JPH0812622A - Tetralin compound, its production and tetralin-type carboxylic acid ester compound, liquid crystal material, liquid crystal composition and liquid crystal element - Google Patents

Abstract

PURPOSE:To provide a new tetralin compound capable of forming a liquid crystal element having a broad working temperature range, a high switching speed, an extremely low power consumption and a stable contrast. CONSTITUTION:This new tetralin carboxylic acid ester is expressed by formula I {R is a 3-20C alkyl or a 3-20C polyfluoroalkyl; X is COO, OCO, O or single bond; A<1> is 1,4-phenylene, 4,4'-biphenylene, a group of formula II, 2,6-naphthylene, etc.; Y<1> is COO, OCO, CH2O or OCH2; Z is group of formula III to formula VII, etc.; R* is Q<1>-C*HQ<2>-Q<3> [Q<1> is (CH2)a; (a) is 0-6; Q<2> is CF3, CH3 or C2H5; Q<3> is a 1-10C alkyl or a 1-10C polyfluoroalkyl; Q<2> is different from Q<3>)]}. This new tetralin compound useful as an intermediate for the compound of formula I is expressed by formula VIII [R is H, a 1-20C alkyl, a 6-20C aryl or a 7-20C aralkyl; Z is group of formula III or formula IV; R' is H, a 1-20C alkyl, a 6-20C aryl or Q<1>-C*HQ<2>-Q<3> (Q<1> and Q<3> are each same as the group defined in formula I; Q<2> is H, CF3, CH3 or C2H5)].

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a novel tetralin compound, a method for producing the same, and a novel tetralin carboxylic acid ester compound, a liquid crystal material, a liquid crystal composition and a liquid crystal element.

[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 an applied electric field, it has very good switching threshold characteristics and 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, etc., the ferroelectric liquid crystal compound has an operating temperature range of around room temperature or below, and an operating temperature range. Is required, a switching speed is high (fast), and a switching threshold voltage is within a proper range. Of these, the operating temperature range is a particularly important characteristic when the ferroelectric liquid crystal compound is put to practical use.

However, the ferroelectric liquid crystal compounds known so far generally have a narrow operating temperature, and even a ferroelectric liquid crystal compound having a wide operating temperature range has a high operating temperature range not including room temperature. In the range, there is no practically satisfactory ferroelectric liquid crystal compound.

[0007]

It is an object of the present invention to provide a novel tetralin compound, a method for producing the same, a tetralinic carboxylic acid ester compound, a liquid crystal material, a liquid crystal composition and a liquid crystal element. More specifically, the present invention provides
To provide a novel tetralin compound, a tetralinic carboxylic acid ester compound, and a use thereof which can form a liquid crystal device having a wide operating temperature, a high switching speed, an extremely low power consumption, and a stable contrast. Has an aim.

[0008]

SUMMARY OF THE INVENTION The tetralin compound according to the present invention is characterized by being represented by the following formula [I].

R-O-Z-C^*H (CH₃) COO-R '... [I] (In the formula, R represents a hydrogen atom or a straight chain having 1 to 20 carbon atoms.
Or branched alkyl group, aryl having 6 to 20 carbon atoms
A group or an aralkyl group having 7 to 20 carbon atoms
And one -CH present in the alkyl group₂-Group, or
Two or more -CH that are not adjacent₂-Group is replaced by -O- group
R'is a hydrogen atom or a carbon atom of 1
-20 straight-chain or branched alkyl groups, 6 to 2 carbon atoms
An aryl group of 0, or -Q¹-C^*H (Q²) -Q
³Shows [Q ¹Is- (CH₂)_aIndicates-, and a is an integer of 0 to 6
And a single -CH present in these groups₂-Base,
Is two or more -CH that are not adjacent₂-Group is placed by -O- group
Q may have been changed²Is a hydrogen atom, CF₃Group, CH
₃Base, C₂H_FiveShows the group, Q³Is an al having 1 to 20 carbon atoms
Indicates a kill group or a polyfluoroalkyl group (however, Q
³And Q², And Z is

[0010]

[Chemical 6]

Is shown. The tetralin compound of the present invention can be a raw material for producing a tetralin carboxylic acid ester compound represented by the following formula [III].

The method for producing a tetralin compound according to the present invention is characterized by obtaining a tetralin compound represented by the above formula [I] by hydrogenating a naphthalene compound represented by the following formula [II].

[0013]

[Chemical 7]

(In the formula, R represents a hydrogen atom or a carbon atom number of 1 to 1.
20 straight or branched alkyl groups, 6 to 20 carbon atoms
Aryl group or aralkyl having 7 to 20 carbon atoms
1-CH present in an alkyl group₂-Base,
Or two or more -CH that are not adjacent₂-Group is -O- group
R ′ is a hydrogen atom or a carbon atom.
Linear or branched alkyl group having 1 to 20 children, number of carbon atoms
6-20 aryl groups, or -Q¹-C^*H
(Q²) -Q³Shows [Q ¹Is- (CH₂)_a-Indicates that a is
An integer of 0 to 6 is shown, and one -C present in these groups is present.
H₂-Group, or two or more -CH that are not adjacent₂-Group is -O-
Q may be replaced by a group, Q²Is a hydrogen atom,
CF₃Group, CH₃Base, C₂H_FiveShows the group, Q³Has 1 to 2 carbon atoms
0 represents an alkyl group or a polyfluoroalkyl group
(However, Q³And Q²Is not the same as))).

The tetralinic carboxylic acid ester compound according to the present invention is characterized by being represented by the following formula [III]. ^{R-X-A 1 -Y 1} -Z-C * H (CH 3) COO-R * ... [III] ( wherein, R is an alkyl group having 3 to 20 carbon atoms, carbon atoms 3 to 20 And a single -CH ₂ -group, -CHF- group or-present in these groups.
CF ₂ -group, or two or more non-adjacent -CH ₂ -groups, -CH
The F- group or the -CF ₂ -group may be replaced by a -O- group, and X represents a group selected from the group consisting of -COO-, -OCO- and -O- or a single bond, A ¹ is

[0016]

Embedded image

Represents a group selected from the group consisting of:
^1, -COO -, - OCO -, - CH 2 CH 2 -, - CH 2 O-, and -OCH ₂ -
Represents a group selected from the group consisting of

[0018]

[Chemical 9]

