JPH0726264A - Ferroelectric liquid crystal composition, element containing the composition and method for driving the element - Google Patents

Abstract

PURPOSE:To obtain a composition which can give a ferroelectric liquid crystal element having good alignability, high contrast, low driving voltage, high-speed response and high capacity by mixing a specified compound with a specified optically active compound. CONSTITUTION:This composition is prepared by mixing a compound of formula I (wherein the group of formula II is a group of formula III, IV or V; R<1> and R<2> are each a linear or branched 1-15C alkyl; X<1> and X<2> are each a single bond or O) with an optically active compound of formula VI [wherein R<3> and R<4> are the same as R<1> and R<2>; X<3> is a single bond, O, COO, OCO or OCOO; X<4> is O or OCO; Y<1> is O, COO or CH2O; A<1> and B<1> are each a (halogen-, cyano- or fluoroalkyl-substituted) six-membered ring group; Z<1> is COO, OCO, CidenticalC, CH2O or OCH2; and (n) is 0 or 1]. A ferroelectric liquid crystal element prepared by using this composition has good alignability, high contrast, low driving voltage, high-speed response and high capacity.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a ferroelectric liquid crystal composition, a device using the same and a method for driving the same.

[0002]

2. Description of the Related Art In recent years, a ferroelectric liquid crystal display device utilizing a chiral smectic phase (NA Clark, et al., Appl.
Phys, Lett., 36, 899 (1980)) are promising.
This display method uses a ferroelectric liquid crystal such as a chiral smectic C phase and a chiral smectic I phase. Since it is a method of utilizing a memory property, a large display capacity can be achieved by a simple matrix drive. It also has the advantage of a wide viewing angle. 2
It is highly promising as an element for large-capacity display such as 000 × 2000 lines.

[0003]

Although there are various problems to be solved for practical use of a ferroelectric liquid crystal display, it is very important to find a method for realizing high contrast in simple matrix driving. Is. To solve this problem, Surguy et al. (PWH Surguy
et al., Ferroelectrics, 122, 63 (1991).), and a ferroelectric liquid crystal display using this method has been prototyped (PW Ross, Proc. SID, 217 (199).
2).). Hereinafter, this method will be described in detail.

An ordinary ferroelectric liquid crystal material having a non-negative dielectric anisotropy exhibits a .tau.-V characteristic as shown in FIG. That is, τ (pulse width required for memory) monotonically decreases as the voltage increases. On the other hand, in the case of a ferroelectric liquid crystal material having a negative dielectric anisotropy, a τ-V characteristic showing a minimum value (τ-Vmin) as shown in FIG. 1B is obtained. Surguy et al. (PWH Surguy et
al., Ferroelectrics, 122, 63 (1991).) reported a driving method shown in FIG. 2 as a driving method using this characteristic. The principle of this driving method is briefly shown in FIG. First, when a voltage of | Vs−Vd | is applied, the memory state of the ferroelectric liquid crystal element is switched, and when | Vs + Vd | which is a voltage higher than this voltage is applied, and | Vd | lower than this voltage is applied. When it does, it is a method of not switching.

However, one of the major problems of this method is that the driving voltage is high. Ross et al. (PW Ross,
Proc. SID, 217 (1992).), The driving voltage of the prototype ferroelectric liquid crystal display is 55V. Since the price of the IC driver for driving the ferroelectric liquid crystal display increases as the voltage increases, the high driving voltage becomes a major factor of cost increase. In order to manufacture a ferroelectric liquid crystal display at a reasonable price, it is necessary to drive it using a general-purpose IC driver that is not so expensive, and it is absolutely necessary to set the drive voltage to 40 V or less. . The reason why a high driving voltage is required at present is the voltage value (Vmin) that gives the minimum value in the τ-V characteristic.
It is because Vmi is high, and Vmi is required to drive below 40V.
It is necessary to develop a ferroelectric liquid crystal material with n around 30V. Surguy et al. (PWH Surguy et al., Fe
According to rroelectrics, 122, 63 (1991).), Vmin is given by the following equation.

[0006]

[Equation 1]

Here, Emin is the minimum value of the electric field strength, d is the cell thickness, Ps is the spontaneous polarization, Δε is the dielectric anisotropy, and θ is the tilt angle. As can be seen from this equation, a large negative dielectric anisotropy and a small spontaneous polarization are required to obtain a low Vmin value. On the other hand, since the response speed of the ferroelectric liquid crystal is related to the spontaneous polarization, it becomes difficult to obtain a high-speed response when the spontaneous polarization is reduced. Therefore, it has been difficult to simultaneously satisfy high-speed response and low-voltage driving. In order to solve this problem, a low viscosity material having a negative dielectric anisotropy is required as a liquid crystal material. Of course, in order to obtain a good ferroelectric liquid crystal device, the following conditions that have been conventionally said must be satisfied.

(1) To exhibit a smectic C phase in a wide temperature range around room temperature. (2) In order to obtain good orientation and bistability, IAC (Is
otropic-Smectic A- Smectic C) or INAC (Isotropi
A liquid crystal material exhibits a phase sequence of c-Nematic-Smectic A-Smectic C). (3) The spiral pitch of the chiral nematic phase and the chiral smectic C phase is sufficiently longer than the cell thickness. (4) It has good chemical stability and light stability. Further, the tilt angle, the refractive index, the specific resistance, etc. may be optimized as necessary.

The present invention has been made under such circumstances, and provides a fast response ferroelectric liquid crystal composition exhibiting a low Vmin value, and a ferroelectric liquid crystal device using the same. .

[0010]

According to the present invention, the general formula (I) is used.

[0011]

[Chemical 6] At least one compound represented by the general formula (II)

[0012]

[Chemical 7](However, R³And R^FourMay be the same or different
A straight or branched alkyl having 1 to 15 carbon atoms
Represents a group, X³Is a single bond, -O-, -COO
Represents-, -OCO- or -OCOO-, and X^FourIs -O
Represents -or-OCO-, and Y¹Is -O-, -COO-
Or -CH₂Represents O-, A¹And B¹ Is halogen,
Cyano group, 6-containing group which may be substituted with fluorine-containing alkyl group
Represents a membered ring group, Z¹Is a single bond, -COO-, -OCO
-, -C≡C-, -CH₂O- or -OCH₂-Show
And n represents 0 or 1. ) Or a compound represented by
General formula (III)

[0013]

[Chemical 8](However, R^FiveAnd R⁶May be the same or different
A straight or branched alkyl having 1 to 15 carbon atoms
Represents a group, X^FiveIs a single bond, -O-, -COO
Represents-, -OCO- or -OCOO-, and X⁶Is -O
Represents -or-OCO-, and Y²Is -O-, -COO-
Or -CH₂Represents O-, A²And B² Is halogen,
Cyano group, 6-containing group which may be substituted with fluorine-containing alkyl group
Represents a membered ring group, Z²Is a single bond, -COO-, -OCO
-, -C≡C-, -CH₂O- or -OCH₂-Show
And n represents 0 or 1. ) Contains a compound
A ferroelectric liquid crystal composition characterized by
It

The compound represented by the general formula (I) has two fluorine groups in the direction perpendicular to the long axis of the molecule, and since the two fluorine groups are bonded to the same phenyl ring, a large negative Dielectric anisotropy of can be expected. Further, since it does not have a highly viscous bonding group such as an ester group and two phenyl groups are bonded by an acetylene bond, low viscosity can be expected. In addition, the smectic C phase can be stably expressed by appropriately selecting R ¹ and R ² .

The linear or branched alkyl group having 1 to 15 carbon atoms which may be the same or different and which can be used for R ¹ and R ² includes methyl, ethyl, propyl, butyl, pentyl, hexyl and heptyl. , Octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, 1-methylpentyl, 1-methylhexyl, 1-methylheptyl, 1-methyloctyl, 1-methylnonyl, 1-methyldecyl, 3-methylpentyl, 4-methylhexyl, 5-methylheptyl,
6-methyloctyl, 7-methylnonyl, 8-methyldecyl, 3-ethylpentyl, 4-ethylhexyl, 5-
Examples include ethylheptyl, 6-ethyloctyl, 7-ethylnonyl, 8-ethyldecyl and the like.

The hydrogen atom of these groups is a fluorine atom, a chlorine atom, --CN, --OCH ₃ , --OCF ₃ or --OC.
OC _n H _{2n + 1} (where n is 1 to 15 and preferably 1 to 10)
May be replaced by The compounds represented by the general formulas (II) and (III) have various stereoisomers, all of which can be used in the present invention, and the stereoisomers may be mixed. As the combination of R ³ and R ⁴ , and R ⁵ and R ⁶ , the same combinations as the groups used for R ¹ and R ² can be used.

In the above general formulas (I) to (III), R ³
To R ⁶ are alkyl groups having 3 to 10 carbon atoms, X ³ and X ⁵ are single bonds or —O—, and Y ¹ and Y ² are —COO— or —CH _2.
—, Z ¹ and Z ² are preferably a single bond, —COO—, —C≡C— or —CH ₂ —. The compound represented by the general formula (I) can be combined with various compounds to form a liquid crystal composition. Compounds particularly suitable for combination include compounds represented by the following general formula (IV).

[0018]

[Chemical 9] (However, R ⁷ and R ⁸ represent the same or different linear or branched alkyl groups having 1 to 15 carbon atoms, X ⁷ and X ⁸ each independently represent a single bond,
Represents O- or -COO-. )

The compound represented by the above general formula (IV) has one fluorine group in the direction perpendicular to the long axis of the molecule and can be expected to have a negative dielectric anisotropy. Although the magnitude of the negative dielectric anisotropy cannot be expected as much as that of the compound represented by the general formula (I), this compound also exhibits a smectic C phase stably by appropriately selecting R ⁷ and R ⁸ . be able to. Therefore,
By combining with the compound represented by the general formula (I), the temperature range, phase series, orientation and the like of the smectic C phase can be improved. As the combination of R ⁷ and R ^8, the same combination as the groups used for R ¹ and R ² can be used. Of these, X ⁷ is preferably —O—,
⁸ is preferably -O- and -COO-, most preferably -COO-.

Here, an example of a method for synthesizing the compounds represented by the general formulas (I) to (IV) is shown below. First, general formula (I)
The compound represented by is synthesized, for example, as follows.

[0021]

[Chemical 10] (In the formula, R ¹ and R ² are the same as above.) That is, 2,3-difluorophenol is halogenated and then reacted with an alkyl halide to give 2,3-difluorophenol.
Difluoro-4-halogeno-alkoxybenzenes can be obtained.

4-Alkoxy-2,3-difluoro-4-halogeno-alkoxybenzene was reacted with 3-methyl-1-butyn-3-ol in the presence of a Pd catalyst and then treated with alkali to give 4-alkoxy-2,2-difluoro-4-halogeno-alkoxybenzene. 3-difluorophenylacetylene can be obtained. 4-alkoxy-2,3-difluorophenylacetylene is reacted with 4-alkoxy-halogenobenzene in the presence of a Pd catalyst to give a compound of the general formula (I
The compounds of A) can be obtained.

[0023]

[Chemical 11] (In the formula, R ¹ and R ² are the same as above.)

That is, after reacting 2-halogeno-5-nitropyridine with 1-alkyne in the presence of a Pd catalyst, Pd /
2-Alkyl-5-aminopyridine can be obtained by hydrogenation with C. 2-Alkyl-5-aminopyridine is diazotized, then iodinated, and 4-alkoxy-2,3- which is a raw material of the general formula (IA) in the presence of Pd catalyst.
The compound of general formula (IB) can be obtained by reacting with difluorophenylacetylene.

[0025]

[Chemical 12] (In the formula, R ¹ and R ² are the same as above.)

That is, 2-bromo-5-nitropyridine can be obtained by hydrogenating 2-bromo-5-nitropyridine with platinum oxide, diazotizing and then iodizing. 2-Bromo-5-alkylpyridine can be obtained by reacting 2-bromo-5-iodopyridine with 1-alkyne in the presence of a Pd catalyst and then hydrogenating using platinum oxide. 2-Bromo-5-alkylpyridine as P
The compound of the general formula (IC) can be obtained by reacting with 4-alkoxy-2,3-difluorophenylacetylene which is a raw material of the general formula (IA) in the presence of the catalyst d.

