Ditopic Calixarene Receptor
FULL PAPER
compound 4 also showed selective binding with CuII, which
was accompanied by autoreduction of CuII to CuI, complex
4·CuI did not show any ditopic behaviour towards anions.
request/cif.
Synthesis of 3:
A mixture of 1,3-dimethyl-2-prop-2-ynyloxybenzene
(1 mol equiv), 1-naphthyl hydroximoyl chloride (1.5 mol equiv) and
excess triethylamine (4 mol equiv) in toluene was heated at reflux for
12 h. The solvent was removed under reduced pressure and the residue
was purified by column chromatography to give compound 3 as a brown-
ish-yellow viscous liquid (69%). 1H NMR (300 MHz, CDCl3): d=2.36 (s,
6H), 5.05 (s, 2H), 6.70 (s, 1H), 7.00–7.08 (m, 3H), 7.53–7.58 (m, 3H),
7.73 (d, J=7.0 Hz, 1H), 7.91–7.98 (m, 2H), 8.36–8.39 ppm (m, 1H);
13C NMR (75.4 MHz, CDCl3): d=16.7 (CH3), 65.1 (CH2), 105.4 (CH),
125.1 (CH), 125.6 (CH), 126.0 (CH), 126.7 (CH), 127.1 (Cq), 127.5 (CH),
128.2 (CH), 128.9 (CH), 129.5 (CH), 130.7 (Cq), 131.4 (CH), 134.2 (Cq),
155.6 (Cq), 163.1 (Cq), 168.6 ppm (Cq); EIMS: m/z: 329 [M]+; HRMS:
m/z: calcd for C22H19NO2: 329.1416; found: 329.1417.
Experimental Section
1
General information: H and 13C NMR spectra were recorded on 300 and
500 MHz instruments. Mass spectra were obtained on a GC–MS instru-
ment. HRMS were recorded on a high-performance mass spectrometer.
Column chromatography was performed by using SiO2 (silica gel 60,
230–400 mesh). UV/Vis spectra were recorded by using a spectrophotom-
eter with a diode array detector with the resolution set at 1 nm. Fluores-
Synthesis of 4: A solution of 3 (1 mol equiv) and molybdenum hexacar-
bonyl (1.5 mol equiv) in CH3CN (18 mL) containing water (3 drops) was
heated at reflux at 808C for 3 h. After the reaction was complete, the sol-
vent was removed under reduced pressure, and the residue obtained was
purified by column chromatography to give the expected product 4 in
cence spectra were recorded on
a luminescence spectrophotometer.
Cyclic voltammetry was performed on solutions in CH3CN by using plati-
num working and counter electrodes, a Ag/AgCl reference electrode and
Bu4NPF6 as the electrolyte. Electrolysis was performed by replacing the
platinum electrode with a platinum coil.
76% yield as
a
yellow solid. M.p. 101–1038C; 1H NMR (300 MHz,
Synthesis of 1: Excess triethylamine (4 mol equiv) was slowly added to a
well-stirred solution of 25,27-dipropargyloxy-26,28-dihydroxycalix[4]ar-
ene (1 mol equiv) and 1-naphthyl hydroximoyl chloride (3.5 mol equiv) in
toluene. The reaction mixture was stirred at reflux for 12 h, diluted with
dichloromethane, washed with water and dried over MgSO4. After filtra-
tion and evaporation of the solvent, the residue was purified over a silica
gel column, which gave the cycloadduct 1 as a yellow solid (80%). M.p.
196–1988C; 1H NMR (300 MHz, CDCl3): d=3.37 and 4.26 (J=13.2 Hz,
8H; ABq), 5.21 (s, 4H), 6.65–6.72 (m, 6H), 6.83 (d, J=7.5 Hz, 4H), 7.06
(d, J=7.5 Hz, 4H), 7.22–7.27 (m, 2H), 7.38–7.60 (m, 8H), 7.81–7.84 (m,
4H), 8.31–8.34 ppm (m, 2H); 13C NMR (75.4 MHz, CDCl3): d=31.2,
68.1, 105.8, 119.3, 125.1, 125.5, 126.0, 126.2, 126.2, 127.0, 127.8, 127.9,
128.5, 128.6, 129.2, 130.3, 130.7, 133.0, 133.7, 151.2, 152.9, 162.6,
166.9 ppm; FAB-MS: m/z: 840 [M+2]+; HRMS (FAB) calcd for
C56H42N2O6: 838.3045; found: 838.3056.
