JPH0625059A - Liquid crystal compound and composition - Google Patents

Abstract

PURPOSE:To obtain a new compound useful as a liquid crystal composition used in a liquid crystal display element. CONSTITUTION:The compound of formula 1 (R<1> is 1-18C alkyl or alkenyl; A is formula 7 to 11; NAP is 2,6-naphthylene; R<2> is 1-18C alkyl). The compound of formula 1 in which A is formula 7 is obtained by reacting a compound of formula 5 derived from 6-bromo-2-naphthol with a compound of formula 6 in the presence of a Pd catalyst. When this compound is used as a component of a chiral smectic C phase liquid crystal composition, a liquid crystal composition good in orienting properties without zigzag defects can be obtained and a liquid crystal display element having a high contrast ratio can be obtained. Since other smectic phases are not exhibited in a low-temperature region, this compound can be used as a component of the chiral smectic C phase liquid crystal composition to extend the temperature range of the chiral smectic C phase.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel liquid crystal compound useful as a component of a liquid crystal composition used for a liquid crystal display device and the like and a liquid crystal composition containing this liquid crystal compound. More specifically, the present invention provides a novel naphthalene-based liquid crystal compound exhibiting a non-chiral smectic C phase (hereinafter abbreviated as Sc phase) and a liquid crystal composition containing the liquid crystal compound.

[0002]

2. Description of the Related Art Recently, a display system using a ferroelectric liquid crystal compound has been reported by Meyer et al., And a high speed response and a memory effect of 100 to 1000 times that of a TN type can be obtained. Expectations are high, and research and development are currently underway. The liquid crystal phase of the ferroelectric liquid crystal compound belongs to the tilt type chiral smectic phase, but in practice, the chiral smectic C (hereinafter, abbreviated as Sc *) phase having the lowest viscosity among them is practically used. Is most desirable. A large number of liquid crystal compounds exhibiting the Sc * phase have already been synthesized and studied, but the conditions for use as a ferroelectric display element are: (a) showing Sc * in a wide temperature range including room temperature, b) showing uniform orientation and having a large helical pitch,
(C) having an appropriate tilt angle, (d) having low viscosity, and the like. However, no liquid crystal compound exhibiting the Sc * phase that satisfies these conditions alone has been known, and efforts have been made to satisfy these conditions by mixing. In addition, the development of new liquid crystal compounds exhibiting the Sc * phase is also in progress. On the other hand, as a method for preparing a liquid crystal composition exhibiting a Sc * phase (hereinafter referred to as a Sc * liquid crystal composition), a chiral compound is added to a liquid crystal compound or composition exhibiting a non-chiral Sc phase without showing ferroelectricity. There is also a method of addition, and development of a liquid crystal compound exhibiting a Sc phase is underway. Conventionally, phenylpyrimidine-based liquid crystal compounds represented by the following chemical formulas 7 and 8 are known as typical liquid crystal compounds exhibiting the Sc phase or Sc * phase.

[0003]

[Chemical 7]

[0004]

[Chemical 8]

In Chemical formula 8, C * represents an asymmetric carbon atom.

[0006]

However, since these phenylpyrimidine-based liquid crystal compounds and compositions using these compounds have poor orientation, zigzag defects are likely to occur when injected into a cell and the contrast ratio does not increase. There's a problem.

[0007]

Means for Solving the Problems As a result of intensive investigations by the present inventors on a liquid crystal compound exhibiting an Sc phase having a better orientation than the above compounds, a new liquid crystal compound having a structure different from the conventional one was found. The invention was reached. That is, the present invention is represented by the following general formula

[0008]

[Chemical 9] [In the formula, R ¹ represents an alkyl group or an alkenyl group having 1 to 18 carbon atoms, A represents a group selected from the following formulas 10 to 14, NAP represents a 2,6-naphthylene group, and R ²
Represents an alkyl group having 1 to 18 carbon atoms]; and a liquid crystal composition containing at least one liquid crystal compound.

[0009]

[Chemical 10]

[0010]

[Chemical 11]

[0011]

[Chemical 12]

[0012]

[Chemical 13]

[0013]

[Chemical 14]

In the general formula (1), the number of carbon atoms represented by R ¹ is 1.
Specific examples of the alkyl group and alkenyl group of to 18 include a methyl group, an ethyl group, an n-propyl group, an n-butyl group, an n-pentyl group, an n-hexyl group, an n-heptyl group,
n-octyl group, n-nonyl group, n-decyl group, n-undecyl group, n-dodecyl group, n-tetradecyl group, n-hexadecyl group, n-octadecyl group and 2-propenyl group, 3-butenyl group, 4-pentenyl group, 5-hexenyl group, 6-heptenyl group, 7-octenyl group, 8-nonenyl group, 9-decenyl group, 10-undecenyl group, 11-dodecenyl group, trans-2-hexenyl group, cis-2 -Hexenyl group, cis-3-hexenyl group, cis-4-hexenyl group, tran
Examples thereof include s-2-heptenyl group, cis-3-nonenyl group, cis-6-nonenyl group, trans-2-decenyl group and trans-5-decenyl group. Of these, preferred as R ¹ are alkyl groups and alkenyl groups having 3 to 14 carbon atoms.

