JPH10287635A - Polymerizable optically active photoisomerizable liquid crystalline compound - Google Patents

Abstract

(57) [Problem] To provide a polymerizable photoisomerizable optically active liquid crystal compound which provides a photoisomerizable ferroelectric polymer liquid crystal as a reversible optically writable memory material. SOLUTION: General formula (I) (A; (meth) acrylic, epoxy, isocyanate,
Y, Z; -O-, -COO-, -OCO-, -NHCO-, -CONH-, single bond,
Ring D, J; 1,4-phenylene, pyrimidine-2,5-diyl, pyridine-2,5-diyl, trans-1,4-cyclohexylene,
Ring E, G; 1,4-phenylene, pyrimidine-2,5-diyl, pyridine-2,5-diyl, R ₁ ; -CH ₃ , -C ₂ H ₅ , -CHF ₂ , -CF ₃ ,-
F, —CN, R ₂ ; linear alkyl of C2-18, C ^* is (R) or (S)
A polymerizable optically active photoisomerizable liquid crystal compound represented by the formula:

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a polymerizable optically active liquid crystal compound containing a photoisomerizable group and a polymerizable optically active liquid crystal containing the same, which constitutes a memory material that can be reversibly written by light irradiation. Composition.

[0002]

2. Description of the Related Art Display devices utilizing the electro-optical characteristics of liquid crystals are widely used for various displays such as watches, word processors, and TVs mounted on vehicles. These are usually controlled by applying an electric field.

[0003] On the other hand, attempts have been made to drive liquid crystal using light energy. According to Tokyo Tech's Ichimura and Ikeda et al., It is possible to store and erase information at high density by using a liquid crystal material containing a photochromic compound and utilizing the phase change of the liquid crystal induced by photochromism by light irradiation. It is known that In particular, if a ferroelectric liquid crystal having a memory property is used, stable information storage can be expected. Recently, it has been reported that by using a ferroelectric liquid crystal containing a photochromic compound, information can be recorded or stored at an extremely high speed.

[0004] Also, studies have been made on optical recording materials using side-chain type polymer liquid crystals. Polymer liquid crystals are very advantageous from low molecular liquid crystals in terms of material properties such as film-forming properties and glass transition points. For example, a polymer liquid crystal has a film-forming property, so that a liquid crystal usually used in a cell can be used in the form of a film. Is frozen, so that a record recorded at or above the glass transition point can be stably stored at or below the glass transition point for a long period of time.

However, high-molecular liquid crystals have a disadvantage that their response speed is inferior to low-molecular liquid crystals. This is probably because the viscosity of the liquid crystal is large. Accordingly, attempts have been made to improve the response speed by using a polymer liquid crystal having ferroelectricity. According to this, it is reported that a significant improvement in response speed was observed as compared with the conventional non-ferroelectric polymer liquid crystal.

[0006]

[Problems to be solved by the invention]

In view of the above prior art, a photo-isomerized ferroelectric polymer liquid crystal is used as a memory material for optical recording, which is excellent in high resolution, high-speed response, memory properties and long-term stable storage of recording. It is expected that it will be possible. However, a polymer liquid crystal having both ferroelectricity and photoresponsiveness has not been synthesized yet. The reason is that the structure of liquid crystal molecules exhibiting ferroelectricity is limited, and the structure of photochromic molecules that can be liquid crystal is few, and furthermore, the compound that can be a raw material of polymer liquid crystal has a polymerizable functional group. The point is that you have to.

Although several ferroelectric liquid crystals having an azobenzene skeleton have been reported as photoisomerized ferroelectric liquid crystals, they did not have a polymerizable structure. Therefore, a polymerizable optically active photoisomerizable liquid crystal compound that can be used as a raw material for photoisomerized ferroelectric polymer liquid crystals has been desired.

An object of the present invention is to provide a photoisomerizable ferroelectric polymer liquid crystal which can be used as a reversibly optically writable memory material in order to obtain a polymer having an azobenzene skeleton as a photoisomerization site. Another object of the present invention is to provide a photoisomerizable optically active liquid crystal compound.

[0010]

According to the present invention, there is provided a compound represented by the general formula (I):

[0011]

Embedded image

Wherein A is an acryl group, a methacryl group,
Represents an epoxy group or an isocyanate group, and m is from 8 to 20.
Y and Z each independently represent -O-,-
Represents COO-, -OCO-, -NHCO-, -CONH- or a single bond, and each of ring D and ring J may be independently substituted with fluorine, chlorine, a cyano group or a trifluoromethyl group. , 4-phenylene group, pyrimidine-
Represents a 2,5-diyl group, a pyridine-2,5-diyl group or a trans-1,4-cyclohexylene group, and ring E and ring G are each independently a fluorine, chlorine, cyano group or trifluoromethyl group; R 1 represents an optionally substituted 1,4-phenylene group, pyrimidine-2,5-diyl group or pyridine-2,5-diyl group, n and k each independently represent an integer of 0 or 1, ₁ is a methyl group, an ethyl group,
Difluoromethyl group, trifluoromethyl group, represents a fluorine or cyano group, R ₂ represents a linear alkyl group having 2 to 18 carbon atoms, when R ₁ is an ethyl group,
R ₂ does not represent an ethyl group. C ^* is (R) or (S)
It indicates that it is an irregular carbon in the configuration. The present invention provides a polymerizable optically active photoisomerized liquid crystalline compound represented by the formula:

The compounds represented by the general formula (I) of the present invention include A, Y, Z, ring D, ring E, ring G, ring J, m,
Depending on the selection of n, k, R ₁ and R ₂ , many kinds of compounds can be included, and among them, the following general formulas (Ia) to (Id)
The compound represented by general formula (Ia) is particularly preferable.

[0014]

Embedded image

(Wherein, A represents an acryl group).

The compounds represented by the general formula (I) of the present invention vary in their production methods depending on the functional group A, the bonding groups Y and Z, and n and k representing the number of rings. be able to.

(I) In the case of two rings (n = k = 0, general formula (II))

[0018]

Embedded image

(Where A, Y, m, R ₁ , R ₂ , ring E and ring G are the same as those in formula (I))

(Ia) Y is -O-, -COO- or-
In the case of CONH-, formula (III)

[0021]

Embedded image

(Wherein ring G is the same as in general formula (I)) after diazotizing a 4-aminobenzoic acid derivative represented by general formula (IV)

[0023]

Embedded image

(Wherein Ra represents a hydroxyl group or an amino group, and ring E represents the same as that of the general formula (I)).

[0025]

Embedded image

(Wherein Ra represents a hydroxyl group or an amino group, and ring E and ring G represent the same as those in formula (I)).

(1) When Y is —O— The compound represented by the general formula (V) obtained above and the compound represented by the general formula (VI)

[0028]

Embedded image

(Wherein Rb represents an alcoholic hydroxyl group, a vinyl group or a protected amino group, and X represents a leaving group such as a halogen). A compound represented by the following general formula (VII) is obtained by forming an ether bond by a conventional method.

(2) When Y is —COO— An ester bond is formed between the compound represented by the general formula (V) obtained above and the compound represented by the general formula (VI) by a conventional method. The following general formula (VI
The compound represented by I) is obtained.

(3) When Y is -CONH- An amide bond is formed by a conventional method between the compound represented by the general formula (V) obtained above and the compound represented by the general formula (VI). The following general formula (VII)
To obtain a compound represented by the formula:

[0032]

Embedded image

(In the formula, Rb represents an alcoholic hydroxyl group, a vinyl group or a protected amino group, and Y, m, ring E and ring G represent the same as in the general formula (I).) The production method is slightly different depending on the type of the functional group A.

(Ia-1) When A is an acrylic group or a methacrylic group: The intermediate represented by the general formula (VII) obtained above and acrylic acid chloride or methacrylic acid chloride are combined with a basic substance such as pyridine. Reacting in the presence of
II)

[0035]

Embedded image

(Wherein A represents an acryl group or a methacryl group, and Y, m, ring E and ring G represent the same as in the general formula (I)).
I get.

The polymerizable intermediate (VIII) represented by the general formula (VIII) and the polymerizable intermediate (IX)

[0038]

Embedded image

(Wherein R ₁ and R ₂ are the same as those represented by the general formula (I)) by reacting with an optically active alcohol represented by the general formula (II). An optically active photoisomerizable compound is obtained.

