Multicyclic Bis[2]catenanes
3324 3330
and 5.85 (two AB d, 4J=1.8 Hz, 16H; Arcalix-H), 7.56 (brt, 8H; Armeta
-
and the mixture was extracted with dichloromethane (4î20 mL). The or-
ganic layer was washed with water (2î30 mL), dried over MgSO4, and
evaporated, to give a yellow oil (0.21 g; 95%). Elemental analysis (%)
calcd for C12H17NO: 75.35, H 8.91, N 7.32; found: C 75.10, H 9.02, N
7.12; 1H NMR ([D]chloroform): d=7.07 (t, 3J=8.2 Hz, 1H; Ar-H), 6.35
(dd, 3J=8.2 Hz, 4J=1.8 Hz, 1H; Ar-H), 6.29 (dd, 3J=8.2 Hz, 4J=1.8 Hz,
H), 7.35 (d, J=7.9 Hz, 8H; Armeta-H), 7.23(t, 3J=8.1 Hz, 8H; Armeta-H),
6.90 (s, 8H; NH), 6.54 (dd, 3J=8.1 Hz, 4J=1.6 Hz, 8H; Armeta-H), 5.73
(m, 8H; -CH=CH2), 4.94 (dd, 3J=18.3Hz, 4J=1.4 Hz, 8H; -CH=CH2),
4.88 (d, 3J=10.8 Hz, 8H; -CH=CH2), 4.21 and 2.83(two d, 2J=11.8 Hz,
16H; Ar-CH2-Ar ax and eq), 3.90 3.75 (m, 16H; OCH2-), 3.70 3.60 (m,
16H; OCH2-), 1.99 (q, 3J=7.1 Hz, 16H; -CH2CH=CH2), 1.92 (q, 3J=
6.7 Hz, 16H; -CH2-), 1.68 (q, 3J=8.0 Hz, 16H; -CH2-), 1.35 (m, 32H;
-CH2-), 1.27 (q, 3J=7.2 Hz, 16H; -CH2-), 0.94 ppm (t, 3J=7.3Hz, 24H;
-CH3); 13C NMR ([D6]DMSO): d=158.94, 152.26, 151.07, 140.95, 138.42,
134.34, 133.25, 129.25, 118.14, 114.81, 110.11, 107.25, 104.15, 74.71, 66.90,
32.75, 30.54, 29.30, 28.08, 27.89, 24.66, 22.25, 13.91 ppm; FD MS: m/z:
1634.1 [M+ + 1].
3
3
1H; Ar-H), 6.25 (t, J=1.8 Hz, 1H; Ar-H), 5.86 (m, 1H; -CH=CH2), 5.07
(dd, 2J=17.0 Hz, 3J=1.8 Hz, 1H; -CH=CH2), 4.96 (d, 3J=10.6 Hz, 1H;
3
CH=CH2), 3.94 (t, J=6.5 Hz, 2H; OCH2-), 3.63 (brs, 2H; NH2), 2.15 (q,
3J=7 Hz, 2H; CH2CH=CH2), 1.81 (q, 3J=8.2 Hz, 2H; -CH2-), 1.59 ppm
(q, 3J=7.6 Hz, 2H; -CH2-); 13C NMR ([D]chloroform): d=160.09,
147.68, 138.44, 129.87, 114.55, 107.60, 104.36, 101.46, 67.35, 33.29, 28.60,
25.19 ppm; FD MS: m/z: 191.6 [M+].