Specific examples of the alkyl group having 1 to 18 carbon atoms represented by R ² include the alkyl groups represented by R ¹ . R ² preferably has 3 to 14 carbon atoms.
Is an alkyl group. Specific examples of the liquid crystal compound of the present invention include compounds having groups shown in Tables 1 to 3 below.

[0016]

[Table 1]

[0017]

[Table 2]

[0018]

[Table 3]

In the above Tables 1 to 3, each symbol represents the following group. _{HEP; nC 7 H 15 - OCT} ; nC 8 H 17 -
_{NON; nC 9 H 19 - DEC} ; nC 10 H 21 - O-HEP; CH 2 = CH-
_{(CH 2) 5 - O-} OCT; CH 2 = CH- (CH 2) 6 - O-NON; CH 2 = CH- (CH 2) 7 - O-DEC; CH 2 = CH- (CH 2) 8 −

The compounds of the present invention are, for example, <I> to <III>
Can be synthesized through the steps shown in each item [R ¹ in the following formula,
NAP and R ² are the same as in general formula (1)]. <I> When A is a group represented by Chemical formula 10

[0021]

[Chemical 15]

That is, 6-bromo-naphthol obtained by reacting 6-bromo-2-naphthol with benzyl chloride in the presence of a base.
A compound of the general formula (3) can be obtained by reacting 2-benzyloxynaphthalene with a 1-alkyne represented by the general formula (2) in the presence of a palladium catalyst. The compound of general formula (4) can be obtained by hydrogenating and hydrolyzing the compound of general formula (3) using palladium carbon. The compound of the present invention is obtained by reacting the compound of general formula (5) obtained by reacting the compound of general formula (4) with trifluoromethanesulfonic anhydride in the presence of a palladium catalyst. A compound of general formula (1a) can be obtained.

Alternatively, it can be synthesized through the following steps.

[0024]

[Chemical 16]

That is, ortho-difluorobenzene at -55 ℃
In the following, 2,3-difluorophenylboric acid obtained by reacting with n-butyllithium to be lithiated, then reacted with trimethyl borate, and then hydrolyzed with an acid and the compound represented by the general formula (5) The compound of the general formula (7) can be obtained by reacting the compound in the presence of a palladium catalyst. A compound of the general formula (8) obtained by reacting the compound of the general formula (7) with n-butyllithium at −55 ° C. or lower to lithiate, reacting with trimethyl borate, and then hydrolyzing with an acid. The compound of the general formula (9) can be obtained by oxidizing the compound of (4) with hydrogen peroxide. The compound of the general formula (1a), which is the compound of the present invention, can also be obtained by etherifying the compound of the general formula (9). The compound of the general formula (6), which is a raw material of the compound (1a), can be synthesized through the following steps.

[0026]

[Chemical 17]

That is, after the compound of the general formula (10) obtained by alkylating 2,3-difluorophenol is treated with n-butyllithium at −55 ° C. or lower to be lithiated,
The compound of the general formula (6) can be obtained by reacting with trimethyl borate and then hydrolyzing with an acid. <II> When A is a group represented by Chemical formula 11, Chemical formula 12 and Chemical formula 13

[0028]

[Chemical 18]

That is, the Grignard reagent prepared from the compound of the general formula (12) obtained by alkylating the compound of the general formula (11) is reacted with trimethyl borate, and then hydrolyzed with an acid to give the general formula ( The compound of 13) can be obtained. By reacting the compound of general formula (13) with the compound of general formula (5) in the presence of a palladium catalyst, the compound of general formula (1b), which is the compound of the present invention, can be obtained.

<III> When A is a group represented by Chemical formula 14,

[0031]

[Chemical 19]

That is, 6-cyano-2-naphthol obtained by reacting 6-bromo-2-naphthol with copper (I) cyanide is reacted with hydrogen chloride gas and then ammonia gas in absolute ethanol. The amidine salt represented by the formula (14) can be obtained by The compound of general formula (16) can be obtained by reacting this amidine salt with acrolein represented by general formula (15) in ethanol in the presence of a base (for example, sodium ethoxide). By reacting a compound of the general formula (17) obtained by reacting a compound of the general formula (16) with trifluoromethanesulfonic anhydride and a 1-alkyne represented by the general formula (2) in the presence of a palladium catalyst. The compound of the general formula (18) can be obtained. By hydrogenating the compound of the general formula (18) using palladium carbon, the compound of the general formula (1c) which is the compound of the present invention can be obtained.

