One-Pot Synthesis of Oxacalixarene Derivatives with Tunable Cavity Size Using Miscellaneous Linkers

Abstract

Five oxacalixarene derivatives with different linkers including fluorescent units, soft donor atoms, and hydrogen-bond acceptors have been prepared via one-pot approach. Crystal structure reveals that oxacalixarene adopts a classical 1,3-alternate conformation. In contrast, the oxacalixarene adopts a cavity-like conformation. The inner cavity size is up to 13.357 Å and guest molecules, such as chloroform, are included in its solid state.

Key words

oxacalixarene - one pot - diphenols - nucleophilic aromatic substitution - linkers

References and Notes

• 1a Gutsche CD. Dhawan B. No KH. Muthukrishnan R. J. Am. Chem. Soc.  1981,  103:  3782 
• 1b Gutsche CD. Calixarenes   RSC; Cambridge: 1989. 
• 1c Gutsche CD. Calixarenes Revisited   RSC; Cambridge: 1998. 
• 2a Calixarenes in Action   Mandolini L. Ungaro R. Imperial College Press; London: 2000. 
• 2b Calixarenes 2001   Asfari Z. Böhmer V. Harrowfield J. Vicens J. Saadioui M. Kluwer Academic Publishers; Dordrecht: 2001. 
• 2c Lumetta GJ. Rogers RD. Gopalan AS. Calixarenes for Separation   American Chemical Society; Washington DC: 2000. 
• 2d Tsukano C. Siegel DR. Danishefsky SJ. Angew. Chem. Int. Ed.  2007,  46:  8840 
• 3a Supramolecular Chemistry of Anions   Bianchi A. Bowman-James K. García-España E. Wiley-VCH; New York: 1997. 
• 3b Schmidtchen FP. Berger M. Chem. Rev.  1997,  97:  1609 
• 3c Mohammad RG. Parviz N. Morteza R. Farnoush F. Mohammad RP. Sensor  2006,  6:  1018 
• 3d Quiocho FA. Kidney Int.  1996,  49:  943 
• 3e Bell TW. Hext NM. Chem. Soc. Rev.  2004,  33:  589 
• 4a König B. Fonseca MH. Eur. J. Inorg. Chem.  2000,  2303 
• 4b Wang M.-X. Chem. Commun.  2008,  4541 
• 4c Maes W. Dehaen W. Chem. Soc. Rev.  2008,  37:  2393 
• Some recent examples:
• 5a Graubaum H. Lutze G. Costisella B. J. Prakt. Chem./Chem.-Ztg.  1997,  339:  266 
• 5b Graubaum H. Lutze G. Costisella B. Linden B.
  J. Prakt. Chem./Chem.-Ztg.  1997,  339:  672 
• 5c Ito A. Ono Y. Tanaka K. Angew. Chem. Int. Ed.  2000,  112:  1114 
• 5d Ito A. Ono Y. Tanaka K. Angew. Chem. Int. Ed.  2000,  39:  1072 
• 5e Fukushima W. Kanbara T. Yamamoto T. Synlett  2005,  2931 
• 5f Suzuki Y. Yanagi T. Kanbara T. Yamamoto T. Synlett  2005,  263 
• 5g Wang M.-X. Zhang X.-H. Zheng Q.-Y. Angew. Chem. Int. Ed.  2004,  43:  838 
• 5h Yao B. Wang D.-X. Gong H.-Y. Huang Z.-T. Wang M.-X. J. Org. Chem.  2009,  74:  5361 
• 5i Yao B. Wang D.-X. Huang Z.-T. Wang M.-X. Chem. Commun.  2009,  2899 
• 5j Zhang E.-X. Wang D.-X. Huang Z.-T. Wang M.-X. J. Org. Chem.  2009,  74:  8595 
• 5k Wang L.-X. Wang D.-X. Huang Z.-T. Wang M.-X. J. Org. Chem.  2010,  75:  741 
• 5l Touil M. Lachkar M. Siri O. Tetrahedron Lett.  2008,  49:  7250 
• 5m Haddoub R. Touil M. Raimundo J. M . Siri O. Org. Lett.  2010,  12:  2722 
