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.

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

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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.

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.

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.