(Ia-2) When A is an epoxide group or an isocyanate group: The intermediate represented by the general formula (VII) obtained above and the optically active alcohol represented by the general formula (IX) are reacted with each other. Reacting the compound with the general formula (X)

[0041]

Embedded image

(Wherein, Rb represents a vinyl group or a protected amino group, and Y, m, ring E, ring G, R ₁ and R ₂ represent the same as in the general formula (I)). Get.

(1) When A is an epoxide group, Rb
Is a vinyl group, (a) a method of subjecting this vinyl group to halohydrinization using a halogen and then cyclizing it, or (b)
An epoxide group can be obtained by a method of directly oxidizing with a peroxide such as perbenzoic acid.

(2) When A is an isocyanate group,
Rb is a protected amino group, which can be deprotected and converted to an amino group, and then (a) can be led to an isocyanate using phosgene. If thiophosgene is used in place of (b) phosgene, it can lead to isothiocyanate. Thus, the polymerizable optically active photoisomerizable compound represented by the general formula (II) can be obtained.

(Ib) Y is -OCO-, -NHCO
-, A single bond General formula (XI)

[0046]

Embedded image

(Wherein Rb represents a hydroxyl group, a vinyl group or a protected amino group, and ring E represents the same as in the general formula (I)) and the nitroso compound represented by the general formula (III) The benzoic acid derivative represented by the general formula (VII) is obtained by subjecting the 4-aminobenzoic acid derivative represented by the condensation reaction to the condensation reaction. The following synthesis is based on (i
By performing in the same manner as in -a-1) or (ia-2), the desired compound represented by the general formula (I) is obtained.

The nitroso compound represented by the general formula (XI) is synthesized by reducing the corresponding nitro compound under mild conditions. This nitro compound has the general formula (XII)

[0049]

Embedded image

(In the formula, ring E represents the same as in the general formula (I).) A 4-nitrobenzoic acid derivative represented by the general formula (I) and the compound represented by the general formula (VI) are usually It can be produced by forming an ester bond or an amide bond by a method. Alternatively, it can be produced by (2) a method of alkylating an aromatic ring such as a benzene ring, a pyridine ring or a pyrimidine ring and then nitrating the aromatic ring.

(Ii) Three rings (when n = 1 and k = 0,
General formula (XIII)

[0052]

Embedded image

Wherein A, Y, m, ring D, ring E, ring G,
R ₁ and R ₂ represent the same as in formula (I). )

In the above (ib), instead of the nitroso compound represented by the general formula (XI), the compound represented by the general formula (XIV)

[0055]

Embedded image

(Wherein Rb represents a hydroxyl group, a vinyl group or a protected amino group, and Y, m, ring D and ring E represent the same as in the general formula (I)). Other than that, the desired compound represented by the general formula (I) can be obtained according to the method described in the above (ib).

(Iii) Three rings (when n = 0 and k = 1, the general formula (XVI))

[0058]

Embedded image

Wherein A, Y, Z, m, ring E, ring G, ring J, R ₁ and R ₂ are the same as those in formula (I).

(Iii-a) Y is -O-, -OCO- or -CONH-, and Z is -COO- or -CO
When it is NH-

(1) When Y is —O— A compound represented by the above general formula (VII) wherein Y is —O— and a compound of the general formula (XVIII)

[0062]

Embedded image

(Wherein Ra represents a phenolic hydroxyl group or an amino group, and rings J, R ₁ and R ₂ represent the same as in the general formula (I)). (A) when Z is -COO-, an ester bond;
(B) When Z is -CONH-, the desired polymerizable optically active photoisomerizable compound represented by the general formula (XVI) can be obtained by forming an amino bond according to a conventional method.

(2) When Y is —COO— A compound represented by the general formula (VII) wherein Y is —COO— and the optically active compound represented by the general formula (XVIII) (A) When Z is -COO-, an ester bond is formed when Z is -CONH-, and when Z is -CONH-, an amino bond is formed by a conventional method, whereby the compound is represented by the above general formula (XVI). A polymerizable optically active photoisomerizable compound can be obtained.

(3) When Y is —CONH— A compound represented by the general formula (VII) wherein Y is —CONH— and the optically active compound represented by the general formula (XVIII) (A) When Z is -COO-, an ester bond is formed when Z is -CONH-, and when Z is -CONH-, an amino bond is formed by a conventional method, whereby the compound is represented by the above general formula (XVI). A polymerizable optically active photoisomerizable compound can be obtained.

(Iii-b) Y is -NHCO- or -OC
O- and Z is -OCO-, -O- or -NH
If it is CO-

(1) When Y is —OCO— A compound represented by the general formula (V) and a compound represented by the general formula (XVI
I)

[0068]

Embedded image

(Wherein, Rc represents an acryl group, a methacryl group, a vinyl group or a protected amino group, X represents an alcoholic hydroxyl group, and m represents the same as in the general formula (I)). An ester bond is formed between the compound and the compound according to a conventional method to obtain a compound represented by the following general formula (XIX).

(2) When Y is -NHCO- The compound represented by the above general formula (V) and the compound represented by the above general formula (XVII) wherein X is an amino group are prepared according to a conventional method. By forming an amide bond, a compound represented by the following general formula (XIX) is obtained.

[0071]

Embedded image

(Where Ra represents a hydroxyl group or an amino group, Rc represents an acryl group, a methacryl group, a vinyl group or a protected amino group, and m, ring E and ring G represent the general formula (I) Represent the same thing.)

(Iii-b-1) Z is -OCO-, -O-
If it is

(1) Formula (XI) wherein Ra is a hydroxyl group
X) and a compound represented by the general formula (XVIII)

[0075]

Embedded image

(Wherein, R represents a carboxyl group;
Ring J, R ₁ and R ₂ are the same as those of the general formula (I) by forming an ester bond with the optically active compound represented by the general formula (I) according to a conventional method. In XVI), a compound in which Z is -OCO- is obtained.

(2) Formula (XI) wherein Ra is a hydroxyl group
X) and a compound represented by the general formula (XVIII)
By forming an ether bond with an optically active compound in which R is a hydroxyl group according to a conventional method, a desired compound in which Z is —O— in the above general formula (XVI) is obtained.

(Iii-b-2) When Z is —NHCO— A compound in which Ra is an amino group in the general formula (XIX) and a compound in which Rd is a carboxylic acid in the general formula (XVIII) To give the desired polymerizable optically active photoisomerizable compound represented by the general formula (XVI).

(Iii-c) Y is-, -O-, -OCO-
Or -CONH-, and Z is -O-, -OCO
-Or -NHCO-

Formula (XX)

[0081]

Embedded image

Wherein Rc represents an acryl group, a methacryl group, a vinyl group or a protected amino group, and m and ring E represent the same as in the general formula (I). Thereafter, a compound represented by the general formula (XIX) is obtained by a coupling reaction with the compound represented by the general formula (IV).

(Iii-c-1) Z is -O- or -OCO
(1) When Z is —O— In the general formula (XIX), the compound is a compound wherein Ra is a hydroxyl group and in the general formula (XVIII) is an optically active compound wherein Ra is a hydroxyl group. Then, an ether bond is formed by a conventional method to obtain the desired compound represented by the general formula (XVI).

(2) When Z is —OCO— In the general formula (XIX), the compound in which Ra is a hydroxyl group and the optically active compound in the general formula (XVIII) in which Ra is a carboxylic acid are esterified. By reacting, the desired compound represented by the general formula (XVI) is obtained.

(Iii-c-2) When Z is —NHCO— A compound in which Ra is an amino group in the general formula (XIX) and an optical compound in which Ra is a carboxylic acid in the general formula (XVIII) By forming an amide bond with the active compound by a conventional method, the desired compound represented by the above general formula (XVI) can be obtained.

(Iv) In the case of four rings (n = k = 1, general formula (XXVII))

[0087]

Embedded image

(Iv-a) When Z is a single bond: General formula (XXI)

[0089]

Embedded image

(Wherein, Rc represents an acryl group, a methacryl group, a vinyl group or a protected amino group;
And ring E represent the same as in formula (I). ) And the general formula (XXII)

[0091]

Embedded image

(Wherein ring G and ring J are the same as those represented by formula (I)) by condensing with an amino group of the compound represented by formula (XXIII)

[0093]

Embedded image

(In the formula, Rc represents an acryl group, a methacryl group, a vinyl group or a protected amino group, and Y, m, ring D, ring E, ring G and ring J are the same as those in the general formula (I). Is obtained.)