Next, the compound represented by the general formula (II) is
For example, they are synthesized as follows. (1) In the case of Y ¹ = -COO-, X ⁴ = -OCO-, and n = 0, the following general formula (D-1) R ³ -X ³ -B ¹ -COHal (D-1) (formula Wherein R ³ , X ³ , and B ¹ are the same as above, Hal represents a halogen such as chlorine, bromine, or iodine) and a compound represented by the following general formula (D-2)

[0028]

[Chemical 13] (In the formula, TBS represents a t-butyldimethylsilyl group.) By reacting with a compound represented by the following general formula (D-3)

[0029]

[Chemical 14] (In the formula, R ³ , X ³ , B ¹ and TBS are the same as above.), And thus a compound represented by the formula can be obtained. This reaction is carried out in a solvent such as toluene, benzene or methylene chloride in the presence of an organic base such as pyridine or triethylamine.
It can be performed at a temperature of 20 to 80 ° C.

Next, the obtained compound represented by the general formula (D-3) is desilylated to obtain the general formula (D-4).

[0031]

[Chemical 15] (In the formula, R ³ , X ³ and B ¹ are the same as the above.) To obtain a compound. This desilylation reaction can be carried out by various methods. For example, it can be carried out at 0 to 50 ° C. in a tetrahydrofuran solvent using tetra-n-butylammonium fluoride as a catalyst. In addition,
The compound represented by the general formula (D-4) is a mixture of two kinds of diastereomers, but can be easily separated by silica gel column chromatography.

The compound represented by the general formula (D-4) is represented by the general formula (D-5) R ⁴ -COHal (D-5) (wherein R ⁴ and Hal are the same as above). The desired compound represented by the general formula (II) can be obtained by reacting with the compound represented. This reaction can be carried out in the presence of an organic base such as pyridine or triethylamine in a solvent such as toluene, benzene or methylene chloride at a temperature of -20 to 80 ° C. ^{(2) Y 1 = -COO-,} X 4 = -O-, when n = 0, the following general formula ^{(D-6) R 11 -OH} (D-6) ( wherein, R ¹¹ is a carbon A linear or branched alkyl group having 1 to 15 carbon atoms, an alkenyl group having 2 to 15 carbon atoms or 7 carbon atoms
The aralkyl groups of 10 are shown. ) And a compound represented by the above general formula (D-2), the following general formula (D-7)

[0033]

[Chemical 16] (In the formula, R ¹¹ and TBS are the same as above.), And thus a compound represented by the formula can be obtained. This reaction can be carried out without solvent or in a solvent such as tetrahydrofuran at 0 to 50 ° C. using, for example, paratoluenesulfonic acid as an acid catalyst. Next, the obtained compound represented by the general formula (D-7) is desilylated to obtain the general formula (D-8).

[0034]

[Chemical 17] (In the formula, R ¹¹ is the same as above.). This desilylation reaction can be carried out by various methods. For example, it can be carried out at 0 to 50 ° C. in a tetrahydrofuran solvent using tetra-n-butylammonium fluoride as a catalyst.

Then, it is represented by the general formula (D-9) R ⁴ -Z (D-9) (wherein R ⁴ is the same as defined above, and Z represents chlorine, bromine, iodine or a tosyl group). By reacting the compound represented by the general formula (D-8) with the compound represented by the general formula (D-10)

[0036]

[Chemical 18] (In the formula, R ¹¹ and R ⁴ are the same as above.), And thus a compound represented by the formula can be obtained. This reaction has the general formula (D-
It can be carried out by reacting the compound represented by 8) with a base such as alkali metal hydride, sodium hydroxide or potassium hydroxide, and then adding the compound represented by the general formula (D-9).

Furthermore, the compound represented by the general formula (D-11) is obtained by reacting the obtained compound represented by the general formula (D-10) in the presence of an acid catalyst.

[0038]

[Chemical 19] (In the formula, R ⁴ is the same as the above.), And thus a compound represented by the formula can be obtained. This reaction can be carried out in the presence of water in a solvent such as tetrahydrofuran, ether or toluene at 0 to 100 ° C. using, for example, paratoluenesulfonic acid, hydrochloric acid or sulfuric acid as an acid catalyst.

The desired compound represented by the general formula (II) is obtained by reacting the compound represented by the general formula (D-11) with the compound represented by the general formula (D-1). Can be obtained. This reaction is carried out in a solvent such as an organic base such as pyridine or triethylamine at -20 to 8
It can be carried out at a temperature of 0 ° C. _{^{(3) Y 1 = -CH 2}} O-, X 4 = -OCO-, when n = 0, the following general formula ^{(D-12) R 3 -X} 3 -B 1 -CH 2 Z (D- 12) (wherein R ³ , X ³ , B ¹ and Z are the same as above) and a compound represented by the general formula (D-2) are reacted with Formula (D-13)

[0040]

[Chemical 20] (In the formula, R ³ , X ³ , B ¹ and TBS are the same as above.), And thus a compound represented by the formula can be obtained. This reaction can be carried out at 0 to 100 ° C. in a solvent such as tetrahydrofuran, diethyl ether, methylene chloride, toluene using paratoluenesulfonic acid, hydrochloric acid, sulfuric acid or the like as an acid catalyst.

Next, the obtained compound represented by the general formula (D-13) is desilylated to obtain the general formula (D-14).

[0042]

[Chemical 21] (In the formula, R ³ , X ³ and B ¹ are the same as the above.) To obtain a compound. This desilylation reaction can be carried out by various methods. For example, it can be carried out at 0 to 50 ° C. in a solvent of tetrahydrofuran using tetra-n-butylammonium fluoride as a catalyst. In addition,
The compound represented by the general formula (D-14), which is a mixture of two types of diastereomers, can be easily separated by silica gel column chromatography. By reacting the compound represented by the general formula (D-14) with the compound represented by the general formula (D-5), an intended compound represented by the general formula (II) can be obtained. You can This reaction can be carried out in the presence of an organic base such as pyridine or triethylamine in a solvent such as toluene, benzene or methylene chloride at a temperature of -20 to 80 ° C.

(4) Y ¹ = -CH ₂ O-, X ⁴ = -O-,
When n = 0, the compound represented by the general formula (D-14) is reacted with the compound represented by the general formula (D-9) to give the desired general formula (II). A compound represented by can be obtained. In this reaction, the compound represented by the general formula (D-14) is reacted with a base such as alkali metal hydride, sodium hydroxide or potassium hydroxide, and then the compound represented by the general formula (D-9). Can be obtained by adding.

(5) Z ¹ = -COO-, Y ¹ = -COO
In the case of −, X ⁴ = −O−, and n = 1, the general formula (D-1
^{5) Bz-O-B 1} -CO-Hal (D-15) ( wherein, Bz represents a benzyl group, Hal, B ¹ is the same as defined above, and.) And a compound represented by the above general formula ( D-
By reacting the compound represented by 11) with the compound of the general formula (D-16)

[0045]

[Chemical formula 22] (In the formula, Bz, B ¹ and R ⁴ are the same as above.), And thus a compound represented by the formula can be obtained. This reaction is carried out in the presence of an organic base such as pyridinetriethylamine in a solvent such as toluene, benzene or methylene chloride at −20.
It can be performed at a temperature of -80 ° C.

Then, the obtained compound represented by the general formula (D-16) is debenzylated to obtain the general formula (D-17).

[0047]

[Chemical formula 23] (In the formula, R ⁴ and B ¹ are the same as the above.) A compound represented by the formula is obtained. This debenzylation reaction can be carried out by various methods. For example, palladium carbon (P
d / C) It can be carried out by hydrogenolysis under normal pressure using an alcohol solvent such as methanol, ethanol, propanol or the like or acetic acid in the presence of a catalyst.

The compound represented by the general formula (D-17) and the general formula (D-18) R ³ -X ³ -A ¹ -CO-Hal (D-18) (in the formula, R ³ , X ³ , A ¹ and Hal are the same as those mentioned above.), Whereby the desired compound represented by the general formula (II) can be obtained.
This reaction can be carried out in the presence of an organic base such as pyridine or trimethylamine in a solvent such as toluene, benzene or methylene chloride at a temperature of -20 to 80 ° C.

Next, the compound represented by the general formula (III) is
For example, they are synthesized as follows. (1) Z ² = single bond, in the case of Y ² = -COO-, n = 1, the formula ^{(E-1) R 5 -X} 5 -A 2 -B 2 -COHal (E-1) ( In the formula, R ⁵ , X ⁵ , A ² , B ² , and Hal are the same as the above), and a compound represented by the general formula (E-2)

[0050]

[Chemical formula 24] (In the formula, R ⁶ and X ⁶ are the same as above.) The compound represented by the general formula (III) can be obtained by reacting the compound. This reaction is carried out with an organic base such as
In the presence of pyridine, trimethylamine, etc., toluene,
In a solvent such as benzene or methylene chloride, -20 to 80 ° C
Can be performed at temperatures of.

(2) Z ² = single bond, Y ² = -CH ₂ O-,
if n = 1, formula ^{(E-3) R 5 -X} 5 -A 2 -B 2 -CH 2 -Z (E-3) ( ^{wherein, R 5, X 5, A} 2, B ² is the same as the above, and Z is a chlorine, bromine, iodine or tosyl group.) The above general formula (E-2) is reacted with a compound represented by the above general formula (E-2). A compound of formula (III) can be obtained. This reaction is carried out by reacting a compound represented by the general formula (E-2) with a base represented by alkali metal hydride, sodium hydroxide or potassium hydroxide, and then adding a compound represented by the general formula (E-3). You can

(3) Z ² = -COO-, Y ² = -COO
-, if n = 1, formula (E-4) Bz-O -B 2 -CO-Hal (E-4) ( wherein, B ^2, Bz, Hal is as defined above.) The compound represented by the formula (E-5) is reacted with the compound represented by the formula (E-2).

[0053]

[Chemical 25] ^{(Wherein, B 2, X 6, R} 6, Bz are as defined above.) To obtain a compound represented by. This reaction is carried out with an organic base such as
In the presence of pyridine, trimethylamine, etc., toluene,
It can be carried out in a solvent such as benzene or methylene chloride at a temperature of -20 to 80 ° C.

Then, the benzyl group in the obtained compound of the general formula (E-5) is eliminated by a conventional method to give the following general formula (E
-6)

[0055]

[Chemical formula 26] (In the formula, B ² , X ⁶ , and R ⁶ are the same as the above.), And a compound represented by the formula is produced. This debenzylation reaction is carried out, for example, in the presence of a Pd / C catalyst, methanol, ethanol,
It can be carried out by hydrogenolysis under normal pressure using an alcohol solvent such as propanol or acetic acid.

Further, the obtained compound of the general formula (E-6) was converted into the following general formula (E-7) R ⁵ —X ⁵ —A ² —CO—Hal (E-7) (wherein R ⁵ , X ⁵ , A ² , and Hal have the same meanings as described above.
The compound of I) can be obtained. This reaction is carried out in the presence of an organic base such as pyridine or trimethylamine,
-20 in a solvent such as toluene, benzene, methylene chloride
It can be performed at a temperature of -80 ° C.

(4) Z ² = -COO-, Y ² = -CH ₂ O
-, if n = 1, formula (E-8) ThpO-B 2 -CH 2 -Z (E-8) ( wherein, Thp represents tetrahydropyranyl group, B ^2,
Z is the same as above. ), The compound represented by the general formula (E-2) is reacted with the compound represented by the general formula (E-2).

[0058]

[Chemical 27] ^{(Wherein, B 2, X 6, R} 6, Thp are as defined above.) To obtain a compound represented by. This reaction has the general formula (E-2)
It can be carried out by reacting a compound represented by the formula (4) with a base represented by alkali metal hydride, sodium hydroxide or potassium hydroxide, and then adding the compound of the general formula (E-8).

Next, Thp in the obtained compound of the general formula (E-9) is eliminated by a conventional method to give the following general formula (E-1)
0)

[0060]

[Chemical 28] (In the formula, B ² , X ⁶ and R ⁶ are the same as those described above.). The elimination of the tetrahydropyranyl group can be carried out in the presence of an acid catalyst such as hydrochloric acid, sulfuric acid and paratoluenesulfonic acid, using a solvent such as ether, tetrahydrofuran and chloroform.

Then, the obtained compound of the general formula (E-10) is reacted with the compound represented by the general formula (E-7) to obtain the compound of the general formula (III). . This reaction can be carried out in the presence of an organic base such as pyridine or trimethylamine in a solvent such as toluene, benzene or methylene chloride at a temperature of -20 to 80 ° C.

