Aromatic heterocycles used as terminal groups of calamitic liquid crystals

Article abstract of DOI:10.1002/jccs.201100220

Three series of compounds 1-21 were prepared by using 2-, 3-, and 4-pyridinemethanol as terminal group of calamitic liquid crystals. These compounds have some similarities in their phase behavior. They all exhibit SmA phase. A tilt smectic phase, SmC, will be formed when their flexible alkoxy chain is longer than hexoxy group. The profound difference between them is that the compounds 15-17 possess a short temperature range of N phase. The compounds 3 and 6 have the widest SmA phase, up to 94 °C, and SmC phase, up to 46 °C, respectively.

Full text of DOI:10.1002/jccs.201100220

JOURNAL OF THE CHINESE
CHEMICAL SOCIETY
Article
Aromatic Heterocycles Used as Terminal Groups of Calamitic Liquid Crystals
Chih-Yin Liu, Chin-Hsu Huang, Pao-Swu Cheng* and Wen-Liang Tsai
Department of Chemistry, National Kaohsiung Normal University,
62 Shen-Chung Road, Kaohsiung 824, Taiwan, R.O.C.
(Received April 27, 2011; Accepted August 3, 2011; Published Online August 24, 2011; DOI: 10.1002/jccs.201100220)
Three series of compounds 1-21 were prepared by using 2-, 3-, and 4-pyridinemethanol as terminal group
of calamitic liquid crystals. These compounds have some similarities in their phase behavior. They all ex-
hibit SmAphase. Atilt smectic phase, SmC, will be formed when their flexible alkoxy chain is longer than
hexoxy group. The profound difference between them is that the compounds 15-17 possess a short tem-
perature range of N phase. The compounds 3 and 6 have the widest SmA phase, up to 94 °C, and SmC
phase, up to 46 °C, respectively.
Keywords: Pyridinemethanol; Terminal group; Liquid crystals; Smectic C phase.
INTRODUCTION
Rigid core is an essential part of liquid crystal mole-
fore, three series of compounds 1-21 were derived from 2-,
3-, and 4-pyridinemethanol and their mesogenic properties
were studied. The synthesis and structures of these com-
pounds are shown in Fig. 1.
cules. Different aromatics and aromatic heterocycles have
been used as core molecule in the science of LCs.1,2,3,4 The
rigid rings are generally not considered as a suitable candi-
date of terminal group for LCs.1,2 However, some studies
have used phenyl ring as terminal group of LCs to investi-
gate their influence on the formation of liquid crystal
phases. In 1971, Gray and Harrison have shown some com-
pounds, derived from phenyl-substituted alkanols, could
exhibit N, SmA, and SmB phases.5,6 We have recently used
benzyl alcohol as terminal group and found those com-
pounds could exhibit SmC phase in addition to other
smectic phases.7 These results point out that benzyl group
can be used not only as a protective group but as a terminal
group of LCs. Chemistry of aromatic heterocycles used as
terminal groups of calamitic liquid crystals, e.g. size8,9 and
dipole moment,10,11 influence the physical properties of
LCs easily. Pyridyl ring is a key component of hydrogen-
bonded LCs.12 And some aromatic heterocycles such as de-
rivatives of oxadiazole, thiodiazole, or pyridine have been
used for the preparation of bent-shaped LCs.13,14,15 Till now
there is no published literature has mentioned to use pyri-
dinemethanol as a terminal group of LCs, to the best of our
knowledge. It is important and interesting to know the
structure effect of the corresponding pyridinemethanol of
benzyl alcohol if they are used as terminal groups. There-
RESULTS AND DISCUSSION
Three series of compounds 1~21 were prepared by
the esterification of seven analogous aromatic carboxylic
acids and 2-pyridinemethanol, 3-pyridinemethanol, or
4-pyridinemethanol. Their structures were identified by
IR, 1H-NMR, 13C-NMR, and MS. The spillting pattern and
chemical shift of H-atom positioned ortho to hetero N-atom
of pyridyl ring will give enough evidence to differentiate
these three pyridyl ring system. The liquid crystal phases
and phase transition temperatures of 1~21 were determined
by DSC measurement and texture observation. These data
Fig. 1. Synthesis and structures of compounds 1-21.