The compound represented by the general formula (XXIII) and the optically active alcohol (IX) represented by the general formula (IX)
Is subjected to an esterification reaction, and then a polymerizable functional group is introduced according to the method described above to obtain a compound represented by the general formula (XXIV):

[0096]

Embedded image

(In the formula, Rc represents an acryl group, a methacryl group, a vinyl group or a protected amino group, and Y, m, ring D, ring E, ring G and ring J are the same as those in the general formula (I). Is obtained.) A polymerizable optically active photoisomerizable compound represented by the formula:

(Iv-b) Z is -COO-, -CONH-
And an aromatic nitroso compound represented by the general formula (XXI) and a general formula (XXV)

[0099]

Embedded image

(Wherein Z is -COO- or -CONH-
Wherein ring G, ring J, R ₁ and R ₂ are the same as those in formula (I). Is condensed with an amino-containing optically active compound represented by the formula (XXVI)

[0101]

Embedded image

The polymerizable optically active photoisomerizable compound (XXVI) represented by the following formula is obtained.

(Iv-c) Z is -OCO-, -O-, -N
When it is HCO-. General formula (XXVIII)

[0104]

Embedded image

(Wherein, Rc represents an acryl group, a methacryl group, a vinyl group or a protected amino group, and Y, m, ring D
And ring E represent the same as in formula (I). ), The compound represented by the general formula (IV) is subjected to a coupling reaction to obtain a compound represented by the general formula (XXIX):

[0106]

Embedded image

(Where Ra represents a hydroxyl group, a carboxylic acid or an amino group, Rc represents an acryl group, a methacryl group, a vinyl group or a protected amino group, and Y, m, ring D, ring E and ring G Represents the same as in the general formula (I).)

(1) When Z is —O— In the general formula (XXVIII), a compound in which Ra is a hydroxyl group and the optically active compound in the general formula (XVIII) in which Ra is a hydroxyl group are represented by the following formula: An ether bond is formed by a conventional method to obtain a compound represented by the general formula (XXVI).

(2) When Z is —OCO— In the general formula (XXVIII), the compound in which Ra is a hydroxyl group and the compound in the general formula (XVIII) in which Ra is a carboxyl group are subjected to an esterification reaction. Thus, the compound represented by the general formula (XXVI) is obtained.

(3) When Z is -NHCO- In the general formula (XXVIII), a compound in which Ra is an amino group and a compound in the general formula (XVIII) in which Ra is a carboxyl group are An amide bond is formed by a conventional method to obtain a compound represented by the general formula (XXVI).

The structural features of the compound represented by formula (I) of the present invention include the following.

(1) Having an azo group in the molecule. The compound represented by the general formula (I) exhibits excellent liquid crystallinity when the azo group has a trans configuration.
This isomerizes into a cis form by ultraviolet irradiation, and returns to a trans form by irradiation with light of another wavelength (generally, visible light) or heat.

(2) Having a polymerizable functional group. When considering the material properties, it is needless to say that a polymer is more advantageous than a low molecule, but since the compound represented by the general formula (I) has polymerizability, the polymer is synthesized by an appropriate polymerization method. be able to. Further, the compound represented by the general formula (I) may be used alone or as a mixture.

Further, even a compound that does not exhibit ferroelectricity or antiferroelectricity by itself can be mixed with a liquid crystal exhibiting ferroelectricity, antiferroelectricity or chiral smectic phase to obtain ferroelectricity or antiferroelectricity. Some of them exhibit antiferroelectricity, and can be used as a guest photoresponsive molecule in such a case. In addition, since this compound has a chiral site, it has a material-specific "winding",
When used as a monomer, it has the potential to give a "roll". In such a case, the completed polymer may exhibit characteristic physical properties, and can be a raw material for a novel functional polymer.

As described above, the compound represented by the general formula (I) of the present invention can be used as a photochromic compound of a light control type polymerizable optically active liquid crystal composition.

[0116]

The present invention will be described in more detail with reference to the following examples. However, the invention is not limited to these examples.

<Example 1> (S) -3-Fluoro-4- (1-methylheptyloxycarbonyl) phenyl-4 '-[3-fluoro-4-
Synthesis of (11-acryloyloxyundecyloxy) phenylazo] benzoate

(1-a) Synthesis of 4- (3-fluoro-4-hydroxyphenylazo) benzoic acid In a separable flask having a capacity of 5 liters, 100 m of hydrochloric acid was added.
1 (HCl, 1.0 mol) and 500 g of ice were added to this mixture, while stirring vigorously, 4-aminobenzoic acid 3
0.0 g (220 mmol) was added and suspended. Further, 30.0 g of sodium nitrite (44
(0 mmol) was dropped over about 1 hour, and gradually became a homogeneous solution (hereinafter, referred to as reaction solution 1).

Next, 24.0 g of 2-fluorophenol was used.
(220 mmol), 24 g of sodium hydroxide (0.6
Mol) and 42 g (0.4 mol) of sodium carbonate were prepared in an amount of 250 ml (hereinafter referred to as reaction liquid 2). The reaction solution 2 was added dropwise to the reaction solution 1 over about 2 hours while adding ice little by little so that the temperature did not rise to 0 ° C. or higher. As a result, an orange precipitate was immediately formed.
After completion of the dropwise addition, the mixture was stirred for about 7 hours to terminate the reaction. The reaction solution was adjusted to be acidic (pH = 1) with hydrochloric acid, and the deposited precipitate was filtered. The obtained precipitate was dissolved by heating in 1.5 liter of ethyl acetate and washed three times with 500 ml of water. The organic layer was dried by adding 500 g of sodium sulfate, and the solvent was distilled off to obtain a crude product. The crude product was purified by recrystallization from acetonitrile-water to obtain the target compound 41.
g (72% yield).

(1-b) Synthesis of 4- [3-fluoro-4- (11-hydroxyundecyloxy) phenylazo] benzoic acid

A 1 liter capacity 3 with a condenser
In a mouth separable flask, 20 g (77 mmol) of 4- (3-fluoro-4-hydroxyphenylazo) benzoic acid and 100 ml of ethanol were added and suspended under reflux. To this suspension was added 16 g of potassium carbonate (11
5 mmol), a trace amount of potassium iodide was triturated well, and a solid was immediately formed.
Was added to form a suspension solution. After the contents were refluxed for about 1 hour, a solution of 21 g (85 mmol) of 11-bromo-1-undecanol in 100 ml of ethanol was added all at once.
Thereafter, the mixture was refluxed and stirred for about 24 hours. After completion of the reaction, 300 ml of water and 50 ml of hydrochloric acid were added to the reaction mixture, the pH of the reaction solution was adjusted to acidic (pH = 2), and a solid was precipitated. The precipitated solid was collected by filtration, and the residue was recrystallized from 1 liter of ethanol and purified to obtain 20 g of the desired product (yield: 60%).
%).

1H-NMR (399.65 MHZ, dimethyl sulfoxide-d6 solution): δ = 8.13 (d, J = 8.3 Hz, 2H), 7.91 (d, J = 8.8 Hz, 2H), 7.
83 (d, J = 8.3Hz, 1H), 7.70 (dd, J = 2.0Hz, 11.7Hz, 1
H), 7.37 (t, J = 9.0 Hz, 1H), 4.17 (t, J = 6.6 Hz, 2H), 3.
39 (t, J = 6.6Hz, 2H), 1.77 (t, J = 7.3, 2H), 1.41 (t, J =
(6.6, 2H), 1.26 (m, 14H)

13C-NMR (100.40 MHz, dimethyl sulfoxide-d6 solution): δ = 166.59, 154.23, 153.31, 150.85, 150.15, 150.0
5, 145.75, 145.70, 132.63, 130.49, 123.22, 122.2
8, 122.16, 114.56, 107, 60, 107.41, 69.22, 60.76,
32.51, 29.01, 28.89, 28.80, 28.63, 28.43, 25.47, 2
5.27

MS (70 eV): m / z = 430 (M ⁺ ), 260, 149, 139 (100), 127, 111, 9
5,83,69,55,41

(1-c) Synthesis of 4- [3-fluoro-4- (11-acryloyloxyundecyloxy) phenylazo] benzoic acid 500 ml of 5 equipped with a dropping funnel and a calcium tube.
In a neck flask, 10 g of 4- {2-fluoro-4- (11-hydroxyundecyloxy) phenylazo} benzoic acid was added.
(23 mmol), 3.5 g (35 mmol) of triethylamine and 200 ml of anhydrous tetrahydrofuran were added to form a solution. After a small amount of 4-dimethylaminopyridine (hereinafter abbreviated as DMAP) was added to this solution, 15 ml of a solution of 4.2 g (47 mmol) of acrylic acid chloride in anhydrous diethyl ether was added dropwise over about 1 hour. After completion of the dropwise addition, stirring was continued for about 5 hours, then the reaction was terminated, and the precipitated triethylamine hydrochloride was separated by filtration. Triethylamine hydrochloride was washed with acetonitrile, 400 ml of diethyl ether was added to the filtrate, and the mixture was washed three times with 200 ml of saturated saline. This was dried over anhydrous sodium sulfate (300 g) and the solvent was distilled off to obtain a crude product as an orange solid. The crude product was recrystallized from acetonitrile to produce 8.4 g of the desired product (yield 75%).