Represents a group selected from the following, and R ^* is --Q ^1-
C ^* H (Q ²⁾ shows a -Q ³ [Q ¹ is - (CH _{2) a} - indicates,
a represents an integer of 0 to 6, and one —CH ₂ — group present in these groups or two or more —CH ₂ — groups which are not adjacent to each other is —O
May be replaced by a group, Q ² is CF ₃ group, C
H ₃ group and C ₂ H ₅ group are shown, and Q ³ is an alkyl group having 1 to 10 carbon atoms or a polyfluoroalkyl group having 1 to 10 carbon atoms (provided that Q ³ and Q ² are not the same. In the present invention, in the above formula [III], A ¹ is

[0020]

[Chemical 10]

It is preferably a group selected from the group consisting of
Good. In the above formula [III], R^*But -C^*H (CF
₃) -C₈H₁₇, -C^*H (CF₃) -C₆H₁₃, -C^*H (CF₃) -C_FiveH₁₁, -C^*H (C
F₃) -C_FourH₉, -C^*H (CF₃) -C₃H₇, -C^*H (CH₃) -C₈H₁₇, -C^*H (CH
₃) -C₇H_Fifteen, -C^*H (CH₃) -C₆H₁₃, -C^*H (CH₃) -C_FiveH₁₁, -C^*H (C
H₃) -C_FourH₉, -C^*H (CH₃) -C₃H₇, -C^*H (C₂H_Five) -C_FiveH₁₁, -C^*H (C
₂H_Five) -C₆H₁₃, -CH₂-C^*H (CH₃) -C₂H_Five,-(CH₂)₃-C^*H (CH₃) -C
₂H_Five, -C^*H (CF₃) -CH₂-COO-C₂H_FiveSelected from the group consisting of
It is preferably a group.

Further, in the above formula [III], Y
It is preferred that ¹ is -COO-. A liquid crystal material according to the present invention is characterized by comprising the tetralinic carboxylic acid ester compound.

The liquid crystal composition according to the present invention is characterized by containing the above-mentioned tetralin carboxylic acid ester compound. A liquid crystal element according to the present invention is a liquid crystal element composed of 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 the tetralinic carboxylic acid ester compound.

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

[0025]

DETAILED DESCRIPTION OF THE INVENTION The tetralin compound, the method for producing the same, the tetralinic carboxylic acid ester compound, the liquid crystal material, the liquid crystal composition and the liquid crystal element according to the present invention will be specifically described below.

The tetralin compound according to the present invention is a compound represented by the following formula [I]. During ^{R-O-Z-C *} H (CH 3) COO-R '... [I] formulas, R is a hydrogen atom, a linear or branched alkyl group having 1 to 20 carbon atoms, 6 to 20 carbon atoms It is an aryl group or an aralkyl group having 7 to 20 carbon atoms. Here, a molecule in which R is a linear alkyl group is likely to have a rod-shaped structure and exhibits excellent liquid crystallinity.

Examples of the linear alkyl group having 1 to 20 carbon atoms include methyl group, ethyl group, propyl group, pentyl group,
Examples thereof include a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, an undecyl group, a dodecyl group, a tetradecyl group, a hexadecyl group, an octadecyl group and an eicosyl group.

Examples of the branched alkyl group having 1 to 20 carbon atoms include iso-propyl group, tert-butyl group and iso-acyl group. Present in these straight or branched alkyl group one -CH ₂ - group or non-adjacent two or more -CH _2, - groups may be replaced by -O- groups. -C present in a straight-chain or branched alkyl group
One of the H ₂ -groups or two or more -C which are not adjacent to each other
H _2- is an alkyl group substituted with an -O- group,
(2-hexyloxy) ethoxy group, [(2'-butoxy)-
Examples include 2-ethoxy] ethoxy group and nonyloxymethyl group.

Examples of the aryl group having 6 to 20 carbon atoms include phenyl group, naphthyl group and anthracenyl group. Examples of the aralkyl group having 7 to 20 carbon atoms include benzyl group.

R'is a hydrogen atom or a C 1-20
A straight chain or branched alkyl group, a group having 1 to 20 carbon atoms,
Or -Q¹-C^*H (Q²) -Q³Is. However
Then Q ¹Is- (CH₂)_aIs shown, and a is an integer of 0 to 6
And a single -CH present in these groups₂-Group or adjacent
Not two or more -CH₂-Group is replaced by -O- group
May be included, Q²Is a hydrogen atom, CF₃Group, CH₃Base, C₂H_Five
Shows the group, Q³Is an alkyl group having 1 to 20 carbon atoms, or
Represents a polyfluoroalkyl group having 1 to 20 carbon atoms
You. However, Q³And Q²Is not the same as.

Examples of the alkyl group having 1 to 20 carbon atoms include the same straight-chain or branched alkyl groups as described above, and alicyclic alkyl groups such as cyclopentyl group and cyclohexyl group. Examples of the polyfluoroalkyl group having 1 to 20 carbon atoms include groups in which some or all of the hydrogen atoms of the above alkyl group are substituted with fluorine atoms.

Z is

[0033]

[Chemical 11]

And among these,

[0035]

[Chemical 12]

It is preferable that Specific examples of the tetralin compound represented by the above formula [I] include the following Table 1-
The compounds described in (1) to Table 1- (2) can be mentioned.

In the tables described below, R,
The bonding state of Z, R ′ and tetralin is represented by the following formula [I].
It shows each state in. ^{R-O-Z-C *} H (CH 3) COO-R '... [I]

[0038]

[Table 1]

[0039]

[Table 2]

Such a tetralin compound [I] according to the present invention can be obtained by hydrogenating a naphthalene compound represented by the following formula [II].

[0041]

[Chemical 13]

Hydrogenation of the naphthalene compound represented by the above formula [II] is carried out by supplying hydrogen in the presence of a catalyst. More specifically, for example, metallic sodium is added to a mixture of the naphthalene compound represented by the above formula [II] and an organic solvent such as 1,2-diethoxyethane, and
Add alcohols such as iso-amyl alcohol dropwise.

The above method is an example of the method for producing the tetralin compound of the present invention, and the tetralin compound of the present invention is not limited by this production method.
The tetralin carboxylic acid ester compound according to the present invention is a compound represented by the following formula [III].

[0044] ^{R-X-A 1 -Y 1} -Z-C * H (CH 3) COO-R * ... [III] wherein, R represents an alkyl group having 3 to 20 carbon atoms or carbon atoms, 3 to 20 polyfluoroalkyl groups.
When R is an alkyl group having 3 to 20 carbon atoms, such an alkyl group may be linear, branched or alicyclic, but R is linear. The molecule of the tetralinic carboxylic acid ester compound, which is an alkyl group of, has a rigid structure in which the molecule extends straight,
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. Can be mentioned.