* Corresponding author. Tel: +886-7-7172930 ext. 7159; Fax: +886-7-6051083; E-mail: t1274@nknucc.nknu.edu.tw
J. Chin. Chem. Soc. 2012, 59, 81-86
© 2012 The Chemical Society Located in Taipei & Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
81

Article
Liu et al.
are summarized in Table 1, 2, and 3. The transition en-
thalpies of SmC phase could not be detected. The corre-
sponding transition temperatures were therefore deter-
mined by texture observation. The results of texture obser-
vation for the compounds 4 are shown in Fig. 2. The SmA
and SmC phase range of 1~21 were shown in Fig. 3, 4, and
5 for comparison.
system is narrower than that in the 2-pyridyl ring system.
The SmC phase range for 11, 13, and 14 is also narrower
than that for 4, 6, and 7 while 12 has wider SmC phase
range than that of 5. In this series the compounds 10 and 12
have the widest temperature range of SmA and SmC phase,
61 °C and 38 °C, respectively. The 3-pyridyl ring, compar-
ing to 2-pyridyl ring, destabilized both SmA and SmC
phase more profoundly. The stability difference might be
induced by the direction difference of dipole moment in
these two terminal pyridyl rings. In the 4-pyridyl com-
pounds an additional effect on the mesogenic properties
could be observed. A very short range of N phase is formed
in 15~18. The chain length effect on the formation of SmA
and SmC phase in this series of compounds is the same as
the former two systems. The compounds 15~21 possess
SmA phase and 18~21 exhibit SmC phase. Among them,
21 has the widest temperature range of SmA, up to 69 °C,
and 18 possesses the widest SmC phase range, up to 41 °C.
The influence of chain length on SmC phase range in 4-pyr-
idyl compounds is different from that in 2- and 3-pyridyl
compounds. The temperature range of SmC phase is de-
creased from n-heptyloxy to n-decyloxy group, that is from
18 to 21.
The data in Table 1 show that the formation of SmA is
not influenced by the length of n-alkoxy chain. But the
chain length has an obvious effect on the SmC phase for-
mation. This tilted phase will be formed in the compounds
whose flexible side chain is longer than hexoxy group. The
formation temperature of SmC phase is 71 °C, 102 °C, 72
°C, and 80 °C for 4, 5, 6, and 7 respectively. The compound
3 has the widest SmA phase range, up to 94 °C, and 6 have
the widest SmC phase range, up to 46 °C. In comparsion
with the data in benzyl system7 2-pyridyl ring could raise
the formation temperature for SmC phase more apparently
than that for SmA phase. This makes the temperature range
of SmC phase in the 2-pyridyl compounds 4~7 narrower.
The carbon number of alkoxy chain in 8~14 has the same
effect as in 1~7 on the formation of SmA and SmC phase.
The temperature range of SmA phase in this 3-pyridyl ring
Table 1. Liquid crystal phases and phase transition temperatures
Table 2. Liquid crystal phases and phase transition temperatures
(°C) of compounds 1-7
(°C) of compounds 8-14
I
SmA
SmC
SmX
K
I
SmA
SmC
SmX
K
1
2
3
4
5
6
7
·
·
·
·
·
·
·
190.5
181.9
177.4
172.7
170.1
166.7
165.9
·
·
·
·
·
·
·
105.2
88.2
·
·
·
·
·
·
·
8
·
·
·
·
·
·
·
180.9
171.5
164.6
157.1
153.1
149.5
144.8
·
·
·
·
·
·
·
121.3
111.8
103.9
122.8
125.5
122.9
116.5
·
·
·
·
·
·
·
·
·
·
·
·
·
68.5
81.2
64.4
65.7
50.9
64.1
9
83.2
10
11
12
13
14
115.4
119.9
118.4
109.8
·
·
·
·
70.8
101.5
72.1
·
·
·
·
94.9
88.1
·
·
·
·
68.4
86.1
108.1
101.2
101.0
83.3
79.7
Table 3. Liquid crystal phases and phase transition temperatures (°C) of compounds 15-21
I
N
SmA
SmC
SmX
K
15
16
17
18
19
20
21
·
·
·
·
186.7
182.2
175.9
170.1
166.1
162.9
162.2
·
·
·
·
185.7
180.6
174.9
168.5
·
·
·
·
161.6
161.9
112.6
120.1
116.7
108.6
92.8
·
·
·
·
105.5
77.9
67.2
69.4
75.2
·
78.7
79.2
85.9
82.3
·
·
·
·
·
·
·
·
·
·
·
·
·
·
·
·
www.jccs.wiley-vch.de
© 2012 The Chemical Society Located in Taipei & Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
J. Chin. Chem. Soc. 2012, 59, 81-86
82

JOURNAL OF THE CHINESE
CHEMICAL SOCIETY
Liquid Crystals Derived from Pyridinemethanol
Pyridine is an electron-deficient aromatic hetero-
cycle. The dipole moment of this terminal heterocyclic ring
does not interrupt the formation of liquid crystal phases.
