JP2598670B2 - Optically active aryl ester compound - Google Patents

Description

The present invention relates to an optically active aryl ester compound useful as a ferroelectric liquid crystal compound, and more particularly to an optically active aryl ester compound having three aryl rings.

Alkoxybenzene derivatives having an asymmetric carbon atom are
In recent years, intermediates for liquid crystal chemicals have attracted particular attention. In particular, alkoxybiphenyl compounds, alkoxyphenylpyrimidine compounds, alkoxybenzoic acid derivatives, and the like are known as ferroelectric smectic liquid crystal chemicals.

As an alkoxy group in these liquid crystal compounds,
Although 6-methyloctoxy group, 2-methylbutoxy group and the like are known, these compounds have a problem that the usable temperature range is not appropriate, or the alignment stability is poor, and these compounds are practically used. It was not a typical thing.

For this reason, various studies have been continued on ferroelectric liquid crystal compounds, including the basic skeleton of the compound.

The present inventors have conducted intensive studies on aryl ester compounds having an asymmetric carbon atom, and as a result, have found that the compound represented by the following general formula (I) has excellent liquid crystallinity.

(Wherein, R ₁ and R ₂ each represent an alkyl group having 1 to 18 carbon atoms which may be substituted with a chlorine atom, and at least one of the groups is a group represented by the formula R ₃ represents a hydrogen atom or a linear alkyl group having 1 to 11 carbon atoms, X represents a hydrogen atom or a chlorine atom,
However, R ₃ and X are not hydrogen atoms at the same time.
m and q each represent 0 or 1, m + q = 0 or 1, n and p each represent 1 or 2, n + p = 3, r represents 3-5, * represents an asymmetric carbon atom Is shown. In the compound represented by the above general formula (I), R ₁ and
As the alkyl group having 1 to 18 carbon atoms represented by R ₂ ,
Methyl, ethyl, propyl, isopropyl, butyl, sec-butyl, tert-butyl, hexyl, octyl, decyl,
Examples include dodecyl, tetradecyl, hexadecyl, octadecyl, and the like, and these groups may be substituted with a chlorine atom. At least one of R ₁ and R ₂ is an optically active group having an asymmetric carbon atom.

Examples of the linear alkyl group having 1 to 11 carbon atoms represented by R ₃ include groups such as methyl, ethyl, propyl, butyl, hexyl, octyl, nonyl, decyl, and undecyl.

The compound represented by the above general formula (I) is easily produced, for example, by reacting an alkoxybiphenylcarboxylic acid with an alkylphenol or by reacting an alkylbenzoic acid with an alkoxybiphenol in the presence of a dehydrating agent. be able to.

 Next, the present invention will be described with reference to examples.

Example 1 Synthesis of (S) -4- (4'-methyloctyloxy) biphenylcarboxylic acid-4-n-octylphenyl ester 0.34 g of (S) -4- (4'-methyloctyloxy) biphenylcarboxylic acid , 0.21 g of 4-n-octylphenol, 0.21 g of N, N'-dicyclohexylcarbodiimide and 0.02 g of 4-pyrrolidinopyridine were added to 10 ml of methylene chloride and stirred at room temperature for 3 hours. After the precipitated dicyclohexylurea was separated by filtration, the filtrate was desolvated. The residue was purified using a silica gel column using n-hexane / ethyl ether (95/5) as a developing solvent, and further recrystallized from a mixed solvent of ethanol / acetone to obtain the desired (S) -4- (4'- Methyloctyloxy) biphenylcarboxylic acid-4-n-octylphenyl ester was obtained.

As a result of infrared spectroscopy, the obtained product had the following characteristic absorption and was confirmed to be the desired product.

3050cm ^-1 (vw), 2930cm ^-1 (s), 2860cm ^-1 (m),
^{1730cm -1 (s), 1605cm -1} (s), 1580cm -1 (w), 15
25cm ^-1 (vw), 1510cm ^-1 (m), 1470cm ^-1 (m), 1425
cm ^-1 (vw), 1400cm ^-1 (vw), 1380cm ^-1 (vw), 1300cm
^-1 (w), 1275 cm ^-1 (s), 1250 cm ^-1 (w), 1210 cm ^-1
(W), 1195cm ^-1 (s), 1170cm ^-1 (w), 1120cm
^{-1 (vw), 1075cm -1 (} s), 1020cm -1 (w), 1000cm -1
(Vw), 925cm ^-1 (vw), 885cm ^-1 (w), 830cm
^-1 (m), 770 cm ^-1 (m), 725 cm ^-1 (w), 700 cm
^-1 (w), 635 cm ^-1 (vw), 500 cm ^-1 (vw) This compound was sandwiched between two glass plates, and the phase morphology was observed with a polarizing microscope. As a result, the following phase transition was confirmed.

