JP2002128743A - Polymerizable liquid crystal compound - Google Patents

Abstract

(57) [Problem] To provide a monofunctional polymerizable liquid crystal compound which exhibits good liquid crystallinity and is useful as a component of a liquid crystal material. SOLUTION: General formula (1) P-S1-A-S2-M (1) (P represents a polymerizable functional group, and A is selected from the group consisting of an aromatic ring, an alicyclic ring, a heterocyclic ring and a condensed ring. M represents a mesogen moiety having the same or different 2 to 16 rings selected from the group consisting of an aromatic ring, an alicyclic ring, a heterocyclic ring, and a condensed ring, and S1 has a main chain of carbon, oxygen, silicon and Represents a linking chain composed of at least one kind of 7 to 18 atoms selected from sulfur, and S2 has a main chain composed of at least one kind of 5 to 18 atoms selected from carbon, oxygen, silicon and sulfur Represents a connecting chain, wherein P is connected to ring A via a connecting chain S1,
Is bonded to ring A via a linking chain S2. A) a polymerizable liquid crystal compound represented by the formula:

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to coatings of pigments, optical fibers and the like utilizing selective reflection of retardation plates, polarizing plates, polarizing prisms, waveguides, piezoelectric elements, non-linear optical elements, various optical filters, cholesteric liquid crystal phases and the like. The present invention relates to a novel monofunctional polymerizable liquid crystal compound applicable as an agent.

[0002]

2. Description of the Related Art A polymerizable liquid crystal material containing a monofunctional polymerizable liquid crystal compound is aligned in a liquid crystal state, and then irradiated with active energy rays such as ultraviolet rays in that state to fix the alignment state structure of the liquid crystal molecules. Polymer can be produced. Since the polymer thus obtained has anisotropy of physical properties such as refractive index, dielectric constant, magnetic susceptibility, elastic modulus, and coefficient of thermal expansion, for example, a retardation plate, It can be applied as a coating material such as a plate, a polarizing prism, a waveguide, a piezoelectric element, a nonlinear optical element, various optical filters, a pigment utilizing selective reflection of a cholesteric liquid crystal phase or the like, and an optical fiber.

The monofunctional polymerizable liquid crystal compounds for such applications can be used in a wide range of materials by exhibiting a low melting point and a wide range of liquid crystal phases, particularly a nematic phase range. Liquid crystalline compounds have the disadvantage that the melting point is high or the liquid crystal temperature range is narrow.

A monofunctional polymerizable liquid crystal compound is composed of two parts of mesogen and a polymer group, or mesogen, a connecting chain connecting the mesogen and the polymer group, and three parts of a polymer group. The structure of the connecting chain of the currently known monofunctional polymerizable liquid crystal compound is disclosed in JP-A-5-61022, which comprises an alkyl group having up to 15 carbon atoms. JP-A-8-277247 discloses an alkylene group having up to 12 atoms which may contain an oxygen atom. WO 98-475 consists of an alkylene group of up to 20 atoms which may contain oxygen, nitrogen or sulfur atoms. And International Patent Application Publication No. 9
In JP-A-8-55473, an alkylene group which can be substituted with a fluorine, chlorine or cyano group having up to 20 atoms which may contain an oxygen or nitrogen atom is used.

[0005]

An object of the present invention is to provide a novel monofunctional polymerizable liquid crystal compound which exhibits good liquid crystallinity and is considered to be useful as a component of a liquid crystal material.

[0006]

The inventors of the present invention have conducted intensive studies on the correlation between the chemical structure and physical properties of a polymerizable liquid crystal material, and as a result, have found that a polymerizable functional group has a linking chain S1 having an alkylene chain.
By providing a compound represented by the following general formula (1) in which the mesogen moiety M is bonded to the ring A via a linking chain S2 having an alkylene chain. The present inventors have found that the above problem can be solved by using a polymerizable liquid crystal compound having a skeleton of -S 1 -A-S 2-as a linking portion for linking a functional functional group and a mesogen, and have completed the present invention. Therefore, the present invention

(A) Formula (1) P-S1-A-S2-M (1) (P represents a polymerizable functional group, and A represents a group consisting of an aromatic ring, an alicyclic ring, a heterocyclic ring, and a condensed ring. M represents a mesogen moiety having the same or different 2 to 16 rings selected from the group consisting of an aromatic ring, an alicyclic ring, a heterocyclic ring and a condensed ring, and S1 represents a main chain composed of carbon, oxygen, Represents a connecting chain composed of 7 to 18 atoms of at least one kind selected from silicon and sulfur, and S2 has a main chain composed of 5 to 18 atoms of at least one kind selected from carbon, oxygen, silicon and sulfur P is connected to ring A via linking chain S1, and M
Is bonded to ring A via a linking chain S2. ),
A polymerizable liquid crystal compound having one polymerizable functional group in one molecule;

(B) The connecting chains S1 and S2 of the general formula (1)
A polymerizable liquid crystal compound according to the above (A) having an alkylene chain therein,

(C) The connecting chains S1 and S2 of the general formula (1)
Wherein the polymerizable liquid crystal compound according to (B) has at least one bond selected from an ether bond, a thioether bond, and an ester bond;

(D) The connecting chain S1 of the general formula (1) is an oxyalkylene chain and / or a general formula (2)

Embedded image (Wherein m represents an integer of 4 to 15), and the polymerizable liquid crystal compound according to any one of the above (A) to (C),

(E) The linking chain S2 of the general formula (1) is an oxyalkylene chain and / or a general formula (3)

Embedded image (Wherein, n represents an integer of 2 to 15), wherein the polymerizable liquid crystal compound according to any one of the above (A) to (C),

(F) at least the ring A in the general formula (1) and / or the ring in the mesogen moiety M is selected from the group consisting of a halogen group, a cyano group, a hydroxyl group, an alkyl group, an alkoxy group, and an alkanoyl group; A polymerizable liquid crystal compound according to any one of the above (A) to (E) having one substituent,

(G) The mesogenic moiety M in the general formula (1) has 2 to 8 identical or different rings selected from the group consisting of aromatic rings, alicyclic rings, heterocyclic rings and condensed rings.
(F) the polymerizable liquid crystal compound according to any one of:

(H) The mesogen moiety M of the general formula (1) has a tranbenzoate, biphenylbenzoate or tolan skeleton having the polymerizable liquid crystal compound described in the above (G);

(I) The polymerizable liquid crystal compound according to any one of the above (A) to (H), wherein the ring A in the general formula (1) is an aromatic ring or an alicyclic ring;

(J) The polymerizable liquid crystal compound according to the above (I), wherein the alicyclic ring of the ring A in the general formula (1) is a cyclohexane ring, and (K) the polymerizable functional group P in the general formula (1). Is a group selected from the group consisting of an acryloyloxy group, a methacryloyloxy group, an epoxy group, a vinyloxy group and a maleimide group, the polymerizable liquid crystal compound according to any one of the above (A) to (J), And

[0017]

BEST MODE FOR CARRYING OUT THE INVENTION The polymerizable liquid crystal compound of the present invention is represented by the following general formula (1). P-S1-A-S2-M (1) (wherein P represents a polymerizable functional group, A represents an aromatic ring, an alicyclic ring,
A ring selected from the group consisting of heterocycles and fused rings,
Represents a mesogen moiety having 2 to 16 identical or different rings selected from the group consisting of an aromatic ring, an alicyclic ring, a heterocyclic ring and a condensed ring. S1 represents a connecting chain whose main chain is composed of at least one kind of 7 to 18 atoms selected from carbon, oxygen, silicon and sulfur, and S2 represents at least one connecting chain whose main chain is selected from carbon, oxygen, silicon and sulfur. Represents a connecting chain composed of 5 to 18 atoms of a species. P is connected to Ring A via a connecting chain S1, and M is connected to Ring A via a connecting chain S2. )

In the general formula (1), the polymerizable functional group P
Is not particularly limited as long as it is a functional group having polymerizability. Specifically, for example, acryloyloxy group, methacryloyloxy group, ClCH ＝ CHC (＝ O) O—,
Acrylamide group, methacrylamide group, ClCH = C
HC (= O) NH-, a vinyl group, CH ₂ = CCl-, C
HCl = CH-, an epoxy group, an ethynyl group, a mercapto group, a vinyloxy group, a maleimide group and the like. Among them, an acryloyloxy group, a methacryloyloxy group, a vinyl group, an epoxy group, a mercapto group, a vinyloxy group, and a maleimide group are preferable, and an acryloyloxy group, a methacryloyloxy group, an epoxy group, a vinyloxy group, and a maleimide group are particularly preferable.

