JPH06329591A - Liquid crystal material, liquid crystal composition, liquid crystal element and ester compound - Google Patents

Abstract

PURPOSE:To provide a liquid crystal material composed of a tetralin compound having optically active carbon in tetralin ring and a hydrocarbon chain structure, having broad working temperature range and high switching speed and useful for the production of liquid crystal element. CONSTITUTION:The liquid crystal material is composed of a compound of formula I [R is 3-20C alkyl or polyfluoroalkyl; X is COO, OCO, CO, etc.; n is 0 or 1; at least one of A<1>, A<2> and A<3> is optically active group of formula II to formula V (atom labeled with * is chiral center of the optically active structure of tetralin ring) and the other A<1>, A<2> and A<3> are group of formula VI etc.; Y<1> and Y<2> are COO, OCO, etc.; Z is O, CO, etc.; R* is 4-20C optically active group having at least one asymmetric carbon (H bonded to C of the optically active group may be replaced with halogen atom)].

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a carboxylic acid ester compound having optically active carbons in at least two positions of a tetralin ring and a hydrocarbon chain structure, a liquid crystal material, a liquid crystal composition containing such a liquid crystal material, and a liquid crystal thereof. A liquid crystal element using a material.

[0002]

BACKGROUND OF THE INVENTION A display device using a liquid crystal compound which is widely used at present is usually driven by a TN (twist nematic) mode.

However, when this system is adopted,
In order to change the displayed image, it is necessary to change the position of the molecules of the liquid crystal compound in the device, so the driving time becomes long and the voltage required to change the molecular position of the liquid crystal compound, that is, the consumption There is a problem that electric power also increases.

A switching element using a ferroelectric liquid crystal compound, unlike a switching element using a TN mode or STN mode, can function as a switching element simply by changing the orientation direction of the molecules of the liquid crystal compound. The switching time is greatly reduced. Furthermore, the spontaneous polarization (P
Since the value of Ps × E given by s) and the electric field intensity (E) is the effective energy intensity for changing the orientation direction of the molecules of the liquid crystal compound, the power consumption is also very small.
Since such a ferroelectric liquid crystal compound has two stable states, that is, bistability, depending on the direction of the applied electric field, the switching threshold characteristic is also very good, and it is used as a display device for moving images. It is particularly suitable for use.

[0005]

2. Description of the Related Art When such a ferroelectric liquid crystal compound is used in an optical switching element or the like, the ferroelectric liquid crystal compound has, for example, an operating temperature range of around room temperature or lower, and an operating temperature range. Is required, a wide switching speed, a high switching speed, and a switching threshold voltage within an appropriate range. Further, among these, the operating temperature range is a particularly important characteristic when putting the ferroelectric liquid crystal compound into practical use.

However, in the known ferroelectric liquid crystal compounds, for example, RB Meyer, et.
l., Thesis [J.de Phy
s.) Vol. 36, L-69, 1975], and Masaaki Taguchi, Takamasa Harada's paper [Proceedings of the 11th Liquid Crystal Symposium, 168, 1985], the operating temperature is generally narrow, Further, even a ferroelectric liquid crystal compound having a wide operating temperature range has not been practically satisfied as a ferroelectric liquid crystal compound, for example, the operating temperature range is a high temperature range not including room temperature.

[0007]

The present invention uses a tetralin compound having optically active carbon in a tetralin ring and a hydrocarbon chain structure, a liquid crystal material comprising the same, a liquid crystal composition containing the liquid crystal material, and the liquid crystal material. It is intended to provide a liquid crystal element. More specifically, the present invention provides a novel liquid crystal material and a liquid crystal element capable of forming a liquid crystal element having a wide operating temperature, a high switching speed, an extremely low power consumption, and a stable contrast. It is an object.

[0008]

SUMMARY OF THE INVENTION The liquid crystal material of the present invention can be represented by the following formula [I]. ^{R-X-A 1 -Y 1} -A 2 - (Y 2 -A 3) n -Z-R * ... [I] However, in the above formula [I], R is 3 carbon atoms
20 alkyl group or polyfluoroalkyl group, in which a part of -CH ₂ -group or -CF ₂ -group may be substituted with -O- group, and -O- group and X is not directly bonded or -O- groups are not bonded to each other.
Is a group or a single bond selected from the group consisting of -COO-, -O-CO-, -CO- and -O-, and n is 0 or 1,
At least one of A ¹ , A ² and A ³ present in the formula [I]
The base of

[0009]

[Chemical 11]

Any one of the optically active groups selected from the group consisting of (* indicates the chiral center of the optically active structure of the tetralin ring) and the remaining A ¹ , A ² and A ³
Each independently,

[0011]

[Chemical 12]

Y ¹ and Y ² are each independently a group selected from the group consisting of —COO—, —O—CO—, —CH ₂ CH
_{2 -, - CH 2 -O -} , - O-CH 2 -, - CO-CH 2 - a and a group selected from -CH ₂ -CO- the group consisting of, Z is, -O -, - CO- , -COO-, and -O-CO- are groups or a single bond, and R ^* is an optically active group having at least one asymmetric carbon atom and having 4 to 20 carbon atoms (the carbon of the optically active group). A hydrogen atom bonded to an atom may be replaced by a halogen atom.)
Is.

The liquid crystal composition of the present invention is characterized by containing a liquid crystal material comprising a tetralin compound represented by the above formula [I]. Further, the liquid crystal element of the present invention is a liquid crystal element including a cell composed of two substrates facing each other and a gap formed by the substrate, and a liquid crystal substance filled in the gap of the cell, The liquid crystal substance is characterized by containing a liquid crystal material composed of a tetralin compound represented by the above formula [I].

Since the ester compound according to the present invention has optically active carbon in at least two positions of the tetralin ring and the hydrocarbon chain structure, it is highly useful as a liquid crystal material and a liquid crystal composition containing this compound. The material and the liquid crystal device filled with this liquid crystal material show excellent liquid crystal characteristics.

By using such a liquid crystal material,
It is possible to obtain various devices having excellent characteristics such as wide operating temperature range, high switching speed, extremely low power consumption, and stable contrast.

[0016]

DETAILED DESCRIPTION OF THE INVENTION The present invention will be described in detail below. First, the liquid crystal material of the present invention will be described.

The liquid crystal material of the present invention comprises a tetralin compound represented by the following formula [I]. ^{R-X-A 1 -Y 1} -A 2 - (Y 2 -A 3) n -Z-R * ... [I] However, in the above formula [I], R is essentially 3 carbon atoms 20 alkyl groups or polyfluoroalkyl groups.

The alkyl group may be linear, branched or alicyclic, but the molecule of the carboxylic acid ester in which R is a linear alkyl group is a straight molecule. Since it has a rigid structure that extends immediately, it exhibits excellent liquid crystallinity. Specific examples of such linear alkyl groups include hexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group, tetradecyl group, hexadecyl group and octadecyl group. You can

Further, examples of the polyfluoroalkyl group include groups in which the hydrogen atom forming the above alkyl group is substituted with a fluorine atom. Furthermore, in the present invention, a part of the -CH ₂ -group or the -CF ₂ -group in the group of R may be substituted with an -O- group, and the -O- group and X are directly bonded. Or the —O— groups do not bond to each other.
For example, in an alkyl group, the above-CH ₂ -group is -O-
Specific examples of the group substituted with a group include a 2-hexyloxyethyl group, a 3,6-dioxa-1-decyl group and a nonyloxymethyl group.

In the above formula [I], X is --COO.
It is a group or a single bond selected from the group consisting of-, -O-CO-, -CO- and -O-. Among these, liquid crystal materials in which X is —O— or a single bond are preferable.

In the above formula [I], n is 0 or 1. Therefore, when n = 0, Y ² and A ³ in the above formula do not exist. A existing in the above formula [I]
^At least one group of ¹ , A ² and A ³ is any optically active group selected from the group represented by the following formula.

[0022]

[Chemical 13]

That is, the tetralin ring of the tetralin compound forming the liquid crystal composition of the present invention has an asymmetric carbon atom indicated by "*" in the above formula. And
When n is 0 in the formula [I], it is necessary that at least one of A ¹ and A ² is a group represented by the above formula. When n is 1, at least one of A ¹ , A ² and A ³ is a group represented by the above formula, and two or three groups are further represented by the above formula. May be

1,2,3, which has the optical activity represented by the above formula,
4-Tetrahydronaphthyl group, R-1,2,3,4-tetrahydro-1,5-naphthyl group, S-1,2,3,4-tetrahydro-1,5-
Naphthyl group, R-1,2,3,4-tetrahydro-1,6-naphthyl group, S-1,2,3,4-tetrahydro-1,6-naphthyl group, R-1,2,
3,4-tetrahydro-2,6-naphthyl group, S-1,2,3,4-tetrahydro-2,6-naphthyl group, R-1,2,3,4-tetrahydro-1,7-
Examples include naphthyl group and S-1,2,3,4-tetrahydro-1,7-naphthyl group.

In particular, in the liquid crystal material of the present invention, it is preferable that the entire molecule be linear, and therefore, it has optical activity.
The 1,2,3,4-tetrahydronaphthyl group includes R-1,2,3,4-
Tetrahydro-2,6-naphthyl group and S-1,2,3,4-tetrahydro-2,6-naphthyl group are particularly preferable.

Further, regarding the optically active 5,6,7,8-tetrahydronaphthyl group, similarly, R-5,6,7,8-tetrahydro-2,6-naphthyl group, S-5,6, The 7,8-tetrahydro-2,6-naphthyl group is particularly preferred.

The example of the structure shown above is an example in which one tetralin ring has optical activity, but in the case where the compound has two or more tetralin rings, at least one of these tetralin rings is It is sufficient that the ring has optical activity, and all the tetralin rings may have optical activity.

A which exists in the formula represented by the above formula [I] and remains unspecified depending on the above conditions.
¹ , A ² and A ³ are each independently a group described below.

[0029]

[Chemical 14]

In the liquid crystal material of the present invention, these groups have no optical activity. Furthermore, in the above formula [I], Y ¹ and Y ² are each independently -COO-, -O-CO.
-, -CH ₂ CH _2- , -CH ₂ -O-, -O-CH _2- , -CO-CH ₂ -and -CH _2-
It is a group selected from the group consisting of CO-. Among these, in the liquid crystal material of the present invention, Y ¹ and Y ² are each independently
It is preferably either -COO- or -O-CO-.
Considering the linearity of the molecule, at least one of Y ¹ and Y ² is preferably —O—CO— or —COO—, and both are —O—CO— or —COO—. Is preferred.

In the above formula [I], Z is -O-,
It is either a group selected from the group consisting of -CO-, -COO- and -O-CO- or a single bond. Particularly in the liquid crystal material of the present invention, Z is preferably -O- or -COO-.

In the formula [I], R ^* represents an optically active group having at least one asymmetric carbon atom and having 4 to 20 carbon atoms. Further, the hydrogen atom bonded to the carbon atom constituting the optically active group may be substituted with a halogen atom such as F, Cl, Br or I.

Particularly, in the above formula [I], R ^* is preferably a group represented by the following formula [II]. ^{-Q 1 -C * H (Q 2} ) -Q 3 ··· [II] However, in the formula [II], Q ¹ is, - (CH _{2) q} - represents a.
Here, q is an integer of 0 to 6. However, one of the —CH ₂ — groups may be replaced with an —O— group. Also,
Q ² and Q ³ each independently have 1 to 10 carbon atoms.
Is an alkyl group, a fluoroalkyl group having 1 to 10 carbon atoms and a halogen atom, and Q ² and Q ³ are different from each other. 1 to 1 carbon atoms
Examples of the alkyl group of 0 include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group and a decyl group. Further, examples of the fluoroalkyl group having 1 to 10 carbon atoms include groups in which at least a part of hydrogen atoms bonded to carbon atoms of the above-described alkyl group is substituted with a fluorine atom. Furthermore, examples of halogen atoms include F, Cl, Br and I. However, Q ² and Q ³ are always different groups or atoms, and they are not the same.
Further, when either Q ² or Q ³ is a halogen atom, the other is usually either an alkyl group or a fluoroalkyl group.

