JP5888544B2 - Polymerizable liquid crystal compound - Google Patents

Description

  The present invention relates to a polymerizable compound, a polymerizable liquid crystal composition containing the compound, and an optical anisotropic body using the polymerizable composition.

  Polymerizable compounds are used as various optical members and printing original plate materials. In these applications, after a polymerizable material is applied on a substrate, a patterned film can be obtained by polymerizing by a method such as laser beam irradiation or mask exposure. To meet the optical properties, pattern resolution, polymerization rate, solubility, melting point, glass transition temperature, polymer film transparency, mechanical strength, surface hardness, heat resistance and light resistance normally required as film physical properties Two or more kinds of polymerizable compounds are mixed and used as a composition having desired physical properties. At that time, the polymerizable compound to be used is required to bring good physical properties to the mixture without adversely affecting other properties.

  When a patterned optical film having a large difference in refractive index anisotropy used for a liquid crystal display is produced using the polymerizable liquid crystal composition, the polymerizable liquid crystal composition has a large refractive index anisotropy and a wide liquid crystal phase. A temperature range and high storage stability are required. At the same time, a film obtained by polymerizing the polymerizable liquid crystal composition needs to have high pattern resolution, high mechanical strength and heat resistance, and less haze and white unevenness. Conventionally, a method for obtaining an oriented liquid crystal film having a high pattern resolution has been reported. According to this method, it is necessary to mix a non-polymerizable compound in order to ensure the liquid crystallinity of the composition. It can be easily imagined that the mechanical strength and heat resistance of the film deteriorated. In addition, a method of adding a polymerization retarder to improve pattern resolution has been reported. However, since the polymerization retarder does not exhibit liquid crystallinity, the liquid crystallinity of the composition is lowered, resulting in a production temperature margin. It is expected to narrow (see Patent Document 1). An example of producing a patterned retardation film having different retardation regions using a polymerizable liquid crystal compound having a photoisomerization site has been reported, but there is no detailed description on the physical properties and appearance of the obtained film. (Patent Document 2). Moreover, although the polymeric compound which has a tolan structure similar to this invention compound is also reported, there is no description regarding the physical property and external appearance of the obtained film (patent document 3). Moreover, although there exists a report regarding preparation of a high quality patterned retardation film, there is no description of the haze value of the obtained film, white nonuniformity, etc. (patent document 4 and patent document 5).

JP 2000-17003 A Special table 2008-508543 gazette US Pat. No. 6,514,578 JP 2009-276664 A JP 2009-276665 A

  The problem to be solved by the present invention is that the liquid crystal composition has a large refractive index anisotropy, a wide liquid crystal phase temperature range and a high storage stability, and by polymerizing the liquid crystal composition, the pattern resolution is high and the heat resistance It is to provide a polymerizable compound that provides a polymer film that is high and has little haze and white unevenness.

  As a result of various studies on the polymerizable compound, the present inventors have found that a polymerizable compound having a specific structure can solve the above-mentioned problems, and have completed the present invention.

  That is, the present invention relates to the general formula (I)

Wherein P is a reactive group represented by the following formula (P-1) to formula (P-15)

And S ¹ and S ² are each independently one —CH ₂ — or two or more non-adjacent —CH ₂ — are each independently replaced with —O—. Represents an alkylene group having 1 to 20 carbon atoms, and X ¹ and X ² are each independently —O—, —S—, —OCH ₂ —, —CH ₂ O—, —CO—, —COO. -, - OCO -, - CO -S -, - S-CO -, - OCO-O -, - CO-NH -, - NH-CO -, - SCH 2 -, - CH 2 S -, - _{CF 2 O -, - OCF 2} -, - CF 2 S -, - SCF 2 -, - CH 2 CH 2 -, - CH 2 CF 2 -, - CF 2 CH 2 -, - CF 2 CF 2 -, - CH = CH—COO—, —CH═CH—OCO—, —COO—CH═CH—, —OCO—CH═CH—, —COO—CH ₂ CH ₂ —, —OCO—CH ₂ CH ₂ —, —CH ₂ CH ₂ —COO—, —CH ₂ CH ₂ —OCO—, —COO—CH ₂ —, —OCO—CH ₂ —, —CH ₂ — COO—, —CH ₂ —OCO—, —CY ¹ ═CY ² —, —C≡C— or a single bond (wherein Y ¹ and Y ² are each independently a hydrogen atom, from 1 carbon atom) 12 represents an alkyl group, a fluorine atom, a chlorine atom or a cyano group.), N1 and n2 each independently represent 0, ¹ , 2, 3 or 4, and A ¹ and A ⁴ each independently represent 1, 4-phenylene group, naphthalene-2,6-diyl group, 1,4-cyclohexylene group, 1,4-cyclohexenylene group, 1,4-bicyclo [2.2.2] octylene group, decahydronaphthalene- 2,6-diyl group or 1,2,3,4-tetrahydrona Talen-2,6-diyl group, pyridine-2,6-diyl group, pyrimidine-2,5-diyl group, 1,3-dioxane-2,5-diyl group are represented, but these groups are unsubstituted. May be substituted by a fluorine atom, a chlorine atom, a cyano group, a nitro group, an alkyl group having 1 to 7 carbon atoms, an alkoxy group having 1 to 7 carbon atoms, or an alkanoyl group having 1 to 7 carbon atoms. In these alkyl groups, alkoxy groups or alkanoyl groups, one or more hydrogen atoms may be replaced by fluorine atoms or chlorine atoms, and when a plurality of A ¹ and / or A ⁴ are present, they are the same. Z ¹ and Z ² may each independently represent —OCH ₂ —, —CH ₂ O—, —COO—, —OCO—, —CO—S—, —S—CO—, -CO-NH-, _{NH-CO -, - SCH 2} -, - CH 2 S -, - CF 2 O -, - OCF 2 -, - CF 2 S -, - SCF 2 -, - CH 2 CH 2 -, - CH 2 CF 2 _{-, - CF 2 CH 2 -} , - CF 2 CF 2 -, - CH = CH-COO -, - CH = CH-OCO -, - COO-CH = CH -, - OCO-CH = CH -, - COO _{-CH 2 CH 2 -, - OCO} -CH 2 CH 2 -, - CH 2 CH 2 -COO -, - CH 2 CH 2 -OCO -, - COO-CH 2 -, - OCO-CH 2 -, - CH ₂ —COO—, —CH ₂ —OCO—, —CY ³ ═CY ⁴ —, —C≡C— or a single bond (wherein Y ³ and Y ⁴ are each independently a hydrogen atom or carbon atom number) 1 to 12 alkyl groups, a fluorine atom, a chlorine atom or a cyano group is represented. ), A plurality of Z ¹ and / or Z ² may be the same or different, m 1 and m 2 each independently represents 0, 1 or 2, and l represents 0 or 1 , A ² and A ³ each independently represents a 1,4-phenylene group in which one —CH═ or two non-adjacent —CH═ may be replaced by —N═, One or more hydrogen atoms in the 4-phenylene group are each independently substituted with a fluorine atom, a chlorine atom, a cyano group, a nitro group, or an alkyl group having 1 to 8 carbon atoms, an alkoxy group, or an alkanoyl group. The alkyl group, alkoxy group or alkanoyl group may be further substituted with a fluorine atom or a chlorine atom, and R represents a hydrogen atom or an alkyl group having 1 to 12 carbon atoms. May be unsubstituted , A fluorine atom, a chlorine atom, may be substituted by a cyano group, also one -CH 2 in the alkyl group _- or nonadjacent two or more -CH 2 _- are each independently -O- , -S- may be substituted. And a polymerizable liquid crystal composition using the compound.

  The polymerizable compound of the present invention is useful as a component of the polymerizable composition because it exhibits a large refractive index anisotropy, a wide liquid crystal phase temperature range, and high storage stability. In addition, by polymerizing a composition containing the polymerizable compound of the present invention, a polymer film having high pattern resolution, high heat resistance, and less haze / white unevenness can be obtained. Useful.

  In the general formula (1), P represents a polymerizable group represented by the formula (P-1) to the formula (P-15), and these polymerizable groups are radical polymerization, radical addition polymerization, cationic polymerization, and anionic polymerization. To cure. In particular, when ultraviolet polymerization is performed as a polymerization method, the formula (P-1), formula (P-2), formula (P-3), formula (P-4), formula (P-5), formula (P -7), formula (P-11), formula (P-13) or formula (P-15) are preferred, and formula (P-1), formula (P-2), formula (P-7), formula (P P-11) or formula (P-13) is more preferred, and formula (P-1) or formula (P-2) is particularly preferred.

S ¹ and S ² are each independently from one —CH ₂ — or two or more non-adjacent —CH ₂ —, each of which may be independently replaced with —O—. An alkylene group having 20 to 20 carbon atoms is preferred, but an alkylene group having 1 to 8 carbon atoms is particularly preferred from the viewpoint of liquid crystallinity and compatibility with other components.

X ¹ and X ² are each independently —O—, —S—, —OCH ₂ —, —CH ₂ O—, —CO—, —COO—, —OCO—, —CO—S—, —S—. CO -, - O-CO- O -, - CO-NH -, - NH-CO -, - SCH 2 -, - CH 2 S -, - CF 2 O -, - OCF 2 -, - CF 2 S- _{, -SCF 2 -, - CH 2} CH 2 -, - CH 2 CF 2 -, - CF 2 CH 2 -, - CF 2 CF 2 -, - CH = CH-COO -, - CH = CH-OCO-, _{-COO-CH = CH -, -} OCO-CH = CH -, - COO-CH 2 CH 2 -, - OCO-CH 2 CH 2 -, - CH 2 CH 2 -COO -, - CH 2 CH 2 -OCO _{-, - COO-CH 2 -} , - OCO-CH 2 -, - CH 2 -COO -, - CH 2 -OCO -, - CY 1 CY ² -, - C≡C- or a represents a single bond (wherein, ^{Y 1} and ^{Y 2} are each independently hydrogen atom, an alkyl group having from 1 to 12 carbon atoms, a fluorine atom, a chlorine atom or a cyano group -O-, -COO-, -OCO-, -CH = CH-COO-, -CH = CH-OCO-, -COO-CH = CH-, -OCO-CH = CH-,- _{, - - COO-CH 2 CH} 2 OCO-CH 2 CH 2 -, - CH 2 CH 2 -COO -, - CH 2 CH 2 -OCO -, - COO-CH 2 -, - OCO-CH 2 -, - CH ₂ —COO—, —CH ₂ —OCO— or a single bond is preferable, and —O— is particularly preferable.

  n1 and n2 each independently represents 0, 1, 2, 3 or 4, preferably 1 or 2, and particularly preferably 1.

A ¹ and A ⁴ are each independently 1,4-phenylene group, naphthalene-2,6-diyl group, 1,4-cyclohexylene group, 1,4-cyclohexenylene group, 1,4-bicyclo [2 2.2.2] Octylene group, decahydronaphthalene-2,6-diyl group or 1,2,3,4-tetrahydronaphthalene-2,6-diyl group, pyridine-2,6-diyl group, pyrimidine-2, 5-diyl group, 1,3-dioxane-2,5-diyl group, these groups may be unsubstituted, fluorine atom, chlorine atom, cyano group, nitro group, carbon number 1 to 7 The alkyl group, the alkoxy group having 1 to 7 carbon atoms, or the alkanoyl group having 1 to 7 carbon atoms, which is substituted with one or more hydrogen atoms. May be replaced by atom or chlorine atom, A ¹ and / or A ⁴ may be those when there are multiple different even identical, unsubstituted or substituted with or fluorine atom, a chlorine atom, 1,4-phenylene group substituted by alkyl group having 1 to 4 carbon atoms or alkoxy group having 1 to 4 carbon atoms, naphthalene-2,6 unsubstituted or substituted by fluorine atom or chlorine atom An unsubstituted 1,4-cyclohexylene group, in which one -CH ₂ -or _two non-adjacent —CH ₂ — may be replaced by —O—, Alternatively, a 1,4-phenylene group substituted by a fluorine atom, a chlorine atom, a CH ₃ group or a CH ₃ O group, an unsubstituted naphthalene-2,6-diyl group, or an unsubstituted 1,4-silane A cyclohexylene group is particularly preferred.