1H-NMR (399.65 MHz, dimethyl sulfoxide-d6 solution): δ = 8.13 (d, J = 8.8 Hz, 2H), 7.9 (d, J = 8.8 Hz, 2H), 7.8
3 (d, J = 8.8Hz, 1H), 7.71 (dd, J = 2.0Hz, 11.7Hz, 1H),
7.38 (t, J = 8.8Hz, 1H), 6.30 (dd, J = 2.0Hz, 17.1Hz, 1
H), 6.18 to 6.11 (m, 1H), 5.90 (dd, J = 1.5Hz, 10.3Hz, 1
H), 4.17 (t, J = 6.6 Hz, 2H), 4.09 (t, J = 6.6 Hz, 2H), 1.
77 (t, J = 7.3 Hz, 2H), 1.59 (t, J = 6.8 Hz, 2H), 1.45 to 1.
40 (m, 2H), 1.40 to 1.00 (m, 12H)

13C-NMR (100.40 MHz, dimethyl sulfoxide-d6 solution): δ = 166.61, 165.42, 154.22, 153.31, 150.85, 150.1
5,150.05,145.75,145.70,132.67,130.90,130.5
6, 130.49, 128.46, 123.24, 122.66, 122.28, 114.5
7, 107.60, 107.41, 69.20, 64.01, 28.78, 28.58, 28.
54, 28.42, 28.07, 25.30, 25.26

MS (70 eV): m / z = 484 (M ⁺ ), 260, 149, 139 (100), 127, 111, 9
7, 69, 55, 41

(1-d) (S) -3-fluoro-4- (1-methylheptyloxycarbonyl) phenyl-4 '-[3-fluoro-4-
Synthesis of (11-acryloyloxyundecyloxy) phenylazo] benzoate 4.0 g of 4- [3-fluoro-4- (11-acryloyloxyundecyloxy) phenylazo] benzoic acid in a 300-ml four-necked flask equipped with a calcium tube.
(8.3 mmol), 2.3 g of (S) -2-fluoro-4-hydroxy- (1-methylheptyl) benzoate
(8.6 mmol) and 1.0 g (8.2 mmol) of DMAP were added and dissolved in 70 ml of anhydrous tetrahydrofuran (hereinafter abbreviated as THF). While stirring this solution at room temperature, a solution of 8.5 g (41 mmol) of N, N'-dicyclohexylcarbodiimide (hereinafter abbreviated as DCC) in 20 ml of anhydrous THF was added dropwise over 30 minutes. Stirring was continued at room temperature for 18 hours to complete the reaction. After completion of the reaction, the precipitated solid was separated by filtration, and the solid was washed with acetonitrile and diethyl ether. The filtrate was added with 500 ml of diethyl ether, washed three times with 200 ml of a saturated saline solution, and dried with 400 g of anhydrous sodium sulfate. The solvent was distilled off to obtain a red oily crude product. The crude product was collected by flash chromatography using stationary phase silica gel and mobile phase chloroform to collect the low-polarity portion, and the solvent was removed to obtain a red oil. The red oil was recrystallized by adding 50 ml of methanol to obtain an orange solid target product. This was further recrystallized from 100 ml of hexane and purified to obtain 3.0 g of the desired product (yield: 50%).

1H-NMR (399.65 MHz, CDCl ₃
Solution): δ = 8.32 (d, J = 8.8 Hz, 2H), 8.01 (d, J = 8.8 Hz, 2H), 7.
97 (d, J = 8.3 Hz, 1H), 7.87 (d, J = 8.8 Hz, 1H), 7.75 (d
d, J = 2.4Hz, 11.7Hz, 1H), 7.48 (dd, J = 2.0Hz, 11.2H
z, 1H), 7.41 (t, J = 8.8 Hz, 1H), 7.35 (dd, J = 2.0 Hz, 8.
8Hz), 6.30 (dd, J = 1.5Hz, 17.1Hz, 1H), 6.15 (dd, J = 1
0.3Hz, 17.6Hz, 1H), 5.90 (dd, J = 1.5Hz, 10.3Hz, 1
H), 5.2 to 5.0 (m, 1H), 4.20 (t, J = 6.6Hz, 2H), 4.09
(t, J = 6.6Hz, 2H), 1.9 to 1.5 (m, 6H), 1.5 to 1.2 (m, 25
H), 0.86 (t, J = 6.8Hz, 3H)

13C-NMR (100.40 MHz, CDCl
₃ solutions): δ = 166.42, 165.41, 163.21, 162.48, 159.91, 154.9
8, 154.74, 153.29, 150.83, 150.39, 150.29, 145.7
2,145.67,132.45,131.31,130.92,129.92,128.4
3, 123.57, 122.59, 118.37, 118.34, 116.77, 116.6
7, 114.60, 111.46, 111.20, 107.65, 107.47, 71.93,
69.22, 63.98, 35.19, 31.03, 28.78, 28.75, 28.72, 2
8.54, 28.49, 28.35, 28.04, 25.26, 25.21, 24.58, 2
1.87, 19.64, 13.74

MS (70 eV): m / z = 736 (M ⁺ ), 680, 663, 624, 606, 567, 551, 467
(100), 395, 243, 139, 127, 120, 83, 69, 55, 41

[0133] (In the above, I represents an isotropic phase, Sc * represents a chiral smectic C phase, and K represents a crystal phase.) Spontaneous polarization value: 71 nC / cm ² (50 ° C., 10 Hz, 22
V)

This compound has a high possibility of exhibiting antiferroelectricity because two kinds of polarization inversion currents are measured when the frequency is reduced. The spontaneous polarization value at that time is 130 n
C / cm ² .

When this compound is irradiated with ultraviolet rays,
A phase transition from Sc * to phase I occurred. Accordingly, it was confirmed that the electric field response was not observed and the ferroelectricity was lost. When the ultraviolet irradiation was stopped, the phase changed from the I phase to the Sc * phase, and the electric field response was confirmed.

Example 2 (S) -4- (1-methylheptyloxycarbonyl)
Phenyl-4 '-[2-trifluoromethyl-4- (1
1-Acryloyloxyundecyloxy) phenylazo] benzoate (2-a) Synthesis of 4- (2-trifluoromethyl-4-hydroxyphenylazo) benzoic acid 200 ml of water, 80 ml of hydrochloric acid (HCl , 0.8 mol), and 20.0 g (146 g) of 4-aminobenzoic acid was added thereto with vigorous stirring.
(Mmol) was added and suspended. Add 0.6 ml of ice to this suspension.
After cooling to about -10 ° C, add sodium nitrite 1
100 g of an aqueous solution of 9.0 g (275 mmol) was added to about 1
When the solution was dropped over time, the solution gradually became a uniform solution (hereinafter, this uniform solution is referred to as a reaction solution 3).

3-trifluoromethylphenol 25.
0 g (154 mmol), sodium hydroxide 20 g
(0.5 mol), 32 g of sodium carbonate (0.3 mol)
Was prepared (hereinafter, this aqueous solution is referred to as reaction solution 4). When the temperature of the reaction solution 3 is 0
The reaction solution 4 was added dropwise over about 2.5 hours while ice was added little by little so that the temperature did not become higher than 0 ° C. As a result, an orange precipitate was immediately generated. After completion of the dropwise addition, the mixture was stirred for about 3 hours to complete the reaction. The reaction solution was adjusted to acidic (pH = 2) with hydrochloric acid, and the deposited precipitate was filtered. The obtained precipitate was dissolved in acetone, and the insoluble portion (salt) was separated by filtration. The solvent was removed to obtain 47.5 g of the desired product (yield 105%).

