JP2002012580A - Optically active compound, method for producing the same, liquid crystal composition containing the same, and liquid crystal device - Google Patents

Abstract

(57) [Problem] To provide a polymerizable optically active compound having a low viscosity and a large helical inducing force, a liquid crystal composition using the optically active compound, a polymer substance, and a liquid crystal element. [Solution] RX ¹ -A ¹ -B ¹ -C ^* HY ¹ -CH _2- (B ² ) _n -X ² -A ² -X ^3-
A ³ -X ⁴ -Z-OCO-CY ² = CH ₂ where R is an alkyl group or the like, X ¹ , X ² , X ³ , X ⁴ is a single bond or -COO-, etc., and Y ¹ and Y ² are methyl Z is an alkylene group or the like, A ¹ , A ² ,
A ³ , B ¹ and B ^{2 each} represent a ring group.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to an optically active compound used for a liquid crystal device or the like, an optically active compound as an intermediate thereof, a method for producing the optically active compound, a liquid crystal composition using the optically active compound, The present invention relates to a polymer material obtained by copolymerizing the optically active compound, and a liquid crystal composition or a liquid crystal device using the polymer material.

[0002]

2. Description of the Related Art A liquid crystal optical element is a display device for OA equipment,
It is used for various purposes such as portable terminals, measuring instruments, automobile instruments, display devices for home appliances, watches, calculators, and the like.
The liquid crystal electro-optical element has a pair of transparent substrates on each of which a transparent electrode, an intermediate protective film and a liquid crystal alignment film are formed,
A structure in which a liquid crystal material is sealed between the substrates at a fixed distance, and a voltage is applied from the electrodes to the liquid crystal material to change the alignment state of the liquid crystal material and change the optical properties. Thereby, it functions as an optical switching element.

[0003] Twisted nematic (TN) type and super twisted nematic (STN) type liquid crystal display elements have a small amount (0. 0. 1) to achieve a uniform twist alignment.
(About 5 to 3% by mass) of an optically active compound (chiral agent). In a reflective cholesteric liquid crystal display device, a cholesteric liquid crystal composition in which an optically active compound is added in a large amount (about 8 to 60% by mass) to a nematic liquid crystal composition is used. The phenomenon of selectively reflecting light having a wavelength that is the product of the pitch is used.

[0004] Also, European Patent EP451905,
Japanese Patent Application Laid-Open No. 7-258638 and the like disclose an anisotropic gel-like liquid crystal material in which a polymerized high molecular weight material forms a permanent alignment network in a low molecular weight liquid crystal material. This form can be obtained by polymerization of a copolymerizable optically active compound. Currently widely used optically active compounds include, for example, a compound represented by the following formula (CN), a compound represented by the following formula (S-811), or a compound represented by the following formula (CB-15) Compounds.

[0005]

Embedded image

The helical pitch length induced when an optically active compound is added to a liquid crystal composition is determined by the helical inducing force inherent to the compound, and is almost proportional to the amount added.
The smaller the optically active compound has a helical inducing force, the longer the induced helical pitch length is. When it is desired to shorten the helical pitch length, the amount of addition must be increased. In general,
When the addition amount of the optically active compound is increased, the performance as a liquid crystal material is reduced as compared with before addition, the viscosity is increased, the response speed is reduced, the driving voltage is increased, the isotropic phase transition temperature is reduced,
Problems arise, such as a reduction in the temperature range exhibiting a particular phase, such as a nematic phase, a cholesteric phase, or a smectic phase. Therefore, an optically active compound having a large helical inducing force is required.

[0007]

SUMMARY OF THE INVENTION An object of the present invention is to provide an optically active compound useful for liquid crystal devices and liquid crystal films which can be used for various optical products, an optically active compound as an intermediate thereof, and those optically active compounds. Method, which can be easily produced at a high yield, a liquid crystal composition using the optically active compound, a polymer material obtained by copolymerizing the optically active compound, and a liquid crystal composition or the polymer material. To provide a liquid crystal device.

[0008]

That is, the present invention provides an optically active compound represented by the following formula (1). RX ¹ -A ¹ -B ¹ -C ^* HY ¹ -CH _2- (B ² ) _n -X ² -A ² -X ³ -A ³ -X ⁴ -Z-OCO-CY ² = CH ₂ … 1) However, the symbols in the formula (1) have the following meanings. R: an alkyl group having 1 to 12 carbon atoms, an alkyl group having 1 to 12 carbon atoms in which at least one hydrogen atom is substituted with a fluorine atom, a hydrogen atom or a halogen atom. X ¹ , X ² , X ³ , X ⁴ : independently of each other, a carbonyloxy group (—COO—), an oxycarbonyl group (—OC
O-), etheric oxygen atom (-O-), oxymethylene group (-OCH ₂ -), a methylene group (-CH ₂
O-) or a single bond. Y ¹ : a methyl group (—CH ₃ ) or a methyl group in which at least one hydrogen atom has been replaced by a fluorine atom. Y ² : a hydrogen atom or a methyl group (—CH ₃ ).

Z: an alkylene group having 1 to 12 carbon atoms or
1 carbon atom in which at least one hydrogen atom has been replaced by a fluorine atom
~ 12 alkylene groups. A¹, A^Two, A^Three: Up to one hydrogen atom independently of each other
Or two of which may be substituted with a fluorine atom
Phenylene group, one or two hydrogen atoms are methyl groups
(-CH_Three1,4-phenylene optionally substituted by
Group, unsubstituted 2,6-naphthylene group, unsubstituted
1,4-cyclohexylene group or single bond. B¹, B^Two: Independently of one another,
1,4-phenyl optionally substituted by two fluorine atoms
Nylene group, one or two hydrogen atoms are methyl group (-
CH_Three1,4-phenylene optionally substituted by
Group, unsubstituted 2,6-naphthylene group, unsubstituted trans
-1,4-cyclohexylene group or -D ¹-CH_TwoC
H_Two-D^TwoA group represented by-(D¹And D^TwoAre each
Independently, one or two of the hydrogen atoms are a fluorine atom and
And / or methyl group (-CH_Three) May be substituted
1,4-phenylene group, unsubstituted 2,6-naphthylene
Group, unsubstituted trans-1,4-cyclohexylene group
Represent. ). n: 1 or 2. C^*: Asymmetric carbon atom.

The compound represented by the formula (1) is preferably a compound represented by the following formula (2). RX ¹ -A ¹ -B ¹ -C ^* HY ¹ -CH _2- (B ² ) _n -COO-A ² -X ³ -A ³ -X ⁴ -Z-OCO-CY ² = CH ₂ … Formula (2) Where the symbols R, X ¹ , X ³ , X ⁴ ,
Y ¹ , Y ² , Z, A ¹ , A ² , A ³ , B ¹ , B ² , n and C ^* have the same meanings as in formula (1).

Further, the present invention provides an optically active compound represented by the following formula (3). RX ¹ -A ¹ -B ¹ -C ^* HY ¹ -CH _2- (B ² ) _n -COOH Formula (3) where symbols R, X ¹ , Y ¹ , A ¹ ,
B ¹ , B ² , n and C ^* have the same meaning as in formula (1).

The present invention also provides a method for producing an optically active compound represented by the formula (3) via the following steps (a) and (b). Step (a): A carboxylic acid represented by the following formula (4) is converted to an acid chloride, and a coupling reaction is performed with a Grignard reagent represented by the following formula (5) to produce a ketone represented by the following formula (6): To obtain an optically active compound represented by the following formula (7). Step (b): a step of converting an optically active compound represented by the following formula (7) into a Grignard reagent represented by the following formula (8) and reacting with carbon dioxide. RX ¹ -A ¹ -B ¹ -C ^* HY ¹ -COOH ... Equation (4) Q'-Mg- (B ² ) _n -Q ... Equation (5) RX ¹ -A ¹ -B ¹ -C ^* HY ¹ -CO- (B ² ) _n -Q… Equation (6) RX ¹ -A ¹ -B ¹ -C ^* HY ¹ -CH _2- (B ² ) _n -Q… Equation (7) RX ¹ -A ^1- B ¹ -C ^* HY ¹ -CH _2- (B ² ) _n -Mg-Q where R in the formulas (4), (5), (6), (7) and (8) , X ¹ , Y ¹ , A ¹ , B ¹ , B ² , n and C ^* have the same meanings as in formula (3),
And Q ′ have the following meanings. Q: a halogen atom. Q ′: a bromine atom or an iodine atom. However, when Q ′ is a bromine atom, Q is not an iodine atom.

In the present invention, the optically active compound represented by the formula (3) is converted to an acid chloride and reacted with an alcohol represented by the following formula (9). Provided is a method for producing an optically active compound. HO-A ² -X ³ -A ³ -X ⁴ -Z-OCO-CY ² = CH ₂ Formula (9) where X ³ , X ⁴ , A ² , A ³ and Y ^{2 in the} formula (9) And Z have the same meaning as in formula (2).

Further, the present invention relates to a method for preparing one or more optically active compounds represented by the formula (1) or (2) in a total amount of 0.1 to
Provided is a liquid crystal composition containing 80% by mass, and a liquid crystal element using the liquid crystal composition. The present invention also provides a polymeric substance obtained by copolymerizing at least one optically active compound represented by the formula (1) or (2). Further, the present invention provides a liquid crystal device using the polymer.

[0015]

BEST MODE FOR CARRYING OUT THE INVENTION [Description of Formula] Hereinafter, the compound represented by the formula (1) is also described as a compound (1).
The same applies to the notation of the compound (2) and the like. Also,
Throughout this specification, C ₃ H _7- , C ₆ H _13- and the like indicate a straight-chain alkyl group. -CH _2- , -C ₆ H _12- and the like represent a linear alkylene group. -CO- is a carbonyl group (> C =
O). The compound represented by the formula (1) or (2) is an optically active compound containing an asymmetric carbon atom (C ^* ) in its structure. The absolute configuration of the group bonded to the asymmetric carbon atom may be either R-form or S-form.

