Synthesis of Polyphilic Mesogens
J. Phys. Chem. B, Vol. 102, No. 1, 1998 59
(t, J ) 22 Hz, CF2CH2), 29.46, 29.35, 29.27, 29.17, 29.06 (CH2),
25.56 (CH2CH2CH2OH), 19.93 (CF2CH2CH2). NMR 1H (CDCl3,
TMS, 300 MHz, δ ppm): 1.32 (br., 12H, CH2), 1.53-1.68 (m,
5H, CH2CH2CF2 + CH2CH2OH + OH), 2.07 (m, 2H, CH2-
CF2), 3.66 (t, J ) 6.61 Hz, CH2OH).
2,2,3,3,4,4,5,5,6,6,7,7,8,8,8-Pentadecafluorooctyl Nonafluo-
robutanesulfonate (14). A solution of 2.15 mL (12 mmol) of
nonafluorobutanesulfonyl fluoride (fluorochem) in 60 mL of
dry dichloromethane was cooled to -40 °C under nitrogen. A
solution of 4.4 g (11.5 mmol) of 1H,1H-perfluorooctanol
(Aldrich) in 2 mL of triethylamine was added with the help of
a separatory funnel. The reaction mixture was brought back to
-15 °C. The white precipitate was collected and recrystallized
1-Bromo-11,11,12,12,13,13,14,14,15,15,16,16,17,17,17-Pen-
tadecafluoroheptadecane (12). 560 mg (1.06 mmol) of 11,-
11,12,12,13,13,14,14,15,15,16,16,17,17,17-pentadecafluorohep-
tadecan-1-ol (11) were placed in the bottom of a 25 mL Pyrex
tube and carefully melted with the aid of an oil bath. A mixture
of 1 g sulfuric acid and 3 g fuming hydrobromic acid (37% in
water) and a piece of carborundum were added. The tube was
fitted with a reflux condenser and heated at 130 °C for 2 h.
After cooling, 10 mL of water and 10 mL CH2Cl2 were added
with stirring. The organic layer was separated and dried over
MgSO4. The solvent was then evaporated and the product
purified by liquid chromatography on silica with a mixture of
cyclohexane/dichloromethane (90:10) as eluent (yield: 80%;
mp ) 38-39 °C). IR (KBr cm-1): 2920.8, 2853.5, 1471.1,
1371.7, 1325.1, 1241.0, 1215.9, 1204.4, 1168.2, 1150.0, 1131.2,
1096.0, 1048.0, 1030.8, 1002.1, 978.1, 948.1, 777.9, 722.6,
699.5, 657.3, 570.6, 542.3, 532.0, 477.7. MS (electron impact,
m/z): 467 [M-C3H6Br]+, 453 [M-C4H8Br]+, 439 [M-C5H10-
Br]+, 425 [M-C6H12]+, 181 [C4F7]+, 163-165 [C6H12Br]+,
149-151 [C5H10Br]+, 135-137 [C4H8Br]+, 121-123 [C3H6-
Br]+, 119 [C2F5]+, 107-109 [C2H4Br]+, 69 [CF3]+ and [C5H9]+,
57 [C4H9]+, 55 [C4H7]+. Anal. Found: C, 35.00; H, 3.56.
Calcd: C, 34.65; H, 3.42. NMR 1H (CDCl3, TMS, 300 MHz,
δ ppm): 1.31 (br., 12H, CH2), 1.61 (m, 2H, CH2CH2CF2), 1.87
(m, 2H, CH2CH2Br), 2.06 (m, 2H, CH2CF2), 3.42 (t, J ) 6.79
Hz, CH2Br). NMR 13C (CDCl3, 75 MHz, δ ppm): 19.93 (br.,
CH2CH2CF2), 27.98 (CH2CH2CH2Br), 28.56, 28.92, 29.02,
29.09, 29.17 (CH2), 30.73 (t, J ) 22.2 Hz, CH2CF2), 32.65 (CH2-
CH2Br), 32.81 (CH2Br). NMR 19F (CDCl3, 235 MHz, δ ppm):
-81.3 (t, J ) 9.6 Hz, CF3), -114.9 (m, CF2CH2), -122.3,
-122.6, -123.3, -124.0, -125.3 (CF2), -126.7 (CF3CF2).
