd, 3
J = 7.0 Hz, 3
J = 5.0 Hz, 4
J = 0.8 Hz, 2 H, Py-5-H), 7.13 (d, J = 8.0 Hz, 2 H, Py-3-H), 7.15-7.23 (m, 10 H, biphenyl-H), 7.36-7.45 (m, 8 H, biphenyl-H), 7.74 (‘t’, J = 8.0 Hz, 2 H, Py-4-H), 8.19 (dd, J = 5.0 Hz, J = 1.8 Hz, 2 H, Py-6-H). 13C NMR (100.6 MHz, CDCl3): δ = 31.59 (t), 110.41 (d, Py-C-3), 118.55 (d, Py-C-5), 126.08 (d), 126.12 (d), 126.98 (d), 127.40 (s), 127.91 (s), 128.00 (d), 129.12 (d), 129.89 (d), 130.38 (d), 130.42 (d), 130.63 (d), 132.55 (s), 132.84 (s), 139.75 (d, Py-C-4), 140.48, 140.53, 142.04 (s), 146.65 (s), 148.06 (d, Py-C-6), 151.81 (s), 163.62 (s, Py-C-2). MS (FAB): m/z (%) = 883.3 (100) [M + H+]. UV/Vis (CH3CN): λmax (log ε) = 224 (5.1), 238 (sh, 5.0), 268 (4.8), 284 (sh, 4.6) nm. Anal. Calcd for C62H46N2O4·H2O (900.46): C, 82.63; H, 5.37; N, 3.11. Found: C, 82.52; H, 5.05; N, 2.79.
To a degassed solution of calixarene 3 (96 mg, 0.11 mmol) in anhyd CH2Cl2 (50 mL) a solution of FeCl3 (465 mg, 2.87 mmol) in anhyd nitromethane (10 mL) was added dropwise over 5 min. A permanent stream of argon was bubbled through the solution. The reaction mixture was stirred for 40 min at r.t., MeOH (25 mL) was added and the volume of the solution was reduced to ca.10 mL. H2O (25 mL) was added and the resulting precipitate was collected and washed with H2O (3 × 10 mL). Flash chromatography (PE-EtOAc, 3:1; R
f
0.36) and recrystallization (CH2Cl2-i-PrOH) gave 60 mg (68%) of the spiro compound 4 as colorless needles.
Mp 253-255 °C. IR (KBr): 3060, 2923, 2854, 1667, 1647, 1597, 1585, 1570, 1470, 1458, 1428, 1395, 1355, 1287, 1271, 1250, 1191, 1142, 1096, 1081, 988, 940, 917, 885, 865, 801, 778, 759, 733, 645, 619 cm-1. 1H NMR (400.1 MHz, CDCl3, 223 K): δ = 2.63 (d, J = 13.6 Hz, 2 H), 2.97 (d, J = 13.1 Hz, 2 H), 3.70 (d, J = 12.9 Hz, 2 H), 3.91 (d, J = 13.2 Hz, 2 H), 6.01 (d, J = 8.4 Hz, 2 H, Py-3-H), 6.30 (s, 2 H), 6.34 (s, 2 H), 6.71 (t, J = 5.5 Hz, 2 H, Py-4-H), 6.81 (d, J = 7.3 Hz, 2 H), 6.94 (t, J = 7.6 Hz, 2 H), 7.25 (t, J = 7.1 Hz, 3 H), 7.31 (m, 6 H), 7.39 (m, 1 H, Ar′H), 7.44 (m, 2 H), 7.57 (m, 2 H), 7.68 (t, J = 7.3 Hz, 1 H), 7.74 (t, J = 7.3 Hz, 1 H), 7.82 (d, J = 7.6 Hz, 1 H), 7.91 (m, 4 H), 7.98 (d, J = 7.3 Hz, 1 H), 9.18 (d, J = 7.6 Hz, 1 H). 13C NMR (100.6 MHz, CDCl3, 223 K): δ = 29.70 (t), 35.07 (t), 56.00 (s, spiro-C), 56.67 (s, spiro-C), 110.57 (d, Py-C-3), 116.92 (d, Py-C-4), 119.99 (d), 120.44, 120.63, 120.83, 124.25 (d), 124.46 (d), 124.72 (s), 124.93 (d), 127.09 (d), 127.54 (d), 127.81 (d), 128.39 (d), 128.48 (s), 128.69 (s), 129.45 (s), 130.64 (d), 130.72 (s), 131.79 (s), 136.78 (s), 139.21 (d, Py-C-3), 140.10 (s), 140.48 (s), 140.98 (s), 141.20 (s), 141.71 (d), 141.99 (s), 143.45 (s), 143.95 (d), 144.67 (s), 147.27 (Py-C-6), 149.28 (s), 163.10 (s, Py-C-1), 183.23, 185.93 (s). MS (FAB): m/z (%) = 901.4 (20)[M + Na+]. UV/Vis (CH3CN): λmax (log ε) = 227 (4.9), 258 (4.6), 291 (4.0), 302 (4.1) nm. Anal. Calcd for C62H42N2O4·0.5H2O (888.02): C, 83.86; H, 4.88; N, 3.15. Found: C, 83.64; H, 4.14; N, 2.96.