36 J . Org. Chem., Vol. 62, No. 1, 1997
Asakawa et al.
inverse 13C-1H correlation) δ 65.5, 67.5, 69.3, 69.4, 70.6, 70.8,
70.9, 71.0, 71.6, 71.6, 71.8, 72.2, 105.0, 109.1, 113.8, 118.5,
126.1, 128.4, 131.7, 145.3, 137.5, 146.5; LSIMS m/ z 1541 [M
- PF6]+, 1396 [M - 2PF6]+, 1251 [M - 3PF6]+; HRLSIMS m/ z
calcd for C68H74N4O10F3P18 [M - PF6]+ m/ z 1541.4330, found
m/ z 1541.4431. Single crystals, suitable for X-ray crystal-
lography, were grown by vapor diffusion of i-Pr2O into a
solution of 9a ‚4PF6 in MeCN.
6.08 (m, 10H), 6.25 (d, 2H, J ) 8 Hz), 6.32 (dd, 1H, J ) 9, 2.5
Hz), 6.71 (d, 2H, J ) 7.5 Hz), 7.06 (d, 1H, J ) 8.5 Hz), 7.17 (d,
1H, J ) 9 Hz), 7.23 (d, 1H, J ) 8 Hz), 7.26 (m, 2H), 7.42 (m,
2H), 7.51 (m, 2H), 7.58 (d, 2H, J ) 6.6 Hz), 8.12 (s, 2H), 8.18
(s, 2H), 8.31 (bs, 4H), 8.77 (m, 2H), 9.03 (d, 2H, J ) 6.5 Hz),
9.17 (d, 2H, J ) 7 Hz), 9.27 (d, 2H, J ) 6.5 Hz); 13C NMR (75
MHz, CD3CN) δ 66.0, 69.0, 69.2, 69.7, 70.7, 70.9, 71.2, 71.9,
72.0, 72.2, 105.0, 105.2, 105.4, 109.3, 120.5, 124.3, 125.0, 125.3,
126.2, 128.6, 129.1, 130.7, 130.8, 131.4, 132.2, 144.6, 145.1,
120.9, 136.5, 137.6, 145.4, 152.0, 155.4, 157.9; LSIMS m/ z
1737 [M + H]+, 1591 [M - PF6]+, 1446 [M - 2PF6]+, 1301 [M
- 3PF6]+; HRLSIMS calcd for C72H76N4O10F3P18 [M - PF6]+
m/ z 1591.4487, found 1591.4552. Single crystals, suitable for
X-ray crystallography, were grown by vapor diffusion of i-Pr2O
into a solution of 9h ‚4PF6 in MeCN.
1
[2]Ca ten a n e 9b‚4P F 6: yield 89%; mp > 300 °C; H NMR
(400 MHz, CD3SOCD3, 300 K) δ 3.20 (s, 4H), 3.51 (m, 4H),
3.78-3.83 (m, 20H), 3.89 (s, 8H), 5.73 (s, 8H), 6.57 (bs, 2H),
6.73 (bd, 2H, J ) 7.5 Hz), 7.19 (bd, 2H, J ) 6.5 Hz), 7.88 (s,
8H), 7.92 (d, 8H, J ) 5.5 Hz), 9.04 (d, 8H, J ) 6 Hz); 13C NMR
(100.6 MHz, CD3SOCD3, 298 K, inverse 13C-1H correlation) δ
63.7, 65.9, 67.7, 68.9, 69.6, 69.9, 70.1, 70.3, 70.7, 106.6, 112.3,
118.7, 125.3, 128.2, 130.7, 144.1, 130.0, 137.0, 145.4, 149.6,
154.5; LSIMS m/ z 1686 [M]+, 1541 [M - PF6]+, 1396 [M -
2PF6]+, 1251 [M - 3PF6]+; HRLSIMS calcd for C68H74N4O10F3P18
[M - PF6]+ m/ z 1541.4330, found m/ z 1541.4269. Single
crystals, suitable for X-ray crystallography, were grown by
vapor diffusion of i-Pr2O into a solution of 9b‚4PF6 in MeCN-
CH3NO2 (1:1, v/v).17
1
[2]Ca ten a n e 9i‚4P F 6: yield 74%; mp > 259 °C; H NMR
(400 MHz, CD3CN, 303 K, 2D-COSY 45) δ 2.29, (d, 2H, J )
8.3 Hz), 3.67 (m, 4H), 3.72 (m, 4H), 3.79 (m, 4H), 3.83 (m, 4H),
3.94 (m, 4H), 4.12 (m, 4H), 4.09 (m, 4H), 4.15 (m, 4H), 5.60,