The liquid crystal compound is generally used as a component of a liquid crystal composition composed of two or more kinds of components, and the liquid crystal compound of the present invention can also be used as a component of the liquid crystal composition. The liquid crystal composition of the present invention comprises a mixture of a plurality of compounds and contains at least one liquid crystal compound of the present invention. Examples of the composition of the present invention include the liquid crystal composition [1] of the present invention exhibiting the Sc phase and the liquid crystal composition [2] of the present invention exhibiting the Sc * phase. The liquid crystal composition [1] of the present invention contains at least 1 part of the liquid crystal compound of the present invention.
A liquid crystal compound (2-4′-alkyloxyphenyl-5-alkylpyrimidine, 2-4′-alkylphenyl-5-alkyloxypyrimidine, 2-4′-, which is an essential component of the seed and which exhibits another Sc phase as an optional component. Alkyloxyoxyphenyl-5-alkyloxypyrimidines, 2-p-alkyloxycarbonylphenyl-5-alkylpyrimidines, 2-
4'-alkyloxy-3'-fluorophenyl-5-alkylpyrimidine, 2-4'-alkyloxy-2 ', 3'-
Difluorophenyl-5-alkylpyrimidine, 2-4'-
Alkyloxyphenyl-5-alkylpyridine, 2-
4′-alkyloxy-3′-fluorophenyl-5-alkylpyridine, etc.), a smectic liquid crystal compound not exhibiting an Sc phase, and a liquid crystal compound exhibiting a nematic phase. In the liquid crystal composition [1] of the present invention, the content of one or more liquid crystal compounds of the present invention is usually 5 to 100% by weight.

The liquid crystal composition [2] of the present invention includes a liquid crystal compound (optically active 4-alkyloxy-4′-biphenylcarboxylic acid-p ′) exhibiting a Sc * phase with the liquid crystal composition [1] of the present invention.
-(2-Methylbutyloxycarbonyl) phenyl ester, optically active 4-n-alkyloxy-4'-biphenylcarboxylic acid-2-methylbutyl ester, etc. and / or a chiral compound (Japanese Patent Laid-Open No. 63-99032, JP Kaisho 63
-190843, JP-A-2-138274, JP-A-2-
256673, JP-A-2-262579, JP-A-2-2
86673, compounds described in JP-A-3-27374, etc.) and, if necessary, a dichroic dye (anthraquinone dye, azo dye, etc.).
In the liquid crystal composition [2] of the present invention, the content of the liquid crystal composition [1] of the present invention is usually 10 to 99% by weight.

A liquid crystal composition exhibiting ferroelectricity causes an optical switching phenomenon when a voltage is applied, and a liquid crystal display element having a fast response can be manufactured by utilizing this phenomenon [see, for example, JP-A-56-1.
07216, JP 59-118744, NA Clark, ST Lagawall (STLage)
rwall) ； Applied Phyth Letter
sics Letter) 36, 899 (1980), etc.].

Liquid crystal composition of the present invention showing Sc * [2]
Can be used as an optical switching element (liquid crystal display element) by vacuum-sealing in a liquid crystal cell having a cell interval of 0.5 to 10 μm, preferably 0.5 to 3 μm and installing polarizers on both sides. The above liquid crystal cell can be produced by providing a transparent electrode and bonding two glass substrates, the surfaces of which are aligned, with a spacer interposed therebetween. Examples of the spacer include alumina beads, glass fiber, and polyimide film. As the alignment treatment method, a normal alignment treatment, such as a rubbing treatment of a polyimide film or an oblique SiO vapor deposition, can be applied.

[0037]

EXAMPLES The present invention will be further described below with reference to examples, but the present invention is not limited thereto. Example 1 No. 1 in Table 1 Preparation of compound 1 6-Bromo-2-naphthol (50 g, 0.22 mol) was dissolved in dimethyl sulfoxide (500 ml), and sodium hydroxide (9.8 g, 0.25 g) was added.
An aqueous solution prepared by dissolving (mol) in 30 ml of water was added and stirred until the solution became uniform. Next, add 30 g of benzyl chloride and mix at room temperature
It was stirred for a day. The reaction solution was poured into 2 l of ice water, and the resulting precipitate was filtered. 6 by recrystallizing with ethanol
65 g (0.20 mol) of -bromo-2-benzyloxynaphthalene was obtained. 6-Bromo-2-benzyloxynaphthalene 10.0g (32mmo
l) and 1-nonine 4.7g (38mmol) 100ml triethylamine
In the catalyst, dichlorobistriphenylphosphine palladium (II) 112 mg (0.16 mmol), copper iodide 28 mg (0.15 mmol) as a catalyst
And 224 mg (0.85 mmol) of triphenylphosphine were heated under reflux for 8 hours in a nitrogen atmosphere. After completion of the reaction, triethylamine was removed and the mixture was extracted with toluene. The toluene layer was washed with 1N hydrochloric acid and washed with water, and then toluene was removed. By recrystallization from ethanol, 9.1 g (26 mmol) of compound (a) represented by the following chemical formula 20 was obtained.

[0038]

[Chemical 20]

9.1 g (26 mmol) of the compound (a) obtained in (1) was subjected to hydrogenation and hydrogenolysis under hydrogen atmosphere in 150 ml of ethanol using 0.5 g of 5% palladium carbon. After confirming that the absorption of hydrogen disappeared, the catalyst was removed by filtration. After removing ethanol, the obtained solid was recrystallized from hexane to obtain 5.9 g (22 mmol) of 6-n-nonyl-2-hydroxynaphthalene. 5.9 g of 6-n-nonyl-2-hydroxynaphthalene obtained in
(22 mmol) was dissolved in 100 ml of anhydrous pyridine and cooled to 10 ° C or lower. Then trifluoromethanesulfonic anhydride 6.5 g
(23 mmol) was added dropwise at 10 ° C or lower, and the mixture was returned to room temperature and stirred for 24 hours. The reaction solution was poured into ice water, hydrochloric acid was added to acidify the mixture, and the mixture was extracted with hexane. After washing the hexane layer with water,
By removing hexane, 8.4 g (17 mmol) of an oily compound (b) represented by the following chemical formula 21 was obtained.