Q ¹ , Q ² and Q ³ in the above formula [II]
Has a CH ₂ group (-CH ₂ -structure) or a CF ₂ group (-CF
₂ -structure), at least some of these are -O
-, -S-, -CO-, -CHX-; (X is a halogen atom), -CHCN-, -O-
It may be substituted with at least one group selected from the group consisting of CO-, -O-COO-, -CO-O- and -CH = CH-.
However, in this case, these groups are introduced so that the heteroatoms (N, O, etc.) forming these groups are not directly bonded. Therefore, by substituting these groups,
No new bond such as -OO- or -NO- can be formed.

Further, among these, R ^* is -C ^* H (CF
₃ ) -C ₄ H ₉ , -C ^* H (CF ₃ ) -C ₅ H ₁₁ , -C ^* H (CF ₃ ) -C ₆ H ₁₃ , -C ^* H (CH
₃ ) -C ₅ H ₁₁ , -C ^* H (CH ₃ ) -C ₆ H ₁₃ , -C ^* H (CH ₃ ) -C ₇ H ₁₅ , -C ^* H (C
_{H 3) -C 8 H 17,} -C * H (C 2 H 5) -C 5 H 11, -C * H (C 2 H 5) -C 6 H 13, -
_{^{CH 2 -C * H (CH 3}} ) -C 2 H 5, - (CH 2) 3 -C * H (CH 3) -C 2 H 5, -C * H (C
_{F 3) -CH 2 -COO-C} 2 H 5, -C * H (CF 3) - (CH 2) 2 -0CH 3, -C * H (CF 3)
-(CH ₂ ) ₃ -0C ₂ H ₅ , -C ^* H (CF ₃ )-(CH ₂ ) ₄ -0CH ₃ , -C ^* H (CF ₃ )-
It is preferably a group selected from the group consisting of (CH ₂ ) ₅ -0C ₂ H ₅ . That is, R ^* is an optically active group having at least one asymmetric carbon. The carbon atom bonded to the carbon atom constituting the optically active group may have a halogen atom such as a fluorine atom as described above.

Of these groups, one of the following groups is particularly preferable in consideration of the characteristics of the liquid crystal material. _{^{-C * H (CF 3) -C}} 6 H 13 -C * H (CH 3) -C 6 H 13 Therefore, the tetralin compound represented by the formula [I], the following table 1 in particular The compounds listed in Table 15 can be mentioned.

In addition, in the following Tables 1 to 15, a tetralin ring represented by the following formula without a bond is shown.

[0038]

[Chemical 15]

Is the structure of the tetralin ring having the following optical activity.

[0040]

[Chemical 16]

Since the two asymmetric carbons represented by the formula [I] and present in the compound have R-form and S-form respectively, the compound number of 1 of the compounds shown in Tables 1 to 15 below. The compounds represented by include a total of 16 compounds.

Specifically, among the compounds represented by the formula [I], specific examples of the compound represented by the following formula [IA] in which n = 1 are shown in Tables 1 to 3 below. A compound can be mentioned.

[0043] ^{R-X-A 1 -Y 1} -A 2 -Y 2 -A 3 -Z-R * ··· [IA]

[0044]

[Table 1]

[0045]

[Table 2]

[0046]

[Table 3]

Further, among the compounds represented by the above formula [I], specific examples of the compound represented by the following formula [IB] in which n = 0 are as shown in Tables 4 to 15 below. Can be mentioned.

[0048] ^{R-X-A 1 -Y 1} -A 2 -Z-R * ··· [IB]

[0049]

[Table 4]

[0050]

[Table 5]

[0051]

[Table 6]

[0052]

[Table 7]

[0053]

[Table 8]

[0054]

[Table 9]

[0055]

[Table 10]

[0056]

[Table 11]

[0057]

[Table 12]

[0058]

[Table 13]

[0059]

[Table 14]

[0060]

[Table 15]

As described above, the liquid crystal material of the present invention includes a compound in which the tetralin ring is an S body or an R body and a compound in which the chain group R ^* in the formula [I] is an S body or an R body. Therefore, when the liquid crystal material of the present invention has one optically active tetralin ring, the following four types of compounds are included in view of the optical activity.

Type 1 Tetralin ring S body Chain group R ^* S body Type 2 Tetralin ring S body Chain group R ^* R body Type 3 Tetralin ring R body Chain group R ^* S body Type 4 Tetralin ring R body Chain Group R ^* R body
.

The liquid crystal material of the present invention may be any of the above types of compounds, or may be a mixture of these compounds. Among these compounds, type 1 and type 4 (group A), or type 2 and type 3 (group B) are in the relationship of enantiomers, and their performance as liquid crystal materials is equal. Therefore, by comparing the compounds of group A and group B having a diastereomer relationship and using the compound of the group having large spontaneous polarization, a liquid crystal element having a higher switching speed than the compounds of other groups can be obtained. it can.

Conventionally, no liquid crystal material having an optical activity in both the ring structure and the side chain has been known, unlike the above liquid crystal materials. That is, for example, a compound represented by the following formula [A] (R ^*
Of the asymmetric carbon of R),

[0065]

[Chemical 17]

The compound represented by the formula [A] has the R-form represented by the following formula [A-1] and the formula [A-
It is a mixture of S-form represented by 2] in the same amount, and therefore, no optical activity was observed in the tetralin ring portion.

[0067]

[Chemical 18]

However, the compound represented by the above formula [A] is replaced by the compound represented by the above formula [A-1] (R-form) and the following formula [A-2].
When separated into a compound (S-form) represented by and examined their respective properties, it was found that the two have different chemical properties and the properties as a liquid crystal material are not the same.

For example, when the switching speed of a liquid crystal device using both liquid crystal materials is measured, the switching speed of the compound represented by the formula [A-1] and that of the compound represented by the formula [A-2] are There was a clear difference in switching speed. Therefore, from the compound (racemate) represented by the formula [A],
When a compound having a low switching speed is extracted and its diastereomer is used alone, the switching speed is remarkably improved as compared with the case where a racemate is used.

That is, in terms of at least the switching speed, generally, when the liquid crystal material has two or more optically active carbons, the compound in which the configuration of each optically active carbon enhances the dipole moment of the whole molecule is a molecular assembly. Since it also increases the spontaneous polarization as, it exhibits a higher switching speed than its diastereomer (compound whose configuration weakens the dipole moment of the entire molecule).

The above compounds can be produced by a specific combination of conventionally known synthetic techniques, that is, a combination including a step of optically resolving a raw material having a tetralin ring.

For example, the carboxylic acid ester represented by the above formula [I] suitable as a liquid crystal material is an optically resolved 1,2,3,4-tetrahydro-6-alkoxynaphthalene-2-carboxylic acid, 2,3,4-tetrahydro-6-hydroxynaphthalene-2-carboxylic acid or 1,2,3,4-tetrahydro-6-benzyloxynaphthalene-2-carboxylic acid and 4 carbon atoms
Obtained from ~ 20 monoalcohols. In the optical resolution of this carboxylic acid, one of the carbon atoms in the tetralin ring is
It is divided into (+) or (-) depending on the optical activity due to the optically active structure in which one is a chiral center.

In the above method, when the optical activity resulting from the optically active structure in which one of the carbon atoms in the tetralin ring of the carboxylic acid is a chiral center is (+),
The optically active monoalcohol having 4 to 20 carbon atoms is 1-methyl alcohol [RCH (CH ₃ ) OH:
R = C _{2 to} C ₁₈ ] is preferable.

When the optical activity due to the optically active structure in which one of the carbon atoms in the tetralin ring of the carboxylic acid is a chiral center is (-), the number of carbon atoms having 4 to 20 carbon atoms having the above-mentioned optical activity is shown. Monoalcohol is 1-trifluoromethyl alcohol [RCH (CF ₃ ) OH: R =
C ₂ -C ₁₈ ] is preferable.

In the present invention, this carboxylic acid ester compound can be synthesized according to the following synthetic route.

[0076]

[Chemical 19]

That is, for example, a mixture of 6-alkoxynaphthalene-2-carboxylic acid and 1,2-diethoxyethane is refluxed while isoamyl alcohol is added dropwise in the presence of metallic sodium to give a racemic compound. Obtain 2,3,4-tetrahydro-6-alkoxynaphthalene-2-carboxylic acid.

1,2,3,4-tetrahydro-6 thus obtained
-Alkoxynaphthalene-2-carboxylic acid, by reacting it with acetic acid and hydrobromic acid, 1,2,3,
4-Tetrahydro-6-hydroxynaphthalene-2-carboxylic acid is obtained.

By reacting 1,2,3,4-tetrahydro-6-hydroxynaphthalene-2-carboxylic acid obtained as described above with benzyl bromide in the presence of potassium hydroxide, 1,2, 3,4-Tetrahydro-6-benzyloxynaphthalene-
2-carboxylic acid is obtained. An acid catalyst is added to this in methanol and refluxed to obtain 1,2,3,4-tetrahydro-6-benzyloxynaphthalene-2-carboxylic acid methyl ester.

The racemic body thus obtained, 1,2,3,4-
Optical separation of tetrahydro-6-benzyloxynaphthalene-2-carboxylic acid methyl ester by high-performance liquid chromatography using an optically resolving column gives the optically active (+) form of 1,2,3,4-tetrahydro. It is possible to separate -6-benzyloxynaphthalene-2-carboxylic acid methyl ester and (-)-isomer 1,2,3,4-tetrahydro-6-benzyloxynaphthalene-2-carboxylic acid methyl ester. Then, the methyl ester is hydrolyzed to obtain optically active 1,2,3,4-tetrahydro-6-benzyloxynaphthalene-2-carboxylic acid.

The optical resolution may be carried out by the same method after synthesizing the methyl 1,2,3,4-tetrahydro-6-alkoxynaphthalene-2-carboxylic acid ester instead of the above-mentioned steps.

Next, using 4-N, N-dimethylaminopyridine and methylene chloride as a solvent, an N, N′-dicyclohexylcarbodiimide solution was added dropwise, and an optically active alkyl alcohol separately synthesized by a conventional method and the above-mentioned step. Optically active 1,2,3,4-tetrahydro-6-benzyloxynaphthalene-2-carboxylic acid obtained by reacting with 1,2,3,4-tetrahydro-6-benzyloxynaphthalene -2-Carboxylic acid ester is obtained.

The obtained optically active 1,2,3,4-tetrahydro
By adding 6-benzyloxynaphthalene-2-carboxylic acid ester to a solvent such as tetrahydrofuran and reducing with hydrogen gas in the presence of a reducing catalyst such as palladium / carbon, an optically active 1,2 , 3,4-tetrahydro-6
-Hydroxynaphthalene-2-carboxylic acid ester is obtained.

Next, using 4-N, N-dimethylaminopyridine and methylene chloride as a solvent, while adding N, N'-dicyclohexylcarbodiimide solution dropwise, 4-alkoxybiphenylcarboxylic acid and the optical obtained in the above step were added. Active 1,2,3,4-tetrahydro-6-hydroxynaphthalene-2-
A tetralin compound, which is a liquid crystal material having at least two optically active carbons, can be obtained by reacting a carboxylic acid ester.

The above method is an example of the method for producing the liquid crystal material of the present invention, and the liquid crystal material of the present invention is not limited to this production method. For example, in order to separate optical isomers, in addition to the high-performance liquid chromatography method using an optical resolution column as described above, crystals of the optically active substance (that is, seeds of crystals) are added to a saturated solution of a racemate to perform crystallization. Of the diastereomeric salt from the acid racemate and the optically active base, which is then separated into the pure one diastereomeric salt by the recrystallization method. However, there is a method of decomposing this salt with an acid or an alkali to obtain an optically active substance, and any method can be used in the present invention.

The tetralin compound represented by the formula [I] obtained as described above can be used as a liquid crystal material. In particular, a tetralin compound having optical activity can be used as a ferroelectric liquid crystal compound or an antiferroelectric liquid crystal compound.

As the tetralin compound obtained as described above, the compounds represented by the following formulas [14] and [15] show excellent liquid crystal characteristics.

