12512 J. Am. Chem. Soc., Vol. 119, No. 51, 1997
Ballardini et al.
oil (5.53 g) was dissolved in CH2Cl2 (120 mL), along with Et3N (2.09
g, 20.71 mmol) and 4-(dimethylamino)pyridine (cat.), and cooled to 0
°C. A solution of p-toluenesulfonyl chloride (3.95 g, 20.71 mmol) in
CH2Cl2 (80 mL) was added during 1 h and the reaction mixture stirred
overnight. The solution was washed with 5% aqueous HCl (2 × 200
mL) and H2O (200 mL) and dried (MgSO4). The solvent was removed,
and the residue was purified by column chromatography (SiO2, CH2-
Cl2/MeOH 50:1) to yield 2 as a colorless oil (6.98 g, 25%): FABMS
p-Phenylene-2,5-difluoro-p-phenylene-34-crown-10 (9). The pro-
cedure described for the preparation of 8 was followed to yield 9 as a
white crystalline solid (290 mg, 12%): mp 84.0-84.5 °C; positive-
ion ES MS m/z 590 [M + NH4]+; 1H NMR (CDCl3, 360 MHz) δ 6.77
(4H, s), 6.73 (2H, m, JHF ) 10 Hz), 4.02 (8H, m), 3.83 (8H, m), 3.69
(16H, m); 19F NMR (CDCl3, 340 MHz) δF -133.1 (s); 13C NMR
(CDCl3, 90 MHz) δC 153.1, 147.8 (m, JCF ) 245 Hz, ArCF), 140.5 (m,
ArCO), 115.6, 70.8, 70.8, 70.8, 70.7, 70.3, 69.7, 69.6, 68.2; HRMS calcd
for [M]+ C28H38F2O10 572.2433, found 572.2421.
1
m/z 843 [M + H]+; H NMR (CDCl3, 300 MHz) δ 7.72 (4H, d, J )
9 Hz), 7.30 (4H, d, J ) 9 Hz), 4.23 (4H, t), 4.10 (4H, t), 3.75 (4H, t),
Bis(tetrafluoro-p-phenylene)-34-crown-10 (10). The procedure
described for the preparation of 8 was followed to yield 10 as a white
amorphous solid (115 mg, 23%): mp 72.0-73.0 °C; FABMS m/z 681
[M + H]+; 1H NMR (CDCl3, 300 MHz) δ 4.27 (8H, m), 3.79 (8H, m),
3.50-3.67 (20H, m), 2.40 (6H, s); 19F NMR (CDCl3, 280 MHz) δF
-158.6 (s); 13C NMR (CDCl3, 75 MHz) δC 144.8, 141.8 (m, JCF
)
252 Hz, ArCF), 132.9 (m, ArCO), 132.9, 129.8, 127.8, 74.4, 70.7, 70.6,
70.5, 70.4, 70.1, 69.3, 68.5, 21.5; HRMS calcd for [M + H]+
C36H47F4O14S2 843.2343, found 843.2328. Anal. Calcd for
C36H46F4O14S2: C 51.30, H 5.50; found C 51.39, H 5.34.
3.55-3.68 (16H, m); 19F NMR (CDCl3, 340 MHz) δF -158.8 (s); 13
C
NMR (CDCl3, 90 MHz) δC 141.8 (m, JCF ) 242 Hz, ArCF), 132.9 (m,
ArCO), 74.4, 70.8, 70.7, 70.2; HRMS calcd for [M]+ C28H32F8O10
680.1868, found 608.1876.
1,4-Difluoro-2,5-bis[2-[2-[2-[2-(p-toluenesulfonyl)ethoxy]ethoxy]-
ethoxy]ethoxy]benzene (3). The procedure described for 2 was
followed to yield 3 as a colorless oil (1.68 g, 5%): FABMS 807 [M +
H]+; 1H NMR (CDCl3, 300 MHz) δ 7.71 (4H, d, J ) 9 Hz), 7.34 (4H,
d, J ) 9 Hz), 6.81 (2H, m, JHF ) 10 Hz), 4.15 (8H, m), 3.83 (4H, t),
3.53-3.75 (20H, m), 2.43 (6H, s); 19F NMR (CDCl3, 280 MHz) δF
-136.7 (s); 13C NMR (CDCl3, 75 MHz) δC 148.5 (m, JCF ) 241 Hz,
ArCF), 144.8, 140.6 (m, ArCO), 133.0, 129.8, 127.9, 105.3, 70.8, 70.7,
70.6, 70.5, 70.2, 69.6, 69.3, 68.6, 21.6; HRMS calcd for [M]+
C36H48F2O14S2 806.2454, found 806.2465.
