Biomacromolecules
Page 8 of 38
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vacuum distillation and the product was purified using silica gel using ethyl acetate and pet
1
ether (20% v/v). Yield = 4.67 g (96 %). H NMR (CDCl , 400 MHz) δ ppm: 6.93 ppm (s, 2H,
3
Ar-H), 4.05-3.96 (m, 8H, -POCH
1.72-1.69 (m, 2H, -OCH CH), 1.46-1.31 (m, 16H, aliphatic protons), 1.23 (t, 12H, -
PCH CH ) and 0.94-0.90 (m, 12 H, CH
19.38, 114.75, 71.24, 61.91, 39.74, 30.67, 29.18, 26.91, 23.98, 23.11, 16.42, 14.13, 11.22.
2
CH
3
), 3.81-3.79 (m, 4H, OCH
2
2
), 3.24-3.19 (d, 4H, CH P),
2
13
2
3
3 3
). C NMR (CDCl , 100 MHz) δ ppm: 150.50,
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-1
FTIR (cm ): 2960, 2926, 2867, 1648, 1509, 1466, 1391, 1247, 1210, 1163, 1097, 1022, 955.
+
+
60 8 2
MALDI-TOF-MS: m/z calculated for C32H O P : 634.77 and found 657.47 [M + Na ] and
+
+
6
73.45 [M + K ].
Synthesis of 4-(2-Hydroxyethoxy) benzaldehyde (4): 4-Hydroxybenzaldehyde (5.0 g, 0.04
mol), potassium carbonate (14.14 g, 0.10 mol) was taken in dry DMF (60.0 mL) and heated
at 80 °C for 10 min and further stirred for 1 h. 2-Bromoethanol (4.35 mL, 0.06mol), catalytic
amount of KI were added and reaction was refluxed for 48 h. DMF was removed from the
reaction mixture by vacuum distillation, and the product was extracted in DCM. The crude
product was further purified in silica gel using pet ether and ethyl acetate system (4:1, v/v).
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Yield: 2.7 g (40 %). H NMR (CDCl
3
, 400 MHz) δ ppm: 9.89 (s, 1H, CHO), 7.84 (d, 2H, Ar-
13
H), 7.03 (d, 2H, Ar-H), 4.16 (t, 2H, ArOCH
2
), and 4.01 (t, 2H, CH
2
OH). C NMR (CDCl
3
,
-1
100 MHz) δppm: 190.99, 163.77, 132.14, 130.27, 114.90, 69.64, 61.23. FTIR (cm ): 3395,
939, 2873, 1673, 1597, 1508, 1395, 1253, 1216, 1158, 1078. GC-MS m/z calculated for
= 166.17 and found 166.
2
9 10 3
C H O
Synthesis of Hydroxyl functionalized oilgo-phenylenevinylene (HO-OPV-OH):
Compound 3 (4.0 g, 6.30 mmol) and compound 4 (2.2 g, 13.0 mmol) were taken in dry
tetrahydrofuran (60.0 mL) and the contents were cooled to 4°C under nitrogen atmosphere.
Potassium t-butoxide (37.0 mL in THF, 6.30 mmol) was added and the reaction was
continued for 12 h with stirring at 25 °C. THF was evaporated and the content was added to
2 4
water, extracted using chloroform. It was dried over Na SO , solvent was removed and the
product was purified in silica gel column using pet ether and ethyl acetate system (50 % v/v).
1
Yield = 2.1 g (50 %) H NMR (CDCl
3
, 400 MHz) δppm: 7.48-7.46 ppm (d, 4H, Ar-H), 7.35
(d, 2H, -CH=CH), 7.11 (d, 2H, -CH=CH) and (s, 2H, Ar-H), 6.94- 6.92 (d, 4H, Ar-H), 4.14-
4.12 (d, 2H, CH OH), 3.96 (d, 2H, Ar-CH ), 3.94 (d, 4H, OCH ), 1.84-1.79 (m, 2H, CH) ,
2
2
2
13
1
3 3
.58-1.34 (m, 16H, aliphatic protons), and 1.01-1.91 (m, 12 H, CH ). C NMR (CDCl , 100
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