Synthesis of Mixed Heterocalixarenes Containing Imidazolium Units

Da-Bin Qin; Feng-Bo Xu; Qing-Shan Li; Hai-Bin Song; Zheng-Zhi Zhang

doi:10.1055/s-2005-918961

LETTER

Synthesis of Mixed Heterocalixarenes Containing Imidazolium Units

Da-Bin Qin^a,b, Feng-Bo Xu*^a, Qing-Shan Li^a, Hai-Bin Song^a, Zheng-Zhi Zhang*^a
^a State Key Laboratory of Elemento-Organic Chemistry, Nankai University, Tianjin 300071, P. R. of China
Fax: +86(22)23503627; e-Mail: zzzhang@nankai.edu.cn;
^b School of Chemistry and Chemical Industry, China West Normal University, Nanchong, Sichuan 637000, P. R. of China

Abstract

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Abstract

Three novel mixed heterocalixarenes containing imidazolium units and a heterocalixarene containing two thiourea functionalities have been synthesized. The molecular structures and anion recognition ability of some of these compounds have been determined.

Key words

condensation - hetrocalixarene - imidazolium cation - structure - binding ability

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References

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General Synthetic Procedure and Analytical Data for 4, 5 and 6.
Imidazole (100 mmol, 6.8 g) in 1,4-dioxane (30 mL) was added dropwise to NaH (110 mmol, 5.28 g 60%) in 1,4-dioxane. The mixture was stirred for 12 h at r.t. under nitrogen. Then, 1,3-bis(bromomethyl)-5-tert-butyl-2-methoxybenzene (1), bis(3-bromomethyl-5-tert-butyl-2-methoxyphenyl)methane (2) or 5-tert-butyl-1,3-bis[(3-bromomethyl-5-tert-butyl-2-methoxyphenyl)methyl]-2-methoxybenzene (3, 50 mmol) was added, respectively, and the solution was stirred for additional 20 h. Solvent was removed and the crude product was purified by column chromatography on SiO₂ or recrystallization to yield 4, 5 or 6, respectively.
Compound 4: yield 83%; mp 162-164 °C. ¹H NMR (300 MHZ, CDCl₃): δ = 7.60 (s, 2 H, imidazole, C2-H), 7.10, 7.03 (s, 4 H, imidazole, C4-H, C5-H), 6.93 (s, 2 H, benzene-H), 5.15 (s, 2 H, CH₂), 3.56 (s, 3 H, OCH₃), 1.20 (s, 9 H, t-Bu). ¹³C NMR (300 MHz, CDCl₃): δ = 153.73, 148.48, 137.45, 129.81, 129.28, 126.84, 119.2, 61.73, 45.94, 34.40, 31.18. MS (ESI): m/z (%) = 325.29 (100) [M + 1]. Anal. Calcd for C₁₉H₂₄N₄O: C, 70.34; H, 7.46. Found: C, 70.13; H, 7.48.
Compound 5: yield 79%; mp 104-105 °C. ¹H NMR (300 MHz, CDCl₃): δ = 7.59 (s, 2 H, imidazole C2-H), 7.07, 7.02 (s, 4 H, imidazole C4-H, C5-H), 6.96, 6.94 (s, 4 H, benzene-H), 5.14 (s, 4 H, CH₂), 4.06 (s, 2 H, CH₂) 3.58 (s, 6 H, OCH₃), 1.18 (s, 18 H, t-Bu). ¹³C NMR (300 MHz, CDCl₃): δ = 154.21, 147.47, 137.35, 133.25, 129.34, 128.58, 128.44, 127.74, 119.25, 61.22, 46.48, 34.32, 31.27, 29.64. MS (ESI): m/z (%) = 501.37 (100) [M + 1], 433.6 (31.20) [M - 67]. Anal. Calcd for C₃₁H₄₀N₄O₂: C, 74.31; H, 8.05. Found: C, 74.49; H, 8.07.
Compound 6: yield 73%; mp 70-80 °C. ¹H NMR (300 MHz, CDCl₃): δ = 7.64 (s, 2 H, imidazole, C2-H), 7.05 (s, 4 H, imidazole, C4-H, C5-H), 6.96, 6.92 (s, 6 H, benzene-H), 5.15 (s, 4 H, CH₂), 4.08 (s, 4 H, CH₂), 3.59 (s, 9 H, OCH₃), 1.17 (s, 27 H, t-Bu). ¹³C NMR (300 MHz, CDCl₃): δ = 154.48, 154.21, 147.52, 146.21, 133.89, 132.43, 128.27, 128.27, 126.13, 124.47, 61.16, 60.79, 46.57, 34.28, 34.23, 31.33, 31.26, 29.74. MS (ESI): m/z (%) = 677.46 (100) [M + 1], 609.75 (42.01) [M - 67]. Anal. Calcd for C₄₃H₅₆N₄O₃: C, 76.29; H, 8.34. Found: C, 76.51; H, 8.31.

