TWI622598B - Polymerizable compound, polymerizable composition, and optical anisotropy - Google Patents

Abstract

An object of the present invention is to provide a polymerizable compound having a large refractive index anisotropy and having high storage stability and high orientation when constituting a polymerizable liquid crystal composition, and a polymerizable liquid crystal composition containing the polymerizable compound. Furthermore, a polymer obtained by polymerizing the polymerizable liquid crystal composition and an optically anisotropic body using the polymer are provided. The solution to this problem is to provide a polymerizable compound represented by the general formula (I), a polymerizable liquid crystal composition using the compound as a constituent member, and further providing a polymerizable liquid crystal composition obtained by polymerizing the polymerizable liquid crystal composition. Polymer and optical anisotropy using the polymer.

Description

Polymerizable compound, polymerizable composition, and optical anisotropy

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

The polymerizable compound is used in various films. For example, a film having a uniform orientation can be produced by arranging polymerizable compounds in a liquid crystal state and polymerizing them. The thus-produced film can be used for a polarizing plate, a retardation plate, and the like required for a liquid crystal display. The polymerizable compound can also be used to produce a film having a cholesteric structure. In many cases, in order to satisfy the required optical characteristics, polymerization speed, solubility, melting point, glass transition temperature, film transparency, mechanical strength, surface hardness, heat resistance, and light resistance, two or more kinds of polymerizability can be used. Composition of compounds. At this time, the polymerizable compound used is required to bring good physical properties to the composition without adversely affecting other characteristics. Especially for the purpose of producing a film having a cholesteric structure, it is necessary to have a polymerizable property that it can exist as a nematic phase or a cholesteric phase in a wide temperature range and has high nematic or cholesteric liquid crystal alignment properties. Compound. In addition, in order to prepare a composition having a large refractive index anisotropy, a polymerizable compound having a large refractive index anisotropy is required. Furthermore, since the composition ratio changes when a specific component is precipitated from the composition during processing of the composition, a polymerizable compound having high storage stability is required.

When this film having a cholesteric structure is used as a brightness-improving film such as a display, a uniform cholesteric structure having a small haze value and no spots is required. Therefore, it is desired to develop a polymerizable compound having high alignment properties in addition to the above characteristics. However, the polymerizable compounds (Patent Documents 1 to 3) developed so far have large refractive index anisotropy, but have problems of low storage stability and low alignment. Therefore, the haze value of the optically anisotropic body obtained by coating a composition containing such a polymerizable compound on PET and drying it becomes large, or spots are generated, and it is difficult to produce a film having a uniform alignment. On the other hand, in Patent Documents 4 and 5, it is described that the refractive index anisotropy is increased by introducing a diphenylacetylene (tolan) skeleton. Polymerizable compounds, but there is no description about storage stability and orientation in this document. Moreover, although patent document 6 and patent document 7 have description about the polymerizable compound which has a naphthalene structure, storage stability and a haze value are not described in detail.

[Prior technical literature] [Patent Literature]

Patent Document 1: Japanese Patent Application Laid-Open No. 2008-88291

Patent Document 2: Japanese Patent Application Laid-Open No. 2008-195762

Patent Document 3: Japanese Patent Application Laid-Open No. 2-238087

Patent Document 4: Japanese Patent Application Laid-Open No. 2002-265421

Patent Document 5: EP1786887B1

Patent Document 6: Japanese Patent Application Laid-Open No. 2008-179654

Patent Document 7: Japanese Patent Application Laid-Open No. 2007-119415

The problem to be solved by the present invention is to provide a polymerizable compound having a large refractive index anisotropy and a high storage stability and a high orientation when constituting a polymerizable liquid crystal composition, and a polymerizable liquid crystal composition containing the polymerizable compound. . Further, a polymer obtained by polymerizing the polymerizable liquid crystal composition and an optically anisotropic body using the polymer are provided.

The present inventors have studied various substituents of a polymerizable compound, and as a result, found that a polymerizable compound having a specific structure can solve the above problems, and completed the present invention.

The present invention provides a polymerizable compound represented by the general formula (I) and a polymerizable liquid crystal composition using the compound.

(In the formula, P represents a substituent selected from a polymerizable group represented by the following formula (P-1) to formula (P-15);

S ¹ represents one -CH ₂ -or two or more non-adjacent -CH ₂ -which can be independently passed through -O-, -S-, -CO-, -COO-, -OCO-, -CO- S-, -S-CO-, -O-CO-O-, -CO-NH-, -NH-CO- substituted alkylene or single bond with 1 to 20 carbon atoms; X ¹ represents 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 single bond (wherein Y ¹ and Y ² each independently represent hydrogen Atom, alkyl group having 1 to 12 carbon atoms, fluorine atom, chlorine atom or cyano group.); L ¹ to L ⁶ each independently represent a hydrogen atom, a fluorine atom, a chlorine atom, a cyano group, a nitro group, and a carbon number. 1 to 7 alkyl groups, 1 to 7 carbon atoms, or 1 to 7 carbon alkyl groups, which are present in the alkyl group and alkoxy group One or more hydrogen atoms in the alkanoyl group may be substituted with a fluorine atom or a chlorine atom; M ¹ ~ M ⁴ each independently represent a hydrogen atom, a fluorine atom, a chlorine atom, a cyano group, a nitro group, having 1 to 7 carbon atoms, Alkyl group, alkoxy group having 1 to 7 carbon atoms, alkanoyl group having 1 to 7 carbon atoms, or -X ² -S ² -P (wherein X ² , S ^2, and P each represent the same as X ¹ , S ¹ and P have the same meaning, and each may be the same group or different groups.), One or more hydrogen atoms present in the alkyl group, alkoxy group, or alkylfluorenyl group may be fluorine Atom or chlorine atom substitution, there is no case where all of M ¹ to M ⁴ are the same hydrogen atom; A ¹ , A ² and A ³ each independently represent 1,4-phenylene, naphthalene-2,6-diyl , 1,4-cyclohexyl, 1,4-cyclohexenyl, 1,4-bicyclo [2.2.2] octyl, decahydronaphthalene-2,6-diyl, 1,2,3, 4-tetrahydronaphthalene-2,6-diyl, pyridine-2,6-diyl, pyrimidine-2,5-diyl, or 1,3-diyl Alkane-2,5-diyl, these groups may be unsubstituted, or may be fluorine, chlorine, cyano, nitro, 1 to 7 carbon atoms, 1 to 7 carbon atoms Alkoxy or alkanoyl having 1 to 7 carbon atoms may be substituted, and one or more hydrogen atoms of such alkyl, alkoxy or alkanoyl may be substituted by fluorine or chlorine atoms, A ¹ and / or A These may be the same or different when there are ^{two or} more; Z ¹ , Z ² and Z ⁴ 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 single bond (where Y ³ and Y ⁴ Each independently represents a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, a fluorine atom, a chlorine atom, or a cyano group.), Z ¹ , Z ^2, and Z ⁴ may be the same or different when there are a plurality of them; Z ³ Means -O CH _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 ⁵ = CY ⁶ -or a single bond (wherein Y ⁵ and Y ⁶ 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); R represents a fluorine atom , A chlorine atom, a cyano group, an alkyl group having 1 to 12 carbon atoms, or -X ³ -S ³ -P (wherein X ³ , S ^3, and P each have the same meaning as the above X ¹ , S ^1, and P, Each may be the same group or different groups. ), One or more hydrogen atoms in the alkyl group may be substituted with a fluorine atom, a chlorine atom, or a cyano group. In addition, one -CH ₂ -or two or more adjacent- CH ₂ -can be independently passed through -O-, -S-, -CO-, -COO-, -OCO-, -CO-S-, -S-CO-, -O-CO-O-, -CO -NH-, -NH-CO-, -CH = CH-, -CH = CF-, -CF = CH- or -C≡C- substitution; m ¹ and m ² each independently represent 0 or 1, R represents -X ³ -S ³ -P, when m ¹ = 0, m ² = 0, A ³ represents a group other than naphthalene-2,6-diyl, and there is no single bond in which only one of S ¹ and S ³ represents a single bond. Happening. ).

The polymerizable compound of the present invention is useful as a constituent member of a polymerizable composition because it has a large refractive index anisotropy and exhibits high storage stability. In addition, an optical anisotropic body using a composition containing the polymerizable compound of the present invention is highly useful for applications such as an optical film because it has high alignment.

(Form of Implementing Invention)

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

S ¹ represents one -CH ₂ -or two or more non-adjacent -CH ₂ -which can be independently passed through -O-, -S-, -CO-, -COO-, -OCO-, -CO- S-, -S-CO-, -O-CO-O-, -CO-NH-, -NH-CO- substituted alkylene or single bond with 1 to 20 carbon atoms, from liquid crystal properties and other The viewpoint of the component's mutual solubility is particularly preferably an alkylene group having 2 to 8 carbon atoms.

X ¹ represents -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 single bond (where Y ¹ and Y ² are independent Ground means a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, a fluorine atom, a chlorine atom, or a cyano group.), More preferably -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, particularly preferably -O-.

L ¹ to L ⁶ each independently represent a hydrogen atom, 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 1 to 7 carbon atoms. Alkyl group of 7, one or more hydrogen atoms present in the alkyl, alkoxy or alkyl group may be replaced by a fluorine atom or a chlorine atom, preferably a hydrogen atom, a fluorine atom or a chlorine atom, more preferably L ¹ , L ² , L ^4, and L ^{5 each} represent a hydrogen atom, and L ³ and L ^{6 each} represent a combination of a hydrogen atom, a fluorine atom, or a chlorine atom. From the viewpoint of ease of production, it is particularly preferred that all of L ¹ to L ⁶ represent hydrogen atoms The combination.

M ¹ to M ⁴ each independently represent a hydrogen atom, 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 1 to 7 carbon atoms. Alkyl group of 7 or -X ² -S ² -P (wherein X ² , S ² and P each have the same meaning as the above X ¹ , S ¹ and P, and each may be the same group or different Group.), One or more hydrogen atoms present in the alkyl group, alkoxy group, or alkylfluorenyl group may be replaced by fluorine atoms or chlorine atoms, and there is no M ¹ to M ^{4 which are} all hydrogen atoms in the same manner. In this case, it is preferable that any one of M ¹ to M ⁴ represents a fluorine atom, a chlorine atom, a cyano group, a nitro group, or an alkane having 1 to 7 carbon atoms which may be substituted with a fluorine atom or a chlorine atom. Group, alkoxy group, alkylsulfonyl group or -X ² -S ² -P (wherein X ² , S ² and P each have the same meaning as the above X ¹ , S ¹ and P, and each may be the same group Different groups may also be used.), When the remaining three represent a combination of hydrogen atoms and represent -X ² -S ² -P, P is preferably 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), more preferably Is the formula (P-1) , Formula (P-2), formula (P-7), formula (P-11) or formula (P-13), particularly preferably formula (P-1) or formula (P-2), S ² from the liquid crystal The viewpoint of the solubility and compatibility with other components is preferably an alkylene group having 2 to 8 carbon atoms, and X ^{2 is} preferably -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 single bond, especially -O-, M ¹ ~ M ^{4 is} particularly preferably a combination of M ¹ representing a fluorine atom, a chlorine atom, a cyano group, a methyl group, or a methoxy group, and M ² to M ⁴ representing a hydrogen atom.

A ¹ , A ² and A ³ each independently represent 1,4-phenylene, naphthalene-2,6-diyl, 1,4-cyclohexyl, 1,4-cyclohexenyl, 1,4 -Bicyclo [2.2.2] octyl, decalin-2,6-diyl, 1,2,3,4-tetralin-2,6-diyl, pyridine-2,6-diyl, Pyrimidine-2,5-diyl, 1,3-diyl Alkane-2,5-diyl, these groups may be unsubstituted, or may be fluorine, chlorine, cyano, nitro, 1 to 7 carbon atoms, 1 to 7 carbon atoms Alkoxy or alkanoyl having 1 to 7 carbon atoms may be substituted. Such alkyl, alkoxy or alkanoyl may be substituted with one or more hydrogen atoms by fluorine or chlorine atoms, A ¹ and / or A ² These may be the same or different when there are a plurality, and are preferably unsubstituted or substituted with 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. 4-phenylene, naphthalene-2,6-diyl, 1,4-cyclohexyl, 1,4-cyclohexenyl, 1,4-bicyclo [2.2.2] octyl, decahydronaphthalene -2,6-diyl, 1,2,3,4-tetrahydronaphthalene-2,6-diyl, pyridine-2,6-diyl, pyrimidine-2,5-diyl, 1,3-diyl Alkane-2,5-diyl is preferably unsubstituted or 1,4-diene substituted by fluorine atom, chlorine atom, alkyl group having 1 to 4 carbon atoms or alkoxy group having 1 to 4 carbon atoms. Phenyl, naphthalene-2,6-diyl or 1,4-cyclohexyl, particularly preferably 1,4-phenylene which is unsubstituted or substituted with a fluorine atom, a chlorine atom, a CH ₃ group or a CH ₃ O group Or naphthalene-2,6-diyl, or unsubstituted 1,4-cyclohexyl.

