JPH1112242A - Polymerizable optically active photo-isomerizable liquid crystalline compound - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject new compound useful for a photo-isomerizable strongly dielectric polymer liquid crystal capable of being used as a memory material capable of optically and reversibly writing therein and having an azobenzene skeleton as the photo-isomerizable site. SOLUTION: This polymerizable optically active photo-isomerizable liquid crystalline compound is a compound expressed by formula I [A is a polymerizable (meth)acryl or the like; (m) is 8-20; Y, Z are each single bond, O, or the like; ring D, J are each a (substituted) 1,4-phenylene or the like; ring E, G are each a (substituted) 1,4-phenylene or the like; (n), (k) are each 0,1; R1 is methyl or the like; R2 is a 2-18C alkyl; C* is an asymmetric carbon atom]. The compound of the formula in the case of e.g. (n)=(k)=O and Y is a single bond, is obtained e.g. by diazotizing a compound expressed by formula II (Rx is an alcoholic hydroxyl group or the like), reacting with a compound expressed by formula III, dehydrating the phenolic hydroxyl group of the obtained compound with the hydroxyl group of an optically active alcohol expressed by formula IV to obtain an optically active compound of formula V as an intermediate compound, and then reacting the obtained intermediate compound with acrylic acid chloride in the presence of a basic compound.

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 having a photoisomerizable group and a polymerizable optically active liquid crystal containing the same, which constitute a memory material which 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 Ikeda and Ikeda of Tokyo Institute of Technology, using a liquid crystal material containing a photochromic compound and utilizing the phase change of the liquid crystal induced by photochromism by light irradiation, high-density storage and erasure of information is possible. It is known to be possible. In particular, stable storage of information can be expected by using a ferroelectric liquid crystal having a memory property. 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, compared to the conventional non-ferroelectric polymer liquid crystal, a significant improvement in response speed was seen,
It has been reported. ("Functional Materials" 1993, Vol.13)

[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]

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(Wherein A represents a polymerizable acrylic, methacrylic, epoxy, vinyl, or isocyanate group, m represents an integer of 8 to 20, and Y and Z represent
Each independently represents -O-, -COO-, -OCO-, -N
Represents HCO-, -CONH- or a single bond, and each of ring D and ring J may be independently substituted with a substituent selected from the group consisting of fluorine, chlorine, a cyano group and a trifluoromethyl group. A ring E which represents a 1,4-phenylene group, a pyrimidine-2,5-diyl group, a pyridine-2,5-diyl group or a trans-1,4-cyclohexylene group;
And ring G are each independently a 1,4-phenylene group which may be substituted with a substituent selected from the group consisting of fluorine, chlorine, cyano group and trifluoromethyl group, pyrimidine-2,5-diyl Represents a group or a pyridine-2,5-diyl group, n and k each independently represent 0 or 1, R ₁ represents a methyl group, an ethyl group, a difluoromethyl group, a trifluoromethyl group, a fluorine atom or It represents a cyano group, R ₂ represents an 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. The present invention provides a polymerizable photoisomerizable optically active liquid crystal 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)

[0014]

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Wherein A represents a polymerizable acrylic group, methacryl group, epoxy group, vinyl group, isocyanate group, m represents an integer of 8 to 20, and R ₁ represents a methyl group, ethyl group. Represents a group, a difluoromethyl group, a trifluoromethyl group, a fluorine or a cyano group, and R ₂ represents an alkyl group having 2 to 18 carbon atoms, and when R ₁ is an ethyl group, R ₂ represents ethyl. Wherein C ^* represents an asymmetric carbon in the (R) or (S) configuration.
e)

[0016]

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(Wherein, A represents a polymerizable acrylic group, m represents 11, and C ^* represents an irregular carbon in the (R) or (S) configuration.) Is preferred.

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 the numbers of rings n and k. be able to.

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

[0020]

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Wherein A, Y, ring E, ring G, R ₁ , R ₂
And C ^* represent the same as in the case of the general formula (I). )
Compound represented by

(Ia) When Y is a single bond: General formula (III)

[0023]

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(Wherein, Rx represents an alcoholic hydroxyl group, a vinyl group, or a protected amino group, and m and ring E represent the same as those in the general formula (I)).
After diazotizing a substituted aniline derivative, the compound represented by the general formula (IV)

[0025]

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(Wherein ring G is the same as in the case of the general formula (I)) and reacted with a phenol derivative of the general formula (V)

[0027]

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A phenol derivative having an azo group represented by the following formula is produced. Next, the phenolic hydroxyl group of the phenol derivative represented by the general formula (V) and the phenol derivative represented by the general formula (VI)

[0029]

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(Wherein R ₁ , R ₂ and C ^* are the same as in the case of the general formula (I)). By forming a bond, the intermediate represented by the general formula (VII)

[0031]

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The optically active compound represented by the formula is produced.

(Ia-1) When A is an acrylic group or a methacrylic group: An optically active compound represented by the above general formula (VII) wherein Rx is an alcoholic hydroxyl group, and acrylic acid chloride or methacrylic chloride. By reacting in the presence of a basic compound such as pyridine or the like to form an ester bond, thereby obtaining a compound of the general formula (II)

[0034]

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Wherein A, Y, ring E, ring G, R ₁ , R ₂
And C ^* represent the same as in the case of the general formula (I). )
And a polymerizable photoisomerizable optically active compound represented by the formula:

(Ia-2) When A is a vinyl group In the above method (ia), a 4-substituted aniline derivative represented by the general formula (III) wherein Rx is a vinyl group is used. The polymerizable photoisomerizable optically active compound represented by the general formula (II) can be produced.

(Ia-3) When A is an epoxide group: A method of subjecting an optically active compound represented by the above general formula (VII), wherein Rx is a vinyl group, to halohydrin using a halogen, followed by cyclization. The polymerizable photoisomerizable optically active compound represented by the above general formula (II) can be produced by a direct oxidation method using a peroxide such as perbenzoic acid or the like.

(Ia-4) When A is an isocyanate group: After removing the protected amino group of the optically active compound represented by formula (VII) wherein Rx is a protected amino group, phosgene is removed. By using the compound to form an isocyanate, the polymerizable photoisomerizable optically active compound represented by the general formula (II) can be produced.

(Ib) When Y is -O- or -COO- General formula (VIII)

[0040]

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(In the formula, ring G is the same as in the case of the compound represented by formula (I).) A 4-nitrophenol derivative and the optically active alcohol represented by formula (VI) are usually A dehydration reaction is performed according to the method to form an ether bond, whereby the compound represented by the general formula (IX)

[0042]

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An optically active 4-nitrobenzene derivative represented by the following formula is produced. Next, the nitro group of the optically active 4-nitrobenzene derivative represented by the general formula (IX) is
The general formula (X) can be obtained by a method of reducing by the action of sodium borohydride in the presence of a palladium carbon catalyst, a method of (2) a reduction by the action of tin (II) chloride in alcohol, or a method of (3) a catalytic reduction )

[0044]

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A 4-substituted optically active aniline derivative represented by the following formula is produced. Further, 4 represented by the general formula (X)
A diazotization of the substituted optically active aniline derivative, followed by the general formula (XI)

[0046]

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(Wherein ring E is the same as that of the compound represented by the general formula (I)) to react with the phenol derivative represented by the general formula (XI)
I)

[0048]

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An optically active phenol derivative having an azo group represented by the following formula is produced.

(Ib-1) When Y is —O— An optically active phenol derivative having an azo group represented by the above formula (XII) and a compound represented by the formula (XIII)

[0051]

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(Wherein, Rx represents an alcoholic hydroxyl group, a vinyl group or a protected amino group, X represents a leaving group such as halogen, and m represents the same as in the case of the compound represented by the general formula (I). And a compound having a straight-chain alkyl represented by the general formula (XIV)

[0053]

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An optically active intermediate represented by the following formula is produced. Subsequent introduction of a polymerizable functional group is performed by the method (i-
By carrying out in the same manner as in a-1) to (ia-3), the polymerizable photoisomerizable optically active compound represented by the general formula (II) can be produced.

(Ib-2) When Y is —COO— The optically active phenol derivative having an azo group represented by the above general formula (XII) and the general formula (XV)

[0056]

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(Wherein Rc represents an acryl group, a methacryl group, a vinyl group or a protected amino group, and m represents the same as in the case of the compound represented by formula (I)). With a carboxylic acid derivative having the general formula (XVI)

[0058]

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An optically active ester represented by the following formula is produced.

When a compound represented by the general formula (XV) in which Rc is an acryl group, a methacryl group or a vinyl group is used, the obtained ester represented by the general formula (XVI) is converted to a compound represented by the general formula (II) It corresponds to the polymerizable photoisomerizable optically active compound represented.

Other polymerizable functional groups are introduced by the above-mentioned method (ia-2) when introducing an epoxide group, and by the above-mentioned method (ia-3) when introducing an isocyanate group.
By carrying out in the same manner as in the above method,
And a polymerizable photoisomerizable optically active compound represented by the formula:

(Ic) When Y is —CONH— In the method of the above (ib), the phenol derivative represented by the general formula (XI) is used instead of the phenol derivative represented by the general formula (XI)

[0063]

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(Wherein ring E is the same as that of the compound represented by the general formula (I)) by reacting with the aniline derivative represented by the general formula (XVII)
I)

[0065]

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An optically active aniline derivative having an azo group represented by the following formula is produced. Next, an amide bond is formed by reacting the optically active aniline derivative having an azo group represented by the general formula (XVIII) and the carboxylic acid derivative having a straight-chain alkyl represented by the general formula (XV) by a conventional method. The general formula (XIV ′)

[0067]

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An optically active amide represented by the formula (XIV) wherein Ra = Rc and Y = CONH is prepared.

When a compound represented by the general formula (XV) in which Rc is an acryl group, a methacryl group or a vinyl group is used, the resulting amide represented by the general formula (XIV ') is converted to a compound represented by the general formula (II) Corresponds to a polymerizable photoisomerizable optically active compound.