• 5n Konishi H. Hashimoto S. Sakakibara T. Matsubara S. Yasukawa Y. Morikawa O. Kobayashi K. Tetrahedron Lett.  2009,  50:  620 
• 5o Yasukawa Y. Kobayashi K. Konishi H. Tetrahedron Lett.  2009,  50:  5130 
• 5p Xue M. Chen C.-F. Org. Lett.  2009,  1:  5294 
• 5q Katz JL. Tschaen B. A. Org. Lett.  2010,  12:  4300 ; and other references cited therein
• Some recent examples:
• 6a Chambers RD. Khalil A. Richmond P. Sandford G. Yufit DS. Howard JAK. J. Fluorine Chem.  2004,  125:  715 
• 6b Chambers RD. Khalil A. Murray CB. Sandford G. Batsanov A. Howard JAK. J. Fluorine Chem.  2005,  126:  1002 
• 6c Li XH. Upton TG. Gibb CLD. Gibb BC. J. Am. Chem. Soc.  2003,  125:  650 
• 6d Wang M.-X. Yang H.-B. J. Am. Chem. Soc.  2004,  126:  15412 
• 6e Chen Y. Wang D.-X. Huang Z.-T. Wang M.-X. J. Org. Chem.  2010,  75:  3786 
• 6f Katz JL. Geller BJ. Foster PD. Chem. Commun.  2007,  1026 
• 6g Wackerly JW. Meyer JM. Crannell WC. King SB. Katz JL. Macrocycles  2009,  42:  8181 
• 6h Van Rossom W. Maes W. Kishore L. Ovaere M. Van Meervel L. Dehaen W. Org. Lett.  2008,  10:  585 
• 6i Van Rossom W. Ovaere M. Van Meervel L. Dehaen W. Maes W. Org. Lett.  2009,  11:  1861 
• 6j Van Rossom W. Kishore L. Robeyns K. Van Meervel L. Dehaen W. Maes W. Eur. J. Org. Chem.  2010,  4122 
• 6k Ma M.-L. Li X.-Y. Wen K. J. Am. Chem. Soc.  2009,  131:  8338 
• 6l Hu S.-Z. Chen C.-F. Chem. Commun.  2010,  46:  4199  ; and other references cited therein
• 7a Montaudo G. Bottino F. Trivellone E. J. Org. Chem.  1972,  37:  504 
• 7b Kumagai H. Hasegawa M. Miyanari S. Sugawa Y. Sato Y. Hori T. Ueda S. Kamiyama H. Miyano S. Tetrahedron Lett.  1997,  38:  3971 
• 7c Freund T. Kubel C. Baumgarten M. Enkelmann V. Gherghel L. Reuter R. Müllen K. Eur. J. Org. Chem.  1998,  555 
• 7d Iki H. Kabuto C. Fukushima T. Kumagai H. Takeya H. Miyanari S. Miyashi T. Miyano S. Tetrahedron  2000,  56:  1437 
• 7e Lhotak P. Eur. J. Org. Chem.  2004,  1675 
• 7f Stoikov II. Yushkov EA. Zharoc I. Antipin I. Konovalov AI. Tetrahedron Lett.  2009,  65:  7109 
• 8a Kauffmann T. Kniese HH. Tetrahedron Lett.  1973,  41:  4043 
• 8b König B. Rödel M. Bubenitschek P. Jones PG. Angew. Chem., Int. Ed. Engl.  1995,  34:  661 ; Angew. Chem. 1995, 107, 752
• 8c König B. Rödel M. Bubenitschek P. Jones PG. Thondorf I. J. Org. Chem.  1995,  60:  7406 
• 8d Yoshida M. Goto M. Nakanishi F. Organometallics  1999,  18:  1465 
• 9a Masci B. Finelli M. Varrone M. Chem. Eur. J.  1998,  4:  2018 
• 9b Darbost U. Sénèque O. Li Y. Bertho G. Marrot J. Rager M.-N. Reinaud O. Jabin I. Chem. Eur. J.  2007,  13:  2078 
• 9c Zhang C. Chen C.-F. J. Org. Chem.  2007,  72:  3880 
• 10a Ma M.-L. Wang H.-X. Li X.-Y. Liu L.-Q. Jin H.-S. Wen K. Tetrahedron  2009,  65:  300 
• 10b Li M. Ma M.-L. Li X.-Y. Wen K. Tetrahedron  2009,  65:  4639 
• 13a