5.63, 5.80, 5.83 (AB system, 8H), 5.84 (t, 2H, J ) 6 Hz), 6.10
(d, 2H, J ) 7 Hz), 6.39 (d, 2H, J ) 2 Hz), 6.70 (dd, 2H, J ) 9,
2 Hz), 6.90 (d, 4H, J ) 6 Hz), 6.96 (d, 4H, J ) 6 Hz), 7.10 (d,
2H, J ) 9 Hz), 7.85-8.08 (bm, 8H), 8.44 (d, 4H, J ) 6.5 Hz),
8.72 (d, 4H, J ) 7 Hz); 13C NMR (75 MHz, CD3CN) δ 65.8,
68.6, 69.0, 69.9, 70.6, 71.2, 72.2, 104.9, 107.5, 109.2, 119.8,
125.2, 126.2, 129.2, 132.0, 132.1, 144.5, 145.4, 131.1, 137.4,
145.1, 152.0, 155.9; LSIMS m/ z 1736 [M]+, 1591 [M - PF6]+,
1446 [M - 2PF6]+, 1301 [M - 3PF6]+; HRLSIMS calcd for
C72H76N4O10F12P2 [M - 2PF6]+ m/ z 1446.4845, found m/ z
1446.4801.
1
[2]Ca ten a n e 9c‚4P F 6: yield 74%; mp > 300 °C; H NMR
(400 MHz, CD3COCD3, 298 K) δ 3.45 (m, 4H), 3.62 (m, 4H),
3.64 (bs, 4H), 3.78 (m, 4H), 3.85 (m, 4H), 3.91 (m, 4H), 3.97-
4.00 (m, 12H), 5.99 (bs, 8H), 6.25 (d, 2H, J ) 2 Hz), 6.93 (dd,
2H, J ) 9.0, 2 Hz), 7.67 (d, 2H, J ) 9 Hz), 7.86 (bs, 8H), 8.01
(s, 8H), 9.14 (bs, 8H); 13C NMR (100.6 MHz, CD3COCD3, 298
K, inverse 13C-1H correlation) δ 65.6, 67.3, 68.5, 70.1, 70.6,
70.9, 71.7, 71.9, 106.1, 113.9, 117.0, 126.3, 130.7, 131.8, 145.5,
125.0, 136.7, 137.8, 147.0, 151.1, 158.0; LSIMS m/ z 1686 [M]+,
1541 [M - PF6]+, 1396 [M - 2PF6]+, 1251 [M - 3PF6]+;
HRLSIMS calcd for C68H74N4O10F3P18 [M - PF6]+ m/ z
1541.4330, found m/ z 1541.4341. Anal. Calcd for
C68H74N4O10P4F24: C, 48.41; H, 4.42; N, 3.32. Found: C, 48.56;
H, 4.32; N, 3.52
1
[2]Ca ten a n e 9j‚4P F 6: yield 84%; mp > 250 °C; H NMR
(400 MHz, CD3COCD3, 303 K, 2D-COSY 45) δ 2.62 (d, 2H, J
) 8 Hz), 3.47 (m, 4H), 3.75 (m, 4H), 3.88 (m, 4H), 3.96 (m,
4H), 4.03 (m, 4H), 4.08 (m, 4H), 4.20 (m, 4H), 4.32 (m, 4H),
5.98, 6.02, 6.09, 6.12 (AB system, 8H), 6.08 (t, 2H, J ) 8 Hz),
6.12 (d, 2H, J ) 3 Hz), 6.26 (d, 2H, J ) 8 Hz), 6.86 (dd, 2H, J
) 9, 2 Hz), 7.31 (bd, 4H), 7.37 (bd, 4H), 7.60 (d, 2H, J ) 9 Hz),
8.15 (s, 4H), 8.35 (s, 4H), 8.91 (d, 4H, J ) 6.0 Hz), 9.17 (d, 4H,
J ) 7 Hz); 13C NMR (75 MHz, CD3CN) δ 65.9, 68.6, 69.0, 70.0,
70.7, 71.2, 71.5, 72.3, 105.1, 106.1, 109.1, 117.0, 125.1, 126.1,
128.5, 129.2, 130.8, 131.3, 132.1, 144.6, 145.5, 118.3, 124.8,
125.2, 136.4, 137.5, 145.3, 151.9, 157.9; LSIMS m/ z 1737 [M
+ H]+, 1591 [M - PF6]+, 1446 [M - 2PF6]+, 1301 [M - 3PF6]+;
HRLSIMS calcd for C72H76N4O10F3P18 [M - PF6]+ m/ z
1591.4587, found 1591.4416. Single crystals, suitable for X-ray
crystallography, were grown by vapor diffusion of i-Pr2O into
a solution of 9j‚4PF6 in MeCN.
