Yu. Li, Yo. Li et al.
ethyl acetate) under nitrogen. The mixture was stirred at room tempera-
ture until the reaction was complete, as determined by TLC (typically
3 h). Then the solvent was evaporated in vacuo to afford a white solid.
This solid was dispersed in CH2Cl2 (50 mL) and a solution of NH4PF6
(1.1 g, 6.75 mmol) in water (50 mL) was added. The biphasic solution was
stirred vigorously for 2 h and the aqueous layer was extracted with
CH2Cl2 (2ꢁ50 mL). The combined organic layers were dried over
Na2SO4, filtered, and concentrated to give the product in quantitative
yield. 1H NMR (400 MHz, CDCl3, 258C, TMS): d=7.29 (d, J=8.2 Hz,
4H), 6.88 (d, J=8.2 Hz, 4H), 4.29 (t, J=6.2 Hz, 4H), 3.99 (t, J=5.8 Hz,
4H), 3.96 (s, 4H), 3.25 (s, 4H), 2.12–2.08 ppm (m, 4H); 13C NMR
(100 MHz, CDCl3, 258C, TMS): d=171.22, 159.61, 131.33, 123.65, 115.21,
64.37, 62.59, 50.52, 28.50, 26.56 ppm; HRMS (ESI): m/z: calcd for
31.35, 31.33, 31.32, 31.30, 31.29, 29.70, 29.40, 28.80, 28.51 ppm; MS
(MALDI-TOF): m/z 2031.9 [MÀPF6À]+; elemental analysis calcd (%) for
C128H160F6NO16PS2: C 70.60, H 7.41, N 0.64; found: C 70.91 , H 7.58, N
0.66.
[2]Rotaxane R-2: The reaction was carried out as described for the prep-
aration of thread T-1. DMPA (5.3 mg, 0.021 mmol) was added to a solu-
tion of compound 7-H·PF6 (26 mg, 0.041 mmol), compound 8 (55.3 mg,
0.10 mmol), and macrocycle M-S[13a] (22.1 mg, 0.049 mmol) in anhydrous
CH2Cl2 (2 mL). The reaction mixture was irradiated at room temperature
for 1 h under a nitrogen atmosphere without stirring. After concentra-
tion, the crude product was purified by chromatography (CH2Cl2/MeOH,
30:1) to afford rotaxane R-2 as a white solid (27 mg, 30%). M.p. 115.9–
117.28C; 1H NMR (400 MHz, CDCl3, 258C, TMS): d=8.00 (s, 2H), 7.63
(m, 2H), 7.34 (m, 2H), 7.29–7.27 (m, 4H), 7.22 (d, J=8.1 Hz, 12H), 7.07
(d, J=8.1 Hz, 16H), 6.87 (s, 2H), 6.74 (d, J=8.3 Hz, 4H), 6.63 (d, J=
8.0 Hz, 4H), 4.58 (m, 4H), 4.19 (t, J=6.2 Hz, 4H), 4.14 (m, 4H), 4.01 (t,
J=5.7 Hz, 4H), 3.81 (t, J=5.7 Hz, 4H), 3.77 (m, 4H), 3.73 (m, 4H), 3.67
(m, 4H), 3.55 (t, J=5.7 Hz, 4H), 3.24 (s, 4H), 3.03 (m, 4H), 2.79 (t, J=
7.0 Hz, 4H), 2.05 (m, 4H), 1.95 (m, 4H), 1.30 ppm (s, 54H); 13C NMR
(100 MHz, CDCl3, 258C, TMS): d=170.49, 159.60, 156.68, 148.38, 146.33,
144.23, 139.79, 132.34, 130.81, 130.59, 129.15, 126.60, 124.86, 124.13,
122.97, 114.77, 113.09, 107.84, 71.68, 71.22, 70.66, 69.94, 68.74, 65.96,
64.08, 63.14, 62.25, 52.03, 38.87, 34.37, 33.71, 31.65, 31.49, 29.78, 29.45,
À
+
C24H32F6NO6PS2: 494.1671 [M-PF6
] ; found: 494.1645.
