Abstract
We have designed and synthesized a new fluorescent receptor 3 utilizing biquinoline as a molecular scaffold. The receptor 3 has two amide hydrogens and two carbamate hydrogens anchored at 4,4′-position of biquinoline. Fluorescence and 1H NMR titration showed that receptor 3 bound anions with different stoichiometry depending on the shape of anions and its association constants for anions reflected the basicities of anions. Receptor 3 bound chloride, acetate and benzoate in 1:2 stoichiometry and had a highest affinity for acetate. Tetrahedral shaped dihydrogen phosphate bound receptor 3 in 1:1 stoichiometry, although its affinity was low.
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Notes
Synthesis of compound 1: To a solution of di-tert-butyl dicarbonate (1.6 g, 7.49 mmol) in methanol (5 ml) was added ethylenediamine (500 mg, 8.3 mmol) at 0 °C. The solution was stirred for an hour and the solution temperature was raised to room temperature slowly. After the solution was stirred for 4 h more, the precipitated solid was removed through filtration. Evaporation of the liquid layer and silicagel chromatography of the residue with 50 % methanol in dichloromethane gave the compound 1 (1.54 g) in 88 % yields. 1H NMR (CDCl3, 500 MHz): 5.37(s, 1H), 3.26(s, 2H), 3.03(m, 2H), 2.64 (t, J = 6.0, 2H), 1.30 (s, 9H). Synthesis of compound 3: The suspension of 2,2′-biquinoline-4,4′-dicarboxylic acid(150 mg, 0.44 mmol) in thionyl chloride (10 ml) was refluxed for 5 h. After all of starting material was dissolved, the reflux was stopped and all of thionyl chloride was evaporated in vacuo to give compound 2. The remained material was directly used for next reaction without purification. The remained material was dissolved in dried DMF (10 ml). Then the compound 1 (209 mg, 1.31 mmol) in dried pyridine (8 ml) was added to this solution in ice bath and the solution temperature was raised to room temperature slowly. Then the reaction mixture was stirred for 2 h. Filtration of precipitated solid gave the desired compound 3 (105 mg) in 38 % yields. 1H NMR (DMSO-d6, 500 MHz) 8.98(t, J = 5.5, 2H), 8.82(s, 2H), 8.27(d, J = 8.0, 2H), 8.22(d, J = 8.0, 2H), 7.91(t, J = 8.0, 2H), 7.73(t, J = 8.0, 2H), 6.97(t, J = 5.5, 2H), 3.45(m, 4H), 3.25(m, 4H), 1.40(s, 18H) 13C NMR(500 MHz, DMSO-d6) 166.81, 155.75, 154.41, 147.53, 143.79, 130.47, 129.67, 128.12, 125.74, 124.56, 116.19, 77.68, 28.26 two peaks are hidden in DMSO solvent peak. LRMS m/z (M+): calcd, 628.30, found, 628.35.
In the NMR titration and fluorescence titration, solution of anion was added to the solution of host. The volume change of host solution was less than 4 % during titration and dilution effect was ignored. In the NMR titrations the mole ratio was measured by integration values between host 3 and tetrabutylammonium anion salts.
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This research was supported by Basic Science Research Program through the National Research Foundation of Korea (NRF) funded by the Ministry of Education, Science and Technology (2010-0021333).
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Kim, YH., Moon, J., Kang, J. et al. A new anion receptor with biquinoline molecular scaffold. J Incl Phenom Macrocycl Chem 76, 119–124 (2013). https://doi.org/10.1007/s10847-012-0180-2
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DOI: https://doi.org/10.1007/s10847-012-0180-2