Examples of the polyfluoroalkyl group having 3 to 20 carbon atoms include groups in which a part or all of the hydrogen atoms of the above alkyl group are substituted with fluorine atoms. One of the -CH ₂ -group, -CHF- group or -CF _2- present in these alkyl groups or polyfluoroalkyl groups
Groups, or two or more non-adjacent -CH ₂ -groups, -CHF
The — group or the —CF ₂ — group may be replaced by an —O— group. 1 -C present in a straight-chain or branched alkyl group
H ₂ -group, -CHF- group or -CF ₂ -group, or two or more -CH ₂ -groups, -CHF- groups or -CF ₂ -groups which are not adjacent to each other,
Examples of the alkyl group substituted with the -O- group include a (2-hexyloxy) ethoxy group, a [(2'-butoxy) -2-ethoxy] ethoxy group and a nonyloxymethyl group.

X represents a group selected from the group consisting of --COO--, --OCO-- and --O-- or a single bond. Of these, when the tetralinic carboxylic acid ester compound of the present invention is used as a liquid crystal material, X is preferably —O— or a single bond in view of characteristics as a liquid crystal substance.

A ¹ is

[0049]

Embedded image

A group selected from the group consisting of: Out of these

[0051]

[Chemical 15]

It is preferably a group selected from the group consisting of: Y ¹ represents a group selected from the group consisting of —COO—, —OCO—, —CH ₂ CH ₂ —, —CH ₂ O—, and —OCH ₂ —. Among these, when the ester of the present invention is used as a liquid crystal material, Y ¹ is -COO-, -OCO-, -CH ₂ CH _2- , -CH ₂ O- and -O.
It is preferably a group selected from the group consisting of CH _2- ,
-COO- or -OCO- is more preferable, and in view of the linearity of the molecule, -COO- is particularly preferable.

Z is

[0054]

Embedded image

A group selected from

[0056]

[Chemical 17]

A group selected from

[0058]

Embedded image

It is particularly preferable that R ^* is -Q
Shows the ^{1 -C * H (Q 2)} -Q 3. However, Q ¹ is-(C
H ₂ ) _a- , a represents an integer of 0 to 6, and one -CH ₂ -group present in these groups or two or more groups not adjacent to each other
-CH ₂ - groups may be replaced by -O- groups.

Q ² represents CF ₃ , CH ₃ or C ₂ H ₅ , and Q ³ is an alkyl group having 1 to 10 carbon atoms or 1 to 10 carbon atoms.
Shows a polyfluoroalkyl group. However, Q ³ and Q ²
Is not the same as.

Among these, -C^*H (CF₃) -C₈H₁₇, -C^*
H (CF₃) -C₆H₁₃, -C^*H (CF₃) -C_FiveH₁₁, -C^*H (CF₃) -C_FourH₉, -C^*
H (CF₃) -C₃H₇, -C^*H (CH₃) -C₈H₁₇, -C^*H (CH₃) -C₇H_Fifteen, -C^*
H (CH ₃) -C₆H₁₃, -C^*H (CH₃) -C_FiveH₁₁, -C^*H (CH₃) -C_FourH₉, -C^*
H (CH₃) -C₃H₇, -C^*H (C₂H_Five)_FiveH_{1 1}, -C^*H (C₂H_Five) -C₆H₁₃, -CH
₂-C^*H (CH₃) -C₂H_Five,-(CH₂)₃-C^*H (CH₃) -C_2-C ^*H (CF₃) -CH ₂-
COO-C₂H_FiveIt is preferably a group selected from sand
Wow, this R^*Is light having at least one asymmetric carbon
It is an academically active group. The carbon that constitutes this optically active group
A carbon atom attached to an atom is, for example,
It may have a fluorine atom.

Of these groups, when the tetralinic carboxylic acid ester compound of the present invention is used as a liquid crystal material, considering the characteristics as a liquid crystal substance, -C ^* H (CF ₃ ) -C ₆
H _13, is preferably _{^{-C * H (CF 3) -C}} 5 H 11.

Specific examples of the tetralinic carboxylic acid ester compound represented by the above formula [III] are shown in Table 2 below.
The compounds described in-(1) to Table 2- (9) may be mentioned. In the table described below, R, X, A ¹ ,
The bonding states of Z, Y ¹ , R ^* and the tetralinic carboxylic acid ester compound show the respective states in the following formula [III].

[0064] ^{R-X-A 1 -Y 1} -Z-C * H (CH 3) COO-R * ... [III]

[0065]

[Table 3]

[0066]

[Table 4]

[0067]

[Table 5]

[0068]

[Table 6]

[0069]

[Table 7]

[0070]

[Table 8]

[0071]

[Table 9]

[0072]

[Table 10]

[0073]

[Table 11]

The tetralinic carboxylic acid ester compound as described above can be produced by combining known synthetic techniques. For example, the above tetralinic carboxylic acid ester compound can be synthesized according to the synthetic route shown below.

That is, for example, a mixture of (S)-(+)-2- (6-alkoxy-2-naphthyl) propionic acid and 1,2-diethoxyethane is added dropwise to isoamyl alcohol in the presence of metallic sodium. While refluxing, (S)-(+)-2-
(1,2,3,4-Tetrahydro-6-alkoxy-2-naphthyl) propionic acid is obtained.

Reacting (S)-(+)-2- (1,2,3,4-tetrahydro-6-alkoxy-2-naphthyl) propionic acid thus obtained with acetic acid and hydrobromic acid By (S)-
(+)-2- (1,2,3,4-Tetrahydro-6-hydroxy-2-naphthyl) propionic acid is obtained.

(S)-(+)-2- (1, obtained as described above
(S)-(+)-2- (1,2,3,4) by reacting 2,3,4-tetrahydro-6-hydroxy-2-naphthyl) propionic acid with benzyl bromide in the presence of potassium hydroxide. -Tetrahydro-6-benzyloxy-2-naphthyl) propionic acid is obtained.

Next, using 4-N, N-dimethylaminopyridine and methylene chloride as a solvent, while adding an N, N'-dicyclohexylcarbodiimide solution dropwise, (R) -1-trifluoromethylheptanol and Obtained in the above process
(S)-(+)-2- (1,2,3,4-tetrahydro-6-benzyloxy-
2-naphthyl) propionic acid by reacting (S)-
(+)-2- (1,2,3,4-Tetrahydro-6-benzyloxy-2-naphthyl) propionic acid (R) -1-trifluoromethylheptyl ester is obtained.

The obtained (S)-(+)-2- (1,2,3,4-tetrahydro-6-benzyloxy-2-naphthyl) propionic acid (R) -1
-By charging trifluoromethylheptyl ester into a solvent such as tetrahydrofuran and reducing with hydrogen gas in the presence of a reducing catalyst such as palladium / carbon,
(S)-(+)-2- (1,2,3,4-tetrahydro-6-hydroxy-2-
Naphthyl) propionic acid (R) -1-trifluoromethylheptyl ester is obtained.