[0040]

[Chemical 21]

2,3-difluorophenol 10 g (77 mmo
l) was dissolved in 100 ml of dimethyl sulfoxide, an aqueous solution of 3.6 g (90 mmol) of sodium hydroxide in 10 ml of water was added, and the mixture was stirred until the solution became uniform. Then, 13.1 g (73 mmol) of n-heptyl bromide was added, and the mixture was stirred at room temperature for 3 days. The reaction solution was poured into 500 ml of ice water and extracted with hexane. The hexane layer was washed with water and then hexane was removed to obtain 15.8 g (70 mmol) of oily 1,2-difluoro-3-n-heptyloxybenzene. 15.8 g (70 mmol) of 1,2-difluoro-3-n-heptyloxybenzene obtained in 1. was dissolved in 200 ml of anhydrous tetrahydrofuran and cooled to −60 ° C. or lower with a dry ice-acetone bath. Next, n-butyllithium in hexane (15
%) 47 ml (76 mmol) was added dropwise at −60 ° C. or lower, and the mixture was stirred as it was for 3 hours. Next, add 8.7 g (83 mmol) of trimethyl borate to -60 ° C.
The mixture was added dropwise below and stirred for another 30 minutes, then the dry ice-acetone bath was removed and the mixture was stirred until it reached 0 ° C. Water and then 1N hydrochloric acid were added, and the mixture was extracted with ether. After washing the ether layer with water, the ether was removed to obtain 17.9 g (66 mmol) of 2,3-difluoro-4-n-heptyloxyphenylboric acid as a white solid. 2, obtained with 3.0 g (7.5 mmol) of the compound (b) obtained in 2.
3-difluoro-4-n-heptyloxyphenyl boric acid 2.
170 mg (0.1 mg) of tetrakistriphenylphosphine palladium (0) as a catalyst in 70 ml of triethylamine (0 g, 7.4 mmol).
5 mmol) and 170 mg (0.65 mmol) of triphenylphosphine were heated under reflux in a nitrogen atmosphere for 10 hours. After completion of the reaction, triethylamine was removed, water was added, and the mixture was extracted with toluene. The toluene layer was washed with 1N hydrochloric acid water, washed with water, purified with a silica gel column, and recrystallized three times with ethanol to give white crystals of the compound of the present invention (No. 1 in Table 1). 2.1 g (4.4 mmol) of the compound of 1 were obtained. The structure of the compound is NMR (nuclear magnetic resonance spectrum analysis), M
Confirmed by S (mass spectrometry), IR (infrared absorption spectrum analysis) and elemental analysis. IR (cm ^-1 ) 2922.0 2854.0 1638.0 1524.0 1464.0 1321.0 1301.0 1100.0 895.0 799.0 NMR (ppm) 0.84 to 0.95 (m, 6H) 1.18 to 1.45 (m, 18H) 1.45 to 1.57 (m, 2H) 1.63 to 1.79 (m, 2H) 1.79 to 1.91 (m, 2H) 2.78 (t, 2H) 4.09 (t, 2H) 6.78 to 6.87 (m, 1H) 7.15 to 7.23 (m, 1H) 7.36 (dd, 1H) 7.57 to 7.65 (m, 2H) 7.82 (t, 2H) 7.93 (s, 1H) ¹⁹ F-NMR -66.0 (dd, 1F) -83.1 (dd, 1F) Elemental analysis value Theoretical value (%) Actual value (%) C: 80.00 C: 79.83 H: 8.75 H: 8.96 F: 7.92 F: 7.99

Example 2 No. 1 in Table 1 Production of Compound 2 The compound (c) represented by the following formula 22 was prepared in the same manner as in Example 1 except that 1-decyne was used in the same molar ratio in place of 1-nonine in Example 1. Got

[0043]

[Chemical formula 22]

No. 1 in Table 1 was carried out in the same manner as in Example 1 except that the compound (c) was used in the same molar ratio in place of the compound (b). Two compounds were obtained.

Example 3 No. 1 in Table 1 Production of compound of 4 In the same manner as in Example 1 except that 1-octyne was used in the same molar ratio as in Example 1 in place of 1-nonine, the compound (d) represented by the following chemical formula 23 was used. Got

[0046]

[Chemical formula 23]

In the same manner as in Example 1 except that n-octyl bromide was used in the same molar ratio in place of n-heptyl bromide in Example 1, 2, 3
-Difluoro-4-n-octyloxyphenyl boric acid was obtained. Compound (d) was reacted with 2,3-difluoro-4-n-octyloxyphenyl boric acid at the same molar ratio as in Example 1 under the same conditions to give No. 1 in Table 1. 4 compound was obtained.

Example 4 No. 1 in Table 1 Production of Compound 10 In the same manner as in Example 1 except that 1-heptin was used at the same molar ratio in place of 1-nonine in Example 1, a compound (e) represented by the following chemical formula 24 was used. Got

[0049]

[Chemical formula 24]

In the same manner as in Example 1 except that n-decyl bromide was used in the same molar ratio in place of n-heptyl bromide in Example 1, 2,3-
Difluoro-4-n-decyloxyphenyl boric acid was obtained. Compound (e) was reacted with 2,3-difluoro-4-n-decyloxyphenyl boric acid in the same molar ratio as in Example 1 under the same conditions to give No. 1 in Table 1. 10 compounds were obtained.