CDCl3): d=2.2 (s, 6H), 4.37 (s, 2H), 5.53 (brs, 1H), 5.98 (s, 1H), 6.89–
7.01 (m, 3H), 7.48–7.61 (m, 4H), 7.88–7.94 (m, 2H), 8.25–8.28 (m, 1H),
10.31 ppm (brs, 1H); 13C NMR (75.4 MHz, CDCl3,): d=16.3 (CH3), 75.4
(CH2), 94.1 (CH), 124.0 (CH), 125.0 (CH), 125.0 (CH), 125.6 (CH),
126.4 (CH), 127.0 (CH), 128.5 (CH), 128.8 (CH), 130.1 (CH), 130.8 (Cq),
133.7 (Cq), 135.4 (Cq), 155.4 (Cq), 163.1 (Cq), 195.1 ppm (Cq); EIMS: m/z:
331 [M]+; HRMS: m/z: calcd for C22H21NO2: 331.1572; found: 331.1567.
Synthesis of 5: Propyl iodide (20 mol equiv) was added to a well-stirred
solution of 1 (1 mol equiv) and NaH (30 mol equiv) in DMF (25 mL) and
was stirred for 12 h at room temperature. When the reaction was com-
plete, water was added to quench the reaction. The solution was diluted
with CH2Cl2 and extracted with water to remove DMF and base, and the
organic layer was dried over MgSO4. After filtration and evaporation of
the solvent, the residue was purified over a silica gel column, which gave
the adduct 5 in 65% yield as a white solid. M.p. 86–888C; 1H NMR
(300 MHz, CDCl3): d=0.81 (t, J=7.4 Hz, 6H), 1.73–1.80 (m, 4H), 3.14
(d, J=13.5 Hz, 4H), 3.62 (t, J=7.2 Hz, 4H), 4.30 (d, J=13.5 Hz, 4H),
5.50 (s, 4H), 6.15–6.28 (m, 6H), 6.43 (s, 2H), 6.90 (t, J=7.4 Hz, 2H), 7.03
(d, J=7.4 Hz, 4H), 7.43–7.48 (m, 6H), 7.62 (d, J=6.0 Hz, 2H), 7.82–7.88
(m, 4H), 8.16–8.19 ppm (m, 2H); 13C NMR (75.4 MHz, CDCl3): 10.5
(CH3), 23.2 (CH2), 31.2 (CH2), 64.8 (CH2), 77.3 (CH2), 106.0 (CH), 122.3
(CH), 123.2 (CH), 125.2 (CH), 125.6 (CH), 126.2 (CH), 126.9 (CH),
127.6 (CH), 127.6 (CH), 128.4 (CH), 129.1 (CH), 130.1 (CH), 131.0 (Cq),
133.1 (Cq), 133.7 (Cq), 137.1 (Cq), 155.4 (Cq), 155.7 (Cq), 162.4 (Cq),
169.0 ppm (Cq); FAB-MS: m/z: 923 [M+H+].
X-ray crystal data for 1: C57.5H43.5Cl4.5N2O6; M=1017.97; monoclinic; a=
38.7769(19), b=17.9986(9), c=15.1865(7) ꢂ; a=90, b=112.227(1), g=
908; V=9811.5(8) ꢂ3; space group C2/c; Z=8; 1calcd =1.378 MgmÀ3; crys-
tal dimensions 0.30ꢁ0.25ꢁ0.22 mm3; T=150(2) K; l (MoKa)=0.71073 ꢂ;
m=0.324 mmÀ1; 38976 reflections collected; 8647 independent reflections
(Rint =0.0660); 644 parameters refined on F2; R1 =0.1424, wR2[F2]=
0.3038 (all data); GOF on F2 =1.030; D1max =1.536 eꢂÀ3. CCDC-707767
contains the supplementary crystallographic data for this paper. These
data can be obtained free of charge from The Cambridge Crystallograph-
Synthesis of 2: A solution of 1 (1 mol equiv) and molybdenum hexacar-
bonyl (1.5 mol equiv) in CH3CN (18 mL) containing water (3 drops) was
heated at reflux at 808C for 5 h. The solvent was removed under reduced
pressure and the residue was purified by column chromatography to give
Synthesis of 6: A solution of compound 5 (1 mol equiv) and molybdenum
hexacarbonyl (3 mol equiv) in CH3CN (10 mL) containing water
(3 drops) was heated at reflux at 808C for 5 h. The solvent was removed
under reduced pressure and the residue was purified by column chroma-
tography to give the expected product 6 as a yellow solid (30%). M.p.