[0088]

[Chemical 20]

Further, as the tetralin compound as defined in the present invention, that is, the carboxylic acid ester compound, the compounds represented by the following formulas (L) and (M) exhibit particularly excellent liquid crystal properties.

One of such carboxylic acid ester compounds of the present invention is represented by the following formula (L).

[0091]

[Chemical 21]

In the above formula, R ¹ is an alkyl group or an alkoxy group having 8 to 14 carbon atoms, and R ² is an alkyl group, preferably an alkyl group having 4 to 7 carbon atoms. One of the —CH ₂ — groups of may be replaced by an —O— group or a —COO— group. Further, the compound has an optical activity of (-) due to an optically active structure in which one of the carbon atoms in the tetralin ring is a chiral center.

Other examples of the carboxylic acid ester compound of the present invention include compounds represented by the following formula (M).

[0094]

[Chemical formula 22]

In the above formula, R ¹ is an alkyl group having 8 to 14 carbon atoms or an alkoxy group, and R ² is an alkyl group, preferably an alkyl group having 4 to 7 carbon atoms. One of the —CH ₂ — groups of may be replaced by an —O— group or a —COO— group. Furthermore, the above compound has (+) optical activity due to an optically active structure in which one of the carbon atoms in the tetralin ring is a chiral center.

Among such tetralin compounds, the following formulas [98-], [104-], [109-],
[164-], [170-], [186-] and [2
The compound represented by [02+] exhibits particularly excellent liquid crystal properties.

[0097]

[Chemical formula 23]

Many of the liquid crystal materials of the present invention exhibit a smectic phase in a wide temperature range, and when a compound exhibiting a liquid crystallinity is used alone, a smectic phase in a wide temperature range like the above compounds is used. Almost no liquid crystal material exhibiting the above is known.

The liquid crystal material of the present invention has a wide temperature range showing a smectic phase, and a liquid crystal element filled with such a liquid crystal material, for example, an optical switching element is excellent in high-speed response. There is.

The liquid crystal material of the present invention can be used alone, or can be mixed with other liquid crystal materials and used as a liquid crystal composition. For example, the liquid crystal material of the present invention can be used as a main component of a ferroelectric liquid crystal composition or an antiferroelectric liquid crystal composition or as an auxiliary component of a liquid crystal composition containing a compound exhibiting a smectic phase as a main component. That is, the liquid crystal material of the present invention exhibiting a smectic phase can be used as a main component of a liquid crystal composition or as an auxiliary agent of a liquid crystal composition containing another liquid crystal material as a main component, and a compound that does not exhibit a smectic phase is , And can be used as an auxiliary agent of a liquid crystal composition containing other liquid crystal material as a main component.

Examples of the liquid crystal compound which can be used in the present invention together with the compound represented by the formula [I] are:
(+)-4 '-(2 "-Methylbutyloxy) phenyl-6-octyloxynaphthalene-2-carboxylic acid ester, 4'-decyloxyphenyl-6-((+)-2" -methylbutyloxy) Naphthalene-2-carboxylic acid ester,

[0102]

[Chemical formula 24]

In addition to liquid crystal compounds such as

[0104]

[Chemical 25]

Examples thereof include compounds having the above-mentioned cyclic structure and having optical activity. further,

[0106]

[Chemical formula 26]

A Schiff base type liquid crystal compound such as

[0108]

[Chemical 27]

An azoxy liquid crystal compound such as

[0110]

[Chemical 28]

A benzoic acid ester liquid crystal compound such as

[0112]

[Chemical 29]

A cyclohexylcarboxylic acid ester liquid crystal compound such as

[0114]

[Chemical 30]

A biphenyl liquid crystal compound such as

[0116]

[Chemical 31]

A terphenyl liquid crystal compound such as

[0118]

[Chemical 32]

A cyclohexyl liquid crystal compound such as

[0120]

[Chemical 33]

Examples of such pyrimidine type liquid crystal compounds are as follows. The liquid crystal composition of the present invention contains the liquid crystal material represented by the above formula [I] and other compounds including the compounds exemplified above. In this liquid crystal composition, the liquid crystal material represented by the formula [I] can be arbitrarily mixed in consideration of the characteristics of the obtained liquid crystal composition. The composition of the present invention has a total amount of liquid crystal components of 10 in the composition.
In 0 parts by weight, the liquid crystal material represented by the above formula [I] is contained in a total amount of usually 1 to 99 parts by weight, preferably 5 to 75 parts by weight.

In addition to the liquid crystal material of the present invention, the liquid crystal composition may further contain additives such as a conductivity-imparting agent and a life-improving agent, which are commonly used in liquid crystal compositions. Good.

The liquid crystal composition used in the present invention can be produced by mixing the liquid crystal material represented by the formula [I], and optionally other liquid crystal material and additives. A liquid crystal composition (liquid crystal substance) containing the above liquid crystal material causes an optical switching phenomenon when a voltage is applied, and thus it is possible to manufacture a display device having good responsiveness by utilizing this phenomenon. In the present invention, for the element or the method of driving the element utilizing such a phenomenon, reference can be made to, for example, JP-A-56-107216 and 59-118744.

Liquid crystal substances used in such a display device include smectic C phase, F phase, G phase, H phase, and I phase.
A compound exhibiting any one of the phase, the J phase and the K phase can be used. However, except for the smectic C phase, the response speed of the display device using such a liquid crystal substance is generally slow (low). Therefore, it has been conventionally considered effective to drive the smectic C phase having a high response speed in practical use.

However, by utilizing the driving method of the display device in the smectic A phase as proposed by the present inventor in Japanese Patent Laid-Open No. 2-918, in the present invention, not only the smectic C phase but also the smectic A phase can be used. It can also be used in phase. That is, by using this driving method, the liquid crystal element of the present invention can be driven in a wide range, and the electro-optical response can be speeded up.

The liquid crystal device of the present invention comprises a cell filled with a liquid crystal substance and a polarizing plate. That is, the liquid crystal device of the present invention includes, for example, as shown in FIG. 14, two transparent substrates 11 arranged so as to form a gap 14 filled with a liquid crystal substance.
Cell 1 comprising a and 11b and transparent electrodes 15a and 15b formed on the surfaces of the two transparent substrates 11a and 11b facing the liquid crystal substance 12
3, the liquid crystal substance 12 filled in the gap 14 of the cell 13, and one polarizing plate (not shown) arranged on both outer sides of the cell 13.

In the present invention, as the transparent substrate, for example, glass or transparent polymer plate can be used. The thickness of the transparent substrate is usually in the range of 0.01 to 1.0 mm in the case of a glass substrate, for example.

In the present invention, a flexible transparent substrate can be used as the transparent substrate. in this case,
A flexible transparent substrate may be used as at least one of the transparent substrates, and both may be flexible substrates. A polymer film or the like can be used as such a flexible transparent substrate.

A transparent electrode is provided on the surface of such a transparent substrate. The transparent electrode is formed by coating the surface of the transparent substrate with, for example, indium oxide or tin oxide. The thickness of the transparent electrode is usually 100-
It is in the range of 2000 Angstroms.

The transparent substrate provided with such a transparent electrode may be further provided with an alignment layer or a ferroelectric layer on the transparent electrode. Examples of the orientation layer include an organic thin film and an inorganic thin film formed by chemically adsorbing an organic silane coupling agent or a carboxylic acid polynuclear complex. Examples of organic thin films include polymeric thin films such as polyethylene, polypropylene, polyester, polyamide, polyvinyl alcohol (Poval) and polyimide.

Further, as an example of the inorganic thin film, silicon oxide,
Mention may be made of oxide thin films such as germanium oxide and alumina, nitride thin films such as silicon nitride and other semiconductor thin films.

Further, as a method for imparting orientation to the thin film as described above, a method for imparting anisotropy or shape specificity to the thin film itself at the time of film formation, and a method for imparting orientation from the outside after forming the thin film. is there. Specifically, after forming a thin film by coating a polymer material such as a polyimide resin on the transparent electrode, a method of rubbing the thin film in a certain direction, a method of imparting orientation by stretching the polymer film, A method of obliquely vapor-depositing an oxide can be mentioned.

Two transparent substrates as described above are arranged so that the respective transparent electrodes face each other and a gap for filling the liquid crystal substance is formed by the transparent substrates. The width of the gap formed as described above is usually 1 to 10 μm,
It is preferably 1 to 5 μm. Such a gap can be formed, for example, by disposing two substrates so as to sandwich the spacer. As such a spacer, for example, a polyimide-based polymer substance obtained by patterning a photosensitive polyimide precursor can be used. By using the spacer, a monodomain is formed by the interface effect between the spacer and the liquid crystal substance.

Further, as shown in FIG. 15, in addition to the spacers as described above, a fiber 46 is mixed in the liquid crystal substance 43 so that the transparent substrate 47 to which the transparent electrode 45 is attached is fixed. It can also be held to form a gap.

Further, instead of the above-mentioned fibers, or together with the above-mentioned fibers, a granular material can be blended. As such a granular material, the particle diameter of melamine resin, urea resin, benzoguanamine resin, or the like is 1 or less.
Granules of 10 μm can be mentioned.

The two transparent substrates arranged with a gap as described above are usually bonded by sealing the periphery with a sealing material. An epoxy resin, a silicone resin, or the like can be used as the sealing material. The epoxy resin or the like may be modified with an acrylic material or silicone rubber.

The gap of the liquid crystal cell having the above structure is filled with the liquid crystal substance containing the compound represented by the above formula [I]. Such a liquid crystal substance filled in the gap of the liquid crystal cell can be aligned by using a uniaxial alignment control method such as a temperature gradient method using a spacer edge or a surface treatment method using an alignment film. Further, in the present invention, for example, the initial alignment of the liquid crystal substance can be performed by applying an electric field using a DC bias voltage while heating the liquid crystal substance.

The liquid crystal cell thus filled with the liquid crystal substance and initially aligned is arranged between two polarizing plates. Further, as shown in FIG. 16, two transparent substrates 57, a transparent electrode 55 and a liquid crystal substance 53 prepared as described above are used.
It is also possible to dispose two or more cells 58 composed of 2 between the two polarizing plates 56.

In the liquid crystal element of the present invention, it is possible to arrange the polarizing plates such that the polarization planes of the respective polarizing plates form an angle of 70 to 110 degrees. The polarizing plates are preferably arranged so that the polarization directions of the two polarizing plates are orthogonal to each other, that is, the angle is 90 degrees.

As such a polarizing plate, for example, a polarizing film obtained by stretching a resin film such as a polyvinyl alcohol resin film or a polyvinyl butyral resin film in the presence of iodine or the like to absorb iodine in the film to impart a polarizing property. A film can be used. The surface of such a polarizing film may be coated with another resin or the like to form a multilayer structure.

In the present invention, in the liquid crystal cell as described above, between the polarizing plates arranged as described above, the amount of transmitted light is the smallest (ie, the darkest state) ± 10.
It can be arranged between two polarizing plates so as to form an angle (rotation angle) within a range of degrees, preferably in the darkest state. Further, it is preferable to form an angle (rotation angle) within a range of ± 10 degrees from the state in which the amount of transmitted light is the largest (that is, the brightest state) between the polarizing plates arranged as described above, preferably the brightest. It can be arranged between two polarizing plates so as to be in a state.

The liquid crystal element of the present invention can be manufactured, for example, as shown in FIG. 14, by filling the gap 14 of the cell 13 with the liquid crystal substance 15 as described above and initially aligning the liquid crystal substance 15. it can.

The liquid crystal substance 15 is usually heated until it becomes a molten state, and in this state, it is filled (injected) into the gap 14 of the cell whose inside is depressurized. After filling the liquid crystal material in this manner, the liquid crystal material injection port provided in the cell 13 is sealed.

Then, the cell 13 with the injection port thus sealed is heated to a temperature above the temperature at which the liquid crystal substance 15 filled in the cell exhibits an isotropic phase, and thereafter, the liquid crystal substance 15 exhibits liquid crystal. Cool to temperature.

