Synthesis and Mesophase Behavior of Phenylthiophene Based Amphiphilic Molecules
J=8.5 Hz, 2H, ArH), 6.90 (s, 1H, ArH), 7.44 (d, J=8.5
Hz, 2H, ArH); HRMS (TOF ES+) calcd for C40H68-
NaO4S+ [(M+Na)+] 667.4838, found 667.4842.
ArH); 13C NMR (CDCl3, 125 MHz) δ: 14.09, 22.68,
29.14—31.92 (multi carbons in alkyl chains), 67.58,
69.63, 69.79, 70.40, 70.51, 70.62 (2C), 114.95 (2C),
121.64, 124.82, 126.71 (2C), 127.98, 141.46, 144.74,
157.96, 173.96. Anal. calcd for C30H45NaO6S (556.73):
C 64.72, H 8.15; found C 64.95, H 8.43.
General procedure for synthesis of 11/n/m
The 10/n/m (140 mg 0.29 mmol) was dissolved in
dry THF (10 mL), added NaH (0.58 mmol), then re-
fluxed for 1.5 h. Sodium 2-chloroacetate was added and
the solution was refluxed for 15 h. The reaction mixture
was extracted with chloroform (10 mL×3). The com-
bined chloroform solution was dried over anhydrous
magnesium sulfate, the solvent was evaporated and the
product was purified by column chromatography (eluent:
chloroform/methanol, V∶V=10∶1).
Sodium 2-(2-(2-(2-(4-(5-hexadecylthiophen-2-yl)-
phenoxy)ethoxy)ethoxy)ethoxy)acetate
(11/16/0)
Synthesized from 10/16/0. Yield 75%, as pale yellow
1
crystal; H NMR (CDCl3, 500 MHz) δ: 0.87 (t, J=7.6
Hz, 3H, CH3), 1.26—1.38 (m, 26H, 13CH2), 1.65—1.69
(m, 2H, ArCH2CH2), 2.78 (t, J=7.5 Hz, 2H, ArCH2),
3.62—3.74 (m, 8H, OCH2CH2OCH2CH2), 3.87 (t, J=
4.1 Hz, 2H, ArOCH2CH2), 4.04 (t, J=4.4 Hz, 2H,
COCH2O), 4.15 (t, J=4.7 Hz, 2H, ArOCH2CH2), 6.69
(d, J=3.3 Hz, 1H, ArH), 6.88 (d, J=8.5 Hz, 2H, ArH),
6.98 (d, J=3.3 Hz, 1H, ArH), 7.45 (d, J=8.6 Hz, 2H,
ArH); 13C NMR (CDCl3, 125 MHz) δ: 14.09, 22.68,
29.14—31.92 (multi carbons in alkyl chains), 67.58,
69.48, 69.81, 70.10, 70.66, 71.29 (2C), 114.97 (2C),
121.66, 124.82, 126.73 (2C), 127.98, 141.47, 144.78,
157.96, 173.96. Anal. calcd for C34H53NaO6S (612.84):
C 66.64, H 8.72; found C 66.79, H 8.93.
Sodium 2-(2-(2-(2-(4-(5-propylthiophen-2-yl)-
phenoxy)ethoxy)ethoxy)ethoxy)acetate
(11/3/0)
Synthesized from 10/3/0. Yield 83%, as pale yellow
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crystal; H NMR (CDCl3, 500 MHz) δ: 1.00 (t, J=7.3
Hz, 3H, CH3), 1.69—1.76 (m, 2H, ArCH2CH2), 2.78 (t,
2H, J=7.5 Hz, ArCH2), 3.62—3.74 (m, 8H, OCH2-
CH2OCH2CH2), 3.87 (t, J=4.1 Hz, 2H, ArOCH2CH2),
4.04 (t, J=4.4 Hz, 2H, COCH2O), 4.15 (t, J=4.7 Hz,
2H, ArOCH2CH2), 6.71 (d, J=2.7 Hz, 1H, ArH), 6.91
(d, J=8.5 Hz, 2H, ArH), 7.00 (d, J=3.1 Hz, 1H, ArH),
7.47 (d, J=8.6 Hz, 2H, ArH); 13C NMR (CDCl3, 125
MHz) δ: 14.08, 24.84, 31.91, 61.80, 67.55, 69.77, 70.43,
70.87 (2C), 72.52, 114.99 (2C), 121.67, 124.94, 126.74
(2C), 128.70, 141.56, 144.45, 158.01, 173.71. Anal.
calcd for C21H27NaO6S (430.49): C 58.59, H 6.32;
found C 58.83, H 6.56.