This compound was injected into a 2 μm-thick glass transparent electrode cell that had been subjected to an alignment treatment by rubbing, and then heated to 180 ° C. to obtain an isotropic liquid. The liquid crystal cell was gradually cooled to 120 ° C., and a rectangular wave of ± 15 V, 1 Hz was applied under crossed Nicols, and a clear switching operation was confirmed. When the spontaneous polarization was measured using the triangular wave method, it was 3.0 nC / cm ²
(80 ° C). The response speed at 80 ° C. (time from application of the electric field to 90% rise) was 1.3 msec.

Example 2 Synthesis of (S) -4- (5'-methylnonyloxy) biphenylcarboxylic acid-4-n-octylphenyl ester Instead of (S) -4- (4'-methyloctyloxy) biphenylcarboxylic acid 0.35 g of (S) -4- (5'-
The same operation as in Example 1 was performed, except that methylnonyloxy) biphenylcarboxylic acid was used. The obtained crude product was purified using a silica gel column using n-hexane / methylene chloride (7/3) as a developing solvent, and further recrystallized with a mixed solution of ethanol / acetone to obtain the desired (S) -4-
(5'-methylnonyloxy) biphenylcarboxylic acid-
4-n-octylphenyl ester was obtained.

As a result of infrared spectroscopy, the obtained product had the following characteristic absorption and was confirmed to be the desired product.

3050cm ^-1 (vw), 2930cm ^-1 (s), 2860cm ^-1 (m),
^{1730cm -1 (s), 1605cm -1} (s), 1580cm -1 (vw), 15
30cm ^-1 (vw), 1510cm ^-1 (m), 1465cm ^-1 (m), 1430
cm ^-1 (vw), 1400cm ^-1 (vw), 1380cm ^-1 (vw), 1290cm
^{-1 (s), 1280cm -1 (} m), 1255cm -1 (w), 1200cm -1
(S), 1175cm ^-1 (w), 1140cm ^-1 (vw), 1080cm
^{-1 (s), 1035cm -1 (} vw), 1020cm -1 (w), 1000cm -1
(Vw), 940cm ^-1 (vw), 830cm ^-1 (m), 770cm
^-1 (m), 720 cm ^-1 (w), 695 cm ^-1 (vw), 630 cm ^-1 (v
w), 515 cm ^-1 (w) The compound was sandwiched between two glass plates, and the phase morphology was observed with a polarizing microscope. As a result, the following phase transition was confirmed.

This compound was injected into a 2 μm-thick glass transparent electrode cell that had been subjected to an alignment treatment by rubbing, and then heated to 180 ° C. to obtain an isotropic liquid. The liquid crystal cell was gradually cooled to 120 ° C., and a rectangular wave of ± 15 V, 1 Hz was applied under crossed Nicols, and a clear switching operation was confirmed. When the spontaneous polarization was measured using the triangular wave method, it was found that 1.4 nC / cm ²
(80 ° C). The response speed at 80 ° C. (time from application of the electric field to 90% rise) was 270 μsec.

Example 3 (S) -4- (5'-methylnonyl) benzoic acid-4-
Synthesis of n-octyloxybiphenyl ester Instead of (S) -4- (4'-methyloctyloxy) biphenylcarboxylic acid, 0.21 g of (S) -4- (5'-
(Methylnonyl) benzoic acid was replaced with 4-n-octylphenol and 0.30 g of 4-n-octyloxybiphenol was used, except that the same operation as in Example 1 was performed. Purification using a silica gel column with methylene chloride (95/5) as a developing solvent, recrystallization with a mixed solution of ethanol / acetone to give the desired (S) -4- (5'-methylnonyl) benzoic acid-4-n
-Octyloxybiphenyl ester was obtained.

As a result of infrared spectroscopy, the obtained product had the following characteristic absorption and was confirmed to be the desired product.