In the present invention, it is preferable that the cooling rate at the time of cooling is 2 ° C./minute or less. In particular, the rate of temperature decrease is preferably in the range of 0.1 to 2.0 ° C./min, and particularly preferably in the range of 0.1 to 0.5 ° C./min. By cooling the cell 13 at such a cooling rate, the initial blending state of the liquid crystal substance 15 is improved,
It is possible to easily form a liquid crystal element having a liquid crystal phase composed of a monodomain with few alignment defects. Here, the initial orientation refers to the alignment state of the liquid crystal substance before changing the orientation vector of the liquid crystal substance by applying a voltage or the like to the liquid crystal element.

The liquid crystal element of the present invention thus formed has remarkably excellent characteristics such as contrast as compared with the conventional liquid crystal element. For example, a surface-stabilized ferroelectric liquid crystal element,
It can be suitably used as a helical modulation element, a transient scattering type element, a guest-host type element, a vertical alignment liquid crystal element and the like.

For example, when the liquid crystal element of the present invention is driven by applying an electric field, the frequency is usually 1 Hz to 100 KHz, preferably 10 H.
z to 10 KHz, electric field is usually 0.01 to 60 Vp-p / μ
m ^t (voltage per 1 μm thickness), preferably 0.05 to 3
It can be driven by applying a controlled electric field to 0 Vp-p / μm ^t .

Then, the liquid crystal element of the present invention using the liquid crystal material represented by the above formula [I] changes the width of the waveform (driving wave) of the electric field applied when driving by applying the electric field. The amount of light transmitted through this liquid crystal element draws two types of hysteresis curves. One of them is a driving method utilizing a so-called bistable type, and the other is a driving method utilizing a so-called tristable type.

A liquid crystal cell filled with a liquid crystal material having optical activity as described above is placed between two polarizing plates arranged so that their polarization planes are orthogonal to each other so as to be in the darkest state without applying an electric field. In the liquid crystal element of the present invention arranged in, for example, a frequency of 50 Hz to 100 KHz,
The liquid crystal element can be driven by applying an electric field having any one of a 10 KHz rectangular wave (or pulse wave), a triangular wave, a sine wave, and a waveform obtained by combining these. For example, when a rectangular wave (or a pulse or a combination wave of both) is applied, the width of the electric field is set to 10 milliseconds or less, preferably 0.01 to 10 milliseconds to drive the liquid crystal element. The speed can be increased, and in this region, the liquid crystal device of the present invention can be used as a bistable liquid crystal device. Further, by making the width of this electric field larger than 10 milliseconds, preferably within the range of 33 to 1000 milliseconds, in a region where it is not necessary to drive at such a high speed,
The liquid crystal device of the present invention can be used as a tristable liquid crystal device. Here, the width of the electric field means, for example, in the case of a rectangular wave, the length (that is, time) of the electric field maintained at a predetermined voltage.

Various liquid crystal display devices and electro-optical display devices can be manufactured using the liquid crystal element of the present invention.
Further, among the liquid crystal elements of the present invention, a liquid crystal element filled with a liquid crystal substance exhibiting a smectic phase is a liquid crystal display device such as a memory type liquid crystal display device such as a heat writing type liquid crystal display element or a laser writing type liquid crystal display element. Alternatively, an electro-optical display device can be manufactured. Furthermore, by using a liquid crystal material having ferroelectricity and having optically active carbon in the tetralin ring and the chain portion, in addition to the applications as described above, an optical switching element such as an optical shutter or a liquid crystal printer, a piezoelectric element and Liquid crystal display devices such as pyroelectric elements or electro-optical display devices can be manufactured.

That is, since the liquid crystal substance used in the present invention exhibits tri-stable or bistable properties, the liquid crystal device of the present invention has an optical switching function or an optical switching function by reversing the electric field so as to achieve the bistable state. It can have a display function.

When the above-mentioned liquid crystal substance exhibits bistable properties, the liquid crystal substance has spontaneous polarization, so that the liquid crystal element of the present invention has a memory effect even after the electric field is erased when a voltage is applied once. Further, it is not necessary to continuously apply an electric field to the liquid crystal element in order to maintain this memory, and it is possible to reduce power consumption in the display device using the liquid crystal element of the present invention. In addition, the memory property can be maintained even when it exhibits three stability. Moreover, since this display device has a stable contrast, it is very clear.

Furthermore, in the switching element of the present invention using the liquid crystal material represented by the above formula [I], the switching operation can be performed only by changing the orientation direction of the molecules. In this case, the primary term of the electric field strength is Since the switching element is driven, the switching element can be driven at a low voltage.

By using this switching element, a high-speed response of several tens of microseconds or less can be realized, so that the operation time of the element is greatly shortened. Therefore, by using the liquid crystal element of the present invention, a large-screen display (liquid crystal display device) having many scanning lines can be easily manufactured. Moreover, since this display can be driven at room temperature or lower,
The display can be driven without the aid of auxiliary means for controlling the drive temperature.

The display device using the liquid crystal element of the present invention can be driven by various methods. Specific examples of this driving method include the methods described below.

In the first method, the liquid crystal element of the present invention is interposed between two polarizing plates, and an external voltage is applied to this liquid crystal element to change the alignment vector of the liquid crystal substance to form two polarizing plates. This is a method of displaying by utilizing the birefringence of a liquid crystal substance.

The second method is a method of utilizing the dichroism of a dye by using a liquid crystal substance containing a dichroic dye. This method is a method of changing the absorption direction of light by the dye by changing the alignment direction of the liquid crystal compound to perform display. The dye used in this case is usually a dichroic dye,
Examples of such dichroic dyes include azo dyes, naphthoquinone dyes, cyanine dyes and anthraquinone dyes.

The display device manufactured by using the liquid crystal element of the present invention can be manufactured by an electrostatic address display system such as static drive, simple matrix drive or composite matrix drive, an optical address display system, a thermal address display system and a light beam display system. It can be driven.

When the display device of the present invention is driven by an electric field, a non-linear element or an active element can be used as an element for driving each picture element. More specifically, as the non-linear element of the two-terminal element, for example, FIG.
As shown in (a), varistor and MIM on one transparent substrate.
(Metal Insulator Metal), place a diode, etc.
An element that utilizes these nonlinearities can be mentioned. Further, as an active element of a three-terminal element, for example, as shown in FIG.
As shown in 7 (b), TFT (thin film transistor), S
i-MOS (Si-metal oxide semi conductor field-eff
ect transistor) and SOS (Sillicon on Sapphir)
An example is a device in which e) and the like are arranged in picture elements.

[0160]

The liquid crystal material of the present invention has a structure in which the dipole moments resulting from two chirality mutually strengthen each other, so that the spontaneous polarization increases and the liquid crystal using the liquid crystal material of the present invention is increased. The element has a faster response speed.

The liquid crystal material of the present invention has good linearity,
Therefore, since the liquid crystallinity (crystallinity) is good and the liquid crystal phase is exhibited even at a high temperature, the temperature range of the liquid crystal is widened. Furthermore, the liquid crystal material of the present invention has a good alignment property, and the alignment property is further improved in combination with the fact that the linearity of the molecule is also good. Therefore, the liquid crystal element formed by using the liquid crystal material of the present invention exhibits good contrast.

Further, by using a compound having a long spiral pitch in the liquid crystal material of the present invention, good switching performance can be maintained even if the cell gap of the liquid crystal element is increased, and therefore, the liquid crystal element can be easily manufactured. There is also an advantage.

By blending a liquid crystal substance of the same kind and / or another kind with the liquid crystal material of the present invention, liquid crystal is used without impairing the ferroelectricity or antiferroelectricity of the liquid crystal material of the present invention. The possible temperature range can be widened.

Therefore, by using such a liquid crystal material, it is possible to obtain a liquid crystal element having a high-speed response in a wide temperature range. Furthermore, in a liquid crystal display using such an element, the operation time can be shortened significantly. In such a display, power consumption can be reduced, and high contrast and stable contrast can be obtained. Further, low voltage driving is also possible.

Further, when the tetralin liquid crystal material of the present invention is used as an antiferroelectric liquid crystal compound, it is easy to realize a memory property and it is possible to impart characteristics such as improving the orientation.

Further, also in the ferroelectric liquid crystal, when the liquid crystal has one or more chiral centers, the response speed can be improved by using a compound having an optically active structure instead of the racemic body. It is possible. This is because the use of a compound having a specific optical activity increases the spontaneous polarization of the liquid crystal and improves the responsiveness of the molecule to an applied voltage.

By using such a liquid crystal material of the present invention, various devices having excellent characteristics such as wide operating temperature range, high switching speed, extremely low power consumption, and stable contrast can be obtained. Obtainable.

[0168]

EXAMPLES Examples of the present invention will be shown below, but the present invention is not limited to these examples. In addition, R and S represent an R form and an S form of an optically active substance, r added to the numbers of the exemplified compounds represents a racemate, and + and-represent when a racemate as a raw material is optically resolved. It indicates the optical activity of tetralin, not the optical activity of the final liquid crystal compound synthesized using optically active tetralin.

[0169]

Example 1 6- [4 '-(4 "-decyloxy) starting from (+)-1,2,3,4-tetrahydronaphthalene-6-benzyloxy-2-carboxylic acid
Synthesis of ester compound of biphenylcarbonyloxy]-(+)-1,2,3,4-tetrahydronaphthalene-2-carboxylic acid and (R) -1-trifluoromethylheptanol.

Step 1 6-decyloxynaphthalene-2-carboxylic acid 3.86 g (1
To a mixture of 1.8 mmol) and 130 ml of 1,2-diethoxyethane, 3.0 g (130 mg atom) of metallic sodium was added with stirring at 120 ° C. under a nitrogen atmosphere, and the mixture was further heated to reflux temperature.

10 g of isoamyl alcohol was added to this mixture.
(114 mmol) was added dropwise over 1 hour, and the mixture was further reacted for 11 hours under reflux. After cooling to room temperature, the remaining metallic sodium was inactivated by adding ethanol to convert it to an alcoholate, and then the reaction mixture was acidified with 20% hydrochloric acid.

After adding 100 ml of water to the reaction mixture,
The organic phase was separated and this organic phase was washed with water. The organic phase was concentrated under reduced pressure to give 4.25 g of solid. By recrystallizing this solid using toluene, 1,2,3,4-tetrahydro-6-decyloxynaphthalene-2-carboxylic acid 2.
95 g (8.89 mmol) were obtained.

Second stage 1,2,3,4-tetrahydro-6-decyloxynaphthalene-2-carboxylic acid obtained by the method of the first stage 16.6 g (50 mmol), acetic acid 250 ml and 47% bromide Hydrogen acid 86.5
g (0.5 mol) was heated to reflux at 130 ° C. for 7 hours. After adding distilled water and concentrating under reduced pressure, 1,2,3,4-tetrahydro-6-hydroxynaphthalene-2-carboxylic acid 10.
60 g (50 mmol) were obtained. This carboxylic acid compound is a mixture (racemic body) of S-form and R-form.

Third Step 10.60 g (50 mmol) of (+)-1,2,3,4-tetrahydro-6-hydroxynaphthalene-2-carboxylic acid obtained in the second step, 12.85 g of benzyl bromide. (75 mmol), 85
% Potassium hydroxide 6.6 g (100 mmol), sodium iodide 0.525 g (3.5 mmol), ethanol 20
A mixture of 0 ml and 25 ml of distilled water was heated to reflux at 100 ° C. for 12 hours. Further, 50 ml of 10% potassium hydroxide was added, and the mixture was heated under reflux for 2 hours. After cooling to room temperature, the mixture was added to cold water, and the reaction mixture was acidified with 36% hydrochloric acid.

The precipitate was separated by filtration and recrystallized from toluene to give 1,2,3,4-tetrahydro.
-6-benzyloxynaphthalene-2-carboxylic acid 13.08
g (46.4 mmol) was obtained.

Fourth Step A mixture of 1,2,3,4-tetrahydro-6-benzyloxynaphthalene-2-carboxylic acid (2.82 g, 10 mmol) obtained in the third step and 50 ml of methanol was added to 1 ml of concentrated hydrochloric acid ( about
(10 mmol) was added and the mixture was refluxed for 4 hours. After the reaction,
By concentrating this and separating and purifying by column chromatography, 1,2,3,4-tetrahydronaphthalene-6-
Benzyloxy-2-carboxylic acid methyl ester 2.90 g
(9.8 mmol) was obtained.

