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Synlett 2016; 27(14): 2095-2100
DOI: 10.1055/s-0035-1561480
DOI: 10.1055/s-0035-1561480
cluster
Synthesis of Unexpected trans-meso Macrocycle from Novel Unsymmetrical Tetraphenylene
Further Information
Publication History
Received: 03 May 2016
Accepted after revision: 21 May 2016
Publication Date:
23 June 2016 (online)
![](https://www.thieme-connect.de/media/synlett/201614/lookinside/thumbnails/st-2016-w0311-c_10-1055_s-0035-1561480-1.jpg)
Abstract
A highly unsymmetrical trisubstituted tetraphenylene was designed and synthesized as a novel superamolecular scaffold for an unexpected trans-meso tetraphenylene macrocycle, whose structure was unequivocally characterized by an X-ray crystallographic analysis. With the defined and electron-rich aromatic cavity, this macrocycle could be further modified to be a potential host for organic cations with biological interest.
Key words
tetraphenylene - nonplanar hydrocarbon - macrocycle - host-guest chemistry - cation π interactionsSupporting Information
- Supporting information for this article is available online at http://dx.doi.org/10.1055/s-0035-1561480.
- Supporting Information
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References and Notes
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- 17 Experimental Procedure for the Synthesis of 20 Under an argon atmosphere, a mixture of 18 (13 mg, 0.035 mmol), 19 (20 mg, 0.035 mmol), and Cs2CO3 (114 mg, 0.35 mmol) in dry MeCN (10–2 M, 4 mL) was stirred at 90 °C for 48 h. The mixture was cooled to room temperature, and the solvent was removed. The crude residue was dissolved in a mixture of CH2Cl2 and water. The organic layer was separated, washed with water and then brine, dried over Na2SO4, and concentrated under reduced pressure. The crude product was purified by column chromatography over silica gel (10 g, eluting with PE–CH2Cl2, 5:2) to give the product 20 (3 mg, 10%) as a white solid. Rf = 0.21 (PE–CH2Cl2, 5:2); mp >250 °C. 1H NMR (400 MHz, CD2Cl2): δ = 7.55 (dd, J = 8.0, 1.7 Hz, 2 H), 7.38 (d, J = 1.8 Hz, 2 H), 7.29–7.24 (m, 6 H), 7.16 (dd, J = 7.4, 1.7 Hz, 2 H), 7.07–6.97 (m, 10 H), 6.61 (d, J = 2.4 Hz, 2 H), 6.57 (d, J = 2.4 Hz, 2 H), 4.48–4.44 (m, 4 H), 4.30 (br s, 4 H). 13C NMR (100 MHz, CD2Cl2): δ = 158.2, 157.7, 146.3, 143.2, 142.9, 141.3, 140.8, 140.6, 134.8, 133.3, 132.9, 131.3, 130.8, 130.3, 130.2, 129.4, 129.4, 128.1, 127.6, 119.0, 116.8, 116.3, 113.7, 113.0, 111.3, 67.3. ESI-MS: m/z = 797 [M + Na]+. ESI-HRMS: m/z calcd for C54H34N2O4Na [M + Na]+: 797.2411; found: 797.2401.
- 18 X-ray Crystallographic Data for 20 C54H34N2O4, M = 774.88, monoclinic, P2(1)/c, a = 10.7287(5) Å, b = 23.4747(11) Å, c = 10.5235(5) Å, α = 90°, β = 106.5140(10)°, γ = 90°, T = 173(2) K, V = 2541.0(2) A3, Z = 2, ρcalc (mg mm–3): 1.243, absorption coefficient = 0.082 mm–1, F(000) = 1000, crystal size: 0.50 × 0.40 × 0.30 mm, 2θ range for data collection: 1.73 to 25.25°, reflections collected: 58557, independent reflections: 4601 [R(int) = 0.0229], data/restraints/parameters: 4601/0/325, goodness-of-fit on F 2: 1.075, final R indexes [I > = 2σ (I)]: R1 = 0.0432, wR2 = 0.1261, final R indexes [all data]: R1 = 0.0478, wR2 = 0.1323, largest diff. peak and hole: 0.405 and –0.342 e A–3. CCDC-1476587 contains the supplementary crystallographic data for 20. The data can be obtained free of charge from The Cambridge Crystallographic Data Centre via www.ccdc.cam.ac.uk/getstructures.
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