Z ¹ , Z ² and Z ⁴ 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 (where Y ³ and Y ⁴ each independently represent a hydrogen atom and a carbon number of 1 to 12 Alkyl group, fluorine atom, chlorine atom or cyano group.), Preferably -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-, -C≡C- or single bond, particularly preferably -COO-, -OCO-, -CH = CH-COO-, -CH = CH-OCO-, -COO-CH = CH-, -OCO-CH = CH- or a single bond.

Z ³ represents -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 ⁵ = CY ⁶ -or a single bond (wherein Y ⁵ and Y ⁶ 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), -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, particularly from the viewpoint of liquid crystallinity, mutual solubility with other components, or affinity to a substrate, -COO-, -OCO-, -CH = CH-COO-, -CH = CH-OCO-, -COO-CH = CH-, -OCO-CH = CH- or single bond.

R represents a fluorine atom, a chlorine atom, a cyano group, an alkyl group having 1 to 12 carbon atoms, or -X ³ -S ³ -P (wherein X ³ , S ^3, and P are the same as those of X ¹ , S ^1, and P has the same meaning and each may be the same group or different groups.), One or more hydrogen atoms present in the alkyl group may be substituted by a fluorine atom, a chlorine atom, and a cyano group. One -CH ₂ -or two or more -CH ₂ -in the group may be independently passed through -O-, -S-, -CO-, -COO-, -OCO-, -CO- S-, -S-CO-, -O-CO-O-, -CO-NH-, -NH-CO-, -CH = CH-, -CH = CF-, -CF = CH- or C≡C -Substituted, which represents a fluorine atom, a chlorine atom, a cyano group, an alkyl group having 1 to 12 carbon atoms, or -X ³ -S ³ -P (wherein X ³ , S ^3, and P represent the same as X ¹ , S ¹ and P have the same meaning, and each may be the same group or different groups.) It is preferably 1 -CH ₂ -or two or more -CH ₂ -which are not adjacent to each other in the alkyl group. When -O-, -S-, -CO-, -COO-, -OCO- can be substituted independently, when -X ³ -S ³ -P is represented, P is preferably formula (P-1), Formula (P-2), Formula (P-3), Formula (P-4), Formula (P-5), Formula (P-7), Formula (P-11), Formula (P-1 3) or formula (P-15), more preferably formula (P-1), formula (P-2), formula (P-7), formula (P-11) or formula (P-13), especially preferred Formula (P-1) or Formula (P-2), S ^{3 is} preferably an alkylene group having 2 to 8 carbon atoms, and X ^{3 is} preferably -O from the viewpoint of liquid crystallinity and mutual solubility with other components. -, -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, particularly preferably -O-, and R is particularly preferably a fluorine atom, a chlorine atom, a cyano group, or an alkyl group having 1 to 8 carbon atoms.

m ¹ and m ² each independently represent 0 or 1, preferably a combination of m ¹ being 0 and m ² being 0 or 1, particularly preferably a combination of m ¹ being 0 and m ² being 0.

Among them, R represents -X ³ -S ³ -P, when m ¹ = 0, m ² = 0, A ³ represents a group other than naphthalene-2,6-diyl, and only one of S ¹ and S ³ does not exist. Represents the case of a single key. At this time, A ^{3 is} preferably a 1,4-phenylene group, an unsubstituted or 1,4-phenylene group substituted with 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. , 4-cyclohexyl, 1,4-cyclohexenyl, 1,4-bicyclo [2.2.2] octyl, decalin-2,6-diyl, 1,2,3,4- Tetrahydronaphthalene-2,6-diyl, pyridine-2,6-diyl, pyrimidine-2,5-diyl, 1,3-diyl Alkane-2,5-diyl, more preferably unsubstituted or 1,4-ethanene substituted with fluorine atom, chlorine atom, alkyl group having 1 to 4 carbon atoms or alkoxy group having 1 to 4 carbon atoms Phenyl or 1,4-cyclohexyl, particularly preferably unsubstituted or substituted with a fluorine atom, a chlorine atom, a CH ₃ group or a CH ₃ O group, or a 1,4-phenylene group or an unsubstituted 1,4- Cyclohexyl.

In addition, when R represents -X ³ -S ³ -P, and m ¹ = 1, m ² = 0, or m ¹ = 0, and m ² = 1, there is no case where only one of S ¹ and S ³ represents a single bond. In this case, it is preferable that at least one of Z ¹ , Z ² and Z ⁴ independently represent -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 ⁵ = CY ^6- (wherein Y ⁵ and Y ⁶ 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) or a single bond , More preferably -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- , -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 -CY ⁵ = CY ⁶ - (wherein, Y ⁵ and Y ⁶ each independently represent a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, and a fluorine atom, a chlorine atom, or Group), and particularly preferably represents -CO-S -., - S -CO -, - CO-NH -, - NH-CO -, - SCH 2 -, - CH 2 S -, - CF 2 S -, - SCF ₂ -or -CY ⁵ = CY ^6- (wherein Y ⁵ and Y ⁶ 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, but Y is not present ⁵ and Y ⁶ both represent a hydrogen atom.).

As a compound represented by general formula (I), the compound represented by following formula (I-1)-formula (I-47) is preferable.

The compound of the present invention can be produced by the following production method.

(Preparation method 1) Synthesis of the following compound (S7)

A protective group is introduced into the hydroxyl group of the hydroxycarboxylic acid (S1). The protective group PG is not particularly limited as long as it is a group that can stably protect a functional group during synthesis and is easily detached. For example, it can be used by John Wiley Co. Wiley & Sons, Inc.) The protective group described in the edition "GREENE'S PROTECTIVE GROUPS IN ORGANIG SYNTHESIS" (Fourth Edition). An ester (S4) is produced by condensing a carboxylic acid (S2) having a hydroxyl group protected by a protecting group PG and a phenol derivative (S3). For the condensation, for example, an acid catalyst such as sulfuric acid, hydrochloric acid, nitric acid, acetic acid, formic acid, trifluoroacetic acid, p-toluenesulfonic acid, or N, N'-dicyclohexylcarbodiimide, N, N'-diisopropylcarbodicarbonate can be used. Carbodiimide-based condensing agents such as imine and 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide hydrochloride are used. Alternatively, it may be a method using a phototransition reaction or a carboxyphosphonium halide. Next, for example, the intermediate (S5) obtained by removing the protective group PG by the method described in the above-mentioned document is condensed with a carboxylic acid (S6) to synthesize a target compound (S7).

(Preparation method 2) Synthesis of the following compound (S12)

A protective group is introduced into the hydroxyl group of the hydroxycarboxylic acid (S8). An ester (S10) is prepared by condensing a carboxylic acid (S9) having a hydroxyl group protected by a protecting group PG and a phenol derivative (S3). Next, the intermediate (S11) obtained by removing the protecting group PG and the carboxylic acid (S6) are condensed to synthesize a target compound (S12).

(Preparation method 3) Synthesis of the following compound (S19)

A protecting group was introduced into one hydroxyl group of hydroquinone (S13). An ester (S16) is produced by condensing a hydroquinone (S14) having a hydroxyl group protected by a protecting group PG and a carboxylic acid (S15). Next, the intermediate (S17) obtained by removing the protecting group PG and the carboxylic acid (S18) are condensed to synthesize a target compound (S19).

(Preparation method 4) Synthesis of the following compound (S23)

An ester (S21) is prepared by condensing a hydroquinone (S14) having a hydroxyl group protected by a protecting group PG and a carboxylic acid (S20). Next, the intermediate (S22) obtained by removing the protecting group PG and the carboxylic acid (S6) are condensed to synthesize a target compound (S23).

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 cholesteric liquid crystal composition. A compound other than the present invention may be added to the liquid crystal composition using the polymerizable compound of the present invention.

The other polymerizable compound used as a mixture with the polymerizable compound of the present invention is specifically preferably a compound represented by the general formula (II),

(In the formula, R ¹¹ and R ¹² each independently have the same meaning as P of the general formula (I); S ¹¹ and S ¹² each independently represent a single bond or an alkylene group having 1 to 18 carbon atoms, 1 -CH ₂ -or non-adjacent 2 or more -CH ₂ -may be substituted by an oxygen atom, -COO-, -OCO-, -OCOO-; L ¹¹ , L ¹² and L ¹³ independently represent 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 = 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- _{, -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 -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 independently represent 1,4-phenylene, 1 , 4-cyclohexyl, pyridine-2,5-diyl, pyrimidine-2,5-diyl, naphthalene-2,6-diyl, tetrahydronaphthalene-2,6-diyl, or 1,3-di Alkane-2,5-diyl, but preferably M ¹¹ and M ¹² are independently unsubstituted or may be alkyl, haloalkyl, alkoxy, haloalkoxy, halogeno group , Cyano or nitro substitution; 1 ¹¹ represents 0, 1, 2 or 3, and 1 ¹¹ represents 2 or 3, when there are 2 or 3 L ¹² and / or M ¹² compounds which may be the same or different, L ¹¹ , L ¹² and L ¹³ independently represent a single bond, -O-, -COO- or -OCO-, and M ¹¹ and M ¹² independently represent 1,4-phenylene and 1,4-cyclohexyl , Pyridine-2,5-diyl, pyrimidine-2,5-diyl, naphthalene-2,6-diyl. ).

R ¹¹ and R ^{12 in the} general formula (II) are more preferably an acryl group or a methacryl group. Specifically, a compound represented by the general formula (III) is preferable,

(In the formula, S ³ and S ⁴ each independently represent an alkylene group having 2 to 18 carbon atoms, X ³ and X ⁴ each independently represent -O-, -COO-, -OCO-, or a single bond, Z ⁵ And Z ⁶ each independently represent -COO- or -OCO-, and A ⁶ , A ⁷ and A ⁸ each independently represent an unsubstituted or fluorine atom, a chlorine atom, an alkyl group having 1 to 4 carbon atoms or a carbon atom An alkoxy-substituted 1,4-phenylene group having a number of 1 to 4) is particularly preferably a compound represented by the following formulae (III-1) to (III-8).

(Wherein, S ³ represents the general formula (III) the same meaning of S ^3, S ⁴ and S represents the general formula (III) is ⁴ the same meaning.) In the above formula (III-1) ~ formula (Ill In 8), it is more preferable that S ³ and S ⁴ are each independently an alkylene group having 3 to 6 carbon atoms.

In addition, a compound represented by the general formula (IV) is preferred,

(In the formula, S ⁵ and S ⁶ each independently represent an alkylene group having 2 to 18 carbon atoms, X ⁵ and X ⁶ each independently represent -O-, -COO-, -OCO-, or a single bond, Z ⁷ Represents -COO- or -OCO-, and A ⁹ , A ¹⁰ and A ¹¹ each independently represent an unsubstituted or fluorine atom, a chlorine atom, an alkyl group having 1 to 4 carbon atoms or an alkyl group having 1 to 4 carbon atoms The oxy-substituted 1,4-phenylene.) Is particularly preferably a compound represented by the following formula (IV-1) to formula (IV-8).

(Wherein, S ⁵ and S denote the same general formula (Ⅳ) means ^5, S ⁶ S represents the general formula (Ⅳ) ⁶ is the same meaning.) In the above formula (Ⅳ-1) ~ formula (IV- In 8), from the viewpoints of heat resistance and durability, Formula (IV-2), Formula (IV-5), Formula (IV-6), Formula (IV-7), and Formula (IV-8) are preferred. The compound represented is more preferably a compound represented by formula (IV-2), and particularly preferably a compound in which S ⁵ and S ⁶ are each independently an alkylene group having 3 to 6 carbon atoms.

Moreover, as a preferable bifunctional polymerizable compound, the compound represented by following General formula (V-1)-formula (V-4) is mentioned.

(In the formula, S ⁷ and S ⁸ each independently represent an alkylene group having 2 to 18 carbon atoms.) Among the above formulae (V-1) to (V-4), the formula (V-2) is preferred ) And the compound represented by the formula (V-3), and particularly preferably a compound in which S ⁷ and S ⁸ are each independently an alkylene group having 3 to 6 carbon atoms.

When the compound of the present invention is used in a cholesteric liquid crystal composition, the addition amount of the polymerizable chiral compound is preferably 0.1 to 40% by mass. Moreover, in the polymerizable liquid crystal composition containing the compound of the present invention, a polymerizable compound that does not exhibit liquid crystallinity may be added to such an extent that the liquid crystallinity of the composition is not impaired. Specifically, any compound that is familiar as a polymer-forming monomer or a 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. Examples of the photopolymerization initiator include benzoin ethers, benzophenones, acetophenones, benzyl ketals, and fluorenylphosphine oxides.

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, etc. The addition amount when using a stabilizer is preferably 0.005 to 1% by mass, and more preferably 0.02 to 0.5% by mass relative to the liquid crystal composition.

In addition, the polymerizable liquid crystal composition containing the compound of the present invention is used for films, optical elements, functional pigments, medical supplies, cosmetics, and coatings. For applications such as agents and synthetic resins, metals, metal complexes, dyes, pigments, pigments, fluorescent materials, phosphorescent materials, surfactants, leveling agents, thixotropic agents, glues can also be added according to their purpose. Coagulants, polysaccharides, ultraviolet absorbers, infrared absorbers, antioxidants, ion exchange resins, metal oxides such as titanium oxide, etc.