Example 5 In Table 2, No. Production of compound 22. 2,6-Difluorophenol (16.6 g) was dissolved in anhydrous tetrahydrofuran (220 ml) and cooled to −60 ° C. or lower with a dry ice-acetone bath. Next, 99 ml of a hexane solution of n-butyllithium (15%) was added dropwise at -60 ° C or lower, and the mixture was stirred for 3 hours as it was. Next, add 20.0 g of trimethyl borate to -60 ° C.
The mixture was added dropwise below and stirred for another 30 minutes, then the dry ice-acetone bath was removed and the mixture was stirred until it reached 0 ° C. Water and then 1N hydrochloric acid were added, and the mixture was extracted with ether. After washing the ether layer with water, the ether was removed to obtain 21.1 g of 2,3-difluorophenylboric acid as a white solid. 2,3-Difluorophenylboric acid (1.9 g) and the compound (c) obtained in Example 2 were added to tetrakistriphenylphosphine palladium as a catalyst in 100 ml of triethylamine.
(0) 278 mg and triphenylphosphine 278 mg were heated to reflux for 10 hours in a nitrogen atmosphere. After completion of the reaction, triethylamine was removed, water was added, and the mixture was extracted with toluene. The toluene layer was washed with 1N hydrochloric acid, washed with water, and then toluene was removed to obtain 3.9 g of 2- (2,3-difluorophenyl) -6-n-decylnaphthalene. 2- (2,
3-difluorophenyl) -6-n-decylnaphthalene 3.9g
Was dissolved in 100 ml of anhydrous tetrahydrofuran and cooled to −60 ° C. or lower with a dry ice-acetone bath. Then, 7 ml of a hexane solution of n-butyllithium (15%) was added dropwise at -60 ° C or lower, and the mixture was stirred for 3 hours as it was. Then trimethyl borate
After 2.0 g was added dropwise at -60 ° C or lower and the mixture was stirred for 30 minutes, the dry ice-acetone bath was removed, and the mixture was stirred until it reached 0 ° C. Water and then 1N hydrochloric acid were added, and the mixture was extracted with ether.
The ether layer was washed with water and then the ether was removed to obtain 4.1 g of a compound (f) represented by the following chemical formula 25 as a white solid.

[0052]

[Chemical 25]

20 ml of 10% aqueous hydrogen peroxide was added to an ether solution containing 4.1 g of the compound (f) obtained in step 1, and the mixture was stirred at room temperature for 1 hour.
After stirring for an hour, the mixture was heated under reflux for another 2 hours. After completion of the reaction, the ether layer was washed with water and then the ether was removed to obtain 3.5 g of white solid 2- (2,3-difluoro-4-hydroxyphenyl) -6-n-decylnaphthalene. 2.0 g of 2- (2,3-difluoro-4-hydroxyphenyl) -6-n-decylnaphthalene obtained in the above was dissolved in 50 ml of dimethyl sulfoxide, and an aqueous solution prepared by dissolving 0.25 g of sodium hydroxide in 5 ml of water was added to obtain a uniform solution. It was stirred until.
Then 10-bromo-1-decene (this compound is 9-decene
1.2 g (obtained by reacting triphenylphosphine and carbon tetrabromide on -1-ol) was added and stirred at room temperature for 3 days. The reaction solution was poured into 200 ml of ice water and extracted with toluene.
After washing the toluene layer with water and purifying with a silica gel column,
By recrystallizing three times with ethanol, a white crystalline compound of the present invention, No. 2 in Table 2 was obtained. 22 g of compound 1.7 g was obtained. IR (cm ^-1 ) 2922.0 2854.0 1640.0 1524.0 1464.0 1319.0 1301.0 1098.0 895.0 814.0 799.0 NMR (ppm) 0.88 (t, 3H) 1.21 to 1.55 (m, 20H) 1.62 to 1.78 (m, 2H) 1.78 to 1.92 (m, 2H ) 2.00 to 2.11 (m, 2H) 2.78 (t, 2H) 4.08 (t, 2H) 4.92 to 5.06 (m, 2H) 5.73 to 5.91 (m, 1H) 6.79 to 6.88 (m, 1H) 7.15 to 7.24 (m , 1H) 7.37 (dd, 1H) 7.57 to 7.66 (m, 2H) 7.82 (t, 2H) 7.94 (s, 1H) ¹⁹ F-NMR -66.0 (dd, 1F) -83.1 (dd, 1F) Elemental analysis value Theoretical value (%) Actual value (%) C: 80.63 C: 80.91 H: 8.70 H: 8.63 F: 7.51 F: 7.38

