Â
M. Perez-Alvarez et al. / Tetrahedron 57 62001) 3799±3808
3807
extracted again with CH2Cl2 22£50 mL). The combined
organic solution was washed with H2O 280 mL), dried
2MgSO4), ®ltered, and concentrated under reduced pressure
to give 14 280 mg, 4%) as a yellow oil. HRFABMS calcd for
re¯ections [uFou.4s2uFou), 2u#1208] and 1201 parameters.
CCDC 159799.
4.2. Association constants
1
C16H24O8: m/z 344.1471. Found: m/z 344.1474; H NMR
2200 MHz, CDCl3) d 7.22 2d, J3.0 Hz, 1H), 6.91 2dd,
J3.0, 9.0 Hz, 1H), 6.81 2d, J9.0 Hz, 1H), 3.95±4.03
2m, 4H), 3.72 2s, 3H), 3.46±3.74 2m, 12H), 2.76 2s, 2H);
1H NMR 2400 MHz, CD3CN) d 7.22 2d, J3.0 Hz, 1H),
7.07 2dd, J3.0, 9.0 Hz, 1H), 7.02 2d, J9.0 Hz, 1H),
3.80±4.09 2m, 4H), 3.80 2s, 3H), 3.73±3.76 2m, 4H),
3.53±3.58 2m, 8H); 13C NMR 250 MHz, CDCl3) d 166.2,
152.8, 152.5, 121.2, 120.4, 116.8, 116.2, 72.6, 72.5, 69.8,
69.5, 69.4, 68.1, 61.5, 52.0.
An equimolar CD3CN solution of host and guest was diluted
from ca. 1022 to ca. 1023 M in 10±15 consecutive steps. The
resulting solutions were analyzed by 1H NMR spectroscopy
at 258C. The association constants of the complexes were
determined17 by nonlinear curve-®tting of the plot of the
chemical shift change associated with the resonance of the
b-bipyridinium protons against the concentration.
References
4.1.11. [2]Catenanes 18´4PF6, 19´4PF6, and 20´4PF6. A
solution of 16´2PF6 270.6 mg, 0.10 mmol), 17 226.4 mg,
0.10 mmol), and 3, 5, or 10 20.20 mmol) in dry MeCN
26 mL) was stirred for 10 d at room temperature. The
solvent was distilled off under reduced pressure and the
residue was puri®ed by column chromatography 2SiO2,
MeOH/2 M NH4Claq/MeNO2 7:2:1). The resulting solid
was dissolved in H2O 27 mL) and a saturated aqueous solu-
tion of NH4PF6 was added until no further precipitation
occurred. The precipitate was ®ltered off, washed with
H2O 210 mL), and dried under reduced pressure to afford
18´4PF6, 19´4PF6, or 20´4PF6 as a red solid.
1. 2a) Alivastos, A. P.; Barbara, P. F.; Castleman, A. W.; Chang,
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Stoddart, J. F., Vogtle, F., Eds.; Wiley-VCH: Weinheim,
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18´4PF6 253%): Mp 2988C 2decomposition). FABMS m/z
1
1635 [M2PF6]1,1498 [M22PF6]1; H NMR 2200 MHz,
CD3CN) d 8.90 2d, J6.4 Hz, 8H), 7.80 2s, 8H), 7.65 2d,
J6.4 Hz, 8H), 6.40 2s, 2H), 5.70 2s, 8H), 4.35 2q,
J7.0 Hz, 4H), 3.62±3.94 2m, 36H), 1.40 2t, J7.0 Hz,
6H); 13C NMR 250 MHz, CDCl3) d 166.5, 151.0, 150.2,
146.4, 145.7, 137.6, 131.8, 126.3, 125.7, 115.3, 113.8,
71.8, 71.1, 70.8, 70.4, 70.3, 69.7, 67.7, 65.7, 62.60, 14.7.
È
È
Chem. Rev. 1995, 95, 2725±2828. 2g) Jager, R.; Vogtle, F.
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J. P.; Seto, C. T.; Chin, D. N.; Mammen, M.; Gordon, D. M.
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19´4PF6 23%): Mp 2958C 2decomposition). FABMS m/z
1
1607 [M2PF6]1, 1462 [M22PF6]1, 1317 [M23PF6]1; H
NMR 2200 MHz, CD3CN) d 8.92±8.95 2m, 8H), 7.80 2s,
8H), 7.73±7.74 2m, 8H), 7.47±7.57 2m, 2H), 5.71 2bs,
8H), 3.40±3.89 2m, 42H), 1.35±1.41 2m, 12H); 13C NMR
250 MHz, CDCl3) d 166.9, 151.8, 151.8, 151.4, 151.3,
148.0, 146.9, 146.5, 145.8, 140.9, 137.6, 135.2, 133.5,
131.7, 131.2, 130.7, 130.6, 128.4, 126.7, 71.4, 71.2, 71.0,
70.6, 70.4, 68.3, 65.6, 65.2, 64.9, 53.2, 46.1.
20´4PF6 210%): Mp 3018C 2decomposition). FABMS m/z
1463 [M22PF6]1, 1317 [M23PF6]1, 1172 [M24PF6]1;
1H NMR 2400 MHz, CD3CN) d 8.92 2bs, 8H), 7.79 2s,
8H), 7.71 2bs, 8H), 6.35 2m, 3H), 5.70 2s, 8H), 3.35±3.95
2m, 41H); 13C NMR 2100 MHz, CD3CN) d 148.7, 146.9,
145.9, 137.65, 131.8, 126.7, 71.5, 71.4, 71.2, 70.4, 65.6.
Single crystals of the [2]catenane 20´4PF6, suitable for
X-ray crystallographic analysis, were grown by slow
evaporation of the compound from a solution in MeCN/
Et2O. Crystal data for 20´4PF6: C68H76N4O14´4PF6´3MeCN,
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È
R.; Vogtle, F. Angew. Chem., Int. Ed. Engl. 1994, 33, 375±
ꢀ
M1876.4, triclinic, P1 2no. 2), a13.36522), b13.81021),
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Ê
c26.90223) A, a87.0121), b80.8721), g61.7221)8,
Ê 3
V4315.628) A , Z2, Dc1.444 g cm23
,
m2CuKa)
18.4 cm21, F2000)1932, T183 K; orange/red rhombic
needles, 0.33£0.15£0.15 mm3, re®ned based on F2 to give
R10.132, wR20.344 for 8122 independent observed