Bis(2,5-difluoro-p-phenylene)-34-crown-10 (11). The procedure
described for the preparation of 8 was followed to yield 11 as a white
crystalline solid (482 mg, 43%): mp 127.0-127.5 °C; FABMS m/z
1
741 [M + Cs]+, 608 [M+]; H NMR (CDCl3, 300 MHz) δ 6.79 (4H,
m, JHF ) 10 Hz), 4.11 (8H, t), 3.86 (8H, t), 3.70 (16H, m); 19F NMR
(CDCl3, 280 MHz) δF -136.7 (s); 13C NMR (CDCl3, 75 MHz) δC 148.1
(m, JCF ) 239 Hz, ArCF), 140.6 (m, ArCO), 105.1, 70.9, 70.8, 70.3,
69.6; HRMS calcd for [M]+ C28H36F4O10 608.2245, found 608.2224.
Anal. Calcd for C28H36F4O10: C 55.26, H 5.90; found C 55.31, H 5.82.
p-Phenylene-35-crown-11 (22). A solution of bis[2-[2-[2-[2-(p-
toluenesulfonyl)ethoxy]ethoxy]ethoxy]ethoxy]benzene (4.50 g, 5.84
mmol) in dry THF (200 mL) was added to a refluxing suspension of
diethylene glycol (0.62 g, 5.84 mmol) and NaH (0.42 g, 17.53 mmol)
in dry THF (400 mL) under N2 and stirred for 4 d. After cooling down
to room temperature, the reaction mixture was quenched with H2O.
The solvent was removed to leave a solid residue which was dissolved
in CH2Cl2 (150 mL) and washed with H2O (3 × 100 mL). The organic
layer was dried (MgSO4) and concentrated to a colorless oil which
was purified by column chromatography (SiO2, CH2Cl2/MeOH 100:2)
to yield 22 as a white crystalline solid (464 mg, 15%): mp 55.0-56.0
°C; positive-ion electrospray MS m/z 550 [M + NH4]+; 1H NMR
(CDCl3, 360 MHz) δ 6.85 (4H, s), 4.09 (4H, t), 3.84 (4H, t), 2.58-
2.74 (32H, m); 13C NMR (CDCl3, 90 MHz) δC 153.1, 115.7, 70.7, 70.6,
70.6, 70.5, 70.5, 70.5, 70.5, 70.4, 69.7, 69.2. Anal. Calcd for
C26H44O11: C 58.63, H 8.33; found C 58.64, H 8.27.
1,2,4,5-Tetrafluoro-3,6-bis[2-(2-hydroxyethoxy)ethoxy]benzene (19).
A solution of tetrafluorohydroquinone (10.0 g, 55.0 mmol) in MeCN
(40 mL) was added to a previously degassed suspension of K2CO3 (60.7
g, 439.6 mmol) and 2-(2-chloroethoxy)ethoxyethanol (20.5 g, 165
mmol) in dry MeCN (80 mL) under N2 with stirring. The reaction
mixture was heated to 60 °C and stirred for 7 d. After cooling down
to room temperature, the reaction mixture was filtered and the solvent
was removed to leave a solid residue which was dissolved in CH2Cl2
(200 mL) and washed with H2O (250 mL). The organic layer was
dried (MgSO4) and concentrated to a residue which was purified by
column chromatography (SiO2, CH2Cl2/MeOH 100:3) to yield 19 as a
1
colorless oil (8.00 g, 40%): EIMS 358 [M+]; H NMR (CDCl3, 300
MHz) δ 3.53-3.73 (16H, m), 3.00 (2H, t); 19F NMR (CDCl3, 280 MHz)
δF -158.5 (s); 13C NMR (CDCl3, 75 MHz) δC 142.0 (m, JCF ) 252
Hz, ArCF), 132.0 (m, ArCO), 72.3, 72.3, 70.9, 70.9. Anal. Calcd for
C14H18F4O6: C 46.93, H 5.06; found C 46.96, H 4.96.
1,4-Difluoro-2,5-bis[2-(2-hydroxyethoxy)ethoxy]benzene (21). The
procedure described for 19 was followed to yield 21 as a colorless oil
[2]Catenane 15‚4PF6. A solution of 8 (234 mg, 0.39 mmol),
12.2PF6 (109 mg, 0.15 mmol), and 13 (45 mg, 0.17 mmol) in dry MeCN
(7 mL) was stirred at room temperature for 5 d. The solvent was
removed, and the resulting solid was purified by column chromatog-
raphy (SiO2, MeOH/2M NH4Cl/MeNO2 7:2:1). After counterion
exchange (NH4PF6/H2O), the solid was recrystallized (CH3COCH3/H2O)
to yield 15‚4PF6 as an orange/red crystalline solid (158 mg, 60%): mp
> 250 °C decomposition; FABMS m/z 1708 [M+], 1563 [M - PF6]+,
1418 [M - 2PF6]+, 1273 [M - 3PF6]+: 1H NMR (CD3CN, 400 MHz)
δ 8.95 (8H, d), 7.78 (8H, s), 7.76 (8H, d), 5.69 (4H, s), 3.98 (4H, t),
3.89 (8H, m), 3.83 (4H, t), 3.75 (4H, t), 3.68 (4H, t), 3.60 (4H, t), 3.57
(4H, s), 3.52 (4H, t); 19F NMR (CD3CN, 380 MHz, 236 K) δF -70.27
1
(0.50 g, 6%): EIMS m/z 322 [M+]; H NMR (CDCl3, 300 MHz) δ
7.08 (2H, m, JHF ) 10 Hz), 4.20 (4H, t), 3.82 (4H, t), 3.55-3.70 (8H,
m); 19F NMR (CDCl3, 280 MHz) δF -136.6 (s); 13C NMR (CDCl3, 75
MHz) δC 148.5 (m, JCF ) 252 Hz, ArCF), 143.5 (m, ArCO), 105.5, 72.7,
72.4, 71.1, 70.2; HRMS calcd for [M]+ C14H20F2O6 322.1228, found
322.1233.
