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Synlett 2005(19): 2987-2989  
DOI: 10.1055/s-2005-918961
LETTER
© Georg Thieme Verlag Stuttgart · New York

Synthesis of Mixed Heterocalixarenes Containing Imidazolium Units

Da-Bin Qina,b, Feng-Bo Xu*a, Qing-Shan Lia, Hai-Bin Songa, 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
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Publication History

Received 5 August 2005
Publication Date:
27 October 2005 (online)

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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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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.

14

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].

15

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.

16

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].

17

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.