JP6304529B2 - Polymerizable compound and optical anisotropic body - Google Patents

Description

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

  A compound having a polymerizable group (polymerizable compound) is used in various optical materials. For example, it is possible to produce a polymer having a uniform orientation by aligning a polymerizable composition containing a polymerizable compound in a liquid crystal state and then polymerizing it. Such a polymer can be used for a polarizing plate, a retardation plate necessary for a display, a lenticular lens necessary for performing 3D display, and the like. In many cases, two or more types of polymerization are used to satisfy the required optical properties, polymerization rate, solubility, melting point, glass transition temperature, polymer transparency, mechanical strength, surface hardness, heat resistance and light resistance. A polymerizable composition containing a functional compound is used. In that case, the polymerizable compound to be used is required to bring good physical properties to the polymerizable composition without adversely affecting other properties.

  Humans feel depth and three-dimensionality when images from the left and right eyes are integrated in the brain. The 3D display is a mechanism that gives a sense of depth and stereoscopic effect by sending images taken at different angles for the right eye and the left eye to the right eye and the left eye, respectively. A method using a lenticular lens is known as a method of sending each image for right eye and left eye to each eye.

  When a polymerizable compound is used for a lenticular lens, when the polymerizable composition before polymerization is prepared, the polymerizable compound in the component is precipitated from the polymerizable composition even if stored for a long time. It is particularly important that when the polymerizable composition is polymerized by electromagnetic waves to produce a lens-shaped polymer, there are few alignment defects and the lens shape is uniform. When a lenticular lens having an alignment defect and / or a lenticular lens having a non-uniform lens shape is used in, for example, a 3D display, the brightness of the display is not uniform, the color of the image is unnatural, There is a problem that the image quality of 3D display deteriorates due to the deviation of the optical axis, and the quality of the display product is greatly deteriorated. Moreover, when using a lenticular lens for 3D display use, it is preferable that the film thickness of a lenticular lens is small from a viewpoint of the design property of a display, and the cost by the usage-amount of the polymeric composition in a manufacturing process. For that purpose, the refractive index anisotropy of the polymerizable composition, that is, the refractive index anisotropy of the polymerizable compound to be used is preferably large.

  Various polymerizable compounds have been reported in the field, but when these polymerizable compounds are added to the polymerizable composition, crystals are precipitated and the storage stability is insufficient (Patent Document 1). 2). In addition, when a polymerizable composition is polymerized by electromagnetic waves to produce a lens-shaped polymer, there are problems that alignment defects occur or the lens shape becomes non-uniform (Patent Documents 1 to 3). .

JP-A-5-132524 JP 2002-105033 A JP 2012-177087 A

  The problem to be solved by the present invention is to provide a polymerizable compound having a high storage stability without causing precipitation of crystals when added to the polymerizable composition, and a polymerizable compound containing the polymerizable compound An object of the present invention is to provide a polymerizable composition having few alignment defects and a uniform lens shape when a lens-like polymer obtained by polymerizing the composition is produced. Furthermore, it is providing the polymer obtained by polymerizing the said polymeric composition, and the optical anisotropic body using the said polymer.

The present invention relates to the general formula (I)

(In the formula, P represents a polymerizable group, S represents a spacer group or a single bond, and when a plurality of S are present, they may be the same or different, and X represents —O—, —S. _{-, - OCH 2 -, -} CH 2 O -, - CO -, - COO -, - OCO -, - CO-S -, - S-CO -, - OCO-O -, - CO-NH- , —NH—CO—, —SCH ₂ —, —CH ₂ S—, —CF ₂ O—, —OCF ₂ —, —CF ₂ S—, —SCF ₂ —, —CH═CH—COO—, —CH = CH-OCO -, - COO -CH = CH -, - OCO-CH = CH -, - COO-CH 2 CH 2 -, - OCO-CH 2 CH 2 -, - CH 2 CH 2 -COO -, - _{CH 2 CH 2 -OCO -, -} COO-CH 2 -, - OCO-CH 2 -, - CH 2 -COO -, - CH 2 - OCO-, -CH = CH-, -CF = CF- or a single bond is represented, but when a plurality of X are present, they may be the same or different, and A ¹ , A ² , A ³ , A ⁴ and A ⁵ each independently represent 1,4-phenylene, naphthalene-1,4-diyl or naphthalene-2,6-diyl, these groups being unsubstituted or substituted by one or more L When a plurality of A ⁵ are present, they may be the same or different, and Z ¹ , Z ² , and Z ³ are each independently —O—, —S—, —OCH ₂ —. , —CH ₂ O—, —COO—, —OCO—, —CO—, —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 _{-, - CH 2 CH 2 -} , - CH 2 CF 2 -, - CF 2 CH 2 -, - CF 2 CF 2 -, - CH = CH-COO -, - CH = CH-OCO -, - COO-CH _{= CH -, - OCO-CH} = CH -, - COO-CH 2 CH 2 -, - OCO-CH 2 CH 2 -, - CH 2 CH 2 -COO -, - CH 2 CH 2 -OCO -, - COO _{-CH 2 -, - OCO-CH} 2 -, - CH 2 -COO -, - CH 2 -OCO -, - CH = CH -, - CF = CF- or represents -C≡C-, R is a hydrogen atom , Fluorine atom, chlorine atom, bromine atom, iodine atom, pentafluorosulfuranyl group, cyano group, nitro group, isocyano group, thioisocyano group, or one —CH ₂ — or two or more not adjacent to each other —CH ₂ — is each independently —O—, — S-, -CO-, -COO-, -OCO-, -CO-S-, -S-CO-, -O-CO-O-, -CO-NH-, -NH-CO-, -CH = Substituted by CH—COO—, —CH═CH—OCO—, —COO—CH═CH—, —OCO—CH═CH—, —CH═CH—, —CF═CF— or —C≡C—. Represents a straight-chain or branched alkyl group having 1 to 12 carbon atoms, l represents an integer of 0 to 8, m1, m2 and m3 represent 0 or 1, n represents 0, 1 or 2; L represents a fluorine atom, a chlorine atom, a bromine atom or an iodine atom, but at least one of A ¹ , A ² , A ³ and A ⁴ is substituted by one or more L, and m1 + m2 + m3 represents 0 or 1 Represent. And a polymer obtained by polymerizing the polymerizable liquid crystal composition, the polymerizable liquid crystal composition containing the compound, and the polymer were used. Provide an optical anisotropic body.

  The compound of the present invention has high storage stability when constituting a polymerizable composition, and is useful as a constituent member of the polymerizable composition. An optical anisotropic body using a polymerizable liquid crystal composition containing the compound of the present invention has few alignment defects and is uniform in lens shape, and thus is useful for optical materials such as lenticular lenses.

  The present invention provides a compound represented by the general formula (I), and a polymer obtained by polymerizing a polymerizable composition, a polymerizable liquid crystal composition, and the polymerizable liquid crystal composition containing the compound together. And an optically anisotropic body using the polymer.

  In general formula (I), P represents a polymerizable group, and from the following formulas (P-1) to (P-18)

Preferably, these polymerizable groups are polymerized by radical polymerization, radical addition polymerization, cationic polymerization and anionic polymerization. In particular, when ultraviolet polymerization is performed as a polymerization method, the formula (P-1), formula (P-2), formula (P-3), formula (P-4), formula (P-5), formula (P -7), formula (P-11), formula (P-13), formula (P-15) or formula (P-18) are preferred, and formula (P-1), formula (P-2), formula (P-18) P-7), formula (P-11) or formula (P-13) is more preferred, formula (P-1), formula (P-2) or formula (P-3) is more preferred, and formula (P- 1) or formula (P-2) is particularly preferred.

S each independently represents a spacer group or a single bond, and when a plurality of S are present, they may be the same or different. In addition, as the spacer group, one —CH ₂ — or two or more non-adjacent —CH ₂ — may each independently represent —O—, —COO—, —OCO— or —OCO—O—. It preferably represents an alkylene group having 1 to 20 carbon atoms which may be replaced. In the case where a plurality of S are present from the viewpoint of availability of raw materials and ease of synthesis, they may be the same or different, and each independently represents one —CH ₂ — or not adjacent 2 It is more preferable that two or more —CH ₂ — each independently represent an alkylene group having 1 to 10 carbon atoms or a single bond which may be replaced by —O—, —COO—, or —OCO—, and a plurality of them are present. Each may be the same or different, more preferably each independently represents an alkylene group having 1 to 10 carbon atoms or a single bond, and when there are a plurality thereof, they may be the same or different. It is particularly preferable that each independently represents an alkylene group having 1 to 8 carbon atoms.

X 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 = CH-COO -, - CH = CH-OCO -, - COO-CH = CH -, - OCO-CH = CH -, - COO-CH 2 CH 2 -, - OCO-CH 2 CH 2 _{-, - CH 2 CH 2 -COO} -, - CH 2 CH 2 -OCO -, - COO-CH 2 -, - OCO-CH 2 -, - CH 2 -COO -, - CH 2 -OCO -, - CH ═CH—, —CF═CF— or a single bond, but when there are a plurality of X, they may be the same or different. Also good. From the viewpoint of ease of raw material availability and synthesis, if there are a plurality may be different from each be the same, each independently -O -, - S -, - OCH 2 -, _{-CH 2 O -, - COO -} , - OCO -, - CO-S -, - S-CO -, - OCO-O -, - CO-NH -, - NH-CO -, - COO-CH ₂ CH ₂ —, —OCO—CH ₂ CH ₂ —, —CH ₂ CH ₂ —COO—, —CH ₂ CH ₂ —OCO— or a single bond are preferred, May be different and each independently represents —O—, —OCH ₂ —, —CH ₂ O—, —COO—, —OCO—, —COO—CH ₂ CH ₂ —, —OCO—CH ₂ CH _{2. -, - CH 2 CH 2 -COO} -, - a _CH 2 CH 2 -OCO- or a single bond In the case where a plurality of groups are present, they may be the same or different, and it is particularly preferable that each independently represent —O—, —COO—, —OCO— or a single bond.

A ¹ , A ² , A ³ , A ⁴ and A ⁵ are each independently unsubstituted or optionally substituted by one or more L, 1,4-phenylene, naphthalene-1,4-diyl or naphthalene-2 , 6-diyl, and when a plurality of A ⁵ are present, they may be the same or different, but at least one of A ¹ , A ² , A ³ and A ⁴ is From the point of view, it must be replaced by one or more Ls. A ¹ , A ² , A ³ , A ⁴ and A ⁵ are each independently unsubstituted or substituted with one or more L from the viewpoint of availability of raw materials and ease of synthesis. Preferably it represents phenylene or naphthalene-2,6-diyl, each independently of the following formulas (A-1) to (A-10)

More preferably, each independently represents a group selected from the formula (A-1) to the formula (A-9), and each independently represents a group selected from the formula (A-1). It is particularly preferable to represent a group selected from the formula (A-7).