Compound 8: Tris(4-tert-butylphenyl)(4-hydroxyphenyl)methane[20] (2.5 g,
4.96 mmol) and allyl bromide (1.8 g, 14.9 mmol) were dissolved in dry
acetonitrile (100 mL) and heated at reflux overnight in the presence of
anhydrous K2CO3 (2.06 g, 14.9 mmol) under nitrogen. The mixture was
filtered and the solvent removed under vacuum. The crude product was
dissolved in CH2Cl2 and washed with water three times. The combined
organic layers were dried over Na2SO4. After removal of the solvent
under reduced pressure, the residue was purified by chromatography (pe-
troleum ether/EtOAC, 30:1) to afford compound 8 as a white solid
(2.62 g, 97%). M.p. 265.3–266.18C; 1H NMR (400 MHz, CDCl3, 258C,
TMS): d=7.23 (d, J=7.3 Hz, 6H), 7.08 (d, J=7.4 Hz, 8H), 6.78 (d, J=
7.6 Hz, 2H), 6.09–6.02 (m, 1H), 5.41 (d, J=17.3 Hz, 1H), 5.27 (d, J=
10.5 Hz, 1H), 4.51 (d, J=5.2 Hz, 2H), 1.30 ppm (s, 27H); 13C NMR
(100 MHz, CDCl3, 258C, TMS): d=156.61, 148.44, 144.32, 139.88, 133.66,
132.40, 130.92, 124.18, 117.70, 113.35, 68.87, 63.23, 34.44, 31.56 ppm; MS
(EI): m/z: 544 [M]+; elemental analysis calcd (%) for C40H48O: C 88.18,
H 8.88; found: C 88.19, H 8.88.
À
28.85, 28.44 ppm; MS (MALDI-TOF): m/z: 2037.4 [MÀPF6 ]+; elemen-
tal analysis calcd (%) for C126H158F6NO14PS4: C 69.30, H 7.29, N 0.64;
found: C 69.63 , H 7.62, N 0.66.
[2]Rotaxane R-3: The reaction was carried out as described for the prep-
aration of thread T-1. DMPA (1.26 mg, 0.005 mmol) was added to a solu-
tion of 9-H·PF6 (2.8 mg, 0.008 mmol) and macrocycle M-S[13a] (4.5 mg,
0.010 mmol) in anhydrous CH2Cl2 (3 mL). The reaction mixture was irra-
diated at room temperature for 1 h under a nitrogen atmosphere without
stirring. After concentration, the crude product was purified by chroma-
tography (CH2Cl2/MeOH, 30:1) to afford rotaxane R-3 as a white solid
(2.5 mg, 38%). 1H NMR (400 MHz, CDCl3, 258C, TMS): d=8.20 (s,
2H), 7.63–7.62 (m, 2H), 7.39–7.37 (m, 6H), 7.16–7.12 (m, 4H), 7.09–7.05
(m, 2H), 6.86 (s, 2H), 4.69–4.66 (m, 4H), 4.14–4.13 (m, 4H), 3.84 (t, J=
6.0 Hz, 4H), 3.76 (m, 4H), 3.71 (m, 4H), 3.60 (m, 4H), 3.05 ppm (t, J=
6.0 Hz, 4H); 13C NMR (100 MHz, CDCl3, 258C, TMS): d=146.24,
130.96, 129.69, 129.17, 126.61, 124.98, 108.00, 71.56, 71.29, 70.76, 69.93,
68.84, 52.73, 39.04, 29.44 ppm; MS (MALDI-TOF): m/z: 652.3
[MÀPF6À]+; elemental analysis calcd (%) for C36H46F6NO6PS2: C 54.19,
H 5.81, N 1.76; found: C 54.41, H 6.09, N 1.85.