But the dipole direction of 2-, 3-, and 4-pyridyl ring could
influence the phase stability in different way. The lowest
formation temperature of SmA phase is the compound 21
of 4-pyridyl compounds, 93 °C, and that of SmC phase is 4
of 2-pyridyl compounds, 71 °C. The widest range of SmA
and SmC phase is the compound 3 and 6, both in the same
2-pyridyl system. These results show that 2-, 3-, and 4-pyr-
idinemethanol are useful terminal group for the preparation
of SmA and SmC mesogens.
and pyridyl-substituted methanol could be used as terminal
group for the preparation of SmC mesogens. Similar meso-
genic properties will be expected from analogous com-
pounds synthesized from furanmethanol, thiophenemeth-
anol, and neopentyl alcohol. Futher investigation on the
preparation and physical properties of analogues with these
terminal substituents are in progress.
EXPERIMENTAL
Commercially available chemical reagent were used
We have till now shown that phenyl-, cycloalkyl-,16,17
Fig. 3. SmA and SmC phase width of 1-7.
Fig. 4. SmA and SmC phase width of 8-14.
Fig. 5. SmA and SmC phase width of 15-21.
Fig. 2. Textures of 4: (a) SmA phase at 170.1 °C; (b)
SmC phase at 105.6 °C; (c) SmX phase at 71.8
°C.
J. Chin. Chem. Soc. 2012, 59, 81-86
© 2012 The Chemical Society Located in Taipei & Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.jccs.wiley-vch.de
83

Article
Liu et al.
directly without further purification. Solvents for chroma-
tography and recrystallization were distilled before use.
Chromatographic purification were performed using flash
chromatography over Merck silica gel 60.
NMR (CDCl3) d 14.07, 22.60, 26.00, 29.05, 29.24, 31.78,
67.31, 68.19, 115.03 (2C), 121.70, 121.90 (2C), 122.89,
126.65 (2C), 126.97, 127.42, 128.39 (2C), 130.79 (2C),
131.46 (2C), 131.82, 136.82, 146.32, 149.50, 154.96,
155.94, 159.69, 164.56, 165.48. MS (FAB) m/z (rel. inten-
sity): 524 ([M+], 22.01), 295 ([M+-229], 100). Anal. Calcd
for C33H33NO5 : C 75.69, H 6.35, N 2.68. Found: C 75.83,
H 6.29, N 2.65.
Infrared and NMR spectra were recorded on Nicolet
550 FTIR and Brucker AV-500 spectrometers, respectively.
Mass spectra were observed on a JMS-D100 instrument.
Elemental analyses were made using a Heraeus CHN-O-
RAPID combustion apparatus. Transition temperatures
and textures of liquid crystal phases were determined using
a Perkin-Elmer DSC-6 differential scanning calorimeter,
and an Zeiss Axioskop 50 polarizing microscope in con-
junction with a Mettler FP 90 heating stage.