In the general formula (1), S1 represents a connecting chain whose main chain is composed of at least one atom selected from carbon, oxygen, silicon and sulfur. The number of atoms constituting the linking chain S1 is preferably 1 to 20, more preferably 2 to 18, and particularly preferably 7 to 18. Specifically, alkyl chains, alkylene chains, alkenylene chains, alkynylene chains,
An oxyalkylene chain, an oxyalkylenoyl chain and the like can be mentioned. In these connecting chains, an ether bond,
It may have a bond such as a thioether bond, an ester bond, an amide bond, an imine bond, a double bond, and a triple bond. Among them, an alkylene chain having an ether bond, a thioether bond, or an ester bond is preferable, and an oxyalkylene chain or the general formula (2):

[0020]

Embedded image (Wherein m represents an integer of 2 to 15), more preferably an alkylene chain, and most preferably an oxyalkylene chain.

In the general formula (1), S2 represents a connecting chain whose main chain is composed of at least one atom selected from carbon, oxygen, silicon and sulfur. The connecting chain is preferably a linear or branched one having flexibility.
The number of atoms constituting 2 is preferably 1 to 20, and 2 to 18
Is more preferable, and 5 to 18 is particularly preferable. Specifically, alkylene chains, alkenylene chains, alkynylene chains,
Oxyalkylene chains and oxyalkylenoyl chains are preferred, and those having an alkylene chain are particularly preferred. Further, these connecting chains may have a bond such as an ether bond, a thioether bond, an ester bond, an amide bond, an imine bond, a double bond, a triple bond, or the like. Among them,
An alkylene chain having an ether bond, a thioether bond or an ester bond is preferable, and an oxyalkylene chain or a compound represented by the general formula (3):

[0022]

Embedded image (Where n represents an integer of 2 to 15), more preferably an alkylene chain, and most preferably an oxyalkylene chain.

In the general formula (1), A represents a ring selected from the group consisting of an aromatic ring, an alicyclic ring, a heterocyclic ring and a condensed ring. For example, cyclopentane ring, furan ring, pyrrole ring, thiophene ring, thiazole ring, thiadiazole ring,
Benzene ring, cyclohexane ring (one CH ₂ group constituting the cyclohexane ring, or two or more _non-adjacent CH ₂ groups to constitute the ring may be replaced by -O- or -S- ), Cyclohexene ring, pyridine ring, pyrimidine ring, pyrazine ring, piperidine ring, piperazine ring, naphthalene ring, tetralin ring, decalin ring, and the like. Among them, a benzene ring and a cyclohexane ring are preferred.

Specifically, for example, a 1,4-phenylene ring, a 1,4-cyclohexylene ring (one CH ₂ group constituting a cyclohexylene ring or two or more non-adjacent groups constituting this ring) CH ₂ groups may be replaced by -O- or -S-.), pyridine-2,5
Diyl ring, pyrimidine-2,5-diyl ring, pyrazine-
2,5-diyl ring, piperidine-2,5-diyl ring, piperazine-diyl ring, 1,4-cyclohexenylene ring,
Naphthalene-2,6-diyl ring, decahydronaphthalene-2,6-diyl ring, 1,2,3,4-tetrahydronaphthalene-2,6-diyl ring, piperidine-1,4-diyl ring, octylene ring, 1,4-bicyclo [2.2.
2] an octylene ring is preferable, and a 1,4-phenylene ring;
1,3-dioxane-2,5-diyl ring, pyridine-
A 2,5-diyl ring, a pyrazine-2,5-diyl ring, a pyridazine-3,6-diyl ring, a pyrimidine-2,5-diyl ring, and a 1,4-cyclohexylene ring are particularly preferred.

The ring A may be further substituted with at least one substituent selected from the group consisting of a halogen group, a cyano group, a hydroxyl group, an alkyl group, an alkoxy group and an alkanoyl group. Specifically, as the halogen group, a fluorine atom, a bromine atom and a chlorine atom are preferable, and a fluorine atom and a chlorine atom are particularly preferable. Examples of the alkyl group include a methyl group, an ethyl group, an n-propyl group, and an n-
A butyl group is preferred, and a methyl group and an ethyl group are particularly preferred. As the alkoxy group, a methoxy group, an ethoxy group,
Propoxy and butoxy groups are preferred. The alkanoyl group is preferably an acetyl group, a propionyl group, or a butyryl group.

In the general formula (1), M is a mesogen moiety having at least two or more identical or different rings selected from the group consisting of an aromatic ring, an alicyclic ring, a heterocyclic ring and a condensed ring, and is not particularly limited. Of these, those having 2 to 16 rings are preferred, those having 2 to 8 rings are more preferred, and those having 2 to 4 rings are most preferred.

M is specifically represented by, for example, the following general formula (4).

Embedded image (Wherein, M 1 represents a mesogen moiety, S 3 represents a substituent, and n represents 0
To 9 represent an integer. )

In the general formula (4), M 1 is an aromatic ring,
A mesogen moiety having at least 2 to 16 identical or different rings selected from the group consisting of alicyclic, heterocyclic and fused rings. The number of atoms constituting the ring constituting the mesogen moiety M1 is not particularly limited, and may be any number as long as the number of atoms constituting the ring can be 3 or more, but the range of 3 to 10 is more preferable.

Examples of the ring having 3 to 5 atoms include cyclopropane, oxirane, cyclobutane, cyclopentane, cyclopentanone, tetrahydrofuran,
Dioxolan-2-one, furan, pyrrole, pyrroline, pyrrolidine, oxazole, isoxazole, thiophene, thiazole, isothiazole, thiadiazole, imidazole, imidazoline, imidazolidine, pyrazole, pyrazoline, pyrazolidine, 1,2,3-triazole, 1, , 2,4-triazole, tetrazole and the like.

Examples of the ring having 6 atoms include benzene, pyridine, pyrazine, pyridazine, pyrimidine,
1,2,4-triazine, 1,3,5-triazine, tetrazine, dihydrooxazine, cyclohexane, cyclohexene, cyclohexadiene, cyclohexanone,
Piperidine, piperazine, tetrahydropyran, dioxane, tetrahydrothiopyran, dithiane, oxathiane, dioxaborinane, and the like.

Examples of the ring having 7 or more atoms include naphthalene, dioxanaphthalene, tetralin, quinoline, coumarin, quinoxaline, decalin, indane, benzoxazole, benzothiazole, phenanthrene, dihydrophenanthrene, and perhydrophenanth. Len, dioxaperhydrophenanthrene, fluorene,
Fluorenone, cycloheptane, cycloheptatrienone, cholesten and the like.