The polymer obtained by polymerizing the polymerizable liquid crystal composition containing the compound of the present invention can be used in various applications. For example, a polymer obtained by polymerizing a polymerizable liquid crystal composition containing a compound of the present invention without alignment can be used as a light-scattering plate, a polarization-removing plate, and an interference fringe prevention plate. Moreover, it is useful that the polymer obtained by superposing | polymerizing after orientation has optical anisotropy. Such an optically anisotropic body can be, for example, by supporting a polymerizable liquid crystal composition containing the compound of the present invention on a substrate subjected to a rubbing treatment with a cloth or the like, a substrate on which an organic thin film is formed, or a substrate having oblique vapor deposition of SiO ₂ . The polymerizable liquid crystal composition is polymerized on the substrate of the alignment film or sandwiched between the substrates to produce the polymerizable liquid crystal composition.

Examples of a method for supporting a polymerizable liquid crystal composition on a substrate include spin coating, die coating, extrusion coating, roll coating, wire bar coating, gravure coating, spray coating, and dipping. Painting, printing, etc. During the application, an organic solvent may be added to the polymerizable liquid crystal composition. Examples of the organic solvent include a hydrocarbon-based solvent, a halogenated hydrocarbon-based solvent, an ether-based solvent, an alcohol-based solvent, a ketone-based solvent, an ester-based solvent, an aprotic solvent, and the like. Examples of the hydrocarbon-based solvent include toluene or hexane Examples of the halogenated hydrocarbon-based solvent include dichloromethane, and examples of the ether-based solvent include tetrahydrofuran, ethoxy-2-ethoxyethane, or propylene glycol monomethyl ether acetate, and examples of the alcohol-based solvent include Examples of the solvent include methanol, ethanol, and isopropanol. Examples of the ketone solvent include acetone, methyl ethyl ketone, cyclohexanone, γ-butyrolactone, and N-methylpyrrolidone. Examples of the solvent include ester solvents. Examples include ethyl acetate or cellosolve, and examples of the aprotic solvent include dimethylformamide or acetonitrile. These materials may be used alone or in combination, as long as the vapor pressure and the solubility of the polymerizable liquid crystal composition are appropriately selected. As a method for volatilizing the added organic solvent, natural drying, heating drying, drying under reduced pressure, and heating under reduced pressure can be used. In order to further improve the coatability of the polymerizable liquid crystal material, it is also effective to provide an intermediate layer such as a polyimide film on the substrate and add a leveling agent to the polymerizable liquid crystal material. An intermediate layer such as a polyimide film is provided on a substrate The method is effective because it can improve the adhesion between the polymer obtained by polymerizing the polymerizable liquid crystal material and the substrate.

Examples of the alignment treatment other than the above include the use of flow alignment of a liquid crystal material and the use of an electric field or a magnetic field. These alignment methods can be used alone or in combination. Furthermore, as an alignment processing method instead of friction, a photo-alignment method may be used. The shape of the substrate may have a curved surface as a constituent in addition to a flat plate. As the material constituting the substrate, any of organic materials and inorganic materials can be used. Examples of the organic material used as the material of the substrate include polyethylene terephthalate, polycarbonate, polyimide, polyimide, polymethyl methacrylate, polystyrene, and polyvinyl chloride. , Polytetrafluoroethylene, polychlorotrifluoroethylene, polyarylate, polyfluorene, triethylcellulose, cellulose, polyetheretherketone, and the like. Examples of the inorganic material include silicon, glass, and calcite. Wait.

When polymerizing a polymerizable liquid crystal composition containing a compound of the present invention, it is desirable to perform the polymerization quickly. Therefore, it is preferable to perform the polymerization by irradiating active energy rays such as ultraviolet rays or electron beams. When using ultraviolet light, a polarized light source or a non-polarized light source can be used. In addition, when the polymerization is performed while the liquid crystal composition is sandwiched between two substrates, at least the substrate on the irradiation surface side must have appropriate transparency for active energy rays. In addition, the following method can also be used: after a specific portion is polymerized using a mask during light irradiation, the orientation state of the unpolymerized portion is changed by changing conditions such as an electric field, a magnetic field, or a temperature, and then active energy is irradiated The rays are polymerized. The temperature during irradiation is preferably within a temperature range in which the liquid crystal state of the polymerizable liquid crystal composition of the present invention can be maintained. In particular, when it is desired to produce an optically anisotropic body by photopolymerization, from the intention of avoiding undesired thermal polymerization, it is also preferable that the temperature is as close to room temperature as possible, that is, typically 25 ° C. Polymerization was carried out. The intensity of the active energy ray is preferably from 0.1 mW / cm ² to 2 W / cm ² . When the strength is 0.1 mW / cm ² or less, it takes a lot of time to complete photopolymerization and productivity deteriorates. When the strength is ² W / cm ² or more, the polymerizable liquid crystal compound or the polymerizable liquid crystal composition may be deteriorated.

The optically anisotropic body obtained by polymerization may be subjected to heat treatment for the purpose of reducing initial characteristic changes and achieving stable characteristic expression. Heat treatment temperature The degree 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 optically anisotropic body produced by such a method may be peeled from the substrate and used as a single body, or may be used without peeling. In addition, the obtained optical anisotropic body may be laminated, and it may be used by being stuck to another substrate.

[Example]

Hereinafter, the present invention will be further described with examples, but the present invention is not limited to these examples. In addition, "%" in the composition of the following examples and comparative examples means "mass%."

(Example 1) Production of compound represented by formula (I-1)

In a reaction vessel having a stirring device, a cooler, and a thermometer, 200 g (1.2 mol) of 4-hydroxy-3-methoxybenzoic acid (a compound represented by the formula (A-1)), 700 mL of acetic acid, and 133 g of acetic anhydride ( 1.3 mol), 3 g sulfuric acid, and heated to 60 ° C. for 9 hours. 1 L of water was added to the reaction solution, and after stirring for 2 hours while cooling with ice, the precipitated solid was filtered. The obtained solid was re-dispersed and washed with 1 L of water. By drying the solid, 203 g of a compound represented by the formula (A-2) was obtained.

In a reaction vessel having a stirring device and a thermometer, 25.0 g (0.12 mole) of the compound represented by the formula (A-2), 13.2 g of 2,4-dimethylphenol (0.11 mole), and N, N-dimethyl 0.7 g (5.4 mmol) of aminoaminopyridine (DMAP) and 125 mL of dichloromethane were stirred while cooling with ice. While maintaining the temperature of the reaction solution at 15 ° C or lower, 16.4 g (0.13 mole) of N, N'-diisopropylcarbodiimide (DIC) was added dropwise. After completion of the dropwise addition, the reaction was carried out by stirring at room temperature for 5 hours. The reaction solution was filtered and the precipitate was removed, and then distilled. Remove the solvent. The obtained solid was dissolved in dichloromethane and purified by column chromatography (refined preparation: 33 g of silica gel, eluent: 264 mL of dichloromethane), and then the solvent was distilled off. The obtained solid substance was dispersedly washed with 102 mL of methanol, and then dried to obtain 29.0 g of a compound represented by the formula (A-3).

A reaction vessel having a stirring device and a thermometer was charged with 29.0 g (0.092 mol) of a compound represented by the formula (A-3), 87 mL of toluene, and 87 mL of tetrahydrofuran. While stirring, 10.1 g (0.14 mol) of butylamine was added dropwise. After the dropwise addition was completed, the mixture was stirred at room temperature overnight. After neutralizing and separating with 100 mL of 5% hydrochloric acid, the organic layer was washed twice with 100 mL of saline. The solvent was distilled off, and the obtained oily substance was recrystallized from a mixed solvent of 90 mL of methanol and 90 mL of water. 20.1 g of a compound represented by the formula (A-4) was obtained by drying the obtained solid.

A reaction vessel having a stirring device and a thermometer was charged with 20.1 g (0.074 mole) of a compound represented by formula (A-4) and 6- (3-propenyloxy-propoxy) -2-naphthoic acid (formula ( Compound represented by A-5)) 24.4 g (0.081 mol), 0.45 g (3.7 mmol) of N, N-dimethylaminopyridine and 122 mL of dichloromethane were stirred while cooling with ice. While maintaining the temperature of the reaction solution at 15 ° C or lower, 11.2 g (0.089 mole) of N, N'-diisopropylcarbodiimide was added dropwise. After completion of the dropwise addition, the reaction was carried out by stirring at room temperature for 6 hours. The reaction solution was filtered to remove precipitates, and then the solvent was distilled off. The obtained solid was dissolved in dichloromethane and purified by column chromatography (refined preparation: 41 g of silica gel, eluent: 328 mL of dichloromethane), and then the solvent was distilled off. The obtained solid was recrystallized twice from a mixed solvent of 41 mL of methylene chloride and 123 mL of methanol, and then dried to obtain 32.7 g of a compound represented by the formula (I-1).

(Physical property value of the compound represented by formula (I-1))

¹ H NMR (CDCl ₃ ) δ 2.21 (s, 3H), 2.27 (quintet, 2H), 2.35 (s, 3H), 3.92 (s, 3H), 4.24 (t, 2H), 4.43 ( t, 2H), 5.85 (dd, 1H), 6.15 (dd, 1H), 6.43 (dd, 1H), 7.01 to 7.10 (m, 3H), 7.20 to 7.24 (m, 2H), 7.34 (d, 1H) , 7.81 ~ 7.95 (m, 4H), 8.17 (dd, 1H), 8.74 (s, 1H) ppm.

¹³ C NMR (CDCl ₃ ) δ 16.2, 20.9, 28.6, 56.2, 61.3, 64.5, 106.5, 114.0, 120.0, 121.6, 123.2, 123.3, 123.9, 126.3, 127.0, 127.5, 127.9, 128.2, 128.3, 129.8, 131.0, 131.1, 131.8, 132.0, 135.7, 137.6, 144.6, 147.3, 151.6, 159.1, 164.4, 164.6, 166.2 ppm.

LRMS (EI) m / z 554 (100).

(Example 2) Production of compound represented by formula (I-3)

In a reaction vessel having a stirring device and a thermometer, 30.0 g (0.14 mol) of the compound represented by the formula (A-2), 14.0 g (0.13 mol) of p-cresol, and N, N-dimethylaminopyridine 0.8 were added. g (6.5 mmol), 150 mL of dichloromethane, and stirred while cooling with ice. While maintaining the temperature of the reaction solution at 15 ° C or lower, 19.7 g (0.16 mol) of N, N'-diisopropylcarbodiimide was added dropwise. After completion of the dropwise addition, the reaction was stirred at room temperature for 8 hours. The reaction solution was filtered to remove precipitates, and then the solvent was distilled off. The obtained solid was dissolved in dichloromethane and purified by column chromatography (refined preparation: 39 g of silica gel, eluent: 312 mL of dichloromethane), and then the solvent was distilled off. The obtained solid matter was dispersed and washed with 117 mL of methanol, and then dried to obtain 35.8 g of a compound represented by the formula (B-1).

A reaction vessel having a stirring device and a thermometer was charged with 35.8 g (0.12 mol) of a compound represented by the formula (B-1), 107 mL of toluene, and 107 mL of tetrahydrofuran. While stirring, 13.1 g (0.18 mol) of butylamine was added dropwise. After the dropwise addition was completed, the mixture was stirred at room temperature overnight. After neutralization and separation with 200 mL of 5% hydrochloric acid, the organic layer was washed twice with 200 mL of brine. The solvent was distilled off, and the obtained oily substance was recrystallized from a mixed solvent of 120 mL of methanol and 120 mL of water. 30.1 g of a compound represented by the formula (B-2) was obtained by drying the obtained solid.

In a reaction vessel having a stirring device and a thermometer, 30.1 g (0.12 mol) of a compound represented by the formula (B-2) and 38.7 g of 6- (3-propenyloxy-propoxy) -2-naphthoic acid ( 0.13 mole), 0.71 g (5.8 mmol) of N, N-dimethylaminopyridine, and 193 mL of dichloromethane, and stirred while cooling with ice. Keep the temperature of the reaction solution at At 15 ° C or lower, 17.7 g (0.14 mole) of N, N'-diisopropylcarbodiimide was added dropwise. After completion of the dropwise addition, the reaction was carried out by stirring at room temperature for 5 hours. The reaction solution was filtered to remove precipitates, and then the solvent was distilled off. The obtained solid was dissolved in dichloromethane and purified by column chromatography (refined preparation: 63 g of silica gel, eluent: 504 mL of dichloromethane), and then the solvent was distilled off. The obtained solid was recrystallized twice from a mixed solvent of 63 mL of methylene chloride and 189 mL of methanol, and then dried to obtain 51.6 g of a compound represented by the formula (I-3).

(Physical properties of the compound represented by formula (I-3))

¹ H NMR (CDCl ₃ ) δ 2.27 (quintet, 2H), 2.39 (s, 3H), 3.91 (s, 3H), 4.24 (t, 2H), 4.42 (t, 2H), 5.85 (dd, 1H ), 6.15 (dd, 1H), 6.43 (dd, 1H), 7.10 (d, 2H), 7.19 ~ 7.26 (m, 4H), 7.33 (d, 1H), 7.81 ~ 7.84 (m, 2H), 7.89 ~ 7.93 (m, 2H), 8.17 (dd, 1H), 8.73 (s, 1H) ppm.

