JP2018070546A - A bisphenol derivative having an ester bond - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a production intermediate useful for obtaining a compound having an ester bond, and a production method to obtain a compound having an ester bond, using the same, with convenience and high purity; specifically, to provide a bisphenol derivative having an ester bond, a method for producing the same, and a compound produced from the bisphenol derivative as an intermediate; and to further provide a polymer obtained by the polymerization of a polymerizable composition containing the compound produced from the bisphenol derivative as an intermediate, and an optical anisotropic body using the polymer.SOLUTION: A bisphenol derivative having an ester bond is represented by general formula (I-C), where at least one of Aand Ais substituted with one substituent L.SELECTED DRAWING: None

Description

  The present invention relates to a bisphenol derivative having an ester bond, a method for producing the bisphenol derivative, a compound produced using the bisphenol derivative, a polymerizable composition, a polymerizable liquid crystal composition, and an optical system using the polymerizable liquid crystal composition. Concerning an anisotropic body.

  Compounds having an ester bond are used in various applications including synthetic resins, liquid crystal materials, pharmaceuticals, agricultural chemicals, pigments, dyes, foods, synthetic fibers, plastics, additives, and cosmetics. In any application, those compounds are desired to have high purity from the viewpoints of quality, safety and reliability. From the viewpoint of profitability, it is important to produce these compounds in a short process with good yield.

  In particular, in the field of electronic materials, it is desired that the compound used has a high purity. For example, polymerizable liquid crystal materials are used in the field of optical anisotropic bodies in the field of electronic materials. The optical anisotropic body can be obtained as a film or a resin having a uniform orientation by aligning the polymerizable liquid crystal composition in a liquid crystal state and then polymerizing it. The film and resin thus produced can be used for polarizing plates, retardation plates and the like necessary for liquid crystal displays. In many cases, two or more types are required to satisfy the required optical properties, polymerization rate, solubility, melting point, glass transition temperature, transparency of the resulting film, mechanical strength, surface hardness, heat resistance and light resistance. A composition comprising a polymerizable compound is used. However, if impurities are mixed in the polymerizable compound constituting the composition, problems such as unevenness and discoloration may occur in the produced film or resin. If a film with unevenness or discoloration is used as an optical film for a liquid crystal display, for example, the brightness of the screen will be uneven and the color of the display will become unnatural. I will let you. For this reason, the management of impurities in the ppm order is required for polymerizable compounds used in the field of electronic materials.

  Various methods are known as a method for producing a compound having an ester bond, but conventionally known methods have a problem that the production process is long and impurities are likely to remain. Therefore, a production intermediate for obtaining a compound having an ester bond with high yield and high purity in a short production process and a production method thereof have been demanded.

JP 2014-198814 A

  The problem to be solved by the present invention is to provide a production intermediate useful for obtaining a compound having an ester bond, and a production method for obtaining a compound having an ester bond in a simple and high purity using the intermediate. .

  That is, the present invention provides a bisphenol derivative having an ester bond, a method for producing the same, and a compound produced using the bisphenol derivative as an intermediate. Furthermore, the present invention provides a polymer obtained by polymerizing a polymerizable composition containing a compound produced using the bisphenol derivative as an intermediate, and an optical anisotropic body using the polymer.

  As a result of intensive studies to solve the above problems, the present inventors have developed a compound containing a specific partial structure. That is, the present invention provides a bisphenol derivative represented by the general formula (IC), a method for producing the bisphenol derivative, and a general formula (ID) produced using the bisphenol derivative as an intermediate. A compound comprising a compound represented by the general formula (ID), a resin using the compound represented by the general formula (ID), a resin additive, an oil, Filters, adhesives, adhesives, oils and fats, inks, pharmaceuticals, cosmetics, detergents, building materials, packaging materials, liquid crystal materials, organic EL materials, organic semiconductor materials, electronic materials, display elements, electronic devices, communication equipment, automobile parts, Aircraft parts, machine parts, agricultural chemicals and foods, products using them, polymerizable liquid crystal compositions, polymers obtained by polymerizing the polymerizable liquid crystal compositions, and the polymers To provide an optically anisotropic body.