(5) Z ² = -COO-, Y ² = -O-, n
In the case of = 1, the compound represented by the general formula (E-11) ThpO-B ² -Hal (E-11) (wherein B ² , Thp and Hal are the same as above) is the above. The compound represented by the general formula (E-2) is reacted with the compound represented by the general formula (E-12) below.

[0063]

[Chemical 29] ^{(Wherein, B 2, X 6, R} 6, Thp are as defined above.) To obtain a compound represented by. This reaction has the general formula (E-2)
After the base represented by alkali metal hydride, sodium hydroxide or potassium hydroxide is allowed to act on the compound of (1), cuprous iodide is used as a catalyst under the reflux condition of dimethylformamide, diethyl sulfoxide, etc. It can be carried out by reacting the compound represented by -11).

Next, the tetrahydropyranyl group in the compound represented by the general formula (E-12) thus obtained can be eliminated by a conventional method to give the following general formula (E-13).

[0065]

[Chemical 30] (In the formula, B ² , X ⁶ , and R ⁶ are the same as the above.) A compound represented by the formula is obtained. The elimination of the tetrahydropyranyl group can be carried out in the presence of an acid catalyst such as hydrochloric acid, sulfuric acid and paratoluenesulfonic acid, using a solvent such as ether, tetrahydrofuran and chloroform.

By reacting the compound of the general formula (E-13) obtained here with the compound of the general formula (E-7), the compound of the general formula (III) can be obtained. This reaction can be carried out in the presence of an organic base such as pyridine or trimethylamine in a solvent such as toluene, benzene or methylene chloride at a temperature of -20 to 80 ° C.

(6) Z ² = -CH ₂ O-, Y ² = -COO
-, if n = 1, the compound represented by general formula (E-6) and the following formula ^{(E-14) R 5 -X} 5 -A 2 -CH 2 -Z (E-14) (In the formula, R ⁵ , X ⁵ , A ² , and Z are the same as the above.) The compound of the general formula (III) can be obtained by reacting the compound. This reaction has the general formula (E-
This can be carried out by reacting the compound of 6) with a base represented by alkali metal hydride, sodium hydroxide or potassium hydroxide, and then reacting with a compound represented by the general formula (E-14).

(7) Z ² = -OCH _2- , Y ² = -COO
- in the case of n = 1 is represented by the general formula _{(E-15) ZCH 2 -B} 2 -COHal (E-15) ( wherein, B ^2, Z, Hal are as defined above.) By reacting a compound represented by the above general formula (E-2) with the following general formula (E-16)

[0069]

[Chemical 31] (In the formula, B ² , X ⁶ , R ⁶ and Z are the same as the above.) A compound represented by the formula is obtained. This reaction can be carried out in the presence of an organic base such as pyridine or trimethylamine in a solvent such as toluene, benzene or methylene chloride at a temperature of -20 to 80 ° C.

[0070] Then, the following formula ^{(wherein, R 5, X 5, A} 2 are as defined above.) (E-17) R 5 -X 5 -A 2 -OH (E-17) in Table The compound of the general formula (III) can be obtained by reacting the compound described above with the compound (E-16).
This reaction is carried out by reacting a compound represented by the general formula (E-17) with a base represented by alkali metal hydride, sodium hydroxide or potassium hydroxide, and then reacting the compound by the general formula (E-16).
It can be performed by adding a compound represented by.

Further, the compound represented by the general formula (IV) is
For example, it can be obtained by the method described in JP-A-3-223225. Needless to say, compounds other than the compounds represented by the general formulas (I) to (IV) may be appropriately added when preparing a practical ferroelectric liquid crystal composition. In order for the produced ferroelectric liquid crystal composition to have a low Vmin, it is necessary to reduce the spontaneous polarization to some extent. From this viewpoint, the spontaneous polarization is preferably 100 μC / m ² or less.

The addition amount of each of the compounds constituting the ferroelectric liquid crystal composition of the present invention is 10 to 99.9% by weight, particularly preferably 50 to 8% by weight for the compound represented by the general formula (I).
0% by weight, the compound represented by the general formula (II) or (III) is 0.1 to 20% by weight, particularly preferably 0.5 to
It is 2.0% by weight. Here, the general formula (II) or (II
When the amount of the compound represented by I) is more than 20% by weight, the added compound may cause practical problems such as crystallization in the ferroelectric liquid crystal composition and a decrease in the maximum temperature of the smectic C phase. However, if the amount added is less than 0.1% by weight, a sufficient effect on the response speed cannot be obtained.

When the compound represented by the general formula (IV) is combined, the addition amount of the general formula (IV) is 1 to 80% by weight, particularly preferably 5 to 30% by weight. If it is more than 80% by weight, practical problems such as crystallization of the added compound in the ferroelectric liquid crystal composition often occur.

When the general formula (I) is used alone or the general formulas (I) and (IV) are combined, τ min
If it is not possible to drive at high speed because it is large, it may not be possible to drive at low voltage even if it can be driven at high speed, but by adding a predetermined amount of the compound of the general formula (II) or (III) as described above, Such a problem does not occur, and a liquid crystal composition that can be driven at low voltage and high speed can be obtained.

Next, the ferroelectric liquid crystal device of the present invention will be described with reference to FIG. FIG. 4 is a sectional view showing an example of a transmissive liquid crystal element using the ferroelectric liquid crystal composition of the present invention. In the figure, 1 and 2 are insulating substrates, 3 and 4 are conductive films,
Reference numeral 5 is an insulating film, 6 is an orientation control layer, 7 is a sealant, 8 is a ferroelectric liquid crystal, and 9 is a polarizing plate.

A transparent substrate is used as the insulating substrates 1 and 2, and a glass substrate is usually used. On this insulating substrate, InO ₃ , SnO ₂ , ITO (Indium
-TinOxide) and other transparent electrodes 3 and 4 having a predetermined pattern are formed of a conductive thin film. The thickness of the transparent electrode is 50
~ 200 nm is preferred. In the case of the reflection type, an opaque insulating substrate is used for either 1 or 2.

An insulating film 5 is formed on this transparent electrode. The thickness of this insulating film is preferably 50 to 200 nm.
As the insulating film, for example, an inorganic thin film such as SiO ₂ , SiN _x , Al ₂ O ₃ or the like, an organic thin film such as polyimide, photoresist resin or polymer liquid crystal can be used.
When the insulating film is an inorganic thin film, vapor deposition, sputtering,
It can be formed by a CVD (Chemical Vapar Deposition) method, a solution coating method, or the like. Further, in the case of an organic thin film, a solution in which an organic substance is dissolved or a precursor solution thereof is used to apply by a spinner coating method, a dip coating method, a screen printing method, a roll coating method, or the like, and a predetermined curing condition ( It can be formed by a method of hardening by heating, light irradiation, etc.), or by a vapor deposition method, a sputtering method, a CVD method, or an LB (Langmuir-Blodgett) method. However, this insulating film can be omitted in some cases.

An orientation control layer 6 is formed on the insulating film 5 with a film thickness of 10 to 100 nm. However, when the insulating film 5 is omitted, the orientation control layer is directly formed on the conductive films 3 and 4. An inorganic or organic layer can be used for this orientation control layer. Silicon oxide can be used for the inorganic orientation control layer, and a known method can be applied to the film formation method thereof. For example, an oblique vapor deposition method, a rotary vapor deposition method, or the like can be used. Nylon, polyvinyl alcohol, polyimide or the like can be used for the organic orientation control layer, and the upper layer is usually rubbed. In addition, polymer liquid crystal, L
Alignment using the B film, alignment by a magnetic field, alignment by the spacer edge method, and the like are also possible. In addition, SiO ₂ ,
It is also possible to use a method in which SiN _x or the like is formed by a vapor deposition method, a sputtering method, a CVD method, or the like, and rubbing is performed thereon.

Next, the two insulating substrates are bonded together, and liquid crystal is injected to form a ferroelectric liquid crystal element. 4 has been described as a switching element having one pixel, the ferroelectric liquid crystal and the liquid crystal element of the present invention can be applied to a display device having a large capacity matrix, and in this case, the schematic plan view of FIG. As shown, the wirings of the upper and lower substrates can be used in combination in a matrix type.

Next, a preferred orientation method of the present invention will be described. Although there are various methods for aligning the ferroelectric liquid crystal element, the rubbing method is most preferable in consideration of mass production. When using the rubbing method, there are mainly three methods of parallel rubbing, anti-parallel rubbing, and one-side rubbing. Parallel rubbing is a rubbing method in which upper and lower substrates are rubbed and the rubbing directions are parallel. Anti-parallel rubbing is a rubbing method in which upper and lower substrates are rubbed and the rubbing directions are anti-parallel. One-side rubbing is a method of rubbing only one of the upper and lower substrates.

Among them, the single rubbing has a drawback that it is difficult to form a good uniform orientation. This is because the ferroelectric liquid crystal material is an optically active liquid crystal, and if the liquid crystal material has a nematic phase on the high temperature side, the nematic phase inevitably has a helical structure, and due to the helical structure, uniform alignment is achieved. Is difficult to obtain. Also, if the ferroelectric liquid crystal material does not have a nematic phase on the high temperature side, this problem does not occur, but on the contrary, a smectic phase will appear directly from the isotropic liquid state, which is also a good uniform This is a cause of difficulty in obtaining orientation.

Next, antiparallel rubbing is used. In the case of this method, linear defects are likely to occur along the rubbing direction, and uniform alignment is also difficult to obtain. The most effective method for obtaining uniform alignment is to combine a ferroelectric liquid crystal material having an INAC phase series with a parallel rubbing cell. In this case, although a helical structure exists in the nematic phase, since the molecular orientation directions are regulated from both sides of the upper and lower substrates, uniform orientation is easily obtained in the nematic phase, and from that state, the smectic A phase,
If the temperature is lowered to the chiral smectic C phase, the alignment with the direction of the layer normal can be easily obtained.

However, even in the parallel rubbing ferroelectric liquid crystal device, the number of alignment states generated in the chiral smectic C phase is not one at all. There are two reasons why the entire surface is not uniform. One is related to the bending of the smectic layer. It is well known that a ferroelectric liquid crystal cell exhibits a bent layer structure (chevron layer structure), and as shown in FIG. 6, two regions can exist. Kannabe et al.
They are named 1, C2. The other is uniform (U) and twist (T). The uniform is an orientation showing the extinction position, and the twist is an orientation not showing the extinction position.
Koden et al., Jpn. J. Appl. Phys., 30,
L1823 (1991).) Is a C1U in a parallel rubbing ferroelectric liquid crystal cell using a high pretilt alignment film.
(C1-uniform), C1T (C1-twist),
It is reported that three C2 orientations were obtained. As a result of further detailed study by the inventors, in the parallel rubbing ferroelectric liquid crystal cell, C1U, C1T, C2U,
It was found that there are four orientation states of C2T.
FIG. 7 shows the molecular orientation in these orientation states.

Comparing four alignment states obtained in a ferroelectric liquid crystal cell having a negative dielectric anisotropy, C1T and C2T have no extinction position and black state is not black, so that good contrast cannot be obtained. In addition, the C1U orientation is difficult to switch, and even if the C1U orientation is switched, the orientation changes to an orientation in which C2 states are mixed during driving. In contrast, the present inventors have found that the C2U state gives good contrast.

The appearance of the C1 and C2 orientations is related to the pretilt, but the C2 state can occur in the pretilt angle range of 0 to 15 °. When the pretilt angle is high, the C2 state has only one state exhibiting an extinction position, as reported by Mukaiden et al., Which is rather preferable. However, C1 tends to be easier than C2 as the pretilt angle increases, so the pretilt angle is preferably 10 ° or less. However, when the pretilt angle is low, C2 is likely to occur. On the contrary, when the pretilt angle is too low, there is a drawback that C2T is likely to occur. In that sense, the particularly preferable range of the pretilt angle is 5 to 10 °.

