Design and Efficient Synthesis of Fullerene Bismalonates as Building Blocks for Metal Organic Frameworks and Organic Nanostructures

Philippe Pierrat; Céline Réthoré; Thierry Muller; Stefan Bräse

doi:10.1055/s-2008-1077880

LETTER

Design and Efficient Synthesis of Fullerene Bismalonates as Building Blocks for Metal Organic Frameworks and Organic Nanostructures

Philippe Pierrat, Céline Réthoré, Thierry Muller*, Stefan Bräse*
Institut für Organische Chemie, Universität Karlsruhe (TH), Fritz-Haber-Weg 6, 76131 Karlsruhe, Germany
Fax: +49(721)6088581; e-Mail: braese@ioc.uka.de;

Abstract

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Abstract

The preparation of bismalonate fullerene derivatives bearing useful sticky sides for the generation of nanostructures has been investigated. In this context, pyridine and cyano heading groups on fullerenes have been designed and synthesized in a straightforward manner and in good yields.

Key words

fullerenes - malonate esters - Bingel reaction - molecular recognition - metal organic frameworks

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References and Notes

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Experimental Procedure for the Preparation of the Fullerene Complex 3: To a solution of CuCl₂·2H₂O (3.1 mg, 18.2 µmol) in MeCN (1 mL) was added a solution of fullerene derivative 1 (5 mg, 4.7 µmol) in CH₂Cl₂ (1 mL). The resulting mixture was shaken leading to the precipitation of a brown solid which was washed with THF, MeCN and CH₂Cl₂ and finally dried in vacuo for 12 h. The expected compound was obtained as a brownish solid (5.4 mg, 95%). Complex 3 has been characterized by FAB spectroscopy, IR and elemental analysis. Unfortunately, we were unable to get single crystals of this complex. IR: 3454, 3071, 2951, 2873, 1751, 1575, 1480, 1434, 1266, 1229, 1111 cm^-1. MS (FAB, NBA): m/z = 1238 [M⁺ + MeCN], 1199 [M⁺], 1163 [M⁺ - Cl], 1130 [M⁺ - 2 × Cl]. Anal. Calcd for C₇₇H₁₆N₂O₆CuCl₂: C, 77.11; H, 1.34; N, 2.34. Found: C, 76.78; H, 1.48; N, 2.19.

<A NAME="RG11808ST-9">9</A> Bourgeois JP. Woods CR. Cardullo F. Habicher T. Nierengarten JF. Gehrig R. Diederich F. Helv. Chim. Acta 2001, 84: 1207

<A NAME="RG11808ST-10A">10a</A> Thilgen C. Sergeyev S. Diederich F. Top. Curr. Chem. 2004, 248: 1

<A NAME="RG11808ST-10B">10b</A> Diederich F. Kessinger R. Acc. Chem. Res. 1999, 32: 537

<A NAME="RG11808ST-11">11</A> Felder D. Guitierrez M. Carcon MP. Eckert JF. Schall MLC. Masson P. Gallani JL. Heinrich B. Guillon D. Nierengarten JF. Helv. Chim. Acta 2002, 85: 288

