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RSC Advances
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Journal Name
DOI: 10.1039/C5RA21140A
ARTICLE
dimethylacetamide (20.0 mL), and potassium carbonate (4.84 mmol, 2 % wt/wt) was rapidly added to the solution. Next, this
g, 35.0 mmol) was added. The reaction mixture was left under reaction mixture was kept under stirring at room temperature
stirring at 160°C for 6 h, then poured into cold water (20 mL) for an additional 30 min, then heated at 85°C for 24 h.
and
filtered
to
afford
4,4'-[1,4-phenylen-bis- Subsequently, the reaction mixture was cooled at room
(oxy)]dibenzaldehyde 16 (4.0 g, 12.6 mmol, 90% yield) as temperature, and the polymer beads were isolated by
brown solid, which was pure according to NMR analysis and filtration, washed with water (50 mL), extracted by using water
1
was used without further purification. H-NMR (CDCl3) δ 7.04- (100 mL), THF (100 mL), and n-hexane (100 mL) in a Soxhlet
7.16 (m, 8H), 7.84-7.93 (m, 4H), 9.99 (s, 2H); 13C-NMR (CDCl3) δ apparatus. Finally, the resin was dried under vacuum for 15 h
117.9, 118.5, 129.8, 131.3, 150.1, 162.7, 190.6.
at room temperature (6.78 g, 3.41 mmol Cl/g, 78% yield).
2.3.2.3. SP-Cl 1c Prepared by following the procedure
In a three-neck round bottom flask, equipped with a magnetic described above for 1b Vinylbenzylchloride/styrene
stirrer and nitrogen inlet/outlet, 0.15/0.83. Yield: 80%. Loading: 1.95 mmol Cl/g.
.
.
=
a
methyltriphenylphosphonium bromide (13.40 g , 37.5 mmol )
was dissolved in dry THF (150 mL) at 0°C. A solution of nBuLi 2.3.3. Synthesis of catalysts SP-TBD 2a-c
(3.8 mL, 1.6 M in n-hexane, 95.3 mmol) was then added
2.3.3.1. SP-TBD 2a. In a round bottomed flask equipped with a
nitrogen inlet, a condenser and a magnetic stirrer, TBD (0.2 g,
1.44 mol) was dissolved in dry THF (2 mL) and SP-Cl 1a (0. 245
g, 4.86 mmol Cl/g, 1.2 mmol) was added. The mixture was left
under stirring at 70°C for 24 h, then allowed to cool at room
temperature. The polymer beads were isolated by filtration,
washed with THF and then dried under vacuum for 15 h at
room temperature. The degree of functionalization was
determined to be 3.28 mmol TBD/g by elemental analysis: C
68.13, H 8.34, N 13.80.
dropwise, and the reaction mixture was left under stirring at
0°C for 3 h, then allowed to warm at room temperature. Next,
a solution of 4,4'-[1,4-phenylenebis(oxy)]dibenzaldehyde 16
(4.0 g , 12.6 mmol ) in dry THF (30.0 mL) was added, and this
mixture was stirred at room temperature for an additional 24
h. After this time, THF was removed under vacuum, and the
residue was recrystallized from methanol, affording 1,4-bis(4-
vinylphenoxy)benzene
4 (3.17 g, 80% yield) as a white solid
(m.p. 146-146.5°C); 1H- NMR (CDCl3) δ 5.18- 5.21 (d, 1H, J=
11.08 Hz), 5.64-5.68 (d, 1H, J= 17.52 Hz), 6.65-6.72 (dd, 1H, J=
11.08, 17.52 Hz) , 6.95-6.97 (d, 2H, J= 8.64 Hz), 7.00 (s, 2H),
7.36-7.39 (d, 2H, J = 8.64 Hz); 13C-NMR (CDCl3) δ 112.79,
118.25, 120.43, 127.54, 132.65, 135.95, 152.62, 157.40. An.
Calcd. for C22H18O2: C, 84.05; H, 5.77% . Found: C, 84.11; H,
5.76%.