  Crystal structure data for compound 1a: CCDC 779459.
  C₃₈H₃₀Cl₈N₆O₄, chemical formula weight: 575.59, monoclinic space group Pmmn, a = 11.4790 (1), b = 12.2555 (1), c = 8.2846 (9) Å; α = 90.000˚, β = 90.000˚, γ = 90.000˚, U = 1165.5 (2) Å^³, T = 298 (2) K, Z = 2, DC = 1.640 mg/m^³, µ = 0.665 mm^-¹, λ = 0.71073 Å, F(000) 578, crystal size 0.16 × 0.15 × 0.10 mm^³, 1128 independent reflections [R(int) = 0.0555], reflections collected 5897, refinement method: full-matrix least-squares on F^²: goodness-of-fit on F^² 1.053, final R indices [I > 2σ(I)], R1 = 0.0631, wR2 = 0.1846, largest diff. peak and hole 0.515 Å^-³ and -0.665 e ^. Å^-³.

• 13b

  Crystal structure data for macrocycle 6a: CCDC 778338.

11

The solvent molecules (CHCl₃) are hydrogen-bond donors, and the two O1 atoms of compound 1a are hydrogen-bond acceptors. The distance of H6˙˙˙O1 is 2.669 Å, and the C6-H6˙˙˙O1 bond angel is 135.380˚.

12

Representative Procedure
To a solution of DIPEA (2.5 equiv) in THF, catechol 1 (1 equiv), and cyanuric chloride (1 equiv) were separately, but simultaneously, added slowly in THF using the high-dilution method. The resulting mixture was then stirred several hours (TLC monitoring). After that, the solvent was removed under reduce pressure, and added H₂O (50 mL) to the residue, then extracted with EtOAc (3 × 50 mL). The organic phase was dried by anhyd Na₂SO₄, and removed the EtOAc under reduce pressure. The final residue was purified by column chromatography on silica gel (PE-EtOAc) to afford the expected oxacalixarenes 1a in 30% yield.
Compound 1a: white solids (30%); mp >300 ˚C. IR (KBr): 3443, 1554, 1493, 1454, 1430, 1379, 1299, 1232, 1211, 1167, 1102, 1080, 986, 954 cm^-¹. ^¹H NMR (600 MHz, CDCl₃): δ = 7.00-7.04 (m, 4 H), 7.13-7.16 (m, 4 H). ^¹³C NMR (150 MHz, CDCl₃): δ = 174.6, 171.6, 143.1, 127.5, 123.4. ESI-HRMS: m/z [M + Na]⁺ calcd for C₁₈H₈N₆NaO₄Cl₂: 464.9876; found: 464.9871.

14

C₃₈H₃₀Cl₈N₆O₄, chemical formula weight: 918.28, monoclinic, space group P2 (1)/n, a = 20.306 (3), b = 10.1760, c = 20.828 (3) Å; α = 90.000˚, β = 104.112 (2)˚, γ = 90.00˚, U = 4173.9 (9) Å^³, T = 200(2) K, Z = 4, DC = 1.461 Mg/M^³, µ = 0.587 mm^-¹, λ = 0.71073 Å, F(000) 1872.00, crystal size 0.26 × 0.20 × 0.15 mm^³, 7333 independent reflections [R(int) = 0.0585], reflections collected 32813, refinement method: full-matrix least-squares on F^²: goodness-of-fit on F^² 1.178, final R indices
[I > 2σ(I)], R1 = 0.0896, wR2 = 0.1908, largest diff. peak and hole 0.753 Å^-³ and -0.524 e ^. Å^-³.