  L represents a fluorine atom, a chlorine atom, a bromine atom or an iodine atom, but preferably represents a fluorine atom, a chlorine atom or a bromine atom, and particularly preferably represents a fluorine atom or a chlorine atom, from the viewpoint of ease of synthesis.

Z ¹ , Z ² and Z ³ are each independently a single bond, —O—, —S—, —OCH ₂ —, —CH ₂ O—, —COO—, —OCO—, —CO—, — 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—, —CH═CH—, —CF═CF— or —C≡C—, each independently represents a single bond from the viewpoint of liquid crystallinity of the compound, availability of raw materials and ease of synthesis. _{-OCH 2 -, - CH 2 O} -, - COO -, - OCO -, - CF 2 O -, - OCF 2 -, - CH 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—, —CH═CH—, —CF═CF— or —C≡C— are preferably represented, and each independently represents a single bond, —OCH ₂ —, —CH _2. O -, - COO -, - OCO -, - COO-CH 2 CH 2 -, - OCO-CH _{CH 2 -, - CH 2 CH} 2 -COO -, - CH 2 CH 2 -OCO -, - more preferably represent a CH = CH- or -C≡C-, each independently a single bond, -COO- Or -OCO- is particularly preferred.

R is a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a pentafluorosulfuranyl group, a cyano group, a nitro group, an isocyano group, a thioisocyano group, or one —CH ₂ — or not adjacent. Two or more —CH ₂ — are each independently —O—, —S—, —CO—, —COO—, —OCO—, —CO—S—, —S—CO—, —O—CO—. O-, -CO-NH-, -NH-CO-, -CH = CH-COO-, -CH = CH-OCO-, -COO-CH = CH-, -OCO-CH = CH-, -CH = A straight or branched alkyl group having 1 to 12 carbon atoms which may be substituted by CH—, —CF═CF— or —C≡C—, represents a hydrogen atom from the viewpoint of liquid crystallinity and ease of synthesis, fluorine atom, a chlorine atom, a cyano group, or one -CH ₂ Or adjacent have not more than one -CH ₂ - are each independently -O -, - COO -, - OCO -, - OCO-O- are also from a good 1 -C 12 substituted by It preferably represents a linear or branched alkyl group, more preferably represents a hydrogen atom, a fluorine atom, a chlorine atom, a cyano group, or a linear alkyl group having 1 to 12 carbon atoms, and has 1 to 12 carbon atoms. It is particularly preferable to represent a linear alkyl group of

  l represents an integer of 0 to 8, but preferably represents an integer of 0 to 4, and preferably represents an integer of 0 to 2, from the viewpoints of liquid crystallinity, availability of raw materials, ease of synthesis, and storage stability. Is more preferable, 0 or 1 is more preferable, and 1 is particularly preferable.

  m1, m2, and m3 each independently represents 0 or 1, but m1 + m2 + m3 represents 0 or 1. From the viewpoint of storage stability and orientation, m1 + m2 + m3 is preferably 0.

  n represents 0, 1 or 2, but preferably represents 0 or 1 and particularly preferably represents 0 from the viewpoint of storage stability and ease of synthesis.

  Specifically, compounds represented by the following formulas (I-1) to (I-96) are preferable as the compounds represented by the general formula (I).

The compound of this invention can be manufactured with the following manufacturing methods.
(Manufacturing method 1) Manufacture of the compound represented by a following formula (S-8)

(In the formula, P, S, L and R each independently represent the same as defined in formula (I), r each independently represents an integer of 0 to 4, and halogen represents halogen. Represents an atomic or halogen equivalent.)
The compound represented by the formula (S-3) can be obtained by reacting the compound represented by the formula (S-1) with the compound represented by the formula (S-2). Examples of the reaction include a method of cross-coupling in the presence of a metal catalyst and a base. Examples of the metal catalyst include allyl palladium (II) chloride, [1,1′-bis (diphenylphosphino) ferrocene] palladium (II) dichloride, palladium (II) acetate, and tetrakis (triphenylphosphine) palladium (0). Can be mentioned. As the base, for example, triethylamine can be used. Reaction conditions include, for example, Metal-Catalyzed Cross-Coupling Reactions (Co-authored by Armin de Meijer, Francois Diedrich, Wiley-VCH), Palladium Reagents and Catalysts: New Perspectives: New Perspective. Cross-Coupling Reactions: A Practical Guide (Topics in Current Chemistry) (SL Buchwald, K. Fugami, T. Hiyama, M. Kourai, M. Miura, M. Miura, M. Miura, M. Miura, M. Miura, N. Mura. a, E. Shiragawa, K. Tamao, Springer) and the like.

  The compound represented by the general formula (S-4) is obtained by boring the compound represented by the general formula (S-3). Examples of the method include a method in which a proton on the aromatic ring of the compound represented by the general formula (S-3) is extracted with a strong base, reacted with a borate ester, and then hydrolyzed. Examples of the strong base include butyl lithium, sec-butyl lithium, tert-butyl lithium, methyl lithium and the like. In order to promote proton extraction, an additive such as tetramethylethylenediamine may be used. Examples of the boric acid ester include triisopropyl borate and trimethyl borate. Alternatively, a method in which a compound represented by the general formula (S-3) is derived from a halogenated compound into a lithiated form by a halogen lithium exchange reaction, reacted with a borate ester, and then hydrolyzed may be mentioned. Alternatively, a method in which the compound represented by the general formula (S-3) is derived from a halogenated compound into a Grignard reagent, reacted with a boric acid ester, and then hydrolyzed may be used.

  The compound represented by the formula (S-6) can be obtained by reacting the compound represented by the formula (S-4) with a compound represented by the formula (S-5). Examples of the reaction include a method of cross-coupling in the presence of a metal catalyst and a base. The above-mentioned catalysts and bases can be used.

  A compound represented by the formula (S-8) is obtained by reacting a compound represented by the general formula (S-6) with a compound represented by the general formula (S-7). As the reaction conditions, for example, Mitsunobu reaction or a compound represented by the general formula (S-7) is reacted with sulfonic acid or the like to form a sulfonic acid ester, or reacted with a halogenating reagent to obtain a halogen compound. Examples thereof include a method of reacting the compound represented by (S-6) in the presence of a base. When the Mitsunobu reaction is used, examples of the azodicarboxylic acid include diethyl azodicarboxylate and diisopropyl azodicarboxylate. Examples of phosphine include triphenylphosphine. A Kakuda reagent such as cyanomethylenetributylphosphorane may also be used. In the case of passing through a sulfonic acid ester, examples of the sulfonic acid include methanesulfonic acid, ethanesulfonic acid, benzenesulfonic acid, and p-toluenesulfonic acid. As the base, for example, triethylamine, pyridine, N-ethyldiisopropylamine and the like can be used.

  Examples of reaction conditions other than those described in the above steps include, for example, Experimental Chemistry Course (edited by the Chemical Society of Japan, published by Maruzen Co., Ltd.), Organic Synthesis (A John Wiley & Sons, Inc., Publication), and Bilstein Handbook of Organic Chemistry (Chemical Chemistry). In Institut Futer Literator der Organischen Chemie, Springer-Verlag Berlin and Heidelberg GmbH & Co. K, Fiesers' Reagents for Organic Science. mical Abstracts Service, American Chemical Society) or Reaxys (condition provided by the online search services Elsevier Ltd.) and the like.

  In each step, a reaction solvent can be appropriately used. The solvent is not particularly limited as long as it gives the target compound. For example, tert-butyl alcohol, isobutyl alcohol, isopropyl alcohol, isopentyl alcohol, cyclohexanol, 1-butanol, 2-butanol, 1-octanol, 2- Methoxyethanol, ethylene glycol, diethylene glycol, methanol, methylcyclohexanol, ethanol, propanol, chloroform, carbon tetrachloride, dichloromethane, 1,2-dichloroethane, 1,2-dichloroethylene, 1,1,2,2-tetrachloroethane, trichloroethylene 1-chlorobutane, carbon disulfide, acetone, acetonitrile, benzonitrile, N, N-dimethylformamide, N, N-dimethylacetamide, dimethyl sulfoxide, 1 3-dimethyl-2-imidazolidinone, diethyl ether, ethylene glycol monoethyl ether, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether, ethylene glycol monomethyl ether, diethylene glycol diethyl ether, o-dichlorobenzene, xylene, o-xylene , P-xylene, m-xylene, chlorobenzene, isobutyl acetate, isopropyl acetate, isoamyl acetate, ethyl acetate, butyl acetate, propyl acetate, pentyl acetate, methyl acetate, 2-methoxyethyl acetate, hexamethylphosphate triamide, tris (dimethyl Amino) phosphine, cyclohexanone, 1,4-dioxane, dichloromethane, styrene, tetrachloroethylene, tetrahydrofuran, pyridine, -Methyl-2-pyrrolidinone, 1,1,1-trichloroethane, toluene, hexane, pentane, cyclohexane, cyclopentane, heptane, benzene, methyl isobutyl ketone, tert-butyl methyl ether, methyl ethyl ketone, methyl cyclohexanone, methyl butyl ketone, diethyl Examples include ketones, gasoline, coal tar naphtha, petroleum ether, petroleum naphtha, petroleum benzine, turpentine oil, and mineral spirits. When the reaction is carried out in an organic solvent and water two-phase system, a phase transfer catalyst can be added. Examples of the phase transfer catalyst include benzyltrimethylammonium chloride, polyoxyethylene (20) sorbitan monolaurate [Tween 20], sorbitan monooleate [Span 80], and the like.

In each step, purification can be performed as necessary. Examples of the purification method include chromatography, recrystallization, distillation, sublimation, reprecipitation, adsorption, and liquid separation treatment. When using a purification agent, silica gel, alumina, activated carbon, activated clay, celite, zeolite, mesoporous silica, carbon nanotube, carbon nanohorn, Bincho charcoal, charcoal, graphene, ion exchange resin, acid clay, silicon dioxide, diatomaceous earth, Examples include perlite, cellulose, organic polymer, and porous gel.
(Production Method 2) Production of a compound represented by the following formula (S-12)

(Wherein P, S, X, L and R each independently represents the same one as defined in formula (I), r each independently represents an integer of 0 to 4; Represents a halogen atom or a halogen equivalent.)
The compound represented by the formula (S-10) can be obtained by reacting the compound represented by the formula (S-4) with the compound represented by the formula (S-9). Examples of the reaction include a method of cross-coupling in the presence of a metal catalyst and a base. As the catalyst and the base, those described in Production Method 1 can be used.