Then, using 4-N, N-dimethylaminopyridine and methylene chloride as a solvent, an N, N'-dicyclohexylcarbodiimide solution was added dropwise, and alkyl or alkoxybiphenylcarboxylic acid was obtained in the above step ( S)-(+)-2- (1,2,3,4-tetrahydro-6-hydroxy
The tetralin carboxylic acid ester compound of the present invention can be obtained by reacting -2-naphthyl) propionic acid (R) -1-trifluoromethylheptyl ester.

The above method is one example of the method for producing the tetralin carboxylic acid ester compound of the present invention, and the tetralin carboxylic acid ester compound of the present invention is not limited by this production method.

Among the tetralinic carboxylic acid ester compounds of the present invention, 6-[(4'-decyloxy-
4-Biphenyl) carbonyloxy]-(S)-(+)-2- (1,2,
3,4-Tetrahydro-2-naphthyl) propionic acid (R) -1-
The ¹ H-NMR chart of trifluoromethylheptyl ester [Exemplified Compound (4)] is shown in FIG.

[0083]

[Chemical 19]

In the above formula, the numbers 1 to 13 represent hydrogen atoms, and these numbers correspond to the numbers given to the peaks in FIG. Further, among the tetralinic carboxylic acid ester compounds of the present invention, 6-represented by the following formula
[(4'-decyloxy-4-biphenyl) carbonyloxy]-(S)-(+)-2- (1,2,3,4-tetrahydro-2-naphthyl)
The ¹ H-NMR chart of propionic acid (R) -1-trifluoromethylhexyl ester [Exemplified compound (98)] is shown in FIG.

[0085]

Embedded image

In the above formula, the numbers 1 to 13 are
A hydrogen atom is shown, and this number corresponds to the number given to the peak in FIG. The tetralinic carboxylic acid ester compound represented by the above formula [III] can be used, for example, as a liquid crystal material.

In particular, the tetralinic carboxylic acid ester compound having optical activity can be used as a ferroelectric liquid crystal material or an antiferroelectric liquid crystal material. Among such tetralinic carboxylic acid ester compounds, the compounds represented by the following formulas [4] and [98] show particularly excellent liquid crystal properties.

[0088]

[Chemical 21]

Table 3 shows the phase transition temperatures of the compounds represented by the formulas [4] and [98], which are particularly excellent as liquid crystal materials. In Table 3 below, Cryst
Represents a crystalline phase, SmC _A ^* represents an antiferroelectric phase, SmC ^* represents a ferroelectric phase, SmA represents a smectic A phase, Ch represents a cholesteric phase, and Iso represents an isotropic liquid.

[0090]

[Table 12]

In the liquid crystal material of the present invention, as shown in Table 3, many compounds exhibit a smectic phase and a cholesteric phase in a wide temperature range. Conventionally, when a liquid crystal material is used alone, a liquid crystal material that exhibits a smectic phase and a cholesteric phase in a wide temperature range like the above compounds is not well known.

The liquid crystal material of the present invention has a wide temperature showing a smectic phase, and an optical switching element manufactured using such a liquid crystal material is also excellent in high-speed response.

The liquid crystal material of the present invention can be used alone, or can be used as a liquid crystal composition by mixing with another liquid crystal material. For example, the liquid crystal material of the present invention can be used as a main ingredient of an antiferroelectric liquid crystal composition or an auxiliary agent of a liquid crystal composition whose main ingredient is another compound exhibiting a smectic phase. That is, among the carboxylic acid ester compounds of the present invention, a compound 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 smectic compound. The compound exhibiting no phase 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 that can be used in the present invention together with the compound represented by the formula [III] are (+)-4 ′-(2 ”-methylbutyloxy) phenyl-6-octyloxynaphthalene. -2-carboxylic acid ester, 4'-decyloxyphenyl-6-((+)-2 "-methylbutyloxy) naphthalene-2-carboxylic acid ester,

[0095]

[Chemical formula 22]

In addition to liquid crystal compounds such as

[0097]

[Chemical formula 23]

Or

[0099]

[Chemical formula 24]

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

[0101]

[Chemical 25]

A Schiff base type liquid crystal compound such as

[0103]

[Chemical formula 26]

An azoxy liquid crystal compound such as

[0105]

[Chemical 27]

A benzoic acid ester liquid crystal compound such as

[0107]

[Chemical 28]

A cyclohexylcarboxylic acid ester liquid crystal compound such as

[0109]

[Chemical 29]

A phenyl liquid crystal compound such as

[0111]

Embedded image

A terphenol liquid crystal compound such as

[0113]

[Chemical 31]

A cyclohexyl liquid crystal compound such as

[0115]

Embedded image

Examples of such pyrimidine type liquid crystal compounds include: The liquid crystal composition of the present invention contains the tetralin carboxylic acid ester compound represented by the above formula [III] and other compounds including the compounds exemplified above. The blending ratio of the tetralinic carboxylic acid ester compound represented by the formula [III] in this liquid crystal composition can be arbitrarily set in consideration of the characteristics of the liquid crystal composition to be obtained. The composition of the present invention is usually 1 to 99 parts by weight, preferably 5 to 75 parts by weight of the tetralinic carboxylic acid ester compound represented by the formula [III] in 100 parts by weight of the liquid crystal material in the composition. It is contained in an amount within the range of parts by weight.

In addition to the above-mentioned liquid crystal material, 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.

The liquid crystal composition used in the present invention can be produced by mixing the above tetralinic carboxylic acid ester compound and, if desired, other liquid crystal compounds and additives.

The liquid crystal composition (liquid crystal substance) containing the above-mentioned liquid crystal material causes an optical switching phenomenon when a voltage is applied. Therefore, it is possible to make use of this phenomenon to manufacture a display device having good responsiveness. it can. In the present invention, an element or an element driving method utilizing such a phenomenon is described in, for example, JP-A-56-107216,
Reference can be made to JP-A-59-118744.

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

However, the inventor of the present invention disclosed in Japanese Patent Laid-Open No. 64-3
In the present invention, not only the smectic C phase but also the smectic A phase can be used by utilizing the driving method of the display device in the smectic A phase as already proposed in Japanese Patent No. 632. That is, by using this driving method, it becomes possible to drive a liquid crystal element in a wide range by using the liquid crystal substance containing the liquid crystal material of the present invention, and to achieve high speed electro-optical compatibility. be able to.

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

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, for example, iridium oxide,
It is formed by coating the transparent substrate surface with tin oxide or the like. The transparent electrode can be formed by a known method. The thickness of the transparent electrode is usually 100-200.
It is within the range of 0Å.