Experimental Procedure for the Preparation of Malonate 2: To a solution of malonic acid (464 mg, 4.4 mmol) and 2-(pyridin-3-yloxy)ethanol (1.21 g, 8.7 mmol) in anhyd MeCN (16 mL) was added dropwise a solution of DCC (1.79 g, 8.7 mmol) in anhyd MeCN (16 mL) over 20 min under argon during which time a white precipitate formed. The reaction mixture was stirred overnight at r.t. Then, the precipitate was filtered off and washed with CH₂Cl₂ (2 × 10 mL). The filtrate was evaporated and dried in vacuo affording a yellow oil which was purified by column chromatography on silica gel using CH₂Cl₂-MeOH (95:5) as eluent. The expected compound was obtained as a yellow oil (1.23 g, 82%). IR: 3061, 2969, 2884, 1763, 1670, 1577, 1477, 1457, 1429, 1377, 1272, 1189, 1050 cm^-1. ¹H NMR (500 MHz, CDCl₃): δ = 3.50 (s, 2 H), 4.22 (t, J = 4.5 Hz, 4 H), 4.51 (t, J = 4.5 Hz, 4 H), 7.20-7.26 (m, 4 H), 8.24 (dd, J = 2.8, 5.0 Hz, 2 H), 8.31 (d, J = 2.8 Hz, 2 H). ¹³C NMR (125 MHz, CDCl₃): δ = 166.1, 154.5, 142.7, 137.9, 123.9, 121.3, 65.9, 63.5, 41.1. EI-MS: m/z (%) = 346 (52) [M⁺], 157 (85), 95 (100).
Experimental Procedure for the Preparation of Fullerene Derivative 1: To a solution of C₆₀ (500 mg, 690 µmol) in freshly distilled toluene (250 mL) were added CBr₄ (347 mg, 1.03 mmol) and malonate 2 (358 mg, 1.03 mmol) under argon. Then, DBU (3 equiv, 0.31 mL, 2.07 mmol) was added slowly to the reaction medium which was stirred for 18 h at r.t. The volatiles were removed and the crude residue was purified by flash column chromatography using CH₂Cl₂ and then CH₂Cl₂-MeOH (95:5) as eluent. The expected compound was recovered as a brown solid (192 mg, 26%). IR: 3053, 2953, 2872, 2329, 1748, 1575, 1474, 1427, 1186, 1110 cm^-1. ¹H NMR (500 MHz, CDCl₃): δ = 4.04 (t, J = 4.5 Hz, 4 H), 4.87 (t, J = 4.5 Hz, 4 H), 7.20-7.26 (m, 4 H), 8.27 (dd, J = 2.5, 4.3 Hz, 2 H), 8.34 (d, J = 2.5 Hz, 2 H). ¹³C NMR (125 MHz, CDCl₃): δ = 163.4, 154.4, 145.3, 145.2, 145.0, 144.9, 144.9, 144.7, 144.6, 144.5, 143.8, 143.0, 143.0, 142.8, 142.2, 141.7, 141.0, 138.9, 137.9, 124.0, 121.1, 71.1, 65.8, 65.1, 51.6. MS (FAB, NBA): m/z = 1067.5 [M⁺ + H], 1067.7 [M⁺].
Experimental Procedure for the Preparation of Compound 4: A mixture of Meldrum’s acid (1.44 g, 10 mmol) and 4-pyridylmethanol (1.10 g, 10 mmol) in anhyd toluene (50 mL) was refluxed overnight. After the reaction mixture was cooled, a white precipitate formed which was filtered off and washed with toluene (2 × 50 mL) and then with pentane. The expected compound was obtained as a white solid (1.38 g, 70%). IR: 3400, 3040, 2991, 2952, 1734, 1617, 1513, 1416, 1337, 1297, 1248, 1215, 1150, 1071, 1036 cm^-1. ¹H NMR (500 MHz, DMSO-d ₆): δ = 3.54 (s, 2 H), 5.22 (s, 2 H), 7.37 (d, J = 6.0 Hz, 2 H), 8.57 (d, J = 6.0 Hz, 2 H), 12.90 (br s, 1 H). ¹³C NMR (125 MHz, DMSO-d ₆): δ = 170.6, 168.4, 150.3, 145.6, 122.3, 64.6, 42.1. EI-MS: m/z (%) = 195 (63) [M⁺], 109 (100). Anal. Calcd for C₉H₉NO₄: C, 55.38; H, 4.64; N, 7.17. Found: C, 55.21; H, 4.67; N, 7.12.