3050cm ^-1 (vw), 2930cm ^-1 (s), 2860cm ^-1 (m),
^{1735cm -1 (s), 1605cm -1} (s), 1570cm -1 (vw), 14
95cm ^-1 (s), 1465cm ^-1 (m), 1415cm ^-1 (vw), 1380
^{cm -1 (w), 1270cm -1} (s), 1215cm -1 (s), 1180cm
^-1 (m), 1170 cm ^-1 (m), 1120 cm ^-1 (vw), 1080 cm ^{-1
(S), 1020cm -1 (w} ), 1000cm -1 (vw), 970cm
^-1 (w), 885 cm ^-1 (w), 840 cm ^-1 (m), 805 cm
^{-1 (m), 760cm -1 (} w), 745cm -1 (w), 725cm -1 (v
w), 645 cm ^-1 (vw), 515 cm ^-1 (w) The compound was sandwiched between two glass plates, and phase morphology was observed with a polarizing microscope. As a result, the following phase transition was confirmed.

This compound was injected into a 2 μm-thick glass transparent electrode cell that had been subjected to an alignment treatment by rubbing, and then heated to 180 ° C. to obtain an isotropic liquid. The liquid crystal cell was gradually cooled to 120 ° C., and a rectangular wave of ± 15 V, 1 Hz was applied under crossed Nicols, and a clear switching operation was confirmed. The response speed at that time was 300 μsec.

Example 4 Synthesis of (S) -4-n-octylbenzoic acid-4- (4'-methyloctyloxy) biphenyl ester 0.23 g of 4-n-octylbenzoic acid, 0.31 g of (S)-
4- (4'-methyloctyloxy) biphenol, 0.
21 g of N, N'-dicyclohexylsilvodiimide and 0.1 g
02 g of 4-pyrrolidinopyridine was added to 10 ml of methylene chloride and stirred at room temperature for 3 hours. After filtering off the precipitated dicyclohexylurea, the filtrate was desolvated to obtain a crude product. The product was purified on a silica gel column using n-hexane / ethyl ether (95/5) as a developing solvent, and then recrystallized from a mixed solvent of ethanol / benzene to give the desired (S) -4-n-octylbenzoic acid-4- (4 'Methyloctyloxy) biphenyl ester was obtained.

As a result of infrared spectroscopy, the obtained product had the following characteristic absorption and was confirmed to be the desired product.

3050cm ^-1 (vw), 2930cm ^-1 (s), 2860cm ^-1 (m),
1735cm ^-1 (s), 1610cm ^-1 (s), 1575cm ^-1 (vw), 14
95cm ^-1 (s), 1470cm ^-1 (m), 1415cm ^-1 (vw), 1380
^{cm -1 (w), 1270cm -1} (s), 1215cm -1 (s), 1180cm
^-1 (m), 1170 cm ^-1 (m), 1120 cm ^-1 (vw), 1080 cm ^{-1
(S), 1020cm -1 (w} ), 1000cm -1 (w), 930cm -1 (v
w), 885cm ^-1 (w), 840cm ^-1 (m), 810cm ^-1 (m),
^{760cm -1 (w), 730cm -1} (vw), 640cm -1 (vw), 520cm
^-1 (w) This compound was sandwiched between two glass plates, and phase morphology was observed with a polarizing microscope. As a result, the following phase transition was confirmed.

This compound was injected into a 2 μm-thick glass transparent electrode cell that had been subjected to an alignment treatment by rubbing, and then heated to 180 ° C. to obtain an isotropic liquid. When the liquid crystal cell was gradually cooled to 100 ° C. and a rectangular wave of ± 15 V, 1 Hz was applied under crossed Nicols, a clear switching operation was confirmed. The response speed at that time was 500 μsec.

Example 5 Synthesis of (R) -4-octylbenzoic acid-4- (6'-chloro-4'-methylhexyloxy) biphenyl ester Instead of (S) -4- (4'-methyloctyloxy) biphenol 0.32 g of (R) -4- (6'-chloro-
The same operation as in Example 4 was performed, except that 4'-methylhexyloxy) biphenol was used. The obtained crude product was purified using a silica gel column using n-hexane / ethyl ether (9/1) as a developing solvent, and further recrystallized with a mixed solution of ethanol / acetone to obtain the desired (R) -4-
-Octylbenzoic acid-4- (6'-chloro-4'-methylhexyloxy) biphenyl ester was obtained.

As a result of infrared spectroscopy, the obtained product had the following characteristic absorption and was confirmed to be the desired product.