¹³ C NMR (CDCl ₃ ) δ 20.9, 28.6, 56.2, 61.3, 64.6, 76.7, 77.0, 77.2, 77.3, 106.5, 113.9, 115.5, 120.0, 121.4, 123.2, 123.2, 123.3, 123.9, 126.4, 127.1, 128.0, 128.3, 130.0, 131.0, 131.2, 132.0, 135.6, 137.6, 144.6, 148.7, 151.5, 159.1, 164.5, 164.8, 166.2 ppm.

LRMS (EI) m / z 540 (100).

(Example 3) Production of compound represented by formula (I-7)

In Example 2, except that p-cresol was replaced with 4-ethylphenol, a compound represented by the formula (I-7) was produced in the same manner.

(Physical properties of the compound represented by formula (I-7))

¹ H NMR (CDCl ₃ ) δ 1.27 (t, 3H), 2.27 (quintet, 2H), 2.69 (q, 2H), 3.91 (s, 3H), 4.24 (t, 2H), 4.43 (t, 2H ), 5.85 (dd, 1H), 6.15 (dd, 1H), 6.44 (dd, 1H), 7.14 (d, 2H), 7.20 ~ 7.27 (m, 4H), 7.33, (d, 1H), 7.81 ~ 7.85 (m, 2H), 7.91 (td, 2H), 8.17 (dd, 1H), 8.73 (1H) ppm.

¹³ C NMR (CDCl ₃ ) δ 15.6, 28.3, 28.6, 56.2, 61.3, 64.6, 106.5, 114.0, 120.0, 121.4, 123.2, 123.4, 123.9, 126.4, 127.1, 128.0, 128.3, 128.9, 131.0, 131.2, 132.0, 137.6, 141.9, 144.6, 148.8, 151.5, 159.1, 164.5, 164.8, 166.2 ppm.

LRMS (EI) m / z 554 (100).

(Example 4) Production of compound represented by formula (I-8)

In a reaction vessel having a stirring device, a cooler, and a thermometer, 105 g (0.58 mol) of 3-chloro-4-hydroxybenzoic acid 0.5 hydrate (compound represented by the formula (D-1)), 350 mL of acetic acid, and 65.0 of acetic anhydride were added. g (0.64 mole) and 1.5 g of sulfuric acid were heated to 60 ° C. for 8 hours to react. 1 L of water was added to the reaction solution, and after stirring for 1 hour while cooling with ice, the precipitated solid was filtered. The obtained solid was washed with 1 L of water. 120.6 g of a compound represented by the formula (D-2) was obtained by drying the solid.

In a reaction vessel having a stirring device and a thermometer, 25.0 g (0.12 mole) of the compound represented by the formula (D-2), 11.4 g (0.11 mole) of p-cresol, and N, N-dimethylaminopyridine 0.6 were added. g (5.2 mmol) and 125 mL of dichloromethane were stirred while cooling with ice. While maintaining the temperature of the reaction solution at 15 ° C or lower, 15.9 g (0.13 mol) of N, N'-diisopropylcarbodiimide was added dropwise. After completion of the dropwise addition, the reaction was carried out by stirring at room temperature for 5 hours. The reaction solution was filtered to remove precipitates, and then the solvent was distilled off. The obtained solid was dissolved in dichloromethane and purified by column chromatography (refined preparation: 32 g of silica gel, eluent: 256 mL of dichloromethane), and then the solvent was distilled off. The obtained solid matter was dispersed and washed with 96 mL of methanol, and then dried to obtain 28.5 g of a compound represented by the formula (D-3).

A reaction vessel having a stirring device and a thermometer was charged with 28.5 g (0.094 mol) of a compound represented by the formula (D-3), 86 mL of toluene, and 86 mL of tetrahydrofuran. 10.3 g (0.14 mole) of butylamine was added dropwise while stirring. After the dropwise addition was completed, the mixture was stirred at room temperature overnight. After neutralization and separation with 150 mL of 5% hydrochloric acid, the organic layer was washed twice with 150 mL of saline. The solvent was distilled off, and the obtained oily substance was recrystallized from a mixed solvent of 74 mL of methanol and 74 mL of water. 23.8 g of a compound represented by the formula (D-4) was obtained by drying the obtained solid.

A reaction vessel with a stirring device and a thermometer was charged with 23.8 g (0.091 mole) of a compound represented by formula (D-4) and 29.9 g of 6- (3-propenyloxy-propoxy) -2-naphthoic acid ( 0.099 mole), 0.55 g (4.5 mmol) of N, N-dimethylaminopyridine, and 150 mL of dichloromethane, and the mixture was stirred while cooling with ice. While maintaining the temperature of the reaction solution at 15 ° C or lower, 13.7 g (0.11 mole) of N, N'-diisopropylcarbodiimide was added dropwise. After completion of the dropwise addition, the reaction was carried out by stirring at room temperature for 6 hours. The reaction solution was filtered to remove precipitates, and then the solvent was distilled off. The obtained solid was dissolved in dichloromethane and purified by column chromatography (refined preparation: 49 g of silica gel, eluent: 392 mL of dichloromethane), and then the solvent was distilled off. The obtained solid was recrystallized twice from a mixed solvent of 49 mL of dichloromethane and 147 mL of methanol, and then dried to obtain 40.5 g of a compound represented by the formula (I-8).

(Physical properties of the compound represented by formula (I-8))

¹ H NMR (CDCl ₃ ) δ 2.25 (quintet, 2H), 2.38 (s, 3H), 4.24 (t, 2H), 4.43 (t, 2H), 5.86 (dd, 1H), 6.15 (dd, 1H) ), 6.44 (dd, 1H), 7.11 (d, 2H), 7.20 ~ 7.26 (m, 4H), 7.49 (d, 1H), 7.83 (d, 1H), 7.91 (d, 1H), 8.18 (m, 2H), 8.36 (m, 1H), 8.76 (s, 1H) ppm.

¹³ C NMR (CDCl ₃ ) δ 20.9, 28.6, 61.3, 64.6, 106.5, 120.2, 121.2, 123.3, 124.2, 126.2, 127.3, 127.8, 127.9, 128.3, 128.6, 129.8, 130.1, 131.0, 131.2, 132.3, 135.8, 137.8, 148.5, 151.6, 159.3, 163.7, 164.0, 166.2 ppm.

LRMS (EI) m / z 544 (100), 546 (30).

(Example 5) Production of compound represented by formula (I-15)

A compound represented by formula (I-15) was produced in the same manner as in Example 2 except that p-cresol was replaced with 6-propyl-2-naphthol.

(Physical properties of the compound represented by formula (I-15))

¹ H NMR (CDCl ₃ ) δ 1.27 (t, 3H), 1.66 (m, 2H), 2.27 (quintet, 2H), 2.66 (t, 2H), 3.91 (s, 3H), 4.24 (t, 2H ), 4.43 (t, 2H), 5.85 (dd, 1H), 6.15 (dd, 1H), 6.44 (dd, 1H), 7.14 (d, 2H), 7.20 ~ 7.27 (m, 4H), 7.30 ~ 7.45, (m, 3H), 7.81 to 7.90 (m, 4H), 8.17 (dd, 1H), 8.73 (1H) ppm.

¹³ C NMR (CDCl ₃ ) δ 13.6, 25.2, 30.3, 38.4, 56.0, 63.1, 68.5, 105.5, 108.9, 116.1, 117.4, 119.7, 122.3, 122.8, 125.5, 125.8, 126.1, 126.4, 127.0, 128.0, 128.4, 128.4, 128.6, 128.8, 129.2, 130.3, 130.4, 130.8, 132.5, 132.8, 136.1, 143.9, 152.1, 154.8, 160.1, 164.0, 164.0, 165.0 ppm.

LRMS (EI) m / z 618 (100).

(Example 6) Production of compound represented by formula (I-16)

In Example 2, trans-4-propylcyclohexanol was used instead of p-cresol, except Other than that, the compound represented by Formula (I-16) was produced similarly.

(Physical properties of the compound represented by formula (I-16))

¹ H NMR (CDCl ₃ ) δ 1.27 to 1.43 (m, 12H), 2.27 to 2.35 (m, 6H), 3.91 (s, 3H), 4.02 (five heavy peaks, 1H), 4.24 (t, 2H), 4.43 (t, 2H), 5.85 (dd, 1H), 6.15 (dd, 1H), 6.44 (dd, 1H), 7.14 (d, 2H), 7.20 (d, 1H), 7.81 ~ 7.85 (m, 2H), 7.91 (td, 2H), 8.17 (dd, 1H), 8.73 (1H) ppm.

¹³ C NMR (CDCl ₃ ) δ 14.3, 20.9, 25.8, 25.8, 29.2, 29.2, 30.3, 32.0, 36.9, 56.0, 63.1, 68.5, 72.3, 105.5, 115.7, 119.7, 122.3, 122.4, 125.8, 126.1, 127.0, 128.0, 128.8, 128.8, 130.3, 130.4, 130.8, 136.1, 143.0, 154.8, 160.1, 165.0, 164.0, 167.0 ppm.

LRMS (EI) m / z 574 (100).

(Example 7) Production of compound represented by formula (I-17)

In a reaction vessel equipped with a stirring device, a cooler, and a thermometer, 100 g (0.52 mole) of 4-hydroxy-3-methoxycinnamic acid (a compound represented by the formula (G-1)), 350 mL of acetic acid, and 57.8 g of acetic anhydride (0.57 moles) and 1.5 g of sulfuric acid were heated to 60 ° C. for 10 hours to react. 1 L of water was added to the reaction solution, and after stirring for 1 hour while cooling with ice, the precipitated solid was filtered. The obtained solid was washed with 1 L of water. 111 g of a compound represented by formula (G-2) was obtained by drying the solid.

In a reaction vessel having a stirring device and a thermometer, 25.0 g (0.106 mole) of the compound represented by the formula (G-2), 10.4 g (0.096 mole) of p-cresol, and N, N-dimethylaminopyridine 0.6 were added. g (4.8 mmol) and 125 mL of dichloromethane were stirred while cooling with ice. While maintaining the temperature of the reaction solution at 15 ° C or lower, 14.6 g (0.12 mol) of N, N'-diisopropylcarbodiimide was added dropwise. After completion of the dropwise addition, the reaction was carried out by stirring at room temperature for 5 hours. The reaction solution was filtered to remove precipitates, and then the solvent was distilled off. The obtained solid was dissolved in dichloromethane, and column chromatography (refined preparation: 31 g of silica gel, washed Extraction liquid: 248 mL of dichloromethane), and the solvent was distilled off. The obtained solid matter was dispersed and washed with 124 mL of methanol, and then dried to obtain 26.7 g of a compound represented by the formula (G-3).

A reaction vessel having a stirring device and a thermometer was charged with 26.7 g (0.082 mol) of a compound represented by formula (G-3), 80 mL of toluene, and 80 mL of tetrahydrofuran. While stirring, 9.0 g (0.12 mol) of butylamine was added dropwise. After the dropwise addition was completed, the mixture was stirred at room temperature overnight. After neutralization and separation with 180 mL of 5% hydrochloric acid, the organic layer was washed twice with 180 mL of brine. The solvent was distilled off, and the obtained oily substance was recrystallized from a mixed solvent of 70 mL of methanol and 70 mL of water. 22.6 g of a compound represented by formula (G-4) was obtained by drying the obtained solid.

A reaction vessel with a stirring device and a thermometer was charged with 22.6 g (0.079 mole) of a compound represented by formula (G-4) and 26.2 g of 6- (3-propenyloxy-propoxy) -2-naphthoic acid ( 0.087 mole), 0.49 g (4.0 mmol) of N, N-dimethylaminopyridine and 131 mL of dichloromethane, and the mixture was stirred while cooling with ice. While maintaining the temperature of the reaction solution at 15 ° C or lower, 12.0 g (0.095 mol) of N, N'-diisopropylcarbodiimide was added dropwise. After completion of the dropwise addition, the reaction was carried out by stirring at room temperature for 6 hours. The reaction solution was filtered to remove precipitates, and then the solvent was distilled off. The obtained solid was dissolved in dichloromethane and purified by column chromatography (refined preparation: 45 g of silica gel, eluent: 360 mL of dichloromethane), and then the solvent was distilled off. The obtained solid was recrystallized twice from a mixed solvent of 45 mL of methylene chloride and 135 mL of methanol, and then dried to obtain 36.9 g of a compound represented by the formula (I-17).

(Physical properties of the compound represented by formula (I-17))

¹ H NMR (CDCl ₃ ) δ 1.99 (quintet, 2H), 2.35 (s, 3H), 3.73 (s, 3H), 4.04 (t, 2H), 4.15 (t, 2H), 5.80 (dd, 1H ), 6.05 (dd, 1H), 6.43 (dd, 1H), 6.39 (d, 1H), 6.88 (d, 1H), 6.93 (d, 1H), 6.95 (d, 2H), 6.97 (s, 1H) , 6.99 (d, 1H), 7.03 (d, 2H), 7.04 (d, 1H), 7.60 (d, 1H), 7.64 (d, 1H), 7.75 (d, 1H), 8.20 (d, 1H), 8.52 (s, 1H) ppm.