Fifth step 1,2,3,4-tetrahydronaphthalene-6 obtained in the fourth step
-Benzyloxy-2-carboxylic acid methyl ester was analyzed by a high performance liquid chromatography method using hexane / isopropanol (8: 2) as a developing solvent to have two peaks having almost the same peak area but different retention times. The compound was obtained. When the optical activity of each was measured, it showed (+) and (-), which confirmed that each was an optically active substance.

Sixth Step (+) or (−)-1,2, which is the optically active substance obtained in the fifth step,
To 0.86 g (2.9 mmol) of 3,4-tetrahydronaphthalene-6-benzyloxy-2-carboxylic acid methyl ester,
Ethanol / water = 50 cc / 10 cc mixed solvent and 0.3 g of potassium hydroxide were added, and the mixture was refluxed for 3 hours. After this, water 3
Add 00 cc, acidify with concentrated hydrochloric acid, and filter the deposited precipitate to obtain optically active (+) or (-)-1,2,3,4-tetrahydronaphthalene-6-benzyloxy-2-carboxylic acid. Acid 0.
8 g (2.83 mmol) were obtained.

Seventh Step Optically active form (+)-1,2,3,4-tetrahydro-6-benzyloxynaphthalene-2-carboxylic acid obtained in the sixth step 5.64
g (20 mmol), (R) -1-trifluoromethylheptanol 3.68 g (20 mmol), 4-N, N-dimethylaminopyridine 0.244 g (0.2 mmol) and methylene chloride 70 ml in a mixture of N 2 25 ml of a methylene chloride solution containing 4.53 g (22 mmol) of N'-dicyclohexylcarbodiimide was added dropwise at room temperature over 2 hours with stirring.

Further, the reaction was carried out at room temperature for 2 hours. The reaction mixture was filtered, and the obtained filtrate was concentrated. By separating the concentrate using column chromatography, a white solid (+)-1,2,3,4-tetrahydro-6-benzyloxynaphthalene-2-carboxylic acid, and (R) -1- Ester compound with trifluoromethylheptanol 8.19 g (18.
3 mmol) was obtained.

Eighth step (+)-1,2,3,4-tetrahydro-6-benzyloxynaphthalene-2-carboxylic acid obtained in the seventh step and (R) -1-tetrafluoromethylheptanol Ester compound with 8.1
9 g (18.3 mmol), 5% palladium / carbon 3.6 g
Hydrogen gas was bubbled into a mixture of 50 ml of tetrahydrofuran and tetrahydrofuran at room temperature under normal pressure for 24 hours.

The reaction mixture was filtered using Celite as a filter aid, and the obtained filtrate was concentrated to give a white solid (+)-1,2,3,4-tetrahydro-6-hydroxynaphthalene- 6.78 g (18.3 mmol) of an ester compound of 2-carboxylic acid and (R) -1-trifluoromethylheptanol
Got

Step 9 4'-hydroxybiphenyl-4-carboxylic acid 21.4 g (0.1
Mol), n-decyl bromide 33.15 g (0.15 mol), 85% potassium hydroxide 13.20 g (0.2 mol),
A mixture of 1.05 g (7 mmol) of sodium iodide, 500 ml of ethanol and 100 ml of distilled water was heated under reflux at 100 ° C. for 12 hours.

Further, 40 ml of 25% potassium hydroxide was added, and heating under reflux was continued for 2 hours. After allowing to cool to room temperature, the reaction mixture was added to cold water, and the reaction mixture was acidified with 36% hydrochloric acid to precipitate the reaction product.

The precipitate was separated by filtration, dissolved in acetone, filtered while hot, and the filtrate was concentrated.
4'-decyloxybiphenyl-4-carboxylic acid 1.97 g
(6 mmol) was obtained.

Stage 10 4'-decyloxybiphenyl-4-carboxylic acid obtained in stage 9 0.35 g (1 mmol), obtained in stage 8
(+)-1,2,3,4-Tetrahydro-6-hydroxynaphthalene-2-
To a mixture of 0.36 g (1 mmol) of an ester compound of carboxylic acid and (R) -1-trifluoromethylheptanol, 0.012 g (0.1 mmol) of N, N'-dimethylaminopyridine and 10 ml of methylene chloride, 5 ml of a methylene chloride solution containing 0.125 g (1.2 mmol) of N'-dicyclohexylcarbodiimide was added dropwise at room temperature over 2 hours with stirring.

Further, the reaction was carried out at room temperature for 48 hours. The reaction mixture was filtered, and the obtained filtrate was concentrated. The concentrate was separated by column chromatography to obtain 0.51 g of a colorless semi-solid.

The value of FD-mass spectrum of this semi-solid was M / e = 694. The ¹ H-NMR spectrum of this compound was measured. The ¹ H-NMR spectrum of the compound obtained as described above is shown in FIG.

From the results of these analyses, this compound is
6- [4 '-(4 "-decyloxy) biphenylcarbonyloxy]
It was identified as an ester compound [Exemplified Compound [98+]] of-(+)-1,2,3,4-tetrahydronaphthalene-2-carboxylic acid and (R) -1-trifluoromethylheptanol.
The structure of this compound is shown below.

[0190]

[Chemical 34]

Table 16 shows the phase transition temperatures of the above-obtained compounds.

[0192]

Example 2 6- [4 '-(4 "-decyloxy) biphenylcarbonyloxy]-(-)-1 using (-)-1,2,3,4-tetrahydronaphthalene-2-carboxylic acid as a raw material , 2,3,4-Tetrahydronaphthalene-2-
Synthesis of ester compound of carboxylic acid and (R) -1-trifluoromethylheptanol.

In Example 1, used in the 7th stage
Instead of (+)-1,2,3,4-tetrahydro-6-benzyloxynaphthalene-2-carboxylic acid, (-)-1,2,3,4-tetrahydro-6-benzyloxynaphthalene-2- Similarly, except that carboxylic acid was used, 6- [4 '-(4 "-decyloxy) biphenylcarbonyloxy] prepared from (-)-1,2,3,4-tetrahydronaphthalene-2-carboxylic acid as a raw material An ester compound of-(-)-1,2,3,4-tetrahydronaphthalene-2-carboxylic acid and (R) -1-trifluoromethylheptanol was obtained.

The value of FD-mass spectrum of this semi-solid was M / e = 694. The ¹ H-NMR spectrum of this compound was measured. The ¹ H-NMR spectrum of the compound obtained as described above is shown in FIG.

From these analysis results, this compound is 6-
[4 '-(4 "-decyloxy) biphenylcarbonyloxy]-
It was identified as an ester compound [Exemplified compound [98-]] of (-)-1,2,3,4-tetrahydronaphthalene-2-carboxylic acid and (R) -1-trifluoromethylheptanol.
The structure of this compound is shown below.

[0196]

[Chemical 35]

Table 16 shows the phase transition temperatures of the above compounds obtained.

[0198]

Comparative Example 1 6- [4 '-(4 "-decyloxy) biphenylcarbonyloxy] -1,2,3,4-tetrahydro using 1,2,3,4-tetrahydronaphthalene-2-carboxylic acid as a raw material Synthesis of ester compound of naphthalene-2-carboxylic acid and (R) -1-trifluoromethylheptanol.

In Example 1, 1,2,3,4-tetrahydro-6-benzyloxy was used instead of (+)-1,2,3,4-tetrahydro-6-benzyloxynaphthalene-2-carboxylic acid. In the same manner except that naphthalene-2-carboxylic acid was used, 1,2,
6- [4 '-(4 "-decyloxy) biphenylcarbonyloxy] -1,2,3,4-tetrahydronaphthalene-2-carboxylic acid starting from 3,4-tetrahydronaphthalene-2-carboxylic acid, ( An ester compound [Comparative compound [98r]] with R) -1-trifluoromethylheptanol was obtained, the structure of which is shown below.

[0200]

[Chemical 36]

Table 16 shows the phase transition temperatures of the above-obtained compounds.
Shown in. In the table, Cry represents a crystalline phase and SmC
_A ^*Represents antiferroelectric phase, SmC ^*Represents the ferroelectric phase, S
mA represents the smectic A phase, and Iso is isotropic
Represents a liquid phase. In addition, "・" means that the compound takes that phase.
, And "-" indicates that the compound does not take that phase.
You Furthermore, the numbers are the phase transition temperatures between the phases indicated by "・".
It is degree.

[0202]

[Table 16]

[0203]

Example 3 6- [4 '-(4 "-octyl) biphenylcarbonyloxy]-(+)-1 using (+)-1,2,3,4-tetrahydronaphthalene-2-carboxylic acid as a raw material Synthesis of ester compound of 2,2,3,4-tetrahydronaphthalene-2-carboxylic acid and (R) -1-trifluoromethylheptanol.

In Example 1, instead of the decyloxybiphenyl-4-carboxylic acid used in the 10th step, octylbiphenyl-4-carboxylic acid (manufactured by Teikoku Kagaku KK; F
A colorless semi-solid was obtained in the same manner except that K-1124-8) was used.

The value of FD-mass spectrum of this semi-solid was M / e = 650. The ¹ H-NMR spectrum of this compound was measured. The result of ¹ H-NMR spectrum of the compound obtained as described above is shown in FIG.

From the results of these analyses, this compound is
6- [4 '-(4 "-octyl) biphenylcarbonyloxy]-(+)
-1,2,3,4-tetrahydronaphthalene-2-carboxylic acid,
It was identified as an ester compound with (R) -1-trifluoromethylheptanol [Exemplified compound [104+]]. The structure of this compound is shown below.

[0207]

[Chemical 37]

Table 17 shows the phase transition temperatures of the above-obtained compounds.

[0209]

Example 4 6- [4 '-(4 "-octyl) biphenylcarbonyloxy]-(-)-1 using (-)-1,2,3,4-tetrahydronaphthalene-2-carboxylic acid as a raw material Synthesis of ester compound of 2,2,3,4-tetrahydronaphthalene-2-carboxylic acid and (R) -1-trifluoromethylheptanol.

In Example 3, instead of (+)-1,2,3,4-tetrahydronaphthalene-2-carboxylic acid, (-)-1,2,3,4
A colorless semi-solid was obtained in the same manner except that -tetrahydronaphthalene-2-carboxylic acid was used.

The value of FD-mass spectrum of this semi-solid was M / e = 650. The ¹ H-NMR spectrum of this compound was measured. The result of ¹ H-NMR spectrum of the compound obtained as described above is shown in FIG.

From the results of these analyses, this compound is
6- [4 '-(4 "-octyl) biphenylcarbonyloxy]-(-)
-1,2,3,4-tetrahydronaphthalene-2-carboxylic acid,
It was identified as an ester compound with (R) -1-trifluoromethylheptanol [Exemplified compound [104-]]. The structure of this compound is shown below.

[0213]

[Chemical 38]

Table 17 shows the phase transition temperatures of the above compounds obtained.

[0215]

Comparative Example 2 6- [4 '-(4 "-octyl) biphenylcarbonyloxy] -1,2,3,4-tetrahydro using 1,2,3,4-tetrahydronaphthalene-2-carboxylic acid as a raw material Synthesis of ester compound of naphthalene-2-carboxylic acid and (R) -1-trifluoromethylheptanol.

In Example 3, 1,2,3,4-tetrahydronaphthalene-2-carboxylic acid was used instead of (+)-1,2,3,4-tetrahydronaphthalene-2-carboxylic acid. Similarly, 6- [4 '-(4 "-octyl) biphenylcarbonyloxy] -1,2,3,4-tetrahydro using 1,2,3,4-tetrahydronaphthalene-2-carboxylic acid as a raw material Naphthalene-2-
An ester compound [comparative compound [104r]] of carboxylic acid and (R) -1-trifluoromethylheptanol was obtained. The structure of this compound is shown below.