1H-NMR (399.65 MHz, MeOH-
d4 solution): δ = 8.18 (d, J = 8.8 Hz, 2H), 7.92 (d, J = 8.3 Hz, 2H), 7.
89 (d, J = 8.8, 1H), 7.26 (d, J = 2.5 Hz, 1H), 7.08 (dd, J
= 9.3Hz, 2.9Hz, 1H)

MS (70 eV): m / z = 310 (M ⁺ ), 189, 161 (100), 149, 121, 113, 65

The reaction product was considered to contain some salt and water, but was not further purified because it did not affect the next reaction.

(2-b) Synthesis of 4- {2-trifluoromethyl-4- (11-hydroxyundecyloxy) phenylazo} benzoic acid A 4-liter (2-liter) flask was placed in a 1-liter three-necked flask equipped with a condenser. 30 g (97 mmol) of trifluoromethyl-4-hydroxyphenylazo) benzoic acid and 250 ml of ethanol were added and dissolved under reflux. To this solution, 40 g (290 mmol) of potassium carbonate and a trace amount of potassium iodide were added by trituration.
Immediately a solid was formed, and 50 ml of water was added to obtain a uniform solution. After refluxing for about 1 hour, a solution of 27 g (110 mmol) of 11-bromo-1-undecanol in ethanol 1
00 ml was added all at once. Thereafter, refluxing and stirring were continued for about 22 hours. After the completion of the reaction, add 500 ml of water to the reaction mixture.
And 50 ml of hydrochloric acid to adjust the pH of the reaction solution to acidic (pH =
Adjusted to 1) to precipitate a solid. To this solution, twice the amount of ethyl acetate (1.5 liter) was added, and the mixture was heated to dissolve the solid and extracted. The organic layer was washed with acidic water (pH = 3), and the organic layer was dried with 300 g of sodium sulfate. The solid obtained by distilling off the solvent was collected, recrystallized from 300 ml of ethanol and purified to obtain 33 g (yield 71%) of the desired product.

1H-NMR (60.0 MH, MeOH-
d4 solution): δ = 8.3 to 7.8 (m, 5H), 7.5 to 7.3 (m, 2H), 4.4 to 4.0 (m,
2H), 3.6-3.2 (m, 2H), 2.0-1.2 (m, 18H)

MS (70 eV): m / z = 480 (M ⁺ ), 359, 310, 291, 189, 176, 161, 14
9, 121, 95, 83, 69, 55, 41

(2-c) Synthesis of 4- [2-trifluoromethyl-4- (11-acryloyloxyundecyloxy) phenylazo] benzoic acid 100 ml of 2 equipped with a dropping funnel and a calcium tube
In a neck flask, add 4- {2-trifluoromethyl-4-
(11-Hydroxyundecyloxy) phenylazo dibenzoic acid (5.0 g, 10 mmol) and THF (50 ml) were added to prepare a solution. To this solution was added triethylamine.
After adding 1 g (21 mmol), a solution of 1.9 g (21 mmol) of acrylic acid chloride in THF in a water bath was added.
ml was added dropwise over 30 minutes. After completion of dropping, at room temperature
Stirring was continued for hours. After completion of the reaction, 500 ml of ethyl acetate was added to the reaction mixture, and the organic layer was washed with 100 ml of saturated saline.
And washed 4 times. After the organic layer was dried over 100 g of sodium sulfate, the solvent was distilled off to obtain a red solid crude product. This crude product is acetonitrile 50m
and 4.3 g of the desired product (yield 77).
%).

1H-NMR (399.65 MHz, dimethyl sulfoxide-d6 solution): δ = 13.08 (s, 1H), 8.24 (d, J = 8.3 Hz, 2H), 8.00 (t, J =
7.8Hz, 3H), 7.5 to 7.4 (m, 2H), 6.37 (t, J = 17.1Hz, 1
H), 6.3 to 6.1 (m, 1H), 5.99 (d, 10.7 Hz, 1H), 4.24 (t,
J = 5.9Hz, 2H), 4.18 (t, J = 6.6Hz, 2H), 1.84 (t, J = 6.6H
z, 2H), 1.68 (t, J = 6.3Hz, 2H), 1.6-1.3 (m, 14H)

MS (70 eV): m / z = 534 (M ⁺ , 9), 413 (7), 310 (3), 189 (11), 177 (3
3), 161 (20), 149 (51), 121 (50), 69 (64), 55 (100), 41
(44)

(2-d) (S) -4- (1-methylheptyloxycarbonyl)
Phenyl-4 '-[2-trifluoromethyl-4- (1
1-acryloyloxyundecyloxy) phenylazo] benzoate 5.0 g of 4- [2-trifluoromethyl-4- (11-acryloyloxyundecyloxy) phenylazo] benzoic acid in a 300 ml four-necked flask equipped with a calcium tube. 9.3 mmol), 2.5 g of (S) -4-hydroxy- (1-methylheptyl) benzoate (1
0 mmol), 1.2 g (9.8 mmol) of DMAP and 50 ml of anhydrous THF were added to form a solution. To this solution was added a solution of 2.0 g (9.7 mmol) of DCC in THF.
ml was added dropwise over 10 minutes while maintaining the temperature at 0 ° C. After completion of the dropwise addition, the temperature was returned to room temperature, and stirring was continued for about 12 hours. After completion of the reaction, dicyclohexylurea was separated by filtration, 500 ml of diethyl ether and 200 ml of acetonitrile were added to the filtrate, and the organic layer was washed three times with 200 ml of saturated saline. After drying the organic layer with 300 g of sodium sulfate,
The solvent was distilled off to obtain a crude product. The desired product was separated by silica gel flash chromatography using a mixed solvent of toluene: ethyl acetate = 4: 1 as a mobile phase, and then recrystallized from hexane and further purified by recrystallization from ethanol. 5 g (yield 63
%).

1H-NMR (399.65 MHz, dimethyl sulfoxide-d6 solution): δ = 8.36 (d, J = 8.3 Hz, 2H), 8.2-7.8 (m, 5H), 7.67
(d, J = 8.3 Hz, 1H), 7.7 to 7.5 (m, 3H), 6.29 (d, J = 17.1H
z, 1H), 6.14 (dd, J = 10.3 Hz, 17.1 Hz, 1H), 5.90 (d, J =
10.3Hz, 1H), 5.1 to 5.0 (m, 1H), 4.2 to 4.1 (m, 2H), 4.0
9 (t, J = 6.6Hz, 2H), 1.9 ~ 1.5 (m, 6H), 1.5 ~ 1.2 (m, 25
H), 0.9-0.8 (m, 3H)

13C-NMR (100.40 MHz, dimethyl sulfoxide-d6 solution): δ = 165.41, 164.57, 131.36, 130.90, 130.66, 128.4
3, 128.22, 128.10, 122.80, 121.99, 118.88, 118.1
1, 71.46, 68.79, 63.98, 35.28, 31.10, 31.04, 30.3
1, 28.80, 28.76, 28.55, 28.51, 28.40, 28.35, 28.0
4, 25.52, 25.27, 25.24, 24.70, 23.92, 21.89, 19.7
2, 13.74

MS (70 eV): m / z = 766 (M ⁺ ), 534 (10), 413 (10), 293 (18), 189
(9), 177 (44), 161 (12), 149 (15), 121 (57), 69 (63), 5
5 (100), 41 (47) Phase transition temperature: 34 ° C. (I → K) at the time of temperature decrease This compound alone did not show a liquid crystal phase.

Example 3 (S) -4- (1-methylheptyloxycarbonyl)
Synthesis of phenyl-4 '-[3-fluoro-4- (11-acryloyloxyundecyloxy) phenylazo] benzoate

(3-a) Synthesis of 4- (3-fluoro-4-hydroxyphenylazo) benzoic acid In a separable flask having a capacity of 5 liters, 100 m of hydrochloric acid was added.
1 (HCl, 1.0 mol) and 500 g of ice, into which 30.0 g of 4-aminobenzoic acid were added with vigorous stirring.
(220 mmol) was added and suspended. When 100 ml of an aqueous solution of 30.0 g (440 mmol) of sodium nitrite was added dropwise to this suspension over about 1 hour, a uniform solution was gradually obtained (hereinafter, referred to as reaction solution 5).

