The Journal of Organic Chemistry
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J = 9.1 Hz, 1H), 6.90 (d, J = 8.4 Hz, 2H), 4.43 (q, J = 7.1 Hz, 2H),
3.84 (s,3H), 1.42 (t, J = 7.1 Hz, 3H). 13C NMR (100 MHz, CDCl3): δ
162.9, 160.0, 156.3, 154.3, 147.9, 137.0, 133.2, 131.9, 120.8, 119.0,
117.9, 117.0, 114.5, 114.2, 90.7, 85.8, 62.1, 55.4, 14.2.
(silica gel, EtOAc:PE = 1:3) to give OC7-AM (1.84 g, 91%) as a
yellow solid. 1H NMR (400 MHz, CDCl3, ppm): δ 8.50 (s, 1H), 7.56
(d, J = 7.9 Hz, 1H), 7.51 (d, J = 8.1 Hz, 2H), 7.44 (s, 1H), 7.41 (s,
1H), 6.91 (d, J = 8.1 Hz, 2H), 4.42 (q, J = 7.1 Hz, 2H), 3.85 (s, 3H),
1.42 (t, J = 7.1 Hz, 3H). 13C NMR (100 MHz, CDCl3, ppm): δ 163.1,
160.6, 156.7, 155.2, 148.0, 133.7, 130.2, 129.3, 128.0, 119.1, 117.9,
117.3, 114.2, 114.1, 95.2, 87.1, 62.1, 55.4, 14.3.
Synthesis of Compound OC7. To a solution of OC7-AM (2 g, 6
mmol) in ethanol (20 mL) was added 20 mL of 10% NaOH aqueous
solution. The result mixture was refluxed for 5 h. The reaction solution
was acidified to pH = 1 by hydrochloric acid under 0 °C. The product
was collected by filtration (1.61 g, 88%). 1H NMR (400 MHz,
DMSO): δ 13.27 (s, 1H), 8.75 (s, 1H), 7.92 (d, J = 8.1 Hz, 1H), 7.57
(s, 1H), 7.56 (d, J = 8.0 Hz, 2H), 7.52 (d, J = 8.0 Hz, 1H), 7.03 (d, J =
8.6 Hz, 2H), 3.35 (s, 3H). 13C NMR (100 MHz, DMSO): δ
163.8,159.7,156.2, 153.9, 147.5, 136.5, 133.0, 132.5, 119.2, 119.1,118.3,
116.82, 114.5, 113.7, 89.9, 86.3, 55.3. HRMS (ESI-TOF) m/z: [M −
H]− C19H11O5 calcd, 319.0606; found, 319.0609.
Synthesis of Compound NC7-AM. Compound 4 (2 g, 6 mmol),
1-ethynyl-4-dimethylaminobenzene (0.92 g, 7.2 mmol), PdCl2(PPh3)2
(42 mg, 0.06 mmol), CuI (23 mg, 0.12 mmol), N(Et)3 (10 mL) and
THF (30 mL) were stirred at room temperature for 3 h under N2
atmosphere. Then it was concentrated under reduced pressure. The
crude product was purified by column chromatography (silica gel,
EtOAc:PE = 1:3) to give NC7-AM (1.87 g, 89%) as a yellow solid. 1H
NMR (400 MHz, CDCl3, ppm): δ 8.49 (s, 1H), 7.52 (d, J = 7.9 Hz,
1H), 7.44 (d, J = 8.6 Hz, 2H), 7.41 (s, 1H), 7.40 (d, J = 8.8 Hz, 1H),
6.67 (d, J = 8.7 Hz, 2H), 4.42 (q, J = 7.1 Hz, 2H), 3.03 (s, 6H), 1.41 (t,
J = 7.1 Hz, 3H). 13C NMR (100 MHz, CDCl3, ppm): δ 163.2, 156.9,
155.2, 150.8, 148.2, 133.5, 130.9, 129.2, 118.7, 117.3, 116.9, 111.7,
108.5, 97.4, 86.9, 61.8, 40.2, 14.2.
