B. Wannalerse et al. / Tetrahedron 64 (2008) 10619–10624
10623
added and heated at reflux for 24 h under nitrogen atmosphere.
4.3. NMR studied on host and guests
The mixture was evaporated in vacuo. The residue was purified by
column chromatography (SiO2) using 50% ethylacetate/dichloro-
methane as eluent to afford compound 2 as colorless liquid (80%
TheNMRexperimentsweremeasuredinDMSO-d6. Thesolutionof
ligand in DMSO, which was added with 4 equiv of solid tetrabutyl-
ammonium salts (Fꢀ, Clꢀ, Brꢀ, AcOꢀ, BzOꢀ, and H2POꢀ4 ) was recorded.
yield). 1H NMR (400 MHz, CDCl3)
d
8.20 (s, 1H, –NCHN–), 7.58 (m,
2H, –ArH–), 7.22 (m, 2H, –ArH–), 4.21 (m, 2H, –NCH2–), 1.75 (m, 2H,
–CH2–), 1.22 (m, 6H, –CH2–), 0.80 (m, 3H, –CH3); FTIR (KBr disk)
n
4.4. UV–vis titrations for binding constants of host–guests
[cmꢀ1] 2928 (m), 1496 (s), 1457 (s), 1368 (s), 743 (s).
All UV–vis experiments were carried out in DMSO with tetra-
butylammoniumhexafluorophosphate as supporting electrolyte.
The solutions of HBIMANQ (7.5ꢁ10ꢀ4 M) and BIMANQ (1.5ꢁ10ꢀ4 M)
were prepared and gradually added with the solution of guests
(0.02 M) until the system reached the equilibrium point observed
by a small change in UV–vis spectrum. Each addition was recorded
and all data were used for the calculation of the stability constants
with Spectfit 32 program.
4.2.2. Chloroethyleneamidoanthraquinone (3)30
A solution of aminoanthraquinone (1.00 g, 4.5 mmol) and pyri-
dine (0.86 mL, 5.4 mmol) was stirred in 50 mL dichloromethane
and cooled to 0 ꢃC. After slowly adding a solution of chloroacetyl-
chloride (0.61 g, 5.4 mmol) in (15 mL) dichloromethane, a brown
precipitate appeared. HCl (3 M) was added to the mixture and the
organic layer was extracted with water (3ꢁ50 mL). The organic
layer was dried with anhydrous sodium sulfate and evaporated
in vacuo to obtain a brown solid and further crystallized with
dichloromethane/hexane. The purified compound 3 yielded as
the brown crystalline solid in 70%. Mp 250 ꢃC. 1H NMR
4.5. CV studies on host and guests
Typically, a 0.001 mol dmꢀ3 solution of a ligand (5ꢁ10ꢀ6 mol) in
0.1 mol dmꢀ3 supporting electrolyte (5 mL of NBu4PF6 in freshly
distilled DMSO) was prepared. A stock solution of an anionic
0.5 mmol in supporting electrolyte (0.1 mol dm3) was prepared. All
electrochemical experiments were carried out in a three-electrode
cell designed in-house comprising of a working electrode, a counter
electrode, and a reference electrode. The working electrode was
a glassy carbon disk with a diameter of 3 mm embedded in Teflon
and the counter electrode was a platinum coil. Ag/AgNO3 electrode
was used as a reference electrode in DMSO solution.
(400 MHz, CDCl3)
1H, –ArH–), 7.85 (m, 2H, –ArH–), 4.30 (s, 2H, –CH2–); FTIR (KBr
disk)
[cmꢀ1] 3344 (m), 1720 (s), 1669 (s), 1420 (m); ESI MS:
d 8.64 (s, 1H, –NH–), 8.36 (m, 4H, –ArH–), 8.26 (s,
n
m/z¼299.03.
4.2.3. 2-(1H-Benzo[d]imidazol-1-yl)-N-(9,10-dioxo-9,10-
dihydroanthracen-2-yl) hexyl actamide, HBIMANQ
To a solution of 2 (0.20 g, 1.0 mmol) and a catalytic amount
of sodium iodide in (15 mL) acetone/chloroform,
3 (0.29 g,
1.00ꢁ10ꢀ3 mol) was added and the mixture was stirred. The pre-
cipitate was separated and recrystallized in a mixture of dichloro-
methane/hexane to obtain the product HBIMANQCl (10% yield).
