Synthesis and liquid crystalline properties of novel pyridine derivatives

Article abstract of DOI:10.1002/jhet.5570450341

(Chemical Equation Presented) The treatment of 4-hydroxypyridine with cholestery p-(ω-bromoalkyloxy)benzoates in N,N-dimethylformamide containing K₂CO₃ gave cholestery p-[ω(4-pyridyloxy) alkyloxy]benzoates, which exhibited liquid cry

Full text of DOI:10.1002/jhet.5570450341

May-Jun 2008
913
Synthesis and Liquid Crystalline Properties of Novel Pyridine
Derivatives
Toshio Itahara
Faculty of Engineering, Kagoshima University, Korimoto, Kagoshima 890-0065, Japan.
Email: itahara@be.kagoshima-u.ac.jp
Received February 19, 2007
OH
N
O
Br(CH2)nO
CO
+
O
N
O
(CH2)nO
CO
(n= 4-12)
Liquid crystalline properties
The treatment of 4-hydroxypyridine with cholestery p-(ω-bromoalkyloxy)benzoates in N,N-
dimethylformamide containing K2CO3 gave cholestery p-[ω-(4-pyridyloxy)alkyloxy]benzoates, which
exhibited liquid crystalline properties
J. Heterocyclic Chem., 45, 913 (2008).
INTRODUCTION
connection, we have studied the reaction of nucleic acid
bases with cholestery p-(ω-bromoalkyloxy)benzoates (1)
[16,17]. The present paper reports a synthesis of new
liquid crystalline compounds with pyridine ring by a
treatment of 4-hydroxypyridine with 1.
The hydrogen-bonded supramolecular liquid crystals
containing pyridine derivatives have been extensively
studied since the pioneering work of Kato and Frechet [1]
and Lehn et al [2]. Although various liquid crystalline
compounds with pyridine ring have been prepared, little
attention has been paid to alkylation of 4-hydroxypyridine
as a method for a preparation of liquid crystalline pyridine
derivatives. The alkylation of 4-hydroxypyridine results
in the alkylation of the phenolic oxygen of 4-
hydroxypyridine or the nitrogen of 4-pyridone, but the
details of the reaction are still unclear [3-9]. Furthermore,
increasing interest is being shown in the tautomeric
equilibrium between 4-hydroxypyridine and 4-pyridone in
connection with the physiological action of pyridine and
pyrimidine derivatives, e.g. pyrimidine nucleic acid bases
[10-14]. On the other hand, cholestery benzoate is the
first liquid crystalline compound [15], and in this
RESULTS AND DISCUSSION
The reaction of 4-hydroxypyridine with 1 in N,N-
dimethylformamide (DMF) in the presence of K2CO3
gave the compounds (2) as main products and the
compounds (3) as minor products. Although the 1H-NMR
data of 2 and 3 were similar, the aromatic regions were
clearly different. The aromatic absorptions of 2 at δ 8.4
(d, 2H, J=6.0Hz) and δ 6.8 (d, 2H, J=6.0Hz) were
assigned to the hydrogens of 4-substituted pyridine, while
the aromatic absorptions of 3 were found at δ 7.3 (d, 2H,
J=7.6Hz) and δ 6.4 (d, 2H, J=7.6Hz). Furthermore, the
absorptions of 2 at δ 4.0 (t, 4H, J=6.0Hz) were assigned to
the two CH2-O parts, while the absorptions of 3 at δ 4.0 (t,
O
O
OH
N
O
(CH2)nO
CO
Br(CH2)nO
CO
2
1
N
O
K2CO3 in DMF
(CH2)nO
CO
+
O
N
3
a: n = 4, b: n = 5, c: n = 6, d: n = 7, e: b = 8, f: n = 9, g: n = 10, h: n = 11, i: n = 12
Figure 1

914
T. Itahara
Vol 45
2H, J=6.0Hz) and δ 3.75 (t, 2H, J=7.0Hz) were assigned
to one CH2-O part and one CH2-N part, respectively.
The IR spectral data provided further evidence for the
structures of 2 and 3. The IR spectra of 2a and 3a are
illustrated in Figure 2. The IR spectra of 2a-i showed one
C=O stretching band at 1703 cm-1. On the other hand,
two C=O stretching bands were found at 1703 and 1639
observation substantiated the cholesteric liquid crystallinity
of 2a-i. Figure 3 shows the polarizing microscopic image
of cholesteric liquid crystal of 2a at 183 °C upon heating.