  The compound of the present invention is useful as a production intermediate for obtaining a compound having an ester bond with high yield and high purity in a shorter production process. In addition, a compound having a polymerizable group and an ester bond produced using the compound of the present invention as an intermediate has few high molecular weight oligomer impurities, and is added to the polymerizable composition to produce a film-like polymer. Since unevenness and discoloration hardly occur, it is useful as a constituent material of the polymerizable composition. Moreover, the said polymeric composition is useful for the use of optical materials, such as a phase difference film and a selective reflection film.

  The present invention provides a bisphenol derivative represented by the general formula (IC), and also represents a production method of the bisphenol derivative and the general formula (ID) produced using the bisphenol derivative as an intermediate. Compound, polymerizable composition containing compound represented by general formula (ID), resin using compound represented by general formula (ID), resin additive, oil, filter, adhesive, Adhesives, oils and fats, inks, pharmaceuticals, cosmetics, detergents, building materials, packaging materials, liquid crystal materials, organic EL materials, organic semiconductor materials, electronic materials, display elements, electronic devices, communication equipment, automobile parts, aircraft parts, mechanical parts , Agricultural chemicals and foods, products using them, polymerizable liquid crystal compositions, polymers obtained by polymerizing the polymerizable liquid crystal compositions, and optical anisotropic bodies using the polymers .

  The compound of the present invention has the following general formula (IC)

(In the formula, A ¹ and A ² are each independently 1,4-phenylene group, 1,4-cyclohexylene group, naphthalene-2,6-diyl group, naphthalene-1,4-diyl group, tetrahydronaphthalene- Represents a 2,6-diyl group or a decahydronaphthalene-2,6-diyl group,
Z ¹ represents -COO- or -OCO-,
However, at least one of A ¹ and A ² is substituted by one substituent L, and each existing L is independently a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a pentafluorosulfuranyl group, a cyano group Group, an optionally substituted phenyl group, or one —CH ₂ — or two or more non-adjacent —CH ₂ — are each independently —O—, —S—, —CO—, —COO—, —OCO—, —CO—S—, —S—CO—, —O—CO—O—, —CO—NR ⁰ —, —NR ⁰ —CO—, —CH═CH—COO—, -CH = CH-OCO -, - COO-CH = CH -, - OCO-CH = CH -, - CH = CH -, - N = N -, - CR 0 = N -, - N = CR 0 -, -CH = N-N = CH - , - CF = CF- or -C≡C- (wherein, ^{R 0} is a hydrogen atom Represents an alkyl group having 1 to 8 carbon atoms.) Represents a linear or branched alkyl group having 1 to 20 carbon atoms which may be substituted, and any hydrogen atom in the alkyl group is fluorine. An atom may be substituted.

In the general formula (IC), A ¹ and A ² are each independently 1,4-phenylene group, 1,4-cyclohexylene group, naphthalene-2,6-diyl group, naphthalene-1,4-diyl. Group, tetrahydronaphthalene-2,6-diyl group or decahydronaphthalene-2,6-diyl group. Ease of synthesis, availability of raw materials, liquid crystallinity of compound represented by general formula (ID) produced using bisphenol derivative represented by general formula (IC) as an intermediate, and production of film A ¹ and A ² are each independently 1,4-phenylene group, 1,4-cyclohexylene group, naphthalene-2,6-diyl group, naphthalene, from the viewpoint of being less likely to cause unevenness and discoloration. -1,4-diyl group is preferred, and each independently represents the following formula (AX-1) to formula (AX-10)