As the ring constituting the mesogen moiety M1, other than these, bicyclo (2,2,2,
2) Octane and bicyclo (2,2,2) octene. Examples of the ring having a spiro bond include 1,5-dioxaspiro (5,5) undecane and 1,5-dithiaspiro (5,5) undecane. Specifically, the mesogen moiety M1 of the general formula (4)
Preferably has one or more structural units represented by the following general formula (5). E- (Y1-F) n-Y2-G (5) (wherein, E, F and G are each independently 1,4-
Phenylene, 1,4-cyclohexylene, 1,4-cyclohexenylene, naphthalene-2,6-diyl, decahydronaphthalene-2,6-diyl, 1,2,3,4-tetrahydronaphthalene-2,6- Diyl, 1,4-bicyclo [2.2.2] octylene, 1,3-dioxane-
2,5-diyl, pyridine-2,5-diyl, pyrazine-2,5-diyl, pyridazine-3,6-diyl, pyrimidine-2,5-diyl, wherein Y1 and Y2 are each independently single _{bond, -CH 2 CH 2 -, -} CH 2 O
−, —OCH ₂ −, —C (＝ O) O—, —OC (=
O)-, -C≡C-, -CH = CH-, -CF = CF
—, — (CH ₂ ) ₄ —, —CH ₂ CH ₂ CH ₂ O—, —O
_{CH 2 CH 2 CH 2 -,} - CH = CH-CH 2 CH 2 -, -
_{CH 2 CH 2 -CH = CH -} , - CH = CH-C (= O)
O— or —OC (＝ O) —CH ＝ CH—, n
Represents an integer of 0 to 3. When there are a plurality of Y1 and F, each of Y1 and F may be the same or different. )

The structural unit represented by the general formula (5) includes, for example, a structural unit represented by the following formula.

[0034]

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[0035]

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[0036]

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[0037]

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[0038]

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[0039]

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[0040]

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[0041]

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[0042]

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[0043]

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[0044]

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[0045]

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[0046]

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[0047]

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[0048]

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[0049]

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[0050]

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[0051]

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[0052]

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[0053]

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[0054]

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[0055]

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[0056]

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[0057]

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[0058]

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[0059]

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[0060]

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[0061]

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[0062]

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[0063]

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[0064]

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[0065]

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(The aromatic ring, alicyclic ring, heterocyclic ring and condensed ring in the formulas (a1) to (a447) are a halogen group, a cyano group, a hydroxyl group, an alkyl group having 1 to 7 carbon atoms, an alkoxy group and an alkanoyl group. May be substituted with one or more substituents selected from the group consisting of:) Among them, a structure represented by a tranbenzoate, a biphenylbenzoate, or a tran skeleton is preferable.

The ring constituting the mesogen moiety M 1 further comprises
It may be substituted with at least one substituent selected from the group consisting of a halogen group, a cyano group, a hydroxyl group, an alkyl group, an alkoxy group and an alkanoyl group represented by S3 in the general formula (4). .

As the halogen group, a fluorine atom, a bromine atom and a chlorine atom are preferred, and a fluorine atom and a chlorine atom are particularly preferred. Examples of the alkyl group include a methyl group, an ethyl group,
An n-propyl group and an n-butyl group are preferred, and a methyl group and an ethyl group are particularly preferred. As the alkoxy group, a methoxy group, an ethoxy group, a propoxy group, and a butoxy group are preferable. As the alkanoyl group, an acetyl group, a propionyl group and a butyryl group are preferred.

The substituent represented by S3 in the general formula (4) is a linear or branched chain composed of at least one atom selected from carbon, oxygen, silicon and sulfur. May be connected to the mesogen part M1. Specific examples of these connecting chains include an alkylene chain, an alkenylene chain, an alkynylene chain, an oxyalkylene chain, and an oxyalkylenoyl chain. Also,
In these chains, ether bonds, thioether bonds,
It may have a bond such as an ester bond, an amide bond, an imine bond, a double bond, and a triple bond. Further, a ring such as A in the general formula (1) may be provided between the substituent represented by S3 in the general formula (4) and the connecting chain.

The polymerizable liquid crystal compound represented by the general formula (1) includes a compound represented by the general formula (1a):

Embedded image (Wherein, P is a polymerizable functional group of the general formula (1), S1 and S2 are linking chains of the general formula (1), M1 is a mesogen moiety in the general formula (4), and S3 is a general formula ( Represents a substituent in 4), and n represents an integer of 0 to 9.) or a polymerizable liquid crystal compound represented by the general formula (1b):

[0071]

Embedded image (Wherein, P is a polymerizable functional group of the general formula (1), S1 and S2 are linking chains of the general formula (1), M1 is a mesogen moiety in the general formula (4), and S3 is a general formula ( 4) represents a substituent, and the portion represented by (S2-A-S3) represents a substituent possessed by M1, and n represents an integer of 0 to 9.) preferable. In the general formula (1b), when one molecule has a plurality of S1, A or S2, S1, A or S2 may be the same or different.

Among the polymerizable liquid crystal compounds represented by the general formula (1), the following general formulas (6) and (7):

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[0073]

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(Wherein, X represents a hydrogen atom or a methyl group, Y3 is a single bond, -OC (= O)-, -C (=
O) O -, - C≡C- and represents -CH ₂ CH ₂ - linking group selected from the group consisting of, R represents at least one hydroxyl group, a cyano group, a halogen group, an alkyl having 1 to 7 carbon atoms A group, an alkoxy group or an alkanoyl group, q
Represents an integer of 1 to 20, m represents an integer of 2 to 15, and p represents an integer of 0 or 1. Further, each 1,4-phenylene group is independently one or more substituents selected from the group consisting of a cyano group, a halogen atom, an alkyl group having 1 to 7 carbon atoms, an alkoxy group and an alkanoyl group. May be substituted. A) a polymerizable liquid crystal compound represented by the formula:

The following general formulas (8), (9) and (10):

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[0076]

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[0077]

Embedded image (Wherein, X represents a hydrogen atom or a methyl group, Y3 and Y4 each independently represent a single bond, -OC (= O)
—, —C (＝ O) O—, —C≡C— and —CH ₂ CH ₂ —
Represents a linking group selected from the group consisting of: R represents at least one hydroxyl group, a cyano group, a halogen group, an alkyl group having 1 to 7 carbon atoms, an alkoxy group or an alkanoyl group, and q represents 1 to 20 Represents an integer, and m is 3 to
Represents an integer of 16, and p represents an integer of 0 or 1.
Further, each 1,4-phenylene group may be independently substituted by one or more of an alkyl group having 1 to 7 carbon atoms, an alkoxy group, an alkanoyl group, or a cyano group, or a halogen atom. A) a polymerizable liquid crystal compound represented by the following general formulas (11) and (12):

[0078]

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[0079]

Embedded image (Wherein, X represents a hydrogen atom or a methyl group, and R is
Represents at least one hydroxyl group, cyano group, halogen group, alkyl group having 1 to 7 carbon atoms, alkoxy group or alkanoyl group; q represents an integer of 1 to 20;
Represents an integer of 2 to 15. Further, each 1,4-phenylene group is independently one or more substituents selected from the group consisting of a cyano group, a halogen atom, an alkyl group having 1 to 7 carbon atoms, an alkoxy group and an alkanoyl group. May be substituted. ), A polymerizable liquid crystal compound represented by the following general formulas (13), (14), (15), and (1).
6) and (17),

[0080]

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[0081]

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[0082]

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[0083]

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[0084]

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(Wherein X represents a hydrogen atom or a methyl group, and Y 3, Y 4 and Y 5 each independently represent a single bond, —OC (＝ O) —, —C (＝ O) O—, -C≡C-
And -CH2CH2- represents a linking group selected from the group consisting of: q represents an integer of 1 to 20, m represents 3 to 1
6 represents an integer, ring J represents a 1,4-cyclohexylene group, 1,4-phenylene group, and R represents at least one hydroxyl group, cyano group, halogen group, and 1 to 1 carbon atoms.
7 represents an alkyl group, an alkoxy group or an alkanoyl group, and p and s each independently represent 0 or 1. The 1,4-cyclohexylene group and the 1,4-phenylene group are each independently selected from the group consisting of a cyano group, a halogen atom, an alkyl group having 1 to 7 carbon atoms, an alkoxy group and an alkanoyl group. It may be substituted with one or more substituents. )) Are particularly preferred.