The thermodynamic data of 2a-i are summarized in
Table 2. The relationship between the mesomorphic ranges
of 2 and the length of the alkyl chain is shown in Figure 4.
In spite of a clear odd-even effect of the melting points of
2a-i, the transition temperature from liquid crystal to
isotropic liquid did not show a similar odd-even effect.
1
cm-1 for 3a-i. On the basis of these H-NMR and IR
spectral data, it can be concluded that 2 and 3 are 4-
alkyloxypyridines and N-alkyl substituted 4-pyridones,
respectively. The structures of 2 and 3 are shown in
Figure 1. The yields of 2 and 3 are summarized in Table
1. It can be seen from Table 1 that the ratio of the isolated
yields of 2 and 3 is about 10:1. Therefore, the alkylation
of 4-hydroxypyridine may be effective for the introduction of
pyridine ring into liquid crystalline molecules.
1 0 3 .4 1 8
1 0 0
9 0
% T
8 0
Figure 3. The polarizing microscopic image of cholesteric liquid crystal
of 2a at 183 °C upon heating.
2a
7 0
Table 2
Thermal behavior of 2
6 0 .5 2 1 2
1 8 0 0
1 6 0 0
1 4 0 0
1 2 0 0
1 0 0 0
Compd.
n
°C (ΔH: kJ/mol) *
W a ve n u m be r[cm -1 ]
2a
2b
2c
2d
2e
2f
2g
2h
2i
4
5
6
7
8
C 153 (30.4) N* 214 (0.7)
C 130 (26.5) N* 205 (0.7)
C 148 (30.8) N* 197 (0.8)
C 114 (25.3) N* 190 (0.8)
C 126 (31.8) N* 188 (0.9)
C 93 (26.4) N* 178 (0.8)
C 110 (32.5) N* 174 (1.0)
C 90 (25.1) N* 170 (0.9)
C 111 (35.4) N* 167 (0.9)
I
I
I
I
I
I
I
I
I
1 0 1 .8 5 6
8 0
9
10
11
12
% T
6 0
3a
* The thermal mesomorphic ranges were determined by DSC upon
heating at a rate of 5 °C. C: Crystal. N*: Cholesteric liquid crystal. I:
Isotropic liquid.
4 1 .6 7 5 2
1 8 0 0
1 6 0 0
1 4 0 0
1 2 0 0
1 0 0 0
W a ve n u m be r[cm -1 ]
Figure 2. IR spectra of 2a and 3a in CDCl3.
Table 1
The reaction of 4-hydroxypyridine with 1
n
Products / Isolated yield (%)
4
2a/44, 3a/4, 1a/12
5
6
7
8
2b/46, 3b/5,
2c/46, 3c/5, 1c/15
2d/41, 3d/5, 1d/12
2e/44, 3e/5, 1e/13
1b/15
9
2f/ 42, 3f/5,
2g/42, 3g/4,
2h/40, 3h/4,
2i/ 42, 3i/4,
1f/13
1g/14
1h/11
1i/12
10
11
12
The thermal mesomorphic phases of 2a-i were analyzed
by using the differential scanning calorimeter (DSC) and
the polarizing microscope. The polarizing microscopy
Figure 4. The relationship between the mesomorphic ranges of 2 and
the carbon numbers (n) of the alkyl chain.

May-Jun 2008
Synthesis and Liquid Crystalline Properties of Novel Pyridine Derivatives
915
EXPERIMENTAL
4.01(t, 4H, J=6.0HZ), 2.45(d, 2H, Chol-4, J=7.6Hz), 1.07 (s, 3H,
Chol-19or18), 0.92 (d, 3H, Chol-21, J=6.4 Hz), 0.87 (dd, 6H,
Chol-26,27, J=6.4, J=1.6 Hz), 0.69 (s, 3H, Chol-18or19), 2.10-
0.90 (m, 32H). IR (CDCl3) 2941, 2870, 1703, 1606, 1598, 1510,
1468, 1421, 1371, 1317, 1284, 1254, 1211, 1169, 1121 cm-1.
Anal. Calcd for C46H67NO4: C: 79.15; H:9.67; N:2.01%. Found:
C:79.48; H:9.97; N:1.97%.