  The compound represented by the general formula (S-12) is obtained by reacting the compound represented by the general formula (S-10) with the compound represented by the general formula (S-11). As the reaction conditions, for example, a method using a condensing agent or a compound represented by the general formula (S-11) is converted into an acid chloride, mixed acid anhydride or carboxylic acid anhydride, and then the general formula (S-10) is used. The method of making it react with the compound represented by base presence is mentioned. When a condensing agent is used, examples of the condensing agent include N, N′-dicyclohexylcarbodiimide, N, N′-diisopropylcarbodiimide, 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide hydrochloride, N- [3- (dimethyl Amino) propyl] -N'-ethylcarbodiimide, N- [3- (dimethylamino) propyl] -N'-ethylcarbodiimide methiodide, N-tert-butyl-N'-ethylcarbodiimide, N-cyclohexyl-N'- (2-morpholinoethyl) carbodiimide meth-p-toluenesulfonate, N, N′-di-tert-butylcarbodiimide, N, N′-di-p-tolylcarbodiimide, 4- (4,6-dimethoxy-1, 3,5-triazin-2-yl) -4-methylmorpholinium chloride, etc. It is below. As the base, amines described in Production Method 1 can be used.

  In each step, a reaction solvent can be appropriately used. The solvent is not particularly limited as long as it provides the target compound, but, for example, those described in Process 1 can be used.

In each step, purification can be performed as necessary. Examples of the purification method include chromatography, recrystallization, distillation, sublimation, reprecipitation, adsorption, and liquid separation treatment. When using a purification agent, silica gel, alumina, activated carbon, activated clay, celite, zeolite, mesoporous silica, carbon nanotube, carbon nanohorn, Bincho charcoal, charcoal, graphene, ion exchange resin, acid clay, silicon dioxide, diatomaceous earth, Examples include perlite, cellulose, organic polymer, and porous gel.
(Production method 3) Production of a compound represented by the following formula (S-22)

(Wherein P, S, L and R each independently represents the same as defined in formula (I), r is independently an integer of 0 to 4, and s is independently Represents an integer of 0 to 3, halogen represents a halogen atom or a halogen equivalent, and PG represents a protecting group.)
A compound represented by the general formula (S-14) is obtained by reacting the compound represented by the general formula (S-13) with, for example, trifluoromethanesulfonic anhydride (Tf ₂ O).

  The compound represented by the formula (S-16) can be obtained by reacting the compound represented by the formula (S-14) with the compound represented by the formula (S-15). Examples of the reaction include a method of cross-coupling in the presence of a metal catalyst and a base. As the catalyst and the base, those described in Production Method 1 can be used.

  The carboxyl group of the compound represented by the general formula (S-17) is protected with a protecting group (PG). The protecting group (PG) is not particularly limited as long as it can give a compound represented by the general formula (S-18) in the reaction process and can be stably protected until the deprotection step. For example, GREENE 'S PROTECTIVE GROUPS IN ORGANIC SYNTHESIS ((Fourth Edition), PETER G.M. . For example, methyl ester, ethyl ester, tert-butyl ester and the like can be mentioned.

  The compound represented by the general formula (S-20) is obtained by reacting the compound represented by the general formula (S-18) with a compound represented by the general formula (S-19) in the presence of a base, for example. As the base, for example, those described in Production Method 1 can be used.

  The protecting group (PG) of the compound represented by the general formula (S-20) is deprotected. The deprotection reaction conditions are not particularly limited as long as they give the compound represented by the general formula (S-21) in the reaction process. , PETER G.M.WUTS, THEODARA W.GREENE, A John Wiley & Sons, Inc., Publication).

  The compound represented by general formula (S-22) is obtained by reacting the compound represented by general formula (S-21) with the compound represented by general formula (S-16). As the reaction conditions, for example, a method using a condensing agent or a compound represented by the general formula (S-21) is converted to an acid chloride, mixed acid anhydride or carboxylic acid anhydride, and then the general formula (S-16) The method of making it react with the compound represented by base presence is mentioned. In the case of using a condensing agent, for example, the condensing agent described in production method 2 can be used. As the base, amines described in Production Method 1 can be used.

  In each step, a reaction solvent can be appropriately used. The solvent is not particularly limited as long as it provides the target compound, but, for example, those described in Process 1 can be used.

  In each step, purification can be performed as necessary. Examples of the purification method include chromatography, recrystallization, distillation, sublimation, reprecipitation, adsorption, and liquid separation treatment. When using a purification agent, silica gel, alumina, activated carbon, activated clay, celite, zeolite, mesoporous silica, carbon nanotube, carbon nanohorn, Bincho charcoal, charcoal, graphene, ion exchange resin, acid clay, silicon dioxide, diatomaceous earth, Examples include perlite, cellulose, organic polymer, and porous gel.

  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. In the liquid crystal composition using the reactive compound of the present invention, a compound other than the present invention may be added.

  Specific examples of other reactive compounds used in combination with the reactive compound of the present invention include those represented by the general formula (II)

(Wherein P ¹ and P ² each independently represent the same meaning as P in formula (I), and S ¹ and S ² each independently represent a single bond or an alkylene group having 1 to 20 carbon atoms) represents a one -CH ₂ - or nonadjacent two or more _-CH 2 - is -O -, - COO -, - OCO -, - OCOO- may be replaced by a, ^{X 1} and X ² each 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 = CH-} COO -, - CH = CH-OCO -, - COO-CH = CH -, - OCO-CH = CH -, - COO _{CH 2 CH 2 -, - OCO} -CH 2 CH 2 -, - CH 2 CH 2 -COO -, - CH 2 CH 2 -OCO -, - COO-CH 2 -, - OCO-CH 2 -, - CH 2 —COO—, —CH ₂ —OCO—, —CH═CH—, —CF═CF—, —C≡C— or a single bond, each Z ⁴ independently represents a single bond, —O—, —S _{-, - OCH 2 -, -} CH 2 O -, - COO -, - OCO -, - CO -, - CO-S -, - S-CO -, - OCO-O -, - CO-NH- , —NH—CO—, —SCH ₂ —, —CH ₂ S—, —CF ₂ O—, —OCF ₂ —, —CF ₂ S—, —SCF ₂ —, —CH ₂ CH ₂ —, —CH _{2 CF 2 -, - CF 2 CH} 2 -, - CF 2 CF 2 -, - CH = CH-COO -, - CH = CH-OCO -, - COO _{-CH = CH -, - OCO-} CH = CH -, - COO-CH 2 CH 2 -, - OCO-CH 2 CH 2 -, - CH 2 CH 2 -COO -, - CH 2 CH 2 -OCO-, —COO—CH ₂ —, —OCO—CH ₂ —, —CH ₂ —COO—, —CH ₂ —OCO—, —CH═CH—, —CF═CF— or —C≡C— represents A ⁶ And A ⁷ are each independently 1,4-phenylene group, 1,4-cyclohexylene group, pyridine-2,5-diyl group, pyrimidine-2,5-diyl group, naphthalene-2,6-diyl group. , Tetrahydronaphthalene-2,6-diyl group or 1,3-dioxane-2,5-diyl group, A ⁶ and A ⁷ are each independently unsubstituted or halogen atoms (fluorine atom, chlorine Atom, bromine atom, iodine atom), 1 carbon atom To an alkyl group, a halogenated alkyl group, an alkoxy group, a halogenated alkoxy group, a cyano group, or a nitro group, and n1 represents 0, 1, 2, or 3, and n1 is 2 or 3 , A ⁶ and Z ⁵ present in two or three may be the same or different from each other. It is preferably a compound represented by), when P ¹ and P ² of the general formula (II) is an acrylic group or methacrylic group are particularly preferable. Specifically, the general formula (II-i)

(Wherein R ¹ and R ² each independently represent hydrogen or a methyl group, S ³ and S ⁴ each independently represent an alkylene group having 2 to 18 carbon atoms, and X ³ and X ⁴ each independently represent -O Te -, - COO -, - OCO- or a single bond, ^{Z 5} and ^{Z 6} each independently represents a -COO- or ^{-OCO-, a 8,} a ⁹ and ^{a 10} are each independently And a compound represented by the following formula (II-i): a fluorine atom, a chlorine atom or a 1,4-phenylene group substituted by an alkyl group having 1 to 4 carbon atoms or an alkoxy group. Particularly preferred are compounds represented by formulas (II) to (II-i-8).

(Wherein, ^{R 1} and ^{R 2} represent a hydrogen atom or a methyl group, ^{S 3} has the same meaning as ^{S 3} in the general formula ^{(II-i), S 4} S 4 in the general formula (II-i) In the above formulas (II-i-1) to (II-i-8), S ³ and S ⁴ are each independently an alkylene group having 2 to 8 carbon atoms. Further preferred.

  Moreover, general formula (II-ii)

(Wherein R ¹ and R ² represent a hydrogen atom or a methyl group, S ⁵ and S ⁶ are each independently an alkylene group having 2 to 18 carbon atoms, and X ⁵ and X ⁶ are each independently —O -, -COO-, -OCO- or a single bond, Z ⁷ represents -COO- or -OCO-, and A ¹¹ , A ¹² and A ¹³ each independently represents an unsubstituted or fluorine atom, chlorine atom or A compound represented by a 1,4-phenylene group substituted by an alkyl group having 1 to 4 carbon atoms or an alkoxy group is preferred, and the following formulas (II-ii-1) to (II-ii-) The compound represented by 8) is particularly preferred.

(Wherein, ^{R 1} and ^{R 2} represent a hydrogen atom or a methyl group, ^{S 5} has the same meaning as ^{S 5} in the general formula (II-ii), ^S in ^{S 6} the general formula (II-ii) ⁶ In the above formulas (II-ii-1) to (II-ii-8), from the viewpoint of heat resistance and durability, the formulas (II-ii-2) and (II-ii) −5), a compound represented by the formula (II-ii-6), a formula (II-ii-7) and a formula (II-ii-8) is preferable, and a compound represented by the formula (II-ii-2) More preferred are compounds, and particularly preferred are compounds in which S ⁵ and S ⁶ are each independently an alkylene group having 2 to 8 carbon atoms.

  In addition, preferable bifunctional polymerizable compounds include compounds represented by the following formulas (II-iii-1) to (II-iii-8).

(In the formula, R ¹ and R ² each represent a hydrogen atom or a methyl group, and S ⁷ and S ⁸ each independently represent an alkylene group having 2 to 18 carbon atoms.) The above formula (II-iii-1) To formula (II-iii-8) in formula (II-iii-2), formula (II-iii-3), formula (II-iii-4), formula (II-iii-6), formula (II) -Iii-7) and the compounds represented by formula (II-iii-8) are preferred, and compounds in which S ⁷ and S ⁸ are each independently an alkylene group having 2 to 8 carbon atoms are particularly preferred.

  Preferred monofunctional polymerizable compounds other than the monofunctional polymerizable compound represented by the general formula (I) include compounds represented by the following general formulas (III-1) to (III-9).