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.

Further, as a method of imparting orientation to the thin film as described above, a method of imparting anisotropy or shape specificity to the thin film itself during film formation, and a method of imparting orientation from the outside after the thin film is formed. is there. Specifically, after forming a thin film by coating a polymer material such as 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 used.

Two transparent substrates as described above are arranged so that the 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, preferably 1 to 5 μm. Such a gap can be formed, for example, by arranging two substrates so as to sandwich a spacer.
It can be easily formed. 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 due to the interface effect between the spacer and the liquid crystal substance.

For example, the alignment film and the spacer can be integrated by using a concentric spacer or a comb-shaped spacer that acts as an alignment film. Moreover, as shown in FIG. 4, in addition to the spacers as described above, a fiber 46 is mixed in the liquid crystal substance 43, and by this fiber,
The transparent substrate 47 provided with the transparent electrode 45 may be held so as to form a constant gap.

Further, instead of the above-mentioned fibers, or together with the above-mentioned fibers, a granular material having a particle diameter of 1 to 10 μm can be blended. 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 gap of the liquid crystal cell having the above structure is filled with the liquid crystal substance containing the tetralin carboxylic acid ester compound represented by the above formula [III].

The liquid crystal substance filled in the gaps of the liquid crystal cell should 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. You can 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. 5, two or more cells 58 composed of the two transparent substrates 57, the transparent electrodes 55 and the liquid crystal substance 53 prepared as described above are arranged between the two polarizing plates 56. You can also do it.

In the liquid crystal element of the present invention, the polarizing plates can be arranged so 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.

In the present invention, the liquid crystal cell as described above is ± 10 from the state where the amount of light transmitted between the polarizing plates arranged as described above is the smallest (that is, the darkest state).
It can be arranged between the 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 placed between two polarizing plates so as to be in a state.

The liquid crystal substance 15 filled in the gaps 14 of the cell 13 having the above-mentioned structure has the above formula [III].
It contains a tetralin carboxylic acid ester compound represented by. The liquid crystal element of the present invention, as shown in FIG.
It can be manufactured 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.

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.

Next, the cell 13 with the injection port thus sealed is heated to a temperature equal to or higher than the temperature at which the liquid crystal substance 15 filled in the cell exhibits an isotropic phase, and then this liquid crystal substance 15 is heated.
Cool to a temperature at which the liquid crystal shows.

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./minute, more preferably 0.1 to 0.5 ° C./minute. By cooling the cell 13 at such a cooling rate, the initial compounding state of the liquid crystal substance 15 is improved, and a liquid crystal element having a liquid crystal phase composed of a monodomain with few alignment defects can be easily formed. 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 is remarkably excellent in 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 /
μmt (voltage per 1 μm thickness), preferably 0.05
It can be driven by applying a controlled electric field of about 30 Vp-p / μmt.

By using the optically active liquid crystal substance containing the tetralinic carboxylic acid ester compound represented by the above formula [III], the liquid crystal device of the present invention can be driven by applying an electric field. By changing the width of the waveform (driving wave) of the electric field applied to the liquid crystal element, the amount of light transmitted through the 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 substance 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, preferably 70 Hz to
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 substance containing a carboxylic acid ester compound having ferroelectricity, in addition to the applications as described above, a liquid crystal such as an optical switching element such as an optical shutter or a liquid crystal printer, a piezoelectric element and a pyroelectric element. A display device or an electro-optical display device can be manufactured.

That is, since the liquid crystal element used in the present invention exhibits, for example, bistability, the liquid crystal element of the present invention is provided with an optical switching function or a display by reversing the electric field so as to achieve a bistable state. It can have a function.

Further, since the liquid crystal substance used in the present invention has spontaneous polarization, once the voltage is applied, it has the memory effect even after the electric field is erased. Therefore, 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. Moreover, since this display device has a stable contrast, it is very clear.

Further, in the switching element of the present invention using the liquid crystal composition containing the tetralinic carboxylic acid ester compound represented by the above formula [III], the switching operation can be performed only by changing the orientation direction of molecules, In this case, since the first term of the electric field strength acts on the driving of this switching element, the switching element of the present invention 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 orientation vector of the liquid crystal substance, thereby forming 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, and examples of such a dichroic dye include an azo dye, a naphthoquinone dye, a cyanine dye and an anthraquinone dye.

A display device manufactured by using the liquid crystal device of the present invention is manufactured by an electrical 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, as shown in FIG.
As shown in (a), varistor
An element that uses M (Metal Insulator Metal), a diode, and the like and uses these nonlinearities can be given. Further, as the active element of the three-terminal element, for example, as shown in FIG. 6B, a TFT (thin film transistor),
Si-MOS (Si-metal oxide semi conductor field-e
ffect transistor) and SOS (Sillicon on Sapp)
hire) etc. can be cited as an element arranged in a picture element.

[0154]

The present invention provides a novel tetralin compound and a method for producing the same. INDUSTRIAL APPLICABILITY The novel tetralin compound of the present invention serves as a raw material for producing a tetralin carboxylic acid ester compound exhibiting excellent liquid crystal performance.

The present invention provides a novel tetralin carboxylic acid ester compound. This novel tetralin carboxylic acid ester compound is optically active,
Moreover, it exhibits a smectic phase in a wide temperature range including room temperature, and can be used as a ferroelectric liquid crystal material or an antiferroelectric liquid crystal material.

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 or the like having a high-speed response in a wide temperature range. Furthermore, in a liquid crystal display manufactured using such an element, the operation time can be shortened significantly.

With such a display, power consumption can be reduced. Further, the tilt angle of the molecules, that is, the tilt angle can be made very large, and the alignment of the liquid crystal molecules, that is, the orientation can be made very high, so that high contrast can be obtained. Further, stable contrast can be obtained.
Further, low voltage driving is also possible.

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

[0160]

EXAMPLES Examples of the present invention will be shown below, but the present invention is not limited to these examples. Note that R and S represent the R and S forms of the optically active substance.

[0161]

Example 1 (S)-(+)-2- (1,2,3,4-tetrahydro-6-decyloxy-2-
Synthesis of naphthyl) propionic acid

[0162]

[Chemical 33]

(S)-(+)-2- (6-decyloxy-2-naphthyl)
To a mixture of 4.98 g (14 mmol) of propionic acid and 140 ml of 1,2-diethoxyethane, under a nitrogen atmosphere,
Under stirring at 120 ° C, 4.19 g of metal sodium (182
Milligram atom) was added and further heated to reflux temperature.