Diurethane 8: Compound 8 was prepared in three steps: a) Dinitro deriv-
ative: A slurry of 3-nitrophenol (1.53 g, 11 mmol), 1,10-dibromodecane
(1.5 g, 5 mmol), and potassium carbonate (1.52 g, 11 mmol) in acetonitrile
(50 mL) was refluxed for two days (TLC control , eluent ethyl acetate/
hexane 1:2). The solvent was evaporated under reduced pressure and the
crude product was taken up in dichloromethane (250 mL). The organic
layer was washed with water until the aqueous phase remained colorless
(2 4î100 mL), dried over MgSO4, and concentrated. Precipitation with
methanol gave the dinitro derivative as a white compound (1.75 g; 84%);
m.p. 80 818C; 1H NMR ([D]chloroform): d=7.79 and 7.77 (ddd, 3J=
8.1 Hz, 4J=2.2 Hz, 4J=0.9 Hz, 2H; Ar-H), 7.70 (t, 4J=2.3Hz, 2H; Ar-
H), 7.39 (t, 3J=8.2 Hz, 2H; Ar-H), 7.20 and 7.18 (ddd, 3J=8.4 Hz, 4J=
2.5 Hz, 4J=0.9 Hz, 2H; Ar-H), 4.01 (t, 3J=6.6 Hz, 4H; OCH2-), 1.80 (q,
c) A solution of 3-hexenyloxyaniline (1.9 g, 10 mmol) and 4-nitrophenyl
chloroformate (2.0 g, 10 mmol) in a mixture of chloroform (45 mL) and
tetrahydrofuran (30 mL) was refluxed for 12 h. The solvents were evapo-
rated and the residue was dissolved in chloroform and precipitated with
diethyl ether, to yield 9 as a white compound (2.7 g; 77%); m.p. 102
1038C; 1H NMR ([D]chloroform): d=8.27 and 7.38 (2d, 3J=9.1 Hz, 4H;
Ar-H), 7.22 (t, 3J=8.2 Hz, 1H; Armeta-H), 7.13(s, 1H; Ar meta-H), 6.92
(brs, 1H; NH), 6.91 and 6.89 (dd, 3J=8.1 Hz, 4J=1.9 Hz, 1H; Armeta-H),
6.69 and 6.67 (dd, 3J=8.2 Hz, 4J=2.3Hz, 2H; Ar meta-H), 5.86 5.76 (m,
1H; -CH=CH2), 5.04 4.95 (m, 2H; -CH=CH2), 3.96 (t, 3J=6.4 Hz, 2H;
OCH2-),2.14 2.09 (m, 2H; -CH2-), 1.82 1.76 (m, 2H; -CH2 -), 1.60
1.52 ppm (m, 2H; -CH2-); 13C NMR ([D]chloroform): d=159.92, 155.31,
150.02, 145.08, 138.45, 137.76, 129.95, 125.20, 122.13, 114.75, 110.91,
110.79, 105.28, 67.86, 33.37, 28.61, 25.26 ppm; FD MS: [M+] was not de-
tected due to decomposition.
3J=6.5 Hz, 4H; -CH2 -), 1.48 1.43(m, 4H; -CH -), 1.37 1.32 ppm (m,
2
8H; -CH2 -); 13C NMR ([D]chloroform): d=159.66, 149.21, 129.82,
121.66, 115.50, 108.65, 68.70, 29.41, 29.26, 28.97, 25.91 ppm; FD MS: m/z:
416.3[ M+].
Bis[2]catenane 10a: a) From the homodimer: A solution of 5 (0.2 g,
0.12 mmol) in benzene (50 mL) was stirred at room temperature for
three hours. The formation of the homodimer was monitored by
1H NMR spectroscopy. The solution was diluted with dichloromethane
(1 L) and a solution of Grubbs’ catalyst (10 mg, 12.4 mmol) in dichloro-
methane (25 mL) was added. The reaction mixture was stirred for two
days, two drops of DMSO were added, and the stirring was continued for
12 h. The solution was concentrated to about 400 mL and washed with
water (2î400 mL), dried over MgSO4, and evaporated. The residue was
disolved in THF (20 mL) and hydrogen (1 atm) added in the presence of
PtO2 (50 mg). A white compound was obtained after chromatographic
separation (eluent chloroform/ethyl acetate 95 : 5) and crystallization
from chloroform/methanol mixture gave 10a (0.4 g, 49%).
b, c) The dinitro derivative (2.0 g, 4.8 mmol) was dissolved in acetone
(125 mL) and hydrogenated (1 atm) in the presence of Raney-nickel until
the hydrogen uptake was completed (~3h). The catalyst was filtered off,
washed with acetone (2î25 mL), and the solvent was evaporated. The
white solid residue was dissolved in dioxane (150 mL). 4-Nitrophenyl
chloroformate (2.25 g, 11.15 mmol) was added and the mixture was re-
fluxed for 24 h (a clear solution was obtained in ~3h). The solvent was
evaporated to dryness and the residue was triturated with chloroform.