The elemental analyses were performed in the Analytical
1
Center of Kyoto University. The H-NMR spectra (400 MHz)
were obtained with a JEOL GSX 400 spectrometer. The
chemical shifts (δ-values) were measured in parts per million
(ppm) down-field from tetramethylsilane as an internal
reference. The IR spectra were recorded with a JASCO FT/IR-
420 spectrometer. The measurements in CDCl3 were made with
a 0.1 mm KBr cell. Differential scanning calorimetry (DSC)
measurements were carried out with a Shimadzu DSC-60.
Microscopy observations were performed under a Nikon Eclipse
E600 POL equipped with a hot stage (Linkam LK-600PH).
Cholestery p-(ω-bromoalkyloxy)benzoates (1) were prepared by
the reaction of cholesteryl p-hydroxybenzoate [18] and α,ω-
dibromoalkane according to the procedure described before
[16,17].
Reaction of 4-hydroxypyridine with cholestery p-(ω-
bromoalkyloxy)benzoates (1). A solution of 4-hydroxypyridine
(0.5 mmol) and 1 (0.5 mmol) in DMF (50 ml) containing K2CO3
(0.5 mmol) was stirred at room temperature for 24 h under
nitrogen atmosphere. The reaction mixture was evaporated to
give a residue, which was chromatographed on silica gel. By
monitoring at 254 nm, elution by chloroform gave 2 together
with a small amount of 3.
Cholestery p-[(4-(4-pyridyloxy)butoxy)benzoate (2a). 1H-
NMR (CDCl3) δ 8.42(d, 2H, Pyridine, J=6.0Hz), 7.99(d, 2H, Ph,
J=8.8Hz), 6.90(d, 2H, Ph, J=8.8Hz), 6.80(d, 2H, Pyridine,
J=6.0Hz), 5.41(d, 1H, Chol-6, J=3.6Hz), 4.83(m, Chol-3, 1H),
4.09(broad t, 4H, J=6.0 Hz), 2.45(d, 2H, Chol-4, J=7.6Hz), 1.07
(s, 3H, Chol-19or18), 0.92 (d, 3H, Chol-21, J=6.4 Hz), 0.87 (dd,
6H, Chol-26,27, J=6.4, J=1.6 Hz), 0.69 (s, 3H, Chol-18or19),
2.10-0.90 (m, 26H). IR (CDCl3) 2951, 2870, 1703, 1606, 1595,
1510, 1470, 1421, 1369, 1317, 1284, 1252, 1211, 1169, 1122
cm-1. Anal. Calcd for C43H61NO4: C: 78,74; H:9.37; N:2.14%.
Found: C:78.75; H:9.47; N:2.08%.
Cholestery p-[(5-(4-pyridyloxy)pentyloxy)benzoate (2b).
1H-NMR (CDCl3) δ8.41(d, 2H, Pyridine, J=6.0Hz), 7.99(d, 2H,
Ph, J=8.8Hz), 6.90(d, 2H, Ph, J=8.8Hz), 6.79(d, 2H, Pyridine,
J=6.0Hz), 5.41(d, 1H, Chol-6, J=3.6Hz), 4.82(m, Chol-3, 1H),
4.04(t, 4H, J=6.0HZ), 2.45(d, 2H, Chol-4, J=7.6Hz), 1.07 (s, 3H,
Chol-19or18), 0.92 (d, 3H, Chol-21, J=6.4 Hz), 0.87 (dd, 6H,
Chol-26,27, J=6.4, J=1.6 Hz), 0.69 (s, 3H, Chol-18or19), 2.10-
0.90 (m, 28H). IR (CDCl3) 2949, 2870, 1703, 1606, 1597, 1508,
1470, 1421, 1371, 1317, 1284, 1254, 1211, 1169, 1122 cm-1.
Anal. Calcd for C44H63NO4: C: 78.88; H:9.48; N:2.09%. Found:
C:79.10; H:9.74; N:2.04%.