[0217]

[Chemical Formula 39]

Table 17 shows the phase transition temperatures of the above-obtained compounds.
Shown in.

[0219]

[Table 17]

[0220]

Example 5 6- [4 '-(4 "-decyloxy) biphenylcarbonyloxy]-(+)-1 using (+)-1,2,3,4-tetrahydronaphthalene-2-carboxylic acid as a raw material , 2,3,4-Tetrahydronaphthalene-2-
Synthesis of ester compound of carboxylic acid and (R) -1-methylheptanol.

In Example 1, used in the 7th step
Instead of (R) -1-trifluoromethylheptanol,
A colorless semi-solid was obtained in the same manner except that (R) -1-methylheptanol was used.

The value of FD-mass spectrum of this semi-solid was M / e = 640. The ¹ H-NMR spectrum of this compound was measured. The result of ¹ H-NMR spectrum of the compound obtained as described above is shown in FIG.

From the results of these analyses, this compound is
6- [4 '-(4 "-decyloxy) biphenylcarbonyloxy]
It was identified as an ester compound of [-(+)-1,2,3,4-tetrahydronaphthalene-2-carboxylic acid and (R) -1-methylheptanol [Exemplified compound [202+]]. The structure of this compound is shown below.

[0224]

[Chemical 40]

Table 18 shows the phase transition temperatures of the above-obtained compounds.

[0226]

Example 6 6- [4 '-(4 "-decyloxy) biphenylcarbonyloxy]-(-)-1 using (-)-1,2,3,4-tetrahydronaphthalene-2-carboxylic acid as a raw material , 2,3,4-Tetrahydronaphthalene-2-
Synthesis of ester compound of carboxylic acid and (R) -1-methylheptanol.

In Example 5, instead of (+)-1,2,3,4-tetrahydronaphthalene-2-carboxylic acid, (-)-1,2,3,4
A colorless semi-solid was obtained in the same manner except that -tetrahydronaphthalene-2-carboxylic acid was used.

The value of FD-mass spectrum of this semi-solid was M / e = 640. The ¹ H-NMR spectrum of this compound was measured. The result of ¹ H-NMR spectrum of the compound obtained as described above is shown in FIG. 6.

From the results of these analyses, this compound was prepared from 6- [4 '-( Ester compound of 4 "-decyloxy) biphenylcarbonyloxy]-(-)-1,2,3,4-tetrahydronaphthalene-2-carboxylic acid and (R) -1-methylheptanol [Exemplified Compound [202
-]] Was identified. The structure of this compound is shown below.

[0230]

[Chemical 41]

Table 18 shows the phase transition temperatures of the above compounds obtained.

[0232]

Comparative Example 3 6- [4 '-(4 "-decyloxy) biphenylcarbonyloxy] -1,2,3,4-tetrahydro using 1,2,3,4-tetrahydronaphthalene-2-carboxylic acid as a raw material Synthesis of ester compound of naphthalene-2-carboxylic acid and (R) -1-methylheptanol.

In Example 5, except that 1,2,3,4-tetrahydronaphthalene-2-carboxylic acid was used instead of (+)-1,2,3,4-tetrahydronaphthalene-2-carboxylic acid. Similarly, 6- [4 '-(4 "-decyloxy) biphenylcarbonyloxy] -1,2,3,4-tetrahydro with 1,2,3,4-tetrahydronaphthalene-2-carboxylic acid as the raw material Naphthalene
An ester compound [comparative compound [202r]] of 2-carboxylic acid and (R) -1-methylheptanol was obtained. The structure of this compound is shown below.

[0234]

[Chemical 42]

Table 18 shows the phase transition temperatures of the above compounds obtained.
Shown in.

[0236]

[Table 18]

[0237]

Example 7 6- [4 '-(4 "-tetradecyl) biphenylcarbonyloxy]-(+)-1 using (+)-1,2,3,4-tetrahydronaphthalene-2-carboxylic acid as a raw material , 2,3,4-Tetrahydronaphthalene-2-
Synthesis of ester compound of carboxylic acid and (R) -1-trifluoromethylheptanol.

A colorless semisolid was obtained in the same manner as in Example 1 except that tetradecylbiphenyl-4-carboxylic acid was used instead of the dexoxyoxyphenyl-4-carboxylic acid used in the 10th step. .

The value of FD-mass spectrum of this semi-solid was M / e = 734. The ¹ H-NMR spectrum of this compound was measured. The result of ¹ H-NMR spectrum of the compound obtained as described above is shown in FIG. 7.

From the results of these analyses, this compound is
6- [4 '-(4 "-tetradecyl) biphenylcarbonyloxy]
It was identified as an ester compound of [-(+)-1,2,3,4-tetrahydronaphthalene-2-carboxylic acid and (R) -1-trifluoromethylheptanol [Exemplified compound [109+]]. The structure of this compound is shown below.

[0241]

[Chemical 43]

Table 19 shows the phase transition temperatures of the above-obtained compounds.

[0243]

Example 8 6- [4 '-(4 "-tetradecyl) biphenylcarbonyloxy]-(-)-1 using (-)-1,2,3,4-tetrahydronaphthalene-2-carboxylic acid as a raw material , 2,3,4-Tetrahydronaphthalene-2-
Synthesis of ester compound of carboxylic acid and (R) -1-trifluoromethylheptanol.

In Example 7, instead of (+)-1,2,3,4-tetrahydronaphthalene-2-carboxylic acid, (-)-1,2,3,4
A colorless semi-solid was obtained in the same manner except that -tetrahydronaphthalene-2-carboxylic acid was used.

The value of FD-mass spectrum of this semi-solid was M / e = 734. The ¹ H-NMR spectrum of this compound was measured. The result of ¹ H-NMR spectrum of the compound obtained as described above is shown in FIG.

From the results of these analyses, this compound is
6- [4 '-(4 "-tetradecyl) biphenylcarbonyloxy]
-(-)-1,2,3,4-Tetrahydronaphthalene-2-carboxylic acid and (R) -1-trifluoromethylheptanol were identified as ester compounds [exemplary compound [109-]]. . The structure of this compound is shown below.

[0247]

[Chemical 44]

Table 19 shows the phase transition temperatures of the above-obtained compounds.

[0249]

Comparative Example 4 6- [4 '-(4 "-tetradecyl) biphenylcarbonyloxy] -1,2,3,4-tetrahydro using 1,2,3,4-tetrahydronaphthalene-2-carboxylic acid as a raw material Synthesis of ester compound of naphthalene-2-carboxylic acid and (R) -1-trifluoromethylheptanol.

In Example 7, 1,2,3,4-tetrahydronaphthalene-2-carboxylic acid was used instead of (+)-1,2,3,4-tetrahydronaphthalene-2-carboxylic acid. Similarly, 6- [4 '-(4 "-tetradecyl) biphenylcarbonyloxy] -1,2,3,4-tetrahydro using 1,2,3,4-tetrahydronaphthalene-2-carboxylic acid as a raw material Naphthalene
An ester compound [comparative compound [109r]] of 2-carboxylic acid and (R) -1-trifluoromethylheptanol was obtained. The structure of this compound is shown below.

[0251]

[Chemical formula 45]

Table 19 shows the phase transition temperatures of the above-obtained compounds.
Shown in.

[0253]

[Table 19]

[0254]

Example 9 6- [4 '-(4 "-dodecyl) biphenylcarbonyloxy]-(+)-1 using (+)-1,2,3,4-tetrahydronaphthalene-2-carboxylic acid as a raw material Synthesis of ester compound of 1,2,3,4-tetrahydronaphthalene-2-carboxylic acid and (R) -1-trifluoromethylpentanol.

In Example 1, dodecylbiphenyl-4-carboxylic acid was used in place of the dexoxyoxybiphenyl-4-carboxylic acid used in Step 10, and the (R) -1-tricarboxylic acid used in Step 7 was used. A colorless semisolid was obtained in the same manner except that (R) -1-trifluoromethylpentanol was used instead of fluoromethylheptanol.

The value of FD-mass spectrum of this semi-solid was M / e = 678. The ¹ H-NMR spectrum of this compound was measured. The result of ¹ H-NMR spectrum of the compound obtained as described above is shown in FIG. 9.

From the results of these analyses, this compound is
6- [4 '-(4 "-dodecyl) biphenylcarbonyloxy]-(+)
-1,2,3,4-tetrahydronaphthalene-2-carboxylic acid,
It was identified as an ester compound with (R) -1-trifluoromethylpentanol [Exemplified compound [164+]]. The structure of this compound is shown below.

[0258]

[Chemical formula 46]

Table 20 shows the phase transition temperatures of the above-obtained compounds.

[0260]

Example 10 6- [4 '-(4 "-dodecyl) biphenylcarbonyloxy]-(-)-1 using (-)-1,2,3,4-tetrahydronaphthalene-2-carboxylic acid as a raw material Synthesis of ester compound of 1,2,3,4-tetrahydronaphthalene-2-carboxylic acid and (R) -1-trifluoromethylpentanol.

In Example 9, instead of (+)-1,2,3,4-tetrahydronaphthalene-2-carboxylic acid, (-)-1,2,3,4
A colorless semi-solid was obtained in the same manner except that -tetrahydronaphthalene-2-carboxylic acid was used.

The value of FD-mass spectrum of this semi-solid was M / e = 678. The ¹ H-NMR spectrum of this compound was measured. The result of ¹ H-NMR spectrum of the compound obtained as described above is shown in FIG. 10.

From the results of these analyses, this compound is
6- [4 '-(4 "-dodecyl) biphenylcarbonyloxy]-(-)
-1,2,3,4-tetrahydronaphthalene-2-carboxylic acid,
It was identified as an ester compound with (R) -1-trifluoromethylpentanol [Exemplified Compound [164-]]. The structure of this compound is shown below.

[0264]

[Chemical 47]

Table 20 shows the phase transition temperatures of the above compounds obtained.

[0266]

Comparative Example 5 6- [4 '-(4 "-dodecyl) biphenylcarbonyloxy]-(-)-1,2,3 using 1,2,3,4-tetrahydronaphthalene-2-carboxylic acid as a raw material Synthesis of ester compound of 1,4-tetrahydronaphthalene-2-carboxylic acid and (R) -1-trifluoromethylpentanol.

In Example 9, 1,2,3,4-tetrahydronaphthalene-2-carboxylic acid was used instead of (+)-1,2,3,4-tetrahydronaphthalene-2-carboxylic acid. Similarly, 6- [4 '-(4 "-dodecyl) biphenylcarbonyloxy]-(-)-1,2,3 starting from 1,2,3,4-tetrahydronaphthalene-2-carboxylic acid , 4-tetrahydronaphthalene
An ester compound [comparative compound [164r]] of 2-carboxylic acid and (R) -1-trifluoromethylpentanol was obtained. The structure of this compound is shown below.

[0268]

[Chemical 48]

Table 20 shows the phase transition temperatures of the above-obtained compounds.
Shown in.

[0270]

[Table 20]

[0271]

Example 11 6- [4 '-(4 "-decyloxy) biphenylcarbonyloxy]-(+)-1 using (+)-1,2,3,4-tetrahydronaphthalene-2-carboxylic acid as a raw material , 2,3,4-Tetrahydronaphthalene-2-
Synthesis of ester compound of carboxylic acid and (R) -1-trifluoromethyl-5-methoxypentanol.

In Example 1, used in the 7th stage
Instead of (R) -1-trifluoromethylheptanol,
A colorless semi-solid was obtained in the same manner except that (R) -1-trifluoromethyl-5-methoxypentanol was used.

The value of FD-mass spectrum of this semi-solid was M / e = 696. The ¹ H-NMR spectrum of this compound was measured. The result of ¹ H-NMR spectrum of the compound obtained as described above is shown in FIG. 11.

From the results of these analyses, this compound is
6- [4 '-(4 "-decyloxy) biphenylcarbonyloxy]
An ester compound of [-(+)-1,2,3,4-tetrahydronaphthalene-2-carboxylic acid and (R) -1-trifluoromethyl-5-methoxypentanol [Exemplified compound [186+]] Was identified. The structure of this compound is shown below.

