7016 J . Org. Chem., Vol. 64, No. 19, 1999
Elemans et al.
C68H58N4O14.0.5CHCl3 C, 67.72; H, 4.85; N, 4.61. Found: C,
67.83; H, 4.86; N, 4.89.
this compound was synthesized as described for H2-1. The
crude product was purified by column chromatography (2×,
first CHCl3/MeOH 97:3 v/v, then gradient elution EtOAc/n-
hexane 1:1 v/v to EtOAc/n-hexane 3:1 v/v). The resulting
compound was dissolved in a minimal amount of CHCl3 and
precipitated in stirred n-hexane (25 mL). After centrifugation
and drying under vacuum, 12 mg (4%) of H2-2 was obtained
as a dark red solid: mp > 400 °C; 1H NMR (500 MHz, CDCl3)
5,7,12,13b,13c,14-Hexa h yd r o-1,4,8,11-tetr a k is[2-(2-ch lo-
r oet h oxy)-et h oxy]-13b ,13c-d ip h en yl-6H ,13H -5a ,6a ,12a ,-
13a -tetr a a za ben z[5,6]-a zu len o[2,1,8-ija ]ben z[f]a zu len e-
6,13-d ion e (9). This compound was synthesized according to
a literature procedure.12
Tetr a -Ald eh yd e Clip Molecu le 10. A mixture of 9 (0.50
g, 0.50 mmol), Na2CO3 (1.6 g, 15 mmol), NaI (5.0 g, 33 mmol),
and m-hydroxybenzaldehyde (0.50 g, 4.1 mmol) in freshly
distilled acetonitrile (100 mL) was refluxed for 10 days. After
cooling, the mixture was filtered, and the filtrate was evapo-
rated to dryness. Water (100 mL) was added, and the resulting
suspension was extracted with CHCl3 (3 × 50 mL). The organic
layer was washed with aqueous 0.5 N NaOH (2 × 100 mL),
filtered, and evaporated to dryness. After column chromatog-
raphy (CHCl3/EtOH 97:3 v/v), 0.43 g (64%) of 10 was obtained
as a white solid: mp 212 °C; 1H NMR (500 MHz, CDCl3) δ
9.95 (s, 4H), 7.43 (d, 4H, 3J ) 7.5 Hz), 7.39 (s, 4H), 7.38 (t,
4H, 3J ) 7.5 Hz), 7.19-7.13 (m, 4H), 7.09-7.01 (m, 10H), 6.63
3
δ 8.92 (s, 4H), 8.80 (s, 4H), 8.06 (d, 4H, J ) 7.3 Hz), 7.71 (br
s, 4H), 7.68 (t, 4H, 3J ) 7.9 Hz), 7.35 (dd, 4H, 3J ) 8.2 Hz,
4J ) 2.3 Hz), 6.85 (m, 6H), 6.70 (m, 4H), 4.92 (d, 4H, 2J ) 16.1
Hz), 4.24 (m, 4H), 4.09 (m, 4H), 3.85 (m, 8H), 3.8 (br s, 4H),
3.55 (m, 8H), 3.21 (d, 4H, 2J ) 16.1 Hz), 3.20 (m, 4H), 2.68
(m, 4H), -2.70 (br s, 2H) ppm; 1H NMR (500 MHz, CDCl3/
3
CD3CN 1:1, v/v) δ 8.92 (s, 4H), 8.85 (s, 4H), 8.03 (d, 4H, J )
7.3 Hz), 7.82 (br s, 4H), 7.71 (t, 4H, 3J ) 7.9 Hz), 7.34 (dd, 4H,
4
3J ) 8.2 Hz, J ) 2.3 Hz), 6.85 (m, 6H), 6.70 (m, 4H), 4.65 (d,
2
4H, J ) 16.1 Hz), 4.35 (m, 4H), 4.16 (m, 4H), 3.85 (m, 12H),
3.55 (m, 8H), 3.16 (d, 4H, 2J ) 16.1 Hz), 3.16 (m, 4H), 2.64
(m, 4H), -2.78 (br s, 2H) ppm; 13C{1H} NMR (75 MHz, CDCl3)
δ 158.00, 156.90, 149.35, 143.30, 133.86, 132.91, 129.83,
128.18, 127.97, 127.56, 127.14, 126.02, 121.69, 120.18, 116.37,
111.56, 84.52, 70.74, 69.76, 68.74, 68.11, 36.40 ppm; MS (FAB)
m/z 1521 (M + H)+; UV-vis (CHCl3) λ/nm (log(ꢀ/M-1cm-1)) 420
(5.6), 515 (4.2), 549 (4.0), 588 (3.7), 644 (3.6). No satisfactory
elemental analysis could be obtained.
