Synthesis of C₅₈ Open-Cage Fullerene Derivatives

Abstract

Several analogous C₅₈ open-cage fullerene derivatives have been prepared through silver acetate mediated decarboxylation of the corresponding C₅₉ open-cage precursors. These C₅₈ open-cage fullerene derivatives can trap one water molecule under mild conditions as shown by spectroscopic data and single-crystal X-ray analysis.

Key words

fullerene - open-cage fullerene - endohedral complex - decarboxylation - amide

• References and Notes


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• 11 General Procedure for the Preparation of Compounds 2a–d CF₃CO₂Ag (30 equiv of 1) was added into a solution of compound 1 (0.1 mmol) in distilled toluene (30 mL). The mixture was stirred at r.t., and progress of the reaction was monitored by TLC. After all the starting material 1 has been converted into a new complex with the silver salt (around 10–30 min), the mixture was then stirred vigorously at 100 °C. When the reaction was completed (about 3 d), the reaction solution was cooled to r.t. and directly chromatographed on a silica gel column and eluted with toluene–EtOAc (20:1). The second red band was collected and evaporated to give compound 2. Yields range from 40–45%. Characterization Data for 2c ¹H NMR (400 MHz, CDCl₃): δ = 8.41 (s, 1 H), 8.32 (s, 1 H), 8.19 (d, J = 7.8 Hz, 2 H), 7.42 (d, J = 7.8 Hz, 2 H), 2.80–2.61 (m, 2 H), 1.87–1.63 (m, 2 H), 1.50–1.36 (m, 4 H), 0.96 (t, J = 6.9 Hz, 3 H). ¹³C NMR (125 MHz, CDCl₃): δ = 188.54, 188.46, 185.32, 164.75, 150.36, 150.28, 149.74, 149.67, 149.66, 149.64, 149.35, 148.84, 148.81, 148.60, 148.49, 147.62, 146.75, 146.66, 146.59, 146.57, 146.33, 146.29, 146.19 (2 C), 146.10, 145.95, 145.94, 145.80, 145.58, 145.56, 144.07, 143.97, 143.72 (2 C), 143.60, 143.46, 142.95, 142.81 (2 C), 142.80 (2 C), 142.00, 141.67, 141.14, 140.13, 139.27, 138.65, 138.58, 137.66, 137.55, 137.05, 136.70 (2 C), 136.52, 135.08, 134.19, 134.14, 133.75, 131.55, 129.16 (2 C), 125.28, 120.84 (2 C), 35.63, 31.56, 31.34, 22.64, 14.10. FT-IR (microscope): 3394, 2923, 2852, 1739, 1676, 1596, 1560, 1517, 1494, 1463, 1411, 1314, 1247, 1133, 1120, 800, 732 cm^–1. ESI-HRMS: m/z calcd for C₆₉H₁₈NO₄ [M + H⁺]: 924.1230; found: 924.1241.
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• 12c Zhang QY, Pankewitz T, Liu SM, Klopper W, Gan LB. Angew. Chem. Int. Ed. 2010; 49: 9935
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• 13 Single crystals of 2b suitable for X-ray diffraction were obtained by slow evaporation of its solution in a mixture of CH₂Cl₂ and hexane. Crystal Data C₆₇H₁₃NO₄ (M = 895.78), orthorhombic, space group Pbca (no. 61), a = 18.1272(12) Å, b = 14.2835(9) Å, c = 33.019(2) Å, V = 8549.4(9) ų, Z = 8, T = 180.01(11) K, μ(Mo Kα) = 0.087 mm^–1, D _calc = 1.392 g mm^–3, 22202 reflections measured (5.7 ≤ 2θ ≤ 52.04), 8359 unique (R _int = 0.0646) which were used in all calculations. The final R ₁ was 0.0989 [>2σ(I)] and wR ₂ was 0.2945 (all data). CCDC 1445320 contains the supplementary crystallographic data for this paper. The data can be obtained free of charge from The Cambridge Crystallographic Data Centre via www.ccdc.cam.ac.uk/getstructures.
• 14 Single crystals of H₂O@2b were obtained as above for 2b: Formula: C₆₇H₁₅NO₅ (M = 913.80). Orthorhombic, space group Pbca (no. 61), a = 18.1277(4) Å, b = 14.3029(2) Å, c = 32.9881(5) Å, V = 8553.1(3) ų, Z = 8, T = 180.15 K, μ(Cu Kα) = 0.723 mm^–1, D _calc = 1.419 g mm^–3, 31623 reflections measured (7.246 ≤ 2θ ≤ 126.44), 6947 unique (R _int = 0.0418) which were used in all calculations. The final R ₁ was 0.0826 [I > 2σ(I)] and wR ₂ was 0.2426 (all data). CCDC 1445363 contains the supplementary crystallographic data for this paper. The data can be obtained free of charge from The Cambridge Crystallographic Data Centre via www.ccdc.cam.ac.uk/getstructures.