The desired product 8, a white powder, was filtered off, washed with
chloroform (2î15 mL) and dried (2.88 g; 94%); m.p. 177 1788C
(decomp); 1H NMR ([D6]DMSO): d=10.41 (s, 2H; NH), 8.30 and 7.53
(2d, 3J=8.9 Hz, 8H; Ar-H), 7.21 (t, 3J=8.1 Hz, 2H; Armeta-H), 7.15 (s,
2H; Armeta-H), 7.06 and 7.04 (dd, 3J=8.1 Hz, 2H; Armeta-H), 6.65 and
6.63(2brd, 3J=7.7 Hz, 2H; Armeta-H), 3.91 (t, 3J=6.24 Hz, 4H; OCH2-),
b) From the heterodimer: A solution of 6 (0.2 g, 0.12 mmol) and 7a
(0.2 g, 0.12 mmol) in benzene (10 mL) was prepared by stirring at 408C
for two days. The complete formation of the heterodimer was monitored
and confirmed and by 1H NMR spectrosocpy. The metathesis reaction,
hydrogenation, and the chromatographic purification was carried out as
described above. Compound 10a was obtained as a white precipitate
(0.26 g; 65%); m.p. >2008C (decomp); 1H NMR ([D6]benzene): d=
10.07 (s, 2H; NH), 10.00 (s, 2H; NH), 9.98 (s, 2H; NH), 9.96 (s, 2H;
NH), 8.47 (brt, 2H; Armeta-H), 8.40 and 8.38 (dd, 3J=8.8 Hz; 4J=0.9 Hz,
2H; Armeta-H), 8.37 (brt, 2H; Armeta-H), 8.31 and 8.29 (dd, 3J=8.2 Hz;
3
1.68 (q, J=6.6 Hz, 4H; -CH2 -), 1.38 (m, 4H; -CH2 -), 1.28 ppm (m, 8H;
-CH2 -); 13C NMR ([D6]DMSO): d=159.01, 155.49, 150.36, 144.49,
139.19, 129.66, 125.12, 122.81, 110.74, 109.14, 104.97, 67.26, 66.25, 28.82,
28.63, 28.51, 25.38 ppm.
Urethane 9: Compound 9 was prepared in three steps: a) 3-Hexenyloxy-
acetanilide: A mixture of 3-hydroxyacetanilide (1.634 g, 10.8 mmol), w-
bromohexene-1 (2.041 g, 11.9 mmol), and K2CO3 (1.641 g, 11.9 mmol) in
DMF (20 mL) was stirred at 708C for 6 h. After cooling, the reaction
mixture was poured into water (150 mL) and extracted with chloroform
(4î20 mL). The organic layer was washed with water (2î20 mL), dried
over MgSO4, and evaporated at reduced pressure. After recrystallization
from hexane (15 mL), a white crystalline powder was obtained (2.04 g;
65%). m.p. 698C; elemental analysis (%) calcd for C12H17NO: 72.07, H
8.21, N 6.00; found: C 72.10, H 8.03, N 5.90; 1H NMR ([D]chloroform):
d=7.30 (brs, 1H; NH), 7.25 (s, 1H; Ar-H), 7.17 (t, 3J=7.6 Hz, 1H; Ar-
4
4J=0.9 Hz, 2H; Armeta-H), 8.21 and 6.39 (two AB d, J=2.5 Hz, 4H; Arca-
lix-H), 8.19 and 6.40 (two AB d, 4J=2.5 Hz, 4H; Arcalix-H), 8.01 and 6.23