Although the (meth) acrylate compound has been mentioned as a preferred example of the compound of the present invention, a compound having an epoxy group as a reactive group is also preferred. As such compounds, for example, the following general formulas (18) and (1)
The compound represented by 9) can be mentioned.

[0087]

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[0088]

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(Wherein, X represents an oxygen atom or a carbon atom, and Y3, Y4 and Y5 each independently represent a single bond, —OC (ＯO) —, —C (＝ O) O—, -C≡C-
And -CH2CH2- represents a linking group selected from the group consisting of: q represents an integer of 1 to 20, m represents 2 to 1
5 represents an integer of 5; n represents an integer of 3 to 16; ring J represents a 1,4-cyclohexylene group or 1,4-phenylene group; and R represents at least one hydroxyl group, cyano group, or halogen. Represents a group, an alkyl group having 1 to 7 carbon atoms, an alkoxy group or an alkanoyl group, and p and s each independently represent 0 or 1. In addition, the 1,4-cyclohexylene group and the 1,4-phenylene group each independently represent a cyano group, a halogen atom, and a C1 to C1 group.
7 may be substituted with one or more substituents selected from the group consisting of an alkyl group, an alkoxy group and an alkanoyl group. )

Although the (meth) acrylate compound has been mentioned as a preferred example of the compound of the present invention, a compound having a vinyloxy group as a reactive group is also preferred. As such a compound, for example, the following general formula (20-1)
And the compounds represented by (20-2).

[0091]

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[0092]

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(Wherein Y3, Y4 and Y5 each independently represent a single bond, -OC (= O)-, -C (= O) O
Represents a linking group selected from the group consisting of-, -C≡C- and -CH2CH2-, q represents an integer of 1 to 20, m represents an integer of 2 to 15, and ring J represents 1, 4-
Represents a cyclohexylene group, a 1,4-phenylene group,
R represents at least one hydroxyl group, cyano group, halogen group, alkyl group having 1 to 7 carbon atoms, alkoxy group or alkanoyl group, and p and s each independently represent 0 or 1. Further, the 1,4-cyclohexylene group and the 1,4-phenylene group each independently represent
It may be substituted with one or more substituents selected from the group consisting of a cyano group, a halogen atom, an alkyl group having 1 to 7 carbon atoms, an alkoxy group and an alkanoyl group. )

Although the (meth) acrylate compound has been mentioned as a preferable example of the compound of the present invention, a compound having a maleimide group as a reactive group is also preferable. Examples of such compounds include compounds represented by the following general formulas (21-1) and (21-2).

[0095]

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[0096]

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(Wherein Y3, Y4 and Y5 each independently represent a single bond, -OC (= O)-, -C (= O) O
Represents a linking group selected from the group consisting of-, -C≡C- and -CH2CH2-, q represents an integer of 1 to 20, m represents an integer of 2 to 15, and ring J represents 1, 4-
Represents a cyclohexylene group, a 1,4-phenylene group,
R represents at least one hydroxyl group, cyano group, halogen group, alkyl group having 1 to 7 carbon atoms, alkoxy group or alkanoyl group, and p and s each independently represent 0 or 1. Further, the 1,4-cyclohexylene group and the 1,4-phenylene group each independently represent
It may be substituted with one or more substituents selected from the group consisting of a cyano group, a halogen atom, an alkyl group having 1 to 7 carbon atoms, an alkoxy group and an alkanoyl group. )

The preferred examples of the compound of the present invention have been described above. In these compounds, the cyclohexane ring is
A transcyclohexane ring is preferred.

The compound represented by the general formula (6) can be synthesized, for example, by the following method represented by the general formulas (21) to (24).

[0100]

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(Wherein, X, Y3, q, m and p represent the same contents as in the case of the general formula (5).
Represents dicyclohexylcarbodiimide. That is, an alcohol derivative represented by the general formula (23) and a carboxylic acid derivative represented by the general formula (22) in an amount of 1.2 equivalents to the alcohol derivative are converted to DCC (dicyclohexylcarbodiimide).
An esterification reaction is carried out using a condensing agent such as the above, and an esterification target product is obtained. Then, a precursor represented by the general formula (24) is synthesized by subjecting a hydroxyl group to deprotection reaction using 10% hydrochloric acid. Subsequently, a precursor represented by the general formula (24) and 1.5 equivalents of the precursor represented by the general formula (2)
By subjecting the carboxylic acid derivative represented by 5) to an esterification reaction using a condensing agent such as DCC (dicyclohexylcarbodiimide), the desired compound represented by the general formula (6) can be synthesized.

The carboxylic acid derivative represented by the general formula (22), which is a raw material for synthesizing the compound represented by the general formula (6), can be synthesized, for example, by the following method.

[0103]

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(In the formula, X and q represent the same contents as in the general formula (6). Me represents a methyl group.) That is, 4-hydroxybenzoic acid represented by the formula (22-1) By reacting methyl with an alcohol derivative having a bromo group represented by the general formula (22-2),
After obtaining the compound represented by -3), the methyl ester is hydrolyzed to obtain a compound represented by the general formula (22-4). By reacting this compound with (meth) acrylic acid in the presence of an acid catalyst while distilling off water, the desired carboxylic acid derivative represented by the general formula (22) can be obtained.

The carboxylic acid derivative represented by the general formula (25), which is a raw material for synthesizing the compound represented by the general formula (6), can be synthesized, for example, by the following method.

[0106]

Embedded image

(In the formula, R and q have the same contents as in the general formula (6).) That is, 4-hydroxybenzoic acid represented by the formula (25-1) and the general formula (25-2) By reacting with a compound having a bromo group, the desired carboxylic acid derivative represented by the general formula (25) can be obtained.

A carboxylic acid derivative represented by the general formula (22), which is a raw material for synthesizing the compound represented by the general formula (6), wherein a hydrogen atom on an aromatic ring is substituted by a fluorine atom (general formula (22) Compound represented by 22-8)
Can be synthesized, for example, by the following method.

[0109]

Embedded image

(In the formula, X and q represent the same contents as in the general formula (5).) That is, 2-fluoro-4-hydroxybenzonitrile represented by the formula (22-5) and the general formula (22- The compound is reacted with an alcohol derivative having a bromo group represented by 2) to obtain a compound represented by the general formula (22-6), and then the cyano group is hydrolyzed to give a compound represented by the general formula (22-7). To obtain the desired compound. By reacting this compound with (meth) acrylic acid while distilling off water in the presence of an acid catalyst, the desired compound represented by the general formula (22-
The carboxylic acid derivative represented by 8) can be obtained.

A carboxylic acid derivative represented by the general formula (22), which is a raw material for synthesizing the compound represented by the general formula (6), wherein a hydrogen atom on an aromatic ring is substituted by a methoxy group (a compound represented by the general formula (22) 22-12) can be synthesized, for example, by the following method.