Anion exchange of HBIMANQCl was carried out using KPF6 in THF
for 24 h to afford HBIMANQ (85%yield); mp 355–357 ꢃC. 1H NMR
Acknowledgements
We thank the Thailand Research Fund (MRG4780187 and
RTA5080006) and National Center of Excellence for Petroleum,
Petrochemical, and Advanced Materials (NCE-PPAM) for financial
supports. B.W. is a Ph.D. student supported by the Commission on
Higher Education.
(400 MHz, DMSO-d6)
d 11.30 (s, 1H, –NH–), 9.78 (s, 1H, –NCHN–),
8.48 (s, 1H, –ArH–), 8.22 (m, 2H, –ArH–), 8.15 (m, 2H, –ArH–), 8.08
(m, 2H, –ArH–), 7.90 (m, 2H, –ArH–), 7.70 (m, 2H, –ArH–), 5.60 (s,
2H, –CH2CON–), 4.58 (m, 2H, –NCH2–), 1.91 (m, 2H, –CH2–), 1.30 (m,
6H, –CH2–), 0.83 (m, 3H, –CH3). 13C NMR (400 MHz, DMSO-d6)
Supplementary data
d
183.4, 182.6, 165.2, 144.5, 143.8, 135.3, 135.3, 134.9, 134.1, 134.1,
132.8, 131.7, 129.7, 129.4, 127.8, 127.6, 127.5, 127.5, 125.0, 117.1, 114.5,
114.3, 50.1, 48.0, 31.4, 29.3, 26.2, 22.8, 14.2; FTIR (KBr disk)
[cmꢀ1
The analysis of the synthesized compounds including NMR
spectra, mass spectrometry, and cyclic voltammograms are pro-
vided. Supplementary data associated with this article can be found
n
]
3384 (m), 2925 (s), 1724 (s), 1672 (s), 841 (s); HRMS (positive ESI)
m/z calcd for C29H28N3O3 (Mþ) 466.213, found 466.223; UV–vis
(DMSO) lmax¼368 nm.
References and notes
4.2.4. 2-(1H-Benzo[d]imidazol-1-yl)-N-(9,10-dioxo-9,10-
dihydroanthracen-2-yl) actamide, BIMANQ
1. (a) Gale, P. A.; Quesada, R. Coordin. Chem. Rev. 2006, 250, 3219–3244; (b)
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Chem. Rev. 2006, 250, 3094–3117; (c) Sukai, C.; Tuntulani, T. Top. Curr. Chem.
2005, 255, 163–198.
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Chem. Soc. 2004, 15, 587–594.
To a solution of benzimidazole (0.123 g, 0.5 mmol) and a cata-
lytic amount of sodium iodide in (60 mL) DMF, 3 (0.179 g, 0.6 mmol)
and NaH (0.012 g., 0.5 mmol) were added and the reaction mixture
was stirred for 24 h under nitrogen atmosphere. Then, the mixture
was evaporated in vacuo. The residue was purified by column
chromatography (SiO2) using ethylacetate as eluent to afford
compound BIMANQ as brown solid (80% yield). Mp 300–301 ꢃC. 1H
6. Welton, T. Chem. Rev. 1999, 99, 2071–2083.
NMR (400 MHz, DMSO-d6)
d 11.13 (s, 1H, –CONH–), 8.45 (s, 1H,
7. Liu, Z.; Chen, Z.-C.; Zheng, Q.-G. Org. Lett. 2003, 5, 3321–3323.
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Chem. Soc. 2002, 124, 4228–4229.
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2693–2695.
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Dyson, P. J. Inorg. Chem. 2006, 45, 10407–10409.
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–NCH]N), 8.27 (s, 1H, –ArH–), 8.20 (m, 3H, –ArH–), 8.07 (d, 1H,
–ArH–), 7.89 (m, 2H, –ArH–), 7.59 (d, 1H, –ArH–(benzimidazole)),
7.56 (d, 1H, –ArH–(benzimidazole)), 7.23 (m, 2H, –ArH–(benz-
imidazole)), 5.28 (s, 2H, –COCH2–); 13C NMR (400 MHz, DMSO-d6)
d
31.2, 36.2, 47.9, 110.9, 116.4, 119.7, 122.2, 123.0, 124.4, 127.1, 127.2,
128.7, 129.0, 133.5, 134.7, 135.1, 144.4, 145.4, 162.7, 181.8, 182.8; FTIR
(KBr disk) n
[cmꢀ1] 3366 (w), 3058 (m), 1712 (s), 1663 (s), 1423 (s);
ESI MS (ESþ): m/z(%)¼381.764 (100) [MþHþ]. Anal. Calcd for
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C
23H15N3O3: C, 72.43; H, 3.96; N, 11.02. Found: C, 72.15; H, 3.97;
N, 11.02.