Molecular ªRubber Glovesº
4085±4096
partitioned between dichloromethane and water. The organic layer was
separated, dried over MgSO4, filtered, and concentrated to dryness. The
solid was redissolved in a mixture of dichloromethane (100 mL) and
methanol (50 mL) and treated with concentrated HCl (2.1 mL) for 3 h at
room temperature. After evaporation of the solvents, the residue was
redissolved in dichloromethane, and the resulting solution was washed
three times with water and dried over MgSO4. Filtration and removal of the
solvent left a white solid (6.394 g), which was purified by chromatography
on silica (200 g), eluting with hexane/dichloromethane (30:70). Yield of
pure product: 3.141 g (54%); m.p. > 2608C; 1H NMR (CD2Cl2, 200 MHz):
d 7.27 (d, J 8.7 Hz, 6H; Hs or Ht), 7.16 (d, J 8.8 Hz, 6H; Ht or Hs),
7.16 (d, J 8.9 Hz, 2H; Hq), 6.79 (d, J 8.9 Hz, 2H; Hr), 4.08 (t, J 6 Hz,
2H; Hg), 3.80 (q, J 5.7 Hz, 2H; Ha), 2.00 (p, J 6.0 Hz, 2H; Hb), 1.68 (t,
J 5.4 Hz, 1H; OH), 1.31 (s, 27H; CH3); elemental analysis calcd (%) for
C40H50O2 ´ H2O (580.86): C 82.71, H 9.02; found: C 82.87, H 8.95.
washed with H2O and concentrated to a volume of 30 mL. It was then
stirred overnight with a solution of KPF6 (0.430 g, 2.37 mmol) in H2O
(10 mL). The organic layer was separated, washed twice with H2O, and
concentrated to dryness. The residue (0.626 g) was purified by chromatog-
raphy on SiO2 (40 g). Gradient elution with hexane/CH2Cl2, 20:80, to
CH2Cl2/0.25% CH3OH afforded pure compound 15 (0.112 g). Elution from
CH2Cl2/0.25% CH3OH to 0.5% CH3OH afforded impure CuI [2]rotaxane
[Cu(6)]PF6. Finally, elution with CH2Cl2/0.5% CH3OH yielded pure
macrocycle 8 (0.006 g). The fractions containing the desired rotaxane
complex were combined and freed of 8 (0.039 g) by column chromatog-
raphy on alumina. Elution with hexane/CH2Cl2, 55:45, afforded a total of
0.289 g (57% yield) of pure CuI [2]rotaxane [Cu(6)]PF6; m.p. 224 ± 2258C;
1H NMR (CD2Cl2, 400 MHz): d 8.180 (d, J 8.44 Hz, 2H; H4'',7''), 8.030
(d, J 8.81 Hz, 2H; Ha''), 7.712 (s, 2H; H5'',6''), 7.688 (d, J 8.43 Hz, 2H;
H3'',8''), 7.632 (d, J 8.81 Hz, 2H; Ho'), 7.527 (s, 1H; H3), 7.517 (d, J
8.07 Hz, 2H; Hm), 7.483 (t, J 8.07 Hz, 2H; Hb''), 7.422 (d, J 8.07 Hz, 2H;