1
Cholestery p-[(8-(4-pyridyloxy)octyloxy)benzoate (2e). H-
NMR (CDCl3) δ 8.41(d, 2H, Pyridine, J=6.0Hz), 7.98(d, 2H, Ph,
J=8.8Hz), 6.89(d, 2H, Ph, J=8.8Hz), 6.79(d, 2H, Pyridine,
J=6.0Hz), 5.41(d, 1H, Chol-6, J=3.6Hz), 4.82(m, Chol-3, 1H),
4.00(t, 4H, J=6.0HZ), 2.45(d, 2H, Chol-4, J=7.6Hz), 1.07 (s, 3H,
Chol-19or18), 0.92 (d, 3H, Chol-21, J=6.4 Hz), 0.87 (dd, 6H,
Chol-26,27, J=6.4, J=1.6 Hz), 0.69 (s, 3H, Chol-18or19), 2.10-
0.90 (m, 34H). IR (CDCl3) 2935, 2856, 1703, 1605, 1597, 1510,
1468, 1421, 1369, 1317, 1284, 1254, 1211, 1169, 1121 cm-1.
Anal. Calcd for C47H69NO4: C: 79.28; H: 9.77; N:1.97%. Found:
C;79.26; H:9.83; N:1.98%.
1
Cholestery p-[(9-(4-pyridyloxy)nonyloxy)benzoate (2f). H-
NMR (CDCl3) δ8.41(d, 2H, Pyridine, J=6.0Hz), 7.98(d, 2H, Ph,
J=8.8Hz), 6.89(d, 2H, Ph, J=8.8Hz), 6.79(d, 2H, Pyridine,
J=6.0Hz), 5.41(d, 1H, Chol-6, J=3.6Hz), 4.82(m, Chol-3, 1H),
4.00(t, 4H, J=6.0HZ), 2.45(d, 2H, Chol-4, J=7.6Hz), 1.07 (s, 3H,
Chol-19or18), 0.92 (d, 3H, Chol-21, J=6.4 Hz), 0.87 (dd, 6H,
Chol-26,27, J=6.4, J=1.6 Hz), 0.69 (s, 3H, Chol-18or19), 2.10-
0.90 (m, 36H). IR (CDCl3) 2941, 2868, 1703, 1605, 1597, 1510,
1468, 1421, 1371, 1317, 1284, 1254, 1211, 1169, 1119 cm-1.
Anal. Calcd for C48H71NO4·½H2O: C: 78.42; H: 9.87; N:1.91%.
Found: C: 78.12; H: 9.81 N: 1.90%.
Cholestery p-[(10-(4-pyridyloxy)decyloxy)benzoate (2g).
1H-NMR (CDCl3) δ 8.41(d, 2H, Pyridine, J=6.0Hz), 7.98(d, 2H,
Ph, J=8.8Hz), 6.89(d, 2H, Ph, J=8.8Hz), 6.79(d, 2H, Pyridine,
J=6.0Hz), 5.41(d, 1H, Chol-6, J=3.6Hz), 4.82(m, Chol-3, 1H),
4.00(t, 4H, J=6.0HZ), 2.45(d, 2H, Chol-4, J=7.6Hz), 1.07 (s, 3H,
Chol-19or18), 0.92 (d, 3H, Chol-21, J=6.4 Hz), 0.87 (dd, 6H,
Chol-26,27, J=6.4, J=1.6 Hz), 0.69 (s, 3H, Chol-18or19), 2.10-
0.90 (m, 38H). IR (CDCl3) 2937, 2856, 1703, 1606, 1597, 1510,
1468, 1421, 1369, 1317, 1284, 1254, 1211, 1169, 1121 cm-1.
Anal. Calcd for C49H73NO4: C: 79.52; H: 9.94; N: 1.89%.
Found: C: 79.35; H: 10.06; N:1.84%.
Cholestery p-[(11-(4-pyridyloxy)undecyloxy)benzoate (2h).
1H-NMR (CDCl3) δ8.40(d, 2H, Pyridine, J=6.0Hz), 7.98(d, 2H,
Ph, J=8.8Hz), 6.89(d, 2H, Ph, J=8.8Hz), 6.79(d, 2H, Pyridine,
J=6.0Hz), 5.41(d, 1H, Chol-6, J=3.6Hz), 4.82(m, Chol-3, 1H),
4.00(t, 4H, J=6.0HZ), 2.45(d, 2H, Chol-4, J=7.6Hz), 1.07 (s, 3H,
Chol-19or18), 0.92 (d, 3H, Chol-21, J=6.4 Hz), 0.87 (dd, 6H,
Chol-26,27, J=6.4, J=1.6 Hz), 0.69 (s, 3H, Chol-18or19), 2.10-
0.90 (m, 40H). IR (CDCl3) 2943, 2870, 1703, 1605, 1597, 1508,
1468, 1421, 1371, 1317, 1284, 1254, 1211, 1169, 1122 cm-1.