The introduction of other polymerizable functional groups is carried out by the above-mentioned method (ia-2) when introducing an epoxide group, and by the above-mentioned method (ia-3) when introducing an isocyanate group.
By carrying out in the same manner as in the above method,
And a polymerizable photoisomerizable optically active compound represented by the formula:

(Ic) Y is -OCO- or -NHCO
If-General formula (XIX)

[0072]

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Wherein ring E is the same as that of the compound represented by formula (I).
After diazotizing an aminobenzoic acid derivative, it is reacted with a phenol derivative represented by the above general formula (IV) to obtain a compound of the general formula (XX)

[0074]

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The azobenzene derivative of 4-hydroxy-4-carboxylic acid represented by the formula is produced. Next, the general formula (X
An azobenzene derivative represented by the general formula (V)
By dehydrating the optically active alcohol represented by I) according to a conventional method to form an ether bond,
General formula (XXI)

[0076]

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A benzoic acid derivative having an azo group represented by the following formula is produced. Further, after the benzoic acid derivative represented by the general formula (XXI) is treated with thionyl chloride in the presence of dimethylformamide to synthesize an acid chloride, Y is -OCO
When a compound having Y is -NHCO- is obtained by performing an esterification reaction with a carboxylic acid derivative having a straight-chain alkyl represented by the general formula (XV). Formula (XXII)

[0078]

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(Wherein Rc represents an acryl group, a methacryl group, a vinyl group or a protected amino group, and m represents the same as in the case of the compound represented by the formula (I)). To form an amide bond by reacting with a primary amine having
General formula (XIV '')

[0080]

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An optically active intermediate represented by the formula (XIV) wherein Ra = Rc is produced.

When a compound represented by the general formula (XXII) wherein Rc is an acryl group, a methacryl group or a vinyl group is used, the resulting intermediate represented by the general formula (XIV ') is ) Corresponds to the polymerizable photoisomerizable optically active compound.

Other polymerizable functional groups are introduced by the above-mentioned method (ia-2) when introducing an epoxide group, and by the above-mentioned method (ia-3) when introducing an isocyanate group.
By carrying out in the same manner as in the above method,
And a polymerizable photoisomerizable optically active compound represented by the formula:

(Ii) In the case of three rings [n = 1, k = 0,
General formula (XXII)

[0085]

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(Wherein, A, m, Y, ring D, ring E, ring G, R ₁ , R ₂ and C ^* are the same as those in formula (I))

In the above method (ia), the 4-substituted aniline derivative (III) represented by the general formula (III) is replaced with the general formula (XXIV)

[0088]

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(In the formula, Rx represents an alcoholic hydroxyl group, a vinyl group, or a protected amino group.)

A 4-substituted-4'-aminobiphenyl derivative represented by the following formula is diazotized and then reacted with a phenol derivative represented by the general formula (IV) to obtain a compound represented by the general formula (XXV)

[0091]

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An intermediate having an azo group represented by the following formula is produced. The intermediate having an azo group represented by the general formula (XXV) and the optically active alcohol represented by the general formula (VI) are dehydrogenated in accordance with a conventional method to form an ether bond, thereby obtaining the compound represented by the general formula (XXVI)

[0093]

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An optically active intermediate represented by the following formula is prepared.

When a compound represented by the general formula (XXIV) wherein Rx is an acryl group, a methacryl group or a vinyl group is used, the obtained intermediate represented by the general formula (XXVI) is Corresponds to a polymerizable photoisomerizable optically active compound.

The introduction of other polymerizable functional groups is performed in the same manner as in the above-mentioned method (ia-2) when introducing an epoxide group, and by introducing the above-described (i) when introducing an isocyanate group. -A-3), the polymerizable photoisomerizable optically active compound represented by the general formula (XXIII) can be produced.

(Iii) In the case of three rings [n = 0, k =
1. General formula (XXVII)

[0098]

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Wherein A, m, Y, ring E, ring G, Z,
Rings J, R ₁ , R ₂ and C ^* represent the same as those in formula (I). Compound represented by)]

(Iii-a) When Z is a single bond (iii-a-1) When Y is -O- or -COO- General formula (XXVIII)

[0101]

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(Wherein, ring G and ring J are the same as those in formula (I)) and a 4-hydroxy-4'-nitrobiphenyl derivative represented by formula (VI) An optically active alcohol is dehydrated according to a conventional method to form an ether bond, thereby producing an optically active 4-substituted-4′-nitrobiphenyl derivative,
By reducing the nitro group of this compound with an amino group, the compound represented by the general formula (XXIX)

[0103]

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An optically active amino compound represented by the following formula is produced. Next, after diazotizing the optically active amino compound represented by the general formula (XXIX), it is reacted with the phenol derivative represented by the general formula (XI) to obtain a compound represented by the general formula (XXX)

[0105]

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An optically active compound having an azo group represented by the following formula is produced.

In order to obtain a compound wherein Y is —O—,
An optically active compound having an azo group represented by the general formula (XXX) and a compound having a linear alkyl represented by the general formula (XI)
II) is dehydrogenated according to a conventional method to form an ether bond, whereby an optically active intermediate represented by the following general formula (XXXIa) is produced.

When a compound wherein Y is —COO— is obtained, an optically active compound having an azo group represented by the general formula (XXX) and a carboxylic acid having a linear alkyl represented by the general formula (XV) An optically active intermediate represented by the following formula (XXXIb) is produced by an esterification reaction with a derivative (Rc is an acryl group, a methacryl group, a vinyl group or a protected amino group).

[0109]

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The method for introducing the polymerizable functional group A is carried out in the same manner as in the above-mentioned (ia-1) to (ia-3), whereby the polymerization represented by the general formula (XXVII) is carried out. The photoisomerizable optically active compound can be produced.

(Iii-a-2) When Y is -CONH- In the above (ia-1), the 4-hydroxy-4'-nitrobiphenyl derivative represented by the general formula (XXVIII) was diazotized. Later, instead of the phenol derivative represented by the general formula (XI), the general formula (XL)

[0112]

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(Wherein ring E represents the same as in the case of the general formula (I)) by reacting the aniline derivative represented by the general formula (XXXII)

[0114]

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An optically active amino compound having an azo group represented by the following formula is produced. Next, the optically active amino compound having an azo group represented by the general formula (XXXII) and the carboxylic acid derivative having a straight-chain alkyl represented by the general formula (XV) are subjected to an amidation reaction to obtain the general formula (XXXIb ) To produce an optically active intermediate.

The method for introducing the polymerizable functional group A is carried out in the same manner as in the above-mentioned (ia-1) to (ia-3), whereby the polymerization represented by the general formula (XXVII) is carried out. The photoisomerizable optically active compound can be produced.

(Iii-a-3) Y is -NHCO-, -O
In the case of CO- General formula (XXXIII)

[0118]

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(Wherein, Rc represents an acryl group, a methacryl group, a vinyl group or a protecting group, and m, Y and ring E represent the same as those in the general formula (I)). After diazotizing the aniline derivative, the compound represented by the general formula (XX)
XIV)

[0120]

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(Wherein, ring G and ring J are the same as those in formula (I)), and are reacted with a 4-hydroxybiphenyl derivative represented by formula (XXXV).

[0122]

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An intermediate compound having an azo group represented by the following formula is produced. Next, the intermediate compound having an azo group represented by the general formula (XXXV) and the optically active alcohol (VI) are dehydrogenated according to a conventional method to form an ether bond, whereby the above-mentioned general formula (XXXIb) To produce an optically active intermediate represented by

The method for introducing the polymerizable functional group A is carried out in the same manner as in the above-mentioned (ia-1) to (ia-3), whereby the polymerization represented by the general formula (XXVII) is carried out. The photoisomerizable optically active compound can be produced.

(Iii-b) Z is -O-, -OCO-,-
When it is NHCO— In the above (iii-a-3), when a 4-substituted aniline derivative represented by the general formula (XXIII) is diazotized to obtain a compound in which Z is —O— or —OCO— Is obtained by coupling a phenol derivative represented by the general formula (IV) to obtain a compound in which Z is -NHCO-,

[0126]

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(Wherein ring G represents the same as in the case of the general formula (I)) and is coupled with an aniline derivative represented by the general formula (XXXVII).

[0128]

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(Wherein Rd represents a phenolic hydroxyl group or an amino group) to produce an intermediate compound having an azo group represented by the formula:

(Iii-b-1) Z is -O- or -OCO
Wherein Rd is a phenolic hydroxyl group;
An intermediate compound having an azo group represented by the formula:
In the case of obtaining a compound of the formula (XXXVIII)

[0131]

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(Wherein rings J, R ₁ , R ₂ and C ^* represent the same as in the case of formula (I)). By forming an ether bond, Z becomes -OC
When obtaining a compound represented by O-, a compound represented by the general formula (XXXIX)

[0133]

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(Wherein, rings J, R ₁ , R ₂ and C ^* are the same as in the case of the general formula (I)) and are subjected to an esterification reaction with an optically active benzoic acid derivative represented by the formula: Gives the general formula (XXXX)

[0135]

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An optically active precursor represented by the following formula is produced.

The method for introducing the polymerizable functional group A is carried out in the same manner as in the above-mentioned (ia-1) to (ia-3), whereby the polymerization represented by the general formula (XXVII) is carried out. The photoisomerizable optically active compound can be produced.

(Iii-b-2) When Z is -NHCO-: an intermediate compound having an azo group represented by the general formula (XXXVII) wherein Rd is an amino group;
An optically active benzoic acid derivative represented by the formula is subjected to an amidation reaction to produce an optically active precursor represented by the general formula (XXXX).

The method for introducing the polymerizable functional group A is carried out in the same manner as in the above-mentioned (ia-1) to (ia-3), whereby the polymerization represented by the general formula (XXVII) is carried out. The photoisomerizable optically active compound can be produced.

(Iii-c) Z is -COO- or -CON
When H is (iii-c-1) Y is -O-, -COO- or -CONH
When is-General formula (XL)

[0141]

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(Wherein ring G is the same as that of formula (I)) after diazotizing a 4-aminobenzoic acid derivative represented by formula (XIL)

[0143]

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(In the formula, Ry represents a phenolic hydroxyl group or an amino group, and ring E represents the same as in the case of the general formula (I).) By reacting with an aromatic compound, the compound represented by the general formula (XLI
I)

[0145]

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A compound having an azo group represented by the following formula is produced.

When a compound in which Y is -O- is obtained,
The compound represented by the general formula (XLII) wherein Ry is a phenolic hydroxyl group and the compound having a linear alkyl group represented by the general formula (XIII) are dehydrogenated according to a conventional method to form an ether bond. , And if necessary,
When Rx is substituted with an acryl or methacryl group according to the method described in (ia-1) to obtain a compound in which Y is -COO-, the compound represented by the general formula (XLII) wherein Ry is a phenolic hydroxyl group In the case where a compound represented by the formula (XV) is subjected to an esterification reaction with a carboxylic acid derivative having a straight-chain alkyl represented by the formula (XV) to obtain a compound wherein Y is -CONH-, Ry is an amino group. By subjecting the compound represented by the general formula (XLII) to an amidation reaction with the carboxylic acid derivative having a straight-chain alkyl represented by the general formula (XV), the compound represented by the general formula (XLIII)

[0148]

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(Wherein Rc represents an acryl group, a methacryl group, a vinyl group or an amino group).