4-(2-Pyridylmethoxycarbonyl)phenyl 4-(4¢-octyloxybi-
phenyl)carboxylate (5)
Pure 5 was obtained as a white solid in 71% yield. IR
(KBr) n/cm-1 3051, 3009, 2925, 2854, 1733, 1716, 1599,
1528, 1500, 1473, 1291, 1210, 1163, 1126, 1087, 995, 886,
831, 762. 1H NMR (CDCl3) d 0.89~0.91 (3H, t, J = 6.9 Hz),
1.30~1.40 (8H, m), 1.46~1.51 (2H, m), 1.80~1.84 (2H, m),
4.01~4.03 (2H, t, J = 6.3 Hz), 5.51 (2H, s), 7.00~7.02 (2H,
d, J = 9.0 Hz), 7.25~7.27 (1H, overlapped), 7.34~7.36 (2H,
d, J = 9.0 Hz), 7.45~7.46 (1H, d, J = 7.8 Hz), 7.59~7.60
(2H, d, J = 8.4 Hz), 7.70~7.74 (3H, m), 8.21~8.24 (4H, q,
J1 = 8.4 Hz, J2 = 3.0 Hz), 8.63 (1H, d, J = 4.2 Hz). 13C
NMR (CDCl3) d 14.08, 22.65, 26.04, 29.24 (2C), 29.35,
31.81, 67.31, 68.19, 115.03 (2C), 121.69, 121.90 (2C),
122.89, 126.65 (2C), 126.97, 127.42, 128.39 (2C), 130.79
(2C), 131.46 (2C), 131.82, 136.82, 146.32, 149.50, 154.96,
155.94, 159.68, 164.56, 165.48. MS(FAB) m/z (rel. inten-
sity): 538 ([M+], 19.58), 309 ([M+-229], 100). Anal. Calcd
for C34H35NO5 : C 75.95, H 6.56, N 2.61. Found: C 75.66,
H 6.54, N 2.56.
The target molecules 1-21 were synthesized by the
esterification of seven 4-(4-(n-alkyloxy)biphenylcarbonyl-
oxy)benzoic acids18 and 2-pyridinemethanol, 3-pyridine-
methanol, or 4-pyridinemethanol respectively. The reac-
tion procedures for these compounds are analogous. There-
fore, a reaction procedure for the synthesis of the targert
compound 4 is described as an example. The data for the
structure identification of the mesogenic compounds 4-6,
11-13, and 18-20 are given.
Preparation of 4-(2-pyridylmethoxycarbonyl)phenyl
4-(4¢-heptyloxybiphenyl)carboxylate (4)
A solution of 443.7 mg (1.03 mmol) of 4-(4¢-octyl-
oxybiphenylcarbonyloxy)benzoic acid, 113.2 mg (4.07
mmol) of 2-pyridinemethanol, 9.2 mg (0.07 mmol) of 4-
(dimethylamino)-pyridine, DMAP, and 305.2 mg (1.59
mmol) of 1-(3-dimethylaminopropyl)-3-ethyl-carbodi-
imide hydrochloride (EDC) in 10 mL of dichloromethane
was stirred at room temperature for 48 hrs. The precipitate
was filtered off. Removal of solvent, purification by flash
chromatography (SiO2, n-hexane/ethyl acetate, 1/1), and
recrystallization from n-hexane and dichloromethane gave
387.7 mg of the product as a white solid in 72% yield. IR
(KBr) n/cm-1 3053, 3012, 2929, 2856, 1732, 1599, 1530,
1500, 1474, 1290, 1205, 1163, 1124, 1085, 995, 886, 832,
4-(2-Pyridylmethoxycarbonyl)phenyl 4-(4¢-nonyloxybi-
phenyl)carboxylate (6)
Pure 6 was obtained as a white solid in 58% yield. IR
(KBr) n/cm-1 3050, 3012, 2921, 2852, 1733, 1716, 1601,
1529, 1500, 1474, 1291, 1209, 1163, 1127, 1087, 1017,
886, 831, 766. 1H NMR (CDCl3) d 0.88~0.91 (3H, t, J = 6.9
Hz), 1.29~1.39 (10H, m), 1.46~1.51 (2H, m), 1.79~1.84