Example 6 In Table 2, No. Preparation of compound 24 Into 30 ml of diethyl ether solution containing 4.3 g of trimethyl borate cooled at -30 ° C or lower, 4-n-heptyloxy-3-fluorobromobenzene (this compound is 4-
Bromo-2-fluorophenol alkali metal salt and n-
60 ml of an ether solution of Grignard reagent prepared from 10 g of heptyl bromide) was added dropwise below -30 ° C. After the dropping, stir for another 1 hour,
Then, the refrigerant was removed and the mixture was stirred until it returned to room temperature. After being poured into ice water, the separated organic layer was washed with 1N hydrochloric acid water and washed with water, and then ether was removed to obtain 7.1 g of 4-n-heptyloxy-3-fluorophenylboric acid. 4-n-heptyloxy-3-fluorophenylboric acid (1.5 g) obtained in Example 2 and the compound (c) obtained in Example 2 (2.5 g) were added to triethylamine (60 ml) in a catalyst, tetrakistriphenylphosphine palladium (0) (139 mg), triphenyl Using 139 mg of phosphine, the mixture was heated under reflux for 10 hours in a nitrogen atmosphere. After completion of the reaction, triethylamine was removed, water was added, and the mixture was extracted with toluene. Wash the toluene layer with 1N hydrochloric acid,
After washing with water, the product was purified by a silica gel column and then recrystallized three times with ethanol to give a white crystalline compound of the present invention, No. 2 in Table 2. 1.8 g of 24 compounds are obtained. IR (cm ^-1 ) 2922.0 2854.0 1528.0 1470.0 1307.0 1270.0 1129.0 866.0 804.0 NMR (ppm) 0.84 to 0.95 (m, 6H) 1.18 to 1.43 (m, 20H) 1.43 to 1.55 (m, 2H) 1.65 to 1.78 (m, 2H ) 1.78 to 1.91 (m, 2H) 2.77 (t, 2H) 4.06 (t, 2H) 7.03 (t, 1H) 7.33 to 7.48 (m, 3H) 7.60 to 7.67 (m, 2H) 7.82 (m, 2H) 7.93 (s, 1H) ¹⁹ F-NMR -58.6 (t, 1F) Elemental analysis value Theoretical value (%) Actual value (%) C: 83.20 C: 83.07 H: 9.45 H: 9.53 F: 3.99 F: 4.13

Example 7 In Table 3, No. Preparation of Compound 43 Into 30 ml of diethyl ether solution containing 3.8 g of trimethyl borate cooled to -30 ° C or lower, 4- (9-decenyloxy) -3-fluorobromobenzene (the compound is 4-bromo-2 60 ml of an ether solution of Grignard reagent prepared from 10 g of an alkali metal salt of fluorophenol and a p-toluenesulfonic acid ester of 9-decen-1-ol were added dropwise below -30 ° C. After completion of dropping, the mixture was stirred for 1 hour as it was, and then the refrigerant was removed and the mixture was stirred until the temperature returned to room temperature. After being poured into ice water, the separated organic layer was washed with 1N hydrochloric acid water, washed with water, and then the ether was removed to give 4- (9-decenyloxy) -3-
8.1 g of fluorophenyl boric acid was obtained. 4- (9-decenyloxy) -3-fluorophenylboric acid (1.6 g) obtained in Example 1 and the compound (e) obtained in Example 4 (2.0 g)
Was heated to reflux in a nitrogen atmosphere for 10 hours using tetrakistriphenylphosphine palladium (0) (124 mg) and triphenylphosphine (124 mg) as catalysts in triethylamine (60 ml). After completion of the reaction, triethylamine was removed, water was added, and the mixture was extracted with toluene. The toluene layer was washed with 1N hydrochloric acid water, washed with water, purified with a silica gel column, and then recrystallized three times from ethanol to give a white crystalline compound of the present invention, No. 3 in Table 3. 1.8 g of 43 compound are obtained. IR (cm ^-1 ) 2924.0 2854.0 1618.0 1531.0 1468.0 1435.0 1313.0 1272.0 1131.0 1017.0 911.0 870.0 803.0 NMR (ppm) 0.90 (t, 3H) 1.22 to 1.58 (m, 18H) 1.62 to 1.78 (m, 2H) 1.78 to 1.92 (m , 2H) 2.00 to 2.10 (m, 2H) 2.78 (t, 2H) 4.08 (t, 2H) 4.91 to 5.07 (m, 2H) 5.76 to 5.90 (m, 1H) 7.05 (t, 1H) 7.32 to 7.50 (m , 3H) 7.58 to 7.68 (m, 2H) 7.82 (t, 2H) 7.94 (d, 1H) ¹⁹ F-NMR -58.6 (dd, 1F) Elemental analysis value Theoretical value (%) Actual value (%) C: 83.54 C: 83.39 H: 9.07 H: 9.23 F: 4.01 F: 3.90