Anal. Calcd for C50H75NO4: C: 79.63; H: 10.02; N: 1.86%.
Found: C: 79.40; H: 10.13; N: 1.89%.
1
Cholestery p-[(6-(4-pyridyloxy)hexyloxy)benzoate (2c). H-
NMR (CDCl3) δ8.41(d, 2H, Pyridine, J=6.0Hz), 7.99(d, 2H, Ph,
J=8.8Hz), 6.89(d, 2H, Ph, J=8.8Hz), 6.79(d, 2H, Pyridine,
J=6.0Hz), 5.41(d, 1H, Chol-6, J=3.6Hz), 4.82(m, Chol-3, 1H),
4.02(t, 4H, J=6.0HZ), 2.45(d, 2H, Chol-4, J=7.6Hz), 1.07 (s, 3H,
Chol-19or18), 0.92 (d, 3H, Chol-21, J=6.4 Hz), 0.87 (dd, 6H,
Chol-26,27, J=6.4, J=1.6 Hz), 0.69 (s, 3H, Chol-18or19), 2.10-
0.90 (m, 30H). IR (CDCl3) 2947, 2870, 1703, 1605, 1597, 1510,
1470, 1421, 1369, 1317, 1284, 1254, 1211, 1169, 1122 cm-1.
Anal. Calcd for C45H65NO4: C: 79.02; H:9.58; N:2.05%. Found:
C:78.89; H:9.79; N:2.03%.
Cholestery p-[(12-(4-pyridyloxy)dodecyloxy)benzoate (2i).
1H-NMR (CDCl3) δ8.40(d, 2H, Pyridine, J=6.0Hz), 7.98(d, 2H,
Ph, J=8.8Hz), 6.89(d, 2H, Ph, J=8.8Hz), 6.79(d, 2H, Pyridine,
J=6.0Hz), 5.41(d, 1H, Chol-6, J=3.6Hz), 4.82(m, Chol-3, 1H),
4.00(t, 4H, J=6.0HZ), 2.45(d, 2H, Chol-4, J=7.6Hz), 1.07 (s, 3H,
Chol-19or18), 0.92 (d, 3H, Chol-21, J=6.4 Hz), 0.87 (dd, 6H,
Chol-26,27, J=6.4, J=1.6 Hz), 0.69 (s, 3H, Chol-18or19), 2.10-
0.90 (m, 42H). IR (CDCl3) 2935, 2856, 1703, 1605, 1597, 1508,
1468, 1421, 1371, 1317, 1284, 1254, 1211, 1169, 1120 cm-1.
Anal. Calcd for C51H77NO4·½H2O: C: 78.82; H: 10.12; N:
1.82%. Found: C: 78.75; H: 10.07; N: 1.80%.
Cholestery p-[(7-(4-pyridyloxy)heptyloxy)benzoate (2d).
1H-NMR (CDCl3) δ 8.41(d, 2H, Pyridine, J=6.0Hz), 7.98(d, 2H,
Ph, J=8.8Hz), 6.89(d, 2H, Ph, J=8.8Hz), 6.79(d, 2H, Pyridine,
J=6.0Hz), 5.41(d, 1H, Chol-6, J=3.6Hz), 4.82(m, Chol-3, 1H),

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T. Itahara
Vol 45
1
Cholestery p-[4-(4-pyridon-1-yl)butoxy)benzoate (3a). H-
NMR (CDCl3) δ8.00(d, 2H, Ph, J=8.8Hz), 7.30(d, 2H, Pyridone,
J=7.6Hz), 6.88(d, 2H, Ph, J=8.8Hz), 6.41(d, 2H, Pyridone,
J=7.6Hz), 5.42(d, 1H, Chol-6, J=3.6Hz), 4.83(m, Chol-3, 1H),
4.06(t, 2H, J=6.0 Hz), 3.87(t, 2H, J=7.0 Hz), 2.45(d, 2H, Chol-4,
J=7.6Hz), 1.07 (s, 3H, Chol-19or18), 0.92 (d, 3H, Chol-21,
J=6.4 Hz), 0.87 (dd, 6H, Chol-26,27,J=6.4, J=1.6 Hz), 0.69 (s,
3H, Chol-18or19), 2.10-0.90 (m, 26H). IR (CDCl3) 2951, 2870,
1703, 1639, 1606, 1576, 1510, 1470, 1371, 1317, 1278, 1252,
1169, 1122 cm-1.