Experimental Procedure for the Preparation of Malonate 5: DCC (1.22 g, 5.9 mmol) dissolved in DMF (2 mL) was added dropwise to an anhyd DMF solution of 4 (1.15 g, 5.9 mmol), 1,3-benzenedimethanol (338 mg, 2.4 mmol) and DMAP (50 mg, 400 µmol) cooled to 0 °C under an argon atmosphere. The reaction mixture was maintained at 0 °C for 2 h and then allowed to warm to r.t. overnight. The crude mixture was filtered and the obtained solid was washed with CH₂Cl₂. The filtrate was evaporated and dried in vacuo affording a yellow oil which was purified by flash chromatography using EtOAc-MeOH (90:10) as eluent. The expected compound was obtained as a pale yellow oil (1.13 g, 95%). IR: 3032, 2951, 1735, 1604, 1563, 1450, 1415, 1381, 1334, 1273, 1147, 1015 cm^-1. ¹H NMR (500 MHz, CDCl₃): δ = 3.56 (s, 8 H), 5.20 (s, 8 H), 7.23 (d, J = 6.0 Hz, 4 H), 7.33-7.37 (m, 4 H), 8.58 (d, J = 6.0 Hz, 4 H). ¹³C NMR (125 MHz, CDCl₃): δ = 165.9, 165.9, 150.1, 144.1, 135.6, 129.0, 128.4, 128.1, 121.8, 67.0, 65.1, 41.3. EI-MS: m/z (%) = 492 (25) [M⁺ + H], 286 (70), 109 (100). Anal. Calcd for C₂₆H₂₄N₂O₈: C, 63.41; H, 4.91; N, 5.68. Found: C, 63.48; H, 4.96; N, 5.74.
Experimental Procedure for the Preparation of Fullerene Derivative 6: To a solution of C₆₀ (200 mg, 277 µmol) in freshly distilled toluene (420 mL) and anhyd MeCN (40 mL) were added I₂ (161 mg, 636 µmol) and bismalonate 5 (136 mg, 228 µmol) under argon. Then, DBU (6 equiv, 240 µL, 1.63 mmol) was added slowly to the reaction medium which was then stirred for 18 h at r.t. The crude reaction mixture was directly purified by flash column chromatography using first toluene as eluent in order to remove unreacted C₆₀ and then CH₂Cl₂-acetone-Et₃N (70:29:1). The expected compound was obtained as a brown solid (112 mg, 33%). IR: 3030, 2946, 2331, 1750, 1603, 1432, 1414, 1230, 1204 cm^-1. ¹H NMR (500 MHz, CDCl₃): δ = 5.03 (d, J = 13.0 Hz, 2 H), 5.32 (d, J = 13.0 Hz, 2 H), 5.47 (d, J = 13.0 Hz, 2 H), 5.87 (d, J = 13.0 Hz, 2 H), 7.32-7.52 (m, 8 H), 8.65 (d, J = 4.0 Hz, 4 H). ¹³C NMR (125 MHz, CDCl₃): δ = 162.7, 162.4, 150.2, 148.4, 147.6, 146.1, 145.8, 145.7, 145.7, 145.6, 145.5, 145.3, 144.9, 144.7, 144.4, 144.2, 144.1, 143.9, 143.9, 143.6, 143.3, 142.5, 142.3, 141.4, 140.9, 140.1, 136.5, 136.2, 135.8, 134.1, 128.8, 127.0, 124.1, 122.6, 70.4, 67.5, 66.6, 48.7. MS (FAB, NBA): m/z = 1209 [M⁺ + H], 1208 [M⁺].