When producing a compound wherein Z is -COO-, an intermediate (XLII) represented by the above formula (XLIII)
After dehydrogenating I) and the optically active phenol derivative represented by the general formula (XXXVIII) according to a conventional method to form an ether bond, the above-mentioned (ia-1) to (i-1)
By introducing the polymerizable functional group A in the same manner as in -a-3), the polymerizable photoisomerizable optically active compound represented by the general formula (XXVII) can be produced.

When a compound wherein Z is -CONH- is produced, an intermediate (XLII) represented by the above formula (XLIII)
After the amidation reaction between I) and the optically active aniline derivative (X) represented by the general formula (X), the above-mentioned (i)
-A-1) to introducing a polymerizable functional group A in the same manner as in (ia-3) to produce a polymerizable photoisomerizable optically active compound represented by the general formula (XXVII). Can be.

(Iii-c-2) Y is-, -OCO-, -N
When it is HCO- General formula (XLIV)

[0153]

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The 4-substituted aromatic nitroso compound represented by the general formula (XL) and the 4-aminobenzoic acid derivative (XL) represented by the general formula (XL) are condensed in glacial acetic acid to give the compound represented by the general formula (XLIII) To produce a carboxylic acid having an azo group.

The introduction of the optically active group and the polymerizable functional group can be performed by the same operation as in the above (iii-c-1). However, the 4-substituted aromatic nitroso compound represented by the general formula (XLIV) can be produced by oxidizing the corresponding amino compound under mild conditions.

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

[0157]

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(In the formula, A, m, Y, ring D, ring E, ring G, Z, ring J, R ₁ , R ₂ and C ^* represent the same as those in formula (I).) Compound represented by

(Iv-a) When Z is —O— or —OCO— An intermediate having an azo group represented by the general formula (XXIV) synthesized in the above (ii) and Z is —O— When a certain compound is obtained, the optically active hydroquinone derivative represented by the general formula (XXXVIII) is dehydrogenated according to a conventional method to form an ether bond, so that Z is -OC.
When a compound represented by O- is obtained, the compound represented by the general formula (XXXI
X) is subjected to an esterification reaction with an optically active benzoic acid derivative represented by the formula (XLVI).

[0160]

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An optically active precursor represented by the following formula is produced.

The method for introducing the polymerizable functional group A is carried out in the same manner as in the above (ia-1) to (ia-3), whereby the polymerization represented by the general formula (XLV) is carried out. The photoisomerizable optically active compound can be produced.

(Iv-b) Z is -COO- or -CONH
When is-General formula (XLVII)

[0164]

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(In the formula, 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 a 4-aminobenzoic acid derivative represented by the general formula (XL)
By condensation in glacial acetic acid, the compound represented by the general formula (XLVIII)

[0166]

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A carboxylic acid having an azo group represented by the following formula is produced.

In order to obtain a compound in which Z is -COO-, the carboxylic acid having an azo group represented by the general formula (XLVIII) is esterified with the optically active hydroquinone derivative represented by the general formula (XXXVIII). When a compound in which Z is -CONH- is obtained by reacting, a carboxylic acid having an azo group represented by the general formula (XLVIII) and an optically active aniline derivative represented by the general formula (X) are used. By performing an amidation reaction, the compound represented by the general formula (XLVI)

[0169]

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An optically active precursor represented by the following formula is produced.

The method for introducing the polymerizable functional group A is carried out in the same manner as in the above (ia-1) to (ia-3), whereby the polymerization represented by the general formula (XLV) is carried out. The photoisomerizable optically active compound can be produced.

The above is the method for producing the polymerizable optically active photoisomerized liquid crystalline compound represented by the general formula (I) of the present invention.

The structural characteristics of the polymerizable optically active photoisomerizable liquid crystal compound represented by the general formula (I) of the present invention are as follows.

(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, which isomerized into a cis-form by irradiation with ultraviolet light, and has another wavelength (light It returns to the transformer by irradiation of visible light (or 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. can do. In addition, the general formula (I)
The compound represented by can be used alone or as a mixture.

As described above, the polymerizable optically active photoisomerizable liquid crystal compound represented by the general formula (I) of the present invention is useful as a photochromic compound of the above-mentioned light control type polymerizable optically active liquid crystal composition.

[0177]

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

<Example 1> {Synthesis of (R) -4- (1-methylheptyloxy) phenyl-4 '-[4- (11-acryloyloxyundecyloxy) phenylazo] benzoate} (1-a) [Synthesis of 4- (4-hydroxyphenylazo) benzoic acid] In a four-neck flask having a capacity of 5 liters, 500 ml of water and 250 ml of hydrochloric acid (equivalent to 2.5 mol of hydrogen chloride) were placed.
To this was added 4-aminobenzoic acid with vigorous stirring.
0 g (365 mmol) was added and suspended. After 1.5 kg of ice was added to the suspension and the liquid temperature was cooled to about -10 ° C, 300 ml of an aqueous solution of 28.0 g (410 mmol) of sodium nitrite was added dropwise over about 1 hour. A homogeneous solution (reaction solution 1) was obtained.

1 liter of an alkaline aqueous solution containing 35.0 g (370 mmol) of phenol, 50 g (1.3 mol) of sodium hydroxide and 130 g (1.2 mol) of sodium carbonate was added to the reaction solution 1 for about 3 hours. It dripped over. Immediately after the addition, an orange precipitate was formed. During the dropping of the alkaline aqueous solution, the liquid temperature was 0 ° C.
Ice was added little by little so as not to go any further. After completion of the dropwise addition, stirring was continued for about 2 hours, and then the reaction was terminated.

The reaction mixture was adjusted to be acidic (pH = 2) by adding sulfuric acid, and the precipitated precipitate was filtered. The precipitate collected by filtration was washed once with water to give 96.2 g of the desired product (yield 10%).
9%).

The obtained target product is considered to contain some salt and water, but it does not affect the next reaction, so that no further purification was carried out.

1H-nuclear magnetic resonance spectrum (NMR)
(399.65 MHz, CD ₃ OD solution): δ = 8.16 (d, J = 8.8H
z, 2H), 7.89 (d, J = 8.3 Hz, 2H), 7.87 (d, J = 8.3 Hz, 2
H), 6.96 (d, J = 8.8Hz, 2H)

Mass spectrometry (MS) (70 eV): m / z =
242 (M ⁺ , 30), 121 (78), 93 (100), 65 (64)

(1-b) {Synthesis of 4- [4- (11-hydroxyundecyloxy) phenylazo] benzoic acid} A 4-liter 4-neck flask equipped with a condenser was charged with 4- (4-hydroxyphenylazo). ) Benzoic acid 5
0.0 g (210 mmol) was weighed and ethanol 50
It was dissolved at 0 ml under reflux. To this solution, 86.0 g (620 mmol) of potassium carbonate and 6 g of potassium iodide were added by trituration, and immediately a precipitate was formed. Therefore, 100 ml of ethanol and 200 ml of water were further added and dissolved. After refluxing for about 30 minutes, 57.0 g (230 mmol) of 11-bromo-1-undecanol.
Was added dropwise over about 4 hours. After the addition was completed, reflux was continued for about 20 hours, and then the reaction was terminated.

The reaction solution was adjusted to acidic (pH = 2) by adding 500 ml of water and an appropriate amount of hydrochloric acid, and the precipitated solid was filtered. The solid collected by filtration was washed with water and recrystallized from tetrahydrofuran to obtain 60 g (yield: 70%) of an orange target compound.

1H-NMR (399.65 MHz, dimethyl sulfoxide (DMSO) -d6 solution): δ = 13.19 (s, 1
H), 8.12 (d, J = 8.8Hz, 2H), 7.94 to 7.90 (m, 4H), 7.14
(d, J = 8.8Hz, 2H), 4.09 (t, J = 6.6Hz, 2H), 3.37 (d, J =
4.4Hz, 2H), 1.75 (t, J = 7.3Hz, 2H), 1.40 to 1.26 (m, 16
H)

MS (70 eV): m / z = 412 (M ⁺ ), 24
2,149,137,121,109,93,55 (100), 41

(1-c) {Synthesis of 4- [4- (11-acryloyloxyundecyloxy) phenylazo] benzoic acid} In a 500 ml eggplant flask, 4- [4- (11-hydroxyundecyloxy) [Phenylazo] benzoic acid (5.0 g, 12 mmol) was weighed and pyridine (110 ml) was added.
And 0.2 g of 4-dimethylaminopyridine were added and dissolved by heating. The eggplant flask was placed in a water bath, and 4 ml (40 mmol) of acrylic acid chloride was added dropwise over 10 minutes with stirring while keeping the temperature near room temperature under a nitrogen stream. After completion of the dropwise addition, stirring was further continued for 4 hours while maintaining the temperature at 50 ° C. in a water bath, and the reaction was terminated.

The solvent was removed from the reaction solution, and the precipitated solid was washed with water. After the precipitate was filtered off, n-butanol 200 ml
To give an orange solid. The obtained solid was washed with petroleum ether and dried under reduced pressure to obtain 4.9 g (yield 87%) of the target product.

1H-NMR (399.65 MHz, C ₅ D ₅ N solution): δ = 8.60 (d, J = 8.3 Hz, 2H), 8.21 to 8.16 (m, 4
H), 7.24 to 7.20 (m, 2H), 6.49 (d, J = 19.0Hz, 1H), 6.28
(dd, J = 10.3Hz, 17.6Hz, 1H), 5.76 (d, J = 10.3Hz, 1
H), 3.91 (t, J = 6.6 Hz, 2H), 3.78 (t, J = 6.1 Hz, 2H), 1.
78-1.18 (m, 18H)

MS (70 eV): m / z = 466 (M ⁺ , 2
3), 242 (7), 165 (14), 121 (65), 109 (33), 97 (38), 69
(69), 55 (100), 41 (48)

(1-d) {Synthesis of (R) -4- (1-methylheptyloxy) phenyl-4 ′-[4- (11-acryloyloxyundecyloxy) phenylazo] benzoate} Four ports having a capacity of 300 ml In a flask, 3.0 g (6.4 mmol) of 4- [4- (11-acryloyloxyundecyloxy) phenylazo] benzoic acid, 0.79 g (6.4 mmol) of 4-dimethylaminopyridine, pyridine 3
0 ml and 2.9 g (12.9 mmol) of (R) -4- (1-methylheptyloxy) phenol were weighed and dissolved by heating. While the flask containing this solution was kept in an ice water bath and kept at 10 ° C. or lower, 6.6 g (32 mmol) of N, N′-dicyclohexylcarbodiimide was added twice in 5 minutes. After 20 minutes, the temperature was returned to room temperature, and stirring was continued for about 5 hours while monitoring the reaction by thin-layer chromatography.