In the compounds (1) to (9), R represents an alkyl group having 1 to 12 carbon atoms, an alkyl group having 1 to 12 carbon atoms in which at least one hydrogen atom is substituted by a fluorine atom, a hydrogen atom or a halogen atom. Is an atom. The alkyl group may be straight-chain or branched, and when branched, may have an asymmetric carbon atom in its structure. Examples of the alkyl group having 1 to 12 carbon atoms include methyl, ethyl, propyl, isopropyl, butyl, 2-methylpropyl, sec-butyl, tert-butyl, pentyl, isopentyl, and neopentyl. , T
ert-pentyl group, 1-methylbutyl group, 2-methylbutyl group, 1,2-dimethylpropyl group, hexyl group,
Isohexyl group, 1-methylpentyl group, 2-methylpentyl group, 3-methylpentyl group, 1,1-dimethylbutyl group, 1,2-dimethylbutyl group, 2,2-dimethylbutyl group, 1,3-dimethyl Butyl group, 2,3-dimethylbutyl group, 3,3-dimethylbutyl group, 1-ethylbutyl group, 2-ethylbutyl group, 1,1,2-trimethylpropyl group, 1,2,2-trimethylpropyl group, 1 −
Examples thereof include an ethyl-1-methylpropyl group and a 1-ethyl-2-methylpropyl group. In addition, those in which these groups contain a double bond or a triple bond are also included. Among these, as R, an alkyl group having 3 to 6 carbon atoms or a hydrogen atom is preferable, and from the viewpoint of availability of raw materials, a 2-methylpropyl group (CH ₃ —CH (CH ₃ ) —CH ₂ -), And a hydrogen atom is particularly preferred.

X ¹ , X ² , X ³ and X ⁴ each independently represent a carbonyloxy group (—COO—), an oxycarbonyl group (—OCO—), an etheric oxygen atom (—
O-), oxymethylene group (-OCH ₂ -), a methylene group (-CH ₂ O-) or a single bond. X ¹ ,
X ² , X ³ and X ⁴ may be the same or different. X ¹ is preferably an etheric oxygen atom or a single bond, particularly preferably a single bond. X ² , X ³ and X
⁴ is preferably a carbonyloxy group, an etheric oxygen atom or a single bond, and particularly preferably X ² is a carbonyloxy group. In the formula (1), when X ² is an etheric oxygen atom and X ³ and X ⁴ are a single bond, or in the formula (2), X ³ and X ⁴ are a single bond Is preferred.

Y ¹ is a methyl group (—CH ₃ ) or a methyl group in which one or more hydrogen atoms have been replaced by fluorine atoms. Y ¹ is preferably a methyl group or a trifluoromethyl group, particularly preferably a methyl group. Y ² is a hydrogen atom or a methyl group (—CH ₃ ), and a hydrogen atom is preferable. Z represents an alkylene group having 1 to 12 carbon atoms, or a carbon atom having 1 to 1 carbon atoms in which at least one hydrogen atom is substituted by a fluorine atom
2 alkylene groups. The alkylene group may be linear or branched, and if branched, may have an asymmetric carbon atom in its structure. Carbon number 1
Examples of the alkylene group having 1 to 12 carbon atoms include the above-described 1 to 12 carbon atoms.
And a divalent group generated by losing one hydrogen atom from the above alkyl group. Among them, Z is preferably an alkylene group having 2 to 6 carbon atoms, and particularly preferably a linear alkylene group having 2 to 6 carbon atoms.

A ¹ , A ² and A ³ each independently represent a 1,4-phenylene group in which one or two hydrogen atoms may be substituted by a fluorine atom, one hydrogen atom or A 1,4-phenylene group, an unsubstituted 2,6-naphthylene group, an unsubstituted trans-1,4-cyclohexylene group or a single bond, two of which may be substituted with a methyl group (—CH ₃ ); is there. A ¹ , A ² and A ³ may be the same or different. A ¹ is preferably an unsubstituted 1,4-phenylene group or a single bond, and particularly preferably a single bond. A ² and A ³ are preferably an unsubstituted 1,4-phenylene group or a single bond, particularly when one of A ² and A ³ is a 1,4-phenylene group and the other is a single bond Or the case where both A ² and A ³ are a single bond.

B¹, B^Two: Independently of each other
One or two may be substituted with a fluorine atom
1,4-phenylene group, one or two hydrogen atoms
Methyl group (-CH_Three1,4-) which may be substituted
Phenylene group, unsubstituted 2,6-naphthylene group, unsubstituted
Trans-1,4-cyclohexylene group or -D ¹
-CH_TwoCH_Two-D^TwoA group represented by-(D¹And D^Two
Is each independently one or two hydrogen atoms
Atom and / or methyl group (-CH_Three)
1,4-phenylene group, unsubstituted 2,6-na
Butylene group, unsubstituted trans-1,4-cyclohexyl
Represents a len group. ). Among them, hydrogen atom
Is a 1,4-phenyl group in which one or two of
A phenylene group or an unsubstituted 2,6-naphthylene group is preferred.
1,4 in which one of the hydrogen atoms is replaced by a fluorine atom
-A phenylene group is particularly preferred. n is 1 or 2
You. If n is 2, B^TwoAre the same but different
May be. n is preferably 1.

Specific examples of the formulas (1) and (2) are shown below. In addition, substituted or unsubstituted 1,
A 4-phenylene group, a trans-1,4-cyclohexylene group and a 2,6-naphthylene group are generically described as a "ring group". A substituted or unsubstituted 2,6-naphthylene group is counted as one ring group. Throughout this specification, Ph is an unsubstituted 1,4-phenylene group, and Ph ^F is monofluoro-1,1.
4-phenylene group, Ph ^FF difluoro-1,4-phenylene group, Ph ^M is monomethyl-1,4-phenylene group, Cy is an unsubstituted trans-1,4-cyclohexylene group, Np is unsubstituted 2 , 6-naphthylene group. The substitution position of a fluorine atom or a methyl group is not particularly limited.

[Specific examples of the compound represented by the formula (1)] Specific examples of the compound (1) are shown below, classified according to the number of ring groups. The number of ring groups is preferably 2, 3 or 4, particularly preferably 2 or 3. Preferred examples of the compound having two ring groups include the following compounds. H-Ph-C ^* H (CH ₃ ) -CH ₂ -Ph-COO-C ₂ H ₄ -OCO-CH = CH ₂ H-Ph-C ^* H (CH ₃ ) -CH ₂ -Ph-COO-C ₃ H ₆ -OCO-CH = CH ₂ H-Ph-C ^* H (CH ₃ ) -CH ₂ -Ph-COO-C ₄ H ₈ -OCO-CH = CH ₂ H-Ph-C ^* H (CH ₃ ) -CH ₂ -Ph-COO-C ₅ H ₁₀ -OCO-CH = CH ₂ H-Ph-C ^* H (CH ₃ ) -CH ₂ -Ph-COO-C ₆ H ₁₂ -OCO-CH = CH ₂ H-Ph-C ^* H (CH ₃ ) -CH ₂ -Ph-COO-C ₁₁ H ₂₂ -OCO-CH = CH ₂ H-Ph-C ^* H (CH ₃ ) -CH ₂ -Ph-COO-C ₁₂ H ₂₄ -OCO-CH = CH ₂ H-Ph-C ^* H (CH ₃ ) -CH ₂ -Ph ^F -COO-C ₆ H ₁₂ -OCO-CH = CH ₂ H-Ph-C ^* H (CH ₃ ) -CH ₂ -Ph ^FF -COO-C ₆ H ₁₂ -OCO-CH = CH ₂ H-Ph-C ^* H (CH ₃ ) -CH ₂ -Ph ^M -COO-C ₆ H ₁₂ -OCO-CH = CH ₂ H-Ph-C ^* H (CH ₃ ) -CH ₂ -Ph-OC ₆ H ₁₂ -OCO-CH = CH ₂ H-Ph-C ^* H (CH ₃ ) -CH ₂ -Ph ^F -OC ₆ H ₁₂ -OCO-CH = CH ₂ H-Ph-C ^* H (CH ₃ ) -CH ₂ -Ph ^FF -OC ₆ H ₁₂ -OCO-CH = CH ₂ H-Ph-C ^* H (CH ₃ ) -CH ₂ -Ph ^M -OC ₆ H ₁₂ -OCO-CH = CH ₂ H-Ph-C ^* H (CF ₃ ) -CH ₂ -Ph-COO-C ₆ H ₁₂ -OCO-CH = CH ₂ H- _{^{Ph-C * H (CF 3}} ) -CH 2 -Ph-OC 6 H 12 -OCO-CH = CH 2 H-Ph-C * H (CH 3) -CH 2 -Ph-COO-C 6 F 12 - OCO-CH = CH ₂ H-Ph-C ^* H (CH ₃ ) -CH ₂ -Ph-OC ₆ F ₁₂ -OCO-CH = CH ₂ H-Ph-C ^* H (CH ₃ ) -CH ₂ -Ph -COO-C ₅ H ₁₀ -C ₅ F ₁₀ -OCO-CH = CH ₂ H-Ph-C ^* H (CH ₃ ) -CH ₂ -Ph-OC ₅ H ₁₀ -C ₅ F ₁₀ -OCO-CH = CH ₂ H-Ph-C ^* H (CH ₃ ) -CH ₂ -Ph-COO-C ₅ F ₁₀ -C ₅ H ₁₀ -OCO-CH = CH ₂ H-Ph-C ^* H (CH ₃ ) -CH ₂ -Ph-OC ₅ F ₁₀ -C ₅ H ₁₀ -OCO-CH = CH ₂ H-Ph-C ^* H (CH ₃ ) -CH ₂ -Ph-COO-C ₂ H ₄ -OCO-C (CH ₃ ) = CH ₂ H-Ph _{^{-C * H (CH 3) -CH}} 2 -Ph-COO-C 4 H 8 -OCO-C (CH 3) = CH 2 H-Ph-C * H (CH 3) -CH 2 -Ph-COO- C ₆ H ₁₂ -OCO-C (CH ₃ ) = CH ₂ H-Ph-C ^* H (CH ₃ ) -CH ₂ -Ph-OC ₆ H ₁₂ -OCO-C (CH ₃ ) = CH ₂ CH _3- CH (CH ₃ ) -CH ₂ -Ph-C ^* H (CH ₃ ) -CH ₂ -Ph-COO-C ₂ H ₄ -OCO-C
H = CH ₂ CH ₃ -CH (CH ₃ ) -CH ₂ -Ph-C ^* H (CH ₃ ) -CH ₂ -Ph-COO-C ₄ H ₈ -OCO-C
H = CH ₂ CH ₃ -CH (CH ₃ ) -CH ₂ -Ph-C ^* H (CH ₃ ) -CH ₂ -Ph-COO-C ₆ H ₁₂ -OCO-
CH = CH ₂ CH ₃ -CH (CH ₃ ) -CH ₂ -Ph-C ^* H (CH ₃ ) -CH ₂ -Ph-COO-C ₁₁ H ₂₂ -OCO
-CH = CH ₂ CH ₃ -CH (CH ₃ ) -CH ₂ -Ph-C ^* H (CH ₃ ) -CH ₂ -Ph ^F -COO-C ₆ H ₁₂ -O
CO-CH = CH ₂ CH ₃ -CH (CH ₃ ) -CH ₂ -Ph-C ^* H (CH ₃ ) -CH ₂ -Ph ^FF -COO-C ₆ H ₁₂ -O
CO-CH = CH ₂ CH ₃ -CH (CH ₃ ) -CH ₂ -Ph-C ^* H (CH ₃ ) -CH ₂ -Ph ^M -COO-C ₆ H ₁₂ -O
CO-CH = CH ₂ CH ₃ -CH (CH ₃ ) -CH ₂ -Ph-C ^* H (CH ₃ ) -CH ₂ -Ph ^F -OC ₆ H ₁₂ -OCO
-CH = CH ₂ CH ₃ -CH (CH ₃ ) -CH ₂ -Ph-C ^* H (CH ₃ ) -CH ₂ -Ph ^M -OC ₆ H ₁₂ -OCO
-CH = CH ₂ CH ₃ -CH (CH ₃ ) -CH ₂ -Ph-C ^* H (CH ₃ ) -CH ₂ -Ph-COO-C ₆ F ₁₂ -OCO-
CH = CH ₂ CH ₃ -CH (CH ₃ ) -CH ₂ -Ph-C ^* H (CH ₃ ) -CH ₂ -Ph-OC ₆ F ₁₂ -OCO-CH
= CH ₂ CH ₃ -CH (CH ₃ ) -CH ₂ -Ph-C ^* H (CH ₃ ) -CH ₂ -Ph-COO-C ₂ H ₄ -OCO-C
(CH ₃ ) = CH ₂ CH ₃ -CH (CH ₃ ) -CH ₂ -Ph-C ^* H (CH ₃ ) -CH ₂ -Ph-COO-C ₄ H ₈ -OCO-C
(CH ₃ ) = CH ₂ CH ₃ -CH (CH ₃ ) -CH ₂ -Ph-C ^* H (CH ₃ ) -CH ₂ -Ph-COO-C ₆ H ₁₂ -OCO-
C (CH ₃ ) = CH ₂ CH ₃ -CH (CH ₃ ) -CH ₂ -Ph-C ^* H (CH ₃ ) -CH ₂ -Ph-OC ₆ H ₁₂ -OCO-C
(CH ₃ ) = CH ₂ C ₆ H ₁₃ -O-Ph-C ^* H (CH ₃ ) -CH ₂ -Ph-COO-C ₆ H ₁₂ -OCO-CH = CH ₂ C ₆ H ₁₃ -O-Ph _{^{-C * H (CH 3) -CH}} 2 -Ph-OC 6 H 12 -OCO-CH = CH 2 C 6 H 13 - C * H (CH 3) -O-Ph- C * H (CH 3) - _{CH 2 -Ph-COO-C 6} H 12 -
OCO-CH = CH ₂ C ₆ H ₁₃ -C ^* H (CH ₃ ) -O-Ph-C ^* H (CH ₃ ) -CH ₂ -Ph-OC ₆ H ₁₂ -OC
OC (CH ₃ ) = CH ₂ C ₅ F ₁₀ -CH ₂ O-Ph- C ^* H (CH ₃ ) -CH ₂ -Ph-COO-C ₆ H ₁₂ -OCO-CH = C
_{H 2 C 5 F 10 -CH 2} O-Ph- C * H (CH 3) -CH 2 -Ph-OC 6 H 12 -OCO-CH = CH 2 CH 3 -O-Np-C * H (CH 3 ) -CH ₂ -Ph-COO-C ₆ H ₁₂ -OCO-CH = CH ₂ CH ₃ -O-Np-C ^* H (CH ₃ ) -CH ₂ -Ph-OC ₆ H ₁₂ -OCO-CH = CH _Two