Hw), 7.376 (d, J 8.43 Hz, 1H; H8), 7.294 (d, J 8.44 Hz, 4H; Ho''), 7.246
(d, J 9.17 Hz, 2H; Hq), 7.244 (d, hidden, 1H; H5), 7.234 (d, J 8.81 Hz,
6H; Ht'), 7.231 (d, J 8.81 Hz, 6H; Ht), 7.230 (d, hidden, 1H; H7), 7.209 (d,
J 9.17 Hz, 2H; Hq'), 7.166 (d, J 8.80 Hz, 6H; Hs'), 7.146 (d, J 8.80 Hz,
6H; Hs), 7.040 (d, J 8.81 Hz, 2H; Ho), 7.013 (d, J 7.71 Hz, 2H; Hc''),
6.893 (d, J 9.17 Hz, 2H; Hr), 6.824 (d, J 9.17 Hz, 2H; Hr'), 6.402 (d, J
9.54 Hz, 1H; H6), 6.239 (d, J 8.80 Hz, 2H; Hm'), 5.932 (d, J 8.80 Hz,
4H; Hm''), 5.823 (d, J 8.81 Hz, 2H; Hm), 4.478 (m, 4H; Hd''), 4.107 (t,
J 5.69 Hz, 4H; Hg,g'), 4.053 (m, J 5.27 Hz, 4H; Hg''), 3.847 (t, J
5.87 Hz, 2H; Ha'), 3.793 (t, J 4.77 Hz, 4H; Hb''), 3.683 (t, J 5.87 Hz,
2H; Ha), 3.537 (t, J 4.77 Hz, 4H; Ha''), 2.601 (s, 3H; CH3), 2.110 (m, J
5.87 Hz, 4H; Hb,b'), 1.273 (s, 27H; CH3), 1.263 (s, 27H; CH3); FAB-MS:
Tris(p-tert-butylphenyl)[4-(4-toluenesulfonyl)propyloxyphenyl]methane
(13): A solution of tosyl chloride (0.957 g, 5 mmol) in dichloromethane
(40 mL) was added to a solution of 12 (2.007 g, 3.6 mmol) in dichloro-
methane (350 mL) at 08C. Triethylamine (1.2 mL, 8.6 mmol) and DMAP
(0.006 g, 0.05 mmol) were subsequently added. The reaction mixture was
stirred at 08C for 4 h and then allowed to warm to room temperature. After
stirring overnight at room temperature, it was poured onto ice and
neutralized with 5% aqueous HCl. The organic layer was separated,
washed with water, and dried over MgSO4. The crude product was purified
by chromatography on silica, eluting with hexane/dichloromethane (1:1).
Yield of pure product: 2.85 g (56%); m.p. 223 ± 2258C; 1H NMR (CD2Cl2,
200 MHz): d 7.72 (d, J 8.3 Hz, 2H; Htosyl), 7.28 (d, J 8.8 Hz, 6H; Hs or
Ht), 7.24 (d, J 8.6 Hz, 2H; Htosyl), 7.16 (d, J 8.8 Hz, 6H; Ht or Hs), 7.13
(d, J 8.7 Hz, 2H; Hq), 6.64 (d, J 9.0 Hz, 2H; Hr), 4.20 (t, J 6.1 Hz,
2H; Hg), 3.92 (t, J 5.9 Hz, 2H; Ha), 2.34 (s, 3H; CH3), 2.08 (p, J 5.9 Hz,
2H; Hb), 1.31 (s, 27H; CH3); elemental analysis calcd (%) for C47H56O4S
(717.02): C 78.73, H 7.87; found: C 78.84, H 8.06.
m/z (%): 2272.2 (100) [M PF6] , 1606.9 (31) [15Cu] , 727.2 (70)
[8Cu] ; elemental analysis calcd (%) for C153H154CuF6N4O10P (2417.43): C
76.02, H 6.42, N 2.32; found: C 76.95, H 6.63, N 2.30.