24.0 g of 2-fluorophenol (22
0 mmol), 24 g (0.6 mol) of sodium hydroxide
Then, 250 ml of an aqueous solution containing 42 g (0.4 mol) of sodium carbonate was prepared (this is hereinafter referred to as reaction solution 6). The reaction solution 6 was added dropwise to the reaction solution 5 over a period of about 2 hours while ice was added little by little so that the temperature did not rise to 0 ° C. or higher. As a result, an orange precipitate immediately formed. After completion of the dropwise addition, stirring was continued for about 7 hours, and then the reaction was terminated. Hydrochloric acid was added to the reaction mixture to adjust the pH of the reaction solution to acidic (pH = 1), and the deposited precipitate was filtered.
The obtained precipitate was dissolved by heating in 1.5 liter of ethyl acetate and then washed three times with 500 ml of water. After 500 g of sodium sulfate was added to the organic layer and dried, the solvent was distilled off to obtain a crude product. This crude product was purified by recrystallization from acetonitrile-water to obtain the desired product 4
1 g (72% yield) was obtained.

(3-b) Synthesis of 4- {3-fluoro-4- (11-hydroxyundecyloxy) phenylazo} benzoic acid A 1-liter 3-neck separable flask equipped with a condenser was charged with 4- (3- 20 g (77 mmol) of fluoro-4-hydroxyphenylazo) benzoic acid and 100 ml of ethanol were added, and suspended under reflux. To this suspension, 16 g (115 mmol) of potassium carbonate and a trace amount of potassium iodide were added by trituration.
Immediately, a solid was formed, and 100 ml of water was added to obtain a suspension solution. After refluxing for about 1 hour, a solution of 21 g (85 mmol) of 11-bromo-1-undecanol in ethanol 1
00 ml was added at a time, and the mixture was refluxed and stirred for about 24 hours. After completion of the reaction, 300 ml of water and 50 ml of hydrochloric acid were added to the reaction mixture, and the pH of the reaction solution was acidified (pH = 2).
And a solid was deposited. The precipitated solid was collected by filtration, recrystallized from 1 liter of ethanol and purified to obtain 20 g (yield 60%) of the desired product.

1H-NMR (399.65 MHz, dimethyl sulfoxide-d6 solution): δ = 8.13 (d, J = 8.3 Hz, 2H), 7.91 (d, J = 8.8 Hz, 2H), 7.
83 (d, J = 8.3Hz, 1H), 7.70 (dd, J = 2.0Hz, 11.7Hz, 1
H), 7.37 (t, J = 9.0 Hz, 1H), 4.17 (t, J = 6.6 Hz, 2H), 3.
39 (t, J = 6.6Hz, 2H), 1.77 (t, J = 7.3H, 2H), 1.5 to 1.3
(m, 2H), 1.3 to 1.1 (m, 14H)

13C-NMR (100.40 MHz, dimethyl sulfoxide-d6 solution): δ = 166.59, 154.23, 153.31, 150.85, 150.15, 150.0
5, 145.75, 145.70, 132.63, 130.49, 123.22, 122.2
8, 122.16, 114.56, 107.60, 107.41, 69.22, 60.76, 3
2.51, 29.01, 28.29, 28.80, 28.63, 28.43, 25.47, 2
5.27

MS (70 eV): m / z = 430 (M ⁺ ), 260, 149, 139 (100), 127, 111, 9
5,83,69,55,41

(3-c) Synthesis of 4- [3-fluoro-4- (11-acryloyloxyundecyloxy) phenylazo] benzoic acid A 500-ml five-necked flask equipped with a dropping funnel and a calcium tube was charged with 4- ｛. 3-Fluoro-4- (11-hydroxyundecyloxy) phenylazo {benzoic acid 19.2
g (44.7 mmol), triethylamine 7.0 g
(70 mmol) and 300 ml of anhydrous THF were added to form a solution. After a small amount of 4-dimethylaminopyridine (DMAP) is added to this solution, acrylic acid chloride is added.
4 g (89 mmol) of anhydrous diethyl ether solution 20
ml was added dropwise over about 1 hour. After completion of the dropwise addition, stirring was continued for about 5 hours, then the reaction was terminated, and the precipitated triethylamine hydrochloride was separated by filtration. The hydrochloride was washed with acetonitrile, 1 liter of diethyl ether was added to the filtrate,
It was washed once with an aqueous solution consisting of 300 ml of saturated saline and 30 ml of acetic acid, and four times with saturated saline. After drying this using 500 g of anhydrous sodium sulfate, the solvent was distilled off to obtain a crude product as an orange solid. The crude product was recrystallized from acetonitrile and purified to obtain the desired product.
8 g (82% yield) were obtained.

1H-NMR (399.65 MHz, dimethyl sulfoxide-d6 solution): δ = 8.13 (d, J = 8.8 Hz, 2H), 7.9 (d, J = 8.8 Hz, 2H), 7.8
3 (d, J = 8.8Hz, 1H), 7.71 (dd, J = 2.0Hz, 11.7Hz, 1H),
7.38 (t, J = 8.8Hz, 1H), 6.30 (dd, J = 2.0Hz, 17.1Hz, 1
H), 6.18 to 6.11 (m, 1H), 5.90 (dd, J = 1.5Hz, 10.3Hz, 1
H), 4.17 (t, J = 6.6 Hz, 2H), 4.09 (t, J = 6.6 Hz, 2H), 1.
77 (t, J = 7.3 Hz, 2H), 1.59 (t, J = 6.8 Hz, 2H), 1.45 to 1.
40 (m, 2H), 1.40 to 1.00 (m, 12H)

13C-NMR (100.40 MHz, dimethyl sulfoxide-d6 solution): δ = 166.61, 165.42, 154.22, 153.31, 150.85, 150.1
5,150.05,145.75,145.70,132.67,130.90,130.5
6, 130.49, 128.46, 123.24, 122.66, 122.28, 114.5
7, 107.60, 107.41, 69.20, 64.01, 28.78, 28.58, 28.
54, 28.42, 28.07, 25.30, 25.26

MS (70 eV): m / z = 484 (M +, 11), 260 (50), 149 (12), 139 (100), 1
27 (56), 121 (34), 69 (40), 55 (76), 41 (39)

(3-d) (S) -4- (1-methylheptyloxycarbonyl)
Synthesis of phenyl-4 ′-[3-fluoro-4- (11-acryloyloxyundecyloxy) phenylazo] benzoate In a 300 ml four-neck flask equipped with a calcium tube, 4- [3-fluoro-4- (11- Acryloyloxyundecyloxy) phenylazo] benzoic acid 5.0 g
(10.3 mmol), (S) -4-hydroxy- (1
2.6 g (10.3 mmol) of-(methylheptyl) benzoate, 1.3 g (10.3 mmol) of DMAP and 60 ml of anhydrous THF were added to form a solution. This solution is
While cooling in a dry ice-ethylene glycol bath and stirring, 10 ml of an anhydrous THF solution of 11 g (52 mmol) of N, N'-dicyclohexylcarbodiimide (DCC) was added in five portions over 30 minutes. After completion of the dropwise addition, stirring was continued for a further 10 minutes at a low temperature, the refrigerant was removed, the temperature was gradually returned to room temperature, and stirring was continued at room temperature for 12 hours to complete the reaction. After the reaction, the precipitated solid was separated by filtration,
The solid was washed with acetonitrile and diethyl ether.
500 ml of diethyl ether was added to the filtrate, and the mixture was washed three times with 200 ml of a saturated saline solution.
g. The solvent was distilled off to obtain a red oily crude product. This crude product is
The low-polarity portion was collected using flash chromatography with stationary phase silica gel and mobile phase chloroform, and the solvent was distilled off to obtain a red oil. The red oil was recrystallized by adding 50 ml of methanol and purified to obtain the target compound as an orange solid. Further, this was recrystallized from 80 ml of ethanol and purified to obtain 1.1 g (yield: 15%) of the desired product.