Example 8 No. 1 in Table 3 Preparation of compound 46 Into 30 ml of a diethyl ether solution containing 4.3 g of trimethyl borate cooled to -30 ° C or lower, 4-n-nonyloxy-3-fluorobromobenzene (the compound is 4-bromo-3-fluoro) is added. 60 ml of an ether solution of a Grignard reagent prepared from 10 g of an alkali metal salt of phenol obtained by reacting n-nonyl bromide) was added dropwise at -30 ° C or lower. After completion of dropping, the mixture was stirred for 1 hour as it was, and then the refrigerant was removed and the mixture was stirred until the temperature returned to room temperature. After being poured into ice water, the separated organic layer was washed with 1N hydrochloric acid water, washed with water, and then the ether was removed to obtain 7.6 g of 4-n-nonyloxy-2-fluorophenylboric acid. 4-n-nonyloxy-2-fluorophenyl boric acid (1.4 g) obtained in Example 1 and 2.0 g of the compound (b) obtained in Example 1 were mixed with 60 ml of triethylamine in a catalyst of tetrakistriphenylphosphine palladium (0) 115 mg and triphenylphosphine. Using 115 mg, the mixture was heated under reflux for 10 hours in a nitrogen atmosphere. After completion of the reaction, triethylamine was removed, water was added, and the mixture was extracted with toluene. Wash the toluene layer with 1N hydrochloric acid,
After washing with water, the product was purified by a silica gel column, and then recrystallized three times with ethanol to give a white crystalline compound of the present invention, No. 3 in Table 3. 1.6 g of 46 compound was obtained. IR (cm ^-1 ) 2922.0 2854.0 1626.0 1516.0 1468.0 1317.0 1238.0 1166.0 1108.0 832.0 NMR (ppm) 0.83 to 0.94 (m, 6H) 1.18 to 1.53 (m, 24H) 1.64 to 1.88 (m, 4H) 2.78 (t, 2H) 3.99 (t, 2H) 6.68 to 6.82 (m, 2H) 7.35 (d, 1H) 7.43 (t, 1H) 7.58 to 7.65 (m, 2H) 7.80 (t, 2H) 8.93 (s, 1H) ¹⁹ F-NMR -39.9 (t, 1F) Elemental analysis value Theoretical value (%) Actual value (%) C: 83.26 C: 83.40 H: 9.59 H: 9.60 F: 3.88 F: 3.97

Example 9 No. 1 in Table 3 Preparation of 48 compounds 6-Bromo-2-naphthol 50g and copper (I) cyanide 24.1
g was dissolved in 80 ml of anhydrous dimethylformamide and heated under reflux for 6 hours. After cooling, an aqueous solution prepared by dissolving 100 g of ferric chloride and 25 g of 35% hydrochloric acid in 200 ml of water was added, and the mixture was stirred at 60 ° C for 20 minutes. After cooling to room temperature, it was extracted twice with 300 ml of ether. After washing the organic phase with water, ether was removed. The obtained solid was recrystallized from toluene to obtain 26.2 g of brown 6-cyano-2-naphthol. 26.2 g of 6-cyano-2-naphthol obtained in Step 2 was dissolved in 200 ml of dehydrated ethanol and cooled to 5 ° C or lower on an ice bath.
57 g of hydrochloric acid gas was blown in at 15 ° C. or lower with stirring, and the mixture was stirred as it was for 2 hours on an ice bath. The mixture was further stirred at room temperature for 4 hours and then left overnight. After standing, ethanol was removed by an aspirator to obtain a brown solid. This solid was directly used for the next reaction without purification. 200 ml of anhydrous ethanol saturated with ammonia gas was added dropwise to the solid obtained in above under ice-cooling, and the mixture was stirred as it was for 1 hour. After further stirring at room temperature for 2 hours, the mixture was left overnight.
Ethanol was removed and the resulting solid was washed with ether to obtain 22 g of amidine hydrochloride as a brown solid. To the ethanol solution of sodium ethoxide prepared from 200 ml of absolute ethanol and 4.7 g of metallic sodium, add 15.0 g of amidine hydrochloride obtained in 1 and 15.2 g of commercially available α-n-heptyloxy-β-dimethylaminoacrolein, and
The mixture was heated under reflux for 0 hours. After the reaction was completed, ethanol was removed, water was added, the mixture was washed with ether, and the aqueous layer was acidified with 1N hydrochloric acid. The resulting precipitate was filtered and dried, and then recrystallized from methylene chloride / hexane to obtain 9.3 g of the compound (g) represented by the following chemical formula 26.

[0058]

[Chemical formula 26]

To 100 ml of a dry pyridine solution containing 5.0 g of the compound (g) obtained in (4), 4.6 g of trifluoromethanesulfonic anhydride was added dropwise at 10 ° C. or lower. After completion of the dropping, the mixture was stirred for 1 hour as it was and further stirred at room temperature for 24 hours. After completion of the reaction, the mixture was poured into 300 ml of ice water and extracted with toluene.
The toluene layer was washed with 1N hydrochloric acid water and washed with water, and then toluene was removed. Recrystallization from hexane gave 5.9 g of a solid compound (h) represented by the following Chemical formula 27.

[0060]

[Chemical 27]

2.5 g of the compound (h) obtained in 1 and 1-decyne
0.9 g of the resulting mixture was heated under reflux for 8 hours in a nitrogen atmosphere using 20 mg of dichlorobistriphenylphosphine palladium (II), 40 mg of copper (I) iodide and 40 mg of triphenylphosphine as catalysts in 60 ml of triethylamine. After completion of the reaction, triethylamine was removed, water was added, and the mixture was extracted with toluene. The toluene layer was washed with 1N hydrochloric acid water, washed with water, and then recrystallized from ethanol to obtain 2.1 g of a compound (i) represented by the following Chemical Formula 28 as a solid.