2.3.3.2. SP-TBD 2b. Prepared by following the procedure
described above for 2a, starting from SP-Cl 1b. The degree of
functionalization was determined to be 2.38 mmol TBD/g by
elemental analysis: C 70.33, H 8.28, N 10.00.
2.3.3.3. SP-TBD 2c. Prepared by following the procedure
described above for 2a, starting from SP-Cl 1c. The degree of
functionalization was determined to be 0.68 mmol TBD/g by
2.3.2. Preparation of SP-Cl supports 1a-c
2.3.2.1. SP-Cl 1a. A three-neck cylinder-shaped glass vessel, elemental analysis: C 81.92, H 7.82, N 2.96.
equipped with a mechanical stirrer, a condenser, and a
nitrogen inlet was charged with an aqueous NaCl (2% wt) 2.3.4. Synthesis of catalysts SP-TEA 3a-c
solution containing acacia gum (4 % wt) (120 mL). After
2.3.4.1. SP-TEA 3a. In a round bottomed flask equipped with a
deoxygenation by purging with nitrogen,
a mixture of
nitrogen inlet,
a
condenser and
a magnetic stirrer,
vinylbenzylchloride (9.68 g, 63.7 mmol), 1,4-bis(4-
vinylphenoxy)benzene (0.41 g, 1.3 mmol), chlorobenzene
(8mL), and dibenzoylperoxide (0.20 g , 0.83 mmol, 2 % wt/wt)
was rapidly added to the solution. Next, this reaction mixture
was kept under stirring at room temperature for an additional
30 min, then heated at 85°C for 24 h. Subsequently, the
reaction mixture was cooled at room temperature, and the
polymer beads were isolated by filtration, washed with water
(50 mL), extracted by using water (100 mL), THF (100 mL), and
n-hexane (100 mL) in a Soxhlet apparatus. Finally, the resin 1a
was dried under vacuum for 15 h at room temperature (7.96
g,4.86 mmol Cl/g, 79% yield).
diethylamine (0.263 g, 3.6 mmol) was dissolved in dry DMF (2
mL) and SP-Cl 1a (0. 245 g, 4.86 mmol Cl/g, 1.2 mmol) was
added. The mixture was left under stirring at 85°C for 24 h,
then allowed to cool at room temperature. The polymer beads
were isolated by filtration, washed with DMF and extracted by
using methanol (100 mL), dichloromethane (100 mL), and
acetone (100 mL) in a Soxhlet apparatus. Subsequently, the
resin was dried under vacuum for 15 h at room temperature.
The degree of functionalization was determined to be 2.74
mmol TEA/g by elemental analysis: C 69.33, H 8.51, N 4.03.
2.3.4.2. SP-TEA 3b. Prepared by following the procedure
described above for 3a, starting from SP-Cl 1b. The degree of
functionalization was determined to be 1.74 mmol TEA/g by
elemental analysis: C 71.86, H 8.50, N 2.37.
2.3.2.2. SP-Cl 1b. A three-neck cylinder-shaped glass vessel,
equipped with a mechanical stirrer, a condenser, and a
nitrogen inlet was charged with an aqueous NaCl (2% wt)
solution containing acacia gum (4% wt) (120 mL). After
deoxygenation by purging with nitrogen, a mixture of styrene
(2.98 g, 28.6 mmol), vinylbenzylchloride (5.36 g, 35.1 mmol),
1,4-bis(4-vinylphenoxy)benzene (0.409 g, 1.3 mmol),
chlorobenzene (8mL), and dibenzoylperoxide (178 mg, 0.72
2.3.4.3. SP-TEA 3c. Prepared by following the procedure
described above for 3a, starting from SP-Cl 1c. The degree of
functionalization was determined to be 0.90 mmol TEA/g by
elemental analysis: C 80.29, H 8.25, N 1.20.
This journal is © The Royal Society of Chemistry 20xx
J. Name., 2013, 00, 1-3 | 3
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