SYNTHESIS OF NEW LIQUID CRYSTALLINE COMPOUNDS
1481
3.50 d.d (1H, J1 = 8, J2 = 16.4 Hz) (C2H2); 4.48–
4.57 m (1H, C3H), 5.74 br.s (1H, 4'-OH), 6.88 d and
7.89 d (2H each, Harom, J = 8.8 Hz).
(22H), 1.45–1.59 m (3H), 1.66–1.79 m (4H), 1.80–
1.88 m (2H), and 2.10–2.22 m (2H) (CH2, alkyl, cyclo-
hexyl); 2.29 d.q (2H, C4'''H2, J1 = 1.2, J2 = 6.8 Hz);
2.46 t.t (1H, 4-H, J1 = 3.6, J2 = 12.4 Hz); 6.83 distorted
d (1H, 2'''-H, J = 15.6 Hz); 7.05 t.d (1H, 3'''-H, J1 =
4-(2-Octenoyl)phenyl 4-pentyloxybenzoate
(VIIIe). A catalytic amount of 4-(dimethylamino)pyr-
idine was added to a solution of 0.1 g (0.46 mmol)
of α,β-unsaturated ketone V, 0.1 g (0.48 mmol) of
4-pentyloxybenzoic acid, and 0.095 g (0.46 mmol) of
N,N'-dicyclohexylcarbodiimide in 15 ml of methylene
chloride. The mixture was stirred for 26 h at 20°C and
filtered through a layer of aluminum oxide, the sorbent
was washed with 40 ml of methylene chloride, the
solvent was removed from the filtrate under reduced
pressure, and the residue was recrystallized from
2-propanol. Yield 0.113 g (61%). IR spectrum, ν, cm–1:
3010 (C–Harom); 2965, 2925, 2870, 2855 (C–Haliph);
1732 (C=O, ester); 1668 (C=O, s-cis); 1648 (C=O,
6.8, J2 = 15.6 Hz); 7.15 d and 7.94 d (2H each, Harom
,
J = 8.8 Hz).
4-(2-Octenoyl)phenyl 4-dodecyloxybenzoate
(VIIIf). A solution of 0.056 g (0.11 mmol) of ester
VIIf (prepared from compound IV according to the
procedure described in [1]) in 10 ml of pyridine was
cooled to 0°C, and 0.03 ml of methanesulfonyl
chloride was added with stirring. The mixture was
stirred for 30 min, the cooling bath was removed, and
the mixture was stirred for 24 h at 20°C and for 1 h at
70°C. Ethyl acetate, 40 ml, and dilute (1:5) hydro-
chloric acid, 50 ml, were added, the aqueous phase was
separated, and the organic phase was treated in succes-
sion with 25 ml of water, 25 ml of a saturated aqueous
solution of sodium hydrogen carbonate, and 25 ml of
water again and dried over sodium sulfate. The solvent
was distilled off under reduced pressure, and the
residue was recrystallized from 2-propanol. Yield of
VIIIf 0.032 g (59%). UV spectrum: λmax 273.1 nm. IR
spectrum, ν, cm–1: 3025, 3010 (C–Harom); 2925, 2855
(C–Haliph); 1732 (C=O, ester); 1668 (C=O, s-cis); 1648
(C=O, s-trans); 1618 (C=C); 1606, 1600, 1581, 1511,
1
s-trans); 1599, 1580, 1511, 1506 (C=Carom). H NMR
spectrum, δ, ppm: 0.90 t (3H, J = 6.8 Hz) and 0.93 t
(3H, J = 7.2 Hz) (C5'H3 and C8''H3); 1.26–1.58 m (10H,
CH2 alkyl); 1.82 quint (2H, C2'H2, J = 7 Hz); 2.31 d.q
(2H, C4''H2, J1 = 1.2, J2 = 7.2 Hz); 4.04 t (2H, OC1'H2,
J = 7 Hz); 6.87 distorted d (1H, 2''-H, J = 15.2 Hz);
7.08 t.d (1H, 3''-H, J1 = 7.2, J2 = 15.2 Hz); 6.96 d
(2H, J = 8.8 Hz), 7.30 d (2H, J = 8.8 Hz), 8.00 d (2H,
J = 8.8 Hz), and 8.13 d (2H, J = 8.8 Hz) (Harom).
Compounds VIIIg and VIIIh were synthesized in
a similar way by esterification of phenol V.
