4948 J. Am. Chem. Soc., Vol. 118, No. 21, 1996
Ashton et al.
6.75 (2H, d, J ) 9 Hz), 4.15-4.22 (2H, m), 3.97-4.03 (2H, m), 3.72-
3.80 (4H, m), 2.31 (3H, s), 2.38 (3H, s), 1.30 (18H, s). Anal.
(C45H52O5S) C, H. 5c (12.1 g, 56%): mp 93-95 °C; FABMS 718
(8H, m), 1.29 (36H, s); 13C NMR (CD3CN) δ 161.3, 157.8, 149.6, 148.6,
148.3, 145.4, 140.6, 132.8, 132.3, 131.6, 131.3, 128.6, 126.8, 125.5,
125.3, 116.5, 114.4, 70.5, 70.3, 68.8, 68.4, 65.4, 64.4, 35.0, 31.6. Anal.
(C98H106N2O6P2F12) C, H, N. 7b (426 mg, 38%): mp 213-215 °C
(dec); FABMS 1436 (M - 2PF6)+; 1H NMR (CD3COCD3) δ 9.48 (4H,
d, J ) 7 Hz), 8.81 (4H, d, J ) 7 Hz), 7.65 (4H, d, J ) 8.5 Hz), 7.32
(8H, d, J ) 8.5 Hz), 7.06-7.16 (24H, m) 6.86 (4H, d, J ) 9 Hz), 6.11
(4H, s), 4.18-4.24 (4H, m), 4.12-4.18 (4H, m), 3.87-3.95 (8H, m),
2.30 (6H, s), 1.31 (36H, s); 13C NMR (CD3CN) δ 161.3, 157.7, 151.1,
149.5, 146.3, 145.6, 145.5, 140.7, 136.4, 132.8, 132.3, 131.5, 131.3,
129.2, 128.3, 125.5, 125.3, 116.5, 114.4, 70.5, 70.3, 68.8, 68.4, 65.4,
64.1, 35.0, 31.6, 20.9. Anal. (C100H110N2O6P2F12) C, H, N. 7c (558
mg, 49%), mp 218-220 °C (dec); FABMS 1464 (M - 2PF6)+; 1H NMR
(CD3COCD3), δ 9.45 (4H, d, J ) 7 Hz), 8.78 (4H, d, J ) 7Hz), 7.63
(4H, d, J ) 8.5), 7.30 (8H, d, 8.5 Hz), 7.04-7.15 (24H, m), 6.84 (4H,
d, J ) 9 Hz), 6.08 (4H, s), 4.16-4.22 (4H, m), 4.10-4.16 (4H, m)
3.85-3.92 (8H, m), 2.60 (4H, q, J ) 7.5 Hz), 1.29 (36H, s), 1.20 (6H,
t, J ) 7.5 Hz); 13C NMR (CD3CN) δ 161.3, 157.7, 151.4, 149.5, 146.3,
145.8, 145.6, 142.7, 140.8, 132.8, 132.3, 131.6, 131.3, 128.3, 128.0,
125.5, 125.3, 116.5, 114.4, 70.5, 70.3, 68.8, 68.4, 65.4, 64.1, 35.0, 31.6,
28.9, 15.9. Anal. (C102H114N2O6P2F12) C, H, N. 7d (530 mg, 44%):
1
(M+); H NMR (CDCl3) δ 7.79 (2H, J ) 8 Hz), 7.20-7.31 (4H, m),
7.03-7.13 (12H, m), 6.74 (2H, d, J ) 9 Hz), 4.16-4.22 (2H, m), 3.98-
4.03 (2H, m), 3.72-3.79 (4H, m), 2.63 (2H, q, J ) 7.5 Hz), 3.39 (3H,
s), 1.30 (18H, s), 1.23 (3H, t, J ) 7.5 Hz). Anal. (C46H54O5S) C, H.