[2]Rotaxane 6: CuI [2]rotaxane [Cu(6)]PF6 (0.064 g, 0.0264 mmol) was
dissolved in CH3CN (9 mL), and a solution of KCN (0.047 g, 0.72 mmol) in
H2O was added in four portions over a period of 6 h. A white precipitate of
free [2]rotaxane 6 gradually appeared. After complete bleaching, the
reaction mixture was diluted with CH2Cl2 to dissolve the precipitate and
washed three times with H2O. The organic layer was separated and
concentrated to dryness, and the residue was purified by chromatography
on alumina (hexane/CH2Cl2, 75:25, to pure CH2Cl2) to afford 0.0541 g of
pure [2]rotaxane 6 (yield: 92%). 1H NMR (CD2Cl2, 400 MHz): d 8.404
(d, J 8.86 Hz, 2H; Ho), 8.294 (d, J 8.86 Hz, 4H; Ho''), 8.145 (d, J
8.44 Hz, 2H; H4'',7''), 8.107 (d, J 8.54 Hz, 1H; H7), 8.009 (d, J 9.92 Hz,
2H; Ho'), 7.997 (s, 1H; H3), 7.946 (d, J 8.44 Hz, 2H; H3'',8''), 7.946 (d, J
8.44 Hz, 2H; Hc''), 7.835 (d, J 9.02 Hz, 1H; H5), 7.716 (d, J 8.50 Hz,
1H; H8), 7.659 (s, 2H; H5'',6''), 7.659 (d, J 8.71 Hz, 1H; H6), 7.508 (d, J
8.04 Hz, 2H; Hw), 7.404 (d, J 7.84 Hz, 2H; Hm), 7.338 (t, J 8.02 Hz, 2H;
Hb''), 7.255 (d, J 8.70 Hz, 6H; Ht'), 7.203 (d, J 8.63 Hz, 6H; Hs or Ht),
7.156 (d, J 8.71 Hz, 6H; Ht or Hs), 7.144 (d, J 8.96 Hz, 2H; Hq), 7.047
(d, J 8.62 Hz, 6H; Hs'), 7.038 (d, J 8.92 Hz, 2H; Hm), 6.861 (d, J
7.67 Hz, 2H; Ha''), 6.788 (d, J 8.87 Hz, 4H; Hm''), 6.796 (d, J 8.91 Hz,
2H; Hq'), 6.784 (d, J 8.91 Hz, 2H; Hr), 6.726 (d, J 8.86 Hz, 2H; Hm'),
6.338 (d, J 8.95 Hz, 2H; Hr'), 4.163 (t, J 6.86 Hz, 2H; Ha), 4.390 (sx,
J 4.99 Hz, 4H; Hd''), 4.129 (t, J 6.17 Hz, 2H; Hg), 3.926 (brs, 4H; Hg''),
3.853 (m, 4H; Ha''), 3.791 (p, J 5.59 Hz, 4H; Hb''), 3.583 (t, J 6.10 Hz,
2H; Ha'), 3.380 (t, J 6.13 Hz, 2H; Hg'), 2.499 (s, 3H; CH3), 2.243 (p, J
6.05 Hz, 2H; Hb), 1.714 (p, J 6.09 Hz, 2H; Hb'), 1.287 (s, 27H; CH3),
Tris(p-tert-butylphenyl)(4-iodopropyloxyphenyl)methane (14): A solution
of NaI (1.0 g, 6.7 mmol) in acetone (5 mL) was added to a hot solution of 13
(0.392 g, 0.55 mmol) in acetone (20 mL). The reaction mixture was heated
under reflux for 3 h. The solvent was then evaporated, and the residue was
partitioned between CH2Cl2 (40 mL) and H2O (50 mL). The organic layer
was dried over MgSO4, filtered, and concentrated to dryness to leave
0.366 g of pure 14 (quantitative yield); m.p. 232 ± 2388C; 1H NMR (CD2Cl2,
200 MHz): d 7.27 (d, J 8.6 Hz, 6H; Hs or Ht), 7.16 (d, J 8.8 Hz, 6H; Ht
or Hs), 7.16 (d, J 8.8 Hz, 2H; Hq), 6.78 (d, J 9.0 Hz, 2H; Hr), 4.01 (t,
J 5.8 Hz, 2H; Hg), 3.38 (t, J 6.8 Hz, 2H; Ha), 2.25 (p, J 6.3 Hz, 2H;
Hb), 1.31 (s, 27H; CH3); elemental analysis calcd (%) for C40H49IO
(672.73): C 71.42, H 7.34; found: C 72.31, H 7.39.