Z ¹ and Z ² are each independently —OCH ₂ —, —CH ₂ O—, —COO—, —OCO—, —CO—S—, —S—CO—, —CO—NH—, —NH—. _{CO -, - SCH 2 -,} - CH 2 S -, - CF 2 O -, - OCF 2 -, - CF 2 S -, - SCF 2 -, - CH 2 CH 2 -, - CH 2 CF 2 -, _{-CF 2 CH 2 -, - CF} 2 CF 2 -, - CH = CH-COO -, - CH = CH-OCO -, - COO-CH = CH -, - OCO-CH = CH -, - COO-CH ₂ CH ₂ —, —OCO—CH ₂ CH ₂ —, —CH ₂ CH ₂ —COO—, —CH ₂ CH ₂ —OCO—, —COO—CH ₂ —, —OCO—CH ₂ —, —CH ₂ — _{COO -, - CH 2 -OCO -} , - CY 3 = CY 4 -, - C≡C- or a single bond (formula Represents Y ³ and Y ⁴ are each independently hydrogen atom, an alkyl group having from 1 to 12 carbon atoms, a fluorine atom, a chlorine atom or a cyano group.), Which if Z ¹ and / or Z ² there are a plurality May be the same or different, but —OCH ₂ —, —CH ₂ O—, —COO—, —OCO—, —CH═CH—COO—, —CH═CH—OCO—, —COO _{-CH = CH -, - OCO-} CH = CH -, - COO-CH 2 CH 2 -, - OCO-CH 2 CH 2 -, - CH 2 CH 2 -COO -, - CH 2 CH 2 -OCO-, —COO—CH ₂ —, —OCO—CH ₂ —, —CH ₂ —COO—, —CH ₂ —OCO— or a single bond is preferable, —COO—, —OCO—, —CH═CH—COO—, — CH = CH-OCO-, -COO-CH = CH-, OCO-CH = CH- or a single bond is particularly preferred.

m1 and m2 each independently represents 0, 1 or 2, but m1 is 0 or 1, m2 is preferably 0 or 1, and m1 is 1 and m2 is 0.
l represents 0 or 1, but 1 is preferred.

A ² and A ³ each independently represents a 1,4-phenylene group in which one —CH═ or two non-adjacent —CH═ may be replaced by —N═; -One or more hydrogen atoms in the phenylene group are each independently substituted with a fluorine atom, a chlorine atom, a cyano group, a nitro group, or an alkyl group having 1 to 8 carbon atoms, an alkoxy group, or an alkanoyl group. The alkyl group, alkoxy group or alkanoyl group may be substituted with a fluorine atom or a chlorine atom, but A ² and A ³ represent a 1,4-phenylene group, and the two 1,4-phenylene groups At least one hydrogen atom in the group is substituted with an alkyl group, alkoxy group or alkanoyl group having 1 to 8 carbon atoms, and the alkyl group, alkoxy group or alkanoyl group is a fluorine atom or chlorine The case where it may be substituted by an atom is preferable, A ² and A ³ represent a 1,4-phenylene group, and at least one hydrogen atom in the two 1,4-phenylene groups has 1 to 8 carbon atoms. It represents an alkoxy group, and at least one hydrogen atom is preferably substituted by a fluorine atom, a chlorine atom, a cyano group or a nitro group, and -A ² -≡-A ³ -is represented by the following formula (A ²³ -1) from the equation ^(a 23 -20)

(In the formula, each L independently represents a fluorine atom, a chlorine atom, a cyano group, or a nitro group.) A combination represented by formula (A ²³ -1) or (A ²³ -5) is preferred. Is particularly preferred.

  R represents a hydrogen atom or an alkyl group having 1 to 12 carbon atoms, and the alkyl group may be unsubstituted or substituted by a fluorine atom, a chlorine atom or a cyano group. An unsubstituted linear alkyl group having 1 to 12 atoms is preferred, and a hydrogen atom is particularly preferred.

  Examples of the compound represented by the general formula (I) include the following formula (Ia)

(Wherein p represents a natural number from 1 to 10 and q represents an integer from 0 to 7).

  Specific examples of the compound represented by the general formula (I) include compounds represented by the following formulas (I-1) to (I-25).

The compound of this invention can be manufactured with the following manufacturing methods.
(Production Method 1) Production of the following compound (S11)

  Phenol (S1) substituted with halogen or halogen equivalent is reacted with alcohol (S2) to give ether (S3). For etherification, Mitsunobu reaction or Williamson reaction can be used by converting alcohol (S2) to mesylate or tosylate. The obtained (S3) is converted into acetylene (S4) by, for example, Sonogashira coupling with trimethylsilylacetylene, and terminal acetylene (S5) is obtained by deprotection using potassium carbonate or the like. As an acetylene reagent, 2-hydroxy-2-methyl-3-butyne can be used instead of trimethylsilylacetylene. In this case, potassium hydroxide, sodium hydroxide or the like can be used for deprotection.

The protecting group PG is applied to the halogenated phenol (S6). The protecting group PG is not particularly limited as long as it is a group that can stably protect the functional group during the synthesis process and can be easily removed, but for example, GREEN'S PROTECTIVE GROUPS IN ORGANIG SYNTHESIS (Fourth Edition). , PETER G. M.M. WUTS, THEODORA W. GREEN, A John Wiley & Sons, Inc. , Publication groups described in Publication can be used. After the Sonogashira coupling with the terminal acetylene (S5), the protecting group PG is removed by the method described in the above literature, for example, to obtain the phenol (S9). Subsequently, for example, carboxylic acid (S10) using a carbodiimide condensing agent such as N, N′-dicyclohexylcarbodiimide, N, N′-diisopropylcarbodiimide, 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide hydrochloride, etc. And the desired compound (S11) can be synthesized.
(Production Method 2) Production of the following compound (S19)

  After the halogenated phenol (S12) is multiplied by the protecting group PG (S13), it is converted into a Grignard reagent, reacted with a borate ester, and hydrolyzed to obtain boric acid (S14). Instead of Grignard reagent, it is possible to react with a lithiating agent such as butyllithium, tert-butyllithium, methyllithium, lithium diisopropylamide, etc., and react with a borate ester. Further, as the borate ester, trimethyl borate, triethyl borate, triisopropyl borate and the like can be used.

Phenol (S9) is reacted with trifluoromethanesulfonic anhydride to give triflate (S15). The triflate (S15) is coupled with boric acid (S14) by the Suzuki-Miyaura coupling reaction to obtain the intermediate (S16). After removing the protecting group PG, the target compound (S19) can be produced by reacting with alcohol (S18) by Mitsunobu reaction.
(Production Method 3) Production of the following compound (S25)

  By the Sonogashira coupling reaction, the aryl halide (S20) is reacted with an acetylene reagent such as trimethylsilylacetylene or 2-hydroxy-2-methyl-3-butyne to obtain an intermediate (S21). Thereafter, deprotection is performed to obtain terminal acetylene (S22). The obtained terminal acetylene (S22) is coupled with an aryl halide (S7) by Sonogashira coupling to obtain an intermediate (S23). The protecting group PG is deprotected to form phenol (S24), and then etherified with alcohol (S18) by Mitsunobu reaction to produce the target compound (S25).

  The compound of the present invention is preferably used in a nematic liquid crystal composition, a smectic liquid crystal composition, a chiral smectic liquid crystal composition, and a cholesteric liquid crystal composition, and particularly preferably used in a nematic liquid crystal composition. In the liquid crystal composition using the polymerizable compound of the present invention, a compound other than the present invention may be added.

  Specific examples of the other polymerizable compound used by mixing with the polymerizable compound of the present invention include the general formula (II)

(Wherein R ¹¹ and R ¹² each independently represent the same meaning as P in formula (I), and S ¹¹ and S ¹² each independently represent a single bond or an alkylene group having 1 to 18 carbon atoms) It represents a one -CH ₂ - or nonadjacent two or more -CH ₂ - represents an oxygen atom, -COO -, - OCO -, - OCOO- may be replaced ^{by, L} 11, L ¹² and L ¹³ are each independently a single bond, —O—, —S—, —OCH ₂ —, —CH ₂ O—, —CO—, —COO—, —OCO—, —CO—S—, _{-S-CO -, - O-} CO-O -, - OCOOCH 2 -, - CH 2 OCOO -, - CO-NR 13 -, - NR 13 -CO -, - SCH 2 -, - CH 2 S-, _{-CH = N -, - SCH 2} -, - CH 2 S -, - CH = CH-COO -, - CH = H-OCO -, - COO- CH = CH -, - OCO-CH = CH -, - COO-CH 2 CH 2 -, - OCO-CH 2 CH 2 -, - CH 2 CH 2 -COO -, - CH ₂ CH ₂ —OCO—, —COO—CH ₂ —, —OCO—CH ₂ —, —CH ₂ —COO—, —CH ₂ —OCO—, —CF ₂ —, —CF ₂ O—, —OCF ₂ — _{, -CH 2 CH 2 -, -} CF 2 CH 2 -, - CH 2 CF 2 -, - CF 2 CF 2 -, - CY 11 = CY 12 - or an -C≡C- ^{(wherein, R 13} Represents an alkyl group having 1 to 4 carbon atoms, and Y ¹¹ and Y ¹² each independently represent a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, a fluorine atom, a chlorine atom, or a cyano group), M ^11. and ^{M 12} are each independently, 1,4-phenylene group, 1,4 Cyclohexylene group, pyridine-2,5-diyl group, pyrimidine-2,5-diyl group, naphthalene-2,6-diyl group, tetrahydronaphthalene-2,6-diyl group or 1,3-dioxane-2,5 -Represents a diyl group, but M ¹¹ and M ¹² are each independently unsubstituted or substituted with an alkyl group, a halogenated alkyl group, an alkoxy group, a halogenated alkoxy group, a halogeno group, a cyano group or a nitro group. L ¹¹ represents 0, 1, 2 or 3, and when l ¹¹ represents 2 or 3, two or three L ¹² and / or M ¹² may be the same or different. preferably good compound ^be, independently L ^{11, L 12} and ^{L 13} are each a single bond, -O -, - COO- or represents ^{-OCO-, M 11,} and ^{M 12} are each independently 1 4-phenylene group, 1,4-cyclohexylene group, pyridine-2,5-diyl group, pyrimidine-2,5-diyl group, a naphthalene-2,6-diyl group. ) Is preferred.

Furthermore, ^{R 11} and ^{R 12} in the general formula (II) is preferably an acrylic group or methacrylic group. Specifically, the general formula (III)

(Wherein S ³ and S ⁴ each independently represent an alkylene group having 2 to 18 carbon atoms, and X ³ and X ⁴ each independently represent —O—, —COO—, —OCO— or a single bond). , Z ³ and Z ⁴ each independently represent —COO— or —OCO—, and A ⁵ , A ⁶ and A ⁷ each independently represents an unsubstituted or fluorine atom, chlorine atom or carbon atom having 1 to 4 carbon atoms. Represents a 1,4-phenylene group substituted by an alkyl group or an alkoxy group.), And compounds represented by the following formulas (III-1) to (III-8) are particularly preferable.

(Wherein, ^{S 3} has the same meaning as ^{S 3} in the general formula (III), ^{S 4} represents the same meaning as ^{S 4} in the general formula (III).) The above formula (III-1) from the formula (III In −8), compounds in which S ³ and S ⁴ are each independently an alkylene group having 3 to 6 carbon atoms are further preferred.

  Moreover, general formula (IV)

(In the formula, S ⁵ and S ⁶ each independently represent an alkylene group having 2 to 18 carbon atoms, and X ⁵ and X ⁶ each independently represent —O—, —COO—, —OCO— or a single bond. , Z ⁵ represents —COO— or —OCO—, and A ⁸ , A ⁹ and A ¹⁰ are each independently unsubstituted or substituted by a fluorine atom, a chlorine atom, an alkyl group having 1 to 4 carbon atoms or an alkoxy group. And a compound represented by the following formula (IV-1) to formula (IV-8) is particularly preferable.

(Wherein, ^{S 5} has the same meaning as ^{S 5} in the general formula (IV), ^{S 6} in the general formula (IV) represents the same meaning as ^{S 6.)} The formula (IV-1) from the formula (IV -8), from the viewpoint of heat resistance and durability, the formula (IV-2), formula (IV-5), formula (IV-6), formula (IV-7) and formula (IV-8) are used. The compound represented by formula (IV-2) is more preferable, and the compound in which S ⁵ and S ⁶ are each independently an alkylene group having 3 to 6 carbon atoms is particularly preferable.

  In addition, preferable bifunctional polymerizable compounds include compounds represented by the following general formulas (V-1) to (V-5).

(In the formula, S ⁷ and S ⁸ each independently represent an alkylene group having 2 to 18 carbon atoms.) In the above formulas (V-1) to (V-5), the formula (V-2), Compounds represented by formula (V-3) and formula (V-5) are preferable, and compounds in which S ⁷ and S ⁸ are each independently an alkylene group having 3 to 6 carbon atoms are particularly preferable.

  To the polymerizable liquid crystal composition containing the compound of the present invention, a polymerizable compound that does not exhibit liquid crystallinity can be added to such an extent that the liquid crystallinity of the composition is not impaired. Specifically, any compound that is recognized as a polymer-forming monomer or polymer-forming oligomer in this technical field can be used without particular limitation.