Next, the driving method will be described. Of course, the drive waveform (A) shown in FIG. 2 can be used, but a drive method as shown in FIG. 8 is conceivable. These driving methods are driving methods capable of partial rewriting, and are preferable driving methods for producing a display having a large display capacity of 2000 × 2000 lines using this ferroelectric liquid crystal element. In the drive waveform (B) shown in FIG. 8, the waveform (1) is applied to the scan electrode coupled to the pixel to be rewritten and the waveform (2) is applied to the other scan electrodes. As the waveform of the signal electrode,
The waveform (3) is applied to the pixels to be rewritten, and the waveform (4) is applied to the pixels not to be rewritten. The voltage waveforms applied to the pixels are represented by (5) to (8), and when the voltages of waveforms (6) to (8) when not rewritten are applied, τ is equal,
Since the amounts of transmitted light are almost equal, a good display without flicker can be obtained. Further, the drive waveform (C) shown in FIG. 9 (see International Publication No. WO 92/02925) is 0 in one time slot.
In contrast to the driving method (A) using a V portion and a main pulse portion that is not 0 V in one time slot, the main pulse width can be changed to an arbitrary length, and the voltage application timing is set between the electrodes. This is one of the preferable driving methods because the line address time can be shortened by reducing the line address time.

As a very preferable example of the use of the ferroelectric liquid crystal composition of the present invention, parallel rubbing, C2
-While the uniform orientation and the specific driving method have been described, it goes without saying that the present invention is not limited to this and is applicable to other types of ferroelectric liquid crystal devices and driving methods. .

[0088]

【Example】

Synthesis Example 1 A compound represented by the general formula (I) was synthesized. The structures and transition temperatures of the compounds are shown in Tables 1 and 2.

[0089]

[Table 1]

[0090]

[Table 2]

(Synthesis Method) (1) Synthesis of Compound 4. (1-a) First, 45.00 g of 2,3-difluorophenol was dissolved in 250 ml of chloroform, and 55.40 g of bromine dissolved in chloroform was added dropwise under ice cooling. After completion of dropping, the mixture was stirred at room temperature for a while and then washed with water to remove chloroform. Then, by recrystallizing four times with hexane, 14.30 g of 2,3-difluoro-4-bromophenol
Got

(1-b) Next, 7.00 g of 2,3-difluoro-4-bromophenol was dissolved in 50 ml of dimethyl sulfoxide, and 1.47 g of sodium hydroxide and n-nonyl bromide 6.
80 g was added and the mixture was stirred at room temperature for 7 days. After completion of the reaction, the reaction mixture was extracted with hexane, washed with water, and then hexane was removed to obtain 9.86 g of oily 2,3-difluoro-4-bromo-nonyloxybenzene.

(1-c) Next, 1.98 g of 2,3-difluoro-4-bromo-nonyloxybenzene and 0.60 g of 3-methyl-1-butyn-3-ol were added to 50 ml of triethylamine and dichlorobistris was used as a catalyst. Phenylphosphine palladium (II)
30 mg, copper (I) iodide 8 mg, triphenylphosphine 60
The mixture was heated under reflux for 12 hours under nitrogen atmosphere using mg. After completion of the reaction, triethylamine was removed and then extracted with hexane. The hexane layer was washed with 1N (N) hydrochloric acid, washed with water, and then removed under reduced pressure with hexane to obtain 1.87 g of the following oily compound (a).

[0094]

[Chemical 32]

(1-d) Next, 1.87 g of the above compound (a)
Was dissolved in 100 ml of anhydrous toluene, 0.47 g of sodium hydroxide powder was added, and the mixture was heated under reflux for 1 hour. After the reaction was completed, toluene was removed and the mixture was extracted with ether. After washing with water and removing the ether under reduced pressure, the following oily compound (b)
Obtained 1.22 g.

[0096]

[Chemical 33]

(1-e) Next, 5.00 g of 2-bromo-5-nitropyridine and 3.95 g of 1-nonine were added to 50 ml of triethylamine.
In the medium, 204 mg of dichlorobistriphenylphosphine palladium (II) and 51 mg of copper (I) iodide were used as catalysts and reacted at room temperature under a nitrogen atmosphere for 24 hours. After completion of the reaction, triethylamine was removed and the mixture was extracted with hexane. The hexane layer was washed with hydrochloric acid water, washed with water, dissolved in toluene, treated with a silica gel column, and recrystallized from methanol to obtain 3.18 g of the following compound (c).

[0098]

[Chemical 34]

(1-f) Next, 3.18 g of the above compound (c)
0.50 g of 5% palladium carbon was added as a catalyst to 30 ml of ethanol containing and hydrogenation and reduction were carried out by stirring at room temperature under a hydrogen atmosphere at normal pressure. After confirming that the absorption of hydrogen disappeared, the catalyst was removed by filtration, and then ethanol was removed under reduced pressure to obtain 2.78 g of oily 2-n-nonyl-5-aminopyridine.

(1-g) Next, 2.78 g of 2-n-nonyl-5-aminopyridine was added to 100 ml of water containing 11.00 g of 36% hydrochloric acid.
Was added and cooled to 5 ° C. or lower. In it, separately prepared sodium nitrite aqueous solution (sodium nitrite 0.72 g,
Water (5 ml) was added dropwise at 5 ° C or lower. After completion of dropping, the mixture was further stirred for 1 hour and then potassium iodide aqueous solution (potassium iodide) was added.
8.60 g and 10 ml of water) were added, and the mixture was gradually returned to room temperature and stirred until the generation of nitrogen was stopped. After the reaction was completed, the solution was made alkaline with sodium hydroxide and extracted with hexane. The hexane layer was washed with water, washed with aqueous sodium hydrogen sulfite and washed with water, and then treated with a silica gel column to obtain 2.51 g of oily 2-n-nonyl-5-iodopyridine.

(1-h) Furthermore, 2.47 g of 2-n-nonyl-5-iodopyridine and 2.09 g of the compound (b) obtained in (1-d) were mixed with 50 ml of triethylamine in a catalyst of dichlorobisphenylphosphine palladium ( II) 26 mg and copper (I) iodide 7 mg
Was stirred at room temperature for 4 hours under a nitrogen atmosphere. After completion of the reaction, triethylamine was removed and the mixture was extracted with toluene. After washed with 1N (N) hydrochloric acid, washed with water, purified with a silica gel column, and recrystallized four times with ethanol to obtain 1.87 g of compound 4.

Compound 1, compound 2, compound 3, compound 5, compound 6 and compound 7 were synthesized in the same manner as in the above compound 4. The physical properties of the obtained compound are shown below. Compound 1 ¹ H-NMR (proton magnetic resonance method); δ (ppm) 0.83 to 0.91 (m, 6H), 1.22 to 1.50 (m, 20H), 1.65 to 1.86
(m, 4H) 2.77 (t, 2H), 4.03 (t, 2H), 6.69 (dt, 1H), 7.12 (d, 1H) 7.17 (dt, 1H), 7.70 (dd, 1H), 8.66 (d, ^{1H) 19 F-NMR; δ} (ppm) -57.64 (dd, 1F), - 82.69 (dd, 1F) compound 2 ¹ H-NMR (proton magnetic resonance); δ (ppm) 0.84~0.92 ( m, 6H ), 1.22 ~ 1.51 (m, 24H), 1.65 ~ 1.88 (m, 4
H) 2.79 (t, 2H), 4.06 (t, 2H), 6.71 (dt, 1H), 7.12〜7.21 (m, 2
H) 7.71 (dd, 1H), 8.68 (d, 1H) ¹⁹ F-NMR; δ (ppm) -57.84 (dd, 1F),-82.69 (dd, 1F) Compound 3 ¹ H-NMR (proton magnetic resonance method ); Δ (ppm) 0.83 to 0.91 (m, 6H), 1.22 to 1.49 (m, 26H), 1.66 to 1.86 (m, 4
H) 2.78 (t, 2H), 4.03 (t, 2H), 6.70 (dt, 1H), 7.12 (d, 1H) 7.18 (dt, 1H), 7.70 (dd, 1H), 8.67 (d, 1H) ¹⁹ F-NMR; δ (ppm) -57.85 (dd, 1F), - 82.69 (dd, 1F) compound 4 ¹ H-NMR (proton magnetic resonance); δ (ppm) 0.82~0.90 ( m, 6H), 1.22 ~ 1.49 (m, 24H), 1.65 ~ 1.86 (m, 4
H) 2.78 (t, 2H), 4.03 (t, 2H), 6.70 (dt, 1H), 7.10 to 7.19 (m, 2
H) 7.70 (dd, 1H), 8.65 (d, 1H) ¹⁹ F-NMR; δ (ppm) -57.84 (dd, 1F),-82.68 (dd, 1F) Compound 5 ¹ H-NMR (proton magnetic resonance method ); Δ (ppm) 0.82 to 0.91 (m, 6H), 1.22 to 1.50 (m, 26H), 1.65 to 1.85 (m, 4
H) 2.78 (t, 2H), 4.03 (t, 2H), 6.69 (dt, 1H), 7.10 ~ 7.20 (m, 2
H) 7.70 (dd, 1H), 8.65 (d, 1H) ¹⁹ F-NMR; δ (ppm) -57.84 (dd, 1F),-82.69 (dd, 1F) Compound 6 ¹ H-NMR (proton magnetic resonance method ); Δ (ppm) 0.82 to 0.91 (m, 6H), 1.22 to 1.50 (m, 24H), 1.66 to 1.88 (m, 4
H) 2.78 (t, 2H), 4.03 (t, 2H), 6.70 (dt, 1H), 7.11 ~ 7.20 (m, 2
H) 7.70 (dd, 1H), 8.67 (d, 1H) ¹⁹ F-NMR; δ (ppm) -57.84 (dd, 1F),-82.68 (dd, 1F) Compound 7 ¹ H-NMR (proton magnetic resonance method ); Δ (ppm) 0.82 to 0.90 (m, 6H), 1.22 to 1.50 (m, 28H), 1.63 to 1.86 (m, 4)
H) 2.78 (t, 2H), 4.03 (t, 2H), 6.70 (dt, 1H), 7.11 ~ 7.20 (m, 2
H) 7.70 (dd, 1H), 8.66 (d, 1H) ¹⁹ F-NMR; δ (ppm) -57.84 (dd, 1F),-82.69 (dd, 1F) (2) Synthesis of compound 8 (2-a ) First, a reaction was carried out in the same manner as in the above (1-a) to (1-d) to synthesize 1.22 g of the above compound (b).

(2-b) Next, 1.00 g of platinum oxide was added as a catalyst to 200 ml of ethanol containing 20.00 g of 2-bromo-5-nitropyridine, and the mixture was reduced by stirring at room temperature under a hydrogen atmosphere at atmospheric pressure. I went. After confirming that the absorption of hydrogen disappeared, the catalyst was removed by filtration, and then ethanol was removed under reduced pressure to give 2-bromo-5-aminopyridine 19.3.
I got 4g.

(2-c) Next, 15.34 g of 2-bromo-5-aminopyridine was added to 500 ml of water containing 77.00 g of 36% hydrochloric acid, and the mixture was cooled to 5 ° C or lower. Separately prepared sodium nitrite aqueous solution (sodium nitrite 5.04 g, water
35 ml) was added dropwise at 5 ° C or lower. After completion of dropping, the mixture was further stirred for 1 hour, and then potassium iodide aqueous solution (potassium iodide 6
(0.00 g, 70 ml of water) was added, and the mixture was gradually returned to room temperature and stirred until the generation of nitrogen was stopped. After the reaction was completed, the solution was made alkaline with sodium hydroxide and extracted with hexane. The hexane layer was washed with water, washed with aqueous sodium hydrogen sulfite and washed with water, and then treated with a silica gel column to obtain 18.45 g of oily 2-bromo-5-iodopyridine.

(2-d) Next, 11.20 g of 2-bromo-5-iodopyridine and 6.36 g of 1-nonine were added to 100 ml of triethylamine.
Among them, 137 mg of dichlorobistriphenylphosphine palladium (II) and 34 mg of copper (I) iodide were used as catalysts, and the mixture was stirred at room temperature for 7 hours under a nitrogen atmosphere. After completion of the reaction, the mixture was extracted with hexane and washed with water, and then hexane was removed under reduced pressure.
Then, it was treated with a silica gel column to obtain 9.98 g of the following compound (d).

[0106]

[Chemical 35]

(2-e) Using 9.98 g of the compound (d) in place of 2-bromopyridine, hydrogenation was carried out in the same manner as in (2-b) above to give 2-bromo-5- n-
8.23 g of nonylpyridine was obtained. (2-f) Furthermore, 1.31 g of 2-nonyl-5-n-nonylpyridine
And 1.29 g of the compound (b) obtained in (2-a) in 50 ml of triethylamine, using 16 mg of dichlorobisphenylphosphine palladium (II), 4 mg of copper (I) iodide and 24 mg of triphenylphosphine as a catalyst, a nitrogen atmosphere The mixture was heated under reflux for 3 hours. After completion of the reaction, triethylamine was removed and the mixture was extracted with toluene. After being washed with 1N (N) hydrochloric acid, washed with water, purified with a silica gel column, and recrystallized four times with ethanol to obtain 1.15 g of compound 8.