(2H, m), 4.01~4.03 (2H, t, J = 6.6 Hz), 5.51 (2H, s),
7.00~7.02 (2H, d, J = 9.0 Hz), 7.25~7.27 (1H, overlapped),
7.34~7.36 (2H, d, J = 9.0 Hz), 7.45~7.46 (1H, d, J = 7.8
Hz), 7.59~7.60 (2H, d, J = 8.4 Hz), 7.70~7.75 (3H, m),
8.21~8.24 (4H, m), 8.63 (1H, d, J = 4.8 Hz). 13C NMR
(CDCl3) d 14.09, 22.66, 26.04, 29.24 (2C) , 29.39, 29.53,
31.86, 67.31, 68.19, 115.03 (2C), 121.69, 121.90 (2C),
122.89, 126.65 (2C), 126.97 , 127.42, 128.39 (2C), 130.79
(2C), 131.46 (2C), 131.82, 136.82, 146.32, 149.50, 154.96,
1
763. H NMR (CDCl3) d 0.88~0.92 (3H, t, J = 6.9 Hz),
1.32~1.41 (6H, m), 1.46~1.51 (2H, m), 1.80~1.85 (2H, m),
4.01~4.03 (2H, t, J = 6.6 Hz), 5.51 (2H, s), 7.00~7.01 (2H,
d, J = 8.4 Hz), 7.25~7.27 (1H, overlapped), 7.34~7.35 (2H,
d, J = 8.4 Hz), 7.45~7.46 (1H, d, J = 7.8 Hz), 7.59~7.60
(2H, d, J = 8.4 Hz), 7.69~7.75 (3H, m), 8.21~8.24 (4H, q,
J1 = 9.0 Hz, J2 = 2.4 Hz), 8.63~8.64 (1H, d, J = 4.8 Hz). 13C
www.jccs.wiley-vch.de
© 2012 The Chemical Society Located in Taipei & Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
J. Chin. Chem. Soc. 2012, 59, 81-86
84

JOURNAL OF THE CHINESE
CHEMICAL SOCIETY
Liquid Crystals Derived from Pyridinemethanol
155.94, 159.68, 164.56, 165.48. MS(FAB) m/z (rel. inten-
sity): 552 ([M+], 9.57), 323 ([M+-229], 27.16). Anal. Calcd
for C35H37NO5 : C 76.20, H 6.76, N 2.54. Found: C 76.33,
H 6.75, N 2.47.
4-(3-Pyridylmethoxycarbonyl)phenyl 4-(4¢-nonyloxybi-
phenyl)carboxylate (13)
Pure 13 was obtained as a white solid in 58% yield. IR
(KBr) n/cm-1 3045, 2921, 2852, 1728, 1712, 1601, 1497,
1
1289, 1208, 1160, 1121, 1085, 888, 832, 766. H NMR
4-(3-Pyridylmethoxycarbonyl)phenyl 4-(4¢-heptyloxy-
biphenyl)carboxylate (11)
(CDCl3) d 0.88~0.90 (3H, t, J = 6.9 Hz), 1.28~1.38 (10H,
m), 1.46~1.50 (2H, m), 1.79~1.84 (2H, m), 4.01~4.03 (2H,
t, J = 6.6 Hz), 5.40 (2H, s), 7.00~7.01 (2H, d, J = 9.0 Hz),
7.33~7.35 (3H, m), 7.59~7.60 (2H, d, J = 9.0 Hz), 7.69~
7.70 (2H, d, J = 8.4 Hz), 7.79~7.80 (1H, d, J = 7.8 Hz),
8.15~8.16 (2H, d, J = 8.4 Hz), 8.22~8.23 (2H, d, J = 7.8
Hz), 8.61~8.62 (1H, d, J = 4.2 Hz), 8.74 (1H, s). 13C NMR
(CDCl3) d 14.09, 22.66, 26.04, 29.24 (2C), 29.39, 29.53,
31.86, 64.28, 68.19, 115.03 (2C), 121.93 (2C), 123.52,
126.65, 126.92 (2C), 127.24, 128.38 (2C), 130.79 (2C),
131.36 (2C), 131.61, 131.80, 136.00, 146.33, 149.71,
149.75, 155.02, 159.69, 164.53, 165.52. MS(FAB) m/z
(rel. intensity): 552 ([M+], 22.28), 323 ([M+-229], 100).
Anal. Calcd for C35H37NO5: C 76.20, H 6.76, N 2.54.
Found: C 75.52, H 6.71, N 2.48.
Pure 11 was obtained as a white solid in 83% yield. IR
(KBr) n/cm-1 3070, 2945, 2917, 2862, 1733, 1719, 1602,
1379, 1269, 1201, 1166, 1201, 1099, 1076, 1014, 887, 765.