(Wherein P ³ represents the same meaning as P in formula (I), S ⁹ represents a single bond or an alkylene group having 1 to 20 carbon atoms, but one —CH ₂ — or adjacent one is Two or more —CH ₂ — that are not present may be replaced by —O—, —COO—, —OCO—, —OCOO—, and X ⁷ is a single bond, —O—, —COO—, —OCO— Z ⁸ represents a single bond, —COO—, —OCO—, —CH═CH—COO—, —OCO—CH═CH—, —CH═CH—, —CF═CF— or —C≡C—. A ¹⁴ represents a 1,4-phenylene group or a naphthalene-2,6-diyl group, and A ¹⁴ is unsubstituted or a halogen atom (a fluorine atom, a chlorine atom, a bromine atom, an iodine atom), C1-C20 alkyl group, halogenated alkyl group, alkoxy group, halo It may be substituted with a generalized alkoxy group, a cyano group or a nitro group, and L ¹ is independently a fluorine atom, a chlorine atom, one —CH ₂ — or two or more —CH ₂ — not adjacent to each other. Represents a linear or branched alkyl group having 1 to 10 carbon atoms that may be replaced by -O-, -COO-, or -OCO-, r represents an integer of 0 to 4, and R ¹ represents A hydrogen atom, a fluorine atom, a chlorine atom, a cyano group, a nitro group, one —CH ₂ — or two or more non-adjacent —CH ₂ — are each independently —O—, —COO—, —OCO. -Represents a linear or branched alkyl group having 1 to 20 carbon atoms which may be replaced by -OCO-O-.
A polymerizable compound that does not exhibit liquid crystallinity can be added to the polymerizable liquid crystal composition containing the compound of the present invention to such an extent that the liquid crystallinity of the composition is not significantly impaired. Specifically, any compound that is recognized as a polymer-forming monomer or polymer-forming oligomer in this technical field can be used without particular limitation. Specific examples include those described in “Photocuring Technology Data Book, Materials (Monomer, Oligomer, Photopolymerization Initiator)” (supervised by Kunihiro Ichimura, Kiyosuke Kato, Technonet).

  The compound of the present invention can be polymerized without using a photopolymerization initiator, but a photopolymerization initiator may be added depending on the purpose. In this case, the concentration of the photopolymerization initiator is preferably 0.1% by mass to 15% by mass, more preferably 0.2% by mass to 10% by mass, and 0.4% by mass to 8% by mass with respect to the compound of the present invention. % Is more preferable. Examples of the photopolymerization initiator include benzoin ethers, benzophenones, acetophenones, benzyl ketals, and acylphosphine oxides. Specific examples of the photopolymerization initiator include 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one (IRGACURE 907). One type of polymerization initiator may be used, or two or more types of polymerization initiators may be used in combination.

  In addition, a stabilizer can be added to the polymerizable liquid crystal composition of the present invention in order to improve its storage stability. Examples of the stabilizer that can be used include hydroquinones, hydroquinone monoalkyl ethers, tert-butylcatechols, pyrogallols, thiophenols, nitro compounds, β-naphthylamines, β-naphthols, nitroso compounds, and the like. It is done. When the stabilizer is used, the addition amount is preferably in the range of 0.005% by mass to 1% by mass, more preferably 0.02% by mass to 0.8% by mass, and 0.03% by mass with respect to the composition. To 0.5% by mass is more preferable. One kind of stabilizer may be used, or two or more kinds of stabilizers may be used in combination. Specifically, as the stabilizer, the formula (IV-1) to the formula (IV-36)

(Wherein n represents an integer of 0 to 20) is preferred.

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

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

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

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

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

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

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

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

  In a reaction vessel, 20.0 g (0.122 mol) of the compound represented by the formula (I-1-1), 21.3 g (0.122 mol) of the compound represented by the formula (I-1-2), carbonic acid Potassium 25.3 g (0.183 mol), tetrahydrofuran 100 mL, and water 100 mL were added. After substituting the system with nitrogen, 1.41 g (1.22 mmol) of tetrakis (triphenylphosphine) palladium (0) was added and heated to reflux for 7 hours. Dilute with toluene and wash with brine. Purification was performed by column chromatography (silica gel) to obtain 22.2 g (0.104 mol) of a compound represented by the formula (I-1-3).

  To a reaction vessel equipped with a dropping funnel, 22.2 g (0.104 mol) of the compound represented by the formula (I-1-3) and 150 mL of tetrahydrofuran were added. 124 mL of a sec-butyllithium solution (1.0 mol / L) was added dropwise at -70 ° C. After stirring for 2 hours, 25.3 g (0.135 mol) of triisopropyl borate was added dropwise. After stirring for 2 hours, 300 mL of 10% hydrochloric acid was added dropwise at 0 ° C. The mixture was stirred at room temperature for 1 hour and washed with brine. By concentrating and drying, 25.7 g (0.0995 mol) of the compound represented by the formula (I-1-4) was obtained.

  In a reaction vessel, 25.7 g (0.0995 mol) of a compound represented by formula (I-1-4), 25.0 g (0.0995 mol) of a compound represented by formula (I-1-5), carbonic acid 20.6 g (0.149 mol) of potassium, 150 mL of tetrahydrofuran and 150 mL of water were added. After the inside of the system was replaced with nitrogen, 1.15 g (0.995 mmol) of tetrakis (triphenylphosphine) palladium (0) was added and heated to reflux for 10 hours. Dilute with toluene and wash with brine. Purification was performed by column chromatography (silica gel) and recrystallization to obtain 31.2 g (0.0812 mol) of a compound represented by the formula (I-1-6).

  To a reaction vessel equipped with a dropping funnel, 12.6 g (0.0943 mol) of aluminum chloride and 38 mL of dichloromethane were added. At room temperature, 8.02 g (0.102 mol) of acetyl chloride was added dropwise. After stirring at room temperature for 2 hours, a solution of 31.2 g (0.0812 mol) of the compound represented by formula (I-1-6) dissolved in 605 mL of dichloromethane was added dropwise while cooling with ice. After stirring at room temperature for 4 hours, it was poured into water. Diluted with dichloromethane and washed with brine. After drying with sodium sulfate, it was concentrated and dried to obtain 22.8 g (0.0535 mol) of a compound represented by the formula (I-1-7).

  To a reaction vessel equipped with a dropping funnel, 364 mL of formic acid and 24.3 g (0.214 mol) of 30% aqueous hydrogen peroxide were added. After stirring at room temperature for 1 hour, a solution in which 22.8 g (0.0535 mol) of the compound represented by the formula (I-1-7) was dissolved in 456 mL of dichloromethane was added dropwise. After heating and stirring at 50 ° C. for 60 hours, an aqueous sodium hydrogen sulfite solution was added. After washing with brine, purification was carried out by column chromatography (silica gel) and recrystallization to obtain 17.4 g (0.0392 mol) of the compound represented by formula (I-1-8).

  To the reaction vessel, 17.4 g (0.0392 mol) of the compound represented by the formula (I-1-8), 400 mL of tetrahydrofuran and 23.2 g (0.392 mol) of propylamine were added and stirred at room temperature for 50 hours. The solvent was distilled off and dissolved in ethyl acetate. After washing with 5% hydrochloric acid and brine, purification was performed by column chromatography (silica gel) and recrystallization to obtain 15.7 g (0.0392 mol) of the compound represented by the formula (I-1-9). .

In a reaction vessel, 15.7 g (0.0392 mol) of a compound represented by formula (I-1-9), 8.11 g (0.0546 mol) of a compound represented by formula (I-1-10), carbonic acid 20.5 g (0.0630 mol) of cesium and 168 mL of dimethyl sulfoxide were added, and the mixture was heated and stirred at 63 ° C. for 5 hours. After diluting with dichloromethane and washing with water and brine, purification was performed by column chromatography (silica gel) and recrystallization to obtain 12.6 g of a compound represented by the formula (I-1).
Transition temperature (temperature rise 5 ° C./min): C 92 N> 200 I
¹ H NMR (CDCl ₃ ) δ 0.98 (t, 3H), 1.69 (sex, 2H), 2, 20 (quin, 2H), 2.65 (t, 2H), 4.13 (t, 2H), 4.39 (t, 2H), 5.84 (dd, 1H), 6.14 (dd, 1H), 6.42 (dd, 1H), 6.99 (d, 2H), 7. 28 (d, 2H), 7.39-7.55 (m, 10H) ppm.
¹³ C NMR (CDCl ₃ ) δ 13.6, 24.5, 28.6, 37.7, 61.3, 64.4, 114.4, 114.5, 114.6, 116.3, 116. 24, 116.6, 116.6, 122.8, 122.8, 124.7, 125.7, 125.9, 126.7, 127.7, 127.8, 128.0, 128.3 129.1, 130.1, 130.1, 130.3, 130.3, 130.5, 130.6, 130.8, 135.9, 136.0, 136.6, 142.8, 142. 8, 158.4, 158.5, 158.8, 160.8, 161.2, 166.1 ppm.
Example 2 Production of Compound Represented by Formula (I-2)

  20.0 g (0.107 mol) of the compound represented by the formula (I-2-1), 12.7 g (0.161 mol) of pyridine, and 100 mL of dichloromethane were added to a reaction vessel equipped with a dropping funnel. While cooling with ice, 36.4 g (0.129 mol) of trifluoromethanesulfonic anhydride was added dropwise. After stirring at room temperature for 10 hours, the mixture was washed with hydrochloric acid and brine. Purification was performed by column chromatography (silica gel) to obtain 33.2 g (0.104 mol) of a compound represented by the formula (I-2-2).

  In a reaction vessel, 33.2 g (0.104 mol) of the compound represented by the formula (I-2-2), 14.6 g (0.104 mol) of the compound represented by the formula (I-2-3), carbonic acid, 21.6 g (0.156 mol) of potassium, 150 mL of tetrahydrofuran and 150 mL of water were added. After substituting the system with nitrogen, 1.20 g (1.04 mmol) of tetrakis (triphenylphosphine) palladium (0) was added and heated to reflux for 9 hours. After diluting with toluene, it was washed with hydrochloric acid and brine, and purified by column chromatography (silica gel) to obtain 23.4 g (0.0885 mol) of the compound represented by the formula (I-2-4). .

  To a reaction vessel equipped with a dropping funnel, 23.4 g (0.0885 mol) of the compound represented by the formula (I-2-4) and 120 mL of tetrahydrofuran were added. 106 mL of a sec-butyllithium solution (1.0 mol / L) was added dropwise at -70 ° C. After stirring for 2 hours, 21.6 g (0.115 mol) of triisopropyl borate was added dropwise. After stirring for 2 hours, 300 mL of 10% hydrochloric acid was added dropwise at 0 ° C. The mixture was stirred at room temperature for 1 hour and washed with brine. By concentration and drying, 22.9 g (0.0744 mol) of the compound represented by the formula (I-2-5) was obtained.