The solvent was removed from the reaction solution, and toluene was added to dissolve the reaction mixture. The white precipitate formed at this time was separated by filtration, the solvent was removed, and the residue was dried under reduced pressure. The reaction product dried under reduced pressure was purified by silica gel column chromatography using a mixed solvent of toluene: ethyl acetate = 2: 1 as a developing solvent to collect a low-polarity portion. Remove the solvent,
After drying under reduced pressure, a mixture of an orange solid and an oil was obtained. The mixture was recrystallized from 10 ml of hexane to give 1.8 g of orange crystals (yield 42%). Further, the product was recrystallized from ethanol to obtain 1.0 g (yield: 23%) of the target product with higher purity.

1H-NMR (399.65 MHz, CDCl ₃ ):
δ = 8.32 (d, J = 8.8 Hz, 2H), 7.96 (d, J = 8.8 Hz, 4H), 7.
13 (d, J = 8.8Hz, 2H), 7.02 (d, J = 8.8Hz, 2H), 6.92 (d,
J = 9.3Hz, 2H), 6.40 (dd, J = 1.5Hz, 17.1Hz, 1H), 6.12
(dd, J = 10.3Hz, 17.1Hz, 1H), 5.81 (dd, J = 1.5Hz, 10.3
Hz, 1H), 4.4 to 4.3 (m, 1H), 4.15 (t, J = 6.8Hz, 2H), 4.
06 (t, J = 6.4Hz, 2H), 1.9 to 1.2 (m, 31H), 0.89 (m, 3H)

MS (70 eV): m / z = 670 (M ⁺ , 3),
449 (100), 225 (51), 120 (58), 110 (40), 55 (30), 41 (2
Five)

[0196] (In the above, I is an isotropic phase, N is a nematic phase, SA
Represents a smectic A phase, and Sx represents a smectic phase of unknown assignment. )

Tilt angle: about 20 degrees No polarization reversal current was observed.

Example 2 {(R) -4- (1-methylheptyloxy) phenyl-4 '-[3-chloro-4-
Synthesis of (11-acryloyloxyundecyloxy) phenylazo] benzoate {(2-a) [Synthesis of 4- (3-chloro-4-hydroxyphenylazo) benzoic acid] 500 ml of water was placed in a 5-liter 4-neck flask. And 250 ml of hydrochloric acid (corresponding to 2.5 mol of hydrogen chloride).
To this was added 4-aminobenzoic acid with vigorous stirring.
0 g (365 mmol) was added and suspended. After 1.5 kg of ice was added to the suspension and cooled to about -10 ° C, an aqueous solution of 28.0 g (410 mmol) of sodium nitrite was added.
When 00 ml was added dropwise over about 1 hour, a homogeneous solution (reaction liquid 2) gradually formed.

48.0 g of 2-chlorophenol (370
Mmol), 50 g (1.3 mol) of sodium hydroxide,
1.5 l of an aqueous solution containing 130 g (1.2 mol) of sodium carbonate was added dropwise to the reaction solution 2 over about 3 hours. Immediately after the addition, an orange precipitate was formed. During the dropwise addition, ice was added little by little so that the liquid temperature did not become 0 ° C. or higher. After completion of the dropwise addition, stirring was continued for about 2 hours, and then the reaction was terminated.

The reaction mixture was adjusted to be 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 92.8 g of the desired product (yield 91.9%).

The obtained target product is thought to contain some salt and water, but it did not affect the next reaction, so that no further purification was carried out.

1H-NMR (60.0 MHz, CD ₃ OD solution): δ = 8.5-7.5 (m, 5H), 7.3-6.8 (m, 2H)

MS (70 eV): m / z = 276 (M ⁺ , 3
8), 155 (57), 129 (33), 127 (100), 121 (51), 99 (34), 6
5 (48)

(2-b) {4- [3-chloro-4- (1
Synthesis of 1-hydroxyundecyloxy) phenylazo] benzoic acid 4- (3-chloro-4-hydroxyphenylazo) was placed in a 1-liter three-necked flask equipped with a condenser.
-30.0 g (108 mmol) of benzoic acid was weighed out, added with 220 ml of ethanol and dissolved under reflux. When 45 g (330 mmol) of potassium carbonate and a trace amount of potassium iodide were added to the solution by trituration, a solid was immediately formed.
And 50 ml of water to obtain a homogeneous solution. After refluxing for about 1 hour, 30.0 g of 11-bromo-1-undecanol
(120 mmol) of ethanol solution (100 ml) was added all at once, and the mixture was further refluxed for about 24 hours, and the reaction was terminated.

When the reaction mixture was adjusted to acidic (pH = 1) by adding 500 ml of water and an appropriate amount of hydrochloric acid, a solid precipitated. To this solution, three times the volume of ethyl acetate (2.5 liters) was added, and the mixture was heated to dissolve the solid. The organic layer was washed with acidic water (pH = 3), and the organic layer was washed with 50% sodium sulfate.
After drying with 0 g, the solid obtained by removing the solvent was collected, recrystallized from 1 liter of methanol and purified to obtain 34 g (yield 70%) of the desired product.

1H-NMR (399.65 MHz, dimethyl sulfoxide-d6 solution): δ = 13.2 (s, 1H), 8.14 (d, J =
8.3Hz, 2H), 8.0 to 7.9 (m, 4H), 7.36 (d, J = 9.3Hz, 1
H), 4.17 (t, J = 6.4 Hz, 2H), 3.38 (t, J = 6.4 Hz, 2H), 1.
8 to 1.7 (m, 2H), 1.5 to 1.2 (m, 16H)

13C-NMR (100.40 MHz, DM
SO-D6): δ = 166.69, 156.96, 154.15, 145.77, 1
32.58, 130.57, 125.72, 122.68, 122.41, 122.33, 11
3.65, 69.21, 60.72, 32.53, 29.07, 28.97, 28.94, 2
8.65, 28.36, 25.51, 25.34

MS (70 eV): m / z = 446 (M ⁺ ), 27
6,155 (100), 143,127,121,109,97,69,55,41

(2-c) {4- [3-chloro-4- (1
1-acryloyloxyundecyloxy) phenylazo]
Synthesis of Benzoic Acid In a 200 ml round-bottom flask equipped with a dropping funnel, under a stream of nitrogen, 5.2 g of 4- {3-chloro-4- (11-hydroxyundecyloxy) phenylazo} benzoic acid (12 g) was added.
(Mmol) was dissolved in 55 ml of tetrahydrofuran. 3.5 g of triethylamine was added to this solution.
(35 mmol) and 10 ml of a solution of 3.2 g (35 mmol) of acrylic acid chloride in tetrahydrofuran was added dropwise over 15 minutes while stirring in a water bath. After completion of the dropwise addition, stirring was continued at room temperature for about 4 hours, and then the reaction was terminated.

The reaction mixture was added with 400 ml of ethyl acetate and washed four times with 200 ml of saturated saline. After adding 400 g of sodium sulfate to the organic layer and drying, the solvent was removed to obtain a red oily crude product. Recrystallization from acetonitrile and purification gave 3.9 g (yield 67%) of the desired product.

1H-NMR (399.65 MHz, dimethyl sulfoxide-d6 solution): δ = 8.13 (d, J = 8.3 Hz, 2H), 8.
0 to 7.9 (m, 4H), 7.33 (d, J = 8.3 Hz, 1H), 6.30 (d, J = 17.
1Hz, 1H), 6.2 to 6.1 (m, 1H), 5.90 (d, J = 10.3Hz, 1H),
4.16 (t, J = 6.4Hz, 2H), 4.08 (t, J = 6.8Hz, 2H), 1.8 ~
1.7 (m, 2H), 1.7 to 1.5 (m.2H), 1.5 to 1.4 (m, 2H), 1.4 to
1.2 (m, 12H)

13C-NMR (100.40 MHz, dimethyl sulfoxide-d6 solution): δ = 166.56, 156.98,
154.24, 145.89, 132.62, 130.89, 130.48, 128.43, 12
5.41, 122.77, 122.45, 122.30, 113.78, 69.28, 63.9
8, 28.80, 28.76, 28.72, 28.51, 28.32, 28.04, 25.24

MS (70 eV): m / z = 500 (M ⁺ ), 44
5,428,367,276,155,55 (100), 41

(2-d) {(R) -4- (1-methylheptyloxy) phenyl-4 '-[3-chloro-4-
Synthesis of (11-acryloyloxyundecyloxy) phenylazo] benzoate In a 100 ml eggplant-shaped flask equipped with a calcium tube, 4- [3-chloro-4- (11-acryloyloxyundecyloxy) phenylazo] benzoic acid was added. 2.0g
(4.0 mmol), 4-dimethylaminopyridine 0.
5 g (4.1 mmol) and (R) -4- (1-methylheptyloxy) phenol (1.8 g (8.0 mmol)) were weighed, dissolved in 25 ml of tetrahydrofuran, and dried. 4.1 g (20 mmol) of N, N'-dicyclohexylcarbodiimide were added in three portions over 15 minutes while maintaining the temperature in the ethylene glycol bath at about -15 DEG C. The mixture was stirred at room temperature for about 12 hours. After that, the reaction was terminated.

The reaction mixture was added with 300 ml of ethyl acetate and washed twice with 150 ml of saturated saline. The precipitated dicyclohexylurea was separated by filtration, and 100 g of sodium sulfate was added to the organic layer.
Was added and dried, and the solvent was removed to obtain a crude product as a reddish brown oil. Toluene: ethyl acetate = 2:
1, followed by hexane: toluene: ethyl acetate = 6: 2:
The low-polar part was collected using silica gel column chromatography using the mixed solvent of No. 1 as a mobile phase, and the solvent was removed to obtain a red oil. Petroleum ether was added thereto to make a uniform solution, and the solution was cooled in a dry ice-acetone bath to precipitate a solid. This was filtered while keeping the temperature low to obtain 0.8 g (yield: 28%) of the desired product.