p-Phenylenetetrafluoro-p-phenylene-34-crown-10 (8). Tetrafluo-
rohydroquinone (0.76 g, 4.15 mmol) was added to a previously degassed
suspension of Cs2CO3 (27.05 g, 83.04 mmol) and CsOTs (1.26 g, 4.15
mmol) in dry MeCN (400 mL) under N2 with stirring. After the mixture
was stirred at 80 °C for 1 h, a solution of 2 (3.33 g, 4.32 mmol) and
CsOTs (1.26 g, 4.15 mmol) in dry, degassed MeCN (200 mL) was
added dropwise over a 1 h period and heating was maintained for 5 d.
After cooling to room temperature, the reaction mixture was filtered.
The filtrate was collected and the solvent removed to leave a solid
residue, which was dissolved in PhMe (200 mL) and washed with H2O
(250 mL). The aqueous layer was washed with PhMe (3 × 100 mL).
The organic layers were combined and dried (MgSO4) and the solvent
concentrated to a brown oil which was purified by column chroma-
tography (SiO2, CH2Cl2/MeOH 50:1), followed by recrystallization
(CHCl3/hexane) to yield 8 as a white crystalline solid (350 mg, 14%):
mp 73.5-74.0 °C; FABMS m/z 608 [M+]; 1H NMR (CDCl3, 300 MHz)
δ 6.78 (4H, s), 4.20 (4H, t), 4.05 (4H, t), 3.80-3.86 (8H, m), 3.64-
3.75 (16H, m); 19F NMR (CDCl3, 380 MHz) δF -158.60 (s); 13C NMR
(CDCl3, 75 MHz) δC 149.7, 139.5 (m, JCF ) 252 Hz, ArCF), 129.4 (m,
ArCO), 111.9, 74.5, 70.8, 70.8, 70.8, 70.8, 70.1, 69.7, 68.2; HRMS calcd
for [M]+ C28H36F4O10 608.2245, found 608.2230. Anal. Calcd for
C28H36F4O10: C 55.26, H 5.90; found C 55.55, H 6.07.
(d, JFP ) 662 Hz, PF6-), -156.73 (s); 13C NMR (CD3CN, 90 MHz)
1
δC 151.0, 146.8, 146.0, 137.6, 131.9, 126.3, 113.9, 75.0, 72.0, 71.8,
70.9, 70.7, 70.3, 67.7, 65.8; HRMS calcd for [M - PF6]+
C64H68F22N4O10P3 1563.3797, found 1563.3731. Anal. Calcd for
C64H68F28N4O10P4: C 44.96, H 4.01, N 3.28; found C 44.79, H 3.92,
3.28.
[2]Catenane 16‚4PF6. The procedure described for the preparation
of 15‚4PF6 was followed to yield 16‚4PF6 as an orange/red crystalline
solid (67 mg, 57%): mp >250 °C decomposition; FABMS m/z 1527
1
[M - PF6]+, 1382 [M - 2PF6]+, 1237 [M - 3PF6]+; H NMR (CD3-
CN, 400 MHz, 353 K) δ 8.97 (8H, d), 7.87 (8H, s), 7.74 (8H, d), 6.36
(2H, m, JHF ) 10.5 Hz), 5.72 (8H, s), 3.88-4.00 (8H, m), 3.87 (4H,
m), 3.76 (4H, m), 3.58-3.65 (16H, m), 3.57 (4H, s); 19F NMR (CD3-
CN, 340 MHz, 300 K) δF -66.0 (d, 1JFP ) 728 Hz, PF6-), -132.7 (s);
13C NMR (CD3CN, 100 MHz) δC 151.0, 146.8, 145.7, 140.3, 137.5,
131.8, 129.7 (m, JCF ) 203 Hz, ArCF), 126.3, 113.8, 104.8 (m, ArCO),
71.7, 71.4, 71.1, 70.8, 70.3, 70.3, 70.0, 67.6, 65.7; HRMS calcd for
[M - PF6]+ C64H70F20N4O10P3 1527.3986, found 1527.3995.