1H NMR (CDCl3) d 0.89~0.92 (3H, t, J = 6.9 Hz), 1.32~
1.40 (6H, m), 1.46~1.51 (2H, m), 1.80~1.84 (2H, m), 4.01~
4.03 (2H, t, J = 6.6 Hz), 5.40 (2H, s), 7.00~7.01 (2H, d, J =
8.4 Hz), 7.33~7.34 (3H, m), 7.59~7.60 (2H, d, J = 8.4 Hz),
7.69~7.71 (2H, d, J = 8.4 Hz), 7.79~7.80 (1H, d, J = 7.8
Hz), 8.15~8.16 (2H, d, J = 9.0 Hz), 8.22~8.23 (2H, d, J =
8.4 Hz), 8.61~8.62 (1H, d, J = 4.2 Hz), 8.74 (1H, s). 13C
NMR (CDCl3) d 14.07, 22.60, 26.00, 29.05, 29.24, 31.77,
64.28, 68.19, 115.03 (2C), 121.93 (2C), 123.53, 126.65,
126.92 (2C), 127.24, 128.39 (2C), 130.79 (2C), 131.37
(2C), 131.61, 131.80, 136.00, 146.33, 149.71, 149.75,
155.02, 159.69, 164.54, 165.52. MS(FAB) m/z (rel. inten-
sity): 524 ([M+], 65.22), 295 ([M+-229], 100). Anal. Calcd
for C33H33NO5 : C 75.69, H 6.35, N 2.68. Found: C 75.80,
H 6.30, N 2.66.
4-(4-Pyridylmethoxycarbonyl)phenyl 4-(4¢-heptyloxy-
biphenyl)carboxylate (18)
Pure 18 was obtained as a white solid in 76% yield. IR
(KBr) n/cm-1 3067, 3035, 2928, 2856, 1727, 1603, 1505,
1
1414, 1272, 1199, 1164, 1101, 1074, 884, 828, 766. H
4-(3-Pyridylmethoxycarbonyl)phenyl 4-(4¢-octyloxybi-
phenyl)carboxylate (12)
NMR (CDCl3) d 0.90~0.92 (3H, t, J = 8.4 Hz), 1.32~1.41
(6H, m), 1.46~1.51 (2H, m), 1.80~1.84 (2H, m), 4.01~4.03
(2H, t, J = 6.6 Hz), 5.40 (2H, s), 7.00~7.02 (2H, d, J = 8.4
Hz), 7.35~7.37 (4H, m), 7.59~7.61 (2H, d, J = 9.0 Hz),
7.70~7.71 (2H, d, J = 8.4 Hz), 8.19~8.20 (2H, q, J = 8.4
Hz), 8.23~8.24 (2H, d, J = 7.8 Hz), 8.64~8.65 (2H, d, J =
5.4 Hz). 13C NMR (CDCl3) d 14.06, 22.59, 26.00, 29.05,
29.24, 31.77, 64.77, 68.19, 115.04 (2C), 121.87 (2C),
122.04 (2C), 126.66 (2C), 126.89, 127.04, 128.39 (2C),
130.80 (2C), 131.41 (2C), 131.79, 144.97, 146.38, 150.10
(2C), 155.14, 159.70, 164.54, 165.35. MS (FAB) m/z (rel.
intensity): 524 ([M+], 27.03), 295 ([M+-229], 100). Anal.
Calcd for C33H33NO5 : C 75.69, H 6.35, N 2.68. Found: C
75.50, H 6.32, N 2.67.