Preferred examples of the compound having three ring groups include the following compounds. H-Ph-Ph- C ^* H (CH ₃ ) -CH ₂ -Ph-COO-C ₆ H ₁₂ -OCO-CH = CH ₂ H-Ph-Ph- C ^* H (CH ₃ ) -CH ₂ -Ph -OC ₆ H ₁₂ -OCO-CH = CH ₂ H-Ph- Ph ^F -C ^* H (CH ₃ ) -CH ₂ -Ph-COO-C ₆ H ₁₂ -OCO-CH = CH ₂ H-Ph- Ph ^F -C ^* H (CH ₃ ) -CH ₂ -Ph-OC ₆ H ₁₂ -OCO-CH = CH ₂ H-Ph- Ph ^F -C ^* H (CH ₃ ) -CH ₂ -Ph-COO-C ₆ H ₁₂ -OCO-C (CH ₃ ) = C
H ₂ H-Ph- Ph ^F -C ^* H (CH ₃ ) -CH ₂ -Ph-OC ₆ H ₁₂ -OCO-C (CH ₃ ) = CH ₂ H-Ph-C ^* H (CH ₃ ) -CH ₂ -Ph-Ph-COO-C ₂ H ₄ -OCO-CH = CH ₂ H-Ph-C ^* H (CH ₃ ) -CH ₂ -Ph-Ph-COO-C ₄ H ₈ -OCO-CH = CH ₂ H-Ph-C ^* H (CH ₃ ) -CH ₂ -Ph-Ph-COO-C ₆ H ₁₂ -OCO-CH = CH ₂ H-Ph-C ^* H (CH ₃ ) -CH ₂ -Ph- Ph-OC ₆ H ₁₂ -OCO-CH = CH ₂ H-Ph-C ^* H (CH ₃ ) -CH ₂ -Ph-Ph-COO-C ₆ H ₁₂ -OCO-C (CH ₃ ) = CH ₂ H _{^{-Ph-C * H (CH 3}} ) -CH 2 -Ph-Ph-OC 6 H 12 -OCO-C (CH 3) = CH 2 H-Ph-C * H (CH 3) -CH 2 - Ph F -Ph-COO-C ₆ H ₁₂ -OCO-CH = CH ₂ H-Ph-C ^* H (CH ₃ ) -CH ₂ -Ph-Ph ^F -OC ₆ H ₁₂ -OCO-CH = CH ₂ H-Ph _{^{-C * H (CH 3) -CH}} 2 - Ph M -Ph-COO-C 6 H 12 -OCO-CH = CH 2 H-Ph-C * H (CH 3) -CH 2 -Ph-Ph FF - OC ₆ H ₁₂ -OCO-CH = CH ₂ H-Ph-C ^* H (CH ₃ ) -CH ₂ -Ph-Ph-COO-C ₅ H ₁₀ -C ₅ F ₁₀ -OCO-CH = CH
₂ H-Ph-C ^* H (CF ₃ ) -CH ₂ -Ph-Ph-COO-C ₆ F ₁₂ -OCO-CH = CH ₂ H-Ph-C ^* H (CF ₃ ) -CH ₂ -Ph- Ph-OC ₆ H ₁₂ -OCO-C (CH ₃ ) = CH ₂ H-Ph-C ^* H (CH ₃ ) -CH ₂ -Ph-COO-Ph-COO-C ₆ H ₁₂ -OCO-C (CH ₃ ) =
^{_{CH 2 H-Ph-C *}} H (CH 3) -CH 2 -Ph-COO-Ph-OC 6 H 12 -OCO-CH = CH 2 H-Ph-C * H (CH 3) -CH 2 -Ph -OCO-Ph-OC ₆ H ₁₂ -OCO-CH = CH ₂ H-Ph-C ^* H (CH ₃ ) -CH ₂ -Ph-Cy-CH ₂ OC ₆ H ₁₂ -OCO-C (CH ₃ ) = ^{_{CH 2 H-Ph-C *}} H (CH 3) -CH 2 -Ph-COO-Cy-COO-C 6 H 12 -OCO-CH = CH 2 H-Ph-C * H (CH 3) -CH 2 -Ph-CH ₂ CH ₂ -Ph-COO-C ₆ H ₁₂ -OCO-C (CH
₃ ) = CH ₂ H-Ph-C ^* H (CH ₃ ) -CH ₂ -Ph-CH ₂ CH ₂ -Ph-OC ₆ H ₁₂ -OCO-CH = CH ₂ H-Ph-C ^* H (CH ₃ ) -CH ₂ -Ph-CH ₂ CH ₂ -Cy-COO-C ₆ H ₁₂ -OCO-CH = C
H ₂ H-Ph-C ^* H (CH ₃ ) -CH ₂ -Ph-CH ₂ CH ₂ -Cy-CH ₂ OC ₆ H ₁₂ -OCO-C (C
H ₃ ) = CH ₂ H-Ph-C ^* H (CH ₃ ) -CH ₂ -Ph-CH ₂ CH ₂ -Cy-OC ₆ H ₁₂ -OCO-C (CH ₃ )
= CH ₂ CH ₃ -CH (CH ₃ ) -CH ₂ -Ph-C ^* H (CH ₃ ) -CH ₂ -Ph-Ph-COO-C ₆ H ₁₂ -O
CO-CH = CH ₂ CH ₃ -CH (CH ₃ ) -CH ₂ -Ph-C ^* H (CH ₃ ) -CH ₂ -Ph-Ph-OC ₆ H ₁₂ -OCO
-CH = CH ₂ CH ₃ -CH (CH ₃ ) -CH ₂ -Ph-C ^* H (CH ₃ ) -CH ₂ -Ph-OCO-Ph-OC ₆ H ₁₂
-OCO-CH = CH ₂ C ₆ H ₁₃ -O-Ph-C ^* H (CH ₃ ) -CH ₂ -Ph-Ph-COO-C ₆ H ₁₂ -OCO-CH = CH
₂ C ₆ H ₁₃ -O-Ph-C ^* H (CH ₃ ) -CH ₂ -Ph-Ph-OC ₆ H ₁₂ -OCO-CH = CH ₂ C ₆ H ₁₃ -O-Ph-C ^* H (CH ₃ ) -CH ₂ -Ph-OCO-Ph-OC ₆ H ₁₂ -OCO-CH =
CH ₂ CH ₃ -O-Np-C ^* H (CH ₃ ) -CH ₂ -Ph-Ph-COO-C ₆ H ₁₂ -OCO-CH = CH ₂ CH ₃ -O-Np-C ^* H (CH ₃ ) -CH ₂ -Ph-Ph-OC ₆ H ₁₂ -OCO-CH = CH ₂ CH ₃ -O-Np-C ^* H (CH ₃ ) -CH ₂ -Ph-OCO-Ph-OC ₆ H ₁₂ -OCO -CH = CH
_Two

