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DOI: 10.1055/s-0030-1259102
One-Pot Synthesis of Oxacalixarene Derivatives with Tunable Cavity Size Using Miscellaneous Linkers
Publication History
Publication Date:
10 December 2010 (online)
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
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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) ų, T = 298 (2) K, Z = 2, DC = 1.640 mg/m³, µ = 0.665 mm-¹, λ = 0.71073 Å, F(000) 578, crystal size 0.16 × 0.15 × 0.10 mm³, 1128 independent reflections [R(int) = 0.0555], reflections collected 5897, refinement method: full-matrix least-squares on F²: goodness-of-fit on F² 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.
References and Notes
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.
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) ų, T = 200(2)
K, Z = 4, DC = 1.461
Mg/M³, µ = 0.587
mm-¹, λ = 0.71073 Å, F(000) 1872.00, crystal size 0.26 × 0.20 × 0.15
mm³, 7333 independent reflections [R(int) = 0.0585],
reflections collected 32813, refinement method: full-matrix least-squares
on F²: goodness-of-fit on F² 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.