Pure 12 was obtained as a white solid in 87% yield. IR
(KBr) n/cm-1 3038, 2926, 2854, 1728, 1711, 1602, 1497,
1289, 1209, 1161, 1121, 1085, 888, 766. 1H NMR (CDCl3)
d 0.89~0.91 (3H, t, J = 6.9 Hz), 1.30~1.39 (8H, m),
1.46~1.51 (2H, m), 1.80~1.84 (2H, m), 4.00~4.03 (2H, t, J
= 6.6 Hz), 5.40 (2H, s), 7.00~7.01 (2H, d, J = 8.4 Hz),
7.33~7.34 (3H, m), 7.59~7.60 (2H, d, J = 8.4 Hz), 7.69~
7.70 (2H, d, J = 7.8 Hz), 7.79~7.80 (1H, d, J = 7.8 Hz),
8.15~8.16 (2H, d, J = 8.4 Hz), 8.22~8.23 (2H, d, J = 8.4
Hz), 8.61~8.62 (1H, d, J = 4.2 Hz), 8.74 (1H, s). 13C NMR
(CDCl3) d 14.07, 22.63, 26.02, 29.22 (2C), 29.33, 31.79,
64.26, 68.19, 115.01 (2C), 121.92 (2C), 123.51, 126.63,
126.90 (2C), 127.23, 128.36 (2C), 130.77 (2C), 131.34
(2C), 131.59, 131.78, 135.98, 146.31, 149.69, 149.74,
155.00, 159.68, 164.51, 165.50. MS(FAB) m/z (rel. inten-
sity): 538 ([M+], 21.11), 309 ([M+-229], 100). Anal. Calcd
for C34H35NO5 : C 75.95, H 6.56, N 2.61. Found: C 75.87,
H 6.55, N 2.57.
4-(4-Pyridylmethoxycarbonyl)phenyl 4-(4¢-octyloxybi-
phenyl)carboxylate (19)
Pure 19 was obtained as a white solid in 75% yield. IR
(KBr) n/cm-1 3067, 3028, 2926, 2855, 1729, 1602, 1500,
1
1289, 1209, 1164, 1124, 1087, 889, 833, 765. H NMR
J. Chin. Chem. Soc. 2012, 59, 81-86
© 2012 The Chemical Society Located in Taipei & Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.jccs.wiley-vch.de
85

Article
Liu et al.
(CDCl3) d 0.89~0.91 (3H, t, J = 6.9 Hz), 1.30~1.40 (8H,
m), 1.46~1.51 (2H, m), 1.79~1.84 (2H, m), 4.01~4.03 (2H,
t, J = 6.6 Hz), 5.40 (2H, s), 7.00~7.02 (2H, d, J = 9.0 Hz),
7.34~7.37 (4H, m), 7.59~7.60 (2H, d, J = 8.4 Hz), 7.70~
7.71 (2H, d, J = 7.8 Hz), 8.19~8.20 (2H, d, J = 9.0 Hz),
8.23~8.24 (2H, d, J = 8.4 Hz), 8.64~8.65 (2H, d, J = 5.4
Hz). 13C NMR (CDCl3) d 14.08, 22.64, 26.04, 29.23 (2C),
29.35, 31.81, 64.77, 68.19, 115.04 (2C), 121.87 (2C),
122.03 (2C), 126.66 (2C), 126.89, 127.04, 128.39 (2C),
130.80 (2C), 131.41 (2C), 131.78, 144.96, 146.37, 150.11
(2C), 155.14, 159.70, 164.53, 165.34. MS (FAB) m/z (rel.
intensity): 538 ([M+], 89.20), 309 ([M+-229], 100). Anal.
Calcd for C34H35NO5 : C 75.95, H 6.56, N 2.61. Found: C
75.66, H 6.54, N 2.56.
for financial support of this work.
REFERENCES
1. Demus, D.; Goodby, J.; Gray, G. W.; Spiess, H. W.; Vill, V.
Handbook of Liquid Crystals; Vol. 1; Wiley-VCH: Weinheim,
1998; Chapter 6.
2. Demus, D. Liq. Cryst. 1989, 5, 75.
3. Andrews, B. M.; Gray, G. W.; Bradshaw, M. J. Mol. Cryst.
Liq. Cryst. 1985, 123, 257.
4. Hird, M.; Toyne, K. J.; Gray, G. W. Liq. Cryst. 1993, 14, 741.
5. Sakurai, T.; Mikami, N.; Higurchi, R.; Honma, M.; Yoshino,
K. Ferroelectrics 1988, 85, 469.
6. Bahr, C.; Heppke, G. Mol. Cryst. Liq. Cryst. 1987, 148, 29.
7. Walba, D. M.; Vohra, R. T.; Clark, N. A.; Handsehy, M. A.;
Xue, J.; Parma, D. S.; Lagerwall, S. T.; Skarp, K. J. Am.
Chem. Soc. 1986, 108, 724.