Synthesis of Compound NC7. To a solution of NC7-AM (2 g,
5.5 mmol) in ethanol (20 mL) was added 20 mL of 10% NaOH
aqueous solution, and the mixture was refluxed for 5 h. Then, reaction
solution was acidified to pH = 1 hydrochloric acid under 0 °C. The
product was collected by filtration (1.71 g, 90%). 1H NMR (400 MHz,
DMSO): δ 8.74 (s, 1H), 7.89 (d, J = 8.1 Hz, 1H), 7.50 (s, 1H), 7.47
(d, J = 8.1 Hz, 1H), 7.42 (d, J = 8.4 Hz, 2H), 6.74 (d, J = 8.6 Hz, 2H),
2.98 (s, 6H). 13C NMR (100 MHz, CF3CO2D): δ 167.5, 165.5, 155.0,
154.3, 142.1, 134.7, 132.5, 131.3, 130.4, 126.4, 120.4, 120.1, 118.8,
113.2, 93.1, 89.6, 47.5. HRMS (ESI-TOF) m/z: [M − H]−
C20H14NO4 calcd, 332.0923; found, 332.0910.
Synthesis of Compound NC6-AM. Compound 2 (2 g, 5.8
mmol), 1-ethynyl-4-dimethylaminobenzene (0.92 g, 7.2 mmol),
PdCl2(PPh3)2 (42 mg, 0.06 mmol), CuI (23 mg, 0.12 mmol), N(Et)3
(10 mL) and THF (30 mL) were stirred at room temperature for 3 h
in N2 atmosphere. Then the mixture was concentrated under reduced
pressure. The crude product was purified by column chromatography
(silica gel, EtOAc:PE = 1:3) to give compound NC6-AM (1.91 g,
1
91%) as yellow solid. H NMR (400 MHz, CDCl3): δ 8.48 (s, 1H),
7.73 (d, J = 7.9 Hz, 1H), 7.72 (s, 1H), 7.41 (d, J = 8.3 Hz, 2H), 7.31
(d, J = 8.6 Hz, 1H), 6.67 (d, J = 8.3 Hz, 2H), 4.43 (q, J = 7.1 Hz, 2H),
3.01 (s, 6H), 1.42 (t, J = 7.1 Hz, 3H). 13C NMR (100 MHz, CDCl3): δ
163.0, 156.4, 154.1, 150.4, 148.1, 137.0, 132.8, 131.6, 121.4, 118.9,
117.9, 116.9, 111.8, 108.9, 92.1, 85.2, 62.1, 40.2, 14.2.
Synthesis of Compound OC6. To the solution of OC6-AM (2 g,
6 mmol) in ethanol (20 mL), 20 mL of 10% NaOH solution was
added. Then the mixture was refluxed for 5 h. After reaction, the
solution was acidified by hydrochloric acid to pH = 1 under 0 °C. The
1
product was collected by filtration yielding OC6 (1.67 g, 91%). H
NMR (400 MHz, DMSO): δ 13.33 (s, 1H), 8.73 (s, 1H), 8.09 (s, 1H),
7.84 (d, J = 8.6 Hz, 1H), 7.52 (d, J = 7.8 Hz, 2H), 7.47 (d, J = 8.6 Hz,
1H), 7.01 (d, J = 8.0 Hz, 2H), 3.34 (s, 3H). 13C NMR (100 MHz,
DMSO): δ 163.8, 159.7, 156.2, 153.9, 147.5, 136.5, 133.0, 132.5, 119.2,
119.1, 118.3, 116.8, 114.5, 113.7, 89.9, 86.3, 55.3. HRMS (ESI-TOF)
m/z: [M − H]− C19H11O5 calcd, 319.0606; found, 319.0600.
Synthesis of Compound NC6. To a solution of NC6-AM (2 g,
5.5 mmol) in ethanol (20 mL) was added 20 mL of 10% NaOH
solution. Then the mixture was refluxed for 5 h. After reaction, the
solution was acidified by hydrochloric acid to pH = 1 under 0 °C. The
1
product was collected by filtration yielding NC6 (1.66 g, 90%). H
NMR (400 MHz, DMSO): δ 8.70 (s, 1H), 8.04 (s, 1H), 7.79 (d, J =
8.7 Hz, 1H), 7.45 (d, J = 8.6 Hz, 1H), 7.38 (d, J = 8.3 Hz, 2H), 6.73
(d, J = 8.4 Hz, 2H), 2.96 (s, 6H). 13C NMR (100 MHz, DMSO): δ
163.9, 156.5, 154.5, 150.6, 147.8, 132.9, 130.3, 129.0, 127.1, 117.7,
117.5, 117.4, 111.8, 107.1, 96.3, 87.0, 55.2. HRMS (ESI-TOF) m/z:
[M − H]− C20H14NO4 calcd, 332.0923; found, 332.0926.