1H-NMR (399.65 MHz, dimethyl sulfoxide-d6 solution): δ = 8.32 (d, J = 8.3 Hz, 2H), 8.06 (d, J = 8.8 Hz, 2H), 8.
00 (d, J = 8.3Hz, 2H), 7.86 (d, J = 8.8Hz, 1H), 7.73 (d
d, J = 2.4Hz, 12.2Hz, 1H), 7.48 (d, J = 8.8Hz, 1H), 7.4
0 (t, J = 8.8Hz, 1H), 6.30 (dd, J = 2.0Hz, 17.1Hz, 1H),
6.15 (dd, J = 17.6Hz, 10.3Hz, 1H), 5.90 (dd, J = 10.3H
z, 1.5 Hz, 1H), 5.2 to 5.0 (m, 1H), 4.18 (t, J = 6.3 Hz, 2
H), 4.09 (t, J = 6.6 Hz, 2H), 1.9 to 1.5 (m, 6H), 1.5 to 1.
2 (m, 24H), 0.85 (t, J = 6.8Hz, 3H)

13C-NMR (100.40 MHz, dimethyl sulfoxide-d6 solution): δ = 165.07, 164.22, 163.17, 154.57, 153.82, 150.4
9, 150.03, 149.92, 145.32, 130.87, 130.57, 130.3
0,129.84,128.08,127.73,123.21,123.18,122.2
4, 121.81, 114.22, 107.29, 107.09, 71.11, 68.87, 6
5.92, 63.65, 34.93, 30.69, 28.44, 28.42, 28.39, 2
8.34, 28.20, 28.16, 28.05, 27.69, 25.27, 24.92, 2
4.88, 24.35, 22.74, 21.54, 19.37, 13.39

MS (70 eV): m / z = 718 (M ⁺ , 2), 467 (100), 243 (68), 139 (20), 12
7 (58), 120 (94), 69 (25), 55 (38), 41 (28)

[0166] (Sx ^* represents a chiral smectic phase whose assignment is unknown.) Spontaneous polarization value: below the measurement limit.

This compound was found to have an electric field response in the Sx ^* phase. When this compound was irradiated with ultraviolet rays, a phase transition from Sc * to the I phase occurred. Accordingly, it was confirmed that the electric field response was not observed and the ferroelectricity was lost. When UV irradiation is stopped, the phase transition from phase I to Sc *,
The electric field response has been confirmed.

Example 4 (S) -4- (1-methylheptyloxycarbonyl)
Synthesis of phenyl-4 '-[2-fluoro-4- (11-acryloyloxyundecyloxy) phenylazo] benzoate

(4-a) Synthesis of 4- (2-fluoro-4-hydroxyphenylazo) benzoic acid In a separable flask having a capacity of 5 liters, 150 m of hydrochloric acid was added.
1 (HCl, 1.5 mol) was added thereto, and suspended under vigorous stirring with 37.0 g (270 mmol) of 4-aminobenzoic acid. To this suspension, 250 ml of an aqueous solution of 28.0 g (410 mmol) of sodium nitrite was added dropwise over about 1.5 hours while adding 550 g of ice to keep the reaction solution at 0 ° C. or lower. A solution was obtained (hereinafter, this is referred to as reaction solution 7).

30.5 g of 3-fluorophenol (27
0 mmol), 36 g (0.9 mol) of sodium hydroxide
And 300 ml of an aqueous solution containing 64 g (0.6 mol) of sodium carbonate (hereinafter referred to as reaction solution 8). The reaction solution 8 was added dropwise to the reaction solution 7 over a period of about 1.5 hours while ice was added little by little so that the temperature did not rise to 0 ° C. or higher. As a result, an orange precipitate immediately formed. After completion of the dropwise addition, stirring was continued for about 5 hours, and then the reaction was terminated. 500 g of ice and 5 ml of hydrochloric acid were added to the reaction mixture.
The pH of the reaction solution was adjusted to acidic (pH = 3) by adding 0 ml. Ethyl acetate (3 L) was added thereto, and the precipitated solid was dissolved by heating, and the organic layer was washed five times with 300 ml of water. After 500 g of sodium sulfate was added to the organic layer and dried, the solvent was distilled off to obtain a crude product. The crude product was recrystallized from acetonitrile-water and purified to obtain 55 g of the desired product (yield 78%).

(4-b) Synthesis of 4- {2-fluoro-4- (11-hydroxyundecyloxy) phenylazo} benzoic acid In a 1-liter 3-neck separable flask equipped with a condenser, 4- (2- 20 g (77 mmol) of fluoro-4-hydroxyphenylazo) benzoic acid and 200 ml of ethanol were added to form a solution while refluxing. To this solution, 16 g (115 mmol) of potassium carbonate and a trace amount of potassium iodide were added by trituration, and immediately a solid was formed, so 50 ml of water was added to make a uniform solution. After refluxing for about 1 hour, a solution of 21 g (85 mmol) of 11-bromo-1-undecanol in 60 ml of ethanol was added all at once. Thereafter, refluxing and stirring were continued for about 24 hours. After the completion of the reaction, add 500 ml of water to the reaction mixture.
And 50 ml of hydrochloric acid to adjust the pH of the reaction solution to acidic (pH =
Adjusting to 1), a solid was deposited. The precipitated solid was collected by filtration, recrystallized from 1 liter of ethanol and purified to obtain 19 g (57%) of the desired product.

1H-NMR (399.65 MHz, dimethyl sulfoxide-d6 solution): δ = 8.12 (d, J = 8.8 Hz, 2H), 7.90 (d, J = 8.8 Hz, 2H), 7.
77 (t, J = 8.8Hz, 1H), 7.08 (dd, J = 13.2Hz, 2.4Hz, 1
H), 6.91 (dd, J = 9.3Hz, 2.0Hz, 1H), 4.11 (t, J = 6.3H
z, 2H), 3.38 (t, J = 6.6 Hz, 2H), 1.8 to 1.7 (m, 2H), 1.5
Up to 1.2 (m, 16H)

13C-NMR (100.40 MHz, dimethyl sulfoxide-d6 solution): δ = 166.59, 163.68, 163.57, 162.46, 159.90, 154.6
4, 134.11, 134.03, 132.54, 130.51, 130.19, 122.2
7, 118.49, 112.02, 102.76, 102.53, 68.76, 60.72, 3
2.48, 28.98, 28.87, 28.60, 28.35, 25.44, 25.29

MS (70 eV): m / z = 430 (M ⁺ ), 309, 297, 260, 149, 139, 127 (10
0), 121, 111, 95, 83, 69, 55, 41

(4-c) Synthesis of 4- [2-fluoro-4- (11-acryloyloxyundecyloxy) phenylazo] benzoic acid 500 ml of 5 equipped with a dropping funnel and a calcium tube.
In a neck flask, 10 g of 4- {2-fluoro-4- (11-hydroxyundecyloxy) phenylazo} benzoic acid was added.
(23 mmol), 3.5 g (35 mmol) of triethylamine and 200 ml of anhydrous THF were added to form a solution. To this solution was added 4-dimethylaminopyridine (DMA
After adding a small amount of P), 4.2 g of acrylic acid chloride (4
7 mmol) in 15 ml of anhydrous diethyl ether.
It was dropped over about 1 hour. After completion of the dropwise addition, stirring was continued for about 5 hours. After the completion of the reaction, the precipitated triethylamine hydrochloride was separated by filtration. The hydrochloride was washed with acetonitrile, 400 ml of diethyl ether was added to the filtrate, and the organic layer was washed three times with 200 ml of saturated saline. After drying the organic layer using 300 g of anhydrous sodium sulfate, the solvent was distilled off to obtain a crude product as an orange solid. The crude product was purified by recrystallization from acetonitrile to obtain 8.4 g of the desired product.
(75% yield).

