(270 MHz; CDCl3) 0.88 (6H, 26t), 1.31 (20H, m), 1.46 (4H,
m), 3.99 (2H, t), 4.02 (2H, t), 6.80 (1H, ddd), 7.30 (1H, ddd),
7.60 (2H, d), 7.90 (2H, d), 8.21 (1H, ddd); IR nmax(KBr)/cm21
2930, 2860, 1745, 1605, 1525, 1505, 1475, 1380, 1285, 1260,
1195, 1145, 1090, 1050, 1015, 930, 830, 765, 720; MS m/z 620
(Mz); found: C, 67.70%; H, 6.60%; C35H41F5O4 requires: C,
67.73%; H, 6.66%.
Yield 0.40 g (97%); dH (270 MHz; CDCl3) 0.92 (6H, 26t),
1.26 (10H, m), 1.90 (4H, m), 5.12 (1H quintet), 5.21 (1H, br s),
7.32 (1H, ddd); IR nmax(KBr)/cm21 3500–3100, 2936, 2861,
1720, 1488, 1363, 1298, 1121, 1051; MS m/z 332 (Mz).
Decyl 5-(4’-dodecyloxybiphenyl-4-ylcarbonyloxy)-2,3,4-
fluorobenzoate (39)
5-Decyloxy-2,3,4-trifluorophenyl 2,3-difluoro-4’-
octyloxybiphenyl-4-carboxylate (22b)
Quantities: compound 34 (0.65 g, 1.97 mmol), compound 16b
(0.77 g, 1.97 mmol), DCC (0.41 g, 1.97 mmol), and DMAP
(0.020 g, 0.20 mmol). The experimental procedure was as
described for the preparation of compound 17a.
Yield 0.95 g (68%); transitions (uC) Cr 47.0 SmC 59.0 SmA
93.5 I; dH (270 MHz; CDCl3) 0.89 (6H, 26t), 1.29 (32H, m),
1.66 (2H, m), 1.71 (2H, quintet), 3.98 (2H, t), 4.20 (2H, t), 7.30
(1H, ddd), 7.42 (2H, d), 7.60 (2H, d), 7.80 (2H, d), 8.22 (2H, d);
IR nmax(KBr)/cm21 2930, 2857, 1741, 1715, 1610, 1523, 1461,
1377, 1251, 1180, 1147, 1092, 1049, 939, 813, 765, 738, 694, 541;
MS m/z 696 (Mz); found: C, 72.33%; H, 7.90%; C42H55F3O5
requires: C, 72.39%; H, 7.96%.
Quantities: compound 15a (0.37 g, 1.21 mmol), compound 21b
(0.46 g, 1.21 mmol), DCC (0.25 g, 1.21 mmol), and DMAP
(0.01 g, 0.12 mmol). The experimental procedure was as
described for the preparation of compound 17a.
Yield 0.60 g (74%); transitions (uC) Cr 67.0 SmA 70.0 I; dH
(270 MHz; CDCl3) 0.88 (6H, 26t), 1.33 (24H, m), 1.46 (4H,
m), 3.98 (2H, t), 4.02 (2H, t), 6.80 (1H, ddd), 7.31 (1H, ddd),
7.64 (2H, d), 7.89 (2H, d), 8.20 (1H, ddd); IR nmax(KBr)/cm21
2930, 2860, 1730, 1620, 1525, 1505, 1460, 1390, 1285, 1245,
1180, 1145, 1085, 1050, 1010, 925, 830, 765, 720; MS m/z 648
(Mz); found: C, 68.44%; H, 6.93%; C37H45F5O4 requires: C,
68.50%; H, 6.99%.
1-Butylpentyl 5-(4’-dodecyloxybiphenyl-4-ylcarbonyloxy)-2,3,4-
fluorobenzoate (40)
2,3,4-Trifluoro-5-octyloxyphenyl 4’-decyloxy-2,3-
difluorobiphenyl-4-carboxylate (22c)
Quantities: compound 35 (0.61 g, 1.91 mmol), compound 16b
(0.75 g, 1.91 mmol), DCC (0.39 g, 1.91 mmol), and DMAP
(0.020 g, 0.20 mmol). The experimental procedure was as
described for the preparation of compound 17a.
Yield 0.91 g (69%); transitions (uC) Cr 50.5 I; dH (270 MHz;
CDCl3) 0.89 (9H, 36t), 1.31 (26H, m), 1.63 (4H, m), 1.71 (2H,
quintet), 4.00 (2H, t), 5.10 (1H, quintet), 7.30 (1H, ddd), 7.42
(2H, d), 7.65 (2H, d), 7.80 (2H, d), 8.22 (2H, d); IR nmax(KBr)/
cm21 2920, 2860, 1740, 1720, 1610, 1523, 1461, 1377, 1251,
1179, 1150, 1090, 1050, 940, 815, 765, 740, 695, 540; MS m/z
682 (Mz); found: C, 72.07%; H, 7.82%; C41H53F3O5 requires:
C, 72.12%; H, 7.82%.
Quantities: compound 15a (0.41 g, 1.50 mmol), compound 21b
(0.53 g, 1.50 mmol), DCC (0.31 g, 1.50 mmol), and DMAP
(0.02 g, 0.15 mmol). The experimental procedure was as
described for the preparation of compound 17a.