Synthesis of Compound 3. 3-Iodophenol (10 g, 45 mmol) was
dissolved in anhydrous acetonitrile (160 mL). The resulted solution
was cooled in an ice bath. Then, magnesium chloride (12.8 g, 134
mmol) was added portion wise to the solution over 10 min.
Triethylamine (25.3 mL, 363 mmol) was added to this mixture over
5 min, followed by the addition of paraformaldehyde (5.47 g, 636
mmol). The result mixture was heated at reflux for 18.5 h, and then
was saturated by aqueous 1 M HCl. The crude product was extracted
with EtOAc, dried over Na2SO4, and then concentrated in vacuum.
The residue was purified by column chromatography (silica gel, pure
X-ray Crystal Structure Analysis. Calculations were performed
with SHELXTL-97 program package.18 Crystallographic data (exclud-
ing structure factors) for the structures reported in this paper have
been deposited with the Cambridge Crystallographic Data Centre as
supplementary publication no. CCDC: 1030851, 1034459, 1030852.
ASSOCIATED CONTENT
* Supporting Information
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1
PE) to give compound 3 (5.6 g, 50%) as white solid. H NMR (400
S
MHz, CDCl3, ppm): δ 11.01 (s, 1H), 9.85 (s, 1H), 7.44 (s, 1H), 7.39
(d, J = 8.1 Hz, 1H), 7.23 (d, J = 8.1 Hz, 1H). 13C NMR (100 MHz,
CDCl3, ppm): δ 196.1, 161.3, 134.2, 129.4, 127.3, 120.0, 105.2.
Synthesis of Compound 4. Compound 3 (5 g, 20 mmol), diethyl
malonate (3.9 g, 24 mmol), piperidine (200 mL, 2 mmol), and acetic
acid (5 droplets) were added to ethanol (50 mL). The mixture was
heated under reflux for 5 h. Then it was cooled to room temperature,
and concentrated under reduced pressure. The crude product was
purified by column chromatography (silica gel, EtOAc:PE = 1:5) to
UV−vis spectra response, Job’s plot, UV−vis ion selectivity,
fluorescent ion selectivity, pH stability of OC7. Cytotoxicity
assay, cell culture of OC7-AM. UV−vis spectra response, Job’s
plot, molecular orbital plots, UV−vis ion selectivity of NC7.
UV−vis spectra, fluorescent spectra response of OC6. UV−vis
spectra, fluorescent spectra response, molecular orbital plots of
NC6. NMR spectra for compounds 1, 2, 3, 4, OC6-AM, OC7-
AM, NC6-AM, NC7-AM, OC6, OC7, NC6, NC7. Mass
spectra for compounds OC6, OC7, NC6, NC7. Crystallo-
graphic data for NC6-AM, OC7-AM, NC7-AM. This material
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give compound 4 (6.5 g, 94%) as a white solid. H NMR (400 MHz,
CDCl3, ppm): δ 8.46 (s, 1H), 7.76 (s, 1H), 7.68 (d, J = 8.2 Hz, 1H),
7.30 (d, J = 8.1 Hz, 1H), 4.41 (q, J = 7.1 Hz, 2H), 1.41 (t, J = 7.1 Hz,
3H). 13C NMR (100 MHz, CDCl3, ppm): δ 162.8, 155.9, 154.8, 148.0,
134.2, 130.1, 126.1, 118.8, 117.2, 100.9, 62.2, 14.2.
Synthesis of Compound OC7-AM. A mixture of 4 (2 g, 6
mmol), 1-ethynyl-4-methoxybenzene (0.92 g, 7.2 mmol),
PdCl2(PPh3)2 (42 mg, 0.06 mmol), CuI (23 mg, 0.1 2 mmol), N(Et)3
(10 mL) and THF (30 mL) was stirred at room temperature for 3 h
under N2 atmosphere. Then it was concentrated under reduced
pressure. The crude product was purified by column chromatography
AUTHOR INFORMATION
Corresponding Author
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Notes
The authors declare no competing financial interest.
F
J. Org. Chem. XXXX, XXX, XXX−XXX