¹³ C NMR (CDCl ₃ ) δ 20.9, 30.3, 56.0, 63.1, 68.5, 105.5, 112.2, 115.7, 118.9, 119.7, 122.3, 122.4, 122.4, 127.0, 125.8, 126.1, 128.0, 128.6, 129.6, 129.6, 130.3, 130.4, 130.8, 132.7, 134.5, 136.1, 137.9, 145.6, 150.1, 154.8, 160.1, 162.0, 164.0, 165.0 ppm.

LRMS (EI) m / z 566 (100).

(Example 8) Production of compound represented by formula (I-13)

In a reaction vessel having a stirring device and a thermometer, 30.0 g (0.14 mole) of a compound represented by the formula (A-2), 17.8 g (0.13 mole) of 4-cyano-3-fluorophenol, and N, N-di 0.8 g (6.5 mmol) of methylaminopyridine and 150 mL of dichloromethane were stirred while cooling with ice. While maintaining the temperature of the reaction solution at 15 ° C or lower, 19.7 g (0.16 mol) of N, N'-diisopropylcarbodiimide was added dropwise. After completion of the dropwise addition, the reaction was carried out by stirring at room temperature for 5 hours. The reaction solution was filtered to remove precipitates, and then the solvent was distilled off. The obtained solid was dissolved in dichloromethane and purified by column chromatography (refined preparation: 31 g of silica gel, eluent: 248 mL of dichloromethane), and then the solvent was distilled off. The obtained solid matter was dispersed and washed with 124 mL of methanol, and then dried to obtain 39.0 g of a compound represented by the formula (H-1).

A reaction vessel having a stirring device and a thermometer was charged with 39.0 g (0.12 mol) of a compound represented by the formula (H-1), 80 mL of toluene, and 80 mL of tetrahydrofuran. While stirring, 13.0 g (0.18 mol) of butylamine was added dropwise. After the dropwise addition was completed, the mixture was stirred at room temperature overnight. After neutralization and separation with 180 mL of 5% hydrochloric acid, the organic layer was washed twice with 180 mL of brine. The solvent was distilled off, and purification was performed by flash column chromatography (refining agent: silica gel, eluent: dichloromethane). 18.3 g of a compound represented by the formula (H-2) was obtained by drying the obtained solid.

In a reaction vessel having a stirring device and a thermometer, 18.3 g (0.064 mol) of a compound represented by formula (H-2) and 21.0 g of 6- (3-propenyloxy-propoxy) -2-naphthoic acid ( 0.071 mole), N, N-dimethylaminopyridine 0.4 g (3.2 mmol) and dichloromethane 105 mL of alkane was stirred while cooling with ice. While maintaining the temperature of the reaction solution at 15 ° C or lower, 9.7 g (0.077 mol) of N, N'-diisopropylcarbodiimide was added dropwise. After completion of the dropwise addition, the reaction was carried out by stirring at room temperature for 6 hours. The reaction solution was filtered to remove precipitates, and then the solvent was distilled off. The obtained solid was dissolved in dichloromethane and purified by column chromatography (refined preparation: 40 g of silica gel, eluent: 360 mL of dichloromethane), and then the solvent was distilled off. The obtained solid was recrystallized twice from a mixed solvent of 45 mL of methylene chloride and 135 mL of methanol, and then dried to obtain 30.5 g of a compound represented by the formula (I-13).

(Physical properties of the compound represented by formula (I-13))

¹ H NMR (CDCl ₃ ) δ 1.99 (quintet, 2H), 3.73 (s, 3H), 4.04 (t, 2H), 4.15 (t, 2H), 5.80 (dd, 1H), 6.05 (dd, 1H) ), 6.43 (dd, 1H), 6.97 (s, 1H), 7.04 (s, 1H), 7.04 (d, 1H), 7.10 (d, 1H), 7.19 (d, 1H), 7.56 (d, 1H) , 7.60 (d, 1H), 7.72 (s, 1H), 7.75 (d, 1H), 7.77 (d, 1H), 8.20 (d, 1H), 8.52 (s, 1H) ppm.

¹³ C NMR (CDCl ₃ ) δ 30.3, 56.0, 63.1, 68.5, 96.3, 105.5, 109.1, 116.1, 116.5, 117.7, 119.7, 122.3, 122.8, 125.8, 126.1, 127.0, 128.0, 128.4, 128.6, 130.3, 130.4, 130.8, 134.0, 136.1, 143.9, 154.8, 159.0, 160.1, 164.0, 164.0, 165.0, 166.0 ppm.

LRMS (EI) m / z 569 (100).

(Example 9) Production of compound represented by formula (I-14)

In a reaction vessel having a stirring device, a cooler, and a thermometer, 50.0 g (0.32 mole) of 2-fluoro-4-hydroxybenzoic acid (a compound represented by the formula (J-1)), 150 mL of acetic acid, and 39.2 g of acetic anhydride ( 0.38 mole) and 2.5 g of sulfuric acid, and the mixture was heated to 60 ° C for 10 hours for reaction. 1 L of water was added to the reaction solution, and the mixture was stirred for 1 hour while cooling with ice. The precipitated solid was filtered. The obtained solid was washed with 1 L of water. 60.9 g of a compound represented by the formula (J-2) was obtained by drying the solid.

In a reaction vessel having a stirring device and a thermometer, 60.9 g (0.31 mole) of a compound represented by the formula (J-2), 31.3 g (0.28 mole) of 4-fluorophenol, and N, N-dimethylaminopyridine were added. 1.7 g (14 mmol) and 300 mL of dichloromethane were stirred while cooling with ice. While maintaining the temperature of the reaction solution at 15 ° C or lower, 42.3 g (0.34 mol) of N, N'-diisopropylcarbodiimide was added dropwise. After completion of the dropwise addition, the reaction was carried out by stirring at room temperature for 5 hours. The reaction solution was filtered to remove precipitates, and then the solvent was distilled off. The obtained solid was dissolved in dichloromethane and purified by column chromatography (refined preparation: 100 g of silica gel, eluent: 1L of dichloromethane), and then the solvent was distilled off. The obtained solid matter was dispersed and washed with 240 mL of methanol, and then dried to obtain 81.5 g of a compound represented by the formula (J-3).

A reaction vessel having a stirring device and a thermometer was charged with 81.5 g (0.28 mol) of a compound represented by formula (J-3), 240 mL of toluene, and 240 mL of tetrahydrofuran. While stirring, 30.6 g (0.42 mole) of butylamine was added dropwise. After the dropwise addition was completed, the mixture was stirred at room temperature overnight. After neutralizing and separating with 240 mL of 5% hydrochloric acid, the organic layer was washed twice with 480 mL of brine. The solvent was distilled off, and purification was performed by flash column chromatography (refining agent: silica gel, eluent: dichloromethane). 25.1 g of a compound represented by the formula (J-4) was obtained by drying the obtained solid.

A reaction vessel with a stirring device and a thermometer was charged with 25.1 g (0.10 mol) of a compound represented by formula (J-4) and 37.7 g (0.11 Mol), 0.61 g (5.0 mmol) of N, N-dimethylaminopyridine, and 180 mL of dichloromethane, and stirred while cooling with ice. 15.1 g (0.12 mole) of N, N'-diisopropylcarbodiimide was added dropwise while maintaining the temperature of the reaction solution at 15 ° C or lower. After completion of the dropwise addition, the reaction was carried out by stirring at room temperature for 6 hours. The reaction solution was filtered to remove precipitates, and then the solvent was distilled off. The obtained solid was dissolved in dichloromethane and purified by column chromatography (refined preparation: 60 g of silica gel, eluent: 600 mL of dichloromethane), and then the solvent was distilled off. The obtained solid was recrystallized twice from a mixed solvent of 60 mL of dichloromethane and 120 mL of methanol, and then dried to obtain 50.6 g of a compound represented by the formula (I-14).

(Physical properties of the compound represented by formula (I-14))

¹ H NMR (CDCl ₃ ) δ 1.29 (quintet, 4H), 1.57 (quintet, 2H), 1.71 (quintet, 2H), 4.04 (t, 2H), 4.15 (t, 2H), 5.80 (dd, 1H), 6.05 (dd, 1H), 6.43 (dd, 1H), 6.97 (s, 1H), 7.04 (m, 3H), 7.13 (d, 2H), 7.28 (d, 1H), 7.60 ( d, 1H), 7.75 (d, 1H), 7.92 (s, 1H), 7.98 (d, 1H), 8.20 (d, 1H), 8.52 (s, 1H) ppm.

¹³ C NMR (CDCl ₃ ) δ 26.3, 26.5, 30.0, 30.6, 66.8, 72.3, 105.5, 115.9, 115.9, 117.5, 119.7, 122.9, 123.0, 123.0, 125.8, 126.1, 126.1, 127.0, 128.0, 128.6, 129.0, 130.3, 130.4, 130.8, 136.1, 145.3, 148.7, 154.9, 158.9, 160.1, 164.0, 164.0, 165.0 ppm.

LRMS (EI) m / z 574 (100).

(Example 10) Production of compound represented by formula (I-2)

In Example 9, except having replaced 4-fluorophenol with p-cresol, the compound represented by formula (I-2) was produced by the same method.

(Physical property value of the compound represented by formula (I-2))

¹ H NMR (CDCl ₃ ) δ 1.43 (m, 4H), 1.62 (t, 2H), 1.76 (t, 2H), 2.34 (s, 3H), 3.97 (t, 2H), 4.16 (t, 2H), 5.59 (dd, 1H), 6.05 (dd, 1H), 6.27 (dd, 1H), 7.23 (d, 1H), 7.25 (d, 2H), 7.30 (d, 2H), 7.39 (s, 1H), 7.50 (d, 1H), 7.87 (d, 1H), 7.88 (d, 1H), 7.93 (d, 1H), 8.06 (d, 1H), 8.32 (d, 1H), 8.64 (s, 1H) ppm.

¹³ C NMR (CDCl ₃ ) δ 21.3, 25.6, 25.8, 29.0, 29.6, 65.3, 68.7, 108.2, 117.8, 118.8, 121.5, 121.5, 123.1, 126.3, 126.3, 126.4, 127.1, 128.2, 128.2, 128.6, 129.4, 129.4, 130.1, 130.9, 131.3, 135.2, 141.0, 142.8, 146.4, 153.7, 158.0, 165.2, 165.2, 166.5 ppm.

LRMS (EI) m / z 570 (100).

(Example 11) Production of compound represented by formula (I-4)

In Example 2, the compound represented by formula (I-4) was produced by the same method except that the compound represented by formula (A-5) was replaced with a compound represented by formula (I-4-1). .

(Physical properties of the compound represented by formula (I-4))

¹ H NMR (CDCl ₃ ) δ 2.11 (quintet, 2H), 2.34 (s, 3H), 3.83 (s, 3H), 4.20 (d, 2H), 4.39 (d, 2H), 5.59 (dd, 1H ), 6.05 (dd, 1H), 6.27 (dd, 1H), 7.03 (d, 1H), 7.25 (d, 2H), 7.30 (d, 2H), 7.41 (d, 1H), 7.58 (d, 1H) , 7.84 (s, 1H), 7.85 (d, 1H), 7.99 (d, 1H), 8.16 (d, 1H), 8.49 (d, 1H) ppm.

¹³ C NMR (CDCl ₃ ) δ 21.3, 28.4, 55.8, 61.6, 64.9, 113.7, 120.2, 120.5, 121.5, 121.5, 123.0, 124.4, 120.6, 126.4, 127.3, 127.3, 128.0, 128.2, 129.4, 129.4, 130.2, 131.3, 131.6, 135.2, 137.0, 143.6, 144.0, 146.4, 151.5, 165.2, 165.2, 166.5 ppm.

LRMS (EI) m / z 558 (100).

(Example 12) Production of compound represented by formula (I-5)

In a reaction vessel having a stirring device and a thermometer, 25.0 g (0.095 mol) of a compound represented by the formula (D-4), 17.1 g (0.095 mol) of 4-ethoxybenzoic acid, and N, N- 0.6 g (5.2 mmol) of dimethylaminopyridine and 125 mL of dichloromethane were stirred while cooling with ice. While maintaining the temperature of the reaction solution at 15 ° C or lower, 14.4 g (0.11 mole) of N, N'-diisopropylcarbodiimide was added dropwise. After completion of the dropwise addition, the reaction was carried out by stirring at room temperature for 5 hours. The reaction solution was filtered to remove precipitates, and then the solvent was distilled off. The obtained solid was dissolved in dichloromethane and purified by column chromatography (refined preparation: 32 g of silica gel, eluent: 256 mL of dichloromethane), and then the solvent was distilled off. The obtained solid matter was dispersedly washed with 96 mL of methanol, and then dried to obtain 32.3 g of a compound represented by the formula (K-1).