[0112]

Embedded image

(In the formula, X and q represent the same contents as in the general formula (6), and Me represents a methyl group.)
That is, a compound represented by the general formula (22-10) is obtained by reacting methyl vanillate represented by the formula (22-9) with an alcohol derivative having a bromo group represented by the general formula (22-2). Then, the methyl ester is hydrolyzed to obtain a compound represented by the general formula (22-11). By reacting this compound with (meth) acrylic acid while distilling off water in the presence of an acid catalyst, the desired carboxylic acid derivative represented by the general formula (22-12) can be obtained.

A carboxylic acid derivative represented by the general formula (22), which is a raw material for synthesizing the compound represented by the general formula (6), wherein a hydrogen atom on an aromatic ring is substituted by a methyl group (general formula (22) Compounds represented by 22-16)
Can be synthesized, for example, by the following method.

[0115]

Embedded image

(In the formula, X and q represent the same contents as in the general formula (5).) That is, 4-hydroxy-2-methylbenzonitrile represented by the formula (22-13) and the general formula (22- After reacting the alcohol derivative having a bromo group represented by 2) to obtain a compound represented by the general formula (22-14), the cyano group is further hydrolyzed to give a compound represented by the general formula (22-15). To obtain the desired compound. By reacting this compound with (meth) acrylic acid while distilling off water in the presence of an acid catalyst, the desired compound represented by the general formula (2)
The carboxylic acid derivative represented by 2-16) can be obtained.

In the general formula (23) which is a raw material for synthesizing the compound represented by the general formula (6), Y3 is -C≡C-, p is 1, and the hydrogen atom on the aromatic ring is fluoro. Group-substituted alcohol derivative (general formula (23-
Compound (8)) can be synthesized, for example, by the following method.

[0118]

Embedded image

(Wherein m represents the same content as in the general formula (6). Base represents a base, and Ph represents
Represents a phenyl group. That is, after protecting the hydroxyl group of 4-bromo-2-fluorophenol represented by the formula (23-1) using tetrapyranyl ether, 2-methyl-3-butyne-2-protection was carried out in the presence of a palladium catalyst. The acetylene derivative represented by the formula (23-4) is obtained by reacting with all and further removing the t-butyl alcohol group. An acetylene derivative represented by the formula (23-4) and a 4-iodophenol represented by the formula (23-5) are subjected to a coupling reaction in the presence of a palladium catalyst to give a compound represented by the formula (23-6). Obtain the compound. Equation (2
The desired alcohol derivative represented by the general formula (23-8) is obtained by reacting the compound represented by 3-6) with an alcohol derivative having a bromo group represented by the general formula (23-7). Can be.

In the general formula (23), which is a raw material for synthesizing the compound represented by the general formula (6), Y3 is -CH2CH
An alcohol derivative (compound represented by the general formula (23-9)) in which 2-, p is 1, and a hydrogen atom on an aromatic ring is substituted with a fluoro group is synthesized by, for example, the following method. can do.

[0121]

Embedded image

(In the formula, m represents the same content as in the general formula (6).) By reducing the triple bond of the alcohol derivative represented by the general formula (23-8), the compound represented by the general formula (2)
An alcohol derivative represented by 3-9) can be obtained. In the general formula (23), which is a raw material for synthesizing the compound represented by the general formula (6), an alcohol derivative in which Y3 is —C (＝ O) O— and p is 1 (general formula ( Compound represented by 23-12))
Can be synthesized, for example, by the following method.

[0123]

Embedded image

(In the formula, m represents the same content as in the general formula (6). DCC represents dicyclohexylcarbodiimide, and Base represents a base.) That is, it is represented by the formula (23-9). The compound represented by the general formula (23-10) is obtained by reacting 4-hydroxybenzoic acid with an alcohol derivative having a bromo group represented by the general formula (23-7). A compound represented by the general formula (23-12) obtained by reacting a compound represented by the general formula (23-10) with a compound represented by the formula (23-11) using a condensing agent such as dicyclohexylcarbodiimide. Can be obtained.

In the general formula (23), which is a raw material for synthesizing the compound represented by the general formula (6), an alcohol derivative wherein Y3 is a single bond and p is 1 (general formula (23-1
Compound 5) can be synthesized, for example, by the following method.

[0126]

Embedded image

(In the formula, m represents the same content as in the general formula (6).)
After protecting 4′-biphenol with tetrapyranyl ether under an acid catalyst, the compound represented by the general formula (23-14) and the alcohol derivative having a bromo group represented by the general formula (23-7) are converted into By reacting, the desired alcohol derivative represented by the general formula (23-15) can be obtained.

Next, the compound represented by formula (7) will be described. The compound represented by the general formula (7) is
For example, it can be synthesized by the following method.

[0129]

Embedded image

(Wherein X, Y3, q, m and p represent the same contents as in the case of the general formula (7).
Represents dicyclohexylcarbodiimide. That is, an alcohol derivative represented by the general formula (23) and 1.2 equivalents of the carboxylic acid derivative represented by the general formula (26) are converted to DCC (dicyclohexylcarbodiimide).
An esterification reaction is carried out using a condensing agent such as the above, and then an esterification target product is obtained. Then, a precursor represented by the general formula (27) is synthesized by subjecting a hydroxyl group to deprotection reaction using 10% hydrochloric acid. Subsequently, a precursor represented by the general formula (26) and 1.5 equivalents of the precursor represented by the general formula (2)
The desired compound represented by general formula (7) can be synthesized by subjecting the carboxylic acid derivative represented by 8) to an esterification reaction using a condensing agent such as DCC (dicyclohexylcarbodiimide).

The carboxylic acid derivative represented by the general formula (26), which is a raw material for synthesizing the compound represented by the general formula (7), can be synthesized, for example, by the following method.

[0132]

Embedded image

(In the formula, X and q represent the same contents as in the general formula (7).) That is, 4 represented by the formula (26-1)
After reacting -hydroxybenzaldehyde with an alcohol derivative having a bromo group represented by the general formula (22-2), nuclear reduction is performed to obtain a compound represented by the general formula (26-4). Further, the compound represented by the general formula (26-4) was distilled off in the presence of an acid catalyst while distilling off water.
By reacting with (meth) acrylic acid and then oxidizing the aldehyde group, the desired carboxylic acid derivative represented by the general formula (26) can be obtained.

The carboxylic acid derivative represented by the general formula (28), which is a raw material for synthesizing the compound represented by the general formula (7), can be synthesized, for example, by the following method.

[0135]

Embedded image

(In the formula, R and q represent the same contents as in the general formula (7).) That is, 4 represented by the formula (28-1)
-Hydroxycyclohexylcarboxylic acid and a compound represented by the general formula (28)
By reacting with a compound having a bromo group represented by -2), the desired carboxylic acid derivative represented by the general formula (28) can be obtained.

Next, the compound represented by formula (8) will be described. The compound represented by the general formula (8) is
For example, it can be synthesized by the following method.

[0138]

Embedded image

(Where X, Y3, q, m and p represent the same contents as in the case of the general formula (8).
Represents dicyclohexylcarbodiimide, Base
Represents a base. That is, by reacting the alcohol derivative represented by the general formula (29) with (meth) acrylic acid in the presence of an acid catalyst while distilling off water,
A phenol derivative represented by the general formula (30) is obtained.
Next, the compound represented by the general formula (32) is obtained by reacting the alcohol derivative represented by the general formula (31) with phosphorus tribromide. The compound represented by the general formula (34) is reacted with the carboxylic acid derivative represented by the general formula (33) using a condensing agent such as dicyclohexylcarbodiimide to obtain a compound represented by the general formula (34). The compound represented by the general formula (34) and the compound represented by the general formula (3)
The desired compound represented by the general formula (8) can be synthesized by reacting the compound represented by the formula (0).