240–2428C; 1H NMR (300 MHz, CDCl3): d=À0.27 (t, J=6.8 Hz, 6H),
1.32–1.40 (m, 4H), 3.07 (d, J=13.7 Hz, 4H), 3.55 (t, J=8.0 Hz, 4H), 4.20
(s, 4H), 4.32 (d, J=13.7 Hz, 4H), 5.23 (brs, 2H), 5.94–5.96 (m, 6H), 6.16
(t, J=7.6 Hz, 2H), 6.78 (t, J=7.4 Hz, 2H), 6.94 (d, J=7.4 Hz, 4H), 7.25–
7.48 (m, 8H), 7.79–7.83 (m, 4H), 8.03–8.06 (m, 2H), 10.27 ppm (brs,
2H); 13C NMR (75.4 MHz, CDCl3): d=8.73 (CH3), 22.7 (CH2), 31.0
(CH2), 76.2 (CH2), 78.8 (CH2), 94.2 (CH), 121.6 (CH), 122.6 (CH), 124.9
(CH), 125.0 (CH), 125.4 (CH), 126.4 (CH), 127.0 (CH), 127.5 (CH),
128.3 (CH), 129.0 (CH), 129.8 (CH),130.0 (CH), 133.0 (Cq), 133.5 (Cq),
135.1 (Cq), 135.4 (Cq), 136.8 (Cq), 154.7 (Cq), 157.8 (Cq), 163.3 ppm (Cq);
FAB-MS: m/z: 950 [M+Na+].
the expected product
2 as a yellow solid (52%). M.p. 212–2148C;
1H NMR (300 MHz, CDCl3): d=3.05 (d, J=13.0 Hz, 4H), 3.80 (d, J=
13.0 Hz, 4H), 4.20 (s, 4H), 6.11 (s, 2H), 6.25 (brs, 2H), 6.57 (t, J=
7.4 Hz, 2H), 6.61–6.66 (m, 4H), 6.75 (d, J=7.4 Hz, 4H), 6.88 (d, J=
7.4 Hz, 2H), 7.11 (t, J=7.8 Hz, 2H), 7.30–7.38 (m, 4H), 7.58 (d, J=
6.2 Hz, 4H), 7.81 (d, J=8.2 Hz, 4H), 8.30 (d, J=8.4 Hz, 2H), 10.38 ppm
(s, 2H); 13C NMR (75.4 MHz, CDCl3): d=30.9, 78.8, 93.7, 118.6, 124.9,
125.2, 125.4, 125.6, 126.0, 126.3, 127.5, 128.0, 128.2, 128.8, 129.4, 130.0,
132.8, 133.4, 135.7, 151.7, 152.6, 163.4, 191.2 ppm; FAB-MS: m/z: 844
[M+2]+; HRMS (FAB) calcd for C56H46N2O6: 842.3356; found: 842.3346.
X-ray crystal data for compound 2: C58H49N3O6; M=884.00; triclinic; a=
11.0578(5), b=14.6102(5), c=16.1385(7) ꢂ; a=114.299(2), b=91.656(2),
g=94.592(3)8; V=2363.18 ꢂ3; space group P1; Z=2; 1calcd
¯
=1.242 MgmÀ3; crystal dimensions 0.25ꢁ0.20ꢁ0.10 mm3; T=295(2) K; l
(MoKa)=0.71073 ꢂ; m=0.081 mmÀ1; 12911 reflections collected; 7918 in-
dependent reflections (Rint =0.0786); 605 parameters refined on F2; R1 =
0.2745; wR2[F2]=0.3748 (all data); GOF on F2 =1.090; D1max
=
0.502 eꢂÀ3. CCDC-707768 contains the supplementary crystallographic
data for this paper. These data can be obtained free of charge from The
Chem. Eur. J. 2009, 15, 6152 – 6160
ꢀ 2009 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
6159