A reaction vessel having a stirring device and a thermometer was charged with 32.3 g (0.076 mol) of a compound represented by formula (K-1), 64 mL of toluene, and 64 mL of tetrahydrofuran. While stirring, 6.68 g (0.091 mol) of butylamine was added dropwise. After the dropwise addition was completed, the mixture was stirred at room temperature overnight. After neutralization and separation with 150 mL of 5% hydrochloric acid, the organic layer was washed twice with 150 mL of saline. The solvent was distilled off, and the obtained oily substance was recrystallized from a mixed solvent of 64 mL of methanol and 64 mL of water. 28.3 g of a compound represented by the formula (K-2) was obtained by drying the obtained solid.

In a reaction vessel having a stirring device and a thermometer, 28.3 g (0.074 moles) of a compound represented by formula (K-2), 22.2 g (0.074 moles) of a compound represented by formula (A-5), and N, N-di 0.55 g (4.5 mmol) of methylaminopyridine and 150 mL of dichloromethane were stirred while cooling with ice. While maintaining the temperature of the reaction solution at 15 ° C or lower, 13.7 g (0.11 mole) of N, N'-diisopropylcarbodiimide was added dropwise. After completion of the dropwise addition, the reaction was carried out by stirring at room temperature for 6 hours. The reaction solution was filtered to remove precipitates, and then the solvent was distilled off. The obtained solid was dissolved in dichloromethane and purified by column chromatography (refined preparation: 49 g of silica gel, eluent: 392 mL of dichloromethane), and then the solvent was distilled off. The obtained solid was recrystallized twice from a mixed solvent of 49 mL of dichloromethane and 147 mL of methanol, and then dried to obtain 39.3 g of a compound represented by the formula (I-5).

(Physical properties of the compound represented by formula (I-5))

¹ H NMR (CDCl ₃ ) δ 2.11 (quintet, 2H), 2.34 (s, 3H), 4.20 (t, 2H), 4.39 (t, 2H), 5.59 (dd, 1H), 6.05 (dd, 1H) ), 6.27 (dd, 1H), 7.23 (d, 1H), 7.25 (d, 2H), 7.30 (d, 2H), 7.39 (s, 1H), 7.46 (d, 1H), 7.52 (d, 2H) , 7.88 (d, 1H), 7.93 (d, 1H), 8.17 (d, 1H), 8.21 (s, 1H), 8.32 (d, 1H), 8.64 (s, 1H) ppm.

¹³ C NMR (CDCl ₃ ) δ 21.3, 28.4, 61.6, 64.9, 108.2, 117.8, 121.5, 121.5, 121.5, 121.5, 122.9, 122.9, 126.3, 126.4, 127.0, 127.1, 128.2, 128.2, 128.4, 128.8, 129.4, 129.4, 129.8, 130.1, 130.7, 130.7, 130.9, 131.3, 132.0, 135.2, 141.0, 146.4, 152.6, 154.6, 158.0, 165.2, 165.2, 165.2, 166.5 ppm.

LRMS (EI) m / z 665 (100), 667 (30).

(Example 13) Production of compound represented by formula (I-6)

In Example 12, 3-chloro-4-hydroxybenzoic acid was replaced with 4-hydroxybenzoic acid, p-cresol was replaced with trans-4-propylcyclohexanol, and 4-acetoxybenzoic acid was replaced with 3-Fluoro-4-ethoxybenzoic acid and the compound represented by the formula (A-5) were replaced with the compound represented by the formula (L-5), and the formula (I-6) was produced by the same method. ).

(Physical property value of the compound represented by formula (I-6))

¹ H NMR (CDCl ₃ ) δ 0.90 (t, 3H), 1.25 (q, 2H), 1.43-1.99 (m, 18H), 2.00 (quintet, 2H), 2.87 (quintet, 2H), 3.21 (dd, 1H), 3.37 (t, 2H), 3.46 (dd, 1H), 3.91 (quintet, 1H), 4.39 (d, 2H), 7.23 (d, 1H), 7.39 (s, 1H), 7.48 (d, 2H), 7.50 (d, 1H), 7.87 (d, 1H), 7.88 (d, 1H), 7.93 (d, 1H), 8.06 (d, 1H), 8.14 (d, 2H), 8.32 (d, 1H), 8.64 (s, 1H) ppm.

¹³ C NMR (CDCl ₃ ) δ 14.4, 20.5, 21.3, 25.8, 29.0, 29.4, 29.7, 29.7, 31.0, 31.0, 32.3, 34.7, 37.1, 52.0, 62.0, 65.0, 69.0, 70.9, 77.9, 108.2, 117.8, 118.8, 121.5, 121.5, 123.1, 126.3, 126.3, 126.4, 126.9, 127.1, 128.2, 128.6, 130.1, 130.3, 130.3, 130.9, 141.0, 142.8, 153.7, 153.7, 158.0, 165.2, 165.2, 165.9 ppm.

LRMS (EI) m / z 738 (100).

(Example 14) Production of compound represented by formula (I-19)

In a flask equipped with a stirring device, 20.0 g (0.14 mol) of chlorohydroquinone and 1.74 g (6.9 mmol) of pyridinium p-toluenesulfonate were added and dissolved in 60 mL of dichloromethane. While cooling with ice, 17.5 g (0.17 mole) of 3,4-dihydro-2H-pyran was added dropwise. After completion of the reaction, purification was performed by column chromatography to obtain 20.5 g of a compound represented by the formula (M-1).

A flask with a thermometer and a stirring device was charged with 20.5 g (0.090 mole) of the compound represented by formula (M-1), 13.5 g (0.090 mole) of 4-propylbenzyl alcohol, and 28.3 g (0.11 mole) of triphenylphosphine Ear) and dissolved in 80 mL of dichloromethane. While cooling with ice, 21.8 g (0.11 mole) of diisopropyl azodicarboxylate was added dropwise so as not to exceed 15 ° C. After stirring at room temperature for 5 hours, purification was performed by column chromatography to obtain 28.6 g of a compound represented by the formula (M-2).

28.6 g (0.079 mol) of the compound represented by the formula (M-2) was added to a flask, and dissolved in 50 mL of tetrahydrofuran and 50 mL of methanol. 0.5 mL of concentrated hydrochloric acid was added and stirred at room temperature for 10 hours. After liquid separation treatment, purification was performed by column chromatography to obtain 21.6 g of a compound represented by the formula (M-3).

In a reaction vessel having a stirring device and a thermometer, 21.6 g (0.078 moles) of a compound represented by formula (M-3), 24.9 g (0.078 moles) of a compound represented by formula (M-4), and N, N-di 0.55 g (4.5 mmol) of methylaminopyridine and 150 mL of dichloromethane were stirred while cooling with ice. While maintaining the temperature of the reaction solution at 15 ° C or lower, 11.9 g (0.094 mol) of N, N'-diisopropylcarbodiimide was added dropwise. Addition completed Then, it stirred at room temperature for 6 hours and reacted. The reaction solution was filtered to remove precipitates, and then the solvent was distilled off. The obtained solid was dissolved in dichloromethane, purified by column chromatography, and recrystallized twice from a mixed solvent of dichloromethane and methanol, and then dried to obtain a formula (I-19) Compound 36.1 g.

(Physical properties of the compound represented by formula (I-19))

¹ H NMR (CDCl ₃ ) δ 0.90 (t, 3H), 1.65 (sexet, 2H), 2.11 (quintet, 2H), 2.62 (t, 2H), 4.20 (t, 2H), 4.39 (t, 2H), 5.16 (s, 2H), 5.59 (dd, 1H), 6.05 (dd, 1H), 6.27 (dd, 1H), 7.00 (d, 1H), 7.03 (d, 1H), 7.14 (d, 1H), 7.18 (d, 2H), 7.38 (d, 2H), 7.46 (d, 1H), 7.58 (d, 1H), 7.99 (d, 1H), 8.16 (d, 1H), 8.49 ( d, 1H) ppm.

¹³ C NMR (CDCl ₃ ) δ 13.7, 24.1, 28.4, 37.9, 61.6, 64.9, 70.3, 116.1, 120.2, 120.5, 120.7, 123.0, 123.4, 126.0, 126.4, 127.2, 127.2, 127.3, 127.3, 128.2, 128.3, 128.3, 130.2, 131.3, 131.6, 134.0, 137.0, 140.9, 144.0, 145.0, 151.4, 165.2, 166.5 ppm.

LRMS (EI) m / z 577 (100), 579 (30).

(Example 15) Production of compound represented by formula (I-28)

In a reaction vessel with a thermometer and a stirring device, add 10.0 g (0.056 mole) of 4-acetoxybenzoic acid, 3.45 g (0.028 mole) of methylhydroquinone, and 0.34 of N, N-dimethylaminopyridine. g (2.8 mmol) and 150 mL of dichloromethane, and stirred while cooling with ice. While maintaining the temperature of the reaction solution at 15 ° C or lower, 7.71 g (0.061 mol) of N, N'-diisopropylcarbodiimide was added dropwise. After completion of the dropwise addition, the reaction was carried out by stirring at room temperature for 6 hours. The reaction solution was filtered to remove precipitates, and then the solvent was distilled off. Make it to The solid substance was dissolved in dichloromethane, purified by column chromatography, and recrystallized twice from a mixed solvent of dichloromethane and methanol, and then dried to obtain a compound represented by formula (N-1) 9.96 g.

A reaction vessel having a stirring device and a thermometer was charged with 9.96 g (0.022 mol) of a compound represented by the formula (N-1), 50 mL of toluene, and 50 mL of tetrahydrofuran. 3.57 g (0.061 mole) of butylamine was added dropwise while stirring. After the dropwise addition was completed, the mixture was stirred at room temperature overnight. After neutralization and liquid separation with 5% hydrochloric acid, purification was performed by column chromatography. By drying the obtained solid, 9.61 g of a compound represented by the formula (N-2) was obtained.

In a reaction vessel having a stirring device and a thermometer, 9.61 g (0.026 moles) of a compound represented by formula (N-2), 15.8 g (0.053 moles) of a compound represented by formula (A-5), and N, N-di 0.32 g (2.6 mmol) of methylaminopyridine and 100 mL of dichloromethane were stirred while cooling with ice. While maintaining the temperature of the reaction solution at 15 ° C or lower, 7.32 g (0.058 mol) of N, N'-diisopropylcarbodiimide was added dropwise. After completion of the dropwise addition, the reaction was carried out by stirring at room temperature for 6 hours. The reaction solution was filtered to remove precipitates, and then the solvent was distilled off. The obtained solid was dissolved in dichloromethane, purified by column chromatography, and then recrystallized twice from a mixed solvent of dichloromethane and methanol, followed by drying to obtain a formula (I-28). Compound 19.6 g.

(Physical properties of the compound represented by formula (I-28))

¹ H NMR (CDCl ₃ ) δ 2.11 (quintet, 4H), 2.15 (s, 3H), 4.20 (t, 4H), 4.39 (t, 4H), 5.59 (dd, 2H), 6.05 (dd, 2H) ), 6.27 (dd, 2H), 7.23 (d, 2H), 7.25 (d, 1H), 7.39 (s, 2H), 7.42 (d, 1H), 7.46 (d, 1H), 7.52 (d, 4H) , 7.88 (d, 2H), 7.93 (d, 2H), 8.29 (d, 4H), 8.32 (d, 2H) ppm.

¹³ C NMR (CDCl ₃ ) δ 15.3, 28.4, 61.6, 64.9, 108.2, 117.8, 119.0, 121.5, 121.5, 121.9, 123.6, 126.3, 126.4, 127.0, 127.1, 128.2, 128.2, 130.1, 130.7, 130.9, 131.1, 131.3, 141.0, 147.1, 150.2, 154.6, 158.0, 165.2, 165.2, 166.5 ppm.

LRMS (EI) m / z 928 (100).

(Example 16) Production of compound represented by formula (I-30)

A reaction vessel having a thermometer and a stirring device was charged with 15.0 g (0.041 mole) of a compound represented by the formula (N-2), 19.0 g (0.082 mole) of 2-ethoxyl-6-naphthoic acid, and N, N. -0.50 g (4.1 mmol) of dimethylaminopyridine and 150 mL of dichloromethane, and stirred while cooling with ice. While maintaining the temperature of the reaction solution at 15 ° C or lower, 11.4 g (0.091 mol) of N, N'-diisopropylcarbodiimide was added dropwise. After completion of the dropwise addition, the reaction was carried out by stirring at room temperature for 6 hours. The reaction solution was filtered to remove precipitates, and then the solvent was distilled off. The obtained solid was dissolved in dichloromethane, purified by column chromatography, and recrystallized twice from a mixed solvent of dichloromethane and methanol, and then dried to obtain a formula (AA-1). Compound 26.0 g.

A reaction vessel having a stirring device and a thermometer was charged with 26.0 g (0.033 mol) of a compound represented by formula (AA-1), 50 mL of toluene, and 50 mL of tetrahydrofuran. While stirring, 6.62 g (0.091 mol) of butylamine was added dropwise. After the dropwise addition was completed, the mixture was stirred at room temperature overnight. After neutralization and liquid separation with 5% hydrochloric acid, purification was performed by column chromatography. 27.6 g of a compound represented by the formula (AA-2) was obtained by drying the obtained solid.