  The concentration of the photopolymerization initiator added to the polymerizable liquid crystal composition containing the compound of the present invention is preferably 0.1 to 10% by mass, and more preferably 0.2 to 5% by mass. preferable. As the photopolymerization initiator, benzoin ethers, benzophenones, acetophenones, benzyl ketals, acylphosphine oxides and the like can be used.

  In addition, a stabilizer may be added to the polymerizable liquid crystal composition containing the compound of the present invention in order to improve its storage stability. Examples of the stabilizer include hydroquinone, hydroquinone monoalkyl ethers, tert-butylcatechols, pyrogallols, thiophenols, nitro compounds, β-naphthylamines, β-naphthols, nitroso compounds and the like. When the stabilizer is used, the addition amount is preferably 0.005 to 1% by mass and more preferably 0.02 to 0.5% by mass with respect to the liquid crystal composition.

  Further, when the polymerizable liquid crystal composition containing the compound of the present invention is used for applications such as films, optical elements, functional pigments, pharmaceuticals, cosmetics, coating agents, synthetic resins, Depending on the purpose, metals, metal complexes, dyes, pigments, dyes, fluorescent materials, phosphorescent materials, surfactants, leveling agents, thixotropic agents, gelling agents, polysaccharides, ultraviolet absorbers, infrared absorbers, antioxidants Further, metal oxides such as ion exchange resin and titanium oxide can be added.

The polymer obtained by polymerizing the polymerizable liquid crystal composition containing the compound of the present invention can be used for various applications. For example, a polymer obtained by polymerizing a polymerizable liquid crystal composition containing the compound of the present invention without orientation can be used as a light scattering plate, a depolarizing plate, and a moire fringe prevention plate. Moreover, the polymer obtained by superposing | polymerizing after orientating has optical anisotropy, and is useful. Such an optical anisotropic body includes, for example, a substrate obtained by rubbing a polymerizable liquid crystal composition containing the compound of the present invention with a cloth, a substrate on which an organic thin film is formed, or an alignment film on which SiO ₂ is obliquely deposited. It can be produced by polymerizing the polymerizable liquid crystal composition after it is supported on a substrate having it or sandwiched between substrates.

  Examples of the method for supporting the polymerizable liquid crystal composition on the substrate include spin coating, die coating, extrusion coating, roll coating, wire bar coating, gravure coating, spray coating, dipping, and printing. . Further, an organic solvent may be added to the polymerizable liquid crystal composition during coating. As the organic solvent, hydrocarbon solvents, halogenated hydrocarbon solvents, ether solvents, alcohol solvents, ketone solvents, ester solvents, aprotic solvents and the like can be used. The solvent is toluene or hexane, the halogenated hydrocarbon solvent is methylene chloride, the ether solvent is tetrahydrofuran, acetoxy-2-ethoxyethane or propylene glycol monomethyl ether acetate, and the alcohol solvent is methanol, ethanol or Isopropanol, acetone, methyl ethyl ketone, cyclohexanone, γ-butyl lactone or N-methylpyrrolidinone as the ketone solvent, ethyl acetate or cellosolve as the ester solvent, dimethyl as the aprotic solvent It can be mentioned formamide or acetonitrile. These may be used alone or in combination, and may be appropriately selected in consideration of the vapor pressure and the solubility of the polymerizable liquid crystal composition. As a method for volatilizing the added organic solvent, natural drying, heat drying, reduced pressure drying, or reduced pressure heat drying can be used. In order to further improve the applicability of the polymerizable liquid crystal material, it is also effective to provide an intermediate layer such as a polyimide thin film on the substrate or to add a leveling agent to the polymerizable liquid crystal material. The method of providing an intermediate layer such as a polyimide thin film on a substrate is effective for improving the adhesion between a polymer obtained by polymerizing a polymerizable liquid crystal material and the substrate.

  Examples of the alignment treatment other than the above include use of fluid alignment of a liquid crystal material, use of an electric field or a magnetic field. These orientation means may be used alone or in combination. Furthermore, a photo-alignment method can be used as an alignment treatment method instead of rubbing. As a shape of the substrate, in addition to a flat plate, a curved surface may be included as a constituent part. The material which comprises a board | substrate can be used regardless of an organic material and an inorganic material. Examples of the organic material used as the substrate material include polyethylene terephthalate, polycarbonate, polyimide, polyamide, polymethyl methacrylate, polystyrene, polyvinyl chloride, polytetrafluoroethylene, polychlorotrifluoroethylene, polyarylate, polysulfone, and triacetyl. Cellulose, cellulose, polyetheretherketone and the like can be mentioned, and examples of the inorganic material include silicon, glass and calcite.

When the polymerizable liquid crystal composition containing the compound of the present invention is polymerized, it is desirable that the polymerization proceeds rapidly. Therefore, a method of polymerizing by irradiating active energy rays such as ultraviolet rays or electron beams is preferable. When ultraviolet rays are used, a polarized light source or a non-polarized light source may be used. Further, when the polymerization is carried out with the liquid crystal composition sandwiched between two substrates, at least the substrate on the irradiation surface side must have appropriate transparency to the active energy rays. Moreover, after polymerizing only a specific part using a mask at the time of light irradiation, the orientation state of the unpolymerized part is changed by changing conditions such as an electric field, a magnetic field, or temperature, and further irradiation with active energy rays is performed. Then, it is possible to use a means for polymerization. Moreover, it is preferable that the temperature at the time of irradiation exists in the temperature range by which the liquid crystal state of the polymeric liquid crystal composition of this invention is hold | maintained. In particular, when an optical anisotropic body is to be produced by photopolymerization, the polymerization is carried out at a temperature as close to room temperature as possible from the viewpoint of avoiding unintentional induction of thermal polymerization, that is, typically at a temperature of 25 ° C. It is preferable to make it. The intensity of the active energy ray is preferably 0.1 mW / cm ^{2 to 2} W / cm ² . When the intensity is 0.1 mW / cm ² or less, a great amount of time is required to complete the photopolymerization and the productivity is deteriorated. When the intensity is 2 W / cm ² or more, the polymerizable liquid crystal compound or the polymerizable liquid crystal is used. There is a risk that the composition will deteriorate.

  The optical anisotropic body obtained by polymerization can be subjected to a heat treatment for the purpose of reducing initial characteristic changes and achieving stable characteristic expression. The heat treatment temperature is preferably in the range of 50 to 250 ° C., and the heat treatment time is preferably in the range of 30 seconds to 12 hours.

  The optical anisotropic body manufactured by such a method may be peeled off from the substrate and used alone or without being peeled off. Further, the obtained optical anisotropic bodies may be laminated or bonded to another substrate for use.

EXAMPLES Hereinafter, although an Example is given and this invention is further described, this invention is not limited to these Examples. Further, “%” in the compositions of the following Examples and Comparative Examples means “% by mass”.
Example 1 Production of Compound Represented by Formula (I-1)

  In a 1 L four-necked flask, 31.9 g (0.44 mol) of 3-buten-1-ol, 107.3 g (0.41 mol) of triphenylphosphine, 75.0 g (0.34 mol) of 4-iodophenol ) Was weighed and dissolved in 300 mL of tetrahydrofuran. While cooling with ice, 82.7 g (0.41 mol) of diisopropyl azodicarboxylate was added dropwise so that the temperature of the reaction solution did not exceed 25 ° C. After stirring at room temperature for 10 hours, 10 mL of water was added. After the solvent was distilled off, 70 mL of toluene and 350 mL of hexane were added, followed by liquid separation treatment with a mixed solvent of 350 mL of methanol and 70 mL of water. The organic layer was further washed with a mixed solvent of 300 mL of methanol and 100 mL of water, and the solvent was distilled off. Purification by column chromatography (silica gel) using dichloromethane / hexane (1: 3) gave 103.4 g of a compound represented by the formula (A-1) in the form of a pale yellow oil.

  In a 1 L four-necked flask, 100.0 g (0.37 mol) of a compound represented by the formula (A-1), 1.4 g (7.3 mmol) of copper (I) iodide, N, N-dimethylformamide 300 mL and trimethylamine 100 mL were added, and the atmosphere in the flask was replaced with nitrogen. Tetrakis (triphenylphosphine) palladium (0) 4.2 g (3.7 mmol) was added. 43.0 g (0.44 mol) of trimethylsilylacetylene was added dropwise at room temperature. After completion of dropping, the mixture was stirred at room temperature for 12 hours. Dichloromethane 300mL and hexane 300mL were added, and liquid separation treatment was performed twice with water 500mL. Purification by column chromatography (silica gel, alumina) using dichloromethane / hexane (1: 1) gave 102.6 g of a compound represented by the formula (A-2) in the form of a brown oil.

  In a 1 L four-necked flask, 89.2 g (0.37 mol) of the compound represented by the formula (A-2) was taken and dissolved in 47 mL of dichloromethane and 312 mL of methanol. 8.9 g (65 mmol) of potassium carbonate was added and stirred at room temperature for 12 hours. The solvent was distilled off, and the residue was purified by column chromatography (silica gel) using dichloromethane / hexane (1: 1) to obtain 54.0 g of a compound represented by the formula (A-3) as a brown oil.

  To a 1 L four-necked flask, 120.0 g (0.59 mol) of 4-bromo-2-methoxyphenol and 51.4 g (0.65 mol) of pyridine were added and dissolved in 320 mL of dichloromethane. While cooling with ice, 66.4 g (0.65 mol) of acetic anhydride was added. Stir at room temperature for 12 hours. After neutralizing with 300 mL of 10% hydrochloric acid, it was washed 3 times with 300 mL of water. Purification by column chromatography (silica gel) using dichloromethane gave 145 g of a compound represented by the colorless oily formula (A-4).

  In a 500 mL four-necked flask, 58.2 g (0.24 mol) of the compound represented by the formula (A-4), 0.9 g (4.7 mmol) of copper (I) iodide, N, N-dimethylformamide 174 mL and triethylamine 58 mL were added. After the atmosphere in the flask was replaced with nitrogen, 2.7 g (2.3 mmol) of tetrakis (triphenylphosphine) palladium (0) was added. While heating at 89 ° C., a solution prepared by dissolving 45.0 g (0.26 mol) of the compound represented by the formula (A-3) in 45 mL of N, N-dimethylformamide was added dropwise. The mixture was stirred at 91 ° C. for 6 hours. Dichloromethane 250mL and water 250mL were added and liquid-separated. Furthermore, it was washed twice with 250 mL of water. The product was purified by column chromatography (silica gel, alumina) using dichloromethane. Recrystallization was performed three times with toluene / hexane to obtain 40.0 g of a compound represented by the formula (A-5) as a pale yellow solid.

  To a 500 mL flask equipped with a thermometer, 38.0 g (0.11 mol) of the compound represented by the formula (A-5) and 190 mL of tetrahydrofuran were added. 38 mL of 25% aqueous ammonia was added, and the mixture was stirred at room temperature for 16 hours. After diluting with 190 mL of ethyl acetate, the mixture was neutralized by adding 190 mL of 10% hydrochloric acid and 190 mL of water, followed by liquid separation treatment. The organic layer was washed sequentially with 300 mL of water and 300 mL of brine, and the solvent was distilled off to obtain 29.2 g of a compound represented by the formula (A-6) as a pale yellow solid.

