M. Zhang, Y. Luo, B. Zheng, X. Yan, F. R. Fronczek, F. Huang
FULL PAPER
H), 6.85 (t, J = 8.4 Hz, 2 H, Ar-H), 6.50 (d, J = 8.4 Hz, 4 H, Ar-
H), 4.90 (s, 4 H, benzyl-H), 4.05 (t, J = 4.8 Hz, 8 H, α-OCH2), 3.75 [1]
(t, J = 4.8 Hz, 8 H, β-OCH2), 3.58–3.60 (m, 8 H, γ-OCH2), 3.50–
3.54 (m, 8 H, δ-OCH2) ppm. 13C NMR (125 MHz, CDCl3, 295 K):
δ = 153.3, 138.5, 128.5, 128.2, 127.8, 123.7, 107.6, 74.9, 71.2, 70.9,
70.0, 69.1 ppm. LRESI-MS: m/z (%) = 766.8 (48.0) [9 + NH4]+,
771.9 (100) [9 + Na]+, 787.8 (50.0) [9 + K]+. HRESI-MS: calcd. for
C42H52NaO12 [9 + Na]+: 771.3351; found 771.3376, error 3.2 ppm.
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Synthesis of the Crown Ether 1a: Pd/C (100 mg) and 9 (1.00 g,
1.35 mmol) were placed in a 150 mL round-bottomed flask. The
flask was evacuated and then hydrogen was introduced. After this
process had been carried out three times, CH3Cl/CH3OH (1:1 v/v,
100 mL) was added. The reaction mixture was heated at 60 °C for
24 h, the solution was filtered, and the filtrate was concentrated to
give a pale yellow crude product, which was purified by flash col-
umn chromatography (ethyl acetate/methanol 1:10) to give 1a
(700 mg, 91.2%) as a white solid; m.p. 92.3–94.8 °C. 1H NMR
(400 MHz, CD3COCD3, 295 K): δ = 7.32 (s, 2 H, –OH), 6.64–6.67
(m, 6 H, Ar-H), 4.13 (t, J = 4.8 Hz, 8 H, α-OCH2), 3.80 (t, J =
4.8 Hz, 8 H, β-OCH2), 3.62–3.70 (m, 16 H, γ-OCH2 and δ-
OCH2) ppm. 13C NMR (125 MHz, CDCl3, 295 K): δ = 147.4,
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2828.
138.2, 118.5, 109.1, 70.9, 70.6, 69.8, 69.6 ppm. LRESI-MS: m/z (%)
= 569.3 (82.0) [1a + H]+, 591.6 (100) [1a + Na]+. HRESI-MS:
calcd. for C28H40NaO12 [1a + Na]+: 591.2412; found 591.2406, er-
ror –1.0 ppm.
[8]
[9]
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Synthesis of the [2]Catenane 4: A solution of [BBIPYXY][PF6]2 (10,
70.6 mg, 0.100 mmol) in dry DMF (5 mL) was added under N2 to
a solution of 1a (142 mg, 0.250 mmol) in dry DMF (5 mL). The
color of the mixture quickly changed to faint yellow. 1,4-Bis(brom-
omethyl)benzene (26.4 mg, 0.100 mmol) in DMF (5 mL) was then
added to the mixture at room temperature. A red deposit gradually
appeared. The reaction mixture was then stirred at room tempera-
ture for 5 d. The solvent was removed in vacuo, and the resulting
residue was dissolved in a mixture of MeOH/2 n NH4Cl/MeNO2
(7:2:1) and subjected to column chromatography (SiO2, MeOH/2 n
NH4Cl/MeNO2 25:2:1). The fractions containing the product (TLC
monitoring) were combined and concentrated under vacuum to
give a residue, which was dissolved in H2O. A red solid, the [2]-
catenane 4 (113 mg, 68.0%), was precipitated from this solution by
addition of a saturated aqueous NH4PF6 solution; m.p. Ͼ200 °C
[10]
[11]
[12]
1
(dec.). H NMR (500 MHz, CD3SOCD3, 295 K): δ = 9.17 (d, J =
6.8 Hz, 8 H, α-pyridinium-H), 7.97 (d, J = 6.8 Hz, 8 H, β-pyridi-
nium-H), 7.91 (s, 8 H, Ar-H of cyclophane 5), 5.77 (s, 8 H, benzyl-
H of cyclophane 5), 5.48 (br., 2 H, Ar-H of crown ether 1a), 5.00
(br., 4 H, Ar-H of crown ether 1a), 3.78–3.81 (m, 8 H, α-OCH2),
3.72–3.76 (m, 8 H, β-OCH2), 3.68–3.72 (m, 8 H, γ-OCH2), 3.52–
3.58 (m, 8 H, δ-OCH2) ppm. 13C NMR (125 MHz, CD3CN,
295 K): δ = 147.0, 145.5, 137.3, 131.9, 126.6, 120.7, 71.1, 71.0, 70.2,
69.5, 65.9 ppm. LRESI-MS: m/z (%) = 689.1 (100) [4 – 2PF6]2+
,
411.1 (40) [4 – 3PF6]3+, 272.1 (96) [4 – 4PF6]4+. HRESI-MS: calcd.
for C64H72F12N4O12P2 [4 – 2PF6]2+: 689.2210; found 689.2262, er-
ror 7.6 ppm.
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Supporting Information (see also the footnote on the first page of
this article): Characterizations, Job plots, UV/Vis data, and crystal
data for 1a2ʛ3 and 4.
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P. Job, Ann. Chim. 1928, 9, 113–203.
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F. Huang, Tetrahedron Lett. 2008, 49, 5009–5012.
Acknowledgments
1
[17]
The H NMR spectroscopic data for 1a and 1b before and after
the addition of KPF6 indicated that host 1a could bind K+ in
acetone whereas 1b could not. See the Supporting Information
for details.
This work was supported by the National Natural Science Founda-
tion of China (20774086, 20834004, and J0830413) and the Funda-
mental Research Funds for the Central Universities (China)
(2010QNA3008).
[18]
J. W. Jones, L. N. Zakharov, A. L. Rheingold, H. W. Gibson, J.
Am. Chem. Soc. 2002, 124, 13378–13379.
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