1H-NMR (399.65 MHz, CDCl ₃ solution): δ = 8.32 (d, J = 8.8 Hz, 2H), 8.05 (d, J = 2.4 Hz, 1
H), 7.96 (d, J = 8.3Hz, 2H), 7.91 (dd, J = 8.8Hz, 2.4H
z, 1H), 7.13 (d, J = 8.8 Hz, 2H), 7.05 (d, J = 9.3 Hz, 1
H), 6.93 (d, J = 9.3 Hz, 2H), 6.40 (dd, J = 17.1 Hz, 1.5H
z, 1H), 6.12 (dd, J = 10.3 Hz, 17.6 Hz, 1H), 5.81 (dd, J
= 1.5Hz, 10.8Hz, 1H), 4.4 to 4.3 (m, 1H), 4.2 to 4.1 (m,
4H), 2.0-1.8 (m, 2H), 1.8-1.2 (m, 34H), 1.0-0.8
(m, 3H)

[0219] (In the above, I represents an isotropic phase, Ch represents a cholesteric phase, and SA represents a smectic A phase.)

In this compound, no ferroelectric liquid crystal phase could be confirmed at -10 ° C. or higher.

<Example 3> {(R) -4- (1-Methylheptyloxy) phenyl-4 '-[2-trifluoromethyl-4- (11-acryloyloxyundecyloxy) phenylazo] benzoate Synthesis (3) (3-a) [Synthesis of 4- (2-trifluoromethyl-4-hydroxyphenylazo) benzoic acid] In a four-neck flask having a capacity of 5 liters, 200 ml of water and 80 ml of hydrochloric acid (0.8 mol of hydrogen chloride were added). Equivalent), and into this,
While stirring vigorously, 20.0 g of 4-aminobenzoic acid (1
(46 mmol) was added and suspended. After adding 0.6 kg of ice to the suspension and cooling to about -10 ° C, 100 ml of an aqueous solution of 19.0 g (275 mmol) of sodium nitrite was added.
Was dropped over about 1 hour, and gradually became a uniform solution (reaction liquid 3).

3-trifluoromethylphenol 25.
0 g (154 mmol), sodium hydroxide 20 g
(0.5 mol) and 200 ml of an aqueous solution containing 32 g (0.3 mol) of sodium carbonate were prepared.
Was added dropwise over about 2.5 hours. Immediately after the addition, an orange precipitate was formed. During this time, ice was added little by little so that the temperature did not reach 0 ° C. or higher. After completion of the dropwise addition, stirring was further continued for 3 hours, and then the reaction was terminated.

The precipitate was filtered by adding hydrochloric acid to the reaction solution to adjust the pH to acidic (pH = 2). 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%).

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

1H-NMR (399.65 MHz, CD ₃ OD solution): δ = 8.18 (d, J = 8.8 Hz, 2H), 7.92 (d, J = 8.3 Hz, 2
H), 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 ⁺ , 3
1), 189 (38), 161 (100), 149 (29), 121 (83), 113 (13),
65 (58)

(3-b) {Synthesis of 4- [2-trifluoromethyl-4- (11-hydroxyundecyloxy) phenylazo] benzoic acid} In a 1-liter three-necked flask equipped with a condenser, (3-chloro-4-hydroxyphenylazo)
30 g (97 mmol) of benzoic acid were weighed, 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. 50 ml of water was further added to obtain a uniform solution. After refluxing for about 1 hour, 100 ml of an ethanol solution of 27 g (110 mmol) of 11-bromo-1-undecanol was added all at once, and the mixture was further refluxed and stirred for about 22 hours, after which the reaction was terminated.

A solid was deposited by adding 500 ml of water and 50 ml of hydrochloric acid to the reaction solution to adjust the acidity (pH = 1). 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 removing the solvent was collected, recrystallized from 300 ml of ethanol and purified to obtain 33 g of the desired product (yield 71%).

1H-NMR (60.0 MH, CD ₃ OD solution): δ = 8.3-7.8 (m, 5H), 7.5-7.3 (m, 2H), 4.4-
4.0 (m, 2H), 3.6 to 3.2 (m, 2H), 2.0 to 1.2 (m, 18H)

MS (70 eV): m / z = 480 (M ⁺ ), 35
9, 310, 291, 189, 176, 161, 149, 121, 95, 83, 69,
55, 41

(3-c) {Synthesis of 4- [2-trifluoromethyl-4- (11-acryloyloxyundecyloxy) phenylazo] benzoic acid} 100 ml two-necked flask equipped with a dropping funnel and a calcium tube In addition, 4- [2-trifluoromethyl-4- (1
1-Hydroxyundecyloxy) phenylazo] benzoic acid (5.0 g, 10 mmol) was weighed and dissolved by adding 50 ml of tetrahydrofuran. To this solution was added 2.1 g (21 mmol) of triethylamine, placed in a water bath, and a solution of 1.9 g (21 mmol) of acrylic acid chloride in 10 ml of tetrahydrofuran was added dropwise over 30 minutes.
After completion of the dropwise addition, stirring was continued at room temperature for another 5 hours, and then the reaction was terminated.

To the reaction mixture was added 500 ml of ethyl acetate, and the mixture was washed four times with 100 ml of saturated saline. After the organic layer was dried over 100 g of sodium sulfate, the solvent was removed to obtain a crude product as a red solid. This was recrystallized from 50 ml of acetonitrile to obtain 4.3 g (yield: 77%) of the desired product.

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 = 7.8 Hz, 3H), 7.5 to 7.4 (m, 2
H), 6.37 (t, J = 17.1 Hz, 1H), 6.3 to 6.1 (m, 1H), 5.99
(d, 10.7Hz, 1H), 4.24 (t, J = 5.9Hz, 2H), 4.18 (t, J =
6.6Hz, 2H), 1.84 (t, J = 6.6Hz, 2H), 1.68 (t, J = 6.3H
z, 2H), 1.6-1.3 (m, 14H)

MS (70 eV): m / z = 534 (M ⁺ ), 41
3,310,291,189,177,149,121,97,83,69,55,4
1

(3-d) Synthesis of (R) -4- (1-methylheptyloxy) phenyl-4 ′-[2-trifluoromethyl-4- (11-acryloyloxyundecyloxy) phenylazo] benzoateに In a 200 ml round bottom flask equipped with a calcium tube,
2.0 g (3.7 mmol) of 4- [2-trifluoromethyl-4- (11-acryloyloxyundecyloxy) phenylazo] benzoic acid, 0.46 g (3.7 mmol) of 4-dimethylaminopyridine and ( R) -4-
1.7 g of (1-methylheptyloxy) phenol
(7.5 mmol) was weighed and stirred in a dry ice-ethylene glycol bath while maintaining the temperature at about -15 ° C.
To this was added 3.9 g (19 mmol) of N, N'-dicyclohexylcarbodiimide in three portions for 15 minutes. Thereafter, the temperature was returned to room temperature and stirring was continued for another 8 hours, and then the reaction was terminated.

The dicyclohexylurea precipitated in the reaction solution was separated by filtration, and the filtrate was diluted with 300 ml of toluene. The organic layer was washed four times with 100 ml of a saturated saline solution, dried over 200 g of sodium sulfate, and then the solvent was removed to obtain a red-brown crude product. Hexane: toluene: ethyl acetate = 6:
The low polarity portion was collected using silica gel column chromatography using a 2: 1 mixed solvent as a mobile phase, and the solvent was removed to obtain a red product. Further, the product was recrystallized from 40 ml of petroleum ether and purified to obtain 1.5 g (yield 54%) of the desired product.

1H-NMR (399.65 MHz, CDCl ₃ solution): δ = 8.34 (d, J = 8.3 Hz, 2H), 8.02 (d, J = 8.8 Hz, 2
H), 7.95 (d, J = 9.3 Hz, 1H), 7.34 (d, J = 2.4 Hz, 1H), 7.
14 (d, J = 9.3Hz, 3H), 6.94 (d, J = 8.8Hz, 2H), 6.41 (d
d, J = 2.0Hz, 17.6Hz, 1H), 6.13 (dd, J = 10.8Hz, 17.6H
z, 1H), 5.82 (dd, J = 1.5Hz, 10.4Hz, 1H), 4.4 to 4.3
(m, 1H), 4.16 (t, J = 6.8 Hz, 2H), 4.09 (t, J = 6.4 Hz, 2
H), 1.9 to 1.2 (m, 31H), 1.0 to 0.8 (m, 3H)

13C-NMR (100.40 MHz, dimethyl sulfoxide-d6 solution): δ = 161.28, 156.62,
153.61, 152.79, 130.89, 128.43, 128.22, 121.99, 12
1.95, 118.88, 118.00, 112.49, 68.70, 63.98, 53.8
7, 49.12, 33.27, 31.10, 31.04, 30.31, 28.73, 28.5
5, 28.49, 28.35, 28.04, 25.53, 25.30, 25.26, 25.0
8, 24.88, 24.36, 23.94

Phase transition temperature: 34 ° C. during cooling (I → K) (In the above, I represents an isotropic phase, and K represents a crystal phase.)

This compound did not exhibit a ferroelectric liquid crystal phase.

Example 4 {(R) -4- (1-Methylheptyloxy) phenyl-4 '-[3-fluoro-4
Synthesis of-(11-acryloyloxyundecyloxy) phenylazo] benzoate (Synthesis of (4-a) [4- (3-fluoro-4-hydroxyphenylazo) benzoic acid] Hydrochloric acid was added to a 5-liter separable flask. 100ml
(Equivalent to 1.0 mol of hydrogen chloride) and 500 g of ice,
To this, with vigorous stirring, 4-aminobenzoic acid.
0 g (220 mmol) was added and suspended. An aqueous solution of 30.0 g (440 mmol) of sodium nitrite (100 ml) was added dropwise to the suspension over about 1 hour, whereby a uniform solution (reaction liquid 4) was gradually obtained.

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 and sodium carbonate was prepared and added dropwise to the reaction solution 4 over about 2 hours. Immediately after the addition, an orange precipitate was formed.
During this time, ice was added little by little so that the temperature did not reach 0 ° C. or higher. After the completion of the dropwise addition, stirring was continued for another 7 hours, and then the reaction was terminated.

The reaction mixture was adjusted to be acidic (pH = 1) by adding hydrochloric acid, and the precipitated precipitate was filtered. The precipitate collected by filtration was dissolved by heating in 1.5 liter of ethyl acetate,
Washed three times with 0 ml of water. Sodium sulfate 50 in organic layer
After adding 0 g and drying, the solvent was removed to obtain a crude product. Purified by recrystallization from acetonitrile-water,
41 g (yield 72%) of the desired product was obtained.