5d (17.1 g, 78%): mp 124-126 °C; FABMS 732 (M+); 1H NMR
(CDCl3) δ 7.79 (2H, d, J ) 8 Hz), 7.20-7.30 (4H, m), 7.04-7.13
(12H, m), 6.74 (2H, d, J ) 9 Hz), 4.16-4.22 (2H, m), 3.98-4.04 (2H,
m), 3.72-3.80 (4H, m), 2.87 (1 H, septet, J ) 7 Hz), 2.38 (3H, s),
1.30 (18H, s), 1.24 (6H, d, J ) 7 Hz). Anal. (C50H60O5S) C, H. 5e
(17.5 g, 78%): mp 197-199 °C; FABMS 746 (M+); 1H NMR (CDCl3)
δ 7.79 (2H, d, J ) 8 Hz), 7.20-7.30 (8H, m), 7.06-7.11 (8H, m),
6.74 (2H, d, J ) 8 Hz), 4.17-4.21 (2H, m), 3.99-4.03 (2H, m), 3.90-
3.96 (4H, m), 2.38 (3H, s), 1.30 (27H, s). Anal. (C48H58O5S) C, H.
General Procedure for the Preparation of the 4-[2-[2-[4-Alkyl-
phenyl-bis(4-tert-butylphenyl)methoxy]ethoxy]ethoxybenzylic Al-
cohols (6a-e). K2CO3 (5 g, 36 mmol) was suspended in dry MeCN
(100 mL) under nitrogen, and 4-hydroxybenzyl alcohol (2.5 g, 20 mmol)
was added during 10 min. The suspension was stirred under reflux
for 30 min. The tosylates (5a-e, 18 mmol) were added and the reaction
mixtures were stirred under reflux for 48 h. After cooling and filtration
through Celite, solvent was evaporated, and the crude products were
recrystallized from PhMe/hexane. 6a (9.3 g, 80%): mp 118-120 °C;
1
mp 209-211 °C (dec); FABMS 1492 (M - 2PF6)+; H NMR (CD3-
COCD3) δ 9.46 (4H, d, J ) 7 Hz), 8.78 (4H, d, J ) 7Hz), 7.63 (4H,
d, J ) 8.5 Hz), 7.30 (8H, d, J ) 8.5 Hz), 7.05-7.17 (24H, m), 6.84
(4H, d, J ) 9 Hz), 6.08 (4H, s), 4.17- 4.22 (4H, m), 4.10-4.17 (4H,
m), 3.85-3.92 (8H, m), 2.86 (2H, septet, J ) 7 Hz), 1.29 (36H, s),
1.22 (12H, d, J ) 7 Hz); 13C NMR (CD3CN) δ 161.3, 157.7, 151.1,
149.5, 146.3, 145.6, 145.5, 141.7, 138.3, 132.6, 132.3, 131.5, 131.3,
129.2, 128.3, 126.5, 125.5, 116.5, 114.4, 70.5, 70.3, 68.8, 68.4, 65.4,
64.1, 35.0, 34.2, 31.6, 24.2. Anal. (C104H118N2O6P2F12) C, H, N. 7e
1
FABMS 642 (M+); H NMR (CDCl3) δ 7.16-7.32 (11H, m), 7.04-
7.14 (6H, m), 6.90 (2H, d, J ) 8.5 Hz), 6.79 (2H, d, J ) 9 Hz), 4.62
(2H, s), 4.09-4.20 (4H, m), 3.88-3.98 (4H, m), 1.30 (18H, s). Anal.
(C44H50O4) C, H. 6b (9.6 g, 81%): mp 102-104 °C; FABMS 656
1
(M+); H NMR (CDCl3) δ 7.19-7.30 (6H, m), 7.01-7.11 (10H, m),
1
(787 mg, 67%): mp 200 °C (dec); FABMS 1518 (M - 2PF6)+; H
6.91 (2 H, d, J ) 8.5 Hz), 6.78 (2H, d, J ) 8.5 Hz), 4.61 (2H, s),
4.10-4.18 (4H, m), 3.89-3.95 (4H, m), 2.31 (3H, s), 1.30 (18H, s).
Anal. (C45H52O4) C, H. 6c (10.3 g, 85%): mp 107-109 °C; FABMS
NMR (CD3COCD3) δ 9.36 (4H, d, J ) 7 Hz), 8.50 (4H, d, J ) 7 Hz),
7.70 (4H, d, J ) 8.5), 7.23 (12H, d, J ) 8.5 Hz), 7.05-7.10 (16H, m),
6.89 (4H, d, J ) 8.5 Hz), 6.78 (4H, d, J ) 9 Hz), 6.07 (4H, s), 4.11-
4.18 (8H, m), 3.90-3.96 (8H, m), 1.30 (54H, s). Anal.