1H-NMR (399.65 MHz, dimethyl sulfoxide-d6 solution): δ = 12.7 (s, 1H), 8.13 (s, J = 7.8 Hz, 2H), 7.90 (d, J =
7.3Hz, 2H), 7.76 (t, J = 8.5Hz, 1H), 7.05 (d, J = 11.7H
z, 1H), 6.89 (d, J = 7.3 Hz, 1H), 6.30 (d, J = 17.1 Hz, 1
H), 6.2 to 6.1 (m, 1H), 5.90 (d, J = 10.3Hz, 1H), 4.1 to
4.0 (m, 4H), 1.8 to 1.7 (m, 2H), 1.7 to 1.5 (m, 2H), 1.5
Up to 1.2 (m, 14H)

13C-NMR (100.40 MHz, dimethylsulfoxide-d6 solution): δ = 166.75, 166.64, 165.44, 163.71, 163.58, 162.5
2,159.97,154.69,134.15,132.57,130.87,130.5
2,130.30,129.54,128.48,122.300,28.47,111.9
8, 102.75, 102.52, 68.78, 64.03, 28.87, 28.84, 28.
64, 28.58, 28.40, 28.10, 25.33

MS (70 eV): m / z = 484 (M ⁺ , 16), 363 (24), 260 (10), 149 (11), 13
9 (46), 127 (56), 121 (35), 69 (59), 55 (100), 41 (47)

(4-d) (S) -4- (1-methylheptyloxycarbonyl)
Synthesis of phenyl-4 '-[2-fluoro-4- (11-acryloyloxyundecyloxy) phenylazo] benzoate In a 300 ml four-necked flask equipped with a calcium tube, 4- [2-fluoro-4- (11- Acryloyloxyundecyloxy) phenylazo] benzoic acid 5.3 g
(11 mmol), 2.8 g (11 mmol) of (S) -4-hydroxy- (1-methylheptyl) benzoate, 1.3 g (10.3 mmol) of DMAP and 60 ml of anhydrous THF were added to form a solution. The solution was cooled in a dry ice-ethylene glycol bath and stirred with N, N'-dicyclohexylcarbodiimide (D
CC) 10 g of 11 g (52 mmol) of anhydrous THF solution
1 was added in five portions over 30 minutes. After stirring was continued at a low temperature for 10 minutes, the refrigerant was removed and gradually returned to room temperature, and stirring was continued at room temperature for 12 hours. After completion of the reaction, the precipitated solid was separated by filtration, and the solid was washed with acetonitrile and diethyl ether. 500 ml of dichloromethane was added to the filtrate,
The organic layer was washed three times with 200 ml of saturated saline, and then dried using 500 g of anhydrous sodium sulfate. The solvent was distilled off to obtain a red oily crude product.
The crude product was collected by flash chromatography using stationary phase silica gel and mobile phase chloroform to collect a low-polar part, and the solvent was distilled off to obtain a red oil. The red oil was added with 50 ml of hexane and recrystallized for purification, whereby an orange solid was obtained. This was further recrystallized from 60 ml of ethanol and purified to obtain 4.8 g (yield 61%) of the desired product.

1H-NMR (399.65 MHz, dimethyl sulfoxide-d6 solution): δ = 8.32 (d, J = 8.3 Hz, 2H), 8.06 (d, J = 8.8 Hz, 2H), 8.
00 (d, J = 8.3Hz, 2H), 7.86 (d, J = 8.8Hz, 1H), 7.73 (d
d, J = 2.4Hz, 12.2Hz, 1H), 7.48 (d, J = 8.8Hz, 1H), 7.4
0 (t, J = 8.8Hz, 1H), 6.30 (dd, J = 2.0Hz, 17.1Hz, 1H),
6.15 (dd, J = 17.6Hz, 10.3Hz, 1H), 5.90 (dd, J = 10.3H
z, 1.5 Hz, 1H), 5.2 to 5.0 (m, 1H), 4.18 (t, J = 6.3 Hz, 2
H), 4.09 (t, J = 6.6 Hz, 2H), 1.9 to 1.5 (m, 6H), 1.5 to 1.
2 (m, 24H), 0.85 (t, J = 6.8Hz, 3H)

13C-NMR (100.40 MHz, dimethyl sulfoxide-d6 solution): δ = 165.07, 164.22, 163.17, 154.57, 153.82, 150.4
9, 150.03, 149.92, 145.32, 130.87, 130.57, 130.3
0,129.84,128.08,127.73,123.21,123.18,122.2
4, 121.81, 114.22, 107.29, 107.09, 71.11, 68.87, 6
5.92, 63.65, 34.93, 30.69, 28.44, 28.42, 28.39, 2
8.34, 28.20, 28.16, 28.05, 27.69, 25.27, 24.92, 2
4.88, 24.35, 22.74, 21.54, 19.37, 13.39

MS (70 eV): m / z = 718 (M ⁺ , 1), 467 (28), 363 (23), 243 (25), 139
(28), 127 (75), 120 (100), 69 (46), 55 (77), 41 (37)

Phase transition temperature: 120 ° C. (I → X) at the time of temperature decrease 128 ° C. (X → I) at the time of temperature increase (X represents a liquid crystal phase of unknown assignment.) This compound alone does not show ferroelectricity. Was.

Example 5 A polymerizable optically active photoisomerized liquid crystal composition having the composition shown below was prepared, and its phase transition temperature was shown below. Further, this composition showed an electric field response in the Sx phase.

[0185]

Embedded image

[0186] (Sx indicates a smectic phase of unknown assignment, and Y indicates a liquid crystal phase of unknown assignment.)

As described above, the compounds listed in the examples exhibited liquid crystallinity and ferroelectricity by themselves, or exhibited liquid crystallinity and ferroelectricity when formed into a composition. In addition, it was suggested that antiferroelectricity may be expressed.

Next, it was confirmed that when ultraviolet rays were irradiated in a temperature range showing a liquid crystal phase, a phase transition to a lower order phase occurred. In addition, it was confirmed that the state returned to the original state when the ultraviolet irradiation was stopped.

[0189]

The compound represented by the general formula (I) according to the present invention is a compound having an azo group and a polymerizable functional group in the molecule, which shows liquid crystallinity either alone or as a composition. The ferroelectricity of the material is obtained by forming a composition. Therefore, the general formula (I) of the present invention
Is very useful as a component of a light-controllable ferroelectric element.

Further, the compound represented by the general formula (I) of the present invention can be converted into a high-molecular weight to obtain a high-molecular liquid crystal. It is also very useful as a component.

Further, the compound represented by the general formula (I) of the present invention can be easily produced industrially as shown in Examples, and currently widely used liquid crystal compounds, liquid crystal compositions or polymerized compounds. It is also very useful as a raw material for optically functional materials including liquid crystals, because of its excellent compatibility with the hydrophilic compound.

Claims (11)

[Claims] 1. A compound of the general formula (I) (Where A is an acryl group, a methacryl group, an epoxy group,
Represents an isocyanate group, m represents an integer of 8 to 20, and Y and Z each independently represent -O-, -COO-,-
OCO-, -NHCO-, -CONH- or a single bond, wherein Ring D and Ring J are each independently 1,4-phenylene which may be substituted with fluorine, chlorine, cyano or trifluoromethyl; Group, pyrimidine-2,5-diyl group, pyridine-2,5-diyl group or trans-1,4
A ring E and a ring G each independently represent a 1,4-phenylene group or a pyrimidine-2,5-diyl group which may be substituted by fluorine, chlorine, cyano or trifluoromethyl; Or n represents a pyridine-2,5-diyl group, n and k each independently represent an integer of 0 or 1, and R ₁ represents a methyl group, an ethyl group, a difluoromethyl group, a trifluoromethyl group, a fluorine or cyano group. And R ₂ represents a straight-chain alkyl group having 2 to 18 carbon atoms, but when R ₁ is an ethyl group, R ₂ does not represent an ethyl group. C ^* represents an asymmetric carbon in the (R) or (S) configuration. A) a polymerizable optically active photoisomerizable liquid crystal compound represented by the formula: 2. The polymerizable optically active photoisomerizable liquid crystal compound according to claim 1, wherein R ₁ is a methyl group and R ₂ is a linear alkyl group having 5 to 12 carbon atoms. 3. The polymerizable optically active photoisomerized liquid crystalline compound according to claim 1, wherein Z is —COO—. 4. The polymerizable optically active photoisomerized liquid crystalline compound according to claim 1, wherein n is 0. 5. The polymerizable optically active photoisomerizable liquid crystal compound according to claim 1, wherein ring E is a 1,4-phenylene group which may be substituted with a fluorine, chlorine or cyano group. . 6. The polymerizable optically active photoisomerizable liquid crystal compound according to claim 1, wherein ring G is a 1,4-phenylene group. 7. The polymerizable optically active photoisomer according to claim 1, wherein ring J is a 1,4-phenylene group which may be substituted with a fluorine, chlorine or cyano group. Liquid crystalline compound. 8. The polymerizable optically active photoisomerizable liquid crystal compound according to claim 1, wherein Y represents —O—, —COO—, or a single bond. 9. A polymerizable optically active photoisomerizable liquid crystal composition comprising the polymerizable optically active photoisomerizable liquid crystal compound according to claim 1. 10. The method of claim 1, 2, 3, or 3, which exhibits ferroelectricity.
The polymerizable optically active photoisomerized liquid crystal composition according to 4, 5, 6, 7, 8, or 9. 11. The method according to claim 1, which exhibits antiferroelectricity.
The polymerizable optically active photoisomerized liquid crystal composition according to 3, 5, 6, 7, 8 or 9.