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New Journal of Chemistry
Page 3 of 9
DOI: 10.1039/C7NJ00851A
New Journal of Chemistry
ARTICLE
Bromine (Br2) (1.1 eq., 1.1 mL, 21.667 mmol) thinned to the acetonitrile (CH3CN) (10 mL) and piperidine (5 drops) which was
proper consistency in CH2Cl2 (5 mL) were dropped into the used as catalyst under nitrogen and stirred at 80°C. Insoluble
mixture. The reaction was covered with a balloon and stirred product in acetonitrile (CH3CN) appeared to suspend in red-black
for 6 h at 63°C. The reaction mixture was then poured into cold solution upon heating. The reaction was stopped until TCL showed
water (200 mL) with Na2SO3 (25 g) in order to balance out the no feed reactants remained (ca. 24 hours). Once cooling to room
residual Br2. Then, a separatory funnel was used to separate temperature, the solution was filtrated with funnel to obtain the
organic phase from water phase with CH2Cl2.The organic layer crude solid product. The crude product was then dissolved with
was extracted and dried over MgSO4. After the organic phase minimal CH2Cl2 and precipitated in methanol. The final product was
solution was removed under reduced pressure, the residue vacuum dried to afford AVPM as a orange-red solid (243.10 mg,
1
was then further purified over
chromatography using petroleum ether as an eluent. The final
product was vacuum dried to yield yellow solid (3.362 g,
60%). 1H-NMR (500 MHz, CDCl3, 25°C, TMS):
= 11.50 (s, 1H),
8.89 (d, J=2H), 8.68 (d, 2H), 7.69 (m, 4H). 13C-NMR (125 MHz,
CDCl3, ppm): = 193.17, 131.83, 131.72, 130.19, 128.94,
a silica gel column
60%). H-NMR (500 MHz, CDCl3, 25°C, TMS): δ= 8.39 (d, 4H), 8.20
(d, 4H), 7.52 (m, 8H), 6.75 (s, 2H), 6.63 (s, 2H), 6.11 (s, 2H), 1.60 (s,
24H). 13C-NMR (125 MHz, CDCl3, ppm): δ= 162.39, 162.14, 158.43,
1583.32, 156.48, 156.43, 135.30, 129.22, 129.01, 128.97, 127.33,
126.24, 125.93, 125.84, 125.82, 125.75, 125.49, 115.02, 114.95,
109.33, 108.02, 106.85, 105.91, 84.92, 84.80, 77.48, 77.36, 77.16,
1
δ
δ
128.82, 127.32, 125.59, 123.78. MALDI-TOF MS for C18H9BrO: 76.84, 68.13, 60.32, 29.86, 25.76, 25.36, 24.73, 20.29, 18.31.
calcd, 283.1; found, 285.0.
MALDI-TOF MS for C52H46B2N2O5: calcd, 800.35928; found,
800.35876.
10-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)anthracene-9-
carbaldehyde 2. A 250 mL two-necked A mixture of 10-
2-(2,6-bis((E)-2-(10-hydroxyanthracen-9-yl)vinyl)-4H-pyran-4-
bromoanthracene-9-carbaldehyde (1) (1.800 g, 6.338 mmol), ylidene)malononitrile HAVPM. 2-(2,6-bis((E)-2-(10-(4,4,5,5-
bis(pinacolato)diboron (3.627 g, 7.606 mmol), potassium tetramethyl-1,3,2-dioxaborolan-2-yl)anthracen-9-yl)vinyl)-4H-
acetate (KOAc) (1.990 g, 20.28 mmol), PdCl2(dppf) (0.139 g, pyran-4-ylidene)malononitrile AVPM (3 mL, 1 × 10-5 M) and
0.190 mmol) and 1,4-dioxane (20 mL) under nitrogen and TEA (5 μL, 11.9 mM) was prepared in a vial bottle. Then H2O2
stirred for 24 h at 90°C. After cooling to room temperature, solution (10 μL, 3.26 mM) was added into the mixture solution.
the mixture was poured into THF (20 mL). Then, the solvent After 2 min, the testing solution was dried in vacuum oven to
was evaporated under reduced pressure. The crude solid remove the solvent remainder. Then the species sample was
product was extracted with H2O-CH2Cl2, and dried over MgSO4. dissolved in CDCl3 and the 1H-NMR spectrum was recorded.