4-(11,11,12,12,13,13,14,14,15,15,16,16,17,17,17-Pentadeca-
fluoroheptadecyl oxy)-4′-methoxybiphenyl (13). 45 mg (320
µmol) K2CO3, 38 mg (190 µmol) of 4′-methoxy-biphenyl-4-
ol,41 and 8 mL DMF were placed in a 50 mL two-necked flask
fitted with reflux condenser, nitrogen inlet, and calcium chloride
tube. The mixture was heated at 90 °C with strirring. After
complete dissolution, 112 mg (190 µmol) of 1-bromo-11,11,-
12,12,13,13,14,14,15,15,16,16,17,17,17-pentadecafluoro hepta-
decane (12) were added. After 2 h of reaction, the mixture was
cooled, and the jelly-like solid was separated from the solvent
by filtration and dried over P2O5. The product was purified by
liquid chromatography on silica at 50 °C (cyclohexane 85%:
ethyl acetate 15%) and recrystallization from cyclohexane
(yield: 67%). IR (KBr cm-1): 2935.9 [C-H asym], 2852.1
[C-H sym], 1608.3 [arom CdC], 1274.5 [C-O], 1247.6,
1217.9, 1145.5 [C-F], 824.8 [δ C-Η out-of-plane]. MS
(electron impact, m/z): 708 [M]+. Anal. Found: C, 50.82; H,
4.33. Calcd: C, 50.86; H, 4.41. NMR 1H (CDCl3, TMS, 300
MHz, δ ppm): 7.49 (2H), 7.47 (2H), 6.97 (2H), 6.95 (2H)
(aa′bb′ patterns, J ) 8.8 Hz arom), 4.01 (t, 2H, J ) 6.6 Hz,
CH2-CH2-O), 3.85 (s, 3H, O-CH3), 2.06 (m, 2H, CH2-CH2-
CF2), 1.81 (m, 2H, J ) 6.6 Hz, CH2-CH2-O), 1.61-1.34
(CH2). NMR 13C (CDCl3, 75 MHz, δ ppm): 158.65 (s, C-O-
CH3), 158.24 (s, C-O-CH2), 135.53 and 132.27 (s, C6H4-
C), 127.8, 114.73 and 114.13 (s, arom CH), 68.04 (CH2-O-
C6H4), 55.33 (CH3-O-C6H4), 30.87 (t, J ) 23.2 Hz, CF2-
CH2), 29.42-20.08 (CH2).
1
from dichloromethane (yield: 49%; mp ) 46 °C). NMR H
(CDCl3, TMS, 300 MHz, δ ppm): 4.86 (t, J ) 12.6 Hz,
CF2CH2). IR (KBr cm-1): 1202.7, 1144.8 [C-F], 1042.7
[CdO], 1010.1 [SdO]. MS (electron impact, m/z): 683 [M]+,
463 [M-C4F9]+, 447 [M-OC4F9]+, 219 [C4F9]+, 169 [C3F7]+,
131 [C3F5]+, 119 [C2F5]+, 69 [CF3]+. Anal. Found: C, 20.76;
H, 0.30; S, 5.04. Calcd: C, 21.12; H, 0.29; S, 4.69.
4-(2,2,3,3,4,4,5,5,6,6,7,7,8,8,8-Pentadecafluorooctyloxy)-4′-
methoxybiphenyl (15). 404 mg (2.34 mmol) of potassium
carbonate, 234 mg (1.17 mmol) of 4′-methoxy-biphenyl-4-ol,41
and 10 mL of DMF were stirred at 90 °C under nitrogen. 800
mg (1.7 mmol) of 2,2,3,3,4,4,5,5,6,6,7,7,8,8,8-pentadecafluo-
rooctyl nonafluorobutanesulfonate (compound 14) was added.
After 2.5 h at 90 °C, the reaction mixture was cooled and poured
into 10 mL of water. The precipitate was collected onto a glass
filter, thoroughly washed with water, and dried over P2O5 under
vacuum. The solid was purified by liquid chromatography at
50 °C on silica (eluent: cyclohenane + ethyl acetate 85:15)
and recrystallization from cyclohexane (yield: 74%; mp ) 168
°C). IR (KBr cm-1): 1610.3, 1505.8 [arom CdC], 1243.6
[C-O], 1209.3, 1149.8 [C-F], 820.9 [δ C-H out-of-plane].
MS (electron impact, m/z): 582 [M]+,567 [M-CH3]+, 199
[CH3O(C6H4)2O]+, 313, 363, 413, 463 [CH3O(C6H4)2OCH2-
(CF2)n]+. Anal. Found: C, 43.17; H, 2.09. Calcd: C, 43.31;
H, 2.24. NMR 1H (CDCl3, TMS, 300 MHz, δ ppm): 7.52 (d,
J ) 9 Hz, 2H, arom), 7.49 (d, J ) 8.8 Hz, 2H, arom), 7.01 (d,
J ) 8.8 Hz, 2H, J ) 9 Hz, arom), 6.98 (d, J ) 9 Hz, 2H, arom),
4.51 (t, J ) 13.2 Hz, OCH2CF2), 3.86 (s, 3H, H3CO). NMR
13C (CDCl3, 75 MHz, δ ppm): 158.87 (s, C-O-CH3), 156.41
(s, C-O-CH2), 135.36 and 132.8 (s, C6H4-C), 127.8, 127.7,
115.12 and 114.1 (s, arom CH), 65.37 (t, J ) 29.9 Hz, CH2-
O-C6H4), 55.19 (CH3-O-C6H4).
Acknowledgment. Robert Corte`s is thanked for his help in
X-ray diffraction experiments.
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