Compound 9 was synthesized in the same manner as the synthesis method of compound 8 above. The physical properties of the obtained compound are shown below. Compound 8 ¹ H-NMR (proton magnetic resonance method); δ (ppm) 0.83 to 0.92 (m, 6H), 1.22 to 1.62 (m, 26H), 1.77 to 1.87
(m, 2H) 2.62 (t, 2H), 4.06 (t, 2H), 6.72 (dt, 1H), 7.22 ~ 7.27 (m, 1
H) 7.43 to 7.51 (m, 2H), 8.46 (d, 1H) ¹⁹ F-NMR; δ (ppm) -57.22 (dd, 1F), -82.64 (dd, 1F) Compound 9 ¹ H-NMR (proton magnetic Resonance method); δ (ppm) 0.83 to 0.92 (m, 6H), 1.22 to 1.68 (m, 26H), 1.77 to 1.88
(m, 2H) 2.62 (t, 2H), 4.06 (t, 2H), 6.72 (dt, 1H), 7.22 ~ 7.29 (m, 1
H) 7.43 to 7.50 (m, 2H), 8.44 (d, 1H) ¹⁹ F-NMR; δ (ppm) -57.22 (dd, 1F), -82.62 (dd, 1F) (3) Synthesis of compound 14.

(3-a) First, 45.00 g of 2,3-difluorophenol was dissolved in 250 ml of chloroform, and bromine was added.
What melt | dissolved 55.40 g in chloroform was dripped under ice-cooling. After completion of dropping, the mixture was stirred at room temperature for a while and then washed with water to remove chloroform. Then, by recrystallizing four times with hexane, 2,3-difluoro-4-bromophenol was obtained.
14.30 g were obtained.

(3-b) Next, 7.00 g of 2,3-difluoro-4-bromophenol was dissolved in 50 ml of dimethyl sulfoxide, and 1.47 g of sodium hydroxide and n-nonyl bromide 6.
80 g was added and the mixture was stirred at room temperature for 7 days. After completion of the reaction, the reaction mixture was extracted with hexane, washed with water, and then hexane was removed to obtain 9.86 g of oily 2,3-difluoro-4-bromo-nonyloxybenzene.

(3-c) Next, 1.98 g of 2,3-difluoro-4-bromo-nonyloxybenzene and 0.60 g of 3-methyl-1-butyn-3-ol were added to dichlorobistris as a catalyst in 50 ml of triethylamine. Phenylphosphine palladium (II)
30 mg, copper (I) iodide 8 mg, triphenylphosphine 60
The mixture was heated under reflux for 12 hours under nitrogen atmosphere using mg. After completion of the reaction, triethylamine was removed and then extracted with hexane. The hexane layer was washed with 1N (N) hydrochloric acid, washed with water, and then removed under reduced pressure with hexane to obtain 1.87 g of the following oily compound (a).

[0112]

[Chemical 36]

(3-d) Next, 1.87 g of the above compound (a)
Was dissolved in 100 ml of anhydrous toluene, 0.47 g of sodium hydroxide powder was added, and the mixture was heated under reflux for 1 hour. After the reaction was completed, toluene was removed and the mixture was extracted with ether. After washing with water and removing the ether under reduced pressure, the following oily compound (b)
Obtained 1.22 g.

[0114]

[Chemical 37]

(3-e) Further, 2.31 g of the compound (b) obtained in (3-d) and 2.89 g of 2,3-difluoro-4-iodo-n-nonyloxybenzene obtained in (3-b). In 50 ml of triethylamine, 26 mg of dichlorobisphenylphosphine palladium (II) and 7 mg of copper (I) iodide were used as catalysts, and the mixture was stirred at room temperature for 10 hours under a nitrogen atmosphere. After completion of the reaction, triethylamine was removed and the mixture was extracted with toluene. After washed with 1N (N) hydrochloric acid, washed with water, purified with a silica gel column, and recrystallized four times with ethanol to obtain 1.92 g of Compound 14.

Compound 10, compound 11, compound 12, compound 13, compound 15, compound 16, and compound 17 were synthesized in the same manner as in the above compound 14. The physical properties of the obtained compound are shown below. Compound 10 ¹ H-NMR (proton magnetic resonance method); δ (ppm) 0.83 to 0.91 (m, 6H), 1.23 to 1.50 (m, 20H), 1.71 to 1.85 (m, 4)
H) 3.94 (t, 2H), 4.02 (t, 2H), 6.67 (dt, 1H), 6.84 (d, 2H) 7.13 (dt, 1H), 7.44 (d, 2H) ¹⁹ F-NMR; δ (ppm ) -58.37 (dd, 1F),-83.02 (dd, 1F) Compound 11 ¹ H-NMR (proton magnetic resonance method); δ (ppm) 0.83 to 0.91 (m, 6H), 1.23 to 1.50 (m, 22H) , 1.70 ~ 1.85 (m, 4
H) 3.95 (t, 2H), 4.03 (t, 2H), 6.68 (dt, 1H), 6.83 (d, 2H) 7.15 (dt, 1H), 7.43 (d, 2H) ¹⁹ F-NMR; δ (ppm ) -58.36 (dd, 1F),-83.02 (dd, 1F) Compound 12 ¹ H-NMR (proton magnetic resonance method); δ (ppm) 0.83 to 0.92 (m, 6H), 1.22 to 1.51 (m, 24H) , 1.71 to 1.85 (m, 4
H) 3.94 (t, 2H), 4.02 (t, 2H), 6.68 (dt, 1H), 6.85 (d, 2H) 7.14 (dt, 1H), 7.43 (d, 2H) ¹⁹ F-NMR; δ (ppm ) -58.36 (dd, 1F), -83.01 (dd, 1F) Compound 13 ¹ H-NMR (proton magnetic resonance method); δ (ppm) 0.83 to 0.92 (m, 6H), 1.22 to 1.50 (m, 20H) , 1.71 to 1.86 (m, 4
H) 3.93 (t, 2H), 4.02 (t, 2H), 6.68 (dt, 1H), 6.84 (d, 2H) 7.13 (dt, 1H), 7.44 (d, 2H) ¹⁹ F-NMR; δ (ppm ) -58.37 (dd, 1F),-83.03 (dd, 1F) Compound 14 ¹ H-NMR (proton magnetic resonance method); δ (ppm) 0.83 to 0.91 (m, 6H), 1.22 to 1.50 (m, 24H) , 1.72 ~ 1.85 (m, 4
H) 3.94 (t, 2H), 4.02 (t, 2H), 6.68 (dt, 1H), 6.86 (d, 2H) 7.14 (dt, 1H), 7.44 (d, 2H) ¹⁹ F-NMR; δ (ppm ) -58.36 (dd, 1F), -83.01 (dd, 1F) Compound 15 ¹ H-NMR (proton magnetic resonance method); δ (ppm) 0.83 to 0.92 (m, 6H), 1.22 to 1.50 (m, 22H) , 1.72 ~ 1.86 (m, 4
H) 3.95 (t, 2H), 4.02 (t, 2H), 6.68 (dt, 1H), 6.83 (d, 2H) 7.13 (dt, 1H), 7.44 (d, 2H) ¹⁹ F-NMR; δ (ppm ) -58.36 (dd, 1F),-83.02 (dd, 1F) Compound 16 ¹ H-NMR (proton magnetic resonance method); δ (ppm) 0.83 to 0.92 (m, 6H), 1.22 to 1.51 (m, 24H) , 1.70 ~ 1.85 (m, 4
H) 3.95 (t, 2H), 4.03 (t, 2H), 6.68 (dt, 1H), 6.84 (d, 2H) 7.13 (dt, 1H), 7.45 (d, 2H) ¹⁹ F-NMR; δ (ppm ) -58.36 (dd, 1F), -83.01 (dd, 1F) Compound 17 ¹ H-NMR (proton magnetic resonance method); δ (ppm) 0.85 to 0.92 (m, 6H), 1.22 to 1.51 (m, 24H) , 1.71 to 1.86 (m, 4
H) 3.93 (t, 2H), 4.03 (t, 2H), 6.68 (dt, 1H), 6.85 (d, 2H) 7.13 (dt, 1H), 7.44 (d, 2H) ¹⁹ F-NMR; δ (ppm ) -58.37 (dd, 1F),-83.02 (dd, 1F)

Synthesis Example 2 The compounds represented by the general formulas (II) and (III) were synthesized. The structures of the compounds are shown in Table 3.

[0118]

[Table 3]

(Synthesis Method) (1) Synthesis of (2S, 5S, 6S) -Tetrahydro-6-trifluoromethyl-5-hexyloxy-2- (4 "-hexyloxybiphenyl-4'-carbonyloxy) pyran (Compound 18) (1-a) First, (5S, 6S) -tetrahydro-5-
6.4 g (21 mmol) of t-butyldimethylsiloxy-6-trifluoromethyl-2-hydroxypyran was dissolved in 40 ml of hexanol, 0.1 g of paratoluenesulfonic acid was added, and the mixture was reacted at room temperature for 18 hours. The reaction solution was directly purified by silica gel column chromatography to obtain 8.0 g (21 mmol) of acetal compound.

(1-b) Next, 8.0 g of the acetal compound obtained in (1-a) was dissolved in 20 ml of tetrahydrofuran, and a solution of tetra-n-butylammonium fluoride in 1.0 mol / liter of tetrahydrofuran 10 was added. Add milliliters, 0 ° C for 1 hour, room temperature 4
The reaction was allowed for 0 hours. Distilled water was added to this reaction solution to stop the reaction, and the reaction product was extracted with ether. Then, the extract was washed with saturated saline and dried over anhydrous magnesium sulfate. After the ether was distilled off under reduced pressure, the residue was separated and purified by silica gel column chromatography to obtain (2R, 5S, 6
S) Alcohol compound having asymmetric carbon 3.0 g (1
(1 mmol) and 2.3 g (8.0 mmol) of an alcohol compound having asymmetric carbons of (2S, 5S, 6S) were obtained.

(1-c) Next, a solution of 0.52 g (2.1 mmol) of the alcohol compound (2R, 5S, 6S) having an asymmetric carbon obtained in (1-b) in tetrahydrofuran (5 ml). Was added dropwise to a solution of 0.10 g (2.5 mmol) of 60% sodium hydride in tetrahydrofuran (3 ml) at 0 ° C. under a nitrogen atmosphere.
Stir for 0 minutes. Then 1-bromohexane 0.35
Milliliters (2.5 milliliters) and dimethyl sulfoxide (2 milliliters) were added and the reaction was carried out at room temperature for 18 hours. Distilled water was added to this reaction solution to stop the reaction, and the reaction product was extracted with ether. Then, the extract was washed with saturated saline and dried over anhydrous magnesium sulfate.
After distilling off the ether under reduced pressure, the residue was purified by silica gel column chromatography to give 0.72 g of an ether compound.
(2.0 mmol) was obtained.

(1-d) Next, 0.52 g (1.5 mmol) of the ether compound obtained in (1-c) was dissolved in 10 ml of tetrahydrofuran, 10 ml of distilled water and 2 ml of concentrated sulfuric acid were added, and 50 Reflux for hours. The reaction was stopped by adding a 1N aqueous potassium hydroxide solution, and the reaction product was extracted with ether. Then, the extract was washed with saturated saline and dried over anhydrous magnesium sulfate. After the ether was distilled off under reduced pressure, the residue was purified by silica gel column chromatography to obtain the hemiacetal compound 0.
37 g (1.4 mmol) were obtained.

(1-e) Next, 0.29 g (1.1 mmol) of the hemiacetal compound obtained in (1-d) and 0.49 g of 4'-hexyloxy-4-biphenylcarboxylic acid chloride (1. Anhydrous pyridine was added to a toluene solution of (6 mmol) and reacted at room temperature. Distilled water was added to this reaction solution to stop the reaction, and the reaction product was extracted with ether. Then, it was washed with saturated saline and dried over anhydrous magnesium sulfate. After the ether was distilled off under reduced pressure, the residue was separated and purified by silica gel column chromatography to obtain the target compound (2S, 5S, 6S) -tetrahydro-6-trifluoromethyl-5-hexyloxy- (4 "-hexyloxybiphenyl-). 0.34 g (0.6 mmol) of 4'-carboxyloxy) pyran was obtained.