In a 200 mL four-necked flask, 14.0 g (0.048 mol) of a compound represented by formula (A-6), 13.1 g (0.052 mol) of a compound represented by formula (A-7), 0.3 g (0.0025 mol) of N, N-dimethylaminopyridine was taken and suspended in 66 mL of dichloromethane. While cooling with ice, 7.2 g (0.057 mol) of N, N′-diisopropylpropylcarbodiimide was added dropwise so that the reaction temperature did not exceed 15 ° C. After completion of dropping, the mixture was stirred at room temperature for 16 hours. The precipitate was removed by filtration and the solvent was distilled off. Purification was performed by column chromatography (silica gel, alumina) using a dichloromethane / hexane mixed solvent. Recrystallization from dichloromethane / hexane gave 20.0 g of a compound represented by the formula (I-1) as a target product.
Physical property values of compounds represented by formula (I-1)
¹ H NMR (CDCl ₃ ) δ 2.21 (quin, 2H), 2.56 (q, 2H), 3.83 (s, 3H), 4.04 (t, 2H), 4.16 (t, 2H), 4.39 (t, 2H), 5.12 (d, 1H), 5.18 (d, 1H), 5.84-5.97 (m, 2H), 6.14 (dd, 1H) ), 6.43 (d, 1H), 6.88 (d, 2H), 6.98 (d, 2H), 7.10 to 7.16 (m, 3H), 7.47 (d, 2H) , 8.15 (d, 2H) ppm.
¹³ C NMR (CDCl ₃ ) δ 28.5, 33.6, 56.0, 61.2, 64.6, 67.3, 87.6, 89.2, 114.3, 114.6, 115. 2, 115.4, 117.2, 121.7, 122.1, 123.1, 124.3, 128.3, 131.0, 132.5, 133.1, 134.2, 140.1, 151.2, 159.0, 163.1, 164.2, 166.1 ppm.
LRMS (EI) m / z 526
Example 2 Production of Compound Represented by Formula (I-2)

In a 200 mL four-necked flask, 6.6 g (0.022 mol) of the compound represented by the formula (A-6), 7.2 g (0.025 mol) of the compound represented by the formula (B-1), N , N-dimethylaminopyridine (0.1 g, 0.0012 mol) was taken and suspended in 36 mL of dichloromethane. While cooling with ice, 3.4 g (0.027 mol) of N, N′-diisopropylpropylcarbodiimide was added dropwise so that the reaction temperature did not exceed 15 degrees. After completion of dropping, the mixture was stirred at room temperature for 16 hours. The precipitate was removed by filtration and the solvent was distilled off. Purification was performed by column chromatography (silica gel, alumina) using a dichloromethane / hexane mixed solvent. Recrystallization from dichloromethane / hexane gave 11.1 g of the compound represented by the formula (I-2) which is the target product.
Physical property value of compound represented by formula (I-2)
¹ H NMR (CDCl ₃ ) δ 1.42-1.59 (m, 4H), 1.73 (quin, 2H), 1.84 (quin, 2H), 2.56 (q, 2H), 3. 83 (s, 3H), 4.02 to 4.06 (m, 4H), 4.18 (t, 2H), 5.12 (d, 1H), 5.18 (d, 1H), 5.82 (D, 1H), 5.86-5.96 (m, 1H), 6.12 (dd, 1H), 6.41 (d, 1H), 6.88 (d, 2H), 6.97 ( d, 2H), 7.09-7.16 (m, 3H), 7.47 (d, 2H), 8.15 (d, 2H) ppm.
¹³ C NMR (CDCl ₃ ) δ 25.7, 25.7, 28.6, 29.0, 33.6, 56.0, 64.5, 67.3, 68.1, 87.7, 89. 2, 114.2, 114.6, 115.2, 115.4, 117.2, 121.3, 122.1, 123.1, 124.2, 128.6, 130.6, 132.4 133.1, 134.2, 140.2, 151.2, 159.0, 163.4, 164.3, 166.3 ppm.
LRMS (EI) m / z 568
Example 3 Production of Compound Represented by Formula (I-3)

  4-Iodophenol 100.0 g (0.45 mol), 4-penten-1-ol 50.9 g (0.59 mol), and triphenylphosphine 143.2 g (0.55 mol) were weighed in a 2 L separable flask. And dissolved in 400 mL of tetrahydrofuran. While cooling with ice, 110.4 g (0.55 mol) of diisopropyl azodicarboxylate was added dropwise so that the temperature of the reaction solution did not exceed 25 ° C. After stirring at room temperature for 10 hours, 10 mL of water was added. After the solvent was distilled off, 70 mL of toluene and 350 mL of hexane were added, followed by liquid separation treatment with a mixed solvent of 350 mL of methanol and 70 mL of water. The organic layer was further washed with a mixed solvent of 300 mL of methanol and 100 mL of water, and the solvent was distilled off. Purification by column chromatography (silica gel) using dichloromethane / hexane (1: 3) gave 138.2 g of a compound represented by the formula (C-1) as a pale yellow oil.

  In a 1 L four-necked flask, 131.1 g (0.46 mol) of the compound represented by the formula (C-1), 1.7 g (8.9 mmol) of copper (I) iodide, N, N-dimethyl Formamide 393 mL and trimethylamine 131 mL were added, and the atmosphere in the flask was replaced with nitrogen. Tetrakis (triphenylphosphine) palladium (0) 5.3 g (4.6 mmol) was added. 58.1 g (0.59 mol) of trimethylsilylacetylene was added dropwise at room temperature. After completion of the dropwise addition, the mixture was stirred at room temperature for 20 hours. 800 mL of hexane was added, and liquid separation treatment was performed 4 times with 500 mL of water. Purification by column chromatography (silica gel, alumina) using hexane gave 112.0 g of a compound represented by the formula (C-2) in the form of a brown oil.

  In a 1 L four-necked flask, 112.0 g (0.43 mol) of the compound represented by the formula (C-2) was taken and dissolved in 56 mL of dichloromethane and 392 mL of methanol. 11.2 g (81 mmol) of potassium carbonate was added and stirred at room temperature for 12 hours. The solvent was distilled off, and the residue was purified by column chromatography (silica gel) using hexane to obtain 69.8 g of a compound represented by the formula (C-3) in the form of a brown oil.

  In a 2 L separable flask, 71.3 g (0.29 mol) of the compound represented by the formula (A-4), 1.1 g (5.8 mmol) of copper (I) iodide, 214 mL of N, N-dimethylformamide, 71 mL of triethylamine was added. After the atmosphere in the flask was replaced with nitrogen, 3.4 g (2.9 mmol) of tetrakis (triphenylphosphine) palladium (0) was added. While heating at 86 ° C., a solution of 65.0 g (0.35 mol) of the compound represented by the formula (C-3) dissolved in 65 mL of N, N-dimethylformamide was added dropwise. Stir at 100 ° C. for 6 hours. Toluene 150 mL, hexane 350 mL, and water 500 mL were added for liquid separation treatment. Furthermore, it was washed twice with 500 mL of water. Purification by column chromatography (silica gel, alumina) using toluene / hexane (1: 2). Recrystallization was performed three times with toluene / hexane to obtain 34.8 g of a compound represented by the formula (C-4) as a pale yellow solid.

  To a 500 mL flask equipped with a thermometer, 34.8 g (0.099 mol) of the compound represented by the formula (C-4) and 174 mL of tetrahydrofuran were added. A 25% aqueous ammonia solution (35 mL) was added, and the mixture was stirred at room temperature for 16 hours. The reaction mixture was diluted by adding 174 mL of ethyl acetate, neutralized by adding 174 mL of 10% hydrochloric acid, and separated. The organic layer was washed sequentially with 300 mL of water and 300 mL of brine, and the solvent was distilled off. Recrystallization from toluene / hexane gave 28.2 g of a compound represented by the formula (C-5) as a pale yellow solid.

In a 200 mL four-necked flask, 13.0 g (0.042 mol) of a compound represented by the formula (C-5), 11.6 g (0.046 mol) of a compound represented by the formula (A-7), 0.3 g (0.0025 mol) of N, N-dimethylaminopyridine was taken and suspended in 58 mL of dichloromethane. While cooling with ice, 6.4 g (0.051 mol) of N, N′-diisopropylpropylcarbodiimide was added dropwise so that the reaction temperature did not exceed 15 degrees. After completion of dropping, the mixture was stirred at room temperature for 16 hours. The precipitate was removed by filtration and the solvent was distilled off. Purification was performed by column chromatography (silica gel, alumina) using a mixed solvent of dichloromethane / hexane (2: 1). Recrystallization from dichloromethane / hexane gave 19.0 g of the compound represented by the formula (I-3) as the target product.
Physical property value of compound represented by formula (I-3)
¹ H NMR (CDCl ₃ ) δ 1.90 (quin, 2H), 2.18 to 2.28 (m, 4H), 3.83 (s, 3H), 3.99 (t, 2H), 4. 16 (t, 2H), 4.39 (t, 2H), 5.01 (d, 1H), 5.07 (d, 1H), 5.81 to 5.91 (m, 2H), 6.14 (Dd, 1H), 6.43 (d, 1H), 6.88 (d, 2H), 6.98 (d, 2H), 7.10 to 7.16 (m, 3H), 7.47 ( d, 2H), 8.15 (d, 2H) ppm.
¹³ C NMR (CDCl ₃ ) δ 28.3, 28.5, 30.1, 56.0, 61.2, 64.6, 67. . 2,87.6,89.2,114.3,114.6,115.0,115.3,115.4,121.7,122.1,123.1,124.3,128.3 131.0, 132.5, 133.0, 137.7, 140.1, 151.2, 159.2, 163.1, 164.2, 166.2 ppm.
LRMS (EI) m / z 540
Example 4 Production of Compound Represented by Formula (I-4)

In a 200 mL four-necked flask, 14.0 g (0.045 mol) of the compound represented by the formula (C-5), 14.6 g (0.050 mol) of the compound represented by the formula (B-1), N , N-dimethylaminopyridine 0.3 g (0.0025 mol) was taken and suspended in 73 mL of dichloromethane. While cooling with ice, 6.9 g (0.055 mol) of N, N′-diisopropylpropylcarbodiimide was added dropwise so that the reaction temperature did not exceed 15 degrees. After completion of dropping, the mixture was stirred at room temperature for 16 hours. The precipitate was removed by filtration and the solvent was distilled off. Purification was performed by column chromatography (silica gel, alumina) using a mixed solvent of dichloromethane / hexane (2: 1). Recrystallization from dichloromethane / hexane gave 23.4 g of a compound represented by the formula (I-4) as a target product.
Physical property values of compounds represented by formula (I-4)
¹ H NMR (CDCl ₃ ) δ 1.45 to 1.57 (m, 4H), 1.73 (quin, 2H), 1.82 (quin, 2H), 1.90 (quin, 2H), 2. 25 (q, 2H), 3.83 (s, 3H), 3.99 (t, 2H), 4.05 (t, 2H), 4.18 (t, 2H), 5.01 (d, 1H) ), 5.07 (d, 1H), 5.81-5.91 (m, 2H), 6.12 (dd, 1H), 6.41 (d, 1H), 6.88 (d, 2H) 6.97 (d, 2H), 7.09-7.16 (m, 3H), 7.46 (d, 2H), 8.15 (d, 2H) ppm.
¹³ C NMR (CDCl ₃ ) δ 25.7, 25.7, 28.3, 28.5, 29.0, 30.1, 56.0, 64.5, 67.2, 68.1, 87. 6, 89.2, 114.2, 114.5, 115.0, 115.3, 115.4, 121.3, 122.1, 123.1, 124.3, 128.6, 130.6, 132.4, 133.0, 137.7, 140.1, 151.2, 159.2, 163.4, 164.3, 166.3 ppm.
LRMS (EI) m / z 582
Example 5 Production of Compound Represented by Formula (I-5)

In Example 1, except that 3-buten-1-ol was changed to trans-crotyl alcohol and the compound represented by the formula (A-7) was changed to a compound represented by the formula (B-1). By the same method, the compound represented by the formula (I-5) was obtained.
Physical property values of compounds represented by formula (I-5)
¹ H NMR (CDCl ₃ ) δ 1.45 to 1.57 (m, 4H), 1.73 (quin, 2H), 1.82 (d, 3H), 1.90 (quin, 2H), 3. 83 (s, 3H), 4.05 (t, 2H), 4.18 (t, 2H), 4.61 (t, 2H), 5.81 to 5.91 (m, 3H), 6.12 (Dd, 1H), 6.41 (d, 1H), 6.88 (d, 2H), 6.97 (d, 2H), 7.09 to 7.16 (m, 3H), 7.46 ( d, 2H), 8.15 (d, 2H) ppm.
¹³ C NMR (CDCl ₃ ) δ 17.0, 25.7, 25.7, 28.3, 28.5, 56.0, 64.5, 67.2, 75.0, 87.6, 89. 2, 114.2, 115.0, 115.3, 115.4, 121.3, 122.1, 123.1, 124.3, 124.5, 128.6, 130.1, 130.6, 132.4, 133.0, 140.1, 151.2, 159.2, 163.4, 164.3, 166.3 ppm.
LRMS (EI) m / z 568
Example 6 Production of Compound Represented by Formula (I-6)

  In a four-necked flask, 27.1 g (0.32 mol) of 4-penten-1-ol, 50.0 g (0.26 mol) of 4-bromo-2-fluorophenol, and 89.3 g (0. 34 mol) was added and dissolved in 250 mL of tetrahydrofuran. While cooling with ice, 68.9 g (0.34 mol) of diisopropyl azodicarboxylate was added dropwise so that the temperature of the reaction solution did not exceed 25 ° C. After stirring at room temperature for 10 hours, 10 mL of water was added. After the solvent was distilled off, 70 mL of toluene and 350 mL of hexane were added, followed by liquid separation treatment with a mixed solvent of 350 mL of methanol and 70 mL of water. The organic layer was further washed with a mixed solvent of 300 mL of methanol and 100 mL of water, and the solvent was distilled off. Purification by column chromatography (silica gel) using dichloromethane / hexane (1: 3) gave 67.9 g of a compound represented by the formula (F-1) as a pale yellow oil.

