Recognition by a Quinoline-Substituted Crown Ether
the solution was stirred at room temperature overnight. The solu-
tion was neutralized by using an excess of AcOH, then the solvents
were evaporated and the residue was dissolved in dichloromethane
and washed with water, dried (MgSO4) and evaporated to give a
yellow solid, which was characterized by 1H NMR and MS and
used without further purification, yield 668 mg (88%). 1H NMR
(400 MHz, CDCl3): δ = 10.94 (s, 1 H), 9.54 (s, 1 H), 8.65 (d, J =
8.0 Hz, 1 H), 7.91 (dd, J = 12.0 Hz, 1 H), 7.80 (s, 1 H), 7.67 (t, J
as KCl, NaCl, NH4Cl etc.) were added in excess as powders, and
the NMR tubes were stirred for 12 h at room temperature. After
standing 1 h, the NMR spectra were acquired.
Supporting Information (see footnote on the first page of this arti-
cle): 1H and 13C NMR spectra, titration curves, Job plots, MS, and
XRD data.
= 8.0 Hz, 1 H), 7.25 (m, 2 H), 7.24–7.21 (m, 2 H), 6.98 (m, 1 H), Acknowledgments
4.22 (d, J = 8.0 Hz, 2 H), 2.34 (m, 1 H), 1.17 (d, J = 8.0 Hz, 6
H) ppm. MS (ESI, +): m/z (%) = 380.16144 (100) [M + H]+. MS
(ESI, –): m/z (%) = 259.11346 (100) [C14H15N2O3]–, 378.15274 (50)
[M – H]–.
Z.-H. S. and F.-F. P. are thankful to the China Scholarship Council
(CSC) for scholarship assistance.
4-Isobutoxy-8-(phenylureido)quinoline-2-carboxylic Acid (6,7,9,10,
12,13,15,16,18,19-decahydro-5,8,11,14,17,20-hexaoxabenzocyclo- [2] C. J. Pedersen, J. Am. Chem. Soc. 1967, 89, 7017–7036.
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octadecen-2-yl)amide
(4):
Diisopropylethylamine
(DIPEA;
0.75 mmol) and HBTU (0.75 mmol) were added successively to an
anhydrous CH2Cl2 (20 mL) and CH3CN (40 mL) solution of a mix-
ture of quinoline acid 3 (189 mg, 0.5 mmol, 1.0 equiv.) and freshly
hydrogenatively reduced 4Ј-aminobenzo-18-crown-6 (0.5 mmol,
1.0 equiv.). The reaction was monitored by TLC. After stirring for
6 h under nitrogen at room temperature, the reaction mixture was
washed with saturated aqueous NH4Cl. The organic extract was
dried with Na2SO4 and filtered. Solvent was evaporated to dryness
and the residue was purified on silica gel (dichloromethane/meth-
anol, 30:1, then 10:1, v/v) to allow isolation of the 4 as a light-
yellow solid, yield 189 mg (55%); m.p. 225–227 °C. 1H NMR
(600 MHz, CDCl3): δ = 9.70 (s, 1 H), 9.20 (s, 1 H), 8.57 (d, J =
7.5 Hz, 1 H), 8.17 (s, 1 H), 7.73 (d, J = 8.2 Hz, 1 H), 7.61 (s, 1 H),
7.42 (t, J = 7.9 Hz, 1 H), 7.36 (d, J = 7.7 Hz, 2 H), 7.21 (s, 1 H),
7.16 (t, J = 7.5 Hz, 2 H), 6.91 (t, J = 7.2 Hz, 1 H), 6.78 (d, J =
8.4 Hz, 1 H), 6.50 (d, J = 8.1 Hz, 1 H), 3.96 (s, 2 H), 3.90 (s, 2 H),
3.83 (d, J = 3.3 Hz, 2 H), 3.78 (d, J = 6.0 Hz, 2 H), 3.72 (s, 4 H),
3.69–3.65 (m, 6 H), 3.63 (s, 4 H), 2.15 (m, 1 H), 1.01 (d, J = 6.6 Hz,
6 H) ppm. 13C NMR (151 MHz, CDCl3): δ = 174.15, 173.72,
164.18, 159.86, 159.62, 156.88, 149.21, 148.77, 146.18, 141.64,
139.82, 138.53, 134.44, 132.86, 131.23, 128.35, 125.51, 125.46,
124.89, 119.13, 109.55, 85.82, 81.52, 81.48, 81.42, 81.38, 81.31,
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80.34, 80.18, 80.01, 79.52, 38.81, 29.86 ppm. IR (KBr): ν = 3532,
˜
3262, 3127, 3070, 2875, 2292, 2108, 1990, 1957, 1693, 1600, 1524,
1600, 1524, 1443, 1392, 1355, 1262, 1202, 1113, 1062, 950, 887,
858, 809, 755, 694 cm–1. MS (ESI, +): m/z (%) = 711.29730 (100)
[M + Na]+. MS (ESI, –): m/z (%) = 723.26831 (100) [M + H2O +
OH]–. C37H44N4O9 (688.78): calcd. C 64.52, H 6.44, N 8.13; found
C 64.14, H 6.30, N 7.92.
X-ray quality crystals were obtained from DMSO:
C37H44N4O9·2(C2H6OS);
0.24ϫ0.09ϫ0.04 mm3; triclinic; space group P1;
11.9166(16) Å, 13.5384(18) Å, 13.9031(19) Å;
Mr
=
845.02;
crystal
size
=
¯
a
b
=
c
=
α
=
83.641(3)°, β = 73.138(3)°, γ = 82.993(3)°; V = 2123.8(5) Å3; Z =
2; ρcalcd. = 1.321 gcm–3; μ = 0.19 mm–1; F(000) = 900.0; 26044 col-
lected reflections θmax = 26.570° of which 8807 were independent
(Rint = 0.069); Tmax = 0.993; Tmin = 0.956; T = 100 K; full-matrix
least-square on F2 with 7 restraint and 551 parameters; GOF =
1.050; R1 = 0.0552[IϾ2σ(I)]; ωR2 (all data) = 0.1254; peak/hole =
0.57/–0.38 eÅ–3.
CCDC-929585 (4 from DMSO) and -932302 (4 from CH2Cl2/
CH3CN) contain the supplementary crystallographic data for this
paper. These data are available free of charge from The Cambridge
Crystallographic Data Centre via www.ccdc.cam.ac.uk/data_
request/cif.
Solid-Liquid Extraction:[24] Receptor 4 is soluble in appropriate
deuterated solvents (CDCl3 or [D6]DMSO). Insoluble guests (such
Eur. J. Org. Chem. 2013, 7922–7932
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7931