(4-b) {4- [3-fluoro-4-
(11-hydroxyundecyloxy) phenylazo]
Synthesis of Benzoic Acid 20 g (77 mmol) of 4- (3-fluoro-4-hydroxyphenylazo) benzoic acid was weighed and placed in a 1-liter three-neck separable flask equipped with a condenser.
100 ml of ethanol was added and the mixture was suspended under reflux.
To this suspension was added 16 g (115 mmol) of potassium carbonate.
When a trace amount of potassium iodide was added by trituration, a solid was immediately formed, and 100 ml of water was further added to form a suspension. After refluxing for 1 hour, a solution of 21 g (85 mmol) of 11-bromo-1-undecanol in 100 ml of ethanol was added all at once. Then 24 more
After continuing refluxing and stirring for hours, the reaction was terminated.

The reaction mixture was adjusted to acidic (pH = 2) by adding 300 ml of water and 50 ml of hydrochloric acid, and the precipitated solid was filtered. The collected solid was 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 = 8.8Hz, 2H), 7.83 (d, J = 8.3Hz, 1H), 7.70 (d
d, J = 2.0Hz, 11.7Hz, 1H), 7.37 (t, J = 9.0Hz, 1H), 4.1
7 (t, J = 6.6Hz, 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, 150.05, 145.75, 145.70, 13
2.63, 130.49, 123.22, 122.28, 122.16, 114.56, 107.
60, 107.41, 69.22, 60.76, 32.51, 29.01, 28.29, 28.
80, 28.63, 28.43, 25.47, 25.27

MS (70 eV): m / z = 430 (M ⁺ ), 26
0, 149, 139 (100), 127, 111, 95, 83, 69, 55, 41

(4-c) {4- [3-fluoro-4-
Synthesis of (11-acryloyloxyundecyloxy) phenylazo] benzoic acid 4- (3-Fluoro-4- (11-hydroxyundecyloxy) phenylazo) was placed in a 500-ml five-necked flask equipped with a dropping funnel and a calcium tube. Benzoic acid19.
2 g (44.7 mmol) and triethylamine 7.0
g (70 mmol) was weighed, and anhydrous tetrahydrofuran 3
00 ml was added to dissolve. 7. A small amount of 4-dimethylaminopyridine was added to this solution, and then acrylic acid chloride was added.
4 g (89 mmol) of anhydrous diethyl ether solution 20
ml was added dropwise over about one hour. After the completion of the dropwise addition, stirring was continued for about 5 hours, and then the reaction was terminated.

The triethylamine hydrochloride precipitated in the reaction solution was separated by filtration, washed with acetonitrile, and 1 liter of diethyl ether was added to the filtrate.
It was washed once with an aqueous solution of 00 ml and 30 ml of acetic acid, and four times with a saturated saline solution. The organic layer was dried over anhydrous sodium sulfate (500 g), and the solvent was removed to obtain a crude orange solid product. Recrystallized from acetonitrile and purified to obtain the desired product 1
7.8 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 = 8.8Hz, 2H), 7.83 (d, J = 8.8Hz, 1H), 7.71 (dd,
J = 2.0Hz, 11.7Hz, 1H), 7.38 (t, J = 8.8Hz, 1H), 6.30 (d
d, J = 2.0Hz, 17.1Hz, 1H), 6.18-6.11 (m, 1H), 5.90 (d
d, J = 1.5Hz, 10.3Hz, 1H), 4.17 (t, J = 6.6Hz, 2H), 4.0
9 (t, J = 6.6Hz, 2H), 1.77 (t, J = 7.3Hz, 2H), 1.59 (t, J
= 6.8Hz, 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, 150.15, 150.05, 145.75, 14
5.70, 132.67, 130.90, 130.56, 130.49, 128.46, 123.
24, 122.66, 122.28, 114.57, 107.60, 107.41, 69.2
0, 64.01, 28.78, 28.58, 28.54, 28.42, 28.07, 25.3
0,25.26

MS (70 eV): m / z = 484 (M ⁺ ), 26
0, 149, 139 (100), 127, 111, 97, 69, 55, 41

(4-d) {(R) -4- (1-methylheptyloxy) phenyl-4 ′-[3-fluoro-4-
Synthesis of (11-acryloyloxyundecyloxy) phenylazo] benzoate｝ In a 300 ml four-necked flask equipped with a calcium tube,
5.0 g of 4- [3-fluoro-4- (11-acryloyloxyundecyloxy) phenylazo] benzoic acid
(10.3 mmol), 2.3 g (10.3 mmol) of (R) -4- (1-methylheptyloxy) phenol
And 1.3 g (10.3 mmol) of 4-dimethylaminopyridine were weighed and dissolved in 60 ml of anhydrous tetrahydrofuran. After cooling in a dry ice-ethylene glycol bath, 10 ml of a solution of 11 g (52 mmol) of N, N'-dicyclohexylcarbodiimide in anhydrous tetrahydrofuran was added over 30 minutes while stirring.
Added in batches. After stirring at low temperature for 10 minutes, the refrigerant was removed, the temperature was gradually returned to room temperature, and stirring was continued at room temperature for further 12 hours, after which the reaction was terminated.

The solid precipitated in the reaction solution was separated by filtration, and the solid was washed with acetonitrile and diethyl ether. 500 ml of diethyl ether was added to the filtrate, and 200 ml of saturated saline was added.
After washing three times with ml, it was dried with 200 g of anhydrous sodium sulfate. The solvent was removed to obtain a crude product as a red oil. The low polarity portion was collected using flash chromatography with stationary phase silica gel and mobile phase chloroform and the solvent was removed to give a red oil. Add methanol 5
Recrystallization from 0 ml and purification gave the desired product as an orange solid. This was further recrystallized from 50 ml of ethanol and purified to obtain 2.1 g (yield 30%) of the desired product.

1H-NMR (399.65 MHz, dimethyl sulfoxide-d6 solution): δ = 8.29 (d, J = 8.8 Hz, 2H), 8.
00 (d, J = 8.8Hz, 2H), 7.87 (d, J = 8.8Hz, 1H), 7.75 (d,
J = 12.2Hz, 1H), 7.41 (t, J = 8.8Hz, 1H), 7.20 (d, J = 8.3
Hz, 2H), 6.98 (d, J = 8.8Hz, 2H), 6.30 (dd, J = 1.5Hz, 1
7.1Hz, 1H), 6.15 (dd, J = 10.3Hz, 17.1Hz, 1H), 5.90 (d
d, J = 2.0Hz, 10.3Hz, 1H), 4.5-4.3 (m, 1H), 4.19 (t,
J = 6.6Hz, 2H), 4.09 (t, J = 6.6Hz, 2H), 1.9 to 1.7 (m, 2
H), 1.7-1.5 (m, 4H), 1.5-1.2 (m, 25H), 0.9-0.8
(m, 3H)

13C-NMR (100.4 MHz, dimethyl sulfoxide-d6 solution): δ = 165.42, 155.63, 14
3.78, 131.03, 130.93, 130.74, 128.43, 123.48, 123.
45, 122.54, 116.30, 114.62, 107.65, 107.45, 73.7
1, 69.20, 62.98, 35.81, 31.12, 28.78, 28.72, 28.5
5, 28.49, 28.35, 28.02, 25.26, 25.21, 24.73, 21.8
9, 19.49, 13.77

MS (70 eV): m / z = 688 (M ⁺ ), 63
4,467 (100), 395,243,139,127,120,110,92,6
9,55,41

[0257] (In the above, K is the crystalline phase, A is the phase of unknown assignment, Sx
Is a ferroelectric liquid crystal phase of unknown identity, SA is smectic A
Phase, Ch represents a cholesteric phase, and I represents an isotropic phase. )

The compound of this example is considered to be a monotropic ferroelectric liquid crystal.

Example 5 {(R) -4- (1-methylheptyloxy) phenyl-4 '-[2-fluoro-4
Synthesis of-(11-acryloyloxyundecyloxy) phenylazo] benzoate (Synthesis of (5-a) [4- (2-fluoro-4-hydroxyphenylazo) benzoic acid] Hydrochloric acid was added to a 5-liter separable flask. 150ml
(Equivalent to 1.5 mol of hydrogen chloride) was added thereto, and 37.0 g (270 mmol) of 4-aminobenzoic acid was added thereto with vigorous stirring to suspend the mixture. 550 g of ice in this suspension
While keeping the reaction solution at 0 ° C. or lower, 250 ml of an aqueous solution of 28.0 g (410 mmol) of sodium nitrite was added dropwise over about 1.5 hours, and a uniform solution (reaction solution 5) was gradually obtained. Was.

30.5 g of 3-fluorophenol (27
0 mmol), 36 g (0.9 mol) of sodium hydroxide
Then, 300 ml of an aqueous solution containing 64 g (0.6 mol) of sodium carbonate was prepared and added dropwise to the reaction solution 5 over about 1.5 hours. Immediately after the addition, an orange precipitate was formed. During this time, make sure that the temperature does not rise above 0 ° C.
Ice was added little by little. After completion of the dropwise addition, stirring was further continued for 5 hours, and then the reaction was terminated.

A solid was deposited by adding 500 g of ice and 50 ml of hydrochloric acid to the reaction solution to adjust it to acidic (pH = 3). Ethyl acetate (3 L) was added thereto, and the precipitated solid was dissolved by heating and washed with 300 ml of water five times. After adding 500 g of sodium sulfate to the organic layer and drying, the solvent was removed to obtain a crude product. Recrystallization from acetonitrile-water and purification gave 55 g of the desired product (yield 78%).

(5-b) {4- [2-fluoro-4-
(11-hydroxyundecyloxy) phenylazo]
Synthesis of benzoic acid｝ 20 g (77 mmol) of 4- (2-fluoro-4-hydroxyphenylazo) benzoic acid was weighed and placed in a 1-liter 3-neck separable flask equipped with a condenser.
200 ml of ethanol was added and dissolved under reflux.
To this solution, 16 g (115 mmol) of potassium carbonate and a trace amount of potassium iodide were added by trituration, and a solid was immediately formed. 50 ml of water was further added to obtain a uniform solution. After refluxing for 1 hour, 11-bromo-
A solution of 21 g (85 mmol) of 1-undecanol in 60 ml of ethanol was added all at once. Then, after continuing refluxing and stirring for further 24 hours, the reaction was terminated.