Examples of the alcohol derivative represented by the general formula (29) as a raw material for synthesizing the compound represented by the general formula (8) include, for example, the following general formulas (29-1) and (29-2) The compounds represented can be mentioned.

[0141]

Embedded image (In the formula, q represents the same content as in the case of the general formula (8).)

Examples of the carboxylic acid derivative represented by the general formula (33) as a raw material for synthesizing the compound represented by the general formula (8) include the following compounds.

Embedded image (In the formula, R and q represent the same contents as in the case of the general formula (8).)

In the method for producing the compound represented by the general formula (8), the compound represented by the general formula (30-1) is replaced with the compound represented by the general formula (30).

[0144]

Embedded image (Wherein X1 and q represent the same contents as in the case of the general formula (8)), and the compound represented by the general formula (33) is used instead of the compound represented by the general formula (33).
-5)

[0145]

Embedded image (Wherein X2 and q represent the same contents as in the case of the general formula (8)) by combining the use of the compounds represented by the general formulas (35) to (37)

[0146]

Embedded image

(Wherein, X represents a hydrogen atom or a methyl group, Y3 is a single bond, —OC (＝ O) —, —C (=
O) represents a linking group selected from the group consisting of O-, -C≡C- and -CH2CH2-, q and n each independently represent an integer of 1 to 20, and m represents 3 to 16 Represents an integer, and p represents an integer of 0 or 1. Also,
The 1,4-cyclohexylene group and the 1,4-phenylene group each independently represent a cyano group, a halogen atom,
And may be substituted with one or more substituents selected from the group consisting of an alkyl group, an alkoxy group and an alkanoyl group. ) Can also be synthesized.

The compound represented by the general formula (30-1), which is a raw material for synthesizing the compound represented by the general formula (8), can be synthesized, for example, by the following method.

[0149]

Embedded image

(In the formula, X and q have the same contents as in the case of the general formula (8).) That is, the hydroquinone represented by the formula (38) and the alcohol derivative represented by the general formula (30-2) To obtain a compound represented by the general formula (30-3). Further, by subjecting the compound represented by the general formula (30-3) to nuclear reduction, the compound represented by the general formula (30) is obtained.
After obtaining the cyclohexane derivative represented by the formula (4), by reacting with (meth) acrylic acid while distilling off water in the presence of an acid catalyst, the desired compound represented by the general formula (30-
The compound represented by 1) can be obtained.

Next, the compound represented by formula (9) will be described. The compound represented by the general formula (9) is
For example, it can be synthesized by the following method.

[0152]

Embedded image

(Where X, Y3, Y4, q, m and p
Represents the same content as in the general formula (9). DCC
Represents dicyclohexylcarbodiimide, and represents Bas
e represents a base. That is, the compound represented by the general formula (40) is obtained by reacting the alcohol derivative represented by the general formula (39) with phosphorus tribromide. A compound represented by the general formula (40) is reacted with a carboxylic acid derivative represented by the general formula (41) using a condensing agent such as dicyclohexylcarbodiimide to obtain a compound represented by the general formula (42)
To obtain a compound represented by the formula: By reacting the compound represented by the general formula (42) with the compound represented by the general formula (43), the desired compound represented by the general formula (9) can be synthesized.

Next, the compound represented by formula (11) will be described. The compound represented by the general formula (11) can be synthesized, for example, by the following method.

[0155]

Embedded image

(Where X, q and m are the same as those of the general formula (11)
Represents the same content as in DCC represents dicyclohexylcarbodiimide, and Base represents a base. That is, an alcohol compound represented by the general formula (44) is reacted with a carboxylic acid derivative represented by the general formula (45) using a condensing agent such as dicyclohexylcarbodiimide to give a compound represented by the general formula (46). obtain. By reacting the compound of the general formula (46) with the compound of the general formula (43), the desired compound of the general formula (11) can be obtained.

Next, the compound represented by formula (12) will be described. The compound represented by the general formula (12) can be synthesized, for example, by the following method.

[0158]

Embedded image

(Wherein X, q and m represent the general formula (12)
Represents the same content as in DCC represents dicyclohexylcarbodiimide, and Base represents a base. That is, a compound represented by the general formula (49) is reacted with a compound represented by the general formula (47) using a condensing agent such as dicyclohexylcarbodiimide to obtain a compound represented by the general formula (49). . next,
The compound represented by the general formula (50), that is, the compound represented by the general formula (12) can be obtained by removing the tetrapyranyl ether protecting group of the compound represented by the general formula (49).

By the above-described synthesis method, a compound having an epoxy group, a compound having a vinyloxy group, and a compound having a maleimide group can also be synthesized.

[0161]

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

Example 1 Synthesis of Liquid Crystalline Acrylate Compound (1) 6.3 g of pyridinium paratoluenesulfonic acid was added to a solution of 48.0 g of 4-bromo-2-fluorophenol and 250 m of dichloromethane, and then cooled in an ice bath. Then, a solution of 42.0 g of dihydropyran and 75 ml of dichloromethane was gradually dropped from the dropping funnel over about 1 hour. After completion of the dropwise addition, the reaction temperature was set to room temperature, and the mixture was stirred for about 4 hours. After confirming the reaction by gas chromatography and terminating the reaction, it was washed once with 250 ml of a saturated aqueous sodium hydrogen carbonate solution and once with 250 ml of a saturated saline solution. After dehydrating the organic layer from anhydrous magnesium sulfate, the solvent was distilled off under reduced pressure to obtain the compound of formula (s-1)

[0163]

Embedded image 67.0 g of the compound represented by were obtained.

1H-NMR (300 MHz, CDCl
3); δ = 1.50 to 2.08 (m, 6H), 3.56
To 3.63 (m, 1H), 3.84 to 3.92 (m, 1H)
H) 5.38-5.40 (m, 1H), 7.00-
7.32 (m, 3H)

(S-1) Compound 3 obtained by the above synthesis
4.4 g, trimethylsilylacetylene 14.7 g, dimethylformimide 120 ml and triethylamine 45
1.73 g of tetrakistriphenylphosphine palladium and 0.57 g of copper iodide were added to the ml solution, and heated at 80 ° C. for 8 hours with stirring. After confirming the reaction by thin layer chromatography (hexane: dichloromethane = 2: 1) and terminating the reaction, the reaction solution was diluted with 300 ml of ethyl acetate. Saturated aqueous ammonium chloride solution 20
It was washed once with 0 ml and twice with 200 ml of saturated saline.
The organic layer was dehydrated from anhydrous magnesium sulfate, the solvent was distilled off under reduced pressure, and the crude product was purified by column chromatography (hexane: dichloromethane = 2: 1) to obtain the compound of the formula (s)
-2)

[0166]

32.8 g of the compound represented by the following formula were obtained.

After cooling a solution of 34.5 g of 75% tetra-n-butylammonium fluoride and 60 ml of dichloromethane in an ice bath, a solution of 30.7 g of the compound represented by the above formula (s-2) and 60 ml of dichloromethane was added. The solution was gradually dropped from the dropping funnel over about 1 hour. After completion of the dropwise addition, the reaction temperature was raised to room temperature, and the mixture was stirred for about 3 hours. After confirming the reaction by thin-layer chromatography (toluene) and terminating the reaction, it was washed twice with 150 ml of saturated saline.
After dehydrating the organic layer from anhydrous magnesium sulfate and evaporating the solvent under reduced pressure, the crude product was purified by column chromatography (toluene) to obtain the compound of formula (s-3)

[0168]

Embedded image 22.1 g of the compound represented by were obtained.