In a reaction vessel having a stirring device and a thermometer, 27.6 g (0.039 mol) of a compound represented by the formula (AA-2) and 5.1 g (0.086 mol) of triethylamine were added and suspended in 100 mL of dichloromethane. While cooling with ice, 7.43 g (0.082 mol) of propylene chloride was added dropwise so that the reaction temperature did not exceed 15 ° C. After stirring for 5 hours at room temperature, the solution was separated with 5% hydrochloric acid and brine. After purification by column chromatography, recrystallization was performed twice from a mixed solvent of dichloromethane and methanol to obtain 31.2 g of a compound represented by the formula (I-30).

(Physical properties of the compound represented by formula (I-30))

¹ H NMR (CDCl ₃ ) δ 2.15 (s, 3H), 5.59 (dd, 2H), 6.05 (dd, 2H), 6.27 (dd, 2H), 7.23 (d, 2H), 7.25 (d, 1H), 7.39 (s, 2H), 7.42 (d, 1H), 7.46 (d, 1H), 7.52 (d, 4H), 7.88 (d, 2H), 7.93 (d, 2H), 8.29 (d, 4H), 8.32 (d, 2H) ppm.

¹³ C NMR (CDCl ₃ ) δ 15.3, 108.2, 117.8, 119.0, 121.5, 121.5, 121.9, 123.6, 126.3, 126.4, 127.0, 127.1, 128.2, 128.2, 130.1, 130.7, 130.9, 131.1, 131.3, 141.0, 147.1, 150.2, 154.6, 158.0, 165.2, 165.2, 166.5 ppm.

LRMS (EI) m / z 939 (100).

(Example 17) Production of compound represented by formula (I-42)

A flask equipped with a stirring device was charged with 20.0 g (0.13 mol) of 3-chloro-4-hydroxybenzaldehyde and 1.74 g (6.9 mmol) of pyridinium p-toluenesulfonate, and dissolved in 80 mL of dichloromethane. While cooling with ice, 17.5 g (0.17 mole) of 3,4-dihydro-2H-pyran was added dropwise. After the reaction is completed, purification is performed by column chromatography to obtain the formula (AB-1) Compound 30.1 g.

In a reaction vessel having a stirring device and a thermometer, 36.1 g (0.14 mol) of triphenylphosphine and 15.5 g (0.14 mol) of potassium tert-butoxide were added and suspended in 100 mL of tetrahydrofuran. While cooling to -20 ° C, a solution of 31.3 g (0.13 mole) of 4-bromobenzyl bromide was added dropwise. After stirring at -20 ° C for 1 hour, a solution of 30.1 g (0.13 mole) of a compound represented by the formula (AB-1) in tetrahydrofuran was added dropwise. After further stirring at -20 ° C for 1 hour, it was stirred at room temperature for 5 hours. Purification by column chromatography gave 39.4 g of a compound represented by the formula (AB-2).

In a pressure-resistant reaction vessel, 39.4 g (0.10 mole) of a compound represented by the formula (AB-2), 200 mL of tetrahydrofuran, and 1.9 g of silk fibroin loaded with 2.5% palladium were loaded, and the reaction was performed in a hydrogen atmosphere (0.5 MPa) for 6 hours . After the catalyst was filtered, purification was performed by column chromatography to obtain 35.7 g of a compound represented by the formula (AB-3).

In a reaction vessel having a heating device, a thermometer, and a stirring device, 35.7 g (0.090 mol) of a compound represented by the formula (AB-3), 0.34 g (1.8 mmol) of copper (I) iodide, and trimethyl silicon were added. 13.3 g (0.14 mole) of acetylacetylene was dissolved in 35 mL of triethylamine and 105 mL of N, N-dimethylformamide. After the reaction vessel was brought to a nitrogen atmosphere, 1.04 g (0.90 mmol) of tris (triphenylphosphine) palladium (0) was added, and the mixture was heated and stirred at 90 ° C for 10 hours. After adding toluene and water to carry out a liquid separation treatment, purification was performed by column chromatography to obtain 24.2 g of a compound represented by the formula (AB-4).

A reaction container having a stirring device was charged with 24.2 g (0.059 mole) of a compound represented by the formula (AB-4), and dissolved in 150 mL of methanol. 12.1 g (0.088 mole) of potassium carbonate was added, and it stirred at room temperature for 10 hours. After adding 5% hydrochloric acid and ethyl acetate and performing a liquid separation treatment, purification was performed by column chromatography to obtain 19.4 g of a compound represented by the formula (AB-5).

A reaction vessel having a heating device, a thermometer, and a stirring device was charged with 19.4 g (0.057 mol) of a compound represented by formula (AB-5), 0.22 g (1.1 mmol) of copper (I) iodide, 12.7 g (0.057 mole) of 2-naphthol was dissolved in 20 mL of triethylamine and 60 mL of N, N-dimethylformamide. After making the reaction vessel into a nitrogen atmosphere, 0.66 g (0.57 mmol) of tris (triphenylphosphine) palladium (0) was added, and the mixture was heated and stirred at 90 ° C for 10 hours. After adding toluene and water for liquid separation treatment, purification was performed by column chromatography to obtain formula (AB-6) The represented compound is 13.7 g.

In a reaction vessel having a stirring device and a thermometer, 13.7 g (0.028 mole) of a compound represented by the formula (AB-6) and 3.7 g (0.037 mole) of triethylamine were added and suspended in 80 mL of dichloromethane. While cooling with ice, 3.1 g (0.034 mol) of propylene chloride was added dropwise so that the reaction temperature did not exceed 15 ° C. After stirring for 5 hours at room temperature, the solution was separated with 5% hydrochloric acid and brine. After purification by column chromatography, recrystallization was performed twice from a mixed solvent of dichloromethane and methanol to obtain 14.5 g of a compound represented by the formula (AB-7).

14.5 g (0.027 moles) of a compound represented by the formula (AB-7) was added to a flask, and dissolved in 50 mL of tetrahydrofuran and 50 mL of methanol. 0.5 mL of concentrated hydrochloric acid was added and stirred at room temperature for 10 hours. After liquid separation treatment, purification was performed by column chromatography to obtain 12.0 g of a compound represented by the formula (AB-8).

In a reaction vessel having a stirring device and a thermometer, 12.0 g (0.026 mol) of a compound represented by the formula (AB-8), 5.56 g (0.026 mol) of 4-acetoxy-3-methoxybenzoic acid, 0.32 g (2.6 mmol) of N, N-dimethylaminopyridine and 50 mL of dichloromethane were stirred while cooling with ice. While maintaining the temperature of the reaction solution at 15 ° C or lower, 4.0 g (0.032 mol) of N, N'-diisopropylcarbodiimide was added dropwise. After completion of the dropwise addition, the reaction was carried out by stirring at room temperature for 6 hours. The reaction solution was filtered to remove precipitates, and then the solvent was distilled off. The obtained solid was dissolved in dichloromethane, purified by column chromatography, and recrystallized twice from a mixed solvent of dichloromethane and methanol, and then dried to obtain a formula (AB-9). Compound 13.7 g.

A reaction vessel having a stirring device and a thermometer was charged with 13.7 g (0.021 mole) of a compound represented by the formula (AB-9), 30 mL of toluene, and 30 mL of tetrahydrofuran. 2.32 g (0.032 mol) of butylamine was added dropwise while stirring. After the dropwise addition was completed, the mixture was stirred at room temperature overnight. After neutralizing and separating with 100 mL of 5% hydrochloric acid, the organic layer was washed with brine. Recrystallization was performed using a mixed solvent of acetone / hexane, and the obtained solid was dried to obtain 11.1 g of a compound represented by the formula (AB-10).

In a reaction vessel having a stirring device and a thermometer, 11.1 g (0.018 mole) of a compound represented by formula (AB-10), 5.53 g (0.018 mole) of a compound represented by formula (A-5), and N, N-di 0.22 g (1.8 mmol) of methylaminopyridine and 100 mL of dichloromethane, Stir while cooling with ice. While maintaining the temperature of the reaction solution at 15 ° C or lower, 2.8 g (0.022 mol) of N, N'-diisopropylcarbodiimide was added dropwise. After completion of the dropwise addition, the reaction was carried out by stirring at room temperature for 6 hours. The reaction solution was filtered to remove precipitates, and then the solvent was distilled off. After purification by column chromatography, recrystallization was performed twice from a mixed solvent of dichloromethane and methanol, and then drying was performed to obtain 13.0 g of a compound represented by the formula (I-42).

(Physical properties of the compound represented by formula (I-42))

¹ H NMR (CDCl ₃ ) δ 2.11 (quintet, 2H), 2.82 (t, 4H), 3.83 (s, 3H), 4.20 (t, 2H), 4.39 (t, 2H), 5.50 (dd, 1H ), 5.59 (dd, 1H), 6.03 (dd, 1H), 6.05 (dd, 1H), 6.10 (dd, 1H), 6.27 (dd, 1H), 7.16 (d, 1H), 7.23 (d, 1H) , 7.24 (d, 1H), 7.25 (d, 2H), 7.39 (s, 1H), 7.40 (d, 1H), 7.41 (d, 1H), 7.54 (d, 2H), 7.55 (d, 1H), 7.56 (s, 1H), 7.63 (d, 1H), 7.84 (s, 1H), 7.85 (d, 1H), 7.88 (d, 1H), 7.93 (d, 1H), 7.95 (d, 1H), 8.29 (d, 1H), 8.32 (d, 1H), 8.64 (s, 1H) ppm.

¹³ C NMR (CDCl ₃ ) δ 28.4, 36.9, 37.4, 55.8, 61.6, 64.9, 89.7, 93.3, 108.2, 109.5, 113.7, 117.3, 117.6, 117.8, 119.9, 122.9, 123.0, 124.4, 126.0, 126.3, 126.4, 127.1, 127.3, 127.5, 128.0, 128.2, 128.2, 128.7, 129.7, 129.8, 129.8, 129.8, 129.9, 130.0, 130.1, 130.9, 131.3, 131.5, 132.2, 132.2, 134.1, 134.4, 137.6, 141.0, 141.8, 143.6, 144.6, 151.5, 153.4, 158.0, 164.3, 165.2, 165.2, 166.5 ppm.

LRMS (EI) m / z 885 (100), 887 (30).

(Example 18) Production of compound represented by formula (I-46)

In Example 8, the compound represented by the formula (A-2) was replaced with 4-acetoxy-2-chlorobenzoic acid, and 4-cyano-3-fluorophenol was replaced with 2,4-dimethylphenol. Except this, the compound represented by Formula (I-46) was manufactured by the same method.

(Physical properties of the compound represented by formula (I-46))

¹ H NMR (CDCl ₃ ) δ 2.11 (quintet, 2H), 2.15 (s, 3H), 2.34 (s, 3H), 4.20 (t, 2H), 4.39 (t, 2H), 5.59 (dd, 1H ), 6.05 (dd, 1H), 6.27 (dd, 1H), 7.11 (d, 1H), 7.13 (d, 1H), 7.17 (s, 1H), 7.23 (d, 1H), 7.39 (s, 1H) , 7.40 (d, 1H), 7.72 (s, 1H), 7.88 (d, 1H), 7.93 (d, 1H), 8.23 (d, 1H), 8.32 (d, 1H), 8.64 (s, 1H) ppm .

¹³ C NMR (CDCl ₃ ) δ 15.6, 21.6, 28.4, 61.6, 64.9, 108.2, 117.8, 119.6, 122.3, 122.9, 126.3, 126.4, 126.4, 127.1, 128.2, 128.2, 128.6, 130.1, 130.4, 130.9, 131.3, 131.3, 132.1, 135.1, 135.4, 141.0, 147.3, 157.9, 158.0, 165.2, 165.2, 166.5 ppm.

LRMS (EI) m / z 559 (100), 561 (30).

(Example 19) Production of compound represented by formula (I-48)

In Example 1, the compound represented by formula (I-48) was produced by the same method except that the compound represented by formula (A-5) was replaced with the compound represented by formula (AC-1).

(Physical properties of the compound represented by formula (I-48))

¹ H NMR (CDCl ₃ ) δ 2.01 (s, 3H), 2.21 (s, 3H), 2.27 (quintet, 2H), 2.35 (s, 3H), 3.92 (s, 3H), 4.24 (t, 2H ), 4.43 (t, 2H), 5.85 (dd, 1H), 6.15 (dd, 1H), 6.43 (dd, 1H), 7.01 ~ 7.10 (m, 3H), 7.20 ~ 7.24 (m, 2H), 7.34 ( d, 1H), 7.81 to 7.95 (m, 4H), 8.17 (dd, 1H), 8.74 (s, 1H) ppm.

¹³ C NMR (CDCl ₃ ) δ 16.2, 17.9, 20.9, 28.6, 56.2, 61.3, 64.5, 106.5, 114.0, 120.0, 121.6, 123.2, 123.3, 123.9, 126.3, 127.0, 127.5, 127.9, 128.2, 128.3, 129.8, 131.0, 131.1, 131.8, 132.0, 135.7, 137.6, 144.6, 147.3, 151.6, 159.1, 164.4, 164.6, 166.2 ppm.

LRMS (EI) m / z 568 (100).

(Example 20) Production of compound represented by formula (I-49)

In Example 10, the compound represented by formula (I-49) was produced by the same method except that the compound represented by formula (I-2-1) was replaced with a compound represented by formula (AD-1). .