1
[2]Ca ten a n e 9d ‚4P F 6: yield 51%, mp > 280 °C; H NMR
(400 MHz, CD3CN, 313 K) δ 2.31 (d, 2H), 3.68-3.72 (bm, 4H),
3.76-3.79 (bm, 4H), 3.79-3.82 (bm, 4H), 3.89-3.94 (bm, 4H),
3.96-4.01 (bm, 4H), 4.02-4.06 (bm, 4H), 4.08-4.12 (bm, 4H),
4.21-4.24 (bm, 4H), 5.63 (d, 4H), 5.82 (t, 2H), 5.84 (d, 4H), 6.09
(d, 2H), 6.36 (d, 2H), 6.88 (bd, 8H), 7.12 (t, 2H), 7.18 (d, 2H),
7.88 (d, 4H), 8.04 (d, 4H), 8.39 (d, 4H), 8.86 (d, 4H); LSIMS
m/ z 1592 [M - PF6]+, 1446 [(M - 2 PF6]+, 1301 [M - 3 PF6]+.
[2]Ca ten a n e 9e‚4P F 6. After counterion exchange with
aqueous NH4PF6, the product was extracted into MeNO2 and
the organic phase was separated and washed with H2O. The
solvent was removed in vacuo, and the residue was dried (70
°C/0.1 Torr, 12 h) to give the [2]catenane 9e‚4PF6. Yield: 35%,
mp > 250 °C. 1H NMR (400 MHz, CD3CN, 238 K, 2D-COSY
45) δ 2.14 (d, 1H, J ) 8.2 Hz), 2.48 (d, 1H, J ) 9 Hz), 3.62-
4.18 (m, 32H), 4.62 (d, 1H, J ) 2 Hz), 5.17 (dd, 1H, J ) 9 Hz,
J ) 2.5 Hz), 5.60, 5.63, 5.70, 5.73 (AB system, 8H), 5.77 (t,
1H, J ) 8 Hz), 6.03 (d, 1H, J ) 8 Hz), 6.20 (d, 1H, J ) 7.5 Hz),
6.52 (d, 1H, J ) 8 Hz), 6.68-6.74 (m, 3H), 6.89 (bs, 2H), 6.98
(bs, 2H), 7.04 (d, 2H, J ) 4.7 Hz), 7.14 (d, 1H, J ) 9 Hz), 7.27
(bs, 2H), 7.91 (m, 8H), 8.34 (d, 2H, J ) 5.5 Hz), 8.49 (d, 2H, J
) 5.5 Hz), 8.65 (d, 2H, J ) 6.5 Hz), 8.90 (bs, 2H); 13C NMR
(75 MHz, CD3CN) δ 65.8, 68.6, 69.1, 70.3, 70.4, 71.0, 71.1, 71.3,
104.5, 108.0, 126.0, 128.3, 128.4, 128.5, 130.2, 131.2, 131.8,
131.9, 145.2, 137.7, 145.9; LSIMS m/ z 1737 [M + H]+, 1591
[M - PF6]+, 1446 [M - 2PF6]+, 1301 [M - 3PF6]+; HRLSIMS
calcd for C72H76N4O10F3P18 [M - PF6]+ m/ z 1591.4487, found
m/ z 1591.4545. Single crystals, suitable for X-ray crystal-
lography, were grown by vapor diffusion of i-Pr2O into a
solution of 9e‚4PF6 in MeCN.
