in 4 ml of benzene to give the corresponding acid chloride, which
was reacted with diethylamine (1.73 g, 2.37 mmol) in benzene to
produce N,N-diethyl-4-acetyloxycinnamamide. The product was
purified by column chromatography on silica gel using ethyl
acetate as an eluent to give a pale brown oil in a 48.6% yield. An
NMR spectrum supported the E-configuration.
6.87 (d, 2H, J~7 Hz, Ar-H), 7.45 (m, 3H, Ar-HzOH), 7.67 (d,
1H, J~15 Hz, ArCHL). Anal. Calcd. for C16H23NO , C: 73.53,
2
H: 8.87, N: 5.36%. Found, C: 73.36, H: 9.09, N: 5.41%.
1,3-Bis{3-[4-(2-diethylaminocarbonylethenyl)phenoxy]propoxy}
benzene (5). To an ethanol solution of resorcinol (5.00 g,
0.0455 mol) was added 1,3-dibromopropane (75.0 g,
0.373 mol) and potassium hydroxide (8.57 g, 0.159 mol), and
the mixture was refluxed for 5 h. After the ethanol was evaporated,
diethyl ether and water were added, and the ethereal layer was
washed with water. The evaporation of the solvent and
unreacted 1,3-dibromopropane under reduced pressure gave
a pale brownish oil, which was purified by column chromato-
graphy on silica gel using a mixture of ethyl acetate and hexane
(1 : 3 v/v) as an eluent to give colorless crystals of 1,2-bis(3-
bromopropoxy)benzene of mp~62–64 uC in 47.3% yield after
recrystallization from a mixture of benzene and hexane.
A solution of 1.00 g of 1,2-bis(3-bromopropoxy)benzene
(2.84 mmol) and 2.49 g of N,N-diethyl-4-hydroxycinnamamide
(1.14 mmol) in 50 ml of THF was refluxed for 10 h in the
presence of 1.58 g of potassium carbonate (1.14 mmol) and
1.71 g of sodium iodide (1.14 mmol). The reaction mixture was
diluted with ethyl acetate and washed with water. The
evaporation of the solvent was followed by silica gel column
chromatography using a 6 : 1 (v/v) mixture of ethyl acetate and
hexane as an eluent to give crystals of mp~116–117 uC in 28%
yield after recrystallization from a mixture of benzene and
hexane.
1
H-NMR(CDCl ) d (ppm)~1.18 (q, 6H, CH ), 2.28 (s, 3H,
3
3
CH CO), 3.45 (q, 4H, NCH ), 6.75 (d, 1H, J~15 Hz,
COCHL),7.07 (d, 2H, J~7 Hz, Ar-H), 7.51 (d, 2H, J~7 Hz,
Ar-H), 7.67 (d, 1H, J~15 Hz, ArCHL). Anal. Calcd. for
3
2
15 3
C H19NO , C: 68.95, H: 7.33, N: 5.36%. Found, C: 68.87,
H: 7.35, N: 5.19%.
The cinnamamide thus prepared (0.97 g, 3.7 mmol) dissolved
in methanol was treated with potassium hydroxide (1.57 g,
0
.028 mol) for 30 minutes at room temperature, followed by
acidification with hydrochloric acid. After removal of the
solvent, the product was extracted with ethyl acetate to give
yellowish white crystals which were purified by recrystallization
with a mixture of ethyl acetate and hexane. Yield was 54%.
1
H-NMR(CDCl
), 6.65 (d, 1H, J~15 Hz, COCHL), 6.87 (d, 2H, J~7 Hz,
Ar-H), 7.38 (m, 3H, Ar-HzOH), 7.64 (d, 1H, J~15 Hz,
ArCHL). Anal. Calcd. for C13 , C: 71.21, H: 7.81,
N: 6.38%. Found, C: 71.10, H: 7.75, N: 6.27%.
3 3
) d (ppm)~1.21 (q, 6H, CH ), 3.47 (q, 4H,
NCH
2
H17NO
2
2,8,14,20-Tetrakis{3-[4-(2-diethylaminocarbonylethenyl)phenoxy]
propyl}-4,6,10,12,16,18,22,24-octakis(carboxymethoxy)calix[4]-
arene (1). The calix[4]resorcinarene possessing four iodopropyl
9
residues (3) was prepared according to the previous paper. To
1
H-NMR(CDCl ) d (ppm)~1.14 (m, 12H, CH ), 2.19 (m,
3
3
a solution of 3 (0.41 g, 0.22 mmol) in 15 ml of THF was added
N,N-diethyl-4-hydroxycinnamamide (0.27 g, 1.2 mmol) and
potassium carbonate (0.18 g, 1.3 mmol). The mixture was
stirred for 24 h at room temperature. After the solvent was
evaporated, a residue was diluted with ethyl acetate and
washed with water. An organic layer was condensed to give a
crude CRA with four cinnamoyl residues (2) as a brown sticky
oil in a 71% yield.