(C106H122N2O6P2F12) C, H, N.
1
670 (M+); H NMR (CDCl3) δ 7.15-7.29 (6H, m), 7.02-7.12 (10H,
m), 6.90 (2H, d, J ) 8.5 Hz), 6.78 (2H, d, J ) 9 Hz), 4.60 (2H, s),
4.09-4.17 (4H, m), 3.88-3.95 (4H, m), 2.62 (2H, q, J ) 6.5 Hz),
1.29 (18H, s), 1.23 (3H, t, J ) 6.5 Hz). Anal. (C46H54O4) C, H. 6d
(9.1 g, 74%): mp 121-123 °C; FABMS 684 (M+); 1H NMR (CDCl3)
δ 7.20-7.29 (6H, m), 7.04-7.12 (10H, m), 6.90 (2H, d, J ) 8.5 Hz),
6.78 (2H, d, J ) 9 Hz), 4.60 (2H, s), 4.09-4.17 (4H, m), 3.88-3.96
(4H, m), 2.87 (1H, septet, J ) 7 Hz), 1.30 (18H, s), 1.24 (6H, d, J )
7 Hz). Anal. (C47H56O4) C, H. 6e (11.4 g, 91%): mp 292-294 °C;
General Procedure for the Preparation of the [2]Rotaxanes 8a-
c. The bipyridinum salts (7a-c, 0.07 mmol) were dissolved in MeCN
(7 mL), and BPP34C10 (150 mg, 0.28 mmol) was added. The reaction
mixtures were stirred at 55 °C for 10 days. MeCN was evaporated
off, and Me2CO (3 mL) added. The white crystals of BPP34C10 were
filtered off and washed with small amounts of Me2CO. The red Me2-
CO solutions were concentrated at room temperature and purified by
PLC [SiO2, MeOH-MeNO2-CH2Cl2 (6:1:1)] which afforded the stable
[2]rotaxanes as deep orange solids. 8a (81 mg, 52%): mp 146-149
1
FABMS 698 (M+); H NMR (CDCl3) δ 7.28 (2H, d, J ) 8 Hz), 7.23
(6H, d, J ) 9 Hz) 7.06-7.11 (8H, m), 6.91 (2H, d, J ) 8 Hz) 6.79
(2H, d, J ) 8.Hz), 4.61 (2H, s), 4.11-4.18 (4H, m), 3.89-3.95 (4H,
m), 1.30 (27 H, s). Anal. (C48H58O4) C, H.
1
°C (dec); FABMS 1944 (M - 2PF6)+; H NMR (CD3COCD3) δ 9.19
(4H, d, J ) 7 Hz), 8.27 (4H, d, J ) 7 Hz), 7.74 (4H, d, J ) 9 Hz),
7.05-7.34 (34H, m), 6.83 (4H, d, J ) 9 Hz), 6.10 (8H, s), 6.04 (4H,
s), 4.18-4.25 (4H, m), 4.09-4.16 (4H, m), 3.85-3.93 (8H, m), 3.78
(16H, br s), 3.72-3.77 (8H, m), 3.62-3.67 (8H, m), 1.29 (36H, s);
13C NMR (CD3CN) δ 161.1, 157.7, 153.0, 149.6, 148.5, 147.2, 146.3,
145.3, 140.5, 132.8, 132.7, 131.6, 131.3, 128.5, 126.8, 126.4, 125.5,
116.3, 116.2, 115.7, 114.4, 71.4, 71.2, 70.7, 70.5, 70.3, 68.8, 68.5, 68.4,
64.9, 64.4, 34.9, 31.6. Anal. (C126H146N2O16P2F12) C, H, N. 8b (71
mg, 45%): mp 137-140 °C (dec); FABMS 1972 (M-2PF6)+; 1H NMR
(CD3COCD3) δ 9.18 (4H, d, J ) 7 Hz), 8.27 (4H, d, J ) 7 Hz), 7.74
(4H, d, J ) 9 Hz), 7.27 (8H, d, J ) 9 Hz), 7.03-7.17 (24H, m), 6.82
(4H, d, J ) 9 Hz), 6.10 (8H, s), 6.04 (4H, s), 4.18-4.25 (4H, m),
4.09-4.16 (4H, m), 3.85-3.93 (8H, m), 3.78 (16H, bs), 3.72-3.77
(8H, m), 3.62-3.67 (8H, m), 2.28 (6H, s), 1.28 (36H, s); 13C NMR
(CD3CN) δ 161.3, 157.7, 153.1, 149.6, 148.5, 147.2, 146.3, 145.6,