4-(4-Pyridylmethoxycarbonyl)phenyl 4-(4¢-nonyloxybi-
phenyl)carboxylate (20)
8. Duebal, H. R.; Escher, C.; Guenter, D.; Hemmerling, W.;
Inoguchi, Y.; Mueller, I.; Murikami, M.; Ohlendorf, D.; Win-
gen, R. Jpn. J. Appl. Phys. 1988, 27, L2241.
Pure 20 was obtained as a white solid in 76% yield. IR
(KBr) n/cm-1 3074, 3032, 2920, 2852, 1728, 1602, 1497,
1
1473, 1289, 1209, 1164, 1124, 1084, 889, 832, 765. H
9. Gray, G. W.; Harrison, K. J. Symp. Chem. Soc. Faraday Div.
1971, 5, 54.
NMR (CDCl3) d 0.88~0.90 (3H, t, J = 6.9 Hz), 1.29~1.39
(10H, m), 1.46~1.51 (2H, m), 1.80~1.84 (2H, m), 4.01~
4.03 (2H, t, J = 6.6 Hz), 5.40 (2H, s), 7.00~7.02 (2H, d, J =
9.0 Hz), 7.34~7.37 (4H, m), 7.59~7.61 (2H, d, J = 8.4 Hz),
7.70~7.71 (2H, d, J = 8.4 Hz), 8.19~8.20 (2H, d, J = 8.4
Hz), 8.23~8.24 (2H, d, J = 8.4.0 Hz), 8.64~8.65 (2H, d, J =
5.4 Hz). 13C NMR (CDCl3) d 14.07, 22.64, 26.02, 29.22
(2C), 29.37, 29.51, 31.85, 64.76, 68.17, 115.02 (2C),
121.85 (2C), 122.02 (2C), 126.65 (2C), 126.87, 127.03,
128.37 (2C), 130.78 (2C), 131.39 (2C), 131.77, 144.94,
146.36, 150.10 (2C), 155.12, 159.68, 164.53, 165.33. MS
(FAB) m/z (rel. intensity): 552 ([M+], 22.46), 323 ([M+-
229], 100). Anal. Calcd for C35H37NO5 : C 76.20, H 6.76, N
2.54. Found: C 76.06, H 6.75, N 2.48.
10. Gray, G. W.; Harrison, K. J. Mol. Cryst. Liq. Cryst. 1971, 13,
37.
11. Tsai, W. L.; Lee, H. C.; Hong, M. Y.; Chen, L. N.; Hu, M. Y.;
Hsu, F. M. Liq. Cryst. 2004, 31, 301.
12. Kato, T. Handbook of Liquid Crystals; Wiley-VCH: Weinheim,
1998; Vol. 2B, Chapter 17.
13. Dingemans, T. J.; Samulski, E. T. Liq. Cryst. 2000, 27, 131;
Madsen L. A.; Dingemans, T. J.; Nakata, M.; Samulski, E. T.
Phys. Rev. Lett. 2004, 92, 145505.
14. Han, J.; Wang, J. Y.; Zhang, F. Y.; Zhu, L. R.; Pang, M. L.;
Meng, J. B. Liq. Cryst., 2008, 35, 1205.
15. Mieczkowski, J.; Gomola, K.; Koseska, J.; Pociecha, D.;
Szydlowska, J.; Gorecka, E. J. Mater. Chem. 2003, 13, 2132.
16. Tsai, W. L.; Hsu, F. M.; Chen, J. N. Liq. Cryst. 2004, 31, 299.
17. Chen, J. N.; Hsu F. M.; Wang, H. C.; Wu, C. W.; Cheng, P. S.;
Tsai, W. L. J. Chin. Chem. Soc. 2006, 53, 931.
18. Chan, L. K. M.; Gray, G. W.; Lacey, D.; Scrowston, R. M.;
Shenouda, I. G.; Toyne, K. J. Mol. Cryst. Liq. Cryst. 1989,
172, 125.
ACKNOWLEDGEMENT
We thank the National Science Council (Grant No.
NSC 97-2113-M-017-001) and the Ministry of Education
www.jccs.wiley-vch.de
© 2012 The Chemical Society Located in Taipei & Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
J. Chin. Chem. Soc. 2012, 59, 81-86
86