1
1506 (C=Carom). H NMR spectrum, δ, ppm: 0.87 t
(3H, J = 7.2 Hz) and 0.90 t (3H, J = 7.2 Hz) (C12'H3
and C8''H3); 1.16–1.40 m (20H) and 1.41–1.58 m (4H)
(CH2, alkyl); 1.81 quint (2H, C2'H2, J = 7 Hz); 2.31 d.q
(2H, C4''H2, J1 = 1.2, J2 = 6.8 Hz); 4.03 t (2H, OC1'H2,
J = 7 Hz); 6.87 distorted d (1H, 2''-H, J = 15.6 Hz);
7.08 t.d (1H, 3''-H, J1 = 6.8, J2 = 15.6 Hz); 6.96 d (2H,
J = 8.8 Hz), 7.30 d (2H, J = 8.4 Hz), 8.00 d (2H, J =
8.4 Hz), and 8.13 d (2H, J = 8.8 Hz) (Harom).
4-(2-Octenoyl)phenyl 4'-decyloxy-1,1'-biphenyl-
4-carboxylate (VIIIg). Yield 80%. IR spectrum, ν,
cm–1: 3025, 3015 (C–Harom); 2955, 2930, 2855
(C–Haliph); 1734 (C=O, ester); 1668 (C=O, s-cis); 1647
(C=O, s-trans); 1618 (C=C); 1605, 1600, 1520, 1505,
1
1498 (C=Carom). H NMR spectrum, δ, ppm: 0.87 t
(3H, J = 6.8 Hz) and 0.90 t (3H, J = 7 Hz) (C10''H3 and
C8'''H3); 1.20–1.58 m (20H, CH2, alkyl); 1.80 quint
(2H, C3''H2, J = 7 Hz); 2.31 d.q (2H, C4'''H2, J1 = 1.2,
J2 = 6.8 Hz); 4.00 t (2H, OC1''H2, J = 7 Hz);
6.88 distorted d (1H, 2'''-H, J = 15.6 Hz); 7.09 t.d (1H,
3'''-H, J1 = 6.8, J2 = 15.6 Hz); 6.99 d (2H, J = 9 Hz),
7.33 d (2H, J = 9 Hz), 7.58 d (2H, J = 9 Hz), 7.69 d
(2H, J = 9 Hz), 8.02 d (2H, J = 9 Hz), and 8.22 d (2H,
J = 9 Hz) (Harom).
Compounds IXa–IXd and IXh were synthesized in
a similar way by esterification of phenol VI.
4-(3-Chlorooctanoyl)phenyl 4-fluorobenzoate
(IXa). Yield 70%. UV spectrum: λmax 250.4 nm. IR
spectrum, ν, cm–1: 3025, 3020 (C–Harom); 2955, 2925,
2875, 2855 (C–Haliph); 1740 (C=O, ester); 1690 (C=O);
1
1600, 1510 (C=Carom). H NMR spectrum, δ, ppm:
0.90 t (3H, C8'H3, J = 7 Hz); 1.20–1.40 m (4H, C6'H2,
C7'H2); 1.42–1.64 m (2H, C5'H2); 1.71–1.91 m (2H,
C4'H2); 3.25 d.d (1H, J1 = 5.6, J2 = 17.2 Hz) and
3.56 d.d (1H, J1 = 7.6, J2 = 17.2 Hz) (C2'H2); 4.50–
4.60 m (1H, 3'-H); 7.19 distorted t (2H, J = 8.8 Hz),
7.32 d (2H, J = 8.8 Hz), 8.04 d (2H, J = 8.8 Hz), and
8.22 distorted d.d (2H, J1 = 5.6, J2 = 8.8 Hz) (Harom).
4-(2-Octenoyl)phenyl 4'-pentyl-1,1'-bi(cyclo-
hexyl)-4-carboxylate (VIIIh). Yield 91%. IR spec-
trum, ν, cm–1: 3025, 3015 (C–Harom); 2930, 2860
(C–Haliph); 1750 (C=O, ester); 1668 (C=O, s-cis); 1648
(C=O, s-trans); 1618 (C=C); 1600, 1505 (C=Carom).
1H NMR spectrum, δ, ppm: 0.87 t (3H, J = 7 Hz) and
0.90 t (3H, J = 7 Hz) (C5''H3 and C8'''H3); 0.80–1.38 m
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 40 No. 10 2004