140.8, 132.8, 132.6, 131.5, 131.3, 129.9, 126.8, 126.2, 125.5, 117.8,
116.5, 116.2, 115.7, 114.4, 71.5, 71.3, 70.7, 70.5, 70.3, 68.9, 68.6, 68.4,
65.1, 64.5, 35.0, 31.6, 20.9. Anal. (C128H150N2O16P2F12) C, H, N. 8c
(75 mg, 47%): mp 140-144 °C (dec); FABMS 2000 (M - 2PF6)+; 1H
NMR (CD3COCD3) δ 9.19 (4H, d, J ) 7 Hz), 8.28 (4H, d, J ) 7 Hz),
7.74 (4H, d, J ) 9 Hz), 7.29 (8H, d, J ) 9 Hz), 7.03-7.17 (24H, m),
6.82 (4H, d, J ) 9 Hz), 6.10 (8H, s), 6.05 (4H, s), 4.18-4.25 (4H, m),
4.09-4.16 (4H, m), 3.85-3.93 (8H, m), 3.78 (16H, bs), 3.72-3.77
(8H, m), 3.62-3.67 (8H, m), 2.60 (4H, q, J ) 7 Hz), 1,29 (36H, s),
1.20 (6H, t, J ) 7 Hz); 13C NMR (CD3CN) δ 161.2, 157.7, 153.1,
149.5, 147.2, 146.2, 145.8, 145.5, 142.7, 140.7, 132.7, 132.6, 131.6,
General Procedure for the Preparation of the N,N′-Bis[4-[2-[2-
[4-Alkylphenylbis(4-tert-butylphenyl)methoxy]ethoxy]ethoxybenzyl]-
4,4′-bipyridinium Bis(hexafluorophosphate) (7a-e). The substituted
benzyl alcohols (6a-e, 3 mmol) were dissolved in dry THF (15 mL),
and N-chlorosuccinimide (0.44 g, 3.3 mmol) and Ph3P (0.87 g, 3.3
mmol) were added under vigorous stirring during 30 min. The reaction
mixtures were stirred under nitrogen at room temperature for 15 h and
then quickly subjected to chromatography on short columns [SiO2,
hexane-EtOAc (4:1)]. Solvent was evaporated off and the glassy solids
were dissolved in dry MeCN (20 mL). 4,4′-Bipyridine (101 mg, 0.65
mmol) was added, and the reaction mixtures were stirred and heated
at reflux under nitrogen for 2 days. After cooling down to room
temperature, the yellowish solids were filtered off and washed with
small amounts of MeCN. The residues were then dissolved in a H2O-
Me2CO mixture, and saturated aqueous NH4PF6 (20 mL) was added.
The Me2CO was evaporated off under reduced pressure, and the
yellowish solids were filtered off and washed with H2O. The crude
products were subjected to chromatography [SiO2, MeOH-CH2Cl2-
MeNO2-2 M NH4Cl (70:16:11:3)], and the purified components were
dissolved in H2O-Me2CO mixtures. Saturated aqueous NH4PF6 was
added, and the Me2CO was evaporated off, leaving yellowish solids,
which were filtered off and washed with H2O, before drying. 7a (254
1
mg, 23%): mp 226-228 °C (dec); FABMS 1408 (M - 2PF6)+; H
NMR (CD3COCD3) δ 9.50 (4H, d, J ) 7 Hz), 8.83 (4H, d, J ) 7 Hz),
7.62 (4H, d, J ) 8.5 Hz), 7.04-7.34 (34H, m), 6.85 (4H, d, J ) 9
Hz), 6.10 (4H, s), 4.17-4.22 (4H, m), 4.11-4.16 (4H, m), 3.86-3.92