The physical properties of the obtained compound are shown below. Molecular _{formula: C 31 H 41 F 3 O} 5 1 H-NMR ( proton nuclear magnetic resonance); δ (ppm) 0.81~0.99 ( m, 6H), 1.19~1.68 (m, 15H), 1.70~1.93
(m, 4H) 2.12 to 2.25 (m, 1H), 2.29 to 2.42 (m, 3H), 3.40 to 3.65
(m, 3H) 4.01 (t, J = 6.6Hz, 2H), 6.14 (dd, J = 2.7, 6.6Hz, 1H) 6.98 (d, J = 8.8Hz, 2H), 7.56 (d, J = 8.8Hz , 2H) 7.62 (d, J = 8.5Hz, 2H), 8.10 (d, J = 8.4Hz, 2H) ¹⁹ F-NMR (reference: CFCl ₃ ); δ (ppm) -74.98 (d, J = 7.4Hz ) IR (cm ^-1 ) 1730, 1605, 1495, 1265, 1180, 1080 Mass spectrometry m / e (M ⁺ ) Calculated value 550.2906 Measured value 550.2914 [α] ²⁶ _D = + 10.7 ° (C (concentration) = 1.03 , Solvent: chloroform)

(2) (2R, 5S, 6S) -Tetrahydro-6-trifluoromethyl-2-hexyloxy-5
Synthesis of-(4 "-hexyloxybiphenyl-4'-carbonyloxy) pyran (Compound 21)

(2-a) First, under a nitrogen atmosphere, furan 1
3.6 g (200 mmol) of tetrahydrofuran 15
In addition to 0 ml, 133 ml of a 1.5 mol / l n-butyllithium hexane solution (200
(Mmol) was added dropwise at -20 ° C and the reaction was carried out for 1 hour. Next, 21.7 g (200 mmol) of trimethylsilyl chloride was added dropwise, and the mixture was stirred at -20 ° C for 1 hour. 1.5 mol / l n-butyllithium hexane solution 133
Add milliliters (200 mmol) and add 1 at -20 ° C.
After reacting for 2 hours, 28.4 g (200 mmol) of ethyl trifluoroacetate was added dropwise at -78 ° C, and the mixture was stirred at -78 ° C for 1 hour.
The reaction was continued for another hour at room temperature. The reaction was stopped by adding 3N hydrochloric acid to the reaction solution, and the mixture was extracted with ethyl acetate. Then, it was washed successively with a saturated sodium hydrogen carbonate solution and saturated saline, and dried over anhydrous magnesium sulfate.
Ethyl acetate was distilled off under reduced pressure to obtain a crude product of furan derivative.

(2-b) Next, 2.3 g (60 mmol) of sodium borohydride was added to 100 ml of dry ethanol, and the crude furan derivative product obtained in the above reaction was added dropwise at 0 ° C. over 30 minutes. . After reacting for 2 hours at room temperature, ethanol was distilled off under reduced pressure, 3N hydrochloric acid was added to stop the reaction, and the mixture was extracted with ethyl acetate. Then
The mixture was washed successively with saturated sodium hydrogen carbonate solution and saturated brine, and dried over anhydrous magnesium sulfate. After distilling off ethyl acetate under reduced pressure, distillation under reduced pressure was performed to obtain alcohol compound 4
0.5 g (170 mmol) was obtained.

(2-c) Next, 200 ml of methylene chloride, 23.8 g (100 mmol) of the alcohol compound obtained by the reaction of the above (2-b) and 8.9 ml (110 mmol) of pyridine were added, and the mixture was added at 0 ° C. Then, 8.6 g (110 mmol) of acetyl chloride was added dropwise, and the mixture was reacted at room temperature for 12 hours. Then, the reaction was stopped by adding 3N hydrochloric acid, and the mixture was extracted with methylene chloride. Then, it was washed successively with saturated sodium hydrogen carbonate and distilled water, and dried over anhydrous magnesium sulfate. After distilling methylene chloride under reduced pressure, distillation under reduced pressure was performed to obtain 27.5 g (98 mmol) of an ester compound.

(2-d) Next, 28.0 g of the ester compound obtained by the above reaction was added to 1000 ml of distilled water.
(100 mmol) was added and the mixture was stirred at 40 ° C. in a mini jar fermenter. Add 20g Lipase PS,
The reaction was carried out for 20 hours. The reaction was stopped by adding 3N hydrochloric acid and cooling at 0 ° C, and the mixture was filtered through Celite. The filtrate was extracted with ethyl acetate, washed with saturated brine, dried over anhydrous magnesium sulfate, and ethyl acetate was evaporated under reduced pressure.
Then, the product was separated and purified by silica gel column chromatography to give 11.7 g (4
9 mmol) and 13.2 g (4
7 mmol) was obtained. The optical purity of the obtained alcohol compound was 97.5% e. e. Met.

(2-e) Next, 11.7 g (49 mmol) of the optically active alcohol compound obtained in the above reaction was dissolved in 100 ml of methylene chloride, and 4.0 g (59 mmol) of imidazole and t-butyldimethylsilyl chloride were dissolved. 8.9 g (59 mmol) was added at 0 ° C. to give 15
The mixture was stirred for a minute and reacted at room temperature for 16 hours. The reaction was stopped by adding distilled water, and the mixture was extracted with methylene chloride. Then, it was washed with distilled water and dried over anhydrous magnesium sulfate. After distilling methylene chloride under reduced pressure, the silyl ether compound 1 was separated and purified by column chromatography.
6.6 g (47 mmol) was obtained.

(2-f) Next, in a nitrogen atmosphere, acetic acid 120
14.1 g (40 mmol) of the silyl ether compound obtained in the above reaction and 23.2 g (60 mmol) of magnesium monoperoxyphthalate were added to ml.
The reaction was carried out at 80 ° C for 12 hours. After the acetic acid was distilled off under reduced pressure,
A saturated sodium hydrogen carbonate solution was added, and the mixture was extracted with ethyl acetate. Then, it was washed with saturated saline and dried over anhydrous magnesium sulfate. After distilling off ethyl acetate under reduced pressure, the residue was purified by column chromatography (4S, 1 ').
4.7 g (16 mmol) of S) butenolide compound and 3.0 g (10 mmol) of (4R, 1 ′S) butenolide compound were obtained. In addition, 4.2 g (12 mmol) of the raw material was also recovered.

(2-g) Next, the compound (4) obtained in the above reaction was obtained.
S, 1'S) and (4R, 1'S) butenolide compound 1
Ethanol 40 without separation of 3.7 g (46 mmol)
Dissolve in milliliter, add 1.4 g of 10% Pd / C (containing 10% by weight of Pd), and add 15% at room temperature under hydrogen atmosphere.
Reacted for hours. The reaction solution was filtered, the solvent was distilled off under reduced pressure, and then the residue was separated and purified by silica gel column chromatography to obtain 8.2 g (2S, 1 ′S) butanolide compound.
9 mmol) and 3.6 g (12 mmol) of the (4R, 1 ′S) butanolide compound were obtained.

(2-h) Then, in a nitrogen atmosphere, 40 ml of diethyl ether was obtained by the above reaction (4).
7.5 g (25 mmol) of (S, 1 ′S) butanolide compound was added, and 32 ml (30 mmol) of a 0.93 mol / l n-hexane solution of diisobutylaluminum hydride was added dropwise at −78 ° C. for 3 hours. Reacted The reaction was stopped by adding distilled water, 1N hydrochloric acid was added for neutralization, and the mixture was extracted with diethyl ether. The extract was washed with saturated brine and dried over anhydrous magnesium sulfate, and diethyl ether was distilled off under reduced pressure. Then, the product is purified by silica gel column chromatography to give 7.3 g of a lactol compound.
(24 mmol) was obtained.

(2-i) Then, under a nitrogen atmosphere, 7.3 g (24 mmol) of the lactol compound obtained by the above reaction was added to 50 ml of tetrahydrofuran, and -7
A solution of 3.0 g (27 mmol) of potassium-t-butoxide in 10 ml of tetrahydrofuran was added dropwise at 8 ° C., and the mixture was reacted for 3 hours. Stop the reaction by adding distilled water,
The mixture was neutralized with 1N hydrochloric acid, and extracted with diethyl ether. The extract was washed with saturated brine and dried over anhydrous magnesium sulfate, and diethyl ether was distilled off under reduced pressure. Then
Purification by silica gel column chromatography gave 6.4 g (21 mmol) of pyranose compound.

(2-j) Next, 6.4 g (21 mmol) of the pyranose compound obtained by the above reaction was dissolved in 40 ml of hexanol, 0.1 g of paratoluenesulfonic acid was added, and the mixture was reacted at room temperature for 18 hours. . The reaction solution was directly purified by silica gel column chromatography to obtain 8.0 g (21 mmol) of acetal compound. Although the obtained compound was a diastereomer mixture, it was used for the next reaction without separation.

(2-k) Next, 8.0 g (21 mmol) of the acetal compound obtained by the above reaction was dissolved in 20 ml of tetrahydrofuran, and a 10 mol / liter tetrahydrofuran solution of tetra-n-butylammonium fluoride was added. The mixture was added with milliliter and reacted at 0 ° C. for 1 hour and at room temperature for 40 hours. The reaction was stopped by adding distilled water, and the mixture was extracted with ether. Then, the extract was washed with saturated brine, dried over anhydrous magnesium sulfate, and diethyl ether was distilled off under reduced pressure, followed by separation and purification by silica gel column chromatography (2R, 5S, 6S) -tetrahydro-6-trifluoromethyl. -2-hexyloxy-5
-Hydroxypyran 3.0 g (11 mmol) and (2
S, 5S, 6S) -Tetrahydro-6-trifluoromethyl-2-hexyloxy-5-hydroxypyran 2.
3 g (8 mmol) was obtained.

The physical properties of the obtained compound are shown below. (2R, 5S, 6S) Body Molecular _{formula: C 12 H 21 F 3 O} 5 1 H-NMR ( proton nuclear magnetic resonance); δ (ppm) 0.88 ( t, J = 6.5Hz, 3H), 1.20~1.39 ( m, 6H), 1.50 ~ 1.71
(m, 4H), 1.83 to 2.04 (m, 2H), 2.13 to 2.22 (m, 1H), 3.46 (d
t, J = 9.4, 6.9Hz, 1H), 3.66 (dq, J = 8.9, 6.3Hz, 1H),
3.81 to 3.93 (m, 2H), 4.52 (dd, J = 2.0, 8.7Hz, 1H) ¹⁹ F-NMR (reference: CFCl ₃ ); δ (ppm) -75.13 (d, J = 6.3Hz) IR (cm ^-1 ) 3450, 1275, 1170, 1145, 1090, 940 Mass spectrometry m / e (M ⁺ + H) Calculated value 271.1521 Actual value 271.1512 [α] ²⁵ _D = -36.0 ° (C (concentration) = 1.05, solvent: methanol ) (2S, 5S, 6S) body Molecular formula: C ₁₂ H ₂₁ F ₃ O ₃ ¹ H-NMR (proton nuclear magnetic resonance method); δ (ppm) 0.90 (t, J = 7.3 Hz, 3H), 1.23 to 1.45 (m, 6H), 1.52 ~ 1.67
(m, 2H), 1.76 ~ 2.00 (m, 5H) 3.42 (dt, J = 9.7, 6.4Hz, 1H), 3.68 (dt, J = 9.7, 6.8Hz,
1H) 3.79 to 3.98 (m, 2H), 4.86 (m, 1H) ¹⁹ F-NMR (reference: CFCl ₃ ); δ (ppm) -75.17 (d, J = 6.2 Hz) IR (cm ^-1 ) 3400, 1270, 1175, 1130, 1045, 945 Mass spectrometry m / e (M ⁺ + H) Calculated value 271.1521 Actual value 271.1493 [α] ²⁵ _D = + 86.5 ° (C (concentration) = 1.08, solvent: methanol)

(2-1) Further obtained from the above reaction (2
R, 5S, 6S) -Tetrahydro-6-trifluoromethyl-2-hexyloxy-5-hydroxypyran 0.
35 g (1.3 mmol) and 4'-hexyloxy-4
1 mL of anhydrous pyridine was added to 5 mL of a toluene solution of 0.49 g (1.6 mmol) of biphenylcarboxylic acid chloride, and the mixture was reacted at room temperature for 24 hours.
Distilled water was added to this reaction solution to stop the reaction, and the mixture was extracted with ether. Then, it was washed with saturated saline and dried over anhydrous magnesium sulfate. After distilling off the ether under reduced pressure,
Purified by silica gel column chromatography, the desired compound (2R, 5S, 6S) -tetrahydro-6-
Trifluoromethyl-2-hexyloxy-5- (4 "
0.44 g (0.8 mmol) of -hexyloxybiphenyl-4'-carbonyloxy) pyran was obtained.