The reaction mixture was adjusted to acidic (pH = 1) by adding 500 ml of water and 50 ml of hydrochloric acid, and the precipitated solid was filtered. The collected solid was purified by recrystallization from 1 liter of ethanol to obtain 19 g of the desired product (57% yield).
I got

1H-NMR (399.65 MHz, dimethyl sulfoxide-d6 solution): δ = 8.12 (d, J = 8.8 Hz, 2H), 7.
90 (d, J = 8.8Hz, 2H), 7.77 (t, J = 8.8Hz, 1H), 7.08 (d
d, J = 13.2Hz, 2.4Hz, 1H), 6.91 (dd, J = 9.3Hz, 2.0Hz,
1H), 4.11 (t, J = 6.3Hz, 2H), 3.38 (t, J = 6.6Hz, 2H),
1.8 to 1.7 (m, 2H), 1.5 to 1.2 (m, 16H)

13C-NMR (100.40 MHz, dimethyl sulfoxide-d6 solution): δ = 166.59, 163.68,
163.57,162.46,159.90,154.64,134.11,134.03,13
2.54, 130.51, 130.19, 122.27, 118.49, 112.02, 102.
76, 102.53, 68.76, 60.72, 32.48, 28.98, 28.87, 28.
60, 28.35, 25.44, 25.29

MS (70 eV): m / z = 430 (M ⁺ ), 30
9,297,260,149,139,127 (100), 121,111,95,8
3, 69, 55, 41

(5-c) {4- [2-fluoro-4-
Synthesis of (11-acryloyloxyundecyloxy) phenylazo] benzoic acid A 4- [2-fluoro-4- (11-hydroxyundecyloxy) phenylazo] was placed in a 500-ml five-necked flask equipped with a dropping funnel and a calcium tube. 10 g of benzoic acid
(23 mmol) and 3.5 g (35
Millimole) and dry tetrahydrofuran 200 ml
Was added and dissolved. After adding a small amount of 4-dimethylaminopyridine to this solution, acrylic acid chloride 4.2
g (47 mmol) in 15 ml of anhydrous diethyl ether
Was added dropwise over about 1 hour. After the completion of the dropwise addition, stirring was continued for about 5 hours, and then the reaction was terminated.

The hydrochloride of triethylamine precipitated in the reaction solution was separated by filtration, the hydrochloride was washed with acetonitrile, 400 ml of diethyl ether was added to the filtrate, and saturated saline 20 was added.
Washed three times with 0 ml. Organic layer is dried over anhydrous sodium sulfate 30
Drying at 0 g and removal of solvent gave the crude product as an orange solid. Purified by recrystallization from acetonitrile,
8.4 g (yield 75%) of the desired product was obtained.

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

13C-NMR (100.40 MHz, dimethyl sulfoxide-d6 solution): δ = 166.75, 166.64,
165.44, 163.71, 163.58, 162.52, 159.97, 154.69, 13
4.15, 132.57, 130.87, 130.52, 130.30, 129.54, 128.
48, 122.300, 28.47, 111.98, 102.75, 102.52, 68.7
8, 64.03, 28.87, 28.84, 28.64, 28.58, 28.40, 28.1
0,25.33

MS (70 eV): m / z = 484 (M ⁺ ), 44
2,429,412,363,260,149,139,127,121,111,9
7, 69, 55 (100), 41

(5-d) {(R) -4- (1-methylheptyloxy) phenyl-4 '-[2-fluoro-4-
Synthesis of (11-acryloyloxyundecyloxy) phenylazo] benzoate｝ In a 300 ml four-necked flask equipped with a calcium tube,
5.0 g of 4- [2-fluoro-4- (11-acryloyloxyundecyloxy) phenylazo] benzoic acid
(10.3 mmol), 2.3 g (10.3 mmol) of (R) -4- (1-methylheptyloxy) phenol
And 1.3 g (10.3 mmol) of 4-dimethylaminopyridine were added thereto.
ml was added and dissolved. This was cooled in a dry ice-ethylene glycol bath, and 11 g (52 mmol) of N, N'-dicyclohexylcarbodiimide was stirred with stirring.
Was added in five portions over 30 minutes, and stirring was continued at a low temperature for 10 minutes.
Next, the refrigerant was removed and gradually returned to room temperature.
After stirring was continued for 2 hours, the reaction was terminated.

The solid precipitated in the reaction solution was separated by filtration, and the solid was washed with acetonitrile and diethyl ether. 500 ml of diethyl ether was added to the filtrate, and 150 ml of saturated saline was added.
And dried over 200 g of anhydrous sodium sulfate. The solvent was removed to obtain a crude product as a red oil.
The low polarity portion was collected using flash chromatography on stationary phase silica gel and mobile phase chloroform, and the solvent was removed to give a red oil. This was recrystallized from 50 ml of hexane and purified to obtain the desired product as an orange solid. This was further recrystallized from 80 ml of ethanol and purified to obtain 4.6 g (yield: 65%) of the desired product.

1H-NMR (399.65 MHz, dimethyl sulfoxide-d6 solution): δ = 8.3-7.6 (m, 6H), 7.2-6.
9 (m, 5H), 6.30 (dd, J = 1.5Hz, 15.6Hz, 1H), 6.15 (dd,
J = 10.3Hz, 17.6Hz, 1H), 5.90 (dd, J = 1.0Hz, 10.3Hz, 1
H), 4.2-4.0 (m, 4H), 1.9-1.2 (m, 31H), 0.9-0.7
(m, 3H)

13C-NMR (100.40 MHz, dimethyl sulfoxide-d6 solution): δ = 152.90, 139.30,
131.04, 130.92, 128.42, 122.53, 121.74, 118.44, 10
2.72, 102.52, 68.70, 63.98, 53.86, 49.12, 35.81, 3
1.13, 30.31, 28.78, 28.73, 28.54, 28.48, 28.32, 2
8.02, 25.52, 25.26, 25.08, 24.88, 24.73, 23.97, 2
1.89, 19.49

MS (70 eV): m / z = 688 (M ⁺ ), 467
(25), 363 (31), 243 (32), 139 (32), 127 (87), 120 (9
5), 69 (59), 55 (100), 41 (45)

Phase transition temperature: 110 ° C. during cooling (I → K) (In the above, K represents a crystal phase, and I represents an isotropic phase.)

The compound of this example did not exhibit a ferroelectric liquid crystal phase.

Example 6 {(R) -3-fluoro-4}
-(1-methylheptyloxy) phenyl-4 '-[2
-Fluoro-4- (11-acryloyloxyundecyloxy) phenylazo] benzoate {(6-a) [synthesis of 4- (2-fluoro-4-hydroxyphenylazo) benzoic acid] In a 5-liter separable flask. , Hydrochloric acid 150ml
(Equivalent to 1.5 mol of hydrogen chloride) was added thereto, and 37.0 g (270 mmol) of 4-aminobenzoic acid was added thereto with vigorous stirring to suspend the mixture. 550 g of ice in this suspension
While keeping the reaction solution at 0 ° C. or lower, 250 ml of an aqueous solution of 28.0 g (410 mmol) of sodium nitrite was added dropwise over about 1.5 hours, and a uniform solution (reaction solution 5) was gradually obtained. Was.

30.5 g of 3-fluorophenol (27
0 mmol), 36 g (0.9 mol) of sodium hydroxide
And an aqueous solution 30 of 64 g (0.6 mol) of sodium carbonate
0 ml was prepared and added dropwise to the above reaction solution 4 over about 1.5 hours. Immediately after the addition, an orange precipitate was formed. During this time, ice was added little by little so that the temperature did not rise above 0 ° C. After completion of the dropwise addition, the mixture was further stirred for 5 hours, and then the reaction was completed.

The reaction mixture was adjusted to acidic (pH = 3) by adding 500 g of ice and 50 ml of hydrochloric acid to precipitate a solid. 3 L of ethyl acetate was added to the reaction solution, and the precipitated solid was dissolved by heating and washed with 300 ml of water five times. The organic layer was dried by adding 500 g of sodium sulfate, and the solvent was removed to obtain a crude product. Recrystallization from acetonitrile-water and purification gave 55 g of the desired product (yield 78%).

(6-b) {4- [2-fluoro-4-
(11-hydroxyundecyloxy) phenylazo]
Synthesis of benzoic acid｝ 20 g (77 mmol) of 4- (2-fluoro-4-hydroxyphenylazo) benzoic acid was weighed and placed in a 1-liter 3-neck separable flask equipped with a condenser.
200 ml of ethanol was added and dissolved under reflux.
To this solution, 16 g (115 mmol) of potassium carbonate and a trace amount of potassium iodide were added by trituration, and a solid was immediately formed. 50 ml of water was further added to obtain a uniform solution. After refluxing for 1 hour, a solution of 21 g (85 mmol) of 11-bromo-1-undecanol in 60 ml of ethanol was added all at once. Then, after continuing refluxing and stirring for 24 hours, the reaction was terminated.

To the reaction solution was added 500 ml of water and 50 ml of hydrochloric acid to adjust the acidity (pH = 1), and the precipitated solid was filtered. The collected solid was purified by recrystallization from 1 liter of ethanol to obtain 19 g of the desired product (57% yield).
I got

1H-NMR (399.65 MHz, dimethyl sulfoxide-d6 solution): δ = 8.12 (d, J = 8.8 Hz, 2H), 7.
90 (d, J = 8.8Hz, 2H), 7.77 (t, J = 8.8Hz, 1H), 7.08 (d
d, J = 13.2Hz, 2.4Hz, 1H), 6.91 (dd, J = 9.3Hz, 2.0Hz,
1H), 4.11 (t, J = 6.3Hz, 2H), 3.38 (t, J = 6.6Hz, 2H),
1.8 to 1.7 (m, 2H), 1.5 to 1.2 (m, 16H)

13C-NMR (100.40 MHz, dimethyl sulfoxide-d6 solution): δ = 166.59, 163.68,
163.57,162.46,159.90,154.64,134.11,134.03,13
2.54, 130.51, 130.19, 122.27, 118.49, 112.02, 102.
76, 102.53, 68.76, 60.72, 32.48, 28.98, 28.87, 28.
60, 28.35, 25.44, 25.29

MS (70 eV): m / z = 430 (M ⁺ ), 30
9,297,260,149,139,127 (100), 121,111,95,8
3, 69, 55, 41

(6-c) {4- [2-fluoro-4-
Synthesis of (11-acryloyloxyundecyloxy) phenylazo] benzoic acid A 4- [2-fluoro-4- (11-hydroxyundecyloxy) phenylazo] was placed in a 500-ml five-necked flask equipped with a dropping funnel and a calcium tube. 10 g of benzoic acid
(23 mmol) and 3.5 g (35
Mmol), anhydrous tetrahydrofuran 20
0 ml was added to dissolve. After adding a small amount of 4-dimethylaminopyridine to this solution, acrylic acid chloride 4.2
g (47 mmol) in 15 ml of anhydrous diethyl ether
Was added dropwise over about 1 hour. After completion of the dropwise addition, the mixture was further stirred for 5 hours, and then the reaction was terminated.

