HMQC spectrometer. FTIR spectra were measured with a
Nicolet Magna-IR spectrometer. Specific rotations were calcu-
lated from observed rotations measured in methylene chloride
on a Perkin Elmer 241-MC polarimeter. Mass spectra were
measured using a Finnigan MAT TSQ-70 spectrometer.
Elemental analyses were performed by Galbraith Laboratories.
DSC measurements were made on a Perkin Elmer Series-7
calorimeter. A scan rate of 5 °C min−1 was used for all
DSC analyses.
After a final wash with saturated aqueous NaCl, the organic
portions were dried over MgSO and solvent was removed by
4
rotary evaporation. The crude material was purified by column
chromatography (eluent 251 hexanes–ethyl acetate) to yield
7.02 g (69%) of colorless oil. 1H NMR (CDCl ): d 1.60 (m,
3
2H, CH ), 1.80 (m, 2H, CH ), 2.13 (m, 2H, CH ), 3.86 (s,
2
2
2
3H, ArCH ), 4.00 (t, J=3.3 Hz, 2H, CH O), 5.02 (m, 1H, Z
CHLCH ), 5.22 (m, 1H, E CHLCH ), 5.80 (m, 1H, CHLCH ),
6.88 (d, J=7.2 Hz, 2H, ArH), 7.97 (d, J=7.2 Hz, 2H).
3
2
2
2
2
Equipment and techniques used to perform electrooptic
measurements of spontaneous polarization, tilt angle and
response time have been previously described.24 Commercial
switching cells were obtained from Displaytech (4 mm spacer,
parallel rubbed, 0.25 cm2 active area) and used for all electric
field studies. Thermal polarized optical microscopy studies
were conducted using an Olympus BX60 polarizing microscope
used in conjunction with a Mettler FP82 HT hot stage
controlled by a Mettler FP90 central processor.
Methyl 4-(oct-7-enyloxy)benzoate. An analogous procedure
as above was employed with 8-bromooct-1-ene (5.00 g,
26.2 mmol). Yield=5.28 g (65%) of a colorless oil. 1H NMR
(ppm, CDCl ): d 1.30–1.50 (m, 6H, (CH ) ), 1.80 (m, 2H,
3
2 3
CH ), 2.05 (m, 2H, CH ), 3.88 (s, 3H, ArCH ), 4.00 (t, J=
2
2
3
3.3 Hz, 2H), 4.98 (m, 1H, Z CHLCH ), 5.14 (m, 1H, E
2
CHLCH ), 5.80 (m, 1H, CHLCH ), 6.91 (d, J=6.9 Hz, 2H,
ArH), 7.97 (d, J=6.9 Hz, 2H, ArH).
2
2
X-Ray diffraction studies were performed on a Scintag X
diffraction system with a theta-theta powder diffractometer
1
Methyl 4-(dec-9-enyloxy)benzoate. An analogous procedure
as above was employed with dec-9-enyl toluene-p-sulfonate
(5.00 g, 16.1 mmol). Yield=2.27 g (69%) of a colorless oil.
1H NMR (ppm, CDCl ): d 1.30–1.52 (br m, 10H, (CH ) ),
fitted with a solid state Si(Li) detector. The diffraction system
was equipped with a Research Instruments heater controlled
by a Micristar temperature processor. Scans were taken at
30 kV and 15 mA at a scan rate of approximately 0.5° min−1.
Samples were prepared by placing the solid material on a glass
cover slip, heating to the isotropic phase to form a continuous
film in the beam path, and then slowly cooling the material
into the liquid crystalline phase.
3
2 5
1.80 (m, 2H, CH ), 2.08 (m, 2H, CH ), 3.90 (s, 3H, ArCH ),
2
2
3
2
4.02 (t, J=3.0 Hz, 2H, CH O), 5.00 (m, 1H, Z CHLCH ),
2
5.16 (m, 1H, E CHLCH ), 5.82 (m, 1H, CHLCH ), 6.91 (d,
2
2
J=6.6 Hz, 2H, ArH), 8.00 (d, J=6.6 Hz, 2H, ArH).
4-(Hex-5-enyloxy)benzoic acid. Methyl 4-(hex-5-enyloxy)-
benzoate (6.90 g, 31.33 mmol) was dissolved in a mixture of
50 ml 5% aqueous KOH and 50 ml ethanol. The solution was
heated to reflux and allowed to stir for 4 h. The mixture was
cooled and the solvent removed to yield a white powder, which
was recrystallized from acetic acid. The solid was redissolved
in diethyl ether and washed repeatedly with water to remove
Synthesis
Hex-5-enyl toluene-p-sulfonate. A few crystals of potassium
iodide were added to a mixture of toluene-p-sulfonyl chloride
(32.44 g, 0.170 mol) in 60 ml dry pyridine. The solution was
cooled to 0 °C under N in a 250 ml round bottomed flask.
Hex-5-en-l-ol (14.2 g, 0.142 mol) was added dropwise and the
mixture was stirred at 0 °C for 4 h. The solution was diluted
with 100 ml water and extracted with three 75 ml portions of
diethyl ether. The organic fractions were combined and washed
with dilute HCl, followed by water, and dilute NaOH. After
a final water wash, the ethereal solution was dried over MgSO
and filtered. The solvent was evaporated under reduced press-
2
traces of acid. After drying over MgSO , the solvent was
4
removed by rotary evaporation to yield 5.40 g (82%) of white
crystals. DSC (5 °C min−1): K–N 99 °C, N–I 129 °C; lit.,25
K–N 101 °C, N–I 141 °C; 1H NMR (ppm, CDCl ): d 1.52 (m,
3
2H, CH ), 1.72 (m, 2H, CH ), 2.16 (m, 2H, CH ), 4.05 (t,
2
2
2
J=3.0 Hz, 2H, OCH ), 4.85 (m, 1H, Z CHLCH ), 5.02 (m,
1H, E CHLCH ), 5.81 (m, 1H, CHLCH ), 7.05 (d, J=6.0 Hz,
4
2
2
2
2
ure to yield 32.0 g (88%) of the desired tosylate as a clear oil.