The physical properties of the obtained compound are shown below. Molecular _{formula: C 31 H 41 F 3 O} 5 1 H-NMR ( proton nuclear magnetic resonance); δ (ppm) 0.86~0.99 ( m, 6H), 1.23~2.07 (m, 19H), 2.39~2.48
(m, 1H), 3.49 (dt, J = 9.4, 6.8Hz, 1H), 3.92 (dt, J = 9.5,
6.7Hz, 1H) 4.00 (t, J = 6.6Hz, 2H), 4.07 (dq, J = 8.8, 6.3Hz, 1H),
4.65 (dd, J = 2.1, 8.2Hz, 1H), 5.22 (ddd, J = 5.0, 9.0,
9.5Hz, 1H) 6.98 (d, J = 8.8Hz, 2H), 7.55 (d, J = 8.7Hz, 2H), 7.62 (d,
J = 8.5Hz, 2H), 8.04 (d, J = 8.4Hz, 2H) ¹⁹ F-NMR (reference: CFCl ₃ ); δ (ppm) -75.79 (d, J = 6.3Hz) IR (cm ^-1 ) 1720, 1610, 1500, 1260, 1190, 1060 Mass spectrometry m / e (M ⁺ ) Calculated value 550.2906 Measured value 550.2899 [α] ²⁵ _D = -13.0 ° (C (concentration) = 1.10, solvent: chloroform)

(3) Synthesis of (2R, 5S, 6S) -Tetrahydro-6-trifluoromethyl-5-hexanoyloxy-2- (4 "-heptylbiphenyl-4'-carbonyloxy) pyran (Compound 20) (3-a) First, 1.40 g (4.5 mmol) of 4'-heptyl-4-biphenylcarboxylic acid chloride and (5S,
2 ml of anhydrous pyridine was added to 5 ml of a toluene solution of 0.90 g (3.0 mmol) of 6S) -tetrahydro-5-t-butyldimethylsiloxy-6-trifluoromethyl-2-hydroxypyran, and the mixture was added at room temperature for 20 hours. It was made to react. Distilled water was added to this reaction solution to stop the reaction, and the mixture was extracted with ether. Then, it was washed with saturated saline and dried over anhydrous magnesium sulfate. After the ether was distilled off under reduced pressure, the residue was purified by silica gel column chromatography to obtain 1.47 g (2.5 mmol) of the ester compound.

(3-b) Next, 1.47 g of the ester compound obtained in (3-a) was dissolved in 10 ml of tetrahydrofuran to prepare a tetrahydrofuran solution 1 of tetra-n-butylammonium fluoride at 1.0 mol / l. 0.0 ml was added, and the mixture was reacted at 0 ° C. for 1 hour and at room temperature for 6 hours. Distilled water was added to this reaction solution to stop the reaction, and the reaction product was extracted with ether. Then, the extract was washed with saturated saline and dried over anhydrous magnesium sulfate. After the ether was distilled off under reduced pressure, the residue was separated and purified by silica gel column chromatography to obtain (2S, 5S, 6
Alcohol compound having asymmetric carbon of S) 0.92 g
0.10 g (0.2 mmol) of an alcohol compound having asymmetric carbons of (2.0 mmol) and (2R, 5S, 6S) was obtained.

(3-c) Next, (2) obtained in (3-b)
R, 5S, 6S) 0.10 g of an alcohol compound having an asymmetric carbon is dissolved in 3 ml of toluene, and 0.5 ml of pyridine and 0.0 of hexanoyl chloride are dissolved.
5 ml (0.3 mmol) was added sequentially and the reaction was carried out at room temperature for 20 hours. Distilled water was added to this reaction solution to stop the reaction, and the reaction product was extracted with ether. Then, the extract was washed with saturated saline and separated and purified with anhydrous magnesium sulfate. After the ether was distilled off under reduced pressure, it was separated and purified by silica gel column chromatography to obtain the desired compound (2R, 5S, 6S) -tetrahydro-6-trifluoromethyl-5-hexanoyloxy-2- (4 ").
0.12 g (0.2 mmol) of -heptylbiphenyl-4'-carbonyloxy) pyran was obtained.

The physical properties of the obtained compound are shown below. Molecular _{formula: C 32 H 41 F 3 O} 5 1 H-NMR ( proton nuclear magnetic resonance); δ (ppm) 0.82~0.97 ( m, 6H), 1.18~1.45 (m, 11H), 1.53~1.76 (m, Five
H), 1.94 to 2.29 (m, 4H) 2.33 (t, J = 7.6Hz, 2H), 2.67 (t, J = 7.7Hz, 2H), 4.29 (d
q, J = 9.8, 5.9Hz, 1H), 5.10 ~ 5.23 (m, 1H), 6.49 (m, 1H), 7.30 (d, J = 8.1Hz, 2H) 7.56 (d, J = 8.2Hz, 2H) , 7.70 (d, J = 8.5Hz, 2H), 8.13
(d, J = 8.5Hz, 2H) ¹⁹ F-NMR (reference: CFCl ₃ ); δ (ppm) -76.07 (d, J = 5.9Hz) IR (cm ^-1 ) 1735, 1610, 1490, 1265, 1170 , 1070 Mass spectrometry m / e (M ⁺ ) Calculated value 562.2906 Measured value 562.2934 [α] ²⁵ _D = + 51.5 ° (C (concentration) = 1.02, solvent: chloroform) Synthesis example 3 Represented by the general formula (IV) Was synthesized. The structure and transition temperature of the compound are shown in Table 4.

[0144]

[Table 4] (Synthesis Method) (1) Synthesis of Compound 23. (1-a) First, 34.0 g of p-iodophenol was dissolved in 350 ml of dimethyl sulfoxide, an aqueous sodium hydroxide solution (7.4 g / 50 ml) and 32.4 g of n-decyl bromide were added, and the mixture was stirred at room temperature for 3 days. The reaction mixture was extracted with hexane and washed 3 times. Hexane was distilled off to obtain 46.6 g of oily pn-decyloxyiodobenzene.

(1-b) Next, 30.0 g of pn-decyloxyiodobenzene and 8.4 g of 3-methyl-1-butyn-3-ol were added to 320 ml of dichlorobistriphenylphosphine palladium (II) as a catalyst in 200 ml of triethylamine. Using 80 mg of copper (I) iodide, the reaction was carried out overnight at room temperature in a nitrogen atmosphere. After completion of the reaction, triethylamine was distilled off and the mixture was extracted with hexane. The hexane layer was washed successively with 1N (N) hydrochloric acid and water, and then hexane was distilled off to obtain 22.8 g of the following compound (e) as a solid.

[0146]

[Chemical 38]

(1-c) Next, 22.8 g of the compound (e) obtained in (1-b) was dissolved in 800 ml of dry toluene, 9.9 g of sodium hydroxide powder was added thereto, and the mixture was heated under reflux for 1 hour. After cooling, the toluene was removed after washing with water. The black oil obtained was extracted with methanol, and the methanol was distilled off to obtain 13.2 g of oily pn-decyloxyphenylacetylene.

(1-d) Next, 1000 ml of water and 1000 of pyridine
109 g of p-iodo-o-fluorotoluene was dissolved in a mixed solvent of ml and refluxed under reflux until the color of potassium permanganate disappeared. After completion of the reaction, unreacted p-iodo-o-fluorotoluene was removed by distillation and then cooled to room temperature.
After removing manganese dioxide by filtration under reduced pressure, concentrated hydrochloric acid was added to the filtrate to acidify it. The resulting white precipitate was isolated by filtration under reduced pressure, washed with water, dried and recrystallized from toluene to obtain 42 g of p-iodo-o-fluorobenzoic acid.

(1-e) Further, 10 ml of thionyl chloride was added to 5.33 g of p-iodo-o-fluorobenzoic acid obtained in (1-d), the mixture was refluxed for 5 hours, and excess thionyl chloride was distilled off. p-Iodo-o-fluorobenzoic acid chloride was obtained. This product was not particularly purified and was dissolved in 20 ml of dry toluene and used as it was in the next reaction. On the other hand 1.50 g of 1-butanol, dried pyridine
A solution prepared by dissolving 3.2 g in 30 ml of dry toluene was ice-cooled, and a toluene solution of the above acid chloride was added thereto with stirring to about 30
The mixture was added dropwise in minutes, and the mixture was further stirred on a hot water bath at 90 ° C for 5 hours. After cooling, 1N (N) hydrochloric acid water, water, sodium hydrogen carbonate water,
After sequentially washing with water, toluene was distilled off under reduced pressure. The hexane-soluble portion was purified by silica gel column chromatography to obtain 6.09 g of oily p-iodo-o-fluorobenzoic acid butyl ester.

(1-f) Further, 1.3 g of pn-decyloxyphenylacetylene obtained in (1-c) and (1-e) were obtained.
1.6 g of p-iodo-o-fluorobenzoic acid butyl ester was added to 30 ml of triethylamine as a catalyst, and 40 mg of dichlorobistriphenylphosphine palladium (II) and copper (I) iodide were used as catalysts.
10 mg was used and reacted at room temperature for 5 hours under a nitrogen atmosphere.
After completion of the reaction, triethylamine was distilled off and the mixture was extracted with toluene. The toluene layer was washed successively with 1N (N) hydrochloric acid and water and then purified by silica gel column chromatography.
The obtained solid was recrystallized twice from ethanol to obtain 1.7 g of compound 23.

Compound 24 and compound 25 were synthesized in the same manner as in the above-mentioned compound 23 synthesis method. The physical properties of the obtained compound are shown below. Compound 23 ¹ H-NMR (proton magnetic resonance method); δ (ppm) 0.87 (m, 3H), 0.96 (t, 3H), 1.23 to 1.56 (m, 16H) 1.70 to 1.83 (m, 4H), 3.96 ( t, 2H), 4.33 (t, 2H), 6.87 (d, 2H) 7.22 (dd, 1H), 7.29 (dd, 1H), 7.45 (d, 2H), 7.88 (t, 1H) ¹⁹ F-NMR; δ (ppm) -33.97 (dd, 1F) compound 24 ¹ H-NMR (proton magnetic resonance method); δ (ppm) 0.83 to 0.92 (m, 6H), 1.22 to 1.50 (m, 20H), 1.70 to 1.82 ( m, 4
H) 3.96 (t, 2H), 4.31 (t, 2H), 6.88 (d, 2H), 7.22 (dd, 1H) 7.30 (dd, 1H), 7.45 (d, 2H), 7.89 (t, 1H) ¹⁹ F-NMR; δ (ppm) -33.96 (dd, 1F) compound 25 ¹ H-NMR (proton magnetic resonance method); δ (ppm) 0.83 to 0.92 (m, 6H), 1.22 to 1.50 (m, 24H), 1.70 ~ 1.81 (m, 4
H) 3.96 (t, 2H), 4.31 (t, 2H), 6.88 (d, 2H), 7.22 (dd, 1H) 7.30 (dd, 1H), 7.45 (d, 2H), 7.89 (t, 1H) ¹⁹ F-NMR; δ (ppm) -33.94 (dd, 1F)

Example 1 An achiral host liquid crystal composition having the composition shown in Table 5 was prepared using the compounds shown in Tables 1, 2, and 4. The transition temperature of the produced composition is shown in Table 6.

[0153]

[Table 5]

[0154]

[Table 6] Ferroelectric liquid crystal compositions having the compositions shown in Table 7 were prepared using the achiral host liquid crystal composition having this composition and the optically active compounds shown in Table 3. This composition is Chiral Smectic C
Phase, smectic A phase, and chiral nematic phase, and the helical pitch of the chiral nematic phase is 2
It was manufactured to have a thickness of 0 μm or more. The phase transition temperatures are shown in Table 7.