3050cm ^-1 (vw), 2940cm ^-1 (s), 2860cm ^-1 (m),
^{1735cm -1 (s), 1605cm -1} (s), 1570cm -1 (vw), 14
95cm ^-1 (s), 1470cm ^-1 (m), 1415cm ^-1 (vw), 1380
^{cm -1 (w), 1270cm -1} (s), 1215cm -1 (s), 1180cm
^-1 (m), 1170 cm ^-1 (m), 1120 cm ^-1 (vw), 1075 cm ^{-1
(S), 1020cm -1 (w} ), 1000cm -1 (w), 920cm -1 (v
w), 885cm ^-1 (w), 840cm ^-1 (m), 805cm ^-1 (m),
760cm ^-1 (w), 730cm ^-1 (w), 640cm ^-1 (vw), 515cm
^-1 (w) This compound was sandwiched between two glass plates, and phase morphology was observed with a polarizing microscope. As a result, the following phase transition was confirmed.

This compound was subjected to an alignment treatment by rubbing to a thickness of 2
After injection into a glass transparent electrode cell of μm, it was heated to 180 ° C. to make an isotropic liquid. When the liquid crystal cell was gradually cooled to 100 ° C. and a rectangular wave of ± 15 V, 1 Hz was applied under crossed Nicols, a clear switching operation was confirmed. The spontaneous polarization measured by the triangular wave method was 3.6 nC / cm ² . The response speed at 100 ° C. (time from application of the electric field to 90% rise) was 240 μsec.

Example 6 Synthesis of (R) -4-n-octylbenzoic acid-4- (6'-chloro-4'-methyloctyloxy) biphenyl ester To (S) -4- (4'-methyloctyloxy) biphenol Alternatively, 0.35 g of (R) -4- (6'-chloro-
The same operation as in Example 4 was performed, except that 4'-methyloctyloxy) biphenol was used. The obtained crude product was purified using a silica gel column using n-hexane / ethyl ether (9/1) as a developing solvent, and further recrystallized from an ethanol / acetone mixed solution to obtain the desired (R) -4.
--- Octylbenzoic acid-4- (6'-chloro-4'-methyloctyloxy) biphenyl ester was obtained.

As a result of infrared spectroscopy, the obtained product had the following characteristic absorption and was confirmed to be the desired product.

3050cm ^-1 (vw), 2930cm ^-1 (s), 2860cm ^-1 (m),
^{1730cm -1 (s), 1605cm -1} (s), 1570cm -1 (vw), 14
95cm ^-1 (s), 1465cm ^-1 (m), 1415cm ^-1 (vw), 1380
^{cm -1 (w), 1270cm -1} (s), 1215cm -1 (s), 1180cm
^-1 (m), 1170 cm ^-1 (vw), 1120 cm ^-1 (vw), 1075 cm ^{-1
(M), 1020cm -1 (w} ), 1000cm -1 (w), 930cm -1 (v
w), 885cm ^-1 (w), 830cm ^-1 (m), 805cm ^-1 (m),
^{740cm -1 (w), 700cm -1} (vw), 640cm -1 (vw), 520cm
^-1 (vw) This compound was sandwiched between two glass plates, and the phase morphology was observed with a polarizing microscope. As a result, the following phase transition was confirmed.

This compound was injected into a 2 μm-thick glass transparent electrode cell that had been subjected to an alignment treatment by rubbing, and then heated to 160 ° C. to obtain an isotropic liquid. When the liquid crystal cell was gradually cooled to 100 ° C. and a rectangular wave of ± 15 V, 1 Hz was applied under crossed Nicols, a clear switching operation was confirmed. When the spontaneous polarization was measured using the triangular wave method, the result was 18.2 nC / cm ²
Met. In addition, the response speed at 100 ° C (90%
The time to rise) was 230 μsec.

These compounds show a wide smectic phase at high temperature, and have a large spontaneous polarization of the SmC ^* phase, so that they are suitable for use as a component of a ferroelectric liquid crystal.

Claims (1)

(57) [Claims] 1. An optically active aryl ester compound represented by the following general formula (I). (Wherein, R ₁ and R ₂ each represent an alkyl group having 1 to 18 carbon atoms which may be substituted with a chlorine atom, and at least one of the groups is a group represented by the formula R ₃ represents a hydrogen atom or a linear alkyl group having 1 to 11 carbon atoms, X represents a hydrogen atom or a chlorine atom, provided that R ₃
And X are not simultaneously hydrogen atoms. m and q each represent 0 or 1; m + q = 0 or 1; n and p each represent 1 or 2;
= 3, r represents 3 to 5, and * represents an asymmetric carbon atom. )