Isoamyl alcohol 18.
9 g (214 mmol) was added dropwise over 2 hours, and the mixture was further reacted for 2 hours under reflux. After cooling to room temperature, the remaining metallic sodium was added with ethanol to decompose it, and the reaction mixture was acidified with 20% hydrochloric acid.

After adding 100 ml of water to the reaction mixture, ether was added to separate the organic phase, and the organic phase was washed with water. The organic phase was concentrated under reduced pressure to give 6.06 g of a solid.
I got This is separated and purified by column chromatography,
3.08 g (8.56 mmol) was obtained.

The value of FD-mass spectrum of this solid is M
/ E = 360. In addition, ¹ H-NMR spectrum analysis was also performed. From the results of these analyses, this compound was identified as the desired (S)-(+)-2- (1,2,3,4-tetrahydro-6-decyloxy-2-naphthyl) propionic acid.

[0167]

[Production Example 1] Synthesis of (S)-(+)-2- (1,2,3,4-tetrahydro-6-hydroxy-2-naphthyl) propionic acid

[0168]

Embedded image

(S)-(+)-2- (1,2,3,4-obtained in Example 1)
Tetrahydro-6-decyloxy-2-naphthyl) propionic acid 3.08 g (8.56 mmol) and acetic acid 50 ml, 4
14.9 g (86 mmol) of 7% hydrobromic acid was added at 120 ° C.
The mixture was heated to reflux for 7 hours. After the reaction was completed, decomposed C ₁₀ H ₂₁
Br was removed. After adding distilled water, ether was added and the organic phase was separated and concentrated under reduced pressure to give 1.89 g.
(8.59 mmol) was obtained.

The value of the FD-mass spectrum of this solid is M
/ E = 220. In addition, ¹ H-NMR spectrum analysis was also performed. From the results of these analyses, this compound was identified as the target (S)-(+)-2- (1,2,3,4-tetrahydro-6-hydroxy-2-naphthyl) propionic acid.

[0171]

[Production Example 2] (S)-(+)-2- (1,2,3,4-tetrahydro-6-benzyloxy-2
-Naphthyl) propionic acid synthesis

[0172]

Embedded image

(S)-(+)-2- (1,2,3,4-obtained in Production Example 1)
Tetrahydro-6-hydroxy-2-naphthyl) propionic acid 1.89 g (8.56 mmol), benzyl bromide 1.6
1 g (9.42 mmol), 85% potassium hydroxide 1.
13 g (17.12 mmol), sodium iodide 0.
A mixture of 09 g (0.6 mmol), 40 ml of ethanol and 8 ml of distilled water was heated under reflux at 100 ° C. for 7.5 hours. Further, 50 ml of 10% potassium hydroxide was added, and heating under reflux was continued 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. This was extracted with ether, the oil layer was concentrated, and separated and purified using column chromatography to give 0.89 g (2.87).
Mmol).

The value of the FD-mass spectrum of this solid is M
/ E = 310. In addition, ¹ H-NMR spectrum analysis was also performed. From these analysis results, this compound was identified as the target (S)-(+)-2- (1,2,3,4-tetrahydro-6-benzyloxy-2-naphthyl) propionic acid. .

[0175]

Production Example 3 (S)-(+)-2- (1,2,3,4-tetrahydro-6-benzyloxy-2
-Naphthyl) propionic acid (R) -1-trifluoromethylheptyl ester synthesis

[0176]

Embedded image

(S)-(+)-2- (1,2,3,4-obtained in Production Example 2)
Tetrahydro-6-benzyloxy-2-naphthyl) propionic acid 0.43 g (1.4 mmol), (R) -1-trifluoromethylheptanol 0.257 g (1.4 mmol), 4-
N, N 'was added to a mixture of 0.017 g (0.14 mmol) of N, N-dimethylaminopyridine and 15 ml of methylene chloride.
-Dicyclohexylcarbodiimide 0.32 g (1.5
4 ml of methylene chloride solution (5 ml) at room temperature,
The mixture was added dropwise with stirring over 1 hour.

Further, the mixture was reacted at room temperature for 96 hours. The reaction mixture was filtered, and the obtained filtrate was concentrated. By separating the concentrate using column chromatography,
0.34 g (0.71 mmol) of a white solid was obtained.

The value of the FD-mass spectrum of this solid is M
/ E = 476. Figure 1 shows the ¹ H-NM of this compound.
The chart of R spectrum is shown. From the results of these analyses, this compound is the target (S)-(+)-2- (1,2,3,4-tetrahydro-6-benzyloxy-2-naphthyl) propionic acid.
It was identified as (R) -1-trifluoromethylheptyl ester.

[0180]

Production Example 4 Synthesis of (S)-(+)-2- (1,2,3,4-tetrahydro-6-hydroxy-2-naphthyl) propionic acid (R) -1-trifluoromethylheptyl ester

[0181]

Embedded image

(S)-(+)-2- (1,2,3,4-obtained in Production Example 3)
Tetrahydro-6-benzyloxy-2-naphthyl) propionic acid (R) -1-trifluoromethylheptyl ester 0.
Hydrogen was bubbled into a mixture of 34 g (0.71 mmol), 5% palladium / carbon 0.07 g and tetrahydrofuran 10 ml at room temperature under atmospheric pressure for 36 hours. The reaction mixture was filtered using Celite as a filter aid, and the obtained filtrate was concentrated to give 0.23 g of a white solid.
(0.6 mmol) was obtained.

The value of FD-mass spectrum of this solid is M
/ E = 386. In addition, ¹ H-NMR spectrum analysis was also performed. From the results of these analyses, this compound is the target (S)-(+)-2- (1,2,3,4-tetrahydro-6-hydroxy-2-naphthyl) propionic acid (R) -1- It was identified as a trifluoromethylheptyl ester.

[0184]

Production Example 5 6-[(4'-decyloxy-4-biphenyl) carbonyloxy]-(S)-(+)-2- (1,2,3,4-tetrahydro-6-hydroxy-
Synthesis of 2-naphthyl) propionic acid (R) -1-trifluoromethylheptyl ester [exemplary compound (4)]

[0185]

[Chemical 38]

0.21 g (0.6 mmol) of 4'-octyloxy-4-biphenylcarboxylic acid, obtained in Preparation Example 4
(S)-(+)-2- (1,2,3,4-tetrahydro-6-hydroxy-2-naphthyl) propionic acid (R) -1-trifluoromethylheptyl ester 0.23 g (0.6 mmol ), 4-N, N-dimethylaminopyridine (0.007 g, 0.06 mmol) and methylene chloride (10 ml) in a mixture of N, N'-dicyclohexylcarbodiimide (0.15 g, 0.72 mmol) and methylene chloride solution (5 ml). Was added dropwise at room temperature over 4 hours with stirring.