Cholestery p-[10-(4-pyridon-1-yl)decyloxy)benzoate (3g).
1H-NMR (CDCl3) δ7.98(d, 2H, Ph, J=8.8Hz), 7.26(d, 2H,
Pyridone, J=7.6Hz), 6.89(d, 2H, Ph, J=8.8Hz), 6.40(d, 2H,
Pyridone, J=7.6Hz), 5.42(d, 1H, Chol-6, J=3.6Hz), 4.82(m,
Chol-3, 1H), 4.00(t, 2H, J=6.0HZ), 3.75(t, 2H, J=7.0HZ),
2.45(d, 2H, Chol-4, J=7.6Hz), 1.07 (s, 3H, Chol-19or18), 0.92
(d, 3H, Chol-21, J=6.4 Hz), 0.87 (dd, 6H, Chol-26,27, J=6.4,
J=1.6 Hz), 0.69 (s, 3H, Chol-18or19), 2.10-0.90 (m, 38H). IR
(CDCl3) 2931, 2856, 1703, 1639, 1606, 1576, 1510, 1468, 1371,
1315, 1277, 1254, 1169, 1119 cm-1.
Cholestery p-[5-(4-pyridon-1-yl)pentloxy)benzoate (3b).
1H-NMR (CDCl3) δ7.99(d, 2H, Ph, J=8.8Hz), 7.26(d, 2H,
Pyridone, J=7.6Hz), 6.88(d, 2H, Ph, J=8.8Hz), 6.40(d, 2H,
Pyridone, J=7.6Hz), 5.42(d, 1H, Chol-6, J=3.6Hz), 4.82(m,
Chol-3, 1H), 4.02(t, 2H, J=6.0HZ), 3.80(t, 2H, J=7.0HZ),2.45(d,
2H, Chol-4, J=7.6Hz), 1.07 (s, 3H, Chol-19or18), 0.92 (d, 3H,
Chol-21, J=6.4 Hz), 0.87 (dd, 6H, Chol-26,27, J=6.4, J=1.6 Hz),
0.69 (s, 3H, Chol-18or19), 2.10-0.90 (m, 28H). IR (CDCl3)
2949, 2870, 1703, 1639, 1606, 1576, 1510, 1468, 1371, 1317,
1279, 1252, 1169, 1122 cm-1.
Cholestery
p-[11-(4-pyridon-1-yl)undecyloxy)benzoate
1
(3h). H-NMR (CDCl3) δ7.98(d, 2H, Ph, J=8.8Hz), 7.26(d, 2H,
Pyridone, J=7.6Hz), 6.89(d, 2H, Ph, J=8.8Hz), 6.40(d, 2H,
Pyridone, J=7.6Hz), 5.42(d, 1H, Chol-6, J=3.6Hz), 4.82(m,
Chol-3, 1H), 4.00(t, 2H, J=6.0HZ), 3.75(t, 2H, J=7.0HZ),
2.45(d, 2H, Chol-4, J=7.6Hz), 1.07 (s, 3H, Chol-19or18), 0.92
(d, 3H, Chol-21, J=6.4 Hz), 0.87 (dd, 6H, Chol-26,27, J=6.4,
J=1.6 Hz), 0.69 (s, 3H, Chol-18or19), 2.10-0.90 (m, 40H). IR
(CDCl3) 2935, 2856, 1703, 1639, 1606, 1574, 1510, 1468, 1371,
1317, 1279, 1254 1169, 1122 cm-1.
Cholestery p-[6-(4-pyridon-1-yl)hexyloxy)benzoate (3c).
1H-NMR (CDCl3) δ7.99(d, 2H, Ph, J=8.8Hz), 7.26(d, 2H,
Pyridone, J=7.6Hz), 6.89(d, 2H, Ph, J=8.8Hz), 6.40(d, 2H,
Pyridone, J=7.6Hz), 5.42(d, 1H, Chol-6, J=3.6Hz), 4.82(m,
Chol-3, 1H), 4.00(t, 2H, J=6.0HZ), 3.77(t, 2H, J=7.0HZ),
2.45(d, 2H, Chol-4, J=7.6Hz), 1.07 (s, 3H, Chol-19or18), 0.92
(d, 3H, Chol-21, J=6.4 Hz), 0.87 (dd, 6H, Chol-26,27, J=6.4,
J=1.6 Hz), 0.69 (s, 3H, Chol-18or19), 2.10-0.90 (m, 30H). IR
(CDCl3) 2944, 2868, 1703, 1639, 1606, 1576, 1510, 1468, 1371,
1317, 1279, 1254, 1169, 1122 cm-1.