[0062]

[Chemical 28]

1.0 g of the compound (i) obtained in (1) was hydrogenated under hydrogen atmosphere using 5% palladium carbon in 100 ml of ethanol. After confirming that the absorption of hydrogen disappeared, the catalyst was removed by filtration and the solvent was removed. The obtained solid was recrystallized three times with ethanol to give white crystals of the compound of the present invention. 48 compounds 0.4g
Got IR (cm ^-1 ) 2924.0 2856.0 1549.0 1441.0 1284.0 1009.0 905.0 812.0 NMR (ppm) 0.82 to 0.93 (m, 6H) 1.20 to 1.43 (m, 20H) 1.43 to 1.52 (m, 2H) 1.64 to 1.77 (m, 2H) 1.77 to 1.89 (m, 2H) 2.75 (t, 2H) 4.09 (t, 2H) 7.35 (dd, 1H) 7.62 (s, 1H) 7.86 (t, 2H) 8.42 (dd, 1H) 8.48 (s, 2H) 8.81 (d, 1H) Elemental analysis value Theoretical value (%) Actual value (%) C: 80.87 C: 80.63 H: 9.56 H: 9.63 N: 6.09 N: 6.21

Example 10 No. 3 in Table 3 Preparation of Compound 52 Into 30 ml of diethyl ether solution containing 4.0 g of trimethyl borate cooled to -30 ° C or lower, 4-n-decyloxybromobenzene (this compound is an alkali metal salt of 4-bromophenol and n 60 ml of an ether solution of Grignard reagent prepared from 10 g of decyl bromide) was added dropwise below -30 ° C. After completion of dropping, the mixture was stirred for 1 hour as it was, and then the refrigerant was removed and the mixture was stirred until the temperature returned to room temperature. After pouring it into ice water, separate the organic layer
After washing with 1N hydrochloric acid and washing with water, ether was removed to obtain 7.5 g of 4-n-decyloxyphenyl boric acid. 1.5 g of the 4-n-decyloxyphenyl boric acid obtained in Example 2 and 2.0 g of the compound (d) obtained in Example 3 were mixed with triethylamine.
In 60 ml, tetrakistriphenylphosphine palladium (0) 119 mg and triphenylphosphine 119 mg were used as catalysts in a nitrogen atmosphere and heated under reflux for 10 hours. After completion of the reaction, triethylamine was removed, water was added, and the mixture was extracted with toluene. The toluene layer was washed with 1N hydrochloric acid water, washed with water, purified with a silica gel column, and then recrystallized three times from ethanol to give a white crystalline compound of the present invention, No. 3 in Table 3. There were obtained 1.4 g of the compound of 52. IR (cm ^-1 ) 2922.0 2854.0 1607.0 1520.0 1502.0 1473.0 1286.0 1257.0 890.0 839.0 818.0 NMR (ppm) 0.83 to 0.92 (m, 6H) 1.17 to 1.42 (m, 22H) 1.42 to 1.54 (m, 2H) 1.55 to 1.86 (m , 4H) 2.77 (t, 2H) 3.99 (t, 2H) 7.34 (dd, 1H) 7.46 (d, 1H) 7.64 (d, 2H) 7.68 (dd, 1H) 7.80 (t, 2H) Elemental analysis theoretical value (%) Actual value (%) C: 86.44 C: 86.59 H: 10.17 H: 10.00

The phase transition temperatures of the compounds obtained in Examples 1 to 10 are shown in Table 4 below.

[0066]

[Table 4] The symbols in Table 4 above have the following meanings. Cry; Crystal phase Sc; Smectic C phase S _A ; Smectic A phase Nem; Nematic phase Iso; Isotropic liquid phase ・; Phase exists-; Phase does not exist (); Represents monotropic phase

[0067]

By using the liquid crystal compound of the present invention as a component of the Sc * liquid crystal composition, the orientation of this composition can be improved and the contrast ratio can be increased.
Further, among the liquid crystal compounds of the present invention, those which do not exhibit other smectic phases in the low temperature region are compounds which can be used in the Sc * liquid crystal composition to broaden the temperature range of the Sc * phase. Therefore, the compounds and compositions of the present invention are useful as liquid crystal materials used in liquid crystal display devices.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁵ Identification number Reference number within the agency FI Technical display location C09K 19/34 7457-4H (72) Inventor Kuniyoshi Yoshio 1-11, Hitotsubashi-honcho, Higashiyama-ku, Kyoto Sanyo Kasei Kogyo Co., Ltd. (72) Inventor Tatsuro Yanagi 1-11, Hitotsubashi-honcho, Higashiyama-ku, Kyoto City Sanyo Kasei Kogyo Co., Ltd.

Claims (2)

[Claims] 1. The following general formula: [In the formula, R ¹ represents an alkyl group or an alkenyl group having 1 to 18 carbon atoms, A represents a group selected from the following formulas 2 to 6, NAP represents a 2,6-naphthylene group, and R ² represents Represents an alkyl group having 1 to 18 carbon atoms]. [Chemical 2] [Chemical 3] [Chemical 4] [Chemical 5] [Chemical 6] 2. A liquid crystal composition comprising a mixture of a plurality of compounds and containing at least one liquid crystal compound according to claim 1.