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General Synthetic Procedure and Analytical Data for Compound 7, 8 and 9.Compound 7: yield 73%; mp >250 °C. ¹H NMR (300 MHz, DMSO-d ₆): δ = 9.23 (s, 2 H, imidazole, C2-H), 7.69 (s, 4 H, imidazole, C4-H, C5-H), 7.52 (s, 4 H, benzene-H), 5.57, 5.52 (d, 4 H, J = 14.19 Hz, CH₂), 5.14, 5.10 (d, 4 H, J = 14.19 Hz, CH₂), 4.09 (s, 6 H, OCH₃), 1.26 (s, 18 H, t-Bu). ¹³C NMR (300 MHz, DMSO-d ₆): δ = 155.89, 148.60, 137.78, 131.01, 130.60, 129.42, 129.02, 123.15, 122.66, 62.81, 49.57, 49.15, 35.05, 31.70. MS (ESI): m/z (%) = 659.29 (100) [M - 145]. Anal. Calcd for C₃₂H₄₂F₁₂N₄O₂P₂: C, 47.77; H, 5.26. Found: C, 47.90; H, 5.24.
Compound 8: yield 54%; mp >270 °C. ¹H NMR (300 MHz, DMSO-d ₆): δ = 9.23 (s, 2 H, imidazole, C2-H), 7.60 (s, 4 H, imidazole, C4-H, C5-H), 7.45, 6.95 (s, 8 H, benzene-H). 5.35 (s, 8 H, CH₂), 3.90 (s, 4 H, CH₂), 3.22 (s, 12 H, -OCH₃, 1.13 (s, 36 H, t-Bu). ¹³C NMR (300 MHz, DMSO-d ₆): δ = 154.19, 146.57, 136.37, 132.46, 129.01, 126.76, 126.39, 122.11, 60.17, 48.81, 33.78, 30.91, 30.86, 29.15. MS (ESI): m/z (%) = 1011.47 (9.7) [M - 145], 809.59 (100) [M - 2 PF₆ - 67]. Anal. Calcd for C₅₆H₇₄F₁₂N₄O₄P₂: C, 58.30; H, 6.45. Found: C, 58.27; H, 6.43.
Compound 9: yield 40%; mp >270 °C. ¹H NMR (300 MHz, DMSO-d ₆): δ = 9.31 (s, 2 H, imidazole, C2-H), 7.67, 7.60 (s, 4 H, imidazole, C4-H, C5-H), 7.21-6.85 (m, 12 H, benzene-H), 5.40 (s, 8 H), 3.97 (s, 4 H), 3.89 (s, 4 H), 3.64 (s, 24 H), 1.13 (s, 54 H). ¹³C NMR (300 MHz, DMSO-d ₆): δ = 154.07, 146.48, 145.77, 136.36, 133.49, 132.01, 126.86, 125.82, 122.76, 64.85, 60.50, 48.71, 33.96, 30.90, 29.05, 28.94. MS (ESI): m/z (%) = 1363.78 (100) [M - 145]. Anal. Calcd for C₈₀H₁₀₆F₁₂N₄O₆P₂: C, 63.65; H, 7.08. Found: C, 63.67; H, 7.10.