2
2
(s, 4H), 5.59 (d, 4H, J ) 15.8 Hz), 3.74 (d, 4H, J ) 15.8 Hz),
4.08-3.81 (m, 32H) ppm; 13C{1H} NMR (CDCl3, 75 MHz) δ
192.21, 159.41, 157.80, 150.72, 137.76, 133.83, 129.96, 128.55,
128.33, 128.14, 122.97, 121.96, 114.25, 113.55, 85.28, 70.47,
69.73, 67.81, 37.02 ppm; MS (FAB) m/z 1331 (M + H)+. Anal.
Calcd for C76H74O18N4‚CH3CH2OH: C, 68.01; H, 5.85; N, 4.07.
Found: C, 68.19; H, 6.06; N, 4.08.
P or p h yr in Clip Zn -2. This compound was prepared from
H2-2 (20 mg, 0.013 mmol) and Zn(OAc)2‚2H2O (7.2 mg, 0.032
mmol) as described for Zn -1. After purification by column
chromatography (EtOAc/n-hexane 2:1 v/v) 20 mg (96%) of Zn -2
P or p h yr in Clip H2-1. To CH2Cl2 (250 mL) were added
compound 8 (0.30 g, 0.26 mmol) and pyrrole (70 mg, 1.0 mmol).
The solution was purged with argon for 15 min and excluded
from light, and BF3‚OEt2 (50 mg, 0.35 mmol) was added. The
mixture was stirred for 16 h at room temperature. 4-Chloranil
(0.17 g, 0.75 mmol) was added and the mixture was refluxed
for 1 h. After the mixture cooled, the solvent was evaporated,
and the residue was purified by column chromatography (2×,
first CH2Cl2/EtOH 95:5 v/v, then CHCl3/MeOH 99:1 v/v). The
product was dissolved in a minimal amount of CHCl3 and
precipitated in stirred n-hexane (25 mL) to yield, after
centrifugation and drying under vacuum, 20 mg (6%) of H2-1
as a dark red solid: mp > 400 °C; 1H NMR (500 MHz, CDCl3)
1
was obtained as a purple solid: mp > 400 °C; H NMR (500
3
MHz, CDCl3) δ 8.96 (s, 4H), 8.94 (s, 4H), 7.98 (d, 4H, J ) 7.4
Hz), 7.85 (br s, 4H), 7.65 (t, 4H, 3J ) 7.5 Hz), 7.33 (dd, 4H,
4
3J ) 8.3 Hz, J ) 2.3 Hz), 6.71 (m, 6H), 6.51 (m, 4H), 4.59 (s,
4H), 4.32 (m, 4H), 4.28 (d, 4H, 2J ) 15.6 Hz), 4.18 (m, 4H),
3.85 (m, 8H), 3.55 (m, 8H), 3.30 (d, 4H, 2J ) 15.6 Hz), 3.34
(m, 4H), 2.95 (m, 4H) ppm;1H NMR (500 MHz, CDCl3:CD3CN
3
1:1, v/v) δ 8.97 (s, 4H), 8.92 (s, 4H,), 8.01 (d, 4H, J ) 7.4 Hz),
7.96 (br s, 4H), 7.70 (t, 4H, 3J ) 7.5 Hz), 7.34 (dd, 4H, 3J ) 8.3
Hz, 4J ) 2.3 Hz), 6.88 (m, 6H), 6.72 (m, 4H), 4.76 (s, 4H), 4.72
(d, 4H, 2J ) 15.6 Hz), 4.56 (m, 4H), 4.27 (m, 4H), 3.88 (m, 8H),
3.58 (m, 8H), 3.20 (d, 4H, 2J ) 15.6 Hz), 3.15 (m, 4H), 3.00
(m, 4H) ppm; 13C{1H} NMR (75 MHz, CDCl3) δ 157.22, 156.89,
150.23, 149.62, 134.28, 132.11, 131.92, 127.84, 127.62, 127.31,
126.61, 121.68, 120.96, 115.83, 112.44, 84.36, 70.74, 70.02,
68.62, 36.49 ppm; MS (FAB) m/z 1585 (M + H)+; UV-vis
(CHCl3) λ/nm (log(ꢀ/M-1cm-1)) 420 (5.6), 546 (4.2). No satisfac-
tory elemental analysis could be obtained.