2 2 2 2 2
4H, CH CH CH ), 3.40 (q, 8H, NCH ), 4.09 (m, 8H, OCH ),
6.40–6.50 (m, 3H, Ar-H), 6.62 (d, 2H, J~15 Hz, COCHL), 6.83
(d, 4H, J~9 Hz, Ar-H), 7.00–7.30 (m, 1H, Ar-H), 7.40 (d, 4H,
J~9 Hz, Ar-H), 7.60 (d, 2H, J~15 Hz, ArCHL). Anal. Calcd.
for C H N O , C: 72.59, H: 7.69, N: 4.45%. Found, C: 72.36,
3
8
48
2
6
H: 7.66, N: 4.36%.
Adsorption experiments for 1
1
H-NMR(CDCl ) d (ppm)~1.28 (m, 48H, CH ), 1.98–2.19
3
3
Fused silica plates were washed ultrasonically in a series of
solvents in the following order; acetone, water, aqueous KOH
solution, water, nitric acid, water, saturated aqueous solution
(
m, 32H, CH
2
CH
2
CH), 3.47 (m, 16H, NCH
2
), 3.99 (t, 32H,
ArOCH ), 4.25 (m, 32H, OCH COzCOOCH ), 4.73 (t, 4H,
2
2
2
CH), 6.23 (s, 4H, Ar-H), 6.63 (d, 4H, J~16 Hz, COCHL), 6.72
s, 4H, Ar-H), 6.79 (d, 8H, J~8 Hz, Ar-H), 7.36 (d, 8H,
J~8 Hz, Ar-H), 7.62 (d, 4H, J~16 Hz, Ar-CHL). Anal. Calcd.
for C N O , C: 67.25, H: 7.10, N: 2.53%. Found, C:
3
of KHCO and water. A fused silica plate was immersed in a
(
2
4
23
THF solution of 1 of 1–2610 mol dm for 10–20 min at
room temperature, followed by washing with acetone to
remove a excess amount of 1. The amount of 1 adsorbed on
the plate was estimated by UV absorption spectroscopy under
the assumption that no modification of absorption coefficient
of the cinnamoyl residue is made by surface adsorption.
H
24 156
1
4
32
6
6.97, H: 7.16, N: 2.31%.
A potassium hydroxide aqueous solution (0.45 g in 20 ml
water) was added to a solution of 2 (0.46 g, 0.21 mmol) in 50 ml
THF, and the mixture was stirred for 1 h at room temperature,
followed by acidification with hydrochloric acid to give a white
Photochemistry
precipitate of mp~153–155 uC in 56% yield.
1
H-NMR(DMSO-d
CH CH), 3.47 (m, 16H, NCH
), 4.20–4.48 (q, 32H, OCH CO), 4.63 (t, 4H, CH), 6.43
s, 4H, Ar-H), 6.70 (s, 4H, Ar-H), 6.80 (d, 8H, J~8 Hz, Ar-H),
6
) d (ppm)~1.09 (m, 24H, CH
3
), 1.69–
), 3.95 (t, 32H,
A spectroirradiator equipped with a diffraction grating and a
Xe-lamp, CRM-FA (JASCO), was used for photoirradiation of
1
.9 (m, 16H, CH
2
2
2
ArOCH
(
2
2
1
and model compounds in acetonitrile solutions and on fused
silica plates. The band width of light was ¡7 nm. Acetonitrile
is convenient for photoreaction study because it is transparent
at w190 nm light. Solution photochemistry was followed by
taking UV-visible absorption spectra on a diode array
spectrometer, HP8452A (Hewlett Packerd), while UV-visible
absorption spectra of surface-modified quartz plates were
recorded on a HITACHI UV-320.
6
.87 (d, 4H, J~16 Hz, COCHL), 7.38 (d, 4H, J~16 Hz, Ar-
CHL), 7.51 (d, 8H, J~8 Hz, Ar-H). Anal. Calcd. for
32, C: 65.18, H: 6.28, N: 2.81%. Found, C:
C
108 124 4
H N O
6
4.89, H: 6.46, N: 2.65%.
N,N-Diethyl-4-propoxycinnamamide (4). A mixture of
-bromopropane (4.01g, 30.0 mmol), potassium carbonate
1
(4.14 g, 0.0300 mol), N,N-diethyl-4-hydroxycinnamamide
(4.38 g, 20.0 mmol) and sodium iodide (2.0 g, 1.3 mmol) in
Fabrication of liquid crystal cells
5
0 ml of acetone was refluxed for 8 h, followed by evaporation
A fused silica plate adsorbing 1 was exposed to light in a
wavelength range from 290 to 390 nm from a super-high
pressure mercury arc (USH-500D, Ushio electronics,
1.5 mW cm at 365 nm) passed through a glass filter (UV-
D35; Toshiba) and a photomask. Subsequently, a liquid crystal
cell was prepared by sandwiching 4-cyano-4’-pentylbiphenyl
(TNI~35.4 uC) as a nematic liquid crystal between the
of the solvent. The residue was dissolved in ethyl ether, and the
organic layer was washed with water and evaporated to yield a
pale brownish oil.
2
2
1
3 3 2 2
H-NMR(CDCl ) d (ppm)~1.03 (t, 3H, CH CH CH ), 1.21
(m, 6H, CH CH N), 1.80 (m, 2H, CH CH CH ), 3.48 (m, 4H,
3 2 3 2 2
NCH
2
), 3.92 (t, 2H, OCH
2
), 6.70 (d, 1H, J~16 Hz, COCHL),
1
806 J. Mater. Chem., 2001, 11, 1805–1811