Sodium 2-(2-(2-(2-(4-(5-hexylthiophen-2-yl)phe-
noxy)ethoxy)ethoxy)ethoxy)acetate (11/6/0) Synthe-
sized from 10/6/0. Yield 83%, as pale yellow crystal; 1H
NMR (CDCl3, 500 MHz) δ: 0.87 (t, J=7.6 Hz, 3H,
CH3), 1.26—1.38 (m, 6H, 3CH2), 1.65—1.69 (m, 2H,
ArCH2CH2), 2.78 (t, J = 7.5 Hz, 2H, ArCH2),
3.62—3.74 (m, 8H, OCH2CH2OCH2CH2), 3.87 (t, J=
4.1 Hz, 2H, ArOCH2CH2), 4.04 (t, J=4.4 Hz, 2H,
COCH2O), 4.15 (t, J=4.7 Hz, 2H, ArOCH2CH2), 6.69
(d, J=3.3 Hz, 1H, ArH), 6.88 (d, J=8.5 Hz, 2H, ArH),
6.98 (d, J=3.3 Hz, 1H, ArH), 7.45 (d, J=8.6 Hz, 2H,
ArH); 13C NMR (CDCl3, 125 MHz) δ: 14.06, 22.58,
28.80—32.79 (multi carbons in alkyl chains), 67.58,
69.78, 70.06, 70.47 (2C), 70.61 (2C), 114.96 (2C),
121.64, 124.83, 126.71 (2C), 127.97, 141.46, 144.71,
157.96, 173.68. Anal. calcd for C24H33NaO6S (472.57):
C 61.00, H 7.04; found C 61.23, H 7.38.
Sodium 2-(2-(2-(2-(4-(4,5-dihexylthiophen-2-yl)-
phenoxy)ethoxy)ethoxy)ethoxy)acetate
(11/6/6)
Synthesized from 10/6/6. Yield 67%, as pale yellow
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crystal; H NMR (CDCl3, 500 MHz) δ: 0.89—0.97 (m,
6H, 2CH3), 1.30—1.37 (m, 12H, 6CH2), 1.54 (t, J=7.9
Hz, 2H, ArCH2CH2), 1.62 (t, J = 7.5 Hz, 2H,
ArCH2CH2), 2.46 (t, J=7.4 Hz, 2H, ArCH2), 2.69 (t,
J = 7.4 Hz, 2H, ArCH2), 3.62—3.74 (m, 8H,
OCH2CH2OCH2CH2), 3.87 (t, J = 4.1 Hz, 2H,
ArOCH2CH2), 4.04 (t, J=4.4 Hz, 2H, COCH2O), 4.15
(t, J=4.7 Hz, 2H, ArOCH2CH2), 6.84 (d, J=8.2 Hz,
2H, ArH), 6.90 (s, 1H, ArH), 7.42 (d, J=8.3 Hz, 2H,
ArH); 13C NMR (CDCl3, 125 MHz) δ: 14.07 (2C),
22.62 (2C), 27.91—31.89 (multi carbons in alkyl
chains), 67.61, 70.31 (2C), 70.47 (2C), 70.76 (2C),
114.89 (2C), 123.80, 126.52 (2C), 128.02, 137.84,
138.77, 139.27, 157.83, 173.65. Anal. calcd for
C30H45NaO6S (556.73): C 64.72, H 8.15; found C 64.93,
H 8.52.
Sodium
2-(2-(2-(2-(4-(4,5-didodecylthiophen-2-
yl)-phenoxy)ethoxy)ethoxy)ethoxy)acetate (11/12/12)
Synthesized from 10/12/12. Yield 69%, as pale yellow
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crystal; H NMR (CDCl3, 500 MHz) δ: 0.93 (m, 6H,
2CH3), 1.30—1.37 (m, 36H, 18CH2), 1.54 (t, J=7.9 Hz,
2H, ArCH2CH2), 1.62 (t, J=7.5 Hz, 2H, ArCH2CH2),
2.46 (t, J=7.4 Hz, 2H, ArCH2), 2.69 (t, J=7.4 Hz, 2H,
ArCH2), 3.62—3.74 (m, 8H, OCH2CH2OCH2CH2),
3.87 (t, J=4.1 Hz, 2H, ArOCH2CH2), 4.04 (t, J=4.4
Hz, 2H, COCH2O), 4.15 (t, J = 4.7 Hz, 2H,
ArOCH2CH2), 6.84 (d, J=8.2 Hz, 2H, ArH), 6.90 (s,
1H, ArH), 7.42 (d, J=8.3 Hz, 2H, ArH); 13C NMR
(CDCl3, 125 MHz) δ: 14.07 (2C), 22.66 (2C),
27.90—31.91 (multi carbons in alkyl chains), 67.67,
69.93 (2C), 70.42 (2C), 70.66 (2C), 114.90 (2C), 123.81,
126.53 (2C), 128.07, 137.86, 138.77, 139.25, 157.81,
Sodium 2-(2-(2-(2-(4-(5-dodecylthiophen-2-yl)-
phenoxy)ethoxy)ethoxy)ethoxy)acetate
(11/12/0)
Synthesized from 10/12/0. Yield 78%, as pale yellow
1
crystal. H NMR (CDCl3, 500 MHz) δ: 0.87 (t, J=7.6
Hz, 3H, CH3), 1.26—1.38 (m, 18H, 9CH2), 1.65—1.69
(m, 2H, ArCH2CH2), 2.78 (t, J=7.5 Hz, 2H, ArCH2),
3.62—3.74 (m, 8H, OCH2CH2OCH2CH2), 3.87 (t, J=
4.1 Hz, 2H, ArOCH2CH2), 4.04 (t, J=4.4 Hz, 2H,
COCH2O), 4.15 (t, J=4.7 Hz, 2H, ArOCH2CH2), 6.69
(d, J=3.3 Hz, 1H, ArH), 6.88 (d, J=8.5 Hz, 2H, ArH),
6.98 (d, J=3.3 Hz, 1H, ArH), 7.45 (d, J=8.6 Hz, 2H,
Chin. J. Chem. 2012, 30, 577—584
© 2012 SIOC, CAS, Shanghai, & WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
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