  In a four-necked flask, 67.9 g (0.26 mol) of the compound represented by the formula (F-1), 1.0 g (5.3 mmol) of copper (I) iodide, 204 mL of N, N-dimethylformamide 68 mL of trimethylamine was added, and the atmosphere in the flask was replaced with nitrogen. Tetrakis (triphenylphosphine) palladium (0) 3.0 g (2.6 mmol) was added. The reaction vessel was heated, and 33.5 g (0.34 mol) of trimethylsilylacetylene was added dropwise at 90 ° C. After completion of dropping, the mixture was stirred at 90 ° C. for 8 hours. The mixture was allowed to cool, 300 mL of hexane was added, and liquid separation treatment was performed 4 times with 500 mL of water. Purification by column chromatography (silica gel, alumina) using hexane gave 61.6 g of a compound represented by the formula (F-2) in the form of a brown oil.

  In a four-necked flask, 61.6 g (0.22 mol) of the compound represented by the formula (F-2) was taken and dissolved in 31 mL of dichloromethane and 216 mL of methanol. 6.2 g (45 mmol) of potassium carbonate was added and stirred at room temperature for 12 hours. The solvent was distilled off and the residue was purified by column chromatography (silica gel) using hexane to obtain 42.8 g of a compound represented by the formula (F-3) in the form of a brown oil.

  In a four-necked flask, 39.6 g (0.16 mol) of the compound represented by the formula (A-4), 0.62 g (3.3 mmol) of copper (I) iodide, 120 mL of N, N-dimethylformamide, 40 mL of triethylamine was added. After the atmosphere in the flask was replaced with nitrogen, 1.9 g (1.6 mmol) of tetrakis (triphenylphosphine) palladium (0) was added. While heating at 86 ° C., a solution of 42.8 g (0.21 mol) of the compound represented by the formula (F-3) dissolved in 43 mL of N, N-dimethylformamide was added dropwise. Stir at 100 ° C. for 8 hours. Toluene 150 mL, hexane 350 mL, and water 500 mL were added for liquid separation treatment. Furthermore, it was washed twice with 500 mL of water. Purification by column chromatography (silica gel, alumina) using toluene / hexane (1: 2). Recrystallization was performed three times with toluene / hexane to obtain 29.8 g of a compound represented by the formula (F-4) as a pale yellow solid.

  To the flask, 29.8 g (0.081 mol) of the compound represented by the formula (F-4) and 150 mL of tetrahydrofuran were added. 30 mL of 25% aqueous ammonia was added, and the mixture was stirred at room temperature for 16 hours. After diluting with 150 mL of ethyl acetate, the mixture was neutralized with 150 mL of 10% hydrochloric acid, followed by liquid separation treatment. The organic layer was washed sequentially with 300 mL of water and 300 mL of brine, and the solvent was distilled off. Recrystallization from toluene / hexane gave 24.0 g of a compound represented by the formula (F-5) as a pale yellow solid.

  3-Chloro-1-propanol 73.0 g (0.77 mol), potassium carbonate 71.0 g (0.51 mol), ferulic acid 50.0 g (0.26 mol) were added to a four-necked flask, and ethanol 150 mL. Suspended in After stirring at 90 ° C. for 10 hours, an aqueous solution in which 20.6 g (0.52 mol) of sodium hydroxide was dissolved in 100 mL of water was added, and the mixture was further stirred at 90 ° C. for 2 hours. The mixture was neutralized with 10% hydrochloric acid, and ethanol was distilled off. The solid was filtered and dispersed and washed three times with water to obtain 59.0 g of a compound represented by the formula (F-6) as a white solid.

  To a four-necked flask equipped with a Dean-Stark trap, 59.0 g (0.23 mol) of a compound represented by the formula (F-6) and 38.1 g (0.35 mol) of 3-chloropropionic acid were added, Suspended in 177 mL of toluene. 3.0 g (0.031 mol) of sulfuric acid was added, and the mixture was heated to reflux at 110 ° C. for 8 hours. Ethyl acetate (177 mL) and water (354 mL) were added to carry out a liquid separation treatment. The organic layer was washed twice with 354 mL of water and the solvent was distilled off to obtain 72.2 g of a compound represented by the formula (F-7) as a pale yellow solid.

  72.2 g (0.21 mol) of a compound represented by the formula (F-7) and 32.0 g (0.32 mol) of triethylamine were added to a four-necked flask and suspended in 361 mL of dichloromethane. The mixture was heated to 40 ° C. and stirred for 10 hours. Ethyl acetate (361 mL) and 10% hydrochloric acid (361 mL) were added, followed by liquid separation treatment. After washing twice with 361 mL of water, the solvent was distilled off. Recrystallization from acetone / hexane gave 55.9 g of a compound represented by the formula (F-8) as a pale yellow solid.

In a four-necked flask, 24.0 g (0.074 mol) of a compound represented by formula (F-5), 24.8 g (0.081 mol) of a compound represented by formula (F-8), N, 0.45 g (3.7 mmol) of N-dimethylaminopyridine was taken and suspended in 124 mL of dichloromethane. While cooling with ice, 11.1 g (0.088 mol) of N, N′-diisopropylpropylcarbodiimide was added dropwise so that the reaction temperature did not exceed 15 degrees. After completion of dropping, the mixture was stirred at room temperature for 16 hours. The precipitate was removed by filtration and the solvent was distilled off. Purification was performed by column chromatography (silica gel, alumina) using a mixed solvent of dichloromethane / hexane (2: 1). Recrystallization from dichloromethane / hexane gave 38.4 g of the compound represented by the formula (I-6), which was the target product.
Physical property value of compound represented by formula (I-6)
¹ H NMR (CDCl ₃ ) 1.75 (quin, 2H), 1.96 (td, 2H), 1.99 (quin, 2H), 3.73 (s, 6H), 3.94 (m, 4H) ), 4.15 (t, 2H), 4.97 (dd, 1H), 5.03 (dd, 1H), 5.70 (m, 1H), 5.80 (dd, 1H), 6.05 (Dd, 1H), 6.39 (d, 1H), 6.43 (dd, 1H), 6.61 (d, 1H), 6.70 (s, 1H), 6.71 (d, 1H) , 6.75 (s, 1H), 6.92 (d, 1H), 6.94 (d, 1H), 6.99 (d, 1H), 7.06 (dd, 1H), 7.12 ( dd, 1H), 7.64 (d, 1H) ppm.
¹³ C NMR (CDCl ₃ ) 29.8, 30.3, 30.3, 56.0, 56.3, 63.1, 68.8, 72.4, 91.9, 91.0, 112.4 115.1, 114.5, 115.4, 115.5, 116.9, 118.1, 119.1, 119.7, 120.1, 122.0, 124.8, 127.5, 128. 3,128.6, 130.3, 138.0, 138.4, 143.6, 145.5, 145.6, 147.4, 147.6, 154.5, 162.0, 165.0 ppm .
LRMS (EI) m / z 614
Example 7 Production of Compound Represented by Formula (I-7)

  In a four-necked flask, 21.3 g (0.30 mol) of 3-buten-1-ol, 50.0 g (0.25 mol) of 4-bromo-2-methoxyphenol, 83.9 g (0.32) of triphenylphosphine Mol) was added and dissolved in 250 mL of tetrahydrofuran. While cooling with ice, 64.7 g (0.32 mol) of diisopropyl azodicarboxylate was added dropwise so that the temperature of the reaction solution did not exceed 25 ° C. After stirring at room temperature for 10 hours, 10 mL of water was added. After the solvent was distilled off, 70 mL of toluene and 350 mL of hexane were added, followed by liquid separation treatment with a mixed solvent of 350 mL of methanol and 70 mL of water. The organic layer was further washed with a mixed solvent of 300 mL of methanol and 100 mL of water, and the solvent was distilled off. Purification by column chromatography (silica gel) using dichloromethane / hexane (1: 3) gave 63.3 g of a compound represented by the formula (G-1) as a pale yellow oil.

  In a four-necked flask, 63.3 g (0.25 mol) of the compound represented by the formula (G-1), 0.9 g (4.7 mmol) of copper (I) iodide, 189 mL of N, N-dimethylformamide 63 mL of trimethylamine was added, and the atmosphere in the flask was replaced with nitrogen. 2.8 g (2.4 mmol) of tetrakis (triphenylphosphine) palladium (0) was added. The reaction vessel was heated, and 31.4 g (0.32 mol) of trimethylsilylacetylene was added dropwise at 90 ° C. After completion of dropping, the mixture was stirred at 90 ° C. for 8 hours. The mixture was allowed to cool, 300 mL of hexane was added, and liquid separation treatment was performed 4 times with 500 mL of water. Purification by column chromatography (silica gel, alumina) using hexane gave 57.4 g of a compound represented by the formula (G-2) in the form of a brown oil.

  In a four-necked flask, 57.4 g (0.21 mol) of the compound represented by the formula (G-2) was taken and dissolved in 29 mL of dichloromethane and 201 mL of methanol. 5.7 g (41 mmol) of potassium carbonate was added and stirred at room temperature for 12 hours. The solvent was distilled off, and the residue was purified by column chromatography (silica gel) using hexane to obtain 39.3 g of a compound represented by the brown oily formula (G-3).

  In a four-necked flask, 53.1 g (0.18 mol) of 1-bromo-2-fluoro-4-iodobenzene, 0.7 g (3.7 mmol) of copper (I) iodide, formula (G-3) 39.3 g (0.19 mol), N, N-dimethylformamide 159 mL, and trimethylamine 53 mL were added, and the atmosphere in the flask was replaced with nitrogen. Tetrakis (triphenylphosphine) palladium (0) (2.0 g, 1.7 mmol) was added, and the mixture was stirred at 90 ° C. for 5 hours. The mixture was allowed to cool, 300 mL of hexane was added, and liquid separation treatment was performed 4 times with 500 mL of water. Purification by column chromatography (silica gel, alumina) using a toluene / hexane mixed solvent gave 46.2 g of a compound represented by the formula (G-4) as a pale yellow solid.

  In a four-necked flask, 46.2 g (0.12 mol) of the compound represented by the formula (G-4), 18.7 g (0.14 mol) of 4-hydroxyphenylboric acid, and 25.5 g (0. 19 mol) was added and dissolved in ethanol 138 mL and water 46 mL. After replacing the atmosphere in the flask with nitrogen, 1.4 g (1.2 mmol) of tetrakis (triphenylphosphine) palladium (0) was added and heated to reflux for 6 hours. 276 mL of ethyl acetate and 276 mL of 5% hydrochloric acid were added to carry out a liquid separation treatment. Subsequently, it was washed with 300 mL of water and 300 mL of brine. After purification by column chromatography (silica gel, alumina) using a mixed solvent of dichloromethane / hexane, recrystallization is performed using toluene / hexane, and compound 42. represented by the formula (G-5) as a pale yellow solid is obtained. 0 g was obtained.

In a four-necked flask, 42.0 g (0.11 mol) of the compound represented by the formula (G-5), 19.3 g (0.14 mol) of 3-chloropropyl acrylate, 22.4 g of potassium carbonate (0. 16 mol) was added and suspended in 126 mL of N, N-dimethylformamide. After heating and stirring at 90 ° C. for 7 hours, 252 mL of dichloromethane and 252 mL of water were added for liquid separation. Subsequently, after washing twice with 252 mL of water and once with 252 mL of brine, the solvent was distilled off. After purification by column chromatography (silica gel / alumina) using a mixed solvent of dichloromethane / hexane, recrystallization is performed using dichloromethane / hexane, which is represented by the formula (I-7), which is a white crystalline target product. 47.6 g of compound was obtained.
Physical property values of compounds represented by formula (I-7)
¹ H NMR (CDCl ₃ ) 1.99 (quin, 2H), 2.38 (q, 2H), 3.73 (s, 3H), 3.94 (t, 2H), 3.98 (t, 2H) ), 4.15 (t, 2H), 4.97 (dd, 1H), 5.03 (dd, 1H), 5.70 (m, 1H), 5.80 (dd, 1H), 6.05 (Dd, 1H), 6.43 (dd, 1H), 6.62 (d, 1H), 6.83 (dd, 2H), 6.86 (d, 1H), 6.91 (dd, 1H) , 7.23 (dd, 1H), 7.29 (dd, 1H), 7.37 (dd, 2H), 7.42 (dd, 1H) ppm.
¹³ C NMR (CDCl ₃ ) 30.3, 33.8, 56.3, 63.1, 68.5, 72.3, 91.0, 91.0, 114.7, 114.8, 114.9 , 115.1, 118.3, 119.6, 122.8, 123.3, 125.0, 128.0.128.0, 128.2, 128.2, 128.6, 128.6, 130 3, 137.3, 144.1, 147.3, 157.7, 160.6, 165.0 ppm.
LRMS (EI) m / z 500
Example 8 Production of Compound Represented by Formula (I-16)