  To a reaction vessel equipped with a dropping funnel, 12.7 g (0.0956 mol) of aluminum chloride and 40 mL of dichloromethane were added. At room temperature, 8.13 g (0.104 mol) of acetyl chloride was added dropwise. After stirring at room temperature for 2 hours, a solution prepared by dissolving 20.0 g (0.0797 mol) of the compound represented by the formula (I-1-5) in 100 mL of dichloromethane was added dropwise while cooling with ice. After stirring at room temperature for 4 hours, it was poured into water. Diluted with dichloromethane and washed with brine. After drying with sodium sulfate, concentration and drying were performed to obtain 22.6 g (0.0773 mol) of the compound represented by the formula (I-2-6).

  To a reaction vessel equipped with a dropping funnel, 220 mL of formic acid and 35.0 g (0.309 mol) of 30% aqueous hydrogen peroxide were added. After stirring at room temperature for 1 hour, a solution in which 22.6 g (0.0773 mol) of the compound represented by the formula (I-2-6) was dissolved in 100 mL of dichloromethane was added dropwise. After heating and stirring at 50 ° C. for 60 hours, an aqueous sodium hydrogen sulfite solution was added. After washing with brine, purification was performed by column chromatography (silica gel) to obtain 22.5 g (0.0726 mol) of a compound represented by the formula (I-2-7).

  To the reaction vessel, 22.5 g (0.0726 mol) of the compound represented by the formula (I-2-7), 150 mL of tetrahydrofuran and 42.9 g (0.726 mol) of propylamine were added and stirred at room temperature for 50 hours. The solvent was distilled off and dissolved in ethyl acetate. After washing with 5% hydrochloric acid and brine, purification was performed by column chromatography (silica gel) to obtain 18.4 g (0.0690 mol) of the compound represented by the formula (I-2-8).

  In the reaction vessel, 18.4 g (0.0690 mol) of the compound represented by the formula (I-2-8), 8.48 g (0.0897 mol) of 3-chloropropanol, 33.7 g (0.103 mol) of cesium carbonate ), 180 mL of dimethyl sulfoxide was added, and the mixture was heated and stirred at 60 ° C. for 5 hours. Diluted with dichloromethane, washed with 10% hydrochloric acid and brine, purified by column chromatography (silica gel) to obtain 20.2 g (0.0621 mol) of the compound represented by formula (I-2-9). Obtained.

  In a reaction vessel, 20.2 g (0.0621 mol) of a compound represented by formula (I-2-9), 19.1 g (0.0621 mol) of a compound represented by formula (I-2-5), carbonic acid 12.9 g (0.0931 mol) of potassium, 100 mL of tetrahydrofuran and 100 mL of water were added. After substituting the system with nitrogen, 0.72 g (0.621 mmol) of tetrakis (triphenylphosphine) palladium (0) was added, and the mixture was heated to reflux for 9 hours. After diluting with toluene, it was washed with hydrochloric acid and brine, purified by column chromatography (silica gel) and recrystallization, and 26.8 g (0.0528 mol) of the compound represented by the formula (I-2-10) Got.

To a reaction vessel equipped with a dropping funnel, 26.8 g (0.0528 mol) of the compound represented by the formula (I-2-10), 10.2 g (0.0792 mol) of diisopropylethylamine, and 125 mL of dichloromethane were added. While cooling with ice, 6.21 g (0.0686 mol) of acryloyl chloride was added dropwise. The mixture was stirred at room temperature for 5 hours, washed with 5% hydrochloric acid and brine, and purified by column chromatography (silica gel) and recrystallization to obtain 22.2 g of a compound represented by the formula (I-2).
Transition temperature (temperature rise 5 ° C./min): C 113 S
¹ H NMR (CDCl ₃ ) δ 0.99 (t, 3H), 1.75 (sex, 2H), 2.21 (quin, 2H), 2.78 (t, 2H), 4.13 (t, 2H), 4.40 (t, 2H), 5.86 (dd, 1H), 6.15 (dd, 1H), 6.44 (dd, 1H), 7.01 (d, 2H), 7. 38-7.60 (m, 9H), 7.65 (s, 1H), 7.74 (dd, 1H), 7.87 (dd, 2H), 8.06 (s, 1H) ppm.
¹³ C NMR (CDCl ₃ ) δ 13.87, 24.44, 28.58, 38.20, 61.33, 64.27, 114.49, 114.74, 114.98, 116.42, 116. 62, 123.19, 123.22, 124.78, 124.93, 125.64, 126.06, 126.20, 127.75, 127.89, 128.12, 128.22, 128.31, 130.13, 130.16, 130.36, 130.40, 130.66, 130.70, 130.98, 132.02, 133.08, 135.71, 135.82, 135.90, 140. 93, 142.79, 142.87, 158.34, 158.48, 158.83, 160.80, 161.30, 166.21 ppm.
Example 3 Production of Compound Represented by Formula (I-3)

In Example 1, the compound represented by the formula (I-1-1) is changed to the compound represented by the formula (I-3-1), and the compound represented by the formula (I-1-2) is changed to the formula (I-3-1). The compound represented by the formula (I-1-10) is replaced with the compound represented by the formula (I-3-9) by the same method as the compound represented by the formula (I-1-10). The compound represented by I-3) was obtained.
IR: 3060-3030, 2975-2920, 1725, 1630, 1200, 1160, 1130, 750, 690 cm ⁻¹ .
LRMS: 600
Example 4 Production of Compound Represented by Formula (I-4)

  To a reaction vessel equipped with a dropping funnel was added 20.0 g (0.0615 mol) of the compound represented by the formula (I-2-9), 0.77 g (3.1 mmol) of pyridinium paratoluenesulfonate, and 100 mL of dichloromethane. It was. While cooling with ice, 5.69 g (0.0677 mol) of 3,4-dihydro-2H-pyran was added dropwise. After stirring at room temperature for 10 hours, the mixture was washed with saturated aqueous sodium hydrogen carbonate and brine, purified by column chromatography (alumina), and 23.9 g (0.0584 mol) of the compound represented by the formula (I-4-1). )

  To a reaction vessel equipped with a dropping funnel, 1.85 g (0.0760 mol) of magnesium and 5 mL of tetrahydrofuran were added, and the system was purged with nitrogen. A solution prepared by dissolving 23.9 g (0.0584 mol) of the compound represented by the formula (I-4-1) in 100 mL of tetrahydrofuran was added dropwise to prepare a Grignard reagent. After stirring for 2 hours, 7.89 g (0.0760 mol) of trimethyl borate was added dropwise. After stirring for 2 hours, an aqueous ammonium chloride solution was added dropwise and the mixture was further stirred for 1 hour. After washing with water and brine, the solvent was distilled off to obtain 19.7 g (0.0526 mol) of the compound represented by the formula (I-4-2).

  In a reaction vessel, 19.7 g (0.0526 mol) of a compound represented by formula (I-4-2), 14.9 g (0.0526 mol) of a compound represented by formula (I-4-3), carbonic acid 10.9 g (0.0789 mol) of potassium, 100 mL of tetrahydrofuran and 100 mL of water were added. After substituting the system with nitrogen, 0.61 g (0.526 mmol) of tetrakis (triphenylphosphine) palladium (0) was added, and the mixture was heated to reflux for 5 hours. After diluting with toluene, it was washed with water and brine, and purified by column chromatography (alumina) to obtain 21.7 g (0.0447 mol) of the compound represented by the formula (I-4-4). .

  To the reaction vessel were added 21.7 g (0.0447 mol) of the compound represented by the formula (I-4-4), 80 mL of tetrahydrofuran, 80 mL of methanol, and 1 mL of concentrated hydrochloric acid, and the mixture was stirred at room temperature for 10 hours. After diluted with ethyl acetate and washed with brine, purification is performed by column chromatography (silica gel) and recrystallization to obtain 17.0 g (0.0425 mol) of the compound represented by the formula (I-4-5). It was.

  In a reaction vessel, 17.0 g (0.0425 mol) of a compound represented by the formula (I-4-5), 8.05 g (0.0467 mol) of a compound represented by the formula (I-4-6), iodine Copper (I) 0.16 g (0.849 mmol), triethylamine 30 mL, N, N-dimethylformamide 90 mL were added. After substituting the system with nitrogen, 0.49 g (0.425 mmol) of tetrakis (triphenylphosphine) palladium (0) was added and heated to reflux for 10 hours. Dilute with ethyl acetate and wash with 5% hydrochloric acid and brine. Purification was performed by column chromatography (silica gel) and recrystallization to obtain 16.7 g (0.0340 mol) of a compound represented by the formula (I-4-7).

To a reaction vessel equipped with a dropping funnel, 16.7 g (0.0340 mol) of the compound represented by the formula (I-4-7), 6.59 g (0.0510 mol) of diisopropylethylamine, and 100 mL of dichloromethane were added. While cooling with ice, 4.00 g (0.0442 mol) of acryloyl chloride was added dropwise. The mixture was stirred at room temperature for 5 hours, washed with 5% hydrochloric acid and brine, and purified by column chromatography (silica gel) and recrystallization to obtain 13.0 g of a compound represented by the formula (I-4).
IR: 3060-3030, 2975-2920, 1725, 1630, 1200, 1160, 1130, 750, 690 cm ⁻¹ .
LRMS: 546
Example 5 Production of Compound Represented by Formula (I-5)

  In a reaction vessel, 20.0 g (0.100 mol) of the compound represented by the formula (I-5-1), 13.8 g (0.100 mol) of the compound represented by the formula (I-5-2), carbonic acid 20.7 g (0.150 mol) of potassium, 120 mL of tetrahydrofuran and 120 mL of water were added. After substituting the system with nitrogen, 1.16 g (1.00 mmol) of tetrakis (triphenylphosphine) palladium (0) was added and heated to reflux for 5 hours. The mixture was diluted with ethyl acetate, washed with 10% hydrochloric acid and brine, and purified by column chromatography (silica gel) to obtain 17.5 g (0.0820 mol) of a compound represented by the formula (I-5-3). Got.

  To the reaction vessel was added 20.0 g (0.0934 mol) of the compound represented by formula (I-5-4), 14.3 g (0.140 mol) of acetic anhydride, 500 mL of acetic acid and 25 mL of concentrated sulfuric acid, and the mixture was stirred at 90 ° C. Stir for hours. After cooling, it was poured into water and the crystals were filtered and washed. By drying, 22.7 g (0.0887 mol) of the compound represented by the formula (I-5-5) was obtained.

