Synthesis, Characterization, and Binding Properties of Novel Penta-Crown Ethers

Abstract

Novel structures of penta-crown ethers were success­fully synthesized from trimethylolpropane triacrylate (TMPTA) with 2-aminomethyl crown ether; further reaction with 1-aza crown ethers, through Michael addition, furnished the newly synthesized host compounds of penta-crown ethers, which were characterized by ¹H NMR, ¹³C NMR, and IR spectroscopy as well as FABMS and elemental analyses. The binding interaction of the new penta-crown ethers with alkali metal cations was studied through ¹H NMR ­spectroscopy and UV spectroscopy.

Key words

2-aminomethyl crown ether - 1-aza-crown ether - penta-crown ether - Michael addition

References and Notes

• 1 Uda RM. Oue M. Kimura K. J. Supramol. Chem.  2002,  2:  311 
• 2 Buchanan GW. Azad M. Yap GPA. J. Mol. Struct.  2001,  598:  145 
• 3 Morey J. Orell M. Barceló MA. Deyá PM. Costa A. Ballester P. Tetrahedron Lett.  2004,  45:  1261 
• 4 Costero AM. Andreu C. Monrabal E. Tortajada A. Ochando LE. Amigó JM. Tetrahedron  1996,  52:  12499 
• 5 Weber E. Skobridis K. Ouchi M. Hakushi T. Inoue Y. Bull. Chem. Soc. Jpn.  1990,  63:  3670 
• 6 Koçak M. Okur AC. Gül A. Bekaroglu Ö. Dyes Pigm.  2000,  45:  9 
• 7 Liu HW. Liu YH. Liu MH. Chen CF. Xi F. Tetrahedron Lett.  2001,  42:  7083 
• 8 Shinmori H. Furuta H. Osuka A. Tetrahedron Lett.  2002,  43:  4881 
• 9 Shinmori H. Furuta H. Osuka A. Tetrahedron Lett.  2000,  41:  8527 
• 10 Murashima T. Uchihara Y. Wakamori N. Uno H. Ogawa T. Ono N. Tetrahedron Lett.  1996,  37:  3133 
• 11 Zeng W. Mao ZH. Wei XY. Li JZ. Hong Z. Qin SY. J. Supramol. Chem.  2002,  2:  501 
• 12 Bartsch RA. Eley MD. Marchand AP. Shukla R. Kumar KA. Reddy GM. Tetrahedron  1996,  52:  8979 
• 13 Lehn JM. Pure Appl. Chem.  1980,  52:  2441 
• 14 Carroy A. Lehn JM. J. Chem. Soc., Chem. Commun.  1986,  1232 
• 15 Chambron JC. Sauvage JP. Tetrahedron Lett.  1986,  27:  865 
• 16 Beer PD. J. Chem. Soc., Chem. Commun.  1986,  1678 
• 17 Huang ZB. Kang TJ. Chang SH. Tetrahedron Lett.  2005,  46:  3461 
• 18 Huang ZB. Chang SH. Synlett  2005,  1703 
• 19 Huang ZB. Chang SH. Synlett  2005,  2257 
• 20 Huang ZB. Kang TJ. Chang SH. New J. Chem.  2005,  29:  1616 
• 21 Mandl CP. König B. J. Org. Chem.  2005,  70:  670 
• 22 Loeb SJ. Tiburcio J. Vella SJ. Org. Lett.  2005,  7:  4923 
• 23 Shinkai S. Ogawa T. Kusano Y. Manabe O. Chem. Lett.  1980,  283 
• 24 Shinkai S. Nakaji T. Ogawa T. Shigematsu K. Manabe O. J. Am. Chem. Soc.  1981,  103:  111 
• 25 Shinkai S. Shigematsu K. Kusano Y. Manabe O. J. Chem. Soc., Perkin Trans. 1  1981,  3279 
• 26 Shinkai S. Minami T. Kusano Y. Manabe O. J. Am. Chem. Soc.  1982,  104:  1967 
• 27 Pedersen CJ. Frensdorff HK. Angew. Chem., Int. Ed. Engl.  1972,  11:  16 
• 28 Dietrich B. J. Chem. Educ.  1985,  62:  954 
• 29 An H. Bradshaw JS. Izatt RM. Yan Z. Chem. Rev.  1994,  94:  939 
• 30 Christensen JJ. Hill JO. Izatt RM. Science (Washington, D.C.)  1971,  174:  459 
• 31 Marcotte N. Rodrigues F. Lavabre D. Fery-Forgues S. New J. Chem.  2004,  28:  295 