In Example 5, 4-iodophenol was changed to 4-bromo-2-methoxyphenol, the compound represented by formula (A-4) was changed to the compound represented by formula (H-4), and the formula (B-1 The compound represented by the formula (I-16) was obtained by substituting the compound represented by) with the compound represented by the formula (H-7).
Physical property value of compound represented by formula (I-16)
¹ H NMR (CDCl ₃ ) 1.43-1.76 (m, 8H), 2.05 (d, 3H), 3.83 (s, 3H), 3.97 (t, 2H), 4.16 (T, 2H), 4.68 (d, 2H), 5.59 (d, 1H), 5.67-5.69 (m, 2H), 6.05 (dd, 1H), 6.27 ( dd, 1H), 6.88 (d, 1H), 7.02 (d, 1H), 7.24 to 7.31 (m, 3H), 7.39 (s, 1H), 7.43 (m , 2H), 7.88 to 7.93 (m, 2H), 8.32 (d, 1H), 8.64 (s, 1H) ppm.
¹³ C NMR (CDCl ₃ ) 17.6, 25.6, 25.8, 29.0, 29.6, 56.1, 65.3, 68.7, 70.0, 93.3, 93.3 , 108.2, 110.3, 110.9, 116.0, 117.8, 119.7, 121.1, 122.8, 125.6, 125.9, 126.3, 126.4, 127 .1, 128.2, 128.2, 128.3, 129.4, 130.1, 130.9, 131.3, 137.3, 141.0, 147.6, 149.4, 158.0 , 159.0, 165.2, 166.5 ppm.
LRMS (EI) m / z 636
Example 9 Production of Compound Represented by Formula (I-21)

  To a three-necked flask, 10.0 g (0.08 mol) of 4-hydroxybenzyl alcohol, 18.0 g (0.12 mol) of 3-chloropropyl acrylate, and 16.7 g (0.12 mol) of potassium carbonate were added. It was suspended in 50 mL of N, N-dimethylformamide. After stirring with heating at 90 ° C. for 7 hours, 100 mL of dichloromethane and 100 mL of water were added for liquid separation. Subsequently, after washing twice with 100 mL of water and once with 100 mL of brine, the solvent was distilled off. Recrystallization was performed using dichloromethane / hexane to obtain 17.6 g of a compound represented by the formula (J-1).

In a three-necked flask, 17.6 g (0.07 mol) of a compound represented by the formula (J-1), 21.9 g (0.07 mol) of a compound represented by the formula (A-6), triphenylphosphine 23.4 g (0.09 mol) was added and dissolved in 70 mL of tetrahydrofuran. While cooling with ice, 18.1 g (0.09 mol) of diisopropyl azodicarboxylate was gradually added dropwise so that the reaction temperature did not exceed 15 degrees. After dropping, the mixture was stirred at room temperature for 5 hours, and then the solvent was distilled off. After purification by column chromatography (silica gel, alumina) using a dichloromethane / hexane mixed solvent, recrystallization is performed using dichloromethane / hexane to obtain 29.0 g of the compound represented by the formula (I-21). It was.
Physical property value of compound represented by formula (I-21)
¹ H NMR (CDCl ₃ ) 2.11 (quin, 2H), 2.38 (q, 2H), 3.83 (s, 3H), 3.98 (t, 2H), 4.20 (t, 2H) ), 4.29 (t, 2H), 5.02 (m, 2H), 5.16 (s, 2H), 5.59 (dd, 1H), 5.82 (m, 1H), 6.05 (Dd, 1H), 6.27 (dd, 1H), 6.84 to 7.04 (m, 8H), 7.45 to 7.48 (m, 3H) ppm.
¹³ C NMR (CDCl ₃ ) 28.4, 34.2, 56.1, 61.6, 64.9, 68.5, 71.1, 89.7, 93.3, 110.3, 110.9 , 114.0, 114.0, 114.3, 114.6, 114.6, 116.0, 116.4, 125.6, 128.2, 128.3, 128.9, 128.9, 131 3, 132.9, 132.9, 134.3, 149.4, 149.5, 158.3, 159.1, 166.5 ppm.
LRMS (EI) m / z 512
Example 10 Production of Compound Represented by Formula (I-22)

  In a three-necked flask, 10.0 g (0.049 mol) of 4-bromo-2-methoxyaniline and 13.0 g (0.060 mol) of di-tert-butyl dicarbonate were taken and dissolved in tetrahydrofuran. After reacting at 40 ° C. for 5 hours, the solvent was distilled off to obtain 14.7 g of a compound represented by the formula (K-1).

  In a three-necked flask, 14.7 g (0.049 mol) of the compound represented by formula (K-1), 0.19 g (1.0 mmol) of copper (I) iodide, compound (F-3) 10 0.0 g (0.049 mol), N, N-dimethylformamide 58 mL, and trimethylamine 19 mL were added, and the atmosphere in the flask was replaced with nitrogen. Tetrakis (triphenylphosphine) palladium (0) 0.57 g (0.49 mmol) was added, and the mixture was stirred at 90 ° C. for 5 hours. The mixture was allowed to cool, 200 mL of toluene was added, and liquid separation treatment was performed twice with 200 mL of water. Purification by column chromatography (silica gel, alumina) using a mixed solvent of toluene / ethyl acetate gave 12.5 g of a compound represented by the formula (K-2).

  In a three-necked flask, 12.5 g (0.034 mol) of the compound represented by the formula (K-2) was taken and dissolved in ethyl acetate. 3M hydrochloric acid was added dropwise and reacted at room temperature for 5 hours, followed by washing with water and brine. Purification by column chromatography (silica gel) using a mixed solvent of dichloromethane / ethyl acetate gave 10.0 g of the compound represented by the formula (K-3).

In a four-necked flask, 10.0 g (0.031 mol) of the compound represented by the formula (K-3), 9.1 g (0.031 mol) of the compound represented by the formula (B-1), N, 0.4 g (3.2 mmol) of N-dimethylaminopyridine was taken and suspended in 40 mL of dichloromethane. While cooling with ice, 4.7 g (0.037 mol) of N, N′-diisopropylpropylcarbodiimide was added dropwise so that the reaction temperature did not exceed 15 ° C. After completion of dropping, the mixture was stirred at room temperature for 16 hours. The precipitate was removed by filtration and the solvent was distilled off. Purification was performed by column chromatography (silica gel, alumina) using a mixed solvent of dichloromethane / hexane (2: 1). Recrystallization from dichloromethane / hexane gave 16.7 g of the compound represented by the formula (I-22) as the target product.
Physical property value of compound represented by formula (I-22)
¹ H NMR (CDCl ₃ ) δ 1.43 (m, 4H), 1.62-1.85 (m, 6H), 2.18 (q, 2H), 3.83 (s, 3H), 3. 97 (t, 2H), 4.06 (m, 4H), 5.02 to 5.07 (m, 2H), 5.59 (dd, 1H), 5.82 (m, 1H), 6.05 (Dd, 1H), 6.27 (dd, 1H), 6.93 (d, 1H), 7.06 to 7.17 (m, 5H), 7.54 (s, H), 7.66 ( d, 1H), 7.92 (s, 2H), 9.15 (s, 1H) ppm.
¹³ C NMR (CDCl ₃ ) δ 25.6, 25.8, 28.9, 29.0, 29.6, 30.2, 55.8, 65.3, 68.7, 68.8, 93. 3, 93.3, 114.5, 114.5, 115.6, 115.8, 115.9, 118.2, 119.3, 119.9, 122.2, 123.2, 123.9, 125.8, 128.1, 128.1, 128.2, 128.5, 131.3, 136.5, 147.5, 151.8, 152.3, 162.8, 164.7, 166. 5 ppm.
LRMS (EI) m / z 599
Example 11 Production of Compound Represented by Formula (I-23)

  4-Bromo-2-chlorophenol 50.0 g (0.24 mol) and pyridine 21.1 g (0.27 mol) were added to a four-necked flask and dissolved in 150 mL of dichloromethane. While cooling with ice, 27.3 g (0.27 mol) of acetic anhydride was added. Stir at room temperature for 12 hours. After neutralizing with 150 mL of 10% hydrochloric acid, it was washed 3 times with 150 mL of water. Purification by column chromatography (silica gel) using dichloromethane gave 59.9 g of a compound represented by the colorless oily formula (L-1).

  In a four-necked flask, 15.0 g (0.060 mol) of the compound represented by the formula (L-1), 0.2 g (1.1 mmol) of copper (I) iodide, 45 mL of N, N-dimethylformamide, 15 mL of triethylamine was added. After the atmosphere in the flask was replaced with nitrogen, 0.7 g (0.6 mmol) of tetrakis (triphenylphosphine) palladium (0) was added. While heating at 90 ° C., a solution prepared by dissolving 13.3 g (0.066 mol) of the compound represented by the formula (G-3) in 13 mL of N, N-dimethylformamide was added dropwise. The mixture was stirred at 91 ° C. for 6 hours. Dichloromethane 250mL and water 250mL were added and liquid-separated. Furthermore, it was washed twice with 250 mL of water. The product was purified by column chromatography (silica gel, alumina) using dichloromethane. Recrystallization was performed three times with toluene / hexane to obtain 15.6 g of a compound represented by the formula (L-2) as a pale yellow solid.

  To a flask equipped with a thermometer, 15.6 g (0.042 mol) of the compound represented by the formula (L-2) and 47 mL of tetrahydrofuran were added. 47 mL of 25% aqueous ammonia was added, and the mixture was stirred at room temperature for 16 hours. After diluting with 94 mL of ethyl acetate, the mixture was neutralized by adding 94 mL of 10% hydrochloric acid and 94 mL of water, followed by liquid separation treatment. The organic layer was washed successively with 200 mL of water and 200 mL of brine, and the solvent was distilled off to obtain 13.3 g of a compound represented by the formula (L-3) as a pale yellow solid.

In a four-necked flask, 13.3 g (0.040 mol) of a compound represented by the formula (L-3), 11.9 g (0.040 mol) of a compound represented by the formula (L-4), N, 0.5 g (4.1 mmol) of N-dimethylaminopyridine was taken and suspended in 48 mL of dichloromethane. While cooling with ice, 6.1 g (0.048 mol) of N, N′-diisopropylpropylcarbodiimide was added dropwise so that the reaction temperature did not exceed 15 degrees. After completion of dropping, the mixture was stirred at room temperature for 16 hours. The precipitate was removed by filtration and the solvent was distilled off. Purification was performed by column chromatography (silica gel, alumina) using a dichloromethane / hexane mixed solvent. Recrystallization from dichloromethane / hexane gave 20.5 g of a compound represented by the formula (I-23) as a target product.
Physical property value of compound represented by formula (I-23)
¹ H NMR (CDCl ₃ ) δ 1.43-1.79 (m, 8H), 2.27 (quin, 1H), 2.38 (q, 2H), 2.79 (quin, 1H), 3. 37 (t, 2H), 3.83 (s, 3H), 3.97 (m, 4H), 5.02 to 5.07 (m, 2H), 5.59 (dd, 1H), 5.82 (M, 1H), 6.05 (dd, 1H), 6.27 (dd, 1H), 6.84 (d, 1H), 7.04 (d, 1H), 7.25 (d, 2H) 7.45 (s, 1H), 7.56 (d, 2H) ppm.
¹³ C NMR (CDCl ₃ ) δ 25.6, 25.8, 25.9, 25.9, 29.0, 30.3, 31.5, 31.5, 34.2, 42.9, 56. 1, 65.3, 68.8, 70.2, 81.7, 89.7, 93.3, 110.4, 110.5, 115.3, 116.4, 119.5, 121.2, 121.2, 125.2, 128.2, 131.3, 132.7, 132.7, 134.3, 149.5, 150.3, 151.0, 166.5, 176.9 ppm.
LRMS (EI) m / z 609
Example 12 Production of Compound Represented by Formula (I-24)

  In a four-necked flask, 10.0 g (0.062 mol) of 4-vinylphenyl acetate, 19.4 g of 5-bromo-2-iodoanisole, and 12.9 g (0.093 mol) of potassium carbonate are taken, and N, N- Suspended in 50 mL of dimethylformamide. After replacing the inside of the flask with nitrogen gas, 0.14 g (0.62 mmol) of palladium acetate was added and heated at 130 ° C. for 2 hours. After cooling to room temperature, the mixture was diluted with 100 mL of toluene and subjected to liquid separation treatment with 100 mL of water three times. The solid obtained by distilling off the solvent was purified by column chromatography (silica gel) using dichloromethane to obtain 15.1 g of a cis-trans mixture represented by the formula (M-1).

  In an autoclave, 15.1 g (0.043 mol) of a cis-trans mixture represented by the formula (M-1) was dissolved in 60 mL of tetrahydrofuran. 0.76 g of 5% palladium carbon was added, and the mixture was stirred for 5 hours in a 5 atm hydrogen gas atmosphere. Palladium carbon was filtered and the solvent was distilled off to obtain 14.7 g of a compound represented by the formula (M-2).