  In a reaction vessel equipped with a dropping funnel, 15.0 g (0.0585 mol) of the compound represented by the formula (I-5-5) and 12.5 g (0.005 mol) of the compound represented by the formula (I-5-3). 0585 mol), 0.72 g (5.85 mmol) of N, N-dimethylaminopyridine and 100 mL of dichloromethane were added. While cooling with ice, 8.86 g (0.0702 mol) of N, N-diisopropylcarbodiimide was added dropwise. The mixture was stirred at room temperature for 5 hours, filtered, and purified by column chromatography (silica gel) and recrystallization to obtain 22.4 g (0.0497 mol) of the compound represented by the formula (I-5-6). .

  To the reaction vessel were added 22.4 g (0.0497 mol) of the compound represented by the formula (I-5-6), 100 mL of tetrahydrofuran, and 5.88 g (0.0994 mol) of propylamine, and the mixture was stirred at room temperature for 10 hours. The mixture was diluted with ethyl acetate and washed with 5% hydrochloric acid and brine, and then purified by column chromatography (silica gel) and recrystallization to obtain 19.3 g (0.0472) of the compound represented by the formula (I-5-7). Mol).

In a reaction vessel equipped with a dropping funnel, 19.3 g (0.0472 mol) of the compound represented by the formula (I-5-7) and 8.85 g (0.85 mol) of the compound represented by the formula (I-5-8). 0614 mol), 14.9 g (0.0567 mol) of triphenylphosphine, and 120 mL of tetrahydrofuran were added. While cooling with ice, 11.5 g (0.0567 mol) of diisopropyl azodicarboxylate was added dropwise. After stirring at room temperature for 5 hours, purification was performed by column chromatography (silica gel) and recrystallization to obtain 20.2 g of a compound represented by the formula (I-5).
IR: 3060-3030, 2975-2920, 1725, 1630, 1200, 1160, 1130, 750, 690 cm ⁻¹ .
LRMS: 535
Example 6 Production of Compound Represented by Formula (I-6)

  In a reaction vessel, 25.0 g (0.0831 mol) of the compound represented by the formula (I-6-1), 11.7 g (0.0914 mol) of tert-butyl acrylate, 17.2 g (0.125) of potassium carbonate Mol), 200 mL of N, N-dimethylacetamide was added. After replacing the system with nitrogen, 0.19 g (0.831 mmol) of palladium (II) acetate was added, and the mixture was heated and stirred at 120 ° C. for 3 hours. After cooling and diluting with toluene, the mixture was washed with 5% hydrochloric acid and brine. Purification by column chromatography (silica gel) gave 21.3 g (0.0706 mol) of the compound represented by formula (I-6-2).

  In a reaction vessel, 21.3 g (0.0706 mol) of a compound represented by formula (I-6-2), 9.74 g (0.0706 mol) of a compound represented by formula (I-5-2), carbonic acid 14.6 g (0.106 mol) of potassium, 120 mL of tetrahydrofuran and 120 mL of water were added. After the inside of the system was replaced with nitrogen, 0.82 g (0.706 mmol) of tetrakis (triphenylphosphine) palladium (0) was added and heated to reflux for 5 hours. The mixture was diluted with ethyl acetate, washed with 5% hydrochloric acid and brine, and purified by column chromatography (silica gel) to obtain 17.8 g (0.0565 mol) of the compound represented by formula (I-6-3). Got.

  To the autoclave, 17.8 g (0.0565 mol) of a compound represented by the formula (I-6-3), 200 mL of tetrahydrofuran and 1.78 g of 5% palladium carbon were added. The mixture was stirred at a hydrogen pressure of 0.5 MPa for 5 hours. The catalyst was filtered off and the solvent was distilled off, followed by purification by column chromatography (silica gel) to obtain 17.0 g (0.0537 mol) of the compound represented by the formula (I-6-4).

  In a reaction vessel equipped with a dropping funnel, 17.0 g (0.0537 mol) of the compound represented by the formula (I-6-4) and 11.0 g of the compound represented by the formula (I-6-5) (0. 0698 mol), 16.9 g (0.0644 mol) of triphenylphosphine, and 200 mL of tetrahydrofuran were added. While cooling with ice, 13.0 g (0.0644 mol) of diisopropyl azodicarboxylate was added dropwise. After stirring at room temperature for 5 hours, purification was performed by column chromatography (silica gel) to obtain 19.0 g (0.0429 mol) of a compound represented by the formula (I-6-6).

  To the reaction vessel, 19.0 g (0.0429 mol) of the compound represented by the formula (I-6-6), 80 mL of dichloromethane, and 20 mL of trifluoroacetic acid were added. The mixture was stirred at room temperature for 10 hours and then washed with brine. Purification by column chromatography (silica gel) gave 14.9 g (0.0386 mol) of a compound represented by the formula (I-6-7).

  In a reaction vessel equipped with a dropping funnel, 20.0 g (0.0775 mol) of the compound represented by the formula (I-1-4) and 100 mL of tetrahydrofuran were added. 20 mL of 30% hydrogen peroxide solution was added dropwise, and the mixture was heated and stirred at 50 ° C. for 5 hours. An aqueous sodium hydrogen sulfite solution was added and stirred, then diluted with ethyl acetate and washed with brine. Purification by column chromatography (silica gel) gave 17.0 g (0.0736 mol) of the compound represented by formula (I-6-8).

In a reaction vessel equipped with a dropping funnel, 8.90 g (0.0386 mol) of the compound represented by the formula (I-6-8) and 14.9 g (0. 0386 mol), 0.47 g (3.86 mmol) of N, N-dimethylaminopyridine and 100 mL of dichloromethane were added. While cooling with ice, 5.85 g (0.0464 mol) of N, N-diisopropylcarbodiimide was added dropwise. After stirring at room temperature for 5 hours, the mixture was filtered and purified by column chromatography (silica gel) and recrystallization to obtain 17.3 g of a compound represented by the formula (I-6).
IR: 3060-3030, 2975-2920, 1725, 1630, 1200, 1160, 1130, 750, 690 cm ⁻¹ .
LRMS: 598
Example 7 Production of Compound Represented by Formula (I-7)

  The compound represented by formula (I-7-3) was prepared in the same manner as in Example 1 except that the compound represented by formula (I-1-1) was replaced with the compound represented by formula (I-7-1). The compound obtained was obtained.

  In a reaction vessel, 15.0 g (0.0551 mol) of a compound represented by the formula (I-7-3), 12.1 g (0.0551 mol) of a compound represented by the formula (I-7-4), carbonic acid 11.4 g (0.0827 mol) of potassium, 120 mL of tetrahydrofuran and 120 mL of water were added. After substituting the system with nitrogen, 0.64 g (0.551 mmol) of tetrakis (triphenylphosphine) palladium (0) was added and heated to reflux for 5 hours. The mixture was diluted with ethyl acetate, washed with 5% hydrochloric acid and brine, purified by column chromatography (silica gel) and recrystallization, and 14.1 g (0. 0.1 g) of the compound represented by the formula (I-7-5). 0441 mol) was obtained.

In a reaction vessel equipped with a dropping funnel, 14.1 g (0.0441 mol) of the compound represented by the formula (I-7-5) and 12.9 g (0.0.1 mol) of the compound represented by the formula (I-7-6). 0441 mol), 0.54 g (4.41 mmol) of N, N-dimethylaminopyridine and 100 mL of dichloromethane were added. While cooling with ice, 6.68 g (0.0529 mol) of N, N-diisopropylcarbodiimide was added dropwise. After stirring at room temperature for 5 hours, the mixture was filtered and purified by column chromatography (silica gel) and recrystallization to obtain 19.6 g of a compound represented by the formula (I-7).
IR: 3060-3030, 2975-2920, 1725, 1630, 1200, 1160, 1130, 750, 690 cm ⁻¹ .
LRMS: 594
Example 8 Production of Compound Represented by Formula (I-8)

  In a reaction vessel, 20.0 g (0.0615 mol) of the compound represented by the formula (I-2-9), 8.48 g (0.0615 mol) of the compound represented by the formula (I-5-2), carbonic acid Potassium 12.8 g (0.0923 mol), tetrahydrofuran 120 mL, and water 120 mL were added. After substituting the system with nitrogen, 0.71 g (0.615 mmol) of tetrakis (triphenylphosphine) palladium (0) was added, and the mixture was heated to reflux for 5 hours. The mixture was diluted with ethyl acetate, washed with 5% hydrochloric acid and brine, purified by column chromatography (silica gel) and recrystallization, and 16.6 g (0. 1) of the compound represented by the formula (I-8-1). 0492 mol) was obtained.

  In a reaction vessel, 20.0 g (0.107 mol) of the compound represented by the formula (I-8-2), 19.7 g (0.160 mol) of propyl bromide, 52.3 g (0.160 mol) of cesium carbonate, 200 mL of dimethyl sulfoxide was added. The mixture was heated and stirred at 60 ° C. for 5 hours, diluted with toluene, and washed with water and brine. Purification by column chromatography (silica gel) gave 22.0 g (0.0962 mol) of the compound represented by the formula (I-8-3).

  In a reaction vessel, 11.3 g (0.0492 mol) of the compound represented by formula (I-8-3), 16.6 g (0.0492 mol) of the compound represented by formula (I-8-1), carbonic acid 24.0 g (0.0738 mol) of cesium and 100 mL of dimethyl sulfoxide were added. The mixture was heated and stirred at 60 ° C. for 5 hours, diluted with toluene, and washed with water and brine. Purification by column chromatography (silica gel) and recrystallization gave 19.2 g (0.0394 mol) of the compound represented by the formula (I-8-4).

To a reaction vessel equipped with a dropping funnel, 19.2 g (0.0394 mol) of the compound represented by the formula (I-8-4), 7.63 g (0.0590 mol) of diisopropylethylamine, and 100 mL of dichloromethane were added. While cooling with ice, 4.63 g (0.0512 mol) of acryloyl chloride was added dropwise. The mixture was stirred at room temperature for 5 hours, washed with 5% hydrochloric acid and brine, and purified by column chromatography (silica gel) and recrystallization to obtain 17.0 g of a compound represented by the formula (I-8).
IR: 3060-3030, 2975-2920, 1725, 1630, 1200, 1160, 1130, 750, 690 cm ⁻¹ .
LRMS: 540
Example 9 Production of Compound Represented by Formula (I-9)

  In Example 6, the compound represented by formula (I-6-1) is changed to the compound represented by formula (I-9-1), and the compound represented by formula (I-5-2) is changed to formula (I A compound represented by the formula (I-9-5) was obtained in the same manner except that the compound represented by -9-3) was replaced.