Furthermore, the reaction was carried out at room temperature for 20 hours. The reaction mixture was filtered, and the obtained filtrate was concentrated. By separating the concentrate using column chromatography,
0.29 g of a colorless semi-solid was obtained.

The value of FD-mass spectrum of this semi-solid was M / e = 722. In addition, ¹ H-NMR spectrum analysis was also performed. From the results of these analyses, this compound was identified as 6-[(4'-decyloxy-4-biphenyl) carbonyloxy]-(S)-(+)-2- (1,2,3,4-tetrahydro). -6
-Hydroxy-2-naphthyl) propionic acid (R) -1-trifluoromethylheptyl ester [the above exemplified compound (4)] was identified.

[0189]

Production Example 6 (S)-(+)-2- (1,2,3,4-tetrahydro-6-benzyloxy-2
Synthesis of (naphthyl) propionic acid (R) -1-trifluoromethylhexyl ester

[0190]

[Chemical Formula 39]

(S)-(+)-2- (1,2,3,4-obtained in Production Example 2)
Tetrahydro-6-benzyloxy-2-naphthyl) propionic acid 0.43 g (1.4 mmol), (R) -1-trifluoromethylhexanol 0.238 g (1.4 mmol), 4-N, N-dimethylaminopyridine 0.017g
To a mixture of (0.14 mmol) and 10 ml of methylene chloride was added 0.32 of N, N'-dicyclohexylcarbodiimide.
5 ml of methylene chloride solution containing g (1.54 mmol)
Was added dropwise at room temperature with stirring over 2.5 hours.

Further, the reaction was carried out at room temperature for 24 hours. The reaction mixture was filtered, and the obtained filtrate was concentrated. By separating the concentrate using column chromatography,
0.26 g (0.56 mmol) of white solid was obtained.

The value of FD-mass spectrum of this solid is M
/ E = 462. In addition, ¹ H-NMR spectrum analysis was also performed. From the results of these analyses, this compound is the target (S)-(+)-2- (1,2,3,4-tetrahydro-6-benzyloxy-2-naphthyl) propionic acid (R) -1 -Identified as trifluoromethylhexyl ester.

[0194]

Production Example 7 Synthesis of (S)-(+)-2- (1,2,3,4-tetrahydro-6-hydroxy-2-naphthyl) propionic acid (R) -1-trifluoromethylhexyl ester

[0195]

[Chemical 40]

(S)-(+)-2- (1,2,3,4-obtained in Production Example 6)
Tetrahydro-6-benzyloxy-2-naphthyl) propionic acid (R) -1-trifluoromethylhexyl ester
Hydrogen was bubbled into a mixture of 26 g (0.56 mmol), 0.05% of 5% palladium / carbon and 10 ml of tetrahydrofuran at room temperature under normal pressure for 16 hours.
The reaction mixture was filtered using Celite, which is a filter aid,
Further, the obtained filtrate was concentrated to obtain 0.24 g of white solid.

The value of the FD-mass spectrum of this solid is M
/ E = 372. In addition, ¹ H-NMR spectrum analysis was also performed. From the results of these analyses, this compound is the target (S)-(+)-2- (1,2,3,4-tetrahydro-6-hydroxy-2-naphthyl) propionic acid (R) -1- It was identified as a trifluoromethylhexyl ester.

[0198]

Production Example 8 6-[(4′-decyloxy-4-biphenyl) carbonyloxy]-(S)-(+)-2- (1,2,3,4-tetrahydro-6-hydroxy-
Synthesis of 2-naphthyl) propionic acid (R) -1-trifluoromethylhexyl ester [exemplary compound (98)]

[0199]

Embedded image

0.198 g (0.56 mmol) of 4'-octyloxy-4-biphenylcarboxylic acid, (S)-(+)-2- (1,2,3,4-) obtained in Preparation Example 7 Tetrahydro-6-hydroxy-2
To a mixture of 0.24 g (0.56 mmol) of 4-naphthyl) propionic acid (R) -1-trifluoromethylhexyl ester, 0.0068 g (0.056 mmol) of 4-N, N-dimethylaminopyridine and 5 ml of methylene chloride, N , N'-Dicyclohexylcarbodiimide 0.138 g (0.67
5 ml of methylene chloride solution containing 2 mmol) at room temperature,
The mixture was added dropwise with stirring over 3 hours.

Further, the reaction was carried out at room temperature for 24 hours. The reaction mixture was filtered, and the obtained filtrate was concentrated. By separating the concentrate using column chromatography,
0.29 g of a colorless semi-solid was obtained.

The value of FD-mass spectrum of this semi-solid was M / e = 708. Fig. 2 shows the ¹ H-N of this compound.
The chart of MR spectrum is shown. From the results of these analyses, this compound was identified as 6-[(4'-decyloxy-
4-Biphenyl) carbonyloxy]-(S)-(+)-2- (1,2,3,
4-Tetrahydro-6-hydroxy-2-naphthyl) propionic acid (R) -1-trifluoromethylhexyl ester [the above exemplified compound (98)] was identified.

[0203]

Example 2 An exemplary compound (4) represented by the following formula [4] obtained in Production Example 5 and a compound represented by the following formula [A] were mixed in a weight ratio of 20:80. To produce the liquid crystal composition of the present invention.

[0204]

Embedded image

The results of measuring the phase transition temperature of this composition are shown in Table 4.

[0206]

[Table 13]

Note) In Table 4 above, [4] represents the exemplified compound (4), and [A] represents the compound (A).

[0208]

Example 3 An exemplary compound (98) represented by the following formula [98] obtained in Production Example 8 and a compound (A) represented by the following formula [A] were mixed at a weight ratio of 20:80. To prepare a liquid crystal composition of the present invention.

[0209]

[Chemical 43]

The results of measuring the phase transition temperature of this composition are shown in Table 5.

[0211]

[Table 14]

Note) In Table 5 above, [98] represents the exemplified compound (98), and [A] represents the compound (A).

[Brief description of drawings]

FIG. 1 ¹ H of (S)-(+)-2- (1,2,3,4-tetrahydro-6-benzyloxy-2-naphthyl) propionic acid (R) -1-trifluoromethylheptyl ester -It is a chart of an NMR spectrum.

FIG. 2 6-[(4′-decyloxy-4-biphenyl) carbonyloxy]-(S)-(+)-2- (1,2,3,4-tetrahydro-6-hydroxy-2-naphthyl) ¹ is a chart of ¹ H-NMR spectrum of propionic acid (R) -1-trifluoromethylhexyl ester.

FIG. 3 is a diagram schematically showing a cross-sectional shape of the liquid crystal element of the present invention.