Cholestery p-[12-(4-pyridon-1-yl)dodecyloxy)benzoate (3i).
1H-NMR (CDCl3) δ7.98(d, 2H, Ph, J=8.8Hz), 7.26(d, 2H,
Pyridone, J=7.6Hz), 6.89(d, 2H, Ph, J=8.8Hz), 6.40(d, 2H,
Pyridone, J=7.6Hz), 5.42(d, 1H, Chol-6, J=3.6Hz), 4.82(m,
Chol-3, 1H), 4.00(t, 2H, J=6.0HZ), 3.75(t, 2H, J=7.0HZ),
2.45(d, 2H, Chol-4, J=7.6Hz), 1.07 (s, 3H, Chol-19or18), 0.92
(d, 3H, Chol-21, J=6.4 Hz), 0.87 (dd, 6H, Chol-26,27, J=6.4,
J=1.6 Hz), 0.69 (s, 3H, Chol-18or19), 2.10-0.90 (m, 42H). IR
(CDCl3) 2933, 2856, 1703, 1639, 1606, 1576, 1510, 1468, 1371,
1317, 1277, 1254, 1169, 1120 cm-1.
Cholestery p-[7-(4-pyridon-1-yl)heptyloxy)benzoate (3d).
1H-NMR (CDCl3) δ7.98(d, 2H, Ph, J=8.8Hz), 7.26(d, 2H,
Pyridone, J=7.6Hz), 6.89(d, 2H, Ph, J=8.8Hz), 6.40(d, 2H,
Pyridone, J=7.6Hz), 5.42(d, 1H, Chol-6, J=3.6Hz), 4.82(m,
Chol-3, 1H), 4.00(t, 2H, J=6.0HZ), 3.75(t, 2H, J=7.0HZ),2.45(d,
2H, Chol-4, J=7.6Hz), 1.07 (s, 3H, Chol-19or18), 0.92 (d, 3H,
Chol-21, J=6.4 Hz), 0.87 (dd, 6H, Chol-26,27, J=6.4, J=1.6 Hz),
0.69 (s, 3H, Chol-18or19), 2.10-0.90 (m, 32H). IR (CDCl3)
2944, 2868, 1703, 1639, 1606, 1576, 1510, 1468, 1371, 1317,
1279, 1254, 1169, 1122 cm-1.
Cholestery p-[8-(4-pyridon-1-yl)oxtyloxy)benzoate (3e). 1H-
NMR (CDCl3) δ7.98(d, 2H, Ph, J=8.8Hz), 7.26(d, 2H, Pyridone,
J=7.6Hz), 6.89(d, 2H, Ph, J=8.8Hz), 6.40(d, 2H, Pyridone,
J=7.6Hz), 5.42(d, 1H, Chol-6, J=3.6Hz), 4.82(m, Chol-3, 1H),
4.00(t, 2H, J=6.0HZ), 3.75(t, 2H, J=7.0HZ), 2.45(d, 2H, Chol-4,
J=7.6Hz), 1.07 (s, 3H, Chol-19or18), 0.92 (d, 3H, Chol-21,
J=6.4 Hz), 0.87 (dd, 6H, Chol-26,27, J=6.4, J=1.6 Hz), 0.69 (s,
3H, Chol-18or19), 2.10-0.90 (m, 34H). IR (CDCl3) 2937, 2868,
1703, 1639, 1606, 1576, 1510, 1468, 1369, 1317, 1279, 1254,
1169, 1121 cm-1.
Acknowledgement. The author thanks Mr. T. Yoshitake for
his technical assistance.
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Cholestery p-[9-(4-pyridon-1-yl)nonyloxy)benzoate (3f).
1H-NMR (CDCl3) δ7.98(d, 2H, Ph, J=8.8Hz), 7.26(d, 2H,
Pyridone, J=7.6Hz), 6.89(d, 2H, Ph, J=8.8Hz), 6.40(d, 2H,
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(CDCl3) 2935, 2856, 1703, 1639, 1606, 1574, 1510, 1468, 1371,
1317, 1279, 1254 1169, 1122 cm-1.
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