(Wherein L ^X represents a group represented by L) is more preferably a group selected from Formula (AX-1) to Formula (AX-7). More preferably, it represents a group selected from the above formulas (AX-1) to (AX-5), and is further selected from the above formulas (AX-1) to (AX-4). It is particularly preferred to represent a group. ^One of A ¹ and A ² represents a group selected from the above formula (AX-3), formula (AX-4), formula (AX-6) or formula (AX-7), and the other represents the above. It preferably represents a group selected from Formula (AX-1), Formula (AX-2), and Formula (AX-5), and ^one of A ¹ and A ² is the above Formula (AX-3) or Formula It is more preferred that the group selected from (AX-4) and the other represents a group selected from the above formula (AX-1), formula (AX-2) or formula (AX-5), and A ¹ and One of A ² represents a group selected from the above formula (AX-3) or formula (AX-4), and the other represents a group selected from the above formula (AX-1) or formula (AX-2). more preferably be represented, one of ^{a 1} and ^{a 2} represents a group selected from the above equation (AX-3) or formula (AX-4), the other And particularly preferably a group represented by the aforementioned formula (AX-1).

In the general formula (IC), each L present is independently a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a pentafluorosulfuranyl group, a cyano group, an optionally substituted phenyl group, or Any hydrogen atom in the group may be substituted with a fluorine atom, and one —CH ₂ — or two or more non-adjacent —CH ₂ — are each independently —O—, —S—, —CO—, —COO—, —OCO—, —CO—S—, —S—CO—, —O—CO—O—, —CO—NR ⁰ —, —NR ⁰ —CO—, —CH═CH -COO -, - CH = CH- OCO -, - COO-CH = CH -, - OCO-CH = CH -, - CH = CH -, - N = N -, - CR 0 = N -, - N = CR ⁰ —, —CH═N—N═CH—, —CF═CF— or —C≡C— (wherein R ⁰ is a hydrogen atom) Or represents a linear or branched alkyl group having 1 to 20 carbon atoms which may be substituted by an alkyl group having 1 to 8 carbon atoms. Ease of synthesis, availability of raw materials, liquid crystallinity of compound represented by general formula (ID) produced using bisphenol derivative represented by general formula (IC) as an intermediate, and production of film In view of the difficulty of causing unevenness and discoloration, L is independently a fluorine atom, a chlorine atom, an optionally substituted phenyl group, or an arbitrary hydrogen atom in the group is substituted with a fluorine atom. One —CH ₂ — or two or more non-adjacent —CH ₂ — may each independently represent —O—, —S—, —CO—, —CH═CH—, —CF═. It preferably represents a linear or branched alkyl group having 1 to 20 carbon atoms which may be substituted by CF- or -C≡C-, and each independently represents a fluorine atom, a chlorine atom, or Arbitrary hydrogen atoms may be substituted with fluorine atoms. Each of —CH ₂ — or two or more non-adjacent —CH ₂ — each independently represents a linear or branched alkyl group having 1 to 20 carbon atoms which may be substituted by —O—. More preferably, any hydrogen atom in the group may be independently substituted with a fluorine atom, and one —CH ₂ — or two or more non-adjacent —CH ₂ — may be independently selected. It is more preferable to represent a linear or branched alkyl group having 1 to 10 carbon atoms which may be substituted by —O—, and each independently represents a methyl group, an ethyl group, a propyl group, a methoxy group, trifluoro It is even more preferred that it represents a methyl group or a trifluoromethoxy group, and especially preferred that it represents a methyl group.

In the general formula (IC), at least one of A ¹ and A ² is substituted with one substituent L. In the formula, the L present may be different. From the viewpoint of the ease of synthesis, the availability of raw materials, and the liquid crystallinity of the compound represented by the general formula (ID) produced using the bisphenol derivative represented by the general formula (IC) as an intermediate, More preferably, only one of A ¹ or A ² is substituted by one substituent L.