[0275]

[Chemical 49]

Table 21 shows the phase transition temperatures of the above-obtained compounds.

[0277]

Example 12 6- [4 '-(4 "-decyloxy) biphenylcarbonyloxy]-(-)-1 using (-)-1,2,3,4-tetrahydronaphthalene-2-carboxylic acid as a raw material , 2,3,4-Tetrahydronaphthalene-2-
Synthesis of ester compound of carboxylic acid and (R) -1-trifluoromethyl-5-methoxypentanol.

In Example 11, instead of (+)-1,2,3,4-tetrahydronaphthalene-2-carboxylic acid, (-)-1,2,
A colorless semi-solid was obtained in the same manner except that 3,4-tetrahydronaphthalene-2-carboxylic acid was used.

The value of FD-mass spectrum of this semi-solid was M / e = 696. The ¹ H-NMR spectrum of this compound was measured. The result of ¹ H-NMR spectrum of the compound obtained as described above is shown in FIG.

From the results of these analyses, this compound is
6- [4 '-(4 "-decyloxy) biphenylcarbonyloxy]
An ester compound of [-(-)-1,2,3,4-tetrahydronaphthalene-2-carboxylic acid and (R) -1-trifluoromethyl-5-methoxypentanol [Exemplified compound [186-]]] Identified as present. The structure of this compound is shown below.

[0281]

[Chemical 50]

Table 21 shows the phase transition temperatures of the above-obtained compounds.

[0283]

Comparative Example 6 6- [4 '-(4 "-decyloxy) biphenylcarbonyloxy] -1,2,3,4-tetrahydro using 1,2,3,4-tetrahydronaphthalene-2-carboxylic acid as a raw material Synthesis of ester compound of naphthalene-2-carboxylic acid and (R) -1-trifluoromethyl-5-methoxypentanol.

In Example 11, 1,2,3,4- was used instead of (+)-1,2,3,4-tetrahydronaphthalene-2-carboxylic acid.
6- [4 '-(4 "-decyloxy) biphenylcarbonyloxy prepared from 1,2,3,4-tetrahydronaphthalene-2-carboxylic acid as a raw material in the same manner except that tetrahydronaphthalene-2-carboxylic acid was used. ] -1,2,3,4-Tetrahydronaphthalene-2-carboxylic acid and (R) -1-trifluoromethyl-5-methoxypentanol ester compound [Comparative compound [1
86r]] was obtained. The structure of this compound is shown below.

[0285]

[Chemical 51]

Table 21 shows the phase transition temperatures of the above-obtained compounds.
Shown in.

[0287]

[Table 21]

[0288]

Example 13 6- [4 '-(4 "-decyloxy) biphenylcarbonyloxy]-(+)-1 using (+)-1,2,3,4-tetrahydronaphthalene-2-carboxylic acid as a raw material , 2,3,4-Tetrahydronaphthalene-2-
Synthesis of ester compound of carboxylic acid and (R) -1-trifluoromethyl-2-ethoxycarbonylethanol.

In Example 1, used in the 7th stage
Instead of (R) -1-trifluoromethylheptanol,
A colorless semisolid was obtained in the same manner except that (R) -1-trifluoromethyl-2-ethoxycarbonylethanol was used.

The value of FD-mass spectrum of this semi-solid was M / e = 696. From the results of these analyses, this compound was identified as 6- [4 '-(4 "-decyloxy) biphenylcarbonyloxy]-(+)-1,2,3,4-tetrahydronaphthalene-2.
-It was identified as the ester compound [exemplary compound [170+]] of carboxylic acid and (R) -1-trifluoromethyl-2-ethoxycarbonylethanol.

[0291]

Example 14 6- [4 '-(4 "-decyloxy) biphenylcarbonyloxy]-(-)-1 using (-)-1,2,3,4-tetrahydronaphthalene-2-carboxylic acid as a raw material , 2,3,4-Tetrahydronaphthalene-2-
Synthesis of ester compound of carboxylic acid and (R) -1-trifluoromethyl-2-ethoxycarbonylethanol.

In Example 13, instead of (+)-1,2,3,4-tetrahydronaphthalene-2-carboxylic acid, (-)-1,2,
A colorless semi-solid was obtained in the same manner except that 3,4-tetrahydronaphthalene-2-carboxylic acid was used.

The value of FD-mass spectrum of this semi-solid was M / e = 696. The ¹ H-NMR spectrum of this compound was measured. The result of ¹ H-NMR spectrum of the compound obtained as described above is shown in FIG. 13.

From the results of these analyses, this compound is
6- [4 '-(4 "-decyloxy) biphenylcarbonyloxy]
An ester compound of-(-)-1,2,3,4-tetrahydronaphthalene-2-carboxylic acid and (R) -1-trifluoromethyl-2-ethoxycarbonylethanol [Exemplified Compound [170
-]] Was identified. The structure of this compound is shown below.

[0295]

[Chemical 52]

Table 22 shows the phase transition temperatures of the above-obtained compounds.

[0297]

Comparative Example 7 6- [4 '-(4 "-decyloxy) biphenylcarbonyloxy] -1,2,3,4-tetrahydro using 1,2,3,4-tetrahydronaphthalene-2-carboxylic acid as a raw material Synthesis of ester compound of naphthalene-2-carboxylic acid and (R) -1-trifluoromethyl-2-ethoxycarbonylethanol.

In Example 13, instead of (+)-1,2,3,4-tetrahydronaphthalene-2-carboxylic acid, 1,2,3,4-
6- [4 '-(4 "-decyloxy) biphenylcarbonyloxy prepared from 1,2,3,4-tetrahydronaphthalene-2-carboxylic acid as a raw material in the same manner except that tetrahydronaphthalene-2-carboxylic acid was used. ] 1,2,3,4-Tetrahydronaphthalene-2-carboxylic acid and (R) -1-trifluoromethyl-2-ethoxycarbonylethanol ester compound [comparative compound [170r]] were obtained. The structures of the compounds are shown below.

[0299]

[Chemical 53]

Table 22 shows the phase transition temperatures of the above-obtained compounds.
Shown in.

[0301]

[Table 22]

[0302]

Example 15 The compound obtained in Example 1 was filled in the cell shown in FIG. 5 to produce a liquid crystal device as follows.

First, the ITO (Indium Tin Oxi) shown in FIG.
de) An alignment control film (thickness: 300Å) made of two rubbed polyimides (PIQ5400 manufactured by Hitachi Chemical Co., Ltd.) so that the alignment control directions are substantially parallel to the inner surface of the transparent electrode 55 and opposite directions. The liquid crystal compound [98+] obtained in Example 1 was injected into the cell in which is formed into an isotropic liquid state, and then gradually cooled to a liquid state at a rate of 1 ° C./minute or less.

This was sandwiched between a polarizer and an analyzer whose transmission axes were orthogonal to each other, and the angle of the cell with respect to the polarizer was adjusted so that the amount of transmitted light was minimized when the applied voltage was 0V. 60 ° C
When the applied voltage was instantaneously changed from 0 V to 30 V, the response time from the dark state to the bright state was 390 μsec, and high-speed switching between states with respect to the applied voltage change was confirmed.

[0305]

Comparative Example 8 The liquid crystal compound [98+] in Example 7 was used.
A liquid crystal device was produced in the same manner as in Example 7 except that the compound of Comparative Example [98r] was used in place of.

The applied voltage at 30 ° C. is changed from 0V to 30V.
The response time from the dark state to the bright state was 3200 μsec when the temperature was instantaneously changed to.

[0307]

Example 16 The liquid crystal compound [98]
A liquid crystal element was produced in the same manner as in Example 15, except that the liquid crystal compound [104−] was used instead of +.

At 40 ° C., the applied voltage is 0V to 30V
The response time from the dark state to the bright state was 46 μs when it was instantaneously changed to, and high-speed switching between states with respect to the applied voltage change was confirmed.

[0309]

Comparative Example 9 The liquid crystal compound [98]
A liquid crystal device was manufactured in the same manner as in Example 15 except that the comparative compound [104r] was used instead of +.

Applied voltage at 0 ° C. to 30 V at 40 ° C.
The response time from the dark state to the bright state was 53 μsec when the temperature was changed instantaneously.

[0311]

Example 17 The liquid crystal compound [98]
A liquid crystal element was manufactured in the same manner as in Example 15 except that the liquid crystal compound [202+] was used instead of +.

Applied voltage at 0 ° C. to 30 V at 50 ° C.
The response time from the dark state to the bright state was 230 μsec when the temperature was instantaneously changed to, and high-speed switching between states with respect to the applied voltage change was recognized.

[0313]

Comparative Example 10 The liquid crystal compound [98]
A liquid crystal device was manufactured in the same manner as in Example 15 except that the comparative compound [202r] was used instead of +.

At 50 ° C., the applied voltage is 0V to 30V
The response time from the dark state to the bright state was 730 μsec when the temperature was changed instantaneously.

[0315]

Example 18 The liquid crystal compound [98]
A liquid crystal element was produced in the same manner as in Example 15, except that the liquid crystal compound [109−] was used instead of +.

At 50 ° C., the applied voltage is 0V to 30V
The response time from the dark state to the bright state was 31 μsec when it was instantaneously changed to, and high-speed switching between states with respect to the applied voltage change was recognized.

[0317]

Comparative Example 11 The liquid crystal compound [98]
A liquid crystal device was manufactured in the same manner as in Example 15 except that the comparative compound [109r] was used instead of +.

Apply voltage at 0 ° C. to 30 V at 50 ° C.
The response time from the dark state to the bright state was 140 μsec when the temperature was changed instantaneously to.

[0319]

Example 19 Liquid crystal compound [98-] represented by the following formula
And a liquid crystal compound [104-] represented by the following formula:
A liquid crystal composition of the present invention was manufactured by mixing in a weight ratio of 0:50.

[0320]

[Chemical 54]

Table 23 shows the phase transition temperatures of the above-obtained compositions.
Shown in.

[0322]

[Table 23]

[0323]

Example 20 A liquid crystal compound represented by the following formula [109-]
And a liquid crystal compound [186-] represented by the following formula:
A liquid crystal composition of the present invention was manufactured by mixing in a weight ratio of 0:50.

[0324]

[Chemical 55]

Table 24 shows the phase transition temperatures of the above-obtained compositions.
Shown in.

[0326]

[Table 24]

[0327]

Example 21 Liquid crystal compound [104-] represented by the following formula
And a liquid crystal compound [202-] represented by the following formula:
A liquid crystal composition of the present invention was manufactured by mixing in a weight ratio of 0:50.

[0328]

[Chemical 56]

Table 25 shows the phase transition temperatures of the above obtained compositions.
Shown in.

[0330]

[Table 25]

[0331]

Example 22 Liquid crystal compound [186-] represented by the following formula
And a liquid crystal compound [164-] represented by the following formula:
A liquid crystal composition of the present invention was manufactured by mixing in a weight ratio of 0:50.

[0332]

[Chemical 57]

Table 26 shows the phase transition temperatures of the above-obtained composition.
Shown in.

[0334]

[Table 26]

[0335]

Example 23 Liquid crystal compound [170-] represented by the following formula
And a liquid crystal compound [109-] represented by the following formula:
A liquid crystal composition of the present invention was manufactured by mixing in a weight ratio of 0:50.

[0336]

[Chemical 58]

Table 27 shows the phase transition temperatures of the above obtained composition.
Shown in.

[0338]

[Table 27]

[Brief description of drawings]

1 is a colorless semi-solid ¹ H-NM obtained in Example 1. FIG.
It is a chart figure of R spectrum.

2 is a colorless semi-solid ¹ H-NM obtained in Example 2. FIG.
It is a chart figure of R spectrum.

FIG. 3 Colorless semi-solid ¹ H-NM obtained in Example 3
It is a chart figure of R spectrum.

4 is a colorless semi-solid ¹ H-NM obtained in Example 4. FIG.
It is a chart figure of R spectrum.

FIG. 5: Colorless semi-solid ¹ H-NM obtained in Example 5
It is a chart figure of R spectrum.

6 is a colorless semi-solid ¹ H-NM obtained in Example 6. FIG.
It is a chart figure of R spectrum.