1H NMR (ppm, CDCl ): d 1.40 (m, 2H, CH ), 1.62 (m, 2H,
2H, ArH), 7.92 (d, J=6.0 Hz, 2H, ArH).
3
2
CH ), 2.00 (m, 2H, CH ), 2.43 (s, 3H, ArCH ), 4.02 (t, J=
4-(Oct-7-enyloxy)benzoic acid. The same procedure as above
was used with methyl 4-(oct-7-enyloxy)benzoate (3.5 g,
13.3 mmol). Yield 2.61 g (76%) of white crystals. DSC
(5 °C min−1): K–S 81 °C, S–N 94 °C, N–I 137 °C; lit.,25 K–S
78 °C, S–N 122 °C, N–I 139 °C; lit.,26 K–S 82 °C, S–N 98 °C,
2
2
3
3.3 Hz, 2H, OCH ), 4.96 (m, 1H, Z CHLCH ), 5.15 (m, 1H,
2
2
E CHLCH ), 5.70 (m, 1H, CHLCH ), 7.35 (d, J=6.6 Hz, 2H,
2
2
ArH), 7.80 (d, J=6.6 Hz, 2H, ArH).
Dec-9-enyl toluene-p-sulfonate. The same procedure as above
was employed with dec-9-en-l-ol (5.00 g, 32.0 mmol). Yield=
4.38 g (44%) clear oil. 1H NMR (ppm, CDCl ): d 1.20–1.40
(br m, 10H, (CH ) ), 1.60 (m, 2H, CH ), 2.00 (m, 2H, CH ),
N–I 140 °C. 1H NMR (ppm, CDCl ): d 1.45 (br m, 6H,
3
(CH ) ), 1.79 (m, 2H, CH ), 2.06 (m, 2H, CH ), 4.02 (t, J=
2 3
2
2
3.3 Hz, 2H, OCH ), 4.95 (m, 1H, Z CHLCH ), 5.12 (m, 1H,
E CHLCH ), 5.80 (m, 1H, CHLCH ), 6.95 (d, J=6.9 Hz, 2H,
3
2
2
2 5
3
2
2
2
2
2.43 (s, 3H, ArCH ), 4.03 (t, J=3.6 Hz, 2H, OCH ), 4.98 (m,
ArH), 8.00 (d, J=6.9 Hz, 2H, ArH).
2
1H, Z CHLCH ), 5.18 (m, 1H, E CHLCH ), 5.80 (m, 1H,
2
2
CHLCH ), 7.38 (d, J=6.9 Hz, 2H, ArH), 7.80 (d, J=6.9 Hz,
4-(Dec-9-enyloxy)benzoic acid. The same procedure as above
was used with methyl 4-(dec-9-enyloxy)benzoate (1.4 g,
4.82 mmol). Yield 0.86 g (65%) of white crystals. DSC
(5 °C min−1): K–S 76 °C, S–N 108 °C, N–I 131 °C; lit.,25 K–S
2
2H, ArH).
Methyl 4-(hex-5-enyloxy)benzoate. Methyl 4-hydroxybenzo-
ate (7.30 g, 0.048 mol) was dissolved in 100 ml dry DMF
77 °C, S–N 116 °C, N–I 137 °C. 1H NMR (ppm, CDCl ): d
3
under N . The flask was chilled to 5 °C and anhydrous NaH
1.28–1.50 (br m, 10H, (CH ) ), 1.79 (m, 2H, CH ), 2.04 (m,
2
2 5
2
(1.25 g, 0.052 mol) was added. The solution was stirred for
2H, CH ), 4.00 (t, J=3.0 Hz, 2H, OCH ), 5.03 (m, 1H, Z
CHLCH ), 5.21 (m, 1H, E CHLCH ), 5.80 (m, 1H, CHLCH ),
6.95 (d, J=6.9 Hz, 2H, ArH), 8.01 (d, J=6.9 Hz, 2H, ArH).
2
2
1 h and 11.00 g (0.043 mmol) hex-5-enyl toluene-p-sulfonate
in 50 ml dry DMF was added dropwise over 30 min. The
mixture was stirred for 1 h at room temperature, heated to
80 °C, and allowed to stir an additional 20 h. After cooling,
the reaction mixture was diluted with 50 ml water. The organic
phase was extracted with three 100 ml fractions of diethyl
ether. This extract was washed with three 100 ml portions of
2
2
2
(R)-1-Methylheptyl 4∞-[4-(hex-5-enyloxy)benzoyloxy]biphen-
yl-4-carboxylate (M-6). A solution of 4-(hex-5-enyloxy)ben-
zoic acid (0.573 g, 2.60 mmol) in dry dichloromethane (40 ml)
was cooled to 0 °C under N in a 100 ml round bottomed
2
1 M HCl followed by three 100 ml portions of 10% NaHCO .
flask. DCC (0.590 g, 2.86 mmol) and DMAP (0.032 g,
3
1454
J. Mater. Chem., 1999, 9, 1453–1460