CuI prerotaxane [Cu(8)(9)]PF6: Under argon,
a
solution of
[Cu(CH3CN)4]PF6 (0.084 g, 0.226 mmol) in CH3CN (5 mL) was transferred
to a solution of macrocycle 8 (0.150 g, 0.226 mmol) in dichloromethane
(7 mL). The solution immediately turned bright orange with the simulta-
neous formation of a small amount of precipitate, which redissolved upon
addition of DMF (2 mL). After stirring for 45 min at room temperature, a
solution of diphenol 9 (0.105 g, 0.23 mmol) in DMF (3 mL) was added,
which resulted in a color change to dark red. The solution was stirred
overnight under argon. The solvents were then removed in vacuo to leave
pure prerotaxane [Cu(8)(9)]PF6 in quantitative yield. 1H NMR (CD2Cl2,
200 MHz): d 8.42 (d, J 8.4 Hz, 2H; H4'',7''), 8.03 (d, J 8.4 Hz, 2H;
Ha''), 7.95 (s, 2H; H5'',6''), 7.80 (d, J 8.4 Hz, 2H; H3'',8''), 7.60 (d, J
8.5 Hz, 2H; Ho'), 7.50 (s, 1H; H3), 7.46 (d, J 7.9 Hz, 4H; Hm,b''), 7.42 (d,
J 8.3 Hz, 2H; Hw), 7.33 (d, J > 6.5 Hz, 1H; H8), 7.32 (d, J 8.6 Hz, 4H;
Ho''), 7.26 (d, J 9.1 Hz, 1H; H7), 7.16 (d, J 8.5 Hz, 1H; H5), 7.01 (d, J
7.7 Hz, 2H; Ho), 6.94 (d, J 8.5 Hz, 2H; Hc''), 6.40 (d, J 9.1 Hz, 1H; H6),
6.23 (d, J 8.5 Hz, 2H; Hm'), 5.94 (d, J 8.7 Hz, 4H; Hm''), 5.78 (d, J
8.4 Hz, 2H; Hm), 4.48 (m, J 4.1 Hz, 4H; Hd''), 4.05 (t, J 3.8 Hz, 4H;
Hg''), 3.80 (t, J 4.5 Hz, 4H; Hb''), 3.56 (t, J 4.5 Hz, 4H; Ha''), 2.59 (s,
3H; CH3).
1.286 (s, 27H; CH3) ; FAB-MS: m/z (%): 2209.2 (81) [MH] , 1544.9 (65)
[15H] , 665.2 (100) [8H] ; elemental analysis calcd (%) for
C153H154N4O10 (2208.92): C 83.19, H 7.03, N 2.54; found: C 82.97, H 7.19,
N 2.56.
Compound 15: See preparation of [Cu(6)]PF6. M.p. 178 1918C; 1H NMR
(CD2Cl2, 400 MHz) d 8.436 (d, J 8.80 Hz, 2H; Ho), 8.430 (d, J
9.17 Hz, 2H; Ho'), 8.270 (d, J 8.44 Hz, 1H; H7), 8.107 (d, J 8.44 Hz,
1H; H8), 8.020 (s, 1H; H3), 7.862 (d, J 9.17 Hz, 1H; H5), 7.698 (d, J
9.17 Hz, 1H; H6), 7.511 (d, J 8.07 Hz, 2H; Hw), 7.407 (d, J 7.70 Hz, 2H;
Hm), 7.262 (d, J 8.44 Hz, 6H; Ht or Ht'), 7.258 (d, J 8.80 Hz, 6H; Ht' or
Ht), 7.163 (d, J 8.81 Hz, 2H; Hq or Hq'), 7.163 (d, J 8.81 Hz, 6H; Hs or
Hs'), 7.159 (d, J 8.80 Hz, 2H; Hq' or Hq), 7.159 (d, J 8.80 Hz, 6H; Hs' or
Hs), 7.150 (d, J 8.80 Hz, 2H; Hm'), 7.137 (d, J 9.17 Hz, 2H; Hm), 6.831
(d, J 8.81 Hz, 2H; Hr or Hr'), 6.825 (d, J 8.81 Hz, 2H; Hr' or Hr), 4.295
(t, J 5.31 Hz, 2H; Ha or Ha'), 4.281 (t, J 5.14 Hz, 2H; Ha' or Ha), 4.200
CuI [2]rotaxane [Cu(6)]PF6: Portions of a suspension of Cs2CO3 (0.264 g,
0.81 mmol) in DMF (10 mL) and a solution of compound 14 (0.387 g,
0.575 mmol) in DMF (20 mL) were alternately added over a period of 1 h
to a solution of prerotaxane [Cu(8)(9)]PF6 (0.21 mmol) in DMF (10 mL) at
608C under argon. The reaction mixture was then stirred at 608C for a
further 20 h, after which the solvent was evaporated in vacuo. The solid
residue was partitioned between CH2Cl2 and H2O. The organic layer was
Chem. Eur. J. 2001, 7, No. 19
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