1
[2]Ca ten a n e 9k ‚4P F 6: yield 25%; mp > 250 °C; H NMR
(400 MHz, CD3COCD3, 273 K, 2D-COSY 45) δ 3.40 (s, 2H),
3.52 (s, 4H), 3.73 (s, 4H), 3.81 (s, 4H), 3.88 (m, 8H), 3.93 (s,
4H), 3.99 (s, 4H), 4.03 (s, 4H), 4.92 (d, 2H, J ) 9 Hz), 5.98 (bs,
4H), 6.04 (bs, 4H), 6.32 (d, 4H, J ) 6.5 Hz), 6.74 (d, 2H, J )
9 Hz), 7.29 (d, 2H, J ) 9 Hz), 7.62 (bs, 4H), 7.80 (bs, 4H), 8.20
(s, 8H), 9.20 (s, 8H); 13C NMR (75 MHz, CD3CN) δ 65.7, 68.4,
70.5, 70.6, 71.1, 71.3, 71.5, 106.5, 107.7, 126.4, 128.1, 128.4,
128.5, 128.6, 130.1, 130.4, 130.4, 132.1, 145.3, 135.3, 138.1,
146.5, 155.1, 158.0; LSIMS m/ z 1591 [M - PF6]+, 1446 [M -
2PF6]+, 1301 [M - 3PF6]+; HRLSIMS calcd for C72H76N4O10F3P18
[M - PF6]+ m/ z 1591.4487, found m/ z 1591.4522.
Meth od B. 1,4-Bis(bromomethyl)benzene (106 mg, 0.40
mmol), the bis(hexafluorophosphate) salt 8‚2PF6 (226 mg, 0.32
mmol), and the macrocyclic polyether (102 mg, 0.16 mmol)
were dissolved in hot, dry DMF (10 mL). The yellow solution
was transferred to an ultrahigh-pressure reaction Teflon
vessel, which was then compressed (12 kbar) at 40 °C for 5
days. After decompression of the reaction vessel, the orange-
red reaction mixture was concentrated in vacuo. The solid
residue was dissolved in a minimum amount of mixture
MeNO2-MeOH (1:1) and subjected to column chromatography
(MeOH/2M NH4Cl/MeNO2, 7:2:1) on silica gel (65 g, 230-400
mesh), and fractions containing the catenane were combined.
Removal of the solvent in vacuo, followed by counterion
exchange, afforded an orange precipitate that was filtered off,
washed with water, and dried (60 °C/0.1 Torr).
1
[2]Ca ten a n e 9h ‚4P F 6: yield 64%; mp > 250 °C; H NMR
(400 MHz, CD3COCD3, 298 K, 2D-COSY 45) δ 2.56 (d, 1H, J
) 8.5 Hz), 2.62 (d, 1H, J ) 8 Hz), 3.72 (s, 4H), 3.86 (s, 6H),
3.94 (m, 2H), 3.97 (m, 2H), 4.05-4.07 (m, 6H), 4.11 (s, 4H),
4.18 (m, 2H), 4.24 (m, 2H), 4.32 (m, 2H), 4.39 (m, 2H), 5.94-
(17) The author has deposited atomic coordinates for this structure
with the Cambridge Crystallographic Data Centre. The coordinates
can be obtained, on request, from the Director, Cambridge Crystal-
lographic Data Centre, 12 Union Road, Cambridge, CB2 1EZ, UK.
1
[2]Ca ten a n e 9g‚4P F 6: yield 27%; mp > 300 °C; H NMR
(400 MHz, CD3CN, 233 K) δ 3.36 (bs, 2H), 3.64-3.87 (m, 32H),