Preferred examples of the compound having four ring groups include the following compounds. H-Ph- Ph ^F -C ^* H (CH ₃ ) -CH ₂ -Ph-Ph-COO-C ₆ H ₁₂ -OCO-CH = CH
₂ H-Ph- Ph ^F -C ^* H (CH ₃ ) -CH ₂ -Ph-Ph-OC ₆ H ₁₂ -OCO-CH = CH ₂ H-Ph- Ph ^F -C ^* H (CH ₃ ) -CH ₂ -Ph-Ph-COO-C ₆ H ₁₂ -OCO-C (C
H ₃ ) = CH ₂ H-Ph- Ph ^F -C ^* H (CH ₃ ) -CH ₂ -Ph-Ph-OC ₆ H ₁₂ -OCO-C (CH ₃ ) =
CH ₂ H-Ph-C ^* H (CH ₃ ) -CH ₂ -Ph-COO-Ph-Ph-COO-C ₆ H ₁₂ -OCO-CH = C
H ₂ H-Ph-C ^* H (CH ₃ ) -CH ₂ -Ph-COO-Ph-Ph-OC ₆ H ₁₂ -OCO-CH = CH ₂ H-Ph-C ^* H (CH ₃ ) -CH ₂ -Ph-COO-Ph-Cy-COO-C ₆ H ₁₂ -OCO-CH = C
H ₂ H-Ph-C ^* H (CH ₃ ) -CH ₂ -Ph-OCH ₂ -Cy-Ph-OC ₆ H ₁₂ -OCO-CH = CH
₂ H-Ph-C ^* H (CH ₃ ) -CH ₂ -Ph-Ph-COO-Ph-COO-C ₆ H ₁₂ -OCO-CH = C
H ₂ H-Ph-C ^* H (CH ₃ ) -CH ₂ -Ph-Ph-OCO-Ph-OC ₆ H ₁₂ -OCO-CH = CH ₂ H-Ph-C ^* H (CH ₃ ) -CH ₂ -Ph-Cy-COO-Ph-COO-C ₆ H ₁₂ -OCO-CH = C
H ₂ H-Ph-C ^* H (CH ₃ ) -CH ₂ -Ph-Cy-CH ₂ O-Ph-OC ₆ H ₁₂ -OCO-CH = CH
₂ H-Ph-C ^* H (CH ₃ ) -CH ₂ -Ph-Ph-CH ₂ CH ₂ -Cy-COO-C ₆ H ₁₂ -OCO-C
H = CH ₂ H-Ph-C ^* H (CH ₃ ) -CH ₂ -Ph-Ph-CH ₂ CH ₂ -Cy-CH ₂ OC ₆ H ₁₂ -OCO-
C (CH ₃ ) = CH ₂ H-Ph-C ^* H (CH ₃ ) -CH ₂ -Ph-Ph-CH ₂ CH ₂ -Cy-OC ₆ H ₁₂ -OCO-CH =
CH ₂ H-Ph-C ^* H (CH ₃ ) -CH ₂ -Ph-Cy-CH ₂ CH ₂ -Cy-COO-C ₆ H ₁₂ -OCO-C
H = CH ₂ H-Ph-C ^* H (CH ₃ ) -CH ₂ -Ph-Cy-CH ₂ CH ₂ -Cy-CH ₂ OC ₆ H ₁₂ -OCO-
C (CH ₃ ) = CH ₂ H-Ph-C ^* H (CH ₃ ) -CH ₂ -Ph-Cy-CH ₂ CH ₂ -Cy-OC ₆ H ₁₂ -OCO-CH =
CH ₂ H-Ph-C ^* H (CH ₃ ) -CH ₂ -Ph-CH ₂ CH ₂ -Ph-Cy-COO-C ₆ H ₁₂ -OCO-C
H = CH ₂ H-Ph-C ^* H (CH ₃ ) -CH ₂ -Ph-CH ₂ CH ₂ -Ph-Cy-CH ₂ OC ₆ H ₁₂ -OCO-
C (CH ₃ ) = CH ₂ H-Ph-C ^* H (CH ₃ ) -CH ₂ -Ph-CH ₂ CH ₂ -Ph-Cy-OC ₆ H ₁₂ -OCO-CH =
CH ₂ H-Ph-C ^* H (CH ₃ ) -CH ₂ -Ph-CH ₂ CH ₂ -Cy-Ph-COO-C ₆ H ₁₂ -OCO-C
H = CH ₂ H-Ph-C ^* H (CH ₃ ) -CH ₂ -Ph-CH ₂ CH ₂ -Cy-Ph-CH ₂ OC ₆ H ₁₂ -OCO-
C (CH ₃ ) = CH ₂ H-Ph-C ^* H (CH ₃ ) -CH ₂ -Ph-CH ₂ CH ₂ -Cy-Ph-OC ₆ H ₁₂ -OCO-CH =
CH ₂

[Specific examples of the compound represented by the formula (3)] As the compound represented by the formula (3), the following compounds are preferably exemplified. ^{H-Ph-C * H (} CH 3) -CH 2 -Ph-COOH H-Ph-C * H (CH 3) -CH 2 - Ph F -COOH H-Ph-C * H (CH 3) -CH ₂ -Ph ^FF -COOH H-Ph-C ^* H (CH ₃ ) -CH ₂ -Ph ^M -COOH H-Ph-C ^* H (CH ₃ ) -CH ₂ -Ph-Ph-COOH H-Ph-C ^* H (CH ₃ ) -CH ₂ -Ph-Cy-COOH H-Ph-C ^* H (CH ₃ ) -CH ₂ -Ph ^F -Ph-COOH H-Ph-C ^* H (CH ₃ ) -CH ₂ -Ph-Ph ^FF -COOH H-Ph-C ^* H (CH ₃ ) -CH ₂ -Ph ^M -Ph-COOH H-Ph-C ^* H (CF ₃ ) -CH ₂ -Ph-COOH H-Ph- C ^* H (CF ₃ ) -CH ₂ -Ph ^F -COOH H-Ph-C ^* H (CF ₃ ) -CH ₂ -Ph ^FF -COOH H-Ph-C ^* H (CF ₃ ) -CH ₂ -Ph ^M -COOH H-Ph-C ^* H (CF ₃ ) -CH ₂ -Ph-Ph-COOH H-Ph-C ^* H (CF ₃ ) -CH ₂ -Ph ^F -Ph-COOH H-Ph-C ^* H (CF ₃ ) -CH ₂ -Ph-Ph ^FF -COOH H-Ph-C ^* H (CF ₃ ) -CH ₂ -Ph ^M -Ph-COOH CH ₃ -CH (CH ₃ ) -CH ₂ -Ph- _{^{C * H (CH 3) -CH}} 2 -Ph-COOH CH 3 -CH (CH 3) -CH 2 -Ph-C * H (CH 3) -CH 2 - Ph F -COOH CH 3 -CH (CH 3 ^{_{) -CH 2 -Ph-C * H}} (CH 3) -CH 2 - Ph FF -COOH CH 3 -CH (CH 3) -CH 2 -Ph-C * H (CH 3) -CH 2 - Ph M - COOH CH ₃ -CH (CH ₃ ) -CH ₂ -Ph-C ^* H (CH ₃ ) -CH ₂ -Ph-Ph-COOH CH ₃ -CH (CH ₃ ) -CH ₂ -Ph-C ^* H (CH ₃ ) -CH ₂ -Ph ^F -Ph-COOH CH ₃ -CH (CH ₃ ) -CH ₂ -Ph-C ^* H (CH ₃ ) -CH _2- Ph-Ph ^FF -COOH CH ₃ -CH (CH ₃ ) -CH ₂ -Ph-C ^* H (CH ₃ ) -CH ₂ -Ph ^M -Ph-COOH CH ₃ -O-Ph-C ^* H (CH ₃ ) -CH ₂ -Ph-COOH CH ₃ -O-Ph-C ^* H (CH ₃ ) -CH ₂ -Ph ^F -COOH CH ₃ -O-Ph-C ^* H (CH ₃ ) -CH ₂ -Ph ^FF -COOH CH ₃ -O-Ph-C ^* H (CH ₃ ) -CH ₂ -Ph ^M -COOH CH ₃ -O-Ph-C ^* H (CH ₃ ) -CH ₂ -Ph-Ph-COOH CH _3- O-Ph-C ^* H (CH ₃ ) -CH ₂ -Ph ^F -Ph-COOH CH ₃ -O-Ph-C ^* H (CH ₃ ) -CH ₂ -Ph-Ph ^FF -COOH CH ₃ -O- Ph-C ^* H (CH ₃ ) -CH ₂ -Ph ^M -Ph-COOH C ₆ H ₁₃ -O-Ph-C ^* H (CH ₃ ) -CH ₂ -Ph-COOH C ₆ H ₁₃ -O-Ph _{^{-C * H (CH 3) -CH}} 2 -Ph-Ph-COOH C 6 H 13 - C * H (CH 3) -O-Ph- C * H (CH 3) -CH 2 -Ph-COOH C 6 ^{_{H 13 - C * H (CH}} 3) -O-Ph- C * H (CH 3) -CH 2 - Ph F -COOH C 6 H 13 - C * H (CH 3) -O-Ph- C * H (CH ₃ ) -CH ₂ -Ph ^FF -COOH C ₆ H ₁₃ -C ^* H (CH ₃ ) -O-Ph-C ^* H (CH ₃ ) -CH ₂ -Ph ^M -COOH C ₆ H ₁₃ -C ^* H (CH ₃ ) -O-Ph- C ^* H (CH ₃ ) -CH ₂ -Ph-Ph-COOH C ₆ H ₁₃ -C ^* H (CH ₃ ) -O-Ph- C ^* H (CH _{3 ^{) -CH 2 - Ph F -Ph-}} COOH C 6 H 13 - C * H (CH 3) -O-Ph- C * H (CH 3) -CH 2 -Ph-Ph FF -COOH C 6 H 13 - _{^{C * H (CH 3) -O}} -Ph- C * H (CH 3) -CH 2 - Ph M -Ph-COOH C 5 F ₁₀ -CH ₂ O-Ph-C ^* H (CH ₃ ) -CH ₂ -Ph-COOH H-Ph- Ph-C ^* H (CH ₃ ) -CH ₂ -Ph-COOH H-Ph- Ph ^F -C ^* H (CH ₃ ) -CH ₂ -Ph-COOH H-Ph- Ph ^F -C ^* H (CH ₃ ) -CH ₂ -Ph ^F -COOH H-Ph- Ph ^F -C ^* H (CH ₃ )- CH ₂ -Ph ^FF -COOH H-Ph- Ph ^F -C ^* H (CH ₃ ) -CH ₂ -Ph ^M -COOH H-Ph- Ph ^F -C ^* H (CH ₃ ) -CH ₂ -Ph-Ph -COOH H-Ph- Ph ^F -C ^* H (CH ₃ ) -CH ₂ -Ph ^F -Ph-COOH H-Ph- Ph ^F -C ^* H (CH ₃ ) -CH ₂ -Ph-Ph ^FF -COOH H-Ph- Ph ^F -C ^* H (CH ₃ ) -CH ₂ -Ph ^M -Ph-COOH CH ₃ -O-Np-C ^* H (CH ₃ ) -CH ₂ -Ph-COOHCH ₃ -O-Np -C ^* H (CH ₃₎ -C
H ₂ -Ph ^F -COOH CH ₃ -O-Np-C ^* H (CH ₃ ) -CH ₂ -Ph ^FF -COOH CH ₃ -O-Np-C ^* H (CH ₃ ) -CH ₂ -Ph ^M- COOH CH ₃ -O-Np-C ^* H (CH ₃ ) -CH ₂ -Ph-Ph-COOH CH ₃ -O-Np-C ^* H (CH ₃ ) -CH ₂ -Ph ^F -Ph-COOH CH ₃ -O-Np-C ^* H (CH ₃ ) -CH ₂ -Ph-Ph ^FF -COOH CH ₃ -O-Np-C ^* H (CH ₃ ) -CH ₂ -Ph ^M -Ph-COOH

[Description of Production Method] The production method of the compound (3) or (2) is shown below. The following production method is merely an example, and the reaction temperature, reaction solvent, reducing agent, catalyst, and the like may be changed as necessary. In each reaction, the configuration of the optically active compound in the formula is maintained.