  To a reaction vessel equipped with a dropping funnel, 20.0 g (0.0601 mol) of the compound represented by the formula (I-9-5), 0.76 g (3.00 mmol) of pyridinium paratoluenesulfonate, and 100 mL of dichloromethane were added. It was. While cooling with ice, 6.57 g (0.0781 mol) of 3,4-dihydro-2H-pyran was added dropwise. After stirring at room temperature for 10 hours, the mixture was washed with saturated aqueous sodium hydrogen carbonate and brine, purified by column chromatography (alumina), and 23.8 g (0.0571 mol) of the compound represented by the formula (I-9-6). )

  To the reaction vessel, 23.8 g (0.0571 mol) of the compound represented by the formula (I-9-6) and 150 mL of tetrahydrofuran were added. After adding 8.67 g of lithium aluminum hydride little by little, the mixture was stirred at room temperature for 8 hours. After adding water and filtering, the solvent was distilled off to obtain 15.8 g (0.0457 mol) of a compound represented by the formula (I-9-7).

  15.8 g (0.0457 mol) of a compound represented by the formula (I-9-7), 7.69 g (0.0685 mol) of potassium tert-butoxide, and 100 mL of propanol were added to a reaction vessel equipped with a dropping funnel. . 8.43 g (0.0685 mol) of propyl bromide was added dropwise and heated to reflux for 10 hours. After diluted with toluene and washed with water and brine, purification was performed by column chromatography (alumina) to obtain 10.7 g (0.0274 mol) of a compound represented by the formula (I-9-8).

  To the reaction vessel were added 10.7 g (0.0274 mol) of the compound represented by the formula (I-9-8), 70 mL of tetrahydrofuran, 70 mL of methanol, and 1 mL of concentrated hydrochloric acid, and the mixture was stirred at room temperature for 10 hours. After diluted with ethyl acetate and washed with brine, purification was performed by column chromatography (silica gel) to obtain 7.93 g (0.0260 mol) of the compound represented by the formula (I-9-9).

  In a reaction vessel equipped with a dropping funnel, 7.93 g (0.0260 mol) of the compound represented by the formula (I-9-9) and 6.67 g (0.67 g) of the compound represented by the formula (I-5-5). 0260 mol), 0.32 g (2.60 mmol) of N, N-dimethylaminopyridine and 50 mL of dichloromethane were added. While cooling with ice, 3.94 g (0.0312 mol) of N, N-diisopropylcarbodiimide was added dropwise. After stirring at room temperature for 5 hours, the mixture was filtered and purified by column chromatography (silica gel) and recrystallization to obtain 11.3 g (0.0208 mol) of the compound represented by the formula (I-9-10). .

  To the reaction vessel, 11.3 g (0.0208 mol) of the compound represented by the formula (I-9-10), 100 mL of tetrahydrofuran and 2.46 g (0.0417 mol) of propylamine were added and stirred at room temperature for 10 hours. After diluting with ethyl acetate and washing with 5% hydrochloric acid and brine, purification was performed by column chromatography (silica gel) and recrystallization, and 9.91 g (0.0198) of the compound represented by the formula (I-9-11) Mol).

To a reaction vessel equipped with a dropping funnel, 9.91 g (0.0198 mol) of the compound represented by the formula (I-9-11), 3.32 g (0.0257 mol) of diisopropylethylamine, and 50 mL of dichloromethane were added. While cooling with ice, 2.33 g (0.0257 mol) of acryloyl chloride was added dropwise. The mixture was stirred at room temperature for 5 hours, washed with 5% hydrochloric acid and brine, and purified by column chromatography (silica gel) and recrystallization to obtain 8.78 g of the compound represented by the formula (I-9).
IR: 3060-3030, 2975-2920, 1725, 1630, 1200, 1160, 1130, 750, 690 cm ⁻¹ .
LRMS: 555
Example 10 Production of Compound Represented by Formula (I-10)

  To a reaction vessel equipped with a dropping funnel was added 20.0 g (0.146 mol) of the compound represented by formula (I-10-1), 1.84 g (7.32 mmol) of pyridinium paratoluenesulfonate, and 100 mL of dichloromethane. It was. While cooling with ice, 14.8 g (0.176 mol) of 3,4-dihydro-2H-pyran was added dropwise. The mixture was stirred at room temperature for 10 hours, washed with saturated aqueous sodium hydrogen carbonate and brine, purified by column chromatography (alumina), and 30.7 g (0.139 mol) of the compound represented by the formula (I-10-2). )

  In a reaction vessel, 30.7 g (0.139 mol) of a compound represented by the formula (I-10-2), 21.6 g (0.107 mol) of a compound represented by the formula (I-10-3), carbonic acid 52.3 g (0.160 mol) of cesium and 200 mL of dimethyl sulfoxide were added. The mixture was heated and stirred at 60 ° C. for 5 hours, diluted with toluene, and washed with water and brine. Purification by column chromatography (alumina) yielded 35.1 g (0.0909 mol) of the compound represented by formula (I-10-4).

  To the reaction vessel was added 35.1 g (0.0909 mol) of the compound represented by the formula (I-10-4), 200 mL of methanol, and 48.5 g (0.182 mol) of a 15% aqueous sodium hydroxide solution, and heated for 5 hours. Refluxed. The mixture was neutralized with an aqueous ammonium chloride solution, diluted with ethyl acetate, and washed with brine. Purification by column chromatography (alumina) yielded 32.2 g (0.0864 mol) of the compound represented by the formula (I-10-5).

  In a reaction vessel equipped with a dropping funnel, 10.0 g (0.0268 mol) of the compound represented by the formula (I-10-5) and 10.8 g (0. 0268 mol), 0.33 g (2.68 mmol) of N, N-dimethylaminopyridine and 50 mL of dichloromethane were added. While cooling with ice, 4.07 g (0.0322 mol) of N, N-diisopropylcarbodiimide was added dropwise. After stirring at room temperature for 5 hours, the mixture was filtered and purified by column chromatography (alumina) to obtain 17.2 g (0.0228 mol) of a compound represented by the formula (I-10-6).

  To the reaction vessel were added 17.2 g (0.0228 mol) of the compound represented by the formula (I-10-6), 70 mL of tetrahydrofuran, 70 mL of methanol, and 1 mL of concentrated hydrochloric acid, and the mixture was stirred at room temperature for 10 hours. After diluted with ethyl acetate and washed with brine, purification is performed by column chromatography (silica gel) and recrystallization to obtain 14.5 g (0.0217 mol) of the compound represented by the formula (I-10-7). It was.

In a reaction vessel equipped with a dropping funnel, 14.5 g (0.0217 mol) of the compound represented by the formula (I-10-7), 3.27 g (0.0282 mol) of 3-ethyl-3-oxetanemethanol, 6.82 g (0.0260 mol) of phenylphosphine and 100 mL of tetrahydrofuran were added. While cooling with ice, 5.26 g (0.0260 mol) of diisopropyl azodicarboxylate was added dropwise. After stirring at room temperature for 5 hours, purification was performed by column chromatography (silica gel) and recrystallization to obtain 11.6 g of a compound represented by the formula (I-10).
LRMS: 768
Example 11 Production of Compound Represented by Formula (I-96)

The compound represented by the formula (I-96) is obtained in the same manner as in Example 9 except that the compound represented by the formula (I-9-11) is replaced with the compound represented by the formula (I-3-8). A compound was obtained.
IR: 3060-3030, 2975-2920, 1725, 1630, 1200, 1160, 1130, 750, 690 cm ⁻¹ .
LRMS: 500
The compounds represented by the following formulas (I-11) to (I-95) were produced using the same methods as in Examples 1 to 11 and a method based on a known method.

(Examples 12 to 21, Comparative Examples 1 to 3)
Compounds represented by formula (I-1) to formula (I-10) and formula (I-96) described in Example 1 to Example 11, and a compound (R-1) described in Patent Document 1, Patent Document The compound (R-2) described in 2 and the compound (R-3) described in Patent Document 3 were evaluated.

  In order to evaluate the storage stability, the stable storage concentration of the compound to be evaluated was measured. The stable storage concentration was determined by preparing a composition in which the compound to be evaluated was added to the base liquid crystal in 5% increments from 5% to 25%, and after leaving the prepared composition at 18.5 ° C. for 10 weeks, Is defined as the maximum concentration of the compound at which no precipitation occurs. A compound having a large maximum addition concentration has a high stable storage concentration, meaning that no crystal precipitation occurs even after long-term storage.

  In order to measure the stable storage concentration, from the following compound (X-1): 20%, compound (X-2): 25%, compound (X-3): 25% and compound (X-4): 30% This liquid crystal composition was used as a base liquid crystal (X). The measurement results are shown in Table 1.

From the table, all of the compounds represented by formula (I-1) to formula (I-10) and formula (I-96) of the present invention of Examples 11 to 21 are those of Comparative Example 1 to Comparative Example 3. Compared with the compound (R-3) from the compound (R-1), the maximum addition concentration at which no precipitation of crystals occurs is high, which indicates that high storage stability is exhibited.
(Examples 22 to 32, Comparative Examples 4 to 6)
The polyimide solution for alignment film was applied to a glass substrate having a thickness of 0.7 mm using a spin coating method, dried at 100 ° C. for 10 minutes, and then baked at 200 ° C. for 60 minutes to obtain a coating film. The obtained coating film was rubbed. The rubbing treatment was performed using a commercially available rubbing apparatus.

1% of photopolymerization initiator Irgacure907 (manufactured by BASF) and 0.1% of 4-methoxyphenol are added to each of the compositions prepared by adding 20% of the target compound to the base liquid crystal (X). did. This composition was applied to a rubbed glass substrate at 70 ° C. by a spin coating method. The resin mold having been subjected to the alignment treatment on the obtained coating film was placed so that the alignment direction of the glass substrate rubbed with the alignment direction of the resin mold was parallel, and then cooled to room temperature. Next, the resin mold was slowly removed, and an ultraviolet curable epoxy acrylate resin was applied by spin coating. Thereafter, ultraviolet rays were irradiated for 25 seconds at an intensity of 40 mW / cm ² using a high-pressure mercury lamp. A lenticular lens was obtained by removing the glass substrate from the obtained polymer. (See Figure 1)
About the obtained polymer, the orientation state was evaluated by visual observation and polarization microscope observation. ◎ if the alignment was uniform and free of defects, ◯, if there were very few defects, △ if there were a few defects, and x if there were very many defects.

  Further, the uniformity of the lens shape of the obtained polymer was evaluated. If the boundary between adjacent lenses is clear and linear by visual observation and microscopic observation, the mark is ◯, if it is slightly unclear or disturbed, Δ, and if not clear or disturbed, it is marked X. The evaluation results are shown in Table 2.