(two AB d, 4J=2.5 Hz, 4H; Arcalix-H), 7.96 and 6.24 (two AB d, 4J=
2.5 Hz, 4H; Arcalix-H), 7.63(brt, 2H; Ar meta-H), 7.50 (brt, 2H; Armeta-H),
7.43and 7.42 (dd, 3J=8.8 Hz; 4J=0.9 Hz, 2H; Armeta-H), 7.41 (s, 2H;
NH), 7.37 (s, 2H; NH), 7.21 7.19 (m, 4H; Arcalix-H), 7.11 (t, 4J=8.2 Hz,
4
4
2H; Armeta-H), 7.09 (t, J=8.2 Hz, 2H; Armeta-H), 7.00 (t, J=8.2 Hz, 2H;
Armeta-H), 6.98 (s, 2H; NH), 6.81 (s, 2H; NH), 6.77 and 7.75 (dd, 3J=
8.2 Hz, 4J=1.8 Hz, 2H; Armeta-H), 6.69 and 6.67 (dd, 3J=8.2 Hz, 4J=
1.4 Hz, 2H; Armeta-H), 6.56 and 6.54 (dd, 3J=8.2 Hz, 4J=1.8 Hz, 2H;
Armeta-H), 6.48 and 6.46 (dd, 3J=8.2 Hz; 4J=1.8 Hz, 2H; Armeta-H), 4.54
(d, 2J=12.0 Hz, 2H; Ar-CH2-Ar ax), 4.51 (d, 2J=11.7 Hz, 2H; Ar-CH2-
Ar ax), 4.47 (d, 2J=10.8 Hz, 2H; Ar-CH2-Ar ax), 4.44 (d, 2J=11.4 Hz,
4H; Ar-CH2-Ar ax), 4.15 3.50 (m, 32H; OCH2-), 3.35 (d, 2J=12.0 Hz,
2H; Ar-CH2-Ar eq), 3.22 (d, 2J=11.7 Hz, 2H; Ar-CH2-Ar eq), 3.21 (d,
2J=11.4 Hz, 2H; Ar-CH2-Ar eq), 3.08 (d, 2J=11.8 Hz, 2H; Ar-CH2-Ar
eq), 2.15 1.90 (m, 16H; -CH2-), 1.72 1.58 (m, 8H; -CH2-), 1.50 1.10 (m,
88H; -CH2-), 1.00 0.93ppm (m, 24H; -CH 3); 13C NMR ([D]chloroform):
d=160.08, 159.96, 159.89, 154.52, 154.24, 154.18, 153.93, 151.45, 151.41,
151.23, 151.18, 140.69, 140.61, 135.52, 135.33, 135.27, 134.99, 134.78,
3
H), 6.92 (d, J=7.6 Hz, 1.H; Ar-H), 6.63(d, 3J=8.2 Hz, 1.H; Ar-H), 5.82
(m, 1H; -CH=CH2), 5.02 (dd, 2J=17.0 Hz, 3J=1.2 Hz, 1H; -CH=CH2),
4.96 (dd, 2J=10.0 Hz, 3J=1.0 Hz, 1H; -CH=CH2), 3.94 (t, 3J=6.5 Hz,
2H; OCH2-), 2.15 (s, 3H; COCH3), 2.10 (q, 3J=7.0 Hz, 2H; CH2CH=
CH2), 1.77 (q, 3J=7.3Hz, 2H; -CH 2-), 1.54 ppm (q, 3J=7.3Hz, 2H;
-CH2-); 13C NMR ([D]chloroform): d=159.66, 139.04, 138.51, 129.58,
129.45, 114.70, 111.72, 110.62, 106.17, 67.77, 33.39, 28.64, 25.28,
24.68 ppm; FD MS: m/z: 233.4 [M+].
b) 3-Hexenyloxyaniline: A solution of 3-hexenyloxyacetanilide (0.27 g,
1.16 mmol) and NaOH (1.62 g, 40.5 mmol) in
a mixture of ethanol
(20 mL) and water (2 mL) was refluxed for 6 h. After cooling, the mix-
ture was evaporated under reduced pressure, water (200 mL) was added,
Chem. Eur. J. 2004, 10, 3324 3330
¹ 2004 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
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