[Explanation of Method for Producing Compound (3)] First, the carboxylic acid represented by the formula (4) is chlorinated to give a compound represented by the formula (1)
0). The chlorinating agent is preferably thionyl chloride or oxalyl chloride. The reaction may be carried out without solvent or with a solvent, but it is preferable to use a solvent such as tetrachloroethylene, dichloromethane, dichloroethane or the like from the viewpoint of workability. The reaction temperature is preferably 50 ° C or lower. RX ¹ -A ¹ -B ¹ -C ^* HY ¹ -COOH ... Equation (4) RX ¹ -A ¹ -B ¹ -C ^* HY ¹ -COCl ... Equation (10)

The obtained acid chloride represented by the formula (10) is subjected to a coupling reaction with a Grignard reagent represented by the formula (5). Q ′ in the formula (5) is a bromine atom or an iodine atom, and is preferably a bromine atom in terms of reactivity and cost. Q is a halogen atom, but when Q ′ is a bromine atom, Q is not an iodine atom. The Grignard reagent represented by the formula (5) can be easily prepared from a halide represented by the following formula (11) and magnesium metal by a conventional method. In this reaction, it is preferable to use an organometallic complex as a catalyst from the viewpoint of improving the yield and suppressing side reactions. Examples of the organometallic complex include iron (III) -acetylacetonate, nickel (II) -acetylacetonate, cobalt (II) -acetylacetonate, copper (II) -acetylacetonate, and dichloro (1,2-bis ( Preferred examples include diphenylphosphino) ethane) nickel and tetrakis (triphenylphosphine) palladium (0). The reaction solvent is preferably tetrahydrofuran from the viewpoint of workability and the like. Since the Grignard reagent represented by the formula (5) is easily decomposed by water, it is preferable to use the reaction solvent after completely dehydrating it with metallic sodium or the like. The reaction temperature is preferably from -10 to 30C. By the above reaction, a ketone represented by the formula (6) is obtained. Q'-Mg- (B ² ) _n -Q ... Equation (5) Q '-(B ² ) _n -Q ... Equation (11) RX ¹ -A ¹ -B ¹ -C ^* HY ¹ -CO- (B ² ) _n -Q… Equation (6)

The compound (7) is obtained by reducing the ketone as the compound (6). The reducing agent in this reaction is not particularly limited, but lithium aluminum hydride in the presence of aluminum chloride, triethylsilane in the presence of trifluoroacetic acid, triethylsilane in the presence of aluminum chloride, and the like are preferable from the viewpoint of workability and the like. The reaction can be carried out without a solvent or using a solvent, but from the viewpoint of workability and safety, it is preferable to use tetrahydrofuran, diethyl ether, methyl-t-butyl ether, or the like. The reaction temperature is preferably from 0 to 30C. RX ¹ -A ¹ -B ¹ -C ^* HY ¹ -CH _2- (B ² ) _n -Q ... Equation (7)

Further, a Grignard reagent represented by the formula (8) is prepared from the compound (7), and the Grignard reagent represented by the formula (8) is reacted with carbon dioxide, followed by hydrolysis with an acid. And the compound (3) of the present invention, which is a carboxylic acid, is obtained. The Grignard reagent represented by the formula (8) can be easily prepared from the compound (7) and magnesium metal or ethylmagnesium bromide by an ordinary method. It is preferable to use ethyl magnesium bromide from the viewpoints of workability and safety, and the reaction solvent is preferably tetrahydrofuran. Since the Grignard reagent is easily decomposed by water as described above, it is preferable to use the reaction solvent after completely dehydrating it with metallic sodium or the like. As carbon dioxide, either gas or solid (dry ice) may be used, but it is preferable to use gas from the viewpoint of workability and safety. The reaction temperature is preferably -30 to 20C. The acid used for the hydrolysis is preferably dilute hydrochloric acid. RX ¹ -A ¹ -B ¹ -C ^* HY ¹ -CH _2- (B ² ) _n -Mg-Q… Equation (8) RX ¹ -A ¹ -B ¹ -C ^* HY ¹ -CH _2- (B ² ) _n -COOH… Equation (3)

[Explanation of Production Method of Compound (2)] The compound (2) of the present invention can be produced from an optically active compound (3) which is an intermediate thereof. First, the compound (3) is chlorinated with thionyl chloride to obtain an acid chloride represented by the formula (12). The reaction solvent is preferably tetrachloroethylene.
The reaction temperature is preferably 50 ° C or lower. Oxalyl chloride may be used instead of thionyl chloride. Next, the compound (2) of the present invention is obtained by reacting the acid chloride represented by the formula (12) with the alcohol represented by the formula (9) in the presence of pyridine. The reaction solvent is preferably dichloromethane or toluene. Further, triethylamine may be used instead of pyridine. The reaction temperature is preferably 40 ° C. or lower. RX ¹ -A ¹ -B ¹ -C ^* HY ¹ -CH _2- (B ² ) _n -COCl… Equation (12) HO-A ² -X ³ -A ³ -X ⁴ -Z-OCO-CY ² = CH ₂ … Equation (9) RX ¹ -A ¹ -B ¹ -C ^* HY ¹ -CH _2- (B ² ) _n -COO-A ² -X ³ -A ³ -X ⁴ -Z-OCO-CY ² = CH ₂ … Equation (2)

[Explanation of Method for Producing Compound (1)] Among the compounds represented by the formula (1), for example, X ² is an etheric oxygen atom (—O—), A ² , A ³ , X ³ And X
^{When 4} is a single bond, it can be produced by the following method.

[0033]

Embedded image

First, the optically active phenol (a)
In the presence of potassium carbonate, a tetrahydropyranyl group (TH
The compound (c) is obtained by reacting the halogen compound (b) having a hydroxyl group protected by P). The reaction solvent is preferably acetone, cyclohexanone or methyl isobutyl ketone. The reaction temperature is preferably from 80 to 150 ° C. Further, a compound in which a hydroxyl group is protected by a methoxymethyl group instead of a tetrahydropyranyl group may be used. Next, the hydroxyl group of compound (c) is deprotected in the presence of an acid catalyst to obtain alcohol (d). The acid catalyst is preferably hydrochloric acid, p-toluenesulfonic acid, pyridinium p-toluenesulfonate or an acidic ion exchange resin, and the reaction solvent is preferably methanol, tetrahydrofuran or water. The reaction temperature is preferably 100 ° C. or lower. The obtained alcohol (d) was added to acrylic acid (e (Y =
H)) or methacrylic acid (e (Y = CH ₃ )) to cause esterification to obtain the desired compound (1-1). The reaction solvent is preferably dichloromethane, dichloroethane, chloroform or toluene. Esterification is performed by dehydration condensate such as DCC or DMAP, or p-
It is preferable to use an acid catalyst such as toluenesulfonic acid, and it is preferable to carry out the reaction under heating and reflux. On this occasion,
It is preferable to add a polymerization inhibitor such as hydroquinone and tri-t-butylphenol.

The compound (1) is composed of at least one compound of another polymerizable compound, a liquid crystal material having no polymerizable functional group, or a non-liquid crystal material having no polymerizable functional group (hereinafter, referred to as a compound having no polymerizable functional group).
These are collectively referred to as "other materials". ) To form a liquid crystal composition. When compound (1) is contained in another material to form a copolymerizable liquid crystal composition, formula (1)
The total amount of the compound represented by the formula (1) is preferably 0.1 to 80% by mass in the copolymerizable liquid crystal composition. More preferably, it is 1 to 70% by mass, further preferably 5 to 60% by mass, particularly preferably 10 to 50% by mass. Further, it is preferable that the liquid crystal composition contains a compound represented by the formula (1) in multiple components. In this case, the compound of one component contains 1 to 10% by mass in the liquid crystal composition. Is preferred. By including multiple components, the compatibility of the composition becomes good and the working temperature range is widened.

As the other polymerizable compound, a liquid crystal monomer or a monomer having no liquid crystal property can be used, but a liquid crystal monomer is preferable from the viewpoint of compatibility.

The other polymerizable compound is not particularly limited, but is preferably a compound represented by the following formula. However, in the following formula, m represents 1 to 12, and R ′ represents an alkyl group. CH ₂ = CHCOO (CH ₂ ) _m O-Ph-COO-Ph-OCO-Ph- O (CH ₂ ) _m -OCOCH
= CH ₂ CH ₂ = CHCOO (CH ₂ ) _m O-Ph-COO- Ph ^M -OCO-Ph-O (CH ₂ ) _m -OCO
CH = CH ₂ CH ₂ = CHCOO (CH ₂ ) _m O-Ph-Ph-O (CH ₂ ) _m -OCOCH = CH ₂ CH ₂ = CHCOO (CH ₂ ) _m O-Ph-Ph-CN CH ₂ = CHCOO -Ph-OCO-Ph-R 'CH ₂ = CHCOO-Ph-COO-Ph-OCO-Ph-OCOCH = CH ₂ CH ₂ = CHCOO-Ph-COO- Ph ^M -OCO-Ph-OCOCH = CH ₂ CH ₂ = CHCOO-Ph-Ph-O (CH ₂ ) _m -OCOCH = CH ₂ CH ₂ = CHCOO-Ph-Ph-CN

Specifically, a compound represented by the following formula is preferably mentioned. CH ₂ = CHCOO (CH ₂ ) ₆ O-Ph-COO-Ph-OCO-Ph-O (CH ₂ ) ₆ -OCOCH = CH
₂ CH ₂ = CHCOO (CH ₂ ) ₁₁ O-Ph-COO- Ph ^M -OCO-Ph-O (CH ₂ ) ₁₁ -OCO
CH = CH ₂ CH ₂ = CHCOO (CH ₂ ) ₆ O-Ph-Ph-O (CH ₂ ) ₆ -OCOCH = CH ₂ CH ₂ = CHCOO (CH ₂ ) ₃ O-Ph-Ph-CN CH ₂ = CHCOO (CH ₂ ) ₆ O-Ph-Ph-CN CH ₂ = CHCOO-Ph-OCO-Ph-C ₅ H ₁₁ CH ₂ = CHCOO-Ph-OCO-Ph-C ₄ H ₉ CH ₂ = CHCOO-Ph-Ph -CN These can be used alone or in combination of two or more.