1H-NMR (300 MHz, CDCl
3); δ = 1.50 to 2.09 (m, 6H), 3.01
(S, 1H), 3.60 to 3.65 (m, 1H), 3.
85 to 3.93 (m, 1H), 5.46 to 5.48
(M, 1H), 7.10 to 7.35 (m, 3H)

(S-3) Compound 2 obtained by the above synthesis
To a solution of 2.5 g, 19.9 g of 4-bromophenol, 120 ml of dimethylformimide and 35 ml of triethylamine were added tetrakistriphenylphosphine palladium.
While adding 25 g and copper iodide 0.41 g and stirring,
Heat at 90 ° C. for 12 hours. After confirming the reaction by thin layer chromatography (toluene: ethyl acetate = 10: 1) and terminating the reaction, the reaction solution was diluted with 200 ml of ethyl acetate. 150 ml of saturated ammonium chloride aqueous solution
And washed twice with 150 ml of a saturated saline solution. After the organic layer was dehydrated from anhydrous magnesium sulfate and the solvent was distilled off under reduced pressure, the crude product was purified by column chromatography (toluene: ethyl acetate = 10: 1) to obtain the compound of formula (s-4)

[0171]

Embedded image 17.5 g of the compound represented by the formula was obtained.

1H-NMR (300 MHz, CDCl
3); δ = 1.60 to 2.06 (m, 6H), 3.62
-3.66 (m, 1H), 3.90-3.98 (m, 1H)
H), 5.11 (s, 1H), 5.47-5.49
(M, 1H), 6.70-7.41 (m, 7H)

(S-4) Compound 1 obtained by the above synthesis
Potassium carbonate was added to a solution of 4.4 g, 6-bromohexanol 16.7 g and dimethylformimide 140 ml.
7 g was added and heated at 85 ° C. for about 4 hours with stirring. Thin layer chromatography (toluene: ethyl acetate =
After confirming the reaction from 4: 1) and terminating the reaction, the reaction solution was diluted with 200 ml of ethyl acetate. It was washed three times with 100 ml of saturated saline. After the organic layer was dehydrated from anhydrous magnesium sulfate and the solvent was distilled off under reduced pressure, the crude product was subjected to column chromatography (toluene: ethyl acetate = 4:
1). After evaporating the solvent under reduced pressure, the residue was purified by recrystallization (chloroform: hexane = 1: 3) to obtain the compound of the formula (s-
5)

[0174]

Embedded image 17.0 g of the compound represented by were obtained.

White crystals, melting point: 96.5-97.0 ° C. 1H-NMR (300 MHz, CDCl 3); δ = 1.
32 to 2.12 (m, 14H), 3.61 to 3.69
(M, 3H), 3.88 to 3.99 (m, 3H), 5.
46-5.48 (m, 1H), 6.84-7.45
(M, 7H)

69.0 g of 4-hydroxybenzoic acid, 6-
A mixture of 68.0 g of chloro-1-hexanol, 42.0 g of sodium hydroxide, 12.5 g of potassium iodide, 220 ml of ethanol and 220 ml of water was heated with stirring at 80 ° C. for 32 hours. After cooling the obtained reaction solution to room temperature, 500 ml of saturated saline was added to the reaction solution,
Dilute hydrochloric acid was added until the aqueous layer of the reaction solution became weakly acidic. The reaction product was extracted by adding 500 ml of ethyl acetate to the reaction solution. After the organic layer was washed with water, the extraction solvent was distilled off under reduced pressure and further air-dried to obtain the compound of the formula (s-6)

[0177]

Embedded image 111.5 g of a compound represented by the formula was obtained.

Compound 55.0 represented by the formula (s-6)
g, 67.0 g of acrylic acid, p-toluenesulfonic acid 1
3.5 g, hydroquinone 3.0 g, toluene 210 ml,
A mixture consisting of 90 ml of n-hexane and 130 ml of tetrahydrofuran was heated and stirred, and refluxed for 6 hours while distilling off generated water. After cooling the reaction to room temperature,
500 ml of saturated saline and 400 ml of ethyl acetate were added to the reaction solution to extract the reaction product. After washing the organic layer with water, the organic solvent was distilled off under reduced pressure to obtain 115.5 g of a crude product. Next, this crude product was recrystallized twice from a mixture of 200 ml of n-hexane and 50 ml of toluene, whereby the formula (s-7) was obtained.

[0179]

Embedded image 55.5 g of the compound represented by the formula was obtained.

1H-NMR (300 MHz, CDCl
3); δ = 1.42 to 1.87 (m, 8H), 4.14
(T, 2H), 4.38 (t, 2H), 5.84 (d,
1H), 6.11 (d, 1H), 6.43 (d, 1
H), 6.94 (d, 2H), 8.06 (d, 2H)

A solution of 5.0 g of the (s-5) compound obtained in the above synthesis, 4.6 g of the (s-7) compound of 4- (6-acryloyloxyhexyloxy) benzoic acid and 150 ml of tetrahydrofuran was added to a solution of 1- Ethyl-3- (3-dimethylaminopropyl) carbodiimide hydrochloride 3.0 g
And 1.92 g of 4-dimethylaminipyridine, and the mixture was reacted at room temperature for about 3 days with stirring. After confirming the reaction by thin layer chromatography (toluene: ethyl acetate = 4: 1) and terminating the reaction, 300 ml of ethyl acetate was added.
The reaction was diluted using. Washed twice with 150 ml of saturated saline. The organic layer is dehydrated from anhydrous magnesium sulfate,
After evaporating the solvent under reduced pressure, the crude product was separated by column chromatography (toluene: ethyl acetate = 4: 1) to obtain the compound of the formula (s-8)

[0182]

Embedded image 7.5 g of a compound represented by the formula was obtained.

10% was added to a solution of 6.6 g of the compound (s-8) obtained in the above synthesis and 60 ml of tetrahydrofuran.
Add 35 ml of hydrochloric acid aqueous solution and stir at room temperature for about 4 hours.
A time reaction was performed. After confirming the reaction by thin layer chromatography (toluene: ethyl acetate = 4: 1) and terminating the reaction, the reaction solution was diluted with 200 ml of ethyl acetate. It was washed twice with 100 ml of saturated saline. After the organic layer was dehydrated from anhydrous magnesium sulfate and the solvent was distilled off under reduced pressure, the crude product was purified by recrystallization (ethanol) to obtain the compound of the formula (s-9)

[0184]

Embedded image 5.0 g of a liquid crystalline acrylate compound represented by the formula was obtained.

The phase transition temperature of the liquid crystalline acrylate compound of the formula (s-9) was 78 ° C. for the isotropic liquid phase-nematic phase and 74 ° C. for the nematic phase-crystal phase as monotropic. 1H-NMR (300 MHz, CDCl3); δ = 1.
42 to 1.81 (m, 16H), 3.95 to 4.33
(M, 8H), 5.81 (d, 1H), 6.12 (d
d, 1H), 6.41 (d, 1H), 6.83-7.3.
0 (m, 7H), 7.44 (d, 2H), 7.98
(D, 2H)

Example 2 Synthesis of Liquid Crystalline Acrylate Compound (2) 45.0 g of 6-bromohexanol and dichloromethane 2
After adding 6.3 g of pyridinium paratoluenesulfonic acid to a 50 m solution, 42.0 g of dihydropyran was added in an ice bath.
And a solution of 75 ml of dichloromethane were gradually dropped from the dropping funnel over about 1 hour. After completion of the dropwise addition, the reaction temperature was set to room temperature, and the mixture was stirred for about 4 hours. After confirming the reaction by gas chromatography and terminating the reaction, the reaction was washed once with 250 ml of a saturated aqueous sodium hydrogen carbonate solution, and washed once with 250 ml of a saturated saline solution.
Washed twice. After dehydrating the organic layer from anhydrous magnesium sulfate, the solvent was distilled off under reduced pressure to obtain the compound of the formula (s-10)

[0187]

Embedded image 65.5 g of the compound represented by the formula was obtained.