[0155]

[Table 7]

Example 2 PSI-A-2101 (manufactured by Chisso Corporation) alignment film was applied onto two glass substrates and rubbed. The cell thickness is 50μ so that the rubbing directions are antiparallel to each other.
Then, the nematic liquid crystal E-8 (manufactured by Merck & Co., Inc.) was injected. Magnetic field capacity method (K. Suzuki, K. Toriyama
and A. Fukuhara, Appl. Phys. Lett 33 (1987) 561.), the pretilt angle of the PSI-A-2101 alignment film was 5 °.

Example 3 A transparent electrode made of ITO having a thickness of 100 nm was formed on two glass substrates, and an insulating film made of SiO _{2 having a} thickness of 120 nm was formed on the transparent electrode. PS on top
An IA-2101 (manufactured by Chisso Corporation) alignment film was applied in a thickness of 50 nm and rubbed. Next, the two glass substrates were attached to each other with a cell thickness of 2 μm so that the rubbing directions were parallel to each other, to prepare a cell.

Ferroelectric liquid crystal compositions shown in Table 7 were injected into this cell. After the injection, the liquid crystal cell was once heated to a temperature at which the liquid crystal composition changed to an isotropic liquid, and then cooled to room temperature at 1 ° C./min to obtain a ferroelectric liquid crystal device having a good C2 orientation.

This ferroelectric liquid crystal element was placed between two orthogonal polarizers, a voltage was applied, and the characteristics were evaluated. Table 8 shows the evaluation conditions and the obtained characteristics. Further, the τ-Vmin characteristic of this ferroelectric liquid crystal element was evaluated. The results are shown in Fig. 10. Vmin is 30V or less, τmin is 16 to
It was obtained around 61 μs.

[0160]

[Table 8]

Example 4 The ferroelectric liquid crystal device manufactured in Example 3 was driven using the drive waveform (B) shown in FIG. The driving conditions and the results of the driving experiment are shown in Table 9. It can be switched with a driving voltage of 40 V or less, and has a good contrast of 100 to 100.
A line address time of about 300 μs / line was obtained. Further, Table 10 shows the results when the driving is performed using the drive waveform (A) shown in FIG. 2 and the drive waveform (C) shown in FIG. 9. It could be driven at a voltage of 40 V or less, and the line address time was 80 μs / line or less.

[0162]

[Table 9]

[0163]

[Table 10]

Example 5 An AC electric field (± 4%) was applied to the ferroelectric liquid crystal device manufactured in Example 3.
By applying 0 V, 100 Hz), the smectic layer structure changed from a chevron structure to a pseudo bookshelf structure. Table 11 shows the evaluation conditions and the evaluation results. The liquid crystal element after the electric field application process was subjected to pressure (10 kg / cm ² ) to cause zigzag defects and disordered alignment. But,
By applying the electric field again, the orientation and characteristics after the initial electric field application treatment were obtained. Drive waveform (B) shown in FIG.
Table 12 shows the results of driving by using. By adopting a pseudo bookshelf structure by applying an electric field, the memory angle was increased and a bright display device was realized.

[0165]

[Table 11]

[0166]

[Table 12]

Comparative Example 1 Ferroelectric liquid crystal compositions SCE-8, ZLI-5014 (manufactured by Merck & Co., Inc.) and C shown in Table 13 were added to the cell prepared in Example 3.
S-1011 (manufactured by Chisso Corporation) was injected into each. After the injection, the liquid crystal cell was once heated to a temperature at which the liquid crystal composition changed to an isotropic liquid, and then cooled to room temperature at 1 ° C./min to obtain a ferroelectric liquid crystal device having good alignment.

This ferroelectric liquid crystal element was placed between two orthogonal polarizers, a voltage was applied, and the characteristics were evaluated. Table 14 shows the evaluation conditions and the obtained characteristics. Further, the τ-Vmin characteristic of this ferroelectric liquid crystal element was evaluated. The results are shown in Fig. 11-1. τ-Vmin characteristics were obtained, but V
The value of min was 30 V or more, and the value of τmin was larger than the value of Example 8.

[0169]

[Table 13]

[0170]

[Table 14]

Comparative Example 2 The achiral host liquid crystal composition prepared in Example 1 was prepared as shown in Table 15.
A ferroelectric liquid crystal composition was prepared by adding the chiral compound shown in (4). Table 16 shows the composition ratio and the phase transition temperature of the produced composition. This composition was injected into the cell prepared in Example 3. After the injection, the liquid crystal cell was once heated to a temperature at which the liquid crystal composition changed to an isotropic liquid, and then cooled to room temperature at 1 ° C./min to obtain a ferroelectric liquid crystal device having good alignment. This ferroelectric liquid crystal element was placed between two polarizers that are orthogonal to each other, a voltage is applied, and the characteristics are evaluated.
Table 17 shows the evaluation conditions and the obtained characteristics. Further, the τ-Vmin characteristic of this ferroelectric liquid crystal element was evaluated. The results are shown in Fig. 11-2. τ-Vmin characteristics were obtained,
The value of Vmin was 30 V or more.

[0172]

[Table 15]

[0173]

[Table 16]

[0174]

[Table 17]

Comparative Example 3 The ferroelectric liquid crystal elements produced in Comparative Examples 1 and 2 were driven using the drive waveform (B) shown in FIG. Table 18 shows the driving conditions and the driving experiment results. It was impossible to drive at 40 V or less, or the line address time was as large as 500 μs / line or more even if it could be driven at 40 V or less.

[0176]

[Table 18]

[0177]

As can be seen from the above examples, the ferroelectric liquid crystal device using the ferroelectric liquid crystal composition of the present invention has a good orientation, a high contrast, a low driving voltage, a high speed response and a large capacity. A ferroelectric liquid crystal element can be obtained.

[Brief description of drawings]

FIG. 1 is a graph showing τ-V characteristics of a ferroelectric liquid crystal material.

FIG. 2 is an example of a drive waveform for driving a ferroelectric liquid crystal element using the τ-V characteristic of FIG. 1 (B).

FIG. 3 is a schematic diagram showing the principle of the driving method of FIG.

FIG. 4 is a schematic sectional view of a ferroelectric liquid crystal device using the ferroelectric liquid crystal composition of the present invention.

FIG. 5 is a schematic view of a large-capacity ferroelectric liquid crystal device using the ferroelectric liquid crystal device of the present invention.

FIG. 6 is a diagram for explaining C1 orientation and C2 orientation of a ferroelectric liquid crystal element.

FIG. 7 is a molecular orientation model of four orientation states of a ferroelectric liquid crystal device.

FIG. 8 is an example of a drive waveform for driving a ferroelectric liquid crystal element by using the τ-V characteristic of FIG. 1 (B).

9 is an example of a drive waveform for driving a ferroelectric liquid crystal element by using the τ-V characteristic of FIG. 1 (B).

FIG. 10 is a τ-V characteristic of a ferroelectric liquid crystal device using the ferroelectric liquid crystal composition of the present invention.

FIG. 11 is a τ-V characteristic of a ferroelectric liquid crystal device using the ferroelectric liquid crystal composition of Comparative Example.

[Explanation of symbols]

 1, 2 Insulating substrate 3, 4 Conductive film 5 Insulating film 6 Alignment control film 7 Sealing agent 8 Ferroelectric liquid crystal 9 Polarizing plate

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Internal reference number FI Technical indication location G02F 1/133 560 9226-2K (72) Inventor Takeshi Kaneko 22-22 Nagaike-cho, Abeno-ku, Osaka-shi, Osaka No. 22 In-house Sharp Co., Ltd. (72) No. 22-22 Nagaike-cho, Abeno-ku, Osaka City, Osaka Prefecture 22-22 Inventor Tetsuya Watanabe 1 Sanyo Kasei Co. (72) Inventor Masahiro Sato 7 at 368 Takagi, Shiga-cho, Shiga-gun, Shiga Prefecture (72) Inventor Kuniyoshi Yoshio 1 at 11-Ichibashi-honcho, Higashiyama-ku, Kyoto Sanyo Chemical Industry Co., Ltd. Tatsuro Yanagi 1-11, Hitotsubashi-honcho, Higashiyama-ku, Kyoto Within Sanyo Kasei Co., Ltd. (72) Inventor Keizo Ito 4 Towada, Kamisu-cho, Kashima-gun, Ibaraki Prefecture Within a stone oil Co., Ltd. (72) inventor Takeda Takashihan Ibaraki Prefecture Kashima-gun, Kamisu Higashiwada address 4 Kashima stone in oil Co., Ltd.

Claims (9)

[Claims] 1. A compound represented by the general formula (I):At least one compound represented by the general formula (II):(However, R³And R^FourMay be the same or different
A straight or branched alkyl having 1 to 15 carbon atoms
Represents a group, X³Is a single bond, -O-, -COO
Represents-, -OCO- or -OCOO-, and X^FourIs -O
Represents -or-OCO-, and Y¹Is -O-, -COO-
Or -CH₂Represents O-, A¹And B¹ Is halogen,
Cyano group, 6-containing group which may be substituted with fluorine-containing alkyl group
Represents a membered ring group, Z¹Is a single bond, -COO-, -OCO
-, -C≡C-, -CH₂O- or -OCH₂-Show
And n represents 0 or 1. ) Optical activation compound represented by
Ferroelectricity characterized by containing at least one substance
Liquid crystal composition. 2. A compound represented by the general formula (I):At least one compound represented by the general formula (III):(However, R^FiveAnd R⁶May be the same or different
A straight or branched alkyl having 1 to 15 carbon atoms
Represents a group, X^FiveIs a single bond, -O-, -COO
Represents-, -OCO- or -OCOO-, and X⁶Is -O
Represents -or-OCO-, and Y²Is -O-, -COO-
Or -CH₂Represents O-, A²And B² Is halogen,
Cyano group, 6-containing group which may be substituted with fluorine-containing alkyl group
Represents a membered ring group, Z²Is a single bond, -COO-, -OCO
-, -C≡C-, -CH₂O- or -OCH₂-Show
And n represents 0 or 1. ) Optical activation compound represented by
Ferroelectricity characterized by containing at least one substance
Liquid crystal composition. 3. A compound represented by the general formula (IV): (However, R ⁷ and R ⁸ represent the same or different linear or branched alkyl groups having 1 to 15 carbon atoms, X ⁷ and X ⁸ each independently represent a single bond,
Represents O- or -COO-. ) At least one compound represented by the formula (1) is contained.
The ferroelectric liquid crystal composition described. 4. The liquid crystal composition exhibits a chiral nematic phase, a smectic A phase, and a chiral smectic C phase, and spontaneous polarization in the chiral smectic C phase is 100 μC / m ² or less. The ferroelectric liquid crystal composition according to any one of claims. 5. A drive means and an optical device for switching the optical axis of the liquid crystal by interposing a ferroelectric liquid crystal between a pair of insulating substrates having at least an electrode film and an alignment film and selectively applying a voltage to the electrodes. A ferroelectric liquid crystal device having means for optically identifying axis switching, wherein the ferroelectric liquid crystal comprises the liquid crystal composition according to any one of claims 1 to 4. Liquid crystal element. 6. The ferroelectric liquid crystal device according to claim 5, wherein the ferroelectric liquid crystal has a chevron layer structure, and its orientation is C2 orientation. 7. The ferroelectric liquid crystal device according to claim 5, which comprises using a pseudo bookshelf layer structure obtained by subjecting the ferroelectric liquid crystal device to an AC electric field treatment. 8. The ferroelectric liquid crystal device according to claim 5, wherein the pretilt angle of liquid crystal molecules at the interface between the alignment film and the liquid crystal phase is 10 ° or less. 9. The liquid crystal device according to claim 5, wherein the voltage-memory pulse width characteristic exhibits a minimum value, the electrodes are arranged in a direction intersecting with each other, and a plurality of scanning electrodes and a plurality of signal electrodes are provided. To a pixel composed of a scan electrode for applying a non-selection voltage and a signal electrode for applying a rewriting voltage, and a positive voltage of a value lower than the minimum value. And apply a negative voltage,
To a pixel composed of a scan electrode for applying a selection voltage and a signal electrode for applying a holding voltage, a positive voltage (or a negative voltage) higher than the minimum value and a negative voltage (or negative voltage) lower than the minimum value ( Alternatively, a driving waveform for applying a positive voltage) is used to drive the ferroelectric liquid crystal element.