In addition, a liquid crystal material having no polymerizable functional group
There is no particular limitation as long as it is a known liquid crystal material.
Phenyl, tolan, pyrimidine, cyclohexane
System, difluorostilbene system, etc.
It is appropriately selected depending on performance and the like. One or more of these
The above can be mixed and used. Has a polymerizable functional group
Examples of non-liquid crystal materials include the following compounds.
It is. Where R¹And R^TwoAre independent of each other
Kill group, alkenyl group, alkoxy group, halogen atom
Or a cyano group;¹And R^TwoOne of the hydrogen atoms in the
Or more are substituted by halogen atoms or cyano groups, etc.
You may. Z¹, Z ^Two, Z^Three, Z^FourAre independent of each other
And a five-membered or six-membered ring (eg, a cyclohexane ring,
Benzene ring, dioxane ring, pyrimidine ring or pyridi
Ring structure), unsubstituted or substituted
Good. Further, the bonding group between the rings is another bonding group.
You may. Other linking groups include -CH_TwoO-, -CH
= CH-, -N = N-, -CH = N-, -COOCH_Two
-, -OCOCH_Two-, -COCH_Two-Etc.
You.

These may be used alone or in combination of two or more.
Can be selected as appropriate for the desired performance.
You. In addition, the following compounds are only examples,
Compounds may be employed. R¹-Z¹-Z^Two-R^Two, R¹-Z¹-COO-Z^Two-R^Two, R¹-Z¹-C ≡C-Z^Two-
R^Two, R¹-Z¹-CH_TwoCH_Two-Z^Two-R^Two, R¹-Z¹-CF = CF-Z^Two-R^Two, R¹-Z¹
-Z^Two-Z^Three-R^Two, R¹-Z¹-COO-Z^Two-Z^Three-R^Two, R¹-Z¹-CH_TwoCH_Two-Z^Two-Z^Three-
R^Two, R¹-Z¹-CF = CF-Z^Two-Z^Three-R^Two, R¹-Z¹-C ≡C-Z^Two-Z^Three-R^Two, R
¹-Z¹-COO-Z^Two-COO-Z^Three-R^Two, R¹-Z¹-CH_TwoCH_Two-Z^Two-COO-Z^Three-
R^Two, R¹-Z¹-CH_TwoCH_Two-Z^Two-C ≡C-Z^Three-R^Two, R¹-Z¹-Z^Two-Z ^Three-Z^Four-
R^Two, R¹-Z¹-CH_TwoCH_Two-Z^Two-C ≡C-Z^Three-Z^Four-R^Two.

Examples of the non-liquid crystal material having no polymerizable functional group include a stabilizer for maintaining the storage stability of the liquid crystal composition, and a dye. Examples of the stabilizer include hydroquinone, hydroquinone monoalkyl ethers and tert-butyl catechol. Examples of the dye include a normal dye and a dichroic dye.

In the case where the liquid crystal composition containing the compound (1) is copolymerized, it is preferable to carry out the copolymerization by irradiation with UV light using an appropriate photopolymerization initiator. At this time, glass, plastic, or the like can be used as the support. The surface of the support may be subjected to an orientation treatment as necessary. The orientation treatment may be performed by directly rubbing the surface of the support with natural fibers such as cotton and wool, synthetic fibers such as nylon and polyester, or applying polyimide or polyamide or the like and rubbing the surface with the above fibers or the like. Good. A spacer such as a glass bead is disposed, a plurality of supports are controlled to face each other at a desired interval, and the composition is injected and filled between the supports. The injected composition is maintained in a liquid crystal state, and is photopolymerized in a state where molecules are oriented. In order to maintain the composition in a liquid crystal state, the ambient temperature may be set in a range from a melting point ( _Tm ) to a nematic-isotropic phase transition temperature ( _Tc ).
At a temperature close to T _c , the refractive index anisotropy is extremely small.
The upper limit of the ambient temperature is preferably (T _c -10) ° C. or lower. It is preferable to use benzoin ethers, dialkoxyphenyl acetophenones and the like as the photopolymerization initiator. The amount of the photopolymerization initiator used is, in the liquid crystal composition,
It is preferable to use within the range of 0.1 to 20% by mass.

The liquid crystal composition of the present invention containing the compound (1) is sandwiched between substrates with electrodes by a method such as injection into a liquid crystal cell to constitute a liquid crystal device. The liquid crystal element is a polymer-dispersed liquid crystal element, a nematic liquid crystal element, a reflective cholesteric liquid crystal element, a GH liquid crystal element using a polychromatic dye, a ferroelectric liquid crystal element, a dimming element, a heat ray reflective film,
Optical filters, optical color filters, colored films, integrated polarizers, waveguides, beam splitters,
It is suitably used for optical gratings, optical recording elements, temperature indicators, and the like.

The polymer substance of the present invention formed by photopolymerizing the liquid crystal composition as described above has a liquid crystal property, and includes a polymer dispersed liquid crystal element, an anisotropic gel, and a liquid crystal. It is suitably used for various applications such as films. In this case, the polymeric substance may be used while being sandwiched between the supports, or may be used after being separated from the supports. Further, the polymeric substance of the present invention can be suitably used particularly for forming a cholesteric thin film exhibiting curable selective reflection.

In general, when a large amount of an optically active compound is added, there is a problem that storage stability at a low temperature is deteriorated and the degree of freedom in designing a viscosity and a phase transition temperature at a high temperature is reduced. In particular, when the viscosity is increased, the response speed is reduced, and the driving voltage is also increased, which is not preferable. However, since the compound (1) of the present invention has a large helical inducing force, a liquid crystal composition having a desired helical pitch can be obtained with a small amount of addition. In addition, since the viscosity of the compound itself is low, the rise in viscosity when added to the liquid crystal composition can be reduced, and the storage stability at low temperatures is also good. Further, the compound (1) of the present invention has a photopolymerizable functional group. A polymeric substance formed by photopolymerizing a liquid crystal composition containing the compound (1) of the present invention has liquid crystallinity, and a liquid crystal element using the same does not require a polarizing plate or an alignment film. Since the whole or a part of the liquid crystal element is cured, the stability of the liquid crystal alignment is high, so that a highly reliable liquid crystal element can be realized.

[0046]

The present invention will be described below more specifically with reference to examples. [Example 1] (R) -1- (p-chlorophenyl) -2-
Synthesis Example of (p- (2-methylpropyl) phenyl) propane <First Step> (S) -1- (p-chlorophenyl)
Synthesis of 2- (p- (2-methylpropyl) phenyl) propan-1-one 100 g of (S) -2- (p- (2-methylpropyl) phenyl) propionic acid was placed in a 1-L eggplant flask A.
mmol), 400 mL of tetrachloroethylene, 115 g (970 mmol) of thionyl chloride and a small amount of dimethylaniline, and the mixture was stirred at room temperature overnight. Then, excess thionyl chloride and tetrachloroethylene were distilled off under reduced pressure to obtain (S) -2-
114 g of (p- (2-methylpropyl) phenyl) propionic acid chloride were obtained.

To a 2 L four-necked flask B were added 13.0 g (533 mmol) of magnesium pieces, 50 mL of anhydrous tetrahydrofuran and a small amount of iodine powder. A solution prepared by dissolving 92.8 g (485 mmol) of p-bromochlorobenzene in 970 mL of anhydrous tetrahydrofuran was dropped in a small amount under a nitrogen atmosphere, and the reaction was started when the color of iodine disappeared. The remaining solution was added dropwise over 1 hour while stirring, and after completion of the addition, the mixture was stirred at room temperature for 2 hours to prepare a Grignard reagent.

In a 3 L four-necked flask C, 114 g of (S) -2- (p- (2-methylpropyl) phenyl) propionic acid chloride prepared in Flask A and 530 mL of anhydrous tetrahydrofuran were added. 10
C. and cooled to 171 mg of iron (III) acetylacetonate.
(0.485 mmol) was added.

While maintaining the reaction temperature at 0 ° C. or lower, the Grignard reagent prepared in Flask B was added dropwise. After completion of the addition, the mixture was heated to room temperature, stirred for 2 hours, cooled to 5 ° C., and added with 500 mL of diluted hydrochloric acid. . The organic phase was separated, the aqueous phase was extracted with toluene, combined with the organic phase, washed with water and saturated saline, and dried over anhydrous magnesium sulfate. The solvent was distilled off, and silica gel column chromatography (developing solvent =
Purified with hexane: toluene = 4: 1) and recrystallized from methanol to give (S) -1- (p-chlorophenyl) -2
-(P- (2-methylpropyl) phenyl) propane-
1-one _{[CH 3 -CH (CH 3)} -CH 2 -Ph-C * H (CH 3) -CO-Ph-Cl]
65.6 g (218 mmol) of white crystals were obtained. (Yield 45%)

[0050]

[Table 1]

<Second Step> Synthesis of (R) -1- (p-chlorophenyl) -2- (p- (2-methylpropyl) phenyl) propane Obtained in the first step in a 500 mL four-necked flask. (S) -1- (p-chlorophenyl) -2- (p- (2
-Methylpropyl) phenyl) propan-1-one 6
0.0 g (199 mmol), trifluoroacetic acid 227
g (1.99 mol), the mixture was cooled to 0 ° C., and 58.0 g (499 mmol) of triethylsilane was added at a reaction temperature of 5
The mixture was added dropwise while maintaining the temperature at not more than 0 ° C, and after completion of the addition, the mixture was heated to room temperature and stirred for 3 hours. After adding 600 mL of toluene and distilling off the solution under reduced pressure until the solution volume becomes about 200 mL, 400 mL of toluene is added, and a 5% aqueous sodium hydrogen carbonate solution is added.
After washing with water and saturated saline and drying over anhydrous magnesium sulfate, the solvent and by-products are distilled off, and the residue is purified by silica gel column chromatography (developing solvent = hexane) to give (R) -1- (p- Chlorophenyl) -2- (p-
(2-methylpropyl) phenyl) propane [CH ₃ -CH (C
_{H 3) -CH 2 -Ph-C} * H (CH 3) colorless liquid -CH ₂ -Ph-Cl] 51.4
g (180 mmol) were obtained. (Yield 90%)