32

Compound 3 2-Aminomethyl-15-crown-5 (150 mg, 0.6 mmol) and TMPTA (440 mg, 1.5 mmol) were dissolved in MeOH (10 mL). The mixture was stirred at 50 °C for 36 h. The solvent was evaporated in vacuo and the residue was subjected to flash chromatography on silica gel (CHCl₃-EtOAc) to afford a colorless oil; isolated yield: 422 mg (71.5%). IR (NaCl): 2937.1, 2882.1, 1727.9, 1633.4, 1618.9, 1463.7, 1408.8, 1352.8, 1269.0, 1187.9, 1125.3, 1062.6, 987.9, 874.6, 843.7 cm^-1. ¹H NMR (300 MHz, CDCl₃): δ = 0.92 (t, J = 7.5 Hz, 6 H), 1.43-1.55 (q, J = 7.5 Hz, 4 H), 2.47 (t, J = 6.0 Hz, 4 H), 2.52 (d, J = 6.0 Hz, 2 H), 2.80 (t, J = 6.6 Hz, 4 H), 3.34-3.75 (m, 19 H), 4.01-4.15 (m, 12 H), 5.85-5.88 (d, J = 10.8 Hz, 4 H), 6.07-6.16 (dd, J = 10.8, 6.9 Hz, 4 H), 6.38-6.43 (d, J = 17.1 Hz, 4 H). ¹³C NMR (75 MHz, CDCl₃): δ = 172.20, 165.73, 131.35, 128.08, 78.04, 71.95, 71.79, 70.92, 70.89, 70.68, 70.53, 70.47, 69.97, 69.84, 63.85, 63.69, 50.03, 42.44, 40.79, 32.53, 23.08, 7.40. FABMS: m/z calcd for C₄₁H₆₃NO₁₇ [M⁺], 841.4; found: 842.6 [M + H]⁺. Anal. Calcd for C₄₁H₆₃NO₁₇: C, 58.49; H, 7.54; N, 1.66. Found: C, 58.27; H, 7.70; N, 1.39.
Penta-Crown Ether 1 Compound 3 (84 mg, 0.1 mmol) and 1-aza-15-crown-5 (110 mg, 0.5 mmol) were dissolved in MeOH (5 mL). The mixture was stirred at 50 °C for 30 h. The solvent was evaporated in vacuo and subjected to flash chromatography on silica gel (EtOAc) to afford a yellow oil; isolated yield: 109 mg (63.4%). IR (NaCl): 2923.1, 2876.3, 1730.1, 1593.9, 1455.0, 1356.7, 1251.6, 1196.2, 1125.3, 988.3, 939.2, 833.1 cm^-1. ¹H NMR (300 MHz, CDCl₃): δ = 0.85 (t, J = 7.2 Hz, 6 H), 1.24-1.27 (q, J = 7.5 Hz, 4 H), 2.43-2.52 (m, 12 H), 2.73 (d, J = 6.3 Hz, 2 H), 2.79 (t, J = 4.5 Hz, 16 H), 2.87 (t, J = 7.5 Hz, 12 H), 3.56-3.76 (m, 95 H). ¹³C NMR (75 MHz, CDCl₃): δ = 173.15, 173.03, 78.56, 71.81, 70.87, 70.82, 70.54, 70.44, 70.38, 70.27, 70.11, 70.07, 69.83, 69.66, 69.63, 65.39, 54.46, 51.94, 51.60, 42.82, 32.57, 32.38, 22.80, 7.51. FABMS: m/z calcd for C₈₁H₁₄₇N₅O₃₃ [M⁺], 1718.0; found: 1719.5 [M + H]⁺. Anal. Calcd for C₈₁H₁₄₇N₅O₃₃: C, 56.59; H, 8.62; N, 4.07. Found: C, 56.88; H, 8.46; N, 4.42.
Penta-Crown Ether 2 Compound 3 (84 mg, 0.1 mmol) and 1-aza-18-crown-6 (132 mg, 0.5 mmol) were dissolved in MeOH (5 mL). The reaction was carried out as for 1 to afford a yellow oil; isolated yield: 116 mg (61.2%). IR (NaCl): 2915.9, 2874.4, 1731.8, 1596.8, 1456.0, 1352.8, 1248.7, 1195.7, 1111.9, 985.5, 950.7, 835.0 cm^-1. ¹H NMR (300 MHz, CDCl₃): δ = 0.85 (t, J = 7.5 Hz, 6 H), 1.22-1.25 (q, J = 7.5 Hz, 4 H), 2.43-2.51 (m, 12 H), 2.74 (d, J = 6.0 Hz, 2 H), 2.79 (t, J = 4.5 Hz, 16 H), 2.88 (t, J = 7.5 Hz, 12 H), 3.53-3.76 (m, 111 H), ¹³C NMR (75 MHz, CDCl₃): δ = 173.20, 173.04, 78.65, 71.82, 70.82, 70.72, 70.58, 70.55, 70.40, 70.35, 70.26, 70.15, 70.09, 69.97, 69.86, 69.61, 65.23, 53.79, 51.59, 51.54, 42.84, 32.58, 32.14, 22.82, 7.54. FABMS: m/z calcd for C₈₉H₁₆₃N₅O₃₇ [M⁺], 1894.1; found, 1895.4 [M + H]⁺. Anal. Calcd for C₈₉H₁₆₃N₅O₃₇: C, 56.40; H, 8.67; N, 3.70. Found: C, 56.71; H, 8.38; N, 3.85.