908
Can. J. Chem. Vol. 84, 2006
Scheme 3. Structures of the cationic 1-(4,5-dihydro-1H-imidazol-2-yl)adamantane and 1,3-bis(4,5-dihydro-1H-imidazol-2-yl)adamantane
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guests with the proton labeling and the complexation-induced chemical shift changes (∆δ (ppm) in parentheses) of the H NMR proton
resonances of the guest upon formation of the inclusion complexes with CB[7].
(+0.44)
(–0.32)
b
b
HN
HN
NH
NH
a
a
1
1
2
(–0.76)
(–0.89)
(–0.77)
H
N
(+0.06)
2
(+0.11)
(–0.32)
2'
2'
4
3
(+0.09)
3'
3
a
4
b
N
H
3' (+0.12)
4a
4'
4b (–0.41)
(+0.09)
IAD+
BIAD2+
J = 8.6 Hz), 8.31 (d, 2H, J = 8.6 Hz), 8.55 (s, 2H). 13C NMR
(D2O, ppm) δ: 44.73 (Cb), 122.32 (C1), 124.46 (C3), 129.65
(C4), 130.74 (C2), 134.23 (Cc), 165.92 (Ca). Lit. (11) (D2O,
ppm) δ: 47.6, 125.3, 132.5, 133.5, 137.2, 169.0. ES-MS m/z:
266.5 [M – H]+.
2H, H4, J3,4 = 8 Hz), 9.04 (s, 2H, H6). 13C NMR (D2O, ppm)
δ: 44.9 (Cb), 120.3 (C5), 123.0 (C3), 138.2 (C4), 148.5 (C6),
158.4 (C2), 164.2 (Ca). ES-MS m/z: 293.1 [M – 3H]+. Anal.
calcd. for C16H20N6Cl4: C 43.86, H 4.60, N 19.18; found: C
43.80, H 4.25, N 19.13.
4,4′-Bis(4,5-dihydro-1H-imidazol-2-yl)biphenyl
1-(4,5-Dihydro-1H-imidazol-2-yl)adamantane
dihydrochloride ([BIBP]Cl2·H2O)
hydrochloride ([IAD]Cl)
Melting point 152–154 °C (dec). H NMR (D2O, ppm) δ:
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1
Melting point > 300 °C (dec). H NMR (D2O, ppm) δ:
4.04 (s, 8H, N-CH2), 7.85 (d, 4H, H2, J2,3 = 8.6 Hz), 7.89 (d,
4H, H3, J2,3 = 8.6 Hz). 13C NMR (D2O, ppm) δ: 44.56 (Cb),
122.03 (C4), 128.05 (C2), 128.70 (C3), 144.55 (C1), 166.05
(Ca). ES-MS m/z: 146.0 [M]2+. Anal. calcd. for
C18H20N4Cl2·H2O: C 56.70, H 5.82, N 14.69; found: C
56.31, H 5.60, N 14.32.
1.65 (d, 3H, H4b, J4a,4b = 12.7 Hz), 1.71 (d, 3H, H4a), 1.78 (d,
6H, H2, J2,3 < 0.5 Hz), 1.97 (s, 3H, H3), 3.53 (s, 4H, NH-
CH2). 13C NMR (D2O, ppm) δ: 27.7 (C3), 35.1 (C1), 35.8
(C2), 39.0 (C4), 46.5 (Cb), 170.4 (Ca). ES-MS m/z: 205.4
[M]+. Anal. calcd. for C13H21N2Cl: C 64.85, H 8.79, N
11.63; found: C 64.46, H 7.75, N 11.53.
1,4-Bis(4,5-dihydro-1H-imidazol-2-yl)benzene
1,3-Bis(4,5-dihydro-1H-imidazol-2-yl)adamantane
dihydrochloride ([BIP]Cl2·H2O)
dihydrochloride ([BIAD]Cl2·3H2O)
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Melting point > 235 °C. H NMR (D2O, ppm) δ: 4.04 (s,
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Melting point > 280 °C (dec). H NMR (D2O, ppm) δ:
8H, N-CH2), 7.93 (s, 4H, H2 and H3). 13C NMR (D2O, ppm)
δ: 44.93 (Cb), 45.30 (C2), 127.94 (C1), 128.79 (C3), 165.69
(Ca). ES-MS m/z: 215.7 [M – H]+. Anal. calcd. for
C12H16N4Cl2·H2O: C 48.04, H 5.73, N 18.53; found: C
47.22, H 5.24, N 18.36.
1.72 (s, 2H, H4′), 1.87 (m, 8H, H2′ and H4), 2.01 (s, 2H, H2),
2.25 (s, 2H, H3′), 3.85 (s, 8H, NH-CH2). 13C NMR (D2O,
ppm) δ: 26.96 (C4), 33.46 (C5), 34.96 (C1), 36.81 (C3),
38.91 (C2), 44.02 (Cb), 175.55 (Ca). ES-MS m/z: 273.4 [M –
H]+. Anal. calcd. for C16H26N4Cl2·3H2O: C 48.12, H 8.08,
N14.03; found: C 47.39, H 7.56, N 13.64.
4,4′-Bis(4,5-dihydro-1H-imidazol-2-yl)stilbene
dihydrochloride ([BIST]Cl2·3H2O)
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Physical measurements
Melting point > 280 °C (dec). H NMR (D2O, ppm) δ:
The NMR spectra were recorded on a Bruker Avance-400
instrument in D2O (the residual solvent proton signal at
4.75 ppm served as the internal reference). Electrospray
mass spectrometry measurements were obtained on a VG
Quattro quadrupole mass spectrometer with an atmospheric
pressure electrospray ionization source and a mass range for
single-charged ions of 4000. Samples were prepared as
solutions in distilled water containing the guest (2.5 ×
10–3 mol/L) and CB[7] (0.015 mol/L). UV–vis spectra were
recorded on a Hewlett-Packard 8452 diode array spectrome-
4.02 (s, 8H, NH-CH2), 7.39 (s, 2H, HC=CH), 7.77 (s, 8H,
H2 and H3). 13C NMR (D2O, ppm) δ: 44.46 (Cb), 127.2 (Cc),
127.5 (C2), 128.51 (C3), 129.6 (C4), 139.8(C1), 157.4 (Ca).
ES-MS m/z: 159.5 [M]2+. Anal. calcd. for C20H22N4Cl2·H2O:
C 54.18, H 6.37, N 12.64; found: C 54.77, H 6.04, N 12.67.
5,5′-Bis(4,5-dihydro-1H-imidazol-2-yl)-2,2′-bipyridine
tetrahydrochloride ([BIBPY]Cl4)
Melting point > 250 °C (dec). H NMR (D2O, ppm) δ:
4.05 (s, 8H, NH-CH2), 8.38 (d, 2H, H3, J3,4 = 8 Hz), 8.42 (d,
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© 2006 NRC Canada