[0052]

[Table 2]

Specific examples of the compounds obtained by the same method as in Example 1 are shown below. _{CH 3 -CH (CH 3) -CH} 2 -Ph-C * H (CH 3) -CH 2 -Ph-Br H-Ph-C * H (CH 3) -CH 2 -Ph-Cl H-Ph- Ph ^F -C ^* H (CH ₃ ) -CH ₂ -Ph-Cl CH ₃ -O-Ph-C ^* H (CH ₃ ) -CH ₂ -Ph-Cl C ₆ H ₁₃ -C ^* H (CH ₃ ) -O-Ph- C ^* H (CH ₃ ) -CH ₂ -Ph-Cl CH ₃ -O-Np-C ^* H (CH ₃ ) -CH ₂ -Ph-Cl CH ₃ -CH (CH ₃ ) -CH ₂ -Ph-C ^* H (CH ₃ ) -CH ₂ -Ph-Ph-Cl CH ₃ -CH (CH ₃ ) -CH ₂ -Ph-C ^* H (CH ₃ ) -CH ₂ -Ph-Ph-Br H-Ph-C ^* H (CH ₃ ) -CH ₂ -Ph-Ph-Cl H-Ph-C ^* H (CH ₃ ) -CH ₂ -Ph ^F -Ph-Cl H-Ph-C ^* H (CH ₃ ) -CH ₂ -Ph ^M -Ph-Cl H-Ph- Ph ^F -C ^* H (CH ₃ ) -CH ₂ -Ph-Ph-Cl CH ₃ -O-Ph-C ^* H (CH ₃ )- CH ₂ -Ph-Ph-Cl C ₆ H ₁₃ -C ^* H (CH ₃ ) -O-Ph- C ^* H (CH ₃ ) -CH ₂ -Ph-Ph-Cl CH ₃ -O-Np-C ^* H (CH ₃ ) -CH ₂ -Ph-Ph-Cl

Example 2 (R) -4- (2- (p- (2-
Example of synthesis of methylpropyl) phenyl) propyl) benzoic acid In a 500 mL four-necked flask, magnesium pieces 7.4 were added.
6 g (307 mmol), anhydrous tetrahydrofuran 15
mL and a small amount of iodine powder were added. Ethyl bromide 16.7
g (153 mmol) in anhydrous tetrahydrofuran 100
A small amount of the solution dissolved in mL was dropped in a nitrogen atmosphere, and the reaction was started when the color of iodine disappeared, and the remaining solution was dropped in 1 hour while maintaining the reaction temperature at 25 ° C or lower. (R) -1- (p-chlorophenyl) obtained in Example 1
A solution obtained by dissolving 40.0 g (139 mmol) of -2- (p- (2-methylpropyl) phenyl) propane in 120 mL of anhydrous tetrahydrofuran was added dropwise, and after completion of the dropwise addition, the mixture was stirred for 10 hours under heated reflux. After cooling to −30 ° C., blowing carbon dioxide gas while keeping the temperature at −20 ° C. or lower, the temperature was raised to room temperature while continuously blowing the carbon dioxide gas after the heat generation disappeared. After filtering unreacted magnesium,
The reaction solution was poured into ice-cooled diluted hydrochloric acid, the organic phase was separated, the aqueous phase was extracted with methyl-t-butyl ether, and the combined organic phase was washed with water and saturated saline, dried over anhydrous sodium sulfate, and dried. The propionic acid as a by-product was distilled off to obtain crystals of a crude product. Which was recrystallized from toluene (R) -4- (2- (p- (2- methylpropyl) phenyl) propyl) benzoic acid _{[CH 3 -CH (CH 3)} -CH 2 -Ph-C * H
(CH ₃ ) —CH ₂ —Ph-COOH] 36.0 g (121 m
mol) was obtained (yield 87%).

[0055]

[Table 3]

Specific examples of the compounds obtained by the same method as in Example 2 are shown below. H-Ph-C ^* H (CH ₃ ) -CH ₂ -Ph-COOH H-Ph- Ph ^F -C ^* H (CH ₃ ) -CH ₂ -Ph-COOH CH ₃ -O-Ph-C ^* H ( CH ₃ ) -CH ₂ -Ph-COOH C ₆ H ₁₃ -C ^* H (CH ₃ ) -O-Ph- C ^* H (CH ₃ ) -CH ₂ -Ph-COOH CH ₃ -O-Np-C ^* _{H (CH 3) -CH 2 -Ph} -COOH CH 3 -CH (CH 3) -CH 2 -Ph-C * H (CH 3) -CH 2 -Ph-Ph-COOH H-Ph-C * H ( CH ₃ ) -CH ₂ -Ph-Ph-COOH H-Ph-C ^* H (CH ₃ ) -CH ₂ -Ph ^F -Ph-COOH H-Ph-C ^* H (CH ₃ ) -CH ₂ -Ph ^M -Ph-COOH H-Ph- Ph ^F -C ^* H (CH ₃ ) -CH ₂ -Ph-Ph-COOH CH ₃ -O-Ph-C ^* H (CH ₃ ) -CH ₂ -Ph-Ph-COOH C ₆ H ₁₃ -C ^* H (CH ₃ ) -O-Ph- C ^* H (CH ₃ ) -CH ₂ -Ph-Ph-COOH CH ₃ -O-Np-C ^* H (CH ₃ ) -CH ₂ -Ph-Ph-COOH

Example 3 (R) -4- (2- (p- (2-
Example of synthesis of 2-acryloyloxyethyl methylpropyl) phenyl) propyl) benzoate (R)-synthesized in Example 2 in a 200 mL eggplant flask.
15.0 g (50.6 mmol) of 4- (2- (p- (2-methylpropyl) phenyl) propyl) benzoic acid, 12.0 g (101 mmol) of thionyl chloride, 60 mL of tetrachloroethylene, and a small amount of dimethylaniline were added.
After heating to 0 ° C. and stirring at the same temperature for 3 hours, excess thionyl chloride and tetrachloroethylene were distilled off under reduced pressure, and (R)
-4- (2- (p- (2-methylpropyl) phenyl)
16.4 g of (propyl) benzoic acid chloride were obtained.

(R) -4 in a 300 mL three-necked flask
-(2- (p- (2-methylpropyl) phenyl) propyl) benzoic acid chloride 16.4 g, acrylic acid 2-
7.64 g (65.8 mmol) of hydroxyethyl, 150 mL of dichloromethane, 4.80 g of pyridine (60.
7 mmol) and stirred at room temperature overnight. The reaction solution was poured into water, the organic phase was separated, the aqueous phase was extracted with dichloromethane, and the combined organic phase was washed with diluted hydrochloric acid, water, and saturated saline, and dried over anhydrous magnesium sulfate. A small amount of p-methoxyphenol was added, the solvent was distilled off, and the residue was purified by column chromatography (fixed layer = silica gel: alumina = 3: 1, developing solvent = toluene) to give (R) -4- (2- (p
- (2-methylpropyl) phenyl) propyl) 2-acryloyloxyethyl acid _{[CH 3 -CH (CH 3)} -CH 2 -Ph
-C ^* H (CH ₃₎ to give the _{-CH 2 -Ph-COO-C 2} H 4 -OCO-CH = CH 2] of a colorless liquid 12.3 g (30.9 mmol) (yield: 62
%).

[0059]

[Table 4]

Example 4 (R) -4- (2- (p- (2-
Synthesis Example of 4-Acryloyloxybutyl Methylpropyl) phenyl) propyl) benzoate (R)-synthesized in Example 2 in a 200 mL eggplant flask.
15.0 g (50.6 mmol) of 4- (2- (p- (2-methylpropyl) phenyl) propyl) benzoic acid, 12.0 g (101 mmol) of thionyl chloride, 60 mL of tetrachloroethylene, and a small amount of dimethylaniline were added.
After heating to 0 ° C. and stirring at the same temperature for 3 hours, excess thionyl chloride and tetrachloroethylene were distilled off under reduced pressure, and (R)
-4- (2- (p- (2-methylpropyl) phenyl)
16.5 g of propyl) benzoic acid chloride were obtained.

(R) -4 in a 300 mL three-necked flask
-(2- (p- (2-methylpropyl) phenyl) propyl) benzoic acid chloride 16.5 g, acrylic acid 4-
9.48 g (65.8 mmol) of hydroxybutyl, 150 mL of dichloromethane, 4.80 g of pyridine (60.
7 mmol) and stirred at room temperature overnight. The reaction solution was poured into water, the organic phase was separated, the aqueous phase was extracted with dichloromethane, and the combined organic phase was washed with diluted hydrochloric acid, water, and saturated saline, and dried over anhydrous magnesium sulfate. A small amount of p-methoxyphenol was added, the solvent was distilled off, and the residue was purified by column chromatography (fixed layer = silica gel: alumina = 2: 1, developing solvent = toluene), and (R) -4- (2- (p
- (2-methylpropyl) phenyl) propyl) benzoic acid 4-acryloyloxy-butyl _{[CH 3 -CH (CH 3)} -CH 2 -Ph
-C ^* H (CH ₃₎ to give the _{-CH 2 -Ph-COO-C 4} H 8 -OCO-CH = CH 2] of a colorless liquid 16.5 g (39.0 mmol) (yield: 77
%).