(Physical properties of the compound represented by formula (I-49))

¹ H NMR (CDCl ₃ ) δ 1.43 (m, 4H), 1.62 (t, 2H), 1.76 (t, 2H), 2.01 (s, 3H), 2.34 (s, 3H), 3.97 (t, 2H), 4.16 (t, 2H), 5.59 (dd, 1H), 6.05 (dd, 1H), 6.27 (dd, 1H), 7.23 (d, 1H), 7.25 (d, 2H), 7.30 (d, 2H), 7.39 (s, 1H), 7.50 (d, 1H), 7.87 (d, 1H), 7.88 (d, 1H), 7.93 (d, 1H), 8.06 (d, 1H), 8.32 (d, 1H), 8.64 ( s, 1H) ppm.

¹³ C NMR (CDCl ₃ ) δ 17.9, 21.3, 25.6, 25.8, 29.0, 29.6, 65.3, 68.7, 108.2, 117.8, 118.8, 121.5, 121.5, 123.1, 126.3, 126.3, 126.4, 127.1, 128.2, 128.2, 128.6, 129.4, 129.4, 130.1, 130.9, 131.3, 135.2, 141.0, 142.8, 146.4, 153.7, 158.0, 165.2, 165.2, 166.5 ppm.

LRMS (EI) m / z 584 (100).

(Example 21) Production of compound represented by formula (I-52)

In Example 12, the compound represented by formula (I-52) was produced by the same method except that the compound represented by formula (A-5) was replaced with the compound represented by formula (AC-1).

(Physical properties of the compound represented by formula (I-52))

¹ H NMR (CDCl ₃ ) δ 2.01 (s, 3H), 2.11 (quintet, 2H), 2.34 (s, 3H), 4.20 (t, 2H), 4.39 (t, 2H), 5.59 (dd, 1H) ), 6.05 (dd, 1H), 6.27 (dd, 1H), 7.23 (d, 1H), 7.25 (d, 2H), 7.30 (d, 2H), 7.39 (s, 1H), 7.46 (d, 1H) , 7.52 (d, 2H), 7.88 (d, 1H), 7.93 (d, 1H), 8.17 (d, 1H), 8.21 (s, 1H), 8.32 (d, 1H), 8.64 (s, 1H) ppm .

¹³ C NMR (CDCl ₃ ) δ 17.9, 21.3, 28.4, 61.6, 64.9, 108.2, 117.8, 121.5, 121.5, 121.5, 121.5, 121.5, 122.9, 126.3, 126.4, 127.0, 127.1, 128.2, 128.2, 128.4, 128.8, 129.4, 129.4, 129.8, 130.1, 130.7, 130.7, 130.9, 131.3, 132.0, 135.2, 141.0, 146.4, 152.6, 154.6, 158.0, 165.2, 165.2, 165.2, 166.5 ppm.

LRMS (EI) m / z 678 (100), 680 (30).

(Example 22, Comparative Example 1)

The compounds represented by Formula (I-1), Formula (I-3), Formula (I-7) and Formula (I-8) of the present invention described in Examples 1 to 4 are used in the technical field. Comparative compound described in Japanese Patent Application Laid-Open No. 2008-88291, which is known to have high refractive index anisotropy. The physical properties of Compound 3 and Comparative Compound 4 described in EP1786887B1, Comparative Compound 5 described in JP-A-2008-179654, and Comparative Compound 6 described in JP-A-2007-119415 are shown in Table 1 below.

The compounds represented by formula (I-1), formula (I-3), formula (I-7), and formula (I-8) of the present invention all show a nematic liquid crystal phase in a wide temperature range. In the composition, an effect of stabilizing the liquid crystal phase of the composition can be expected. Comparative compound 2 is a monomer, and does not show a liquid crystal phase during the temperature rise. Therefore, when added to the composition, there is a disadvantage that the temperature range of the liquid crystal phase of the composition becomes narrow.

In addition, in order to evaluate the storage stability of the compound, the compounds were prepared with respect to compounds VI (30%), compound VII (30%), compound VIII (30%), and compound. IX (10%) is a polymerizable liquid crystal composition in which the parent liquid crystal is added from 10% to 60% per 5% of the compound. The maximum added concentration of the prepared polymerizable liquid crystal composition without crystal precipitation after standing at 25 ° C for 10 hours is described in Table 1 above. It can be seen that any one of the compounds represented by the formula (I-1), the formula (I-3), the formula (I-7), and the formula (I-8) of the present invention is any one of the compounds of the comparative compound 1 to the comparative compound 6. In contrast, the maximum added concentration of the compound without crystal precipitation was high, and showed high storage stability.

Preparation of the formula (I-1), formula (I-3), formula (I-7), formula (I-8), formula (I-28), formula (I-30), formula (I) -48) and the polymerizable liquid crystal composition of the compound represented by Formula (I-52) and Comparative Compound 1 to Comparative Compound 6 are shown in Tables 2 and 3 below.

It can be seen that the present composition 1 to the present composition 4 containing the compounds represented by formula (I-1), formula (I-3), formula (I-7) and formula (I-8) of the present invention Each of them shows a chiral nematic liquid crystal phase in a wide temperature range and has a high refractive index anisotropy.

Next, 2% of the photopolymerization initiator Irgacure 907 was added to 98% of the polymerizable liquid crystal composition of the present application composition 1 to the present application composition 8 and the comparative composition 1 to the comparative composition 6. (Produced by Ciba Refining Co., Ltd.), dissolved in cyclohexanone, spin-coated on glass with polyimide, and irradiated with 4 mW / cm ² of ultraviolet light for 120 seconds using a high-pressure mercury lamp to obtain polymer 1 of the present application ~ Polymer 8 and Comparative Polymer 1-Comparative Polymer 6 of the present application. The haze value and appearance of the obtained polymer were evaluated. Haze value is expressed by the following formula: Haze (%) = Td / Tt × 100

(In the formula, Td is the diffusion transmittance, and Tt is the total light transmittance.) The haze measuring device (NHD2000 manufactured by Nippon Denshoku Industries Co., Ltd.) was used for the measurement. The measurement was performed at five places on the substrate, and the average was taken. In addition, if there is no spot or the like on the polymer and it is uniform throughout, it is recorded as ◎, and when a spot is found, it is recorded as Δ or × depending on the degree of the spot. Formulas (I-1), (I-3), (I-7), (I-8), and (I-28), Formula (I-30), Formula (I-48) and Formula (I-52) The compounds of the present application polymer 1 to the present application polymer 8 can all obtain low haze values No spots and uniform polymer. On the other hand, in Comparative Polymer 1 and Comparative Polymer 3, a polymer having a high haze value, white linear spots on the polymer, and unevenness was obtained. In Comparative Polymer 2, Comparative Polymer 4, Comparative Polymer 5, and Comparative Polymer 6, several white linear spots were generated on the polymer.

From this, it can be seen that the compounds of the present invention have large refractive index anisotropy and have high storage stability relative to the comparative compounds. In addition, when the polymerizable liquid crystal composition containing the compound of the present invention is polymerized, the haze value is low and there are no spots. Therefore, it is found that the compound of the present invention has high alignment. Therefore, it is useful for applications, such as an optical film which has a cholesteric structure.

Claims (11)

A polymerizable compound represented by the general formula (I), (In the formula, P represents a substituent selected from a polymerizable group represented by the following formula (P-1), (P-2), or (P-11); , S ¹ represents an alkylene group having 1 to 20 carbon atoms, one -CH _2- , or two or more non-adjacent -CH ₂ -each independently through -O-, -S-, -CO-, -COO-, -OCO-, -CO-S-, -S-CO-, -O-CO-O-, -CO-NH-, -NH-CO- substituted carbon number 1-20 Group, or single bond; X ¹ independently represents -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 single bond, formula Herein, Y ¹ and Y ² 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; and L ¹ to L ⁶ each independently represent a hydrogen atom, a fluorine atom, and a chlorine atom. , Cyano, nitro, alkyl having 1 to 7 carbon atoms, alkoxy having 1 to 7 carbon atoms or alkyl fluorenyl having 1 to 7 carbon atoms Present in the alkyl group, alkoxy group or acyl of one or more hydrogen atoms may be substituted with a fluorine atom or a chlorine atom; M ¹ ~ M ⁴ each independently represent a hydrogen atom, a fluorine atom, a chlorine atom, a cyano group , Nitro, alkyl group having 1 to 7 carbon atoms, alkoxy group having 1 to 7 carbon atoms, alkylfluorenyl group having 1 to 7 carbon atoms or -X ² -S ² -P, where X ² , S ² and P each have the same meaning as the above-mentioned X ¹ , S ¹ and P, and each may be the same group or different groups, and the groups existing in the alkyl group, alkoxy group, or alkylfluorenyl group One or more hydrogen atoms may be substituted by fluorine atoms or chlorine atoms, and there is no case where all of M ¹ to M ⁴ are hydrogen atoms; A ¹ , A ² and A ³ each independently represent 1,4-phenylene Naphthalene-2,6-diyl, 1,4-cyclohexyl, 1,4-cyclohexenyl, 1,4-bicyclo [2.2.2] octyl, decahydronaphthalene-2,6- Diyl, 1,2,3,4-tetrahydronaphthalene-2,6-diyl, pyridine-2,6-diyl, pyrimidine-2,5-diyl, or 1,3-diyl Alkane-2,5-diyl, these groups may be unsubstituted, or may be fluorine, chlorine, cyano, nitro, 1 to 7 carbon atoms, 1 to 7 carbon atoms Alkoxy or alkanoyl having 1 to 7 carbon atoms may be substituted, and one or more hydrogen atoms of such alkyl, alkoxy or alkanoyl may be substituted by fluorine or chlorine atoms, A ¹ and / or A These may be the same or different when there are ^{two or} more; Z ¹ , Z ² and Z ⁴ 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 single bond, where Y ³ and Y ⁴ Each independently represents a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, a fluorine atom, a chlorine atom, or a cyano group. When there are a plurality of Z ¹ , Z ^2, and Z ⁴ , these may be the same or different; Z ³ represents- 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 ⁵ = CY ⁶ -or a single bond, where Y ⁵ and Y ⁶ 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; R represents -X ³ -S ³ -P, S ¹ and S ^{3 are} not single bonds; in the formula, X ³ , S ³ and P respectively represent the same meaning as the X ¹ , S ¹ and P, and each may be the same group or different Group, one or more hydrogen atoms present in the alkyl group may be substituted with a fluorine atom, a chlorine atom, or a cyano group, and one -CH ₂ -or two or more non-adjacent groups in the alkyl group may be substituted. -CH ₂ -can be independently passed through -O-, -S-, -CO-, -COO-, -OCO-, -CO-S-, -S-CO-, -O-CO-O-, -CO-NH-, -NH-CO-, -CH = CH-, -CH = CF-, -CF = CH- or -C≡ C-substituted; m ¹ and m ² each independently represent 0 or 1, and when m ¹ = 0 and m ² = 0, A ³ represents a group other than naphthalene-2,6-diyl). For example, the polymerizable compound according to the first patent application range, in the general formula (I), any one of M ¹ to M ⁴ is selected from a fluorine atom, a chlorine atom, a cyano group, a nitro group, and a carbon number of 1. ~ 7 alkyl groups, alkoxy groups having 1 to 7 carbon atoms, alkanoyl groups having 1 to 7 carbon atoms, and 1 to 7 carbon atoms having 1 to 7 carbon atoms substituted with fluorine or chlorine atoms Group, 1 to 7 carbon atoms having 1 to 7 carbon atoms substituted with fluorine atom or chlorine atom, or 1 to 7 carbon atoms having 1 to 7 hydrogen atom substituted with fluorine atom or chlorine atom Fluorenyl; the remaining three of M ¹ to M ⁴ represent hydrogen atoms. For example, the polymerizable compound according to item 1 or 2 of the scope of patent application, wherein in the general formula (I), L ¹ to L ⁶ represent a hydrogen atom, a fluorine atom, or a chlorine atom. For example, the polymerizable compound in the first or second scope of the patent application, wherein in the general formula (I), Z ¹ , Z ² and Z ⁴ each independently represent -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-, -C≡C-, or a single bond. For example, the polymerizable compound according to item 1 or 2 of the scope of patent application, wherein, in the general formula (I), Z ³ represents -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. For example, in the polymerizable compound of the first or second patent application range, in the general formula (I), Z ² and Z ³ each independently represent -COO-, -OCO-, -CH = CH-COO-,- CH = CH-OCO-, -COO-CH = CH-, -OCO-CH = CH- or single bond. For example, in the polymerizable compound of claim 1 or 2, in the general formula (I), M ¹ represents a fluorine atom, a chlorine atom, a cyano group, a methyl group, or a methoxy group, and M ² to M ⁴ represent hydrogen atom. For example, the polymerizable compound according to item 1 or 2 of the patent application range, wherein m ¹ in the general formula (I) represents 0. A polymerizable composition containing a polymerizable compound according to any one of claims 1 to 8. A polymer is obtained by polymerizing a polymerizable composition such as the item 9 in the patent application. An optically anisotropic body uses a polymer such as item 10 of the scope of patent application.