Experimental Procedure for the Preparation of Compound 8: A mixture of Meldrum’s acid (441 mg, 3 mmol) and 4-cyanobenzylalcohol (400 mg, 3 mmol) was heated at 120 °C for 4 h. Then, the crude mixture was cooled and dried in vacuo for 12 h. The expected compound was obtained as a yellow oil (652 mg, 98%). IR: 3220, 3062, 2951, 2230, 1928, 1738, 1612, 1567, 1508, 1414, 1379, 1332, 1230, 1148, 1034, 1018 cm^-1. ¹H NMR (400 MHz, CDCl₃): δ = 3.53 (s, 2 H), 5.27 (s, 2 H), 7.48 (d, J = 8.1 Hz, 2 H), 7.68 (d, J = 8.1 Hz, 2 H), 10.20 (br s, 1 H). ¹³C NMR (100 MHz, CDCl₃): δ = 171.3, 166.0, 140.3, 132.4, 128.4, 118.4, 112.2, 66.2, 40.9. EI-MS: m/z (%) = 219.1 (29) [M⁺], 133.1 (75), 116.1 (100).
Experimental Procedure for the Preparation of Malonate 9: DCC (605 mg, 2.9 mmol) dissolved in CH₂Cl₂ (2 mL) was added dropwise to a CH₂Cl₂ solution of 8 (630 mg, 2.8 mmol), 1,3-benzenedimethanol (187 mg, 1.36 mmol) and DMAP (53 mg, 0.42 mmol) cooled at 0 °C under an argon atmosphere. The reaction mixture was maintained at 0 °C for 2 h and then allowed to warm to r.t. overnight. The solution was filtered and washed with CH₂Cl₂. The filtrate was evaporated and dried in vacuo affording a yellow oil which was purified by flash chromatography using CH₂Cl₂-Et₂O (97:3) as eluent. The expected compound was obtained as a pale yellow oil (310 mg, 42%). IR: 3062, 2952, 2229, 1927, 1735, 1612, 1509, 1452, 1378, 1332, 1271, 1015 cm^-1. ¹H NMR (400 MHz, CDCl₃): δ = 3.54 (s, 4 H), 5.19 (s, 4 H), 5.24 (s, 4 H), 7.32-7.36 (m, 4 H), 7.43 (d, J = 8.0 Hz, 4 H), 7.63 (d, J = 8.0 Hz, 4 H). ¹³C NMR (100 MHz, CDCl₃): δ = 165.9, 140.4, 135.6, 132.4, 129.0, 128.3, 128.2, 128.0, 118.4, 112.2, 67.0, 65.9, 41.3. EI-MS: m/z (%) = 540.2 (42) [M⁺], 203 (100).
Experimental Procedure for the Preparation of Fullerene Derivative 10: To a solution of C₆₀ (150 mg, 207 µmol) in freshly distilled toluene (360 mL) were added I₂ (132 mg, 518 µmol) and the bismalonate 9 (123 mg, 228 µmol) under argon. Then, DBU (5 equiv, 160 µL, 1.06 mmol) was added slowly to the reaction medium which was stirred for 18 h at r.t. Then, the crude reaction mixture was directly purified by flash column chromatography using first toluene as eluent in order to remove unreacted C₆₀ and then CH₂Cl₂. The expected compound was obtained as a brown solid (81 mg, 31%). IR: 2953, 2228, 1750, 1611, 1444, 1371, 1282, 1232, 1204, 1102 cm^-1. ¹H NMR (500 MHz, CDCl₃): δ = 5.10 (d, J = 13.0 Hz, 2 H), 5.40 (d, J = 13.0 Hz, 2 H), 5.53 (d, J = 13.0 Hz, 2 H), 5.87 (d, J = 13.0 Hz, 2 H), 7.36 (m, 2 H), 7.46 (d, J = 7.0 Hz, 2 H), 7.57 (d, J = 8.3 Hz, 4 H), 7.72 (d, J = 8.3 Hz, 4 H). ¹³C NMR (125 MHz, CDCl₃): δ = 162.7, 162.5, 148.4, 147.6, 147.6, 147.4, 146.2, 145.9, 145.8, 145.7, 145.6, 145.5, 145.4, 145.3, 144.9, 144.8, 144.5, 144.3, 144.2, 144.2, 143.9, 143.7, 143.3, 142.6, 142.3, 141.4, 140.9, 140.1, 139.7, 138.1, 136.5, 136.1, 135.8, 134.1, 132.5, 129.2, 128.9, 127.0, 124.1, 118.3, 112.8, 70.4, 67.6, 48.8. MS (FAB, NBA): m/z = 1256.9 [M⁺].