Yield 0.74 g (80%); transitions (uC) Cr 70.5 (SmA 69.0) I; dH
(270 MHz: CDCl3) 0.89 (6H, 26t), 1.31 (24H, m), 1.44 (4H,
m), 3.96 (2H, t), 4.00 (2H, t), 6.78 (1H, ddd), 7.29 (1H, ddd),
7.62 (2H, d), 7.88 (2H, d) and 8.18 (1H, ddd); IR nmax(KBr)/
cm21 2925, 2855, 1740, 1610, 1520, 1500, 1465, 1385, 1290,
1255, 1190, 1155, 1090, 1050, 1015, 930, 830, 765, 720; MS m/z
648 (Mz); found: C, 68.42%; H, 6.99%; C37H45F5O4 requires:
C, 68.5%; H, 6.99%.
(S)-1-Methylheptyl 5-(4’-dodecyloxybiphenyl-4-ylcarbonyloxy)-
2,3,4-fluorobenzoate (41)
5-Decyloxy-2,3,4-trifluorophenyl 4’-decyloxy-2,3-
difluorobiphenyl-4-carboxylate (22d)
Quantities: compound 36 (0.33 g, 1.10 mmol), compound 16b
(0.42 g, 1.10 mmol), DCC (0.23 g, 1.10 mmol), and DMAP
(0.010 g, 0.110 mmol). The experimental procedure was as
described for the preparation of compound 17a.
Quantities: compound 15b (0.30 g, 1.00 mmol), compound 21b
(0.39 g, 1.00 mmol), DCC (0.21 g, 1.00 mmol), and DMAP
(0.01 g, 0.10 mmol). The experimental procedure was as
described for the preparation of compound 17a.
Yield 0.40 g (36%); transitions (uC) Cr 38.0 (SmX* 30.0)
SmA* 70.0 I; dH (270 MHz; CDCl3) 0.88 (6H, 26t), 0.92 (3H,
d), 1.29 (26H, m), 1.61 (2H, m), 1.71 (2H, quintet), 4.00 (2H, t),
5.10 (1H, sextet), 7.29 (1H, ddd), 7.43 (2H, d), 7.66 (2H, d), 7.81
(2H, d), 8.19 (2H, d); IR nmax(KBr)/cm21 2922, 2860, 1730,
1715, 1620, 1520, 1465, 1380, 1249, 1180, 1145, 1080, 1045, 950,
820, 760, 740, 695, 540; MS m/z 668 (Mz); found: C, 71.77%;
H, 7.67%; C40H51F3O5 requires: C, 71.83%; H, 7.69%.
Yield 0.49 g (71%); transitions (uC) Cr 57.5 SmA 70.0 I; dH
(270 MHz; CDCl3) 0.89 (6H, 26t), 1.31 (28H, m), 1.44 (4H,
m), 3.96 (2H, t), 4.02 (2H, t), 6.82 (1H, ddd), 7.29 (1H, ddd),
7.66 (2H, d), 7.88 (2H, d), 8.19 (1H, ddd); IR nmax(KBr)/cm21
2930, 2850, 1720, 1615, 1520, 1515, 1465, 1385, 1290, 1240,
1175, 1140, 1080, 1055, 1005, 930, 825, 760, 720; MS m/z 676
(Mz); found: C, 69.18%; H, 7.25%; C39H49F5O4 requires: C,
69.21%; H, 7.30%.
(¡)-1-Propylheptyl 5-benzyloxy-2,3,4-trifluorobenzoate (32)
(¡)-1-Propylheptyl 5-(4’-dodecyloxybiphenyl-4-ylcarbonyloxy)-
2,3,4-fluorobenzoate (42)
Quantities: compound 23 (0.71 g, 2.50 mmol), compound 27
(0.40 g, 2.50 mmol), DCC (0.52 g, 2.50 mmol), and DMAP
(0.030 g, 0.250 mmol). The experimental procedure was as
described for the preparation of compound 17a.
Yield 0.52 g (98%); dH (270 MHz; CDCl3) 0.92 (6H, 26t),
1.26 (10H, m), 1.90 (4H, m), 5.12 (1H quintet), 5.16 (2H, s),
7.40 (6H, m); IR nmax(KBr)/cm21 2936, 2861, 2122, 1720, 1488,
1363, 1298, 1121, 1051; MS m/z 422 (Mz).
Quantities: compound 37 (0.95 g, 2.85 mmol), compound 16b
(1.10 g, 2.85 mmol), DCC (0.60 g, 2.85 mmol), and DMAP
(0.030 g, 0.290 mmol). The experimental procedure was as
described for the preparation of compound 17a.
Yield 1.47 g (74%); transitions (uC) Cr 38.0 SmX* 50.0 SmA
76.5 I; dH (270 MHz; CDCl3) 0.88 (9H, 36t), 1.31 (28H, m),
1.63 (4H, m), 1.70 (2H, quintet), 4.00 (2H, t), 5.05 (1H, sextet),
7.28 (1H, ddd), 7.40 (2H, d), 7.71 (2H, d), 7.78 (2H, d), 8.12
(2H, d); IR nmax(KBr)/cm21 2920, 2850, 1725, 1715, 1610, 1525,
1460, 1385, 1250, 1175, 1150, 1075, 1050, 945, 820, 755, 740,
690, 540; MS m/z 696 (Mz); found: C, 72.34%; H, 7.91%;
C42H55F3O5 requires: C, 72.39%; H, 7.96%.
(¡)-1-Propylheptyl 2,3,4-trifluoro-5-hydroxybenzoate (37)
Quantities: compound 32 (0.52 g, 1.23 mmol) and 10%
palladium on charcoal (0.10 g). The experimental procedure
was as described for the preparation of compound 15a.
J. Mater. Chem., 2001, 11, 2732–2742
2741