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Crystal Data for C ₅₆ H ₇₄ F ₁₂ N ₄ O ₄ P ₂ ·OEt ₂ ·MeCN(8). M _w = 1272.31, monoclinic, space group P2 (1)/n, a = 14.73 (4), b = 19.91 (5), c = 23.49 (1)Å, β = 98.34 (5)°, V = 6817 (3) Å³, Z = 4, D _calcd = 1.240 mg/m³, µ = 0.145 mm^-1, T = 293 (2) K, refinement for data with I>2σ(I) (12024 reflections, R _int = 0.0648) gave R1 (F) = 0.0764 and wR2 (F ^²) = 0.2085 for all data. These data have been deposited with the Cambridge Crystallographic Data Centre, CCDC-280721. These data can be obtained on line free of charge [or from the Cambridge Crystallographic Data Centre, 12 Union Road, Cambridge CB2 1EZ, UK; fax: +44(1223)336033; or deposit@ccdc.cam.ac.uk].

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General Procedure and Analytical Data for Compound 10. Compound 8 (0.3 g, 0.26 mmol) was dissolved in THF, NaH (0.02 g, 0.4 mmol) and potassium tert-butoxide (0.058 g, 5.2 mmol) were added to the solution under nitrogen at r.t. Stirring was kept for 4 h. Sulfur (S₈, 0.02 g, 6.25 mmol) was added, then the solution was stirred for additional 3 h. The solvent was removed in vacuo, the crude product was recrystallized in MeCN and was obtained as a pale yellow crystal.
Compound 10: yield 34%; mp >270 °C. ¹H NMR (300 MHz, DMSO-d ₆): δ = 7.43, 6.97 (s, 8 H, benzene-H), 5.35 (s, 4 H), 5.20 (s 8 H, CH₂), 3.87 (s, 4 H, CH₂), 3.24 (s, 12 H, OCH₃), 1.12 (s, 36 H, t-Bu). ¹³C NMR (300 MHz, DMSO-d ₆): δ = 163.52, 136.25, 131.15, 129.45, 126.53, 122.45, 118.72, 60.20, 45.21, 32.68, 29.17. MS (ESI): m/z (%) = 929.21 (35.21) [M + 1]. Anal. Calcd for C₅₆H₇₂N₄O₄S₂: C, 72.38; H, 7.81. Found: C, 72.16; H, 7.82.

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Crystal Data for C ₅₆ H ₇₂ N ₄ O ₄ S ₂ 10. M _w = 929.30, monoclinic, space group C2/c, a = 19.24 (1), b = 13.17 (2), c = 22.50 (4) Å, β = 105.02 (1)°, V = 5506.0(16) Å³, Z = 4, D _calcd = 1.121 mg/m³, µ = 0.142 mm^-1, T = 293 (2) K, refinement for data with I>2σ(I) (4850 reflections, R _int = 0.0682) gave R1 (F) = 0.0581 and wR2 (F ^²) = 0.1441 for all data. Crystallographic data of 10 have been deposited with the Cambridge Crystallographic Data Centre, CCDC-280722. These data can be obtained on line free of charge [or from the Cambridge Crystallographic Data Centre, 12 Union Road, Cambridge CB2 1EZ, UK; fax: +44 (1223)336033; or deposit@ccdc.cam.ac.uk].

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¹H NMR spectra were recorded on Bruker AC 300 spectrometer and TMS was used as an internal standard. To 20-Mm DMSO-d ₆ solutions of compound 7 in NMR tubes were added 0, 0.2, 0.4, 0.6, 0.8, 1.0, 1.5, 2.0, 3.0, 4.0, 5.0, 6.0(equiv) of tetrabutylammonium salts, respectively. The chemical shift values of the C₂-H protons of the imidazolium ring moved downfield.