Thread T-1: The reaction was carried out in a quartz cell (diameter:
1 cm; wall thickness: 1 cm) sealed with a natural rubber plug located
5.5 cm away from the UV lamp. DMPA (5.6 mg, 0.022 mmol) was added
to a solution of compound 7-H·PF6 (28 mg, 0.044 mmol) and compound 8
(59.6 mg, 0.11 mmol) in anhydrous CH2Cl2 (2 mL). The reaction mixture
was irradiated at room temperature for 1 h under a nitrogen atmosphere
without stirring. After concentration, the crude product was purified by
chromatography (CH2Cl2/MeOH=20:1) to afford thread T-1 as a white
solid (68 mg, 90%). M.p. 125.4–125.88C; 1H NMR (400 MHz, CDCl3,
258C, TMS): d=7.22 (d, J=8.2 Hz, 14H), 7.07 (d, J=8.1 Hz, 16H), 6.88
(d, J=8.1 Hz, 4H), 6.73 (d, J=8.4 Hz, 4H), 4.30 (t, J=6.2 Hz, 4H), 4.02–
3.99 (m, 8H), 3.96 (s, 4H), 3.23 (s, 4H), 2.80 (t, J=7.1 Hz, 4H), 2.14–2.09
(m, 4H), 2.05–2.00 (m, 4H), 1.30 ppm (s, 54H); 13C NMR (100 MHz,
CDCl3, 258C, TMS): d=170.66, 159.65, 156.68, 148.43, 144.26, 139.87,
132.39, 131.18, 130.85, 124.17, 123.79, 115.29, 113.12, 65.96, 64.37, 63.18,
62.21, 50.86, 34.41, 33.78, 31.52, 29.50, 28.90, 28.60 ppm; MS (MALDI-
TOF): m/z: 1606.1 [MÀPF6À +Na]+, 1622.2 [MÀPF6À +K]+; elemental
analysis calcd (%) for C104H128F6NO8PS2: C 72.24, H 7.46, N 0.81; found:
C 72.46, H 7.51, N 0.86.
Acknowledgements
This work was supported by the National Nature Science Foundation of
China (20971127 and 20831160507) and the National Basic Research 973
Program of China.
[2]Rotaxane R-1: The reaction was carried out as described for the prep-
aration of thread T-1. DMPA (5.6 mg, 0.022 mmol) was added to a solu-
tion of 7-H·PF6 (28 mg, 0.044 mmol), compound 8 (59.6 mg, 0.11 mmol),
and dibenzo-24-crown-8 (DB24C8; 29.4 mg, 0.066 mmol) in anhydrous
CH2Cl2 (2 mL). The reaction mixture was irradiated at room temperature
for 1 h under a nitrogen atmosphere without stirring. After concentra-
tion, the crude product was purified by chromatography (CH2Cl2/MeOH,
30:1) to afford rotaxane R-1 as a white solid (71.5 mg, 75%). M.p. 127.8–
Jeppesen, J. F. Stoddart, Y. Luo, C. P. Collier, J. R. Heath, Acc.
ska, S. M. Mendoza, E. M. Pꢃrez, P. Rudolf, G. Teobaldi, F. Zerbet-
to, Nat. Mater. 2005, 4, 704–710; d) C. P. Collier, G. Mattersteig,
E. W. Wong, Y. Luo, K. Beverly, J. Sampaio, F. M. Raymo, J. F. Stod-
1
128.38C; H NMR (400 MHz, CDCl3, 258C, TMS): d=7.47 (s, 2H), 7.23–
7.19 (m, 16H), 7.07 (d, J=7.8 Hz, 16H), 6.90–6.89 (m, 4H), 6.81–6.80 (m,
4H), 6.75–6.73 (m, 8H), 4.47–4.45 (m, 4H), 4.31 (t, J=6.2 Hz, 4H), 4.12–
4.11 (m, 8H), 4.03–3.99 (m, 8H), 3.76–3.75 (m, 8H), 3.45 (m, 8H), 3.25
(s, 4H), 2.82 (t, J=6.9 Hz, 4H), 2.13–2.10 (m, 4H), 2.07–2.05 (m, 4H),
1.29 ppm (s, 54H); 13C NMR (100 MHz, CDCl3, 258C, TMS): d=170.47,
159.33, 156.63, 148.32, 147.53, 144.17, 139.73, 132.27, 130.78, 130.75,
124.15, 124.13, 124.12, 124.10, 124.05, 124.02, 123.85, 121.73, 114.54,
113.04, 112.80, 70.75, 70.20, 68.27, 65.90, 64.27, 63.08, 62.23, 52.00, 34.33,
34.31, 34.30, 33.66, 31.52, 31.49, 31.48, 31.46, 31.45, 31.41, 31.38, 31.36,
´
E. W. Wong, M. Belohradsky, F. M. Raymo, J. F. Stoddart, P. J.
f) G. Fioravanti, N. Haraszkiewicz, E. R. Kay, S. M. Mendoza, C.
Bruno, M. Marcaccio, P. G. Wiering, F. Paolucci, P. Rudolf, A. M.
49, 4710–4712.
2166
ꢀ 2011 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Chem. Eur. J. 2011, 17, 2160 – 2167