After the triethylamine hydrochloride precipitated in the reaction solution was separated by filtration, the 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. The organic layer was dried over anhydrous sodium sulfate (300 g) and the solvent was removed to obtain a crude product as an orange solid. The product was recrystallized from acetonitrile and purified to obtain 8.4 g of the desired product (yield: 75%).

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

13C-NMR (100.40 MHz, dimethyl sulfoxide-d6 solution): δ = 166.75, 166.64,
165.44, 163.71, 163.58, 162.52, 159.97, 154.69, 13
4.15, 132.57, 130.87, 130.52, 130.30, 129.54, 128.
48, 122.300, 28.47, 111.98, 102.75, 102.52, 68.7
8, 64.03, 28.87, 28.84, 28.64, 28.58, 28.40, 28.1
0,25.33

MS (70 eV): m / z = 484 (M ⁺ ), 44
2,429,412,363,260,149,139,127,121,111,9
7, 69, 55 (100), 41

(6-d) ｛(R) -3-fluoro-4-
(1-methylheptyloxy) phenyl-4 ′-[2-
Fluoro-4- (11-acryloyloxyundecyloxy) phenylazo] benzoate} In a 300 ml four-necked flask equipped with a calcium tube,
5.2 g of 4- [2-fluoro-4- (11-acryloyloxyundecyloxy) phenylazo] benzoic acid
(11 mmol), (R) -3-fluoro-4- (1-
2.6 g (11 mmol) of methyl heptyloxy) phenol and 1.3 g (11 mmol) of 4-dimethylaminopyridine were weighed and dissolved by adding 80 ml of anhydrous tetrahydrofuran. 11 g of N, N'-dicyclohexylcarbodiimide (5 g
5 mmol) in anhydrous tetrahydrofuran
It was added dropwise over 30 minutes. After completion of the dropwise addition, the mixture was further cooled to room temperature for 18 hours.
After continued stirring for an hour, the reaction was terminated.

The solid precipitated in the reaction solution was separated by filtration, and the solid was washed with acetonitrile and diethyl ether. 500 ml of diethyl ether was added to the filtrate, and saturated saline 150
After washing three times with ml and drying with 200 g of anhydrous sodium sulfate, the solvent was removed to obtain a red oily crude product. The low-polarity part was collected by flash chromatography using stationary phase silica gel and mobile phase chloroform, and the solvent was removed to obtain a red oil. This was recrystallized from 50 ml of hexane and purified to obtain the desired product as an orange solid. This was further recrystallized from 80 ml of ethanol and purified to obtain 4.9 g (yield: 65%) of the desired product.

1H-NMR (399.65 MHz, CDCl ₃ solution): δ = 8.30 (d, J = 8.3 Hz, 2H), 7.99 (d, J = 8.8 Hz, 2
H), 7.83 (t, J = 9.0 Hz, 1H), 7.1 to 6.9 (m, 3H), 7.9 to 7.
7 (m, 2H), 6.40 (dd, J = 1.5Hz, 17.6Hz, 1H), 6.12 (dd,
J = 10.8Hz, 17.6Hz, 1H), 5.81 (dd, J = 1.5Hz, 10.3Hz, 1
H), 4.4-4.3 (m, 1H), 4.15 (t, J = 6.6Hz, 2H), 4.04
(t, J = 6.6Hz, 1H), 1.9 to 1.2 (m, 31H), 1.0 to 0.8 (m, 3
H)

13C-NMR (100.40 MHz, CD
Cl ₃ solution): δ = 166.36, 164.65, 163.87, 155.95, 1
54.74, 144.17, 131.22, 130.49, 130.42, 128.67, 12
2.78, 118.62, 118.00, 117.92, 117.11, 117.08, 111.
55, 111.52, 110.97, 110.75, 102.47, 102.25, 68.9
3, 64.71, 36.52, 31.82, 29.48, 29.31, 29.28, 29.2
4, 29.01, 28.63, 25.93, 25.47, 22.62, 19.84, 14.09

MS (70 eV): m / z = 706 (M ⁺ ), 65
1,635,595,647,395,243,139,127,120 (100), 5
5,43

[0297] (In the above, K is a crystalline phase, A is an unknown phase, SA
Represents a smectic A phase, Ch represents a cholesteric phase, and I represents an isotropic phase. It was difficult to confirm the temperature range showing the Ch phase at the time of temperature decrease. )

The compound of this example was sealed in a cell manufactured by EC Corporation (EHC) (distance between cells: 2 μm).
When a voltage of 1 Hz is applied at an applied voltage of 50 V or more,
Although the response speed and the polarization inversion voltage could not be measured,
An electric field response was confirmed at around ℃, and a ferroelectric liquid crystal phase of unknown assignment could be confirmed.

<Example 7> (Polymerizable optically active photoisomerized liquid crystal composition) The (R) -4- (1-methylheptyloxy) phenyl-4 '-[4- (11-) obtained in Example 1 was obtained. (Acryloyloxyundecyloxy) phenylazo] benzoate 75% by weight and (R) -4- (1-methylheptyloxy) phenyl-4 '-[3-fluoro-4- obtained in Example 4.
A polymerizable optically active photoisomerizable liquid crystal composition comprising 25% by weight of (11-acryloyloxyundecyloxy) phenylazo] benzoate was prepared.

The phase transition temperature of this composition was as follows. (In the above, I represents an isotropic phase, Ch represents a cholesteric phase, SA represents a smectic A phase, and Sx represents a ferroelectric liquid crystal phase whose assignment is unknown. In addition, the Ch phase at the time of temperature drop is unstable. It was difficult to confirm the temperature range showing the Ch phase because the phase was changed to the phase.)

The composition of this example was sealed in a cell manufactured by EC Corporation (EHC) (distance between cells: 2 μm).
When a voltage of 1 Hz is applied at an applied voltage of 50 V or more,
Although the response speed and polarization reversal voltage could not be measured, Sx
The electric field response could be confirmed in the phase.

Example 8 (Polymerizable Optically Active Photoisomerized Liquid Crystal Composition) The (R) -4- (1-methylheptyloxy) phenyl-4 ′-[4- (11-) obtained in Example 1 [Acryloyloxyundecyloxy) phenylazo] benzoate 50
% By weight and the (R) -4- (1-methylheptyloxy) phenyl-4 ′-[3-fluoro-4- obtained in Example 4.
A polymerizable optically active photoisomerized liquid crystal composition comprising 50% by weight of (11-acryloyloxyundecyloxy) phenylazo] benzoate was prepared.

The phase transition temperature of this composition was as follows. (In the above, I represents an isotropic phase, Ch represents a cholesteric phase, SA represents a smectic A phase, and Sx represents a ferroelectric liquid crystal phase whose assignment is unknown. In addition, the Ch phase at the time of temperature drop is unstable. It was difficult to confirm the temperature range showing the Ch phase because the phase was changed to the phase.)

The composition of this example was sealed in a cell manufactured by EC Corporation (EHC) (distance between cells: 2 μm).
When a voltage of 1 Hz is applied at an applied voltage of 50 V or more,
Although the response speed and polarization reversal voltage could not be measured, Sx
The electric field response could be confirmed in the phase.

When this composition was irradiated with ultraviolet rays in a temperature range showing a liquid crystal phase, it was confirmed that a phase transition to a lower order phase was obtained. In addition, it was confirmed that the state returned to the original state when the ultraviolet irradiation was stopped.

[0306]

The compound represented by the general formula (I) of the present invention is a liquid crystal compound which has an azo group and a polymerizable functional group in the molecule and may exhibit ferroelectricity by itself. Even if a compound does not exhibit ferroelectricity by itself, a mixed liquid crystal obtained by mixing with another liquid crystal, particularly a parent liquid crystal exhibiting ferroelectricity, is also a compound exhibiting ferroelectricity.

Therefore, the compound represented by the general formula (I) of the present invention is very useful as a component of a light-controllable ferroelectric element. Further, a polymer liquid crystal can be synthesized using the compound represented by the general formula (I) of the present invention, and is very useful as a component of an optical recording medium that does not require a cell. Moreover, as shown in the examples, the compound represented by the general formula (I) of the present invention can be easily produced industrially, and can be used with a liquid crystal compound, a liquid crystal composition or a polymerizable compound which is currently widely used. Since it has excellent compatibility, it is very useful as a raw material for an optical functional material including liquid crystal.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁶ Identification symbol FI C09K 19/38 C09K 19/38 G02F 1/13 500 G02F 1/13 500 // C07M 7:00

Claims (11)

[Claims] 1. A compound of the general formula (I) (Where A represents a polymerizable acrylic group, methacryl group, epoxy group, vinyl group, isocyanate group,
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 optionally substituted with a substituent selected from the group consisting of fluorine, chlorine, cyano and trifluoromethyl; -Phenylene group, pyrimidine-2,5-
Diyl group, pyridine-2,5-diyl group or trans-
Represents a 1,4-cyclohexylene group, a ring E and a ring G
Are each independently a 1,4-phenylene group which may be substituted with a substituent selected from the group consisting of fluorine, chlorine, a cyano group and a trifluoromethyl group, and a pyrimidine-
A 2,5-diyl group or a pyridine-2,5-diyl group, n and k each independently represent 0 or 1,
R ₁ represents a methyl group, an ethyl group, a difluoromethyl group, a trifluoromethyl group, a fluorine or a cyano group,
₂ represents an alkyl group having 2 to 18 carbon atoms,
_{When 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 photoisomerized liquid crystal according to claim 1, wherein ring G is a 1,4-phenylene group which may be substituted with a fluorine, chlorine or cyano group. Compounds. 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 is —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 polymerizable optically active photoisomerized liquid crystal composition according to claim 9, which exhibits ferroelectricity. 11. The polymerizable optically active photoisomerized liquid crystal composition according to claim 9, which exhibits antiferroelectricity.