After the organic phase solution was removed under reduced The mass spectrum (MS) and the 1H-NMR spectroscopies
1
pressure, the residue was then further purified over a silica gel exhibit that the structure of the final product was HAVPM. H-
column chromatography using CH2Cl2-petroleum ether (v/v =
NMR (500 MHz, CDCl3, 25°C, TMS):
4H), 8.19 (d, 4H), 7.29 (m, 8H), 6.75 (s, 2H), 6.64 (s, 2H), 6.11
(s, 2H). 13C-NMR (125 MHz, CDCl3, ppm):
=162.39, 162.14,
δ= 9.63 (s, 2H), 8.37 (d,
1/4) as an eluent. The final product was vacuum dried to yield
1
yellow solid
TMS):
7.55 (t, 2H), 1.60 (s, 12H). 13C-NMR (125 MHz, CDCl3, ppm):
2
(1.326 g, 63%). H-NMR (500 MHz, CDCl3, 25°C,
δ
δ
= 11.53 (s, 1H), 8.89 (d, 2H), 8.34 (d, 2H), 7.65 (t, 2H),
158.43, 158.32, 156.48, 156.43, 135.30, 129.22, 129.01,
128.97, 127.33, 126.24, 125.93, 125.84, 128.82, 125.75,
δ
=194.00, 134.74, 130.73, 129.18, 128.35, 126.80, 125.78, 125.49, 115.02, 114.95, 109.33, 108.02, 106.85, 84.92, 84.80,
123.85, 85.11, 25.23. MALDI-TOF MS for C18H9BrO: calcd, 77.48, 77.36, 77.16, 76.84, 68.13, 29.86, 25.76, 25.36, 25.00,
332.2; found, 333.2.
24.00. MALDI-TOF MS for C40H24N2O3: calcd, 580.18; found,
2-(2,6-dimethyl-4H-pyran-4-ylidene)malononitrile 3. A 100 mL 580.2.
two-necked flask was filled with 2,6-dimethyl-gamma-pyrone
(465.52 mg, 3.75 mmol), malononitrile (247.73 mg, 3.75 mmol) and
acetic anhydride (20 mL). The reaction was covered with a balloon
and stirred for 4 h at 120°C under reflux condition. The temperature
dropped to 25°C, then the solution was removed under reduced
pressure. The final product was vacuum dried to afford 3 as a dark-
red solid (419.40 mg, 65%). 1H-NMR (500 MHz, CDCl3, 25°C, TMS):
δ= 6.55 (s, 2H), 2.32 (s, 6H). 13C-NMR (125 MHz, CDCl3, ppm): δ
=162.95, 156.79, 114.85, 106.68, 58.50, 19.84. MALDI-TOF MS for
C10H8N2O: calcd, 172.0; found, 172.0.
H2O2 solution detection
For preparation of test solutions, 1 × 10-3 M probe AVPM THF
solution was prepared by diluting with THF in 10 mL volumetric
flasks. Then, 1 × 10-5 M probe AVPM test solution was
prepared by diluting a 1 × 10-3 M (3 μL) AVPM THF solution
with 3 mL THF in quartz cuvettes (10 mm × 10 mm × 45 mm). A
series of test solutions were prepared by adding different
volumes of H2O2 (30 wt%, 9.79 M) solution to the solution of
probe AVPM (10 μM, 3 mL) in quartz cuvettes. A series of test
solutions were kept for 2 min, and the absorption and
fluorescence measurements were carried out.
2-(2,6-bis((E)-2-(10-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-
yl)anthracen-9-yl)vinyl)-4H-pyran-4-ylidene)malononitrile AVPM.
A
mixture of 10-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-
yl)anthracene-9-carbaldehyde (2) (332.16 mg, 1 mmol), 2-(2,6-
dimethyl-4H-pyran-4-ylidene)malononitrile (3) (86 mg, 0.5 mmol),
This journal is © The Royal Society of Chemistry 2016
J. Name., 2013, 00, 1-3 | 3
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