3
δ 8.75 (s, 4H), 8.66 (s, 4H), 8.07 (d, 4H, J ) 7.3 Hz), 7.75 (t,
3
3
3
4H, J ) 8.0 Hz), 7.37 (t, 4H, J ) 7.4 Hz), 7.34 (d, 4H, J )
8.4 Hz), 6.97-6.91 (m, 6H), 6.83-6.78 (m, 4H), 6.20 (s, 4H),
2
4.30-4.20 (m, 4H), 4.24 (d, 4H, J ) 15.8 Hz), 4.09-4.01 (m,
4H), 3.74 (d, 4H, 2J ) 15.8 Hz), 3.53-3.43 (m, 4H), 3.37-3.30
(m, 4H), -2.72 (br s, 4H) ppm; 13C{1H} NMR (75 MHz, CDCl3)
δ 158.76, 156.99, 146.60, 135.75, 133.63, 131.90, 129.82,
129.57, 128.45, 128.10, 119.82, 115.21, 111.93, 84.76, 67.43,
66.87, 44.39; MS (FAB) m/z 1345 (M + H)+; UV-vis (CHCl3)
λ/nm (log(ꢀ/M-1 cm-1)) 418 (5.63), 485 (3.44), 515 (4.27), 548
(3.82), 587 (4.02), 639 (3.70). Anal. Calcd for C84H64N8O10: C,
74.97; H, 4.79; N, 8.33. Found: C, 74.84; H, 4.93; N, 8.32.
P or p h yr in Clip Zn -1. To a degassed solution of H2-1 (20
mg, 0.015 mmol) in a mixture of CHCl3 (2 mL) and MeOH (1
mL) was added Zn(OAc)2‚2H2O (8.0 mg, 0.036 mmol). The
mixture was refluxed for 3 h. After the mixture cooled, the
solvent was evaporated, and the product was dissolved in CH2-
Cl2 (10 mL) The organic layer was washed with water (2×)
and concentrated in vacuo. After purification by column
chromatography (CH2Cl2/MeOH 97:3, v/v) 20 mg (95%) of Zn -1
(N,N′)-Dim eth yl-4,4′-bip yr id in iu m Dih exa flu or op h os-
p h a te (G1). This compound was prepared from the com-
mercially available dichloride salt by anion exchange with
NH4PF6.
(N,N′)-Di(2-eth a n ol)-4,4′-bip yr id in iu m Dih exa flu or o-
p h osp h a te (G2). 4,4′-Bipyridine (3.7 g, 24 mmol) and 2-bro-
moethanol (16 g, 0.13 mol) were refluxed in acetonitrile (75
mL) for 24 h. After the mixture cooled, the precipitate was
filtered off, washed with diethyl ether, and dried under
vacuum. The product was dissolved in a minimal amount of
water, and this solution was then added to a saturated aqueous
NH4PF6 solution to yield, after filtration and drying under
1
1
vacuum, 6.0 g (47%) of G2 as a white solid: mp 185 °C; H
was obtained as a purple solid: mp > 400 °C; H NMR (500
3
3
NMR (300 MHz, CD3CN) δ 9.39 (d, 4H, J ) 7.2 Hz), 8.85 (d,
MHz, CDCl3) δ 8.89 (s, 4H), 8.77 (s, 4H), 8.10 (d, 4H, J ) 6.6
3
3
3
3
3
4H, J ) 7.2 Hz), 5.05 (t, 4H, J ) 5.1 Hz), 4.68 (t, 2H, J )
5.2 Hz), 4.24-4.17 (m, 4H) ppm; MS (FAB) m/z 391 (M -
PF6)+. Anal. Calcd for C14H18N2O2P2F12: C, 31.36; H, 3.38; N,
5.22. Found: C, 31.18; H, 3.39; N, 5.18.
Hz), 7.74 (t, 4H, J ) 7.2 Hz), 7.38 (t, 4H, J ) 7.5 Hz), 7.34
(d, 4H, 3J ) 8.2 Hz), 7.00-6.92 (m, 6H), 6.85-6.74 (m, 4H),
6.17 (s, 4H), 4.27-4.15 (m, 4H), 4.19 (d, 4H, 2J ) 15.6 Hz),
2
4.09-3.99 (m, 4H), 3.72 (d, 4H, J ) 15.6 Hz), 3.57-3.47 (m,
4H), 3.35-3.23 (m, 4H) ppm; 13C{1H} NMR (CDCl3, 75 MHz)
δ 158.87, 150.13, 149.88, 146.63, 135.56, 133.66, 132.72,
131.44, 130.89, 129.90, 129.36, 128.50, 128.11, 119.87, 116.14,
115.41, 112.16, 84.76, 67.50, 67.02, 44.33 ppm; UV-vis (CHCl3)
λ/nm (log(ꢀ/M-1 cm-1)) 420 (5.6), 545 (4.1). No satisfactory
elemental analysis could be obtained.
Hexyl 3,5-Dih yd r oxyben zoa te (G7). This compound was
synthesized according to a literature procedure.10b
Su p p or tin g In for m a tion Ava ila ble: 1H NMR peak as-
signments for all compounds and protocols for determining
1
association constants using H NMR and UV titrations. This
material is available free of charge on the Internet at
http://pubs.acs.org.
P or p h yr in Clip H2-2. From 10 (0.30 g, 0.23 mmol) and
pyrrole (61 mg, 0.91 mmol) in CH2Cl2 (250 mL) using BF3‚
OEt2 (50 mg, 0.35 mmol) and 4-chloranil (0.17 g, 0.75 mmol),
J O990112C