7 is a colorless semi-solid ¹ H-NM obtained in Example 7. FIG.
It is a chart figure of R spectrum.

8 is a colorless semi-solid ¹ H-NM obtained in Example 8. FIG.
It is a chart figure of R spectrum.

9 is a colorless semi-solid ¹ H-NM obtained in Example 9. FIG.
It is a chart figure of R spectrum.

10 is a colorless semi-solid ¹ H-obtained in Example 10. FIG.
It is a chart figure of a NMR spectrum.

11 is a colorless semi-solid ¹ H-obtained in Example 11. FIG.
It is a chart figure of a NMR spectrum.

12 is a colorless semi-solid ¹ H-obtained in Example 12.
It is a chart figure of a NMR spectrum.

13 is a colorless semi-solid ¹ H-obtained in Example 14.
It is a chart figure of a NMR spectrum.

FIG. 14 is a diagram schematically showing a cross-sectional shape of the liquid crystal element of the present invention.

FIG. 15 is a diagram showing a cross-sectional structure of a liquid crystal element of the present invention using a fiber as a spacer.

FIG. 16 is a diagram showing a cross-sectional structure of a liquid crystal element of the present invention in which cells of two polarizing plates are arranged.

FIG. 17 is a diagram showing an example of a non-linear element and a three-terminal element.

[Explanation of symbols]

 11a, 11b, 47,57 ・ ・ ・ Transparent substrate 12,43,53 ・ ・ ・ Liquid crystal material 13,58 ・ ・ ・ Cell 14 ・ ・ ・ Gap 15a, 15b, 45,55 ・ ・ ・ Transparent electrode 46 ・ ・ ・Fiber 56 ・ ・ ・ Polarizer

Continuation of front page (51) Int.Cl. ⁵ Identification code Internal reference number FI Technical display area C07C 69/773 9279-4H 69/92 9279-4H 69/94 9279-4H C07D 239/26 8615-4C 239 / 34 8615-4C C09K 19/32 9279-4H 19/34 9279-4H // G02F 1/13 500

Claims (15)

[Claims] 1. A liquid crystal material represented by the following formula [I]; R-X- A 1 -Y 1 -A 2 - (Y 2 -A 3) n -Z-R * ... [I] [ the formula [ In the above [I], R is an alkyl group having 3 to 20 carbon atoms or a polyfluoroalkyl group, and a part of the —CH ₂ — group or the —CF ₂ — group in the group is substituted with an —O— group. And -O- group and X are not directly bonded, or -O- groups are not bonded to each other, X is -COO-, -O-CO-, -CO- and Is a group selected from the group consisting of —O— or a single bond, n is 0 or 1, and at least 1 of A ¹ , A ² and A ³ present in the formula [I] is present.
The group of is Which is an optically active group selected from the group consisting of (the * mark indicates the chiral center of the optically active structure of the tetralin ring), and the remaining A ¹ , A ² and A ³ are each independently, [Chemical 2] A group selected from the group consisting of: Y ¹ and Y ² are each independently -COO-, -O-CO-, -CH;
₂ CH ₂ —, —CH ₂ O—, —O—CH ₂ —, —CO—CH ₂ —, and —CH ₂ —CO—, and Z is —O—, —CO. -, -COO-, and -O-CO- are a group or a single bond selected from the group consisting of, and R ^* is a carbon atom having at least one asymmetric carbon atom;
To 20 optically active groups (a hydrogen atom bonded to a carbon atom of the optically active group may be substituted with a halogen atom)]. 2. In the above formula [I], R ^* is the following formula [II]
In the liquid crystal material as in claim 1 wherein the possible wherein a group represented ^{by; -Q 1 -C * H (Q} 2) -Q 3 ··· [II] [ In Expression [II] , Q ¹ is-(CH ₂ ) _q- ; [q represents an integer of 0 to 6] (provided that one of-
CH ₂ - group -O- may be replaced by a group), Q ² and Q ³ are each independently an alkyl group having 1 to 10 carbon atoms, fluoroalkyl group having 1 to 10 carbon atoms and At least a part of CH ₂ groups or CF ₂ groups which are groups or atoms different from each other and are present in Q ¹ , Q ² and Q ³ selected from the group consisting of halogen atoms, are —O—, —S— , -C
O-, -CHX-; (X is a halogen atom), -CHCN-, -O-CO-, -O-CO
At least one kind of group selected from the group consisting of O-, -CO-O-, and -CH = CH-, which may be substituted so that two heteroatoms are not directly bonded. 3. In the above formula [I], Y ¹ and Y
The liquid crystal material according to claim 1, wherein ² is each independently -O-CO- or -COO-. 4. In the above formula [I], Z is —O— or —C.
The liquid crystal material according to claim 1, which is OO-. 5. In the above formula [I], R ^* is -C ^* H (C
F ₃ ) -C ₄ H ₉ , -C ^* H (CF ₃ ) -C ₅ H ₁₁ , -C ^* H (CF ₃ ) -C ₆ H ₁₃ , -C ^* H (C
_{H 3) -C 5 H 11,} -C * H (CH 3) -C 6 H 13, -C * H (CH 3) -C 7 H 15, -C * H
_{(CH 3) -C 8 H 17} , -C * H (C 2 H 5) -C 5 H 11, -C * H (C 2 H 5) -C
₆ H ₁₃ , -CH ₂ -C ^* H (CH ₃ ) -C ₂ H ₅ ,-(CH ₂ ) ₃ -C ^* H (CH ₃ ) -C
₂ H ₅ , -C ^* H (CF ₃ ) -CH ₂ -COO-C ₂ H ₅ , -C ^* H (CF ₃ )-(CH ₂ ) ₂ -0C
H ₃ , -C ^* H (CF ₃ )-(CH ₂ ) ₃ -0C ₂ H ₅ , -C ^* H (CF ₃ )-(CH ₂ ) ₄ -0C
^{_{H 3, -C * H (CF}} 3) - (CH 2) 5 -0C 2 liquid crystal material according to claim paragraph 1 or 2, wherein it is a group selected from the group consisting of H _5. 6. A liquid crystal material is represented by the following formula (L): (In the above formula, R ¹ is an alkyl group or an alkoxy group having 8 to 14 carbon atoms, R ² is an alkyl group, and one of the —CH ₂ — groups is an —O— group or -COO- group), and the optical activity resulting from the optically active structure in which one of the carbon atoms in the tetralin ring of the material is a chiral center is (-). The liquid crystal material according to item 1. 7. A liquid crystal material is represented by the following formula (M): (In the above formula, R ¹ is an alkyl group or an alkoxy group having 8 to 14 carbon atoms, R ² is an alkyl group, and one of the —CH ₂ — groups is an —O— group or -COO- group), and the optical activity resulting from the optically active structure in which one of the carbon atoms in the tetralin ring of the material is a chiral center is (+). The liquid crystal material according to item 1. 8. A 1,2,3,4-tetrahydro-6-alkoxynaphthalene-2-carboxylic acid having an optical activity of (−) due to an optically active structure in which one of the carbon atoms in the tetralin ring is a chiral center. , 1,2,3,4-Tetrahydro-6-hydroxynaphthalene-2-carboxylic acid or 1,2,3,4-tetrahydro-6-benzyloxynaphthalene-2-carboxylic acid and the number of carbon atoms having optical activity The liquid crystal material according to claim 1, wherein the liquid crystal material is obtained from 4 to 20 monoalcohols. 9. The number of carbon atoms having optical activity of 4 to 2
The liquid crystal material according to claim 8, wherein the monoalcohol of 0 is 1-trifluoromethyl alcohol [RCH (CF ₃ ) OH: R = C _{2 to} C ₁₈ ]. 10. A 1,2,3,4-tetrahydro-6-alkoxynaphthalene-2-carboxylic acid having an optical activity of (+) due to an optically active structure in which one of the carbon atoms in the tetralin ring is a chiral center. , 1,2,3,4-Tetrahydro-6-hydroxynaphthalene-2-carboxylic acid or 1,2,3,4-tetrahydro-6-benzyloxynaphthalene-2-carboxylic acid and the number of carbon atoms having optical activity The liquid crystal material according to claim 1, wherein the liquid crystal material is obtained from 4 to 20 monoalcohols. 11. The optically active carbon atom number of 4 to
20 monoalcohols are 1-methyl alcohol [RCH
_{(CH 3) OH: R =} C 2 ~C 18] The liquid crystal material according to claim 10 wherein, wherein the a. 12. A tetralination represented by the following formula [I]:
Liquid crystal composition containing compound; R-X-A¹-Y¹-A²-(Y²-A³)_n-Z-R^* [I] [In the above formula [I], R represents an alkyl group having 3 to 20 carbon atoms or polyfluoride.
An oroalkyl group, in which -CH₂-Group or -CF₂-Group
Part of may be substituted with an -O- group, and
X is directly bonded, or -O- groups are bonded together
X is selected from the group consisting of -COO-, -O-CO-, -CO- and -O-.
Is a group or a single bond, n is 0 or 1, and A in the formula [I] is present.¹, A²And A³At least one of
The group of isAn optically active group selected from the group consisting of
Indicates the chiral center of the optically active structure of the tetralin ring.
You ) And the remaining A¹, A²And A³Is that
Independently,A group selected from the group consisting of Y¹And Y²Are independently -COO-, -O-CO-, -CH
₂CH₂-, -CH₂O-, -O-CH ₂-, -CO-CH₂-And-CH₂-CO-
Z is a group selected from the group consisting of -O-, -CO-, -COO- and -O-CO-.
A group or a single bond, R^*Has 4 carbon atoms having at least one asymmetric carbon
~ 20 optically active groups (bonded to a carbon atom of the optically active group
A hydrogen atom may be replaced by a halogen atom)
]]. 13. A liquid crystal element comprising a cell composed of two substrates facing each other and a gap formed by the substrates, and a liquid crystal element filled with a liquid crystal substance filled in the gap between the cells, wherein the liquid crystal substance is following type liquid crystal element, characterized in that it contains the tetralin compound represented by [I]; R-X- a 1 -Y 1 -A 2 - (Y 2 -A 3) n -Z-R * ... [ I] [In the above formula [I], R is an alkyl group having 3 to 20 carbon atoms or a polyfluoroalkyl group, and a part of —CH ₂ — group or —CF ₂ — group in the group is — It may be substituted with an O-group, and the -O- group and X are not directly bonded to each other, or the -O- groups are not bonded to each other, and X is -COO-, -O-CO. -, - CO- and -O- are more becomes group or a single bond selected from the group, n is 0 or 1, a ^1, a ² and a ³ present in the formula [I] At least 1
The group of is Which is an optically active group selected from the group consisting of (* indicates a chiral center of the optically active structure of the tetralin ring), and the remaining A ¹ , A ² and A ³ are each independently, [Chemical 8] A group selected from the group consisting of: Y ¹ and Y ² are each independently -COO-, -O-CO-, -CH;
₂ CH ₂ —, —CH ₂ —O—, —O—CH ₂ —, —CO—CH ₂ — and —CH ₂ —CO—, and Z is —O—, — Is a group selected from the group consisting of CO-, -COO-, and -O-CO-, or a single bond, and R ^* is 4 carbon atoms having at least one asymmetric carbon atom.
To 20 optically active groups (a hydrogen atom bonded to a carbon atom of the optically active group may be substituted with a halogen atom)]. 14. A compound represented by the following formula (L): (In the above formula, R ¹ is an alkyl group or an alkoxy group having 8 to 14 carbon atoms, R ² is an alkyl group, and one of the —CH ₂ — groups is an —O— group or -COO- group) and the optical activity due to the optically active structure in which one of the carbon atoms in the tetralin ring of the above material is a chiral center is (-). Ester compound. 15. A compound represented by the following formula (M): (In the above formula, R ¹ is an alkyl group or an alkoxy group having 8 to 14 carbon atoms, R ² is an alkyl group, and one of the —CH ₂ — groups is an —O— group or -COO- group) and the optical activity resulting from the optically active structure in which one of the carbon atoms in the tetralin ring of the above material is a chiral center is (+). Ester compound.