[0062]

[Table 5]

Specific examples of the compounds obtained in the same manner as in Examples 3 and 4 are shown below. CH ₃ -CH (CH ₃ ) -CH ₂ -Ph-C ^* H (CH ₃ ) -CH ₂ -Ph-COO-C ₆ H ₁₂ -OCO-
CH = CH ₂ CH ₃ -CH (CH ₃ ) -CH ₂ -Ph-C ^* H (CH ₃ ) -CH ₂ -Ph-COO-C ₁₁ H ₂₂ -OCO
-CH = CH ₂ CH ₃ -CH (CH ₃ ) -CH ₂ -Ph-C ^* H (CH ₃ ) -CH ₂ -Ph-COO-C ₆ H ₁₂ -OCO-
C (CH ₃ ) = CH ₂ CH ₃ -CH (CH ₃ ) -CH ₂ -Ph-C ^* H (CH ₃ ) -CH ₂ -Ph-COO-C ₁₁ H ₂₂ -OCO
-C (CH ₃ ) = CH ₂ H-Ph-C ^* H (CH ₃ ) -CH ₂ -Ph-COO-C ₂ H ₄ -OCO-CH = CH ₂ H-Ph-C ^* H (CH ₃ ) -CH ₂ -Ph-COO-C ₄ H ₈ -OCO-CH = CH ₂ H-Ph-C ^* H (CH ₃ ) -CH ₂ -Ph-COO-C ₆ H ₁₂ -OCO-CH = CH ₂ H _{^{-Ph-C * H (CH 3}} ) -CH 2 -Ph-COO-C 11 H 22 -OCO-CH = CH 2 H-Ph-C * H (CH 3) -CH 2 -Ph-COO-C 6 H ₁₂ -OCO-C (CH ₃ ) = CH ₂ H-Ph-C ^* H (CH ₃ ) -CH ₂ -Ph-COO-C ₁₁ H ₂₂ -OCO-C (CH ₃ ) = CH ₂ H-Ph -Ph ^F -C ^* H (CH ₃ ) -CH ₂ -Ph-COO-C ₆ H ₁₂ -OCO-CH = CH ₂ CH ₃ -O-Ph-C ^* H (CH ₃ ) -CH ₂ -Ph- _{COO-C 6 H 12 -OCO-} CH = CH 2 C 6 H 13 - C * H (CH 3) -O-Ph- C * H (CH 3) -CH 2 -Ph-COO-C 6 H 12 -
OCO-CH = CH ₂ CH ₃ -O-Np-C ^* H (CH ₃ ) -CH ₂ -Ph-COO-C ₆ H ₁₂ -OCO-CH = CH ₂ CH ₃ -CH (CH ₃ ) -CH ₂ -Ph-C ^* H (CH ₃ ) -CH ₂ -Ph-Ph-COO-C ₆ H ₁₂ -O
CO-CH = CH ₂ H-Ph-C ^* H (CH ₃ ) -CH ₂ -Ph-Ph-COO-C ₆ H ₁₂ -OCO-CH = CH ₂ H-Ph-C ^* H (CH ₃ )- CH ₂ -Np-COO-C ₆ H ₁₂ -OCO-CH = CH ₂

Example 5 A liquid crystal composition manufactured by Merck (trade name:
(ZLI-1565) and 100 parts by mass of 2-acryloyloxyethyl (R) -4- (2- (p- (2-methylpropyl) phenyl) propyl) benzoate synthesized in Example 3 (composition) % By mass of the optically active compound contained in the substance; c = 0.01) and the liquid crystal composition (S _A ) was prepared in Example 4.
The liquid crystal composition (S _B ) was added with 1 part by mass (c = 0.01) of 4-acryloyloxybutyl (R) -4- (2- (p- (2-methylpropyl) phenyl) propyl) benzoate synthesized in (1). ) Got. Liquid crystal composition manufactured by Merck (trade name: Z
LI-1565) and 100 parts by mass of the compound (CN), which is a commercially available chiral agent, is 1 part by mass (c = 0.01).
In addition, a liquid crystal composition (S _C ) was obtained. For the obtained liquid crystal compositions (S _A ), (S _B ) and (S _C ), the helical pitch length P (m) at 25 ° C.
The helix inducing force (HTP) of each optically active compound was determined by the following formula by measuring by the wedge method. The direction of helix induction was measured by the contact method. Table 1 shows the results. Helix inducing force: HTP = 1 / (P · c)

[0065]

[Table 6] The helix-inducing power of the optically active compound of the present invention was larger than that of a commercially available chiral agent.

[0066]

The compounds (1) to (3) of the present invention are optically active substances. Since the compound (1) of the present invention has a large helical inducing force, it is possible to obtain a liquid crystal composition having a desired helical pitch by adding a smaller amount than a conventional optically active compound. The compound (1) of the present invention is a copolymerizable optically active compound. Therefore, the liquid crystal composition to which the compound (1) of the present invention is added is useful as a liquid crystal composition used for a polymer-dispersed liquid crystal device, an anisotropic gel, a liquid crystal film, and the like. In addition, the production method of the present invention makes it possible to produce the above compound at low cost and in high yield.

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁷ Identification code FI Theme coat ゛ (Reference) C08F 20/26 C08F 20/26 C09K 19/38 C09K 19/38 19/54 19/54 B G02F 1/13 500 G02F 1/13 500 // C07M 7:00 C07M 7:00 (72) Inventor Takeshi Koike 3-2-1-10 Chigasaki, Chigasaki City, Kanagawa Prefecture Inside Seimi Chemical Co., Ltd. (72) Inventor Osamu Yokokoji Chigasaki, Kanagawa Prefecture 3-2-10, Chigasaki, Seimi Chemical Co., Ltd. Address Asahi Glass Co., Ltd. F-term (reference) 4H006 AA01 AA02 AB64 AC46 AC48 BE90 BJ50 BS10 BS30 KA14 4H027 BA11 BB11 BD03 BD16 4J100 AL 08P BA02P BA15P BB07P BB12P BB18P BC04P BC43P BC49P CA01 CA04 DA66 JA32 JA39

Claims (9)

[Claims] 1. An optically active compound represented by the following formula (1). R-X¹-A¹-B¹-C^*HY¹-CH_Two-(B^Two)_n-X^Two-A^Two-X^Three-A^Three-X^Four-Z-OCO-CY^Two= CH_Two ... Formula (1) However, the symbol in Formula (1) has the following meaning. R: an alkyl group having 1 to 12 carbon atoms, at least one hydrogen atom
Is a C1-C12 alkyl substituted with a fluorine atom
Group, hydrogen atom or halogen atom. X¹, X^Two, X^Three,
X^Four: Independently of each other, a carbonyloxy group (—COO
-), Oxycarbonyl group (-OCO-), etheric
Oxygen atom (-O-), oxymethylene group (-OCH_Two
-), Methyleneoxy group (-CH_TwoO-) or single bond
Go. Y¹: Methyl group (-CH_Three) Or one or more hydrogen atoms
Is a methyl group substituted by a fluorine atom. Y^Two: Hydrogen atom or methyl group (-CH_Three). Z: one of an alkylene group having 1 to 12 carbon atoms or a hydrogen atom
Having 1 to 12 carbon atoms in which at least one is substituted with a fluorine atom
Kilen group. A¹, A^Two, A^Three: Up to one hydrogen atom independently of each other
Or two of which may be substituted with a fluorine atom
Phenylene group, one or two hydrogen atoms are methyl groups
(-CH_Three1,4-phenylene optionally substituted by
Group, unsubstituted 2,6-naphthylene group, unsubstituted
1,4-cyclohexylene group or single bond. B¹, B^Two: Independently of one another,
1,4-phenyl optionally substituted by two fluorine atoms
Nylene group, one or two hydrogen atoms are methyl group (-
CH_Three1,4-phenylene optionally substituted by
Group, unsubstituted 2,6-naphthylene group, unsubstituted trans
-1,4-cyclohexylene group or -D ¹-CH_TwoC
H_Two-D^TwoA group represented by-(D¹And D^TwoAre each
Independently, one or two of the hydrogen atoms are a fluorine atom and
And / or methyl group (-CH_Three) May be substituted
1,4-phenylene group, unsubstituted 2,6-naphthylene
Group, unsubstituted trans-1,4-cyclohexylene group
Represent. ). n: 1 or 2. C^*: Asymmetric carbon atom. 2. The optically active compound according to claim 1, wherein the compound represented by the formula (1) is a compound represented by the following formula (2). RX ¹ -A ¹ -B ¹ -C ^* HY ¹ -CH _2- (B ² ) _n -COO-A ² -X ³ -A ³ -X ⁴ -Z-OCO-CY ² = CH ₂ … Formula (2) Where the symbols R, X ¹ , X ³ , X ⁴ ,
Y ¹ , Y ² , Z, A ¹ , A ² , A ³ , B ¹ , B ² , n and C ^* have the same meanings as in formula (1). 3. An optically active compound represented by the following formula (3). RX ¹ -A ¹ -B ¹ -C ^* HY ¹ -CH _2- (B ² ) _n -COOH Formula (3) where symbols R, X ¹ , Y ¹ , A ¹ ,
B ¹ , B ² , n and C ^* have the same meaning as in formula (1). 4. A method for producing an optically active compound represented by the formula (3) via the following steps (a) and (b). Step (a): A carboxylic acid represented by the following formula (4) is converted to an acid chloride, and a coupling reaction is performed with a Grignard reagent represented by the following formula (5) to produce a ketone represented by the following formula (6): To obtain an optically active compound represented by the following formula (7). Step (b): a step of converting an optically active compound represented by the following formula (7) into a Grignard reagent represented by the following formula (8) and reacting with carbon dioxide. RX ¹ -A ¹ -B ¹ -C ^* HY ¹ -COOH ... Equation (4) Q'-Mg- (B ² ) _n -Q ... Equation (5) RX ¹ -A ¹ -B ¹ -C ^* HY ¹ -CO- (B ² ) _n -Q… Equation (6) RX ¹ -A ¹ -B ¹ -C ^* HY ¹ -CH _2- (B ² ) _n -Q… Equation (7) RX ¹ -A ^1- B ¹ -C ^* HY ¹ -CH _2- (B ² ) _n -Mg-Q where R in the formulas (4), (5), (6), (7) and (8) , X ¹ , Y ¹ , A ¹ , B ¹ , B ² , n and C ^* have the same meanings as in formula (3),
And Q ′ have the following meanings. Q: a halogen atom. Q ′: a bromine atom or an iodine atom. However, when Q ′ is a bromine atom, Q is not an iodine atom. 5. An optically active compound represented by the formula (2), wherein the optically active compound represented by the formula (3) is converted to an acid chloride and reacted with an alcohol represented by the following formula (9). A method for producing a compound. HO-A ² -X ³ -A ³ -X ⁴ -Z-OCO-CY ² = CH ₂ Formula (9) where X ³ , X ⁴ , A ² , A ³ and Y ^{2 in the} formula (9) And Z have the same meaning as in formula (2). 6. A liquid crystal composition containing at least one of the optically active compounds according to claim 1 or 2 in a total amount of 0.1 to 80% by mass. 7. A high molecular substance obtained by copolymerizing at least one of the optically active compounds according to claim 1 or 2. 8. A liquid crystal device using the liquid crystal composition according to claim 6. 9. A liquid crystal device using the polymeric substance according to claim 7.