  In a four-necked flask, 14.7 g (0.042 mol) of a compound represented by the formula (M-2), 7.8 g (0.042 mol) of a compound represented by the formula (C-3), copper iodide (I) 0.16 g (0.84 mmol) was taken and suspended in 15 mL of triethylamine and 44 mL of N, N-dimethylformamide. After replacing the inside of the flask with nitrogen gas, 0.49 g (0.42 mmol) of tetrakistriphenylphosphine palladium (0) was added, and the mixture was heated and stirred at 80 ° C. for 8 hours. After diluting with 100 mL of toluene, liquid separation treatment was performed 3 times with 100 mL of water. After the solvent was distilled off, the residue was purified by column chromatography (silica gel) using dichloromethane to obtain 9.5 g of a compound represented by the formula (M-3).

  9.5 g (0.021 mol) of a compound represented by the formula (M-3) was taken in a flask and dissolved in 19 mL of tetrahydrofuran and 19 mL of toluene. 10 mL of 28% aqueous ammonia was added and stirred at room temperature for 24 hours. After adding 5% hydrochloric acid to acidify, the organic layer was subjected to liquid separation treatment twice with 100 mL of water and once with brine. After adding anhydrous sodium sulfate and drying, the solvent was distilled off to obtain 8.5 g of a compound represented by the formula (M-4).

In a four-necked flask, 8.5 g (0.021 mol) of a compound represented by the formula (M-4), 4.4 g (0.032 mol) of potassium carbonate, 4.7 g of 3-chloropropyl acrylate (0.032) Mol) and suspended in 34 mL of N, N-dimethylformamide. The mixture was heated and stirred at 90 ° C. for 5 hours, diluted with 100 mL of dichloromethane, and subjected to liquid separation treatment with 100 mL of water three times and with 100 mL of brine once. After the solvent was distilled off, the residue was purified by column chromatography (silica gel, alumina) using a dichloromethane / hexane mixed solvent. Recrystallization from dichloromethane / hexane gave 9.4 g of the compound of formula (I-24), which was the target product.
Physical property values of compounds represented by formula (I-24)
¹ H NMR (CDCl ₃ ) δ 1.85 (quin, 2H), 2.11 to 2.18 (m, 4H), 2.82 (m, 4H), 4.06 (t, 2H), 4. 20 to 4.29 (m, 4H), 5.02 to 5.07 (m, 2H), 5.59 (dd, 1H), 5.82 (m, 1H), 6.05 (dd, 1H) 6.27 (dd, 1H), 6.94-6.95 (m, 4H), 7.18-7.25 (m, 4H), 7.48-7.54 (m, 4H) ppm.
¹³ C NMR (CDCl ₃ ) δ 28.4, 28.9, 30.2, 37.4, 37.4, 61.6, 64.9, 68.8, 89.7, 89.7, 114. 0, 114.0, 114.3, 114.3, 114.3, 115.8, 119.9, 128.2, 129.4, 129.4, 129.8, 129.8, 131.3, 132.2, 132.2, 132.9, 132.9, 133.7, 136.5, 141.8, 156.6, 159.1, 166.5 ppm.
LRMS (EI) m / z 524
Example 13 Production of Compound Represented by Formula (I-25)

  10 g (0.045 mol) of 4-iodophenol and 1.1 g (4.4 mmol) of pyridinium p-toluenesulfonate were taken in a flask and dissolved in 40 mL of dichloromethane. While cooling with ice, 4.5 g (0.053 mol) of 3,4-dihydro-2H-pyran was added dropwise. After stirring at room temperature for 5 hours, liquid separation was sequentially performed with 50 mL of water and 50 mL of brine. By distilling off the solvent, 13.5 g of a compound represented by the formula (N-1) was obtained.

  In a four-necked flask, 13.5 g (0.044 mol) of a compound represented by the formula (N-1), 5.6 g (0.066 mol) of 4-pentyn-1-ol, copper (I) 0 .17 g (0.89 mmol) was taken and suspended in 14 mL of triethylamine and 42 mL of N, N-dimethylformamide. After replacing the inside of the flask with nitrogen gas, 0.51 g (0.44 mmol) of tetrakistriphenylphosphine palladium (0) was added, and the mixture was heated and stirred at 90 ° C. for 8 hours. After diluting with 80 mL of toluene, it was washed with 80 mL of water and 80 mL of brine, and the solvent was distilled off to obtain 8.0 g of the compound represented by the formula (N-2).

  8.0 g (0.031 mol) of the compound represented by the formula (N-2) was taken in an autoclave and dissolved in 80 mL of tetrahydrofuran. 0.4 g of 5% palladium carbon was added, and the mixture was stirred for 5 hours in a 5 atm hydrogen gas atmosphere. After filtering 5% palladium on carbon, the solvent was distilled off to obtain 8.2 g of a compound represented by the formula (N-3).

  8.2 g (0.031 mol) of the compound represented by the formula (N-3) was dissolved in 41 mL of dichloromethane. 0.24 g (3.0 mmol) of pyridine was added. While cooling with ice, 9.6 g (0.034 mol) of trifluoromethanesulfonic anhydride was added dropwise. After stirring at room temperature for 8 hours, the mixture was washed with 5% hydrochloric acid (40 mL), water (40 mL), and saturated aqueous sodium bicarbonate (40 mL), and the solvent was distilled off. The obtained solid was distilled under reduced pressure to obtain 7.4 g of a compound represented by the formula (N-4).

  In a flask, 7.4 g (0.019 mol) of the compound represented by the formula (N-4) was taken and dissolved in 37 mL of toluene. 4.3 g (0.038 mol) of potassium tert-butoxide was added and stirred for 8 hours. Washing was performed twice with 100 mL of water and once with 100 mL of brine, and the solvent was distilled off to obtain 4.5 g of a compound represented by the formula (N-5).

  In a flask, 4.5 g (0.018 mol) of the compound represented by the formula (N-5) was taken and dissolved in 18 mL of dichloromethane and 18 mL of methanol. 9 mL of 10% hydrochloric acid was added and stirred at room temperature for 5 hours. After diluting with 50 mL of dichloromethane, the mixture was washed twice with 50 mL of water and once with 50 mL of brine, and the solvent was distilled off. Recrystallization using a mixed solvent of dichloromethane / hexane gave 2.9 g of the compound represented by the formula (N-6).

  In a flask, 2.9 g (0.018 mol) of the compound represented by the formula (N-6) was taken and dissolved in 15 mL of dichloromethane. 0.14 g (1.8 mmol) of pyridine was added. While cooling with ice, 6.1 g (0.022 mol) of trifluoromethanesulfonic anhydride was added dropwise. The mixture was stirred at room temperature for 5 hours, diluted with 50 mL of dichloromethane, and subjected to liquid separation three times with 50 mL of 5% hydrochloric acid and 50 mL of brine. Purification by column chromatography (silica gel) using dichloromethane gave 5.3 g of the compound represented by the formula (N-7).

  In a four-necked flask, 5.3 g (0.018 mol) of the compound represented by the formula (N-7), 0.07 g (0.37 mmol) of copper (I) iodide, 2.7 g of trimethylsilylacetylene (0. 027 mol) was taken and suspended in 10 mL of triethylamine and 30 mL of N, N-dimethylformamide. After replacing the inside of the flask with nitrogen gas, tetrakistriphenylphosphine palladium (0) 0.21 g (0.18 mmol) was added, and the mixture was heated and stirred at 80 ° C. for 5 hours. After diluting with 50 mL of toluene, liquid separation was performed twice with 50 mL of water and with 50 mL of brine. After distilling off the solvent, the residue was purified by column chromatography (silica gel) using dichloromethane to obtain 3.1 g of a compound represented by the formula (N-8).

  3.1 g (0.013 mol) of the compound represented by the formula (N-8) was taken in a flask and dissolved in 9 mL of dichloromethane and 9 mL of methanol. 2.7 g (0.020 mol) of potassium carbonate was added and stirred at room temperature for 6 hours. The precipitate was filtered and subjected to a liquid separation treatment with 30 mL of water. After distilling off the solvent, 1.5 g of the compound represented by the formula (N-9) was obtained by distillation under reduced pressure.

  In a four-necked flask, 10.0 g (0.036 mol) of 4-iodo-2,6-dimethoxyphenol and 3.4 g (0.043 mol) of pyridine were taken and dissolved in 50 mL of dichloromethane. While cooling with ice, 4.4 g (0.043 mol) of acetic anhydride was added. Stir at room temperature for 8 hours. The mixture was neutralized with 50 mL of 10% hydrochloric acid and then washed 3 times with 50 mL of water. Purification by column chromatography (silica gel) using dichloromethane gave 11.5 g of the compound represented by the formula (N-10).

  In a four-necked flask, 2.8 g (8.7 mmol) of the compound represented by the formula (N-10), 0.03 g (0.16 mmol) of copper (I) iodide, 17 mL of N, N-dimethylformamide, 6 mL of triethylamine was added. After the atmosphere in the flask was replaced with nitrogen, 0.10 g (0.087 mmol) of tetrakis (triphenylphosphine) palladium (0) was added. While heating at 90 ° C., a solution of 1.5 g (8.8 mmol) of the compound represented by the formula (N-9) dissolved in 2 mL of N, N-dimethylformamide was added dropwise. The mixture was stirred at 91 ° C. for 6 hours. Dichloromethane 25mL and water 25mL were added and liquid-separated. Furthermore, it was washed twice with 25 mL of water. The product was purified by column chromatography (silica gel, alumina) using dichloromethane. Recrystallization was performed twice with toluene / hexane to obtain 2.5 g of a compound represented by the formula (N-11).

  To a flask equipped with a thermometer, 2.5 g (6.9 mmol) of the compound represented by the formula (N-11) and 10 mL of tetrahydrofuran were added. 3 mL of 25% aqueous ammonia solution was added and stirred at room temperature for 6 hours. After diluting by adding 50 mL of ethyl acetate, the mixture was acidified by adding 20 mL of 10% hydrochloric acid and 20 mL of water, followed by liquid separation treatment. The organic layer was washed sequentially with 50 mL of water and 50 mL of brine, and the solvent was distilled off to obtain 2.1 g of the compound represented by the formula (N-12).

In a four-necked flask, 2.1 g (6.5 mmol) of the compound represented by formula (N-12), 2.5 g (7.7 mmol) of cesium carbonate, 1.5 g (7.9) of 6-chlorohexyl acrylate Mmol) and suspended in 10 mL of dimethyl sulfoxide. After stirring with heating at 80 ° C. for 7 hours, the mixture was diluted with 30 mL of dichloromethane and subjected to liquid separation treatment with 30 mL of water three times. After purification by column chromatography (silica gel) using dichloromethane, recrystallization using a dichloromethane / methanol mixed solvent yields 2.5 g of the compound represented by the formula (I-25) which is the target product. Obtained.
Physical property values of compounds represented by formula (I-25)
¹ H NMR (CDCl ₃ ) δ 1.43-1.46 (m, 6H), 1.62 (quin, 2H), 1.76 (quin, 2H), 2.18 (q, 2H), 2. 62 (t, 2H), 3.97 (t, 2H), 4.06 (t, 2H), 5.02 to 5.07 (m, 2H), 5.59 (dd, 1H), 5.82 (M, 1H), 6.05 (dd, 1H), 6.27 (dd, 1H), 6.95 (d, 2H), 7.25 (d, 2H), 7.48 to 7.54 ( m, 4H) ppm.
¹³ C NMR (CDCl ₃ ) δ 25.6, 25.8, 29.0, 29.6, 31.1, 33.5, 35.8, 65.3, 68.7, 89.7, 89. 7, 114.0, 114.0, 114.3, 115.8, 120.0, 128.2, 130.2, 130.2, 131.3, 132.4, 132.4, 132.9, 132.9, 136.5, 141.7, 159.1, 166.5 ppm.
LRMS (EI) m / z 476
(Examples 14-26, Comparative Examples 1-2)
It is represented by formula (I-1) to formula (I-7), formula (I-16) and formula (I-21) to formula (I-25) of the present invention described in Examples 1 to 13. Similar to the non-liquid crystalline comparative compound 1 having a polymerization retardation described in JP-A No. 2000-17003 (Patent Document 1) and the present invention compound described in US Pat. No. 6,514,578 (Patent Document 3) The physical properties of Comparative Compound 2 having the Tran structure are shown in Table 1 below.

  It can be seen that the compounds represented by formulas (I-1) to (I-4) of the present invention all exhibit a sufficient nematic liquid crystal phase in a temperature range that can be easily handled in the production process.