FIG. 4 is a diagram showing a cross-sectional structure of a liquid crystal element of the present invention using a fiber as a spacer.

FIG. 5 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. 6 is a diagram showing an example of a non-linear element and a three-terminal element.

[Explanation of symbols]

 11a, 11b, 27a, 27b, 37,47,57… Transparent substrate 12,23,33,43,53… Liquid crystal material 13,58… Cell 14… Gap 15a, 15b, 25a, 25b, 35,45,55… Transparent electrode 46… Fiber 56… Polarizing plate

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Internal reference number FI Technical indication C07C 69/92 9546-4H 69/94 9546-4H C07D 239/26 239/34 239/54 C09K 19 / 30 9279-4H 19/32 9279-4H 19/34 9279-4H 19/46 9279-4H G02F 1/13 500

Claims (9)

[Claims] 1. A structure represented by the following formula [I]:
Tetralin compound; R-O-Z-C^*H (CH₃) COO-R '... [I] (In the formula, R represents a hydrogen atom or a straight chain having 1 to 20 carbon atoms.
Or branched alkyl group, aryl having 6 to 20 carbon atoms
A group or an aralkyl group having 7 to 20 carbon atoms
And one -CH present in the alkyl group₂-Group, or
Two or more -CH that are not adjacent₂-Group is replaced by -O- group
R ′ may be a hydrogen atom, a straight chain or a branched chain having 1 to 20 carbon atoms.
Miki alkyl group, aryl group having 6 to 20 carbon atoms, if
Kuha-Q¹-C^*H (Q²) -Q³Shows [Q ¹Is- (CH
₂)_a-Indicates an integer of 0 to 6 in these groups
-CH present in₂-Group or two or more that are not adjacent
-CH₂-Group may be replaced by -O- group
Q²Is a hydrogen atom, CF₃Group, CH₃Base, C₂H_FiveShows the group, Q
³Is an alkyl group having 1 to 20 carbon atoms or polyfluor
Represents a lower alkyl group (provided that Q³And Q²Is not the same as
I)], and Z isIs shown. ) 2. A naphthalene compound represented by the following formula [II]:
Tetralination according to claim 1, by hydrogenating the product.
Method for producing tetralin compound characterized by obtaining compound
Law;(In the formula, R represents a hydrogen atom or a straight chain having 1 to 20 carbon atoms.
Or branched alkyl group, aryl having 6 to 20 carbon atoms
A group or an aralkyl group having 7 to 20 carbon atoms
And one -CH present in the alkyl group₂-Group, or next to
Two or more -CHs that are not in contact₂-Group is replaced by -O- group
R'is a hydrogen atom, a straight chain or a branched chain having 1 to 20 carbon atoms.
Miki alkyl group, aryl group having 6 to 20 carbon atoms, if
Kuha-Q¹-C^*H (Q²) -Q³Shows [Q ¹Is- (CH
₂)_a-Indicates an integer of 0 to 6 in these groups
-CH present in₂-Group or two or more that are not adjacent
-CH₂-Group may be replaced by -O- group
Q²Is a hydrogen atom, CF₃Group, CH₃Base, C₂H_FiveShows the group, Q
³Is an alkyl group having 1 to 20 carbon atoms or polyfluor
Represents a lower alkyl group (provided that Q³And Q²Is not the same as
I))). 3. The tetralin-based carboxylic acid ester compound characterized by being represented by the following formula [III]; R-X- A 1 -Y 1 -Z-C * H (CH 3) COO-R * ... [ III] (In the formula, R represents an alkyl group having 3 to 20 carbon atoms and a polyfluoroalkyl group having 3 to 20 carbon atoms, and one of the —CH ₂ — groups present in these groups, CHF- group or-
CF ₂ -group, or two or more non-adjacent -CH ₂ -groups, -CH
The F- group or the -CF ₂ -group may be replaced by a -O- group, and X represents a group selected from the group consisting of -COO-, -OCO- and -O- or a single bond, A ¹ is Represents a group selected from the group consisting of, Y ¹ is -COO-, -OCO-, -CH ₂ CH _2- , -CH ₂ O-, and -OCH
₂ represents a group selected from the group consisting of _2- , and Z is Represents a group selected from, R ^* represents a ^{-Q 1 -C * H (Q 2} ) -Q 3 [Q ¹ represents -
(CH _{2) a} - are shown, a is an integer of 0 to 6, one -CH ₂ present in the group - group or not adjacent two or more -CH ₂ - groups, -O _{May be} replaced by a-group, Q ² represents a CF ₃ group, a CH ₃ group, a C ₂ H ₅ group, and Q ³ represents an alkyl group having 1 to 10 carbon atoms or a poly group having 1 to 10 carbon atoms. Indicates a fluoroalkyl group (however, Q ³ and Q ² are not the same)]) 4. In the above formula [III], A ¹ is The tetralinic carboxylic acid ester compound according to claim 3, which is a group selected from the group consisting of: 5. In the above formula [III], R^*But -C^*H (CF
₃) -C₈H₁₇, -C^*H (CF₃) -C₆H₁₃, -C^*H (CF₃) -C_FiveH₁₁, -C^*H (C
F₃) -C_FourH₉, -C^*H (CF₃) -C₃H₇, -C^*H (CH₃) -C₈H_{1 7}, -C^*H (CH
₃) -C₇H_Fifteen, -C^*H (CH₃) -C₆H₁₃, -C^*H (CH₃) -C_FiveH₁₁, -C^*H (C
H₃) -C_FourH₉, -C ^*H (CH₃) -C₃H₇, -C^*H (C₂H_Five) -C_FiveH₁₁, -C^*H (C
₂H_Five) -C₆H₁₃, -CH₂-C^*H (CH₃) -C₂H_Five,-(CH₂)₃-C^*H (CH₃) -C
₂H_Five, -C^*H (CF₃) -CH₂-COO-C₂H_FiveSelected from the group consisting of
A tetralin-based carbo according to claim 3 or 4,
Acid ester compounds. 6. In the above formula [III], Y ¹ is —COO—
The tetralin carboxylic acid ester compound according to any one of claims 3 to 5. 7. A liquid crystal material comprising the tetralinic carboxylic acid ester compound according to any one of claims 3 to 6. 8. A liquid crystal composition comprising the tetralinic carboxylic acid ester compound according to claim 3. 9. A liquid crystal element comprising a cell composed of two substrates facing each other and a gap formed by the substrate, and a liquid crystal element filled with a liquid crystal substance filled in the gap between the cells, wherein the liquid crystal substance is A liquid crystal device comprising the tetralinic carboxylic acid ester compound according to claim 3.