  From the table, all of the compounds represented by formula (I-1) to formula (I-10) and formula (I-96) of the present invention of Examples 22 to 32 are those of Comparative Example 4 to Comparative Example 6. From the compound (R-1) to the compound (R-3), it can be seen that the orientation is high or comparable. The compounds represented by formulas (I-1) to (I-10) and (I-96) of the present invention of Examples 22 to 32 are all compounds of Comparative Examples 4 to 6. It can be seen that the uniformity of the lens shape is high or comparable as compared with the compound (R-3) from (R-1). Although the optical anisotropic body using the composition containing the compound (R-3) of Comparative Example 6 had a low lens shape uniformity, it was considered that shrinkage occurred when the polymerizable composition was cured. It is done.

  From the above results, the compounds represented by formulas (I-1) to (I-10) and (I-96), which are the inventions described in Examples 1 to 11, are polymerizable compositions. When configured, the storage stability is high, and the optical anisotropic body using the composition containing the compound of the present invention has few alignment defects and the lens shape is uniform. Therefore, the compound of the present invention is useful as a constituent member of the polymerizable composition. Moreover, the optical anisotropic body using the polymeric liquid crystal composition containing the compound of this invention is useful for uses, such as an optical film.

The structure of a lenticular lens is shown with a schematic diagram.

(A) When glass substrate is present (B) When glass substrate is peeled 1: Polymer of epoxy acrylate resin 2: Polymer of polymerizable composition 3: Glass substrate

Claims (15)

Formula (I)

(Wherein P is the following formula (P-1) to formula (P-3), formula (P-7) to formula (P-18)

Represents a group selected from, S represents an spacer group or a single bond, they if S there are a plurality may be different even in the same, X is -O -, - S -, - OCH 2 _{-, - CH 2 O -,} - CO -, - COO -, - OCO -, - CO-S -, - S-CO -, - OCO-O -, - CO-NH -, - NH-CO _{-, - SCH 2 -, -} CH 2 S -, - CF 2 O -, - OCF 2 -, - CF 2 S -, - SCF 2 -, - CH = CH-COO -, - CH = CH-OCO- , —COO—CH═CH—, —OCO—CH═CH—, —COO—CH ₂ CH ₂ —, —OCO—CH ₂ CH ₂ —, —CH ₂ CH ₂ —COO—, —CH ₂ CH ₂ — _{OCO -, - COO-CH 2} -, - OCO-CH 2 -, - CH 2 -COO -, - CH 2 -OCO -, -CH = CH-, -CF = CF- or a single bond, but when a plurality of X are present, they may be the same or different, and A ¹ , A ² , A ³ , A ⁴ And A ⁵ each independently represents 1,4-phenylene, naphthalene-1,4-diyl or naphthalene-2,6-diyl, but these groups may be unsubstituted or substituted by one or more Ls. When a plurality of A ⁵ are present, they may be the same or different, and Z ¹ , Z ² , and Z ³ are each independently —O—, —S—, —OCH ₂ —, —CH ₂ O—, —COO—, —OCO—, —CO—, —CO—S—, —S—CO—, —O—CO—O—, —CO—NH—, —NH—CO—, _{-SCH 2 -, - CH 2 S-} , - 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 -, - CH = CH -, - CF = CF- or represents -C≡C-, R is full Tsu atom, a chlorine atom, a bromine atom, an iodine atom, Shi Anomoto, nitro group, an isocyano group, Chioisoshiano group, or one -CH ₂ - or nonadjacent two or more -CH ₂ - are each independently -O -, - S -, - CO -, -COO-, -OCO-, -CO-S-, -S-CO-, -O- O—O—, —CO—NH—, —NH—CO—, —CH═CH—COO—, —CH═CH—OCO—, —COO—CH═CH—, —OCO—CH═CH—, — Represents a linear or branched alkyl group having 1 to 12 carbon atoms which may be substituted by CH═CH—, —CF═CF— or —C≡C—, wherein l represents an integer of 0 to 8, m1, m2 and m3 represent 0 or 1, n represents 0, 1 or 2, and L represents a fluorine atom, a chlorine atom, a bromine atom or an iodine atom, and among A ¹ , A ² , A ³ and A ⁴ At least one is substituted by one or more L, m1 + m2 + m3 is table 0 or 1, if m1 + m2 + m3 represents ^1, a ^1, a 2, ^{a 3} and the total number of L in the ^{a 4} are two or more It is . ) A compound represented by In the general formula (I), X, A ¹ , A ² , A ³ , A ⁴ , A ⁵ , Z ¹ , Z ² , Z ³ , R, L, 1, m1, m2, m3 , n and P are claimed. Represents the same as defined in 1 .
In S , one —CH ₂ — or two or more non-adjacent —CH ₂ — may be independently replaced with —O—, —COO—, —OCO— or —OCO—O—. The compound according to claim 1, which represents an alkylene group having 1 to 20 carbon atoms or a single bond, and when a plurality of S are present, they may be the same or different. In the general formula (I), P, S, X, A ¹ , A ² , A ³ , A ⁴ , A ⁵ , R, L, l, m1, m2, m3 and n are defined in claim 1 or claim 2 In the case where a plurality of Z ¹ , Z ² and Z ³ appear, they may be the same or different from each other, and each may be independently a single bond, —OCH ₂ —, —CH _{2. O -, - COO -, -} OCO -, - COO-CH 2 CH 2 -, - OCO-CH 2 CH 2 -, - CH 2 CH 2 -COO -, - CH 2 CH 2 -OCO -, - CH = 3. A compound according to claim 1 or claim 2 representing CH- or -C≡C-. In the general formula (I), P, S, X, A ¹ , A ² , A ³ , A ⁴ , A ⁵ , Z ¹ , Z ² , Z ³ , L, 1, m1, m2, m3 and n are claims. each as from 1 the same as those defined in claim 3, R is full Tsu atom, a chlorine atom, a cyano group or one -CH 2 _- or adjacent have not more than one - CH ₂ - are each independently -O -, - COO -, - OCO -, - claims represents a linear or branched alkyl group having 12 good 1 -C be substituted by OCO-O- The compound according to any one of claims 1 to 3. In the general formula (I), P, S, A ¹ , A ² , A ³ , A ⁴ , A ⁵ , Z ¹ , Z ² , Z ³ , R, L, 1, m1, m2, m3 and n are claims. 5. The same as defined in any one of claims 1 to 4, wherein X represents -O-, -COO-, -OCO- or a single bond. Compound described in 1. In the general formula (I), P, S, X, Z ¹ , Z ² , Z ³ , R, L, l, m1, m2, m3 and n are those defined in any one of claims 1 to 5 And A ¹ , A ² , A ³ , A ⁴ and A ⁵ are each independently the following formulas (A-1) to (A-10):

The compound as described in any one of Claims 1-5 showing group selected from these. In the general formula (I), P, S, X, A ¹ , A ² , A ³ , A ⁴ , A ⁵ , Z ¹ , Z ² , Z ³ , R, 1, m1, m2, m3 and n are claims. 7. The compound according to any one of claims 1 to 6, which represents the same as defined in any one of claims 1 to 6, wherein L represents a fluorine atom or a chlorine atom. In the general formula (I), P, S, X, A ¹ , A ² , A ³ , A ⁴ , A ⁵ , Z ¹ , Z ² , Z ³ , R, L, m1, m2, m3 and n are claims. 8. A compound according to any one of claims 1 to 7 which represents the same as defined in any one of claims 1 to 7, wherein l represents 0 or 1. In the general formula (I), P, S, X, A ¹ , A ² , A ³ , A ⁴ , A ⁵ , Z ¹ , Z ² , Z ³ , R, L, l, m1, m2, and m3 are claims. 9. A compound according to any one of claims 1 to 8 which represents the same as defined in any of 1 to 8 and n represents 0.   The polymeric composition containing the compound as described in any one of Claims 1-9.   The polymeric liquid crystal composition containing the compound as described in any one of Claims 1-9. The polymerizable liquid crystal composition further has the general formula (II)

(Wherein P ¹ and P ² each independently represent the same meaning as P in formula (I), and S ¹ and S ² each independently represent a single bond or an alkylene group having 1 to 20 carbon atoms) represents a one -CH ₂ - or nonadjacent two or more _-CH 2 - is -O -, - COO -, - OCO -, - OCOO- may be replaced by a, ^{X 1} and X ² each 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 = CH-} COO -, - CH = CH-OCO -, - COO-CH = CH -, - OCO-CH = CH -, - COO _{CH 2 CH 2 -, - OCO} -CH 2 CH 2 -, - CH 2 CH 2 -COO -, - CH 2 CH 2 -OCO -, - COO-CH 2 -, - OCO-CH 2 -, - CH 2 —COO—, —CH ₂ —OCO—, —CH═CH—, —CF═CF—, —C≡C— or a single bond, each Z ⁴ independently represents a single bond, —O—, —S _{-, - OCH 2 -, -} CH 2 O -, - COO -, - OCO -, - CO -, - CO-S -, - S-CO -, - OCO-O -, - CO-NH- , —NH—CO—, —SCH ₂ —, —CH ₂ S—, —CF ₂ O—, —OCF ₂ —, —CF ₂ S—, —SCF ₂ —, —CH ₂ CH ₂ —, —CH _{2 CF 2 -, - CF 2 CH} 2 -, - CF 2 CF 2 -, - CH = CH-COO -, - CH = CH-OCO -, - COO _{-CH = CH -, - OCO-} CH = CH -, - COO-CH 2 CH 2 -, - OCO-CH 2 CH 2 -, - CH 2 CH 2 -COO -, - CH 2 CH 2 -OCO-, —COO—CH ₂ —, —OCO—CH ₂ —, —CH ₂ —COO—, —CH ₂ —OCO—, —CH═CH—, —CF═CF— or —C≡C— represents A ⁶ And A ⁷ are each independently 1,4-phenylene group, 1,4-cyclohexylene group, pyridine-2,5-diyl group, pyrimidine-2,5-diyl group, naphthalene-2,6-diyl group. , Tetrahydronaphthalene-2,6-diyl group or 1,3-dioxane-2,5-diyl group, A ⁶ and A ⁷ are each independently unsubstituted or an alkyl group or a halogenated alkyl group , Alkoxy groups, halogenated alkoxy groups, A1 may be substituted with a halogen atom, a cyano group or a nitro group, and n1 represents 0, 1, 2 or 3, but when n1 represents 2 or 3, two or three A ⁶ and Z ⁵ are present. May be the same or different. The polymerizable liquid crystal composition according to claim 11, comprising at least one selected from the group consisting of compounds represented by:   A polymer obtained by polymerizing the polymerizable liquid crystal composition according to any one of claims 10 to 12.   An optical anisotropic body using the polymer according to claim 13.   A resin, a resin additive, an oil, a filter, an adhesive, an adhesive, a fat, an ink, a pharmaceutical, a cosmetic, a detergent, a building material, a packaging material, a liquid crystal containing the compound according to any one of claims 1 to 9. Materials, agricultural chemicals, foods and products using them.

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