  In order to evaluate the storage stability of the compound, 10% from 20% to 80% of the compound with respect to a base liquid crystal composed of compound VI (40%), compound VII (30%) and compound VIII (30%) Each composition added in increments was prepared. Table 1 below shows the maximum concentration of the compound at which no crystal precipitation occurs after the prepared composition is allowed to stand at 25 ° C. for 15 hours. The compounds represented by formula (I-1) to formula (I-7), formula (I-16), and formula (I-21) to formula (I-25) of the present invention are both Comparative Compound 1 and Comparative Example 1. It can be seen that the maximum addition concentration at which crystal precipitation does not occur is equal to or higher than that of Compound 2 and shows high storage stability.

  It is represented by formula (I-1) to formula (I-7), formula (I-16) and formula (I-21) to formula (I-25) of the present invention described in Examples 1 to 13. A polymerizable liquid crystal composition containing the compound, comparative compound 1 and comparative compound 2 was prepared as shown in Table 2 below.

  Examples 14 to 17 including the compounds represented by formulas (I-1) to (I-4) of the present invention all exhibit a sufficient nematic liquid crystal phase in a temperature range that can be easily handled in the production process. I understand that.

(Examples 27 to 39, Comparative Examples 3 to 4)
Next, a photopolymerization initiator Irgacure 907 (Ciba Specialty Chemical Co., Ltd.) was added to each of the polymerizable liquid crystal compositions of Examples 14 to 26, which are the present composition, and Comparative Examples 1 and 2, which are comparative compositions. Made of 5.0%, liquid paraffin with a weight average molecular weight of 600 (made by Kanto Chemical Co., Ltd.) 0.1%, FTX-730LS (made by Neos) 0.05%, and polymerization inhibitor 4-methoxyphenol 0 A polymerizable liquid crystal composition added with 1% was prepared, and a propylene glycol monomethyl ether acetate solution containing 25% of the polymerizable liquid crystal composition was prepared. This was spin-coated on a glass with polyimide (1200 rpm / 15 seconds) and dried at 80 ° C. for 2 minutes. On the polymerizable liquid crystal composition layer thus formed, a mask (1951 USAF test target, positive pattern, manufactured by Edmund Optics, Inc.) was placed with an interval of 23 μm, and UV irradiation (20 mW / cm ² , 5 seconds) was applied from above. Then, mask exposure was performed (see FIG. 1). After UV irradiation, the glass plate was immersed in propylene glycol monomethyl ether acetate for 30 seconds to remove uncured portions. The obtained glass plate was naturally dried and the solvent was evaporated to obtain patterned films of Example 27 to Example 39, Comparative Example 3 and Comparative Example 4.

  The pattern resolution, haze value, and appearance of the resulting patterned film were evaluated, and the results are shown in Table 6. The pattern resolution was measured using a laser microscope (VK-9510 manufactured by Keyence Corporation), and the group number / line number with the highest resolution at which the pattern corresponding to the mask pattern was completely reproduced was described. In this pattern, the spatial frequency (lines / mm) is defined as shown in Table 5 below.

The haze value is the following formula haze (%) = Td / Tt × 100
(In the formula, Td represents diffuse transmittance, and Tt represents total light transmittance.) For measurement, a haze measurement device (NHD2000 manufactured by Nippon Denshoku Industries Co., Ltd.) was used, and measurement was performed at five locations on the substrate. And took the average. Moreover, when there was no nonuniformity etc. on the film by visual observation and it was uniform as a whole, it was evaluated as “◯”, and when nonuniformity was observed, it was evaluated as “X”.

  From Example 14 containing the compound represented by Formula (I-1) to Formula (I-7), Formula (I-16), and Formula (I-21) to Formula (I-25) of the present invention. In each of the patterned film Example 27 to the patterned film Example 39 obtained from Example 26, a uniform film having a small haze value and no occurrence of unevenness was obtained. On the other hand, in the patterned film comparative example 4 obtained from the composition comparative example 2 containing the comparative compound 2, the appearance was good, but the haze was slightly larger compared to the case containing the compound of the present invention. became. In the patterned film comparative example 3 obtained from the comparative example 1 containing the comparative compound 1, the haze was high and white stripe-shaped unevenness occurred. Moreover, in the patterned film Example 27 to the patterned film Example 39 obtained from Example 14 to Example 26 containing the compound of the present invention, the pattern resolution is high, and up to the group 6 in the test pattern. All patterns were fully reproduced. On the other hand, in the patterned film comparative example 4 obtained from the comparative example 2 containing the comparative compound 2, the pattern resolution was low, and the patterns up to the group 4 in the test pattern were reproduced, but the groups 5 and above were blurred in the whole. And it was not completely reproduced. In Patterned Film Comparative Example 3 obtained from Comparative Example 1 containing Comparative Compound 1, the pattern shape was barely recognizable up to Group 5 / Line 1.

* Appearance: ○ Good, × Unevenness As described above, all of the compounds of the present invention have a high refractive index anisotropy and are compared with Comparative Compound 1 and Comparative Compound 2 having a similar high refractive index anisotropy. Thus, it can be seen that the storage stability is equal to or higher and the liquid crystal phase temperature range is sufficiently wide. In addition, it can be seen that by producing a patterned film using the compound of the present invention, a film having a higher pattern resolution and less haze / unevenness can be obtained as compared with the prior art.

This figure shows a shape defined by the USAF 1951 resolution test pattern (positive pattern), and a black area is a portion that is shielded from light.

Claims (11)

Formula (I)

(In the formula, P represents a reactive group represented by the following formula (P-1) to formula (P-3) and formula (P-7) to formula (P-15)).

And S ¹ and S ² are each independently one —CH ₂ — or two or more non-adjacent —CH ₂ — are each independently replaced with —O—. Represents an alkylene group having 1 to 8 carbon atoms, and X ¹ and X ² are each independently —O— , —OCH ₂ —, —CH ₂ O—, —CO—, —COO—, —OCO. _{-, -O-CO-O-,} -CF 2 O -, - OCF 2 -, -CH 2 CH 2 -, - CH 2 CF 2 -, - CF 2 CH 2 -, - CF 2 CF 2 -, - CH═CH—COO—, —CH═CH—OCO—, —COO—CH═CH—, —OCO—CH═CH—, —COO—CH ₂ CH ₂ —, —OCO—CH ₂ CH ₂ —, — _{CH 2 CH 2 -COO -, -} CH 2 CH 2 -OCO -, - COO-CH 2 -, - O CO—CH ₂ —, —CH ₂ —COO—, —CH ₂ —OCO—, —CY ¹ ═CY ² —, —C≡C— or a single bond (wherein Y ¹ and Y ² are each independently A hydrogen atom, an alkyl group having 1 to 12 carbon atoms, a fluorine atom, a chlorine atom or a cyano group.), N1 represents 1 , 2, 3 or 4, and n2 represents 0, 1 , 2, 3 or 4 and A ¹ and A ⁴ are each independently 1,4-phenylene group, naphthalene-2,6-diyl group, 1,4-cyclohexylene group, 1,4-cyclohexenylene group, 1,4 -Bicyclo [2.2.2] octylene group, decahydronaphthalene-2,6-diyl group or 1,2,3,4-tetrahydronaphthalene-2,6-diyl group, pyridine-2,6-diyl group, Pyrimidine-2,5-diyl group, 1,3-dioxane-2,5-di These groups may be unsubstituted, fluorine atom, chlorine atom, cyano group, nitro group, alkyl group having 1 to 7 carbon atoms, alkoxy group having 1 to 7 carbon atoms or The alkanoyl group having 1 to 7 carbon atoms may be substituted, and in these alkyl group, alkoxy group or alkanoyl group, one or more hydrogen atoms may be replaced by fluorine atom or chlorine atom, and A ¹ and When a plurality of A ⁴ are present, they may be the same or different, and Z ¹ and Z ² are each independently —OCH ₂ —, —CH ₂ O—, —COO—, —OCO—. , —CF ₂ O—, —OCF ₂ — , —CH ₂ CH ₂ —, —CH ₂ CF ₂ —, —CF ₂ CH ₂ —, —CF ₂ CF ₂ —, —CH═CH—COO— , —CH = CH-OCO _{, -COO-CH = CH -,} - OCO-CH = CH -, - COO-CH 2 CH 2 -, - OCO-CH 2 CH 2 -, - CH 2 CH 2 -COO -, - CH 2 CH 2 - _{OCO -, - COO-CH 2} -, - OCO-CH 2 -, - CH 2 -COO -, - CH 2 -OCO -, - CH = CH -, - CH = CF -, - CF = CH -, - ^{CY 3 = CY 4 -, -} C≡C- or a single bond and represents (wherein, ^{Y 3} and ^{Y 4} are each independently hydrogen atom, an alkyl group having 1 to 12 carbon atoms, a fluorine atom, a chlorine atom or a Represents a cyano group. ), A plurality of Z ¹ and / or Z ² may be the same or different, m 1 and m 2 each independently represents 0, 1 or 2, and l represents 0 or 1 , A ² and A ³ each independently represents a 1,4-phenylene group in which one —CH═ or two non-adjacent —CH═ may be replaced by —N═, One or more hydrogen atoms in the 4-phenylene group are each independently substituted with a fluorine atom, a chlorine atom, a cyano group, a nitro group, or an alkyl group having 1 to 8 carbon atoms, an alkoxy group, or an alkanoyl group. The alkyl group, alkoxy group or alkanoyl group may be further substituted with a fluorine atom or a chlorine atom, and R represents a hydrogen atom or an alkyl group having 1 to 12 carbon atoms. May be unsubstituted , A fluorine atom, a chlorine atom, may be substituted by a cyano group, also one -CH 2 in the alkyl group _- or nonadjacent two or more -CH 2 _- are each independently -O- , -S- may be substituted. ) A polymerizable compound represented by: The polymerizable compound according to claim 1, wherein l represents 1 in the general formula (I). In the general formula (I), X ¹ and X ² are each independently —O—, —COO—, —OCO—, —CH═CH—COO—, —CH═CH—OCO—, —COO—CH═. _{CH -, - OCO-CH =} CH -, - COO-CH 2 CH 2 -, - OCO-CH 2 CH 2 -, - CH 2 CH 2 -COO -, - CH 2 CH 2 -OCO -, - COO- _{CH 2 -, - OCO-CH} 2 -, - CH 2 -COO -, - CH 2 -OCO- or polymerizable compound according to claim 1 or 2 represents a single bond. In the general formula (I), Z ¹ and Z ² are each independently —OCH ₂ —, —CH ₂ O—, —COO—, —OCO—, —CH═CH—COO—, —CH═CH—OCO. _{-, - COO-CH = CH} -, - OCO-CH = CH -, - COO-CH 2 CH 2 -, - OCO-CH 2 CH 2 -, - CH 2 CH 2 -COO -, - CH 2 CH 2 _{-OCO -, - COO-CH 2} -, - OCO-CH 2 -, - CH 2 -COO -, - polymerization according CH 2 -OCO- or claims 1 represents a single bond to any one of 3 Sex compounds. In general formula (I), A ¹ and A ⁴ are each independently unsubstituted or substituted by a fluorine atom, a chlorine atom, an alkyl group having 1 to 4 carbon atoms, or an alkoxy group having 1 to 4 carbon atoms. 1,4-phenylene group, unsubstituted or substituted by fluorine or chlorine atom, naphthalene-2,6-diyl group, or one —CH ₂ — or _two non-adjacent — The polymerizable compound according to claim 1, wherein CH ₂ — represents an unsubstituted 1,4-cyclohexylene group which may be replaced by —O—. In the general formula (I), A ² and A ³ represent a 1,4-phenylene group, and at least one hydrogen atom in the two 1,4-phenylene groups is an alkyl group having 1 to 8 carbon atoms, an alkoxy group The polymerizable compound according to claim 1, wherein the polymerizable compound is substituted with a group or an alkanoyl group, and the alkyl group, alkoxy group or alkanoyl group may be substituted with a fluorine atom or a chlorine atom. In general formula (I), A ² and A ³ represent a 1,4-phenylene group, and at least one hydrogen atom in the two 1,4-phenylene groups represents an alkoxy group having 1 to 8 carbon atoms. The polymerizable compound according to claim 6, wherein at least one hydrogen atom is substituted with a fluorine atom, a chlorine atom, a cyano group or a nitro group. In the general formula (I), -A ² -≡-A ³ -is changed from the following formulas (A ²³ -1) to (A ²³ -20).

(In formula, L represents a fluorine atom, a chlorine atom, a cyano group, or a nitro group each independently.) The polymeric compound of Claim 6 represented. A polymerizable liquid crystal composition containing the polymerizable compound according to claim 1. A polymer obtained by polymerizing the polymerizable liquid crystal composition according to claim 9. A film, an optical element, a functional pigment, a pharmaceutical, a cosmetic, a coating agent or a synthetic resin using the polymer according to claim 10.

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