A solution of 18.5 g of the compound (s-10) obtained in the above synthesis and 10 ml of ethanol was added through a dropping funnel to 10.14 g of 4-hydroxybenzoic acid, 1.75 g of potassium iodide, 30 ml of ethanol and 17% water. While stirring into a mixture consisting of 36.0 g of aqueous sodium oxide solution,
It was added dropwise at 80 ° C. for about 20 minutes. After the completion of the dropwise addition, the reaction was further performed at a reaction temperature of 80 ° C. for 7.5 hours. After confirming the reaction by thin-layer chromatography (toluene: ethyl acetate = 1: 1), the reaction was terminated, and the resulting reaction solution was cooled to room temperature. Dilute hydrochloric acid was added until it became weakly acidic. The reaction product was extracted by adding 500 ml of ethyl acetate to the reaction solution. After the organic layer was washed with water, the extraction solvent was distilled off under reduced pressure and further air-dried to obtain the compound represented by the formula (s-11).

[0189]

Embedded image 20.0 g of a compound represented by the formula was obtained.

1H-NMR (300 MHz, CDCl
3); δ = 1.40-1.87 (m, 14H), 3.3
8-3.91 (m, 4H), 4.02 (t, 2H),
4.59 (m, 1H), 6.92 (d, 2H), 8.0
6 (d, 2H)

6.8 g of the (s-11) compound obtained in the above synthesis and the (s-9) compound synthesized in Example 1 were used.
To a solution of 1 g and 150 ml of tetrahydrofuran are added 4.1 g of 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide hydrochloride and 4-dimethylaminipyridine.
The reaction was carried out at room temperature for about 2 days while adding 6 g and stirring. Thin layer chromatography (toluene: ethyl acetate =
After confirming the reaction from 4: 1) and terminating the reaction, the reaction solution was diluted with 300 ml of ethyl acetate. Washed twice with 150 ml of saturated saline. After the organic layer was dehydrated from anhydrous magnesium sulfate and the solvent was distilled off under reduced pressure, the crude product was subjected to column chromatography (toluene: ethyl acetate = 4:
Separated from 1), formula (s-12)

[0192]

Embedded image 9.6 g of a compound represented by the formula was obtained.

10% was added to a solution of 9.6 g of the compound (s-12) obtained in the above synthesis and 80 ml of tetrahydrofuran.
Add 35 ml of hydrochloric acid aqueous solution and stir at room temperature for about 4 hours.
A time reaction was performed. After confirming the reaction by thin layer chromatography (toluene: ethyl acetate = 4: 1) and terminating the reaction, the reaction solution was diluted with 200 ml of ethyl acetate. It was washed twice with 100 ml of saturated saline. The organic layer was dried over anhydrous magnesium sulfate, and the solvent was distilled off under reduced pressure.
The obtained crude product was separated by column chromatography (toluene: ethyl acetate = 4: 1) and then purified by recrystallization (ethanol) to obtain the compound of the formula (s-13)

[0194]

Embedded image 7.8 g of a liquid crystal acrylate compound represented by the formula was obtained.

The phase transition temperature of the liquid crystal acrylate compound of the formula (s-13) was 45 ° C. for the crystal phase-nematic phase and 111 ° C. for the nematic phase-isotropic liquid phase. 1H-NMR (300 MHz, CDCl3); δ = 1.
43 to 1.84 (m, 24H), 3.64 to 4.33
(M, 12H), 5.80 (d, 1H), 6.12 (d
d, 1H), 6.40 (d, 1H), 6.85 to 7.4.
6 (m, 11H), 7.98 (d, 2H), 8.14
(D, 2H)

[0196]

The compound of the present invention is a novel monofunctional polymerizable liquid crystal which is considered to be useful as a component of a liquid crystal material by exhibiting a low temperature at which a liquid crystal phase is exhibited and exhibiting a wider liquid crystal phase range, particularly a nematic phase range. Compound. Therefore, the compound of the present invention is, for example, a phase difference plate, a polarizing plate, a polarizing prism, a waveguide, a piezoelectric element, a non-linear optical element, various optical filters, a pigment utilizing selective reflection of a cholesteric liquid crystal phase, and a coating agent such as an optical fiber. It is very useful for the application of.

 ──────────────────────────────────────────────────続 き Continued on the front page F term (reference) 2H049 BA02 BA06 BA43 BC22 2H091 FA08X FA08Z FA11X FA11Z FB02 LA30 4H006 AA01 AB64 BJ50 BN10 BP30 4J100 AL08P AT08P BA02P BA03P BA15P BA16P BB07P BC43P BC53P CA01

Claims (11)

[Claims] 1. General formula (1) P-S1-A-S2-M (1) (P represents a polymerizable functional group, and A is selected from the group consisting of an aromatic ring, an alicyclic ring, a heterocyclic ring and a condensed ring. M represents a mesogen moiety having 2 to 16 identical or different rings selected from the group consisting of an aromatic ring, an alicyclic ring, a heterocyclic ring and a condensed ring, and S1 has a main chain of carbon, oxygen, silicon And a connecting chain composed of at least one kind of 7 to 18 atoms selected from sulfur and S2, wherein the main chain is composed of at least one kind of 5 to 18 atoms selected from carbon, oxygen, silicon and sulfur. P is connected to ring A via linking chain S1, and M
Is bonded to ring A via a linking chain S2. ),
A polymerizable liquid crystal compound having one polymerizable functional group in one molecule. 2. The polymerizable liquid crystal compound according to claim 1, having an alkylene chain in the connecting chains S1 and S2 of the general formula (1). 3. In the connecting chains S1 and S2 of the general formula (1),
The polymerizable liquid crystal compound according to claim 2, wherein the compound has at least one kind of bond selected from an ether bond, a thioether bond, and an ester bond. 4. The connecting chain S1 in the general formula (1) is an oxyalkylene chain and / or the general formula (2). (Wherein m represents an integer of 4 to 15), wherein the polymerizable liquid crystal compound according to any one of claims 1 to 3. 5. The connecting chain S2 in the general formula (1) is an oxyalkylene chain and / or a general formula (3). The polymerizable liquid crystal compound according to claim 1, wherein n is an integer of 2 to 15. 5. 6. The ring A in formula (1) and / or at least one ring selected from the group consisting of halogen, cyano, hydroxyl, alkyl, alkoxy and alkanoyl groups in the mesogen moiety M. Claims 1 to 3 having one substituent
6. The polymerizable liquid crystal compound according to any one of 5. 7. The mesogen moiety M in the general formula (1) is an aromatic ring,
The polymerizable liquid crystal compound according to any one of claims 1 to 6, having 2 to 8 identical or different rings selected from the group consisting of an alicyclic ring, a heterocyclic ring, and a condensed ring. 8. The polymerizable liquid crystal compound according to claim 7, wherein the mesogen moiety M in the general formula (1) has a tranbenzoate, a biphenylbenzoate or a tolan skeleton. 9. The polymerizable liquid crystal compound according to claim 1, wherein the ring A in the general formula (1) is an aromatic ring or an alicyclic ring. 10. The polymerizable liquid crystal compound according to claim 9, wherein the alicyclic ring A in the general formula (1) is a cyclohexane ring. 11. The polymerizable functional group P of the general formula (1) is one group selected from the group consisting of an acryloyloxy group, a methacryloyloxy group, an epoxy group, a vinyloxy group and a maleimide group. The polymerizable liquid crystal compound according to any one of the above.