  As the compound represented by the general formula (IC), the following general formula (IC-1) to general formula (IC-14)

(In the formula, each of L ¹¹ and L ²¹ is independently a fluorine atom, a chlorine atom, or an arbitrary hydrogen atom in the group may be substituted with a fluorine atom, and one —CH ₂ — or adjacent group. And two or more —CH ₂ — each independently represents a linear or branched alkyl group having 1 to 20 carbon atoms which may be substituted by —O—, and nL 1 and nL 2 are each independently 0 Or n1 and nL2 do not represent 0 at the same time.), And the following general formulas (I-C-1-1) to (I-C-12) are preferred. 2)

(In the formula, each of L ¹¹¹ and L ²¹¹ independently represents that any hydrogen atom in the group may be substituted with a fluorine atom, and one —CH ₂ — or two or more —CH ₂ not adjacent to each other may be substituted. -Represents a linear or branched alkyl group having 1 to 10 carbon atoms which may be independently substituted with -O-, more preferably a compound represented by the following general formula (I- C-1-1-1) to general formula (I-C-12-2-1)

( ^Wherein L ¹¹¹¹ and L ²¹¹¹ each independently represent a methyl group, an ethyl group, a propyl group, a methoxy group, a trifluoromethyl group, or a trifluoromethoxy group) are more preferable.

  Specifically, compounds represented by the following formulas (C-1) to (C-205) are preferable as the compounds represented by the general formula (IC).

  The compounds represented by the general formula (IC) are represented by the following formulas (I-A1) and (I-B1), respectively.

(In the formula, A ¹ and A ² represent the same meaning as A ¹ and A ² in formula (IC), provided that at least one of A ¹ and A ² is substituted by one of the substituents L. Or the following formulas (I-B2) and (I-A2):

(In the formula, A ¹ and A ² represent the same meaning as A ¹ and A ² in formula (IC), provided that at least one of A ¹ and A ² is substituted by one of the substituents L. It is preferably produced by reacting a compound represented by In the above formula (I-A1), formula (I-B1), formula (I-A2) and formula (I-B2), preferred structures of A ¹ and A ² are the same as described above.

  As the compound represented by the formula (I-A1), the following general formula (I-A1-1) to general formula (I-A1-4)

(Wherein L ¹¹ represents the same meaning as L described above, and nL1 represents 0 or 1). A compound represented by the following general formula (I-A1-1-1) to general formula (I -A1-4-1)

(Wherein L ¹¹¹ represents the same meaning as described above) is more preferable, and the following general formula (I-A1-1-1-1) and general formula (I-A1-1-2) are preferred. -1)

(Wherein L ¹¹¹¹ represents the same meaning as described above) is more preferable.

  Examples of the compound represented by the formula (I-B1) include the following general formula (I-B1-1) to general formula (I-B1-4).

(Wherein L ²¹ represents the same meaning as described above, and nL2 represents 0 or 1). A compound represented by the following general formula (I-B1-1-1) to general formula (I- B1-3-1)

(Wherein L ²¹¹ represents the same meaning as described above) is more preferable, and the following general formula (I-B1-1-2-1) and general formula (I-B1-1-3) are preferred. -1)

(Wherein L ²¹¹¹ represents the same meaning as described above) is more preferable.

  As the compound represented by the formula (I-B2), the following general formula (I-B2-1) to general formula (I-B2-4)

(Wherein L ¹¹ represents the same meaning as described above, and nL1 represents 0 or 1). A compound represented by general formula (I-B2-1-1) to general formula (I- B2-3-1)

(Wherein L ¹¹¹ represents the same meaning as described above) is more preferable, and the following general formula (I-B2-1-2-1) and general formula (I-B2-1-3) are preferred. -1)

(Wherein L ¹¹¹¹ represents the same meaning as described above) is more preferable.

  The compounds represented by the formula (I-A2) include the following general formulas (I-A2-1) to (I-A2-4)

(Wherein L ²¹ represents the same meaning as described above, and nL2 represents 0 or 1). A compound represented by the following general formula (I-A2-1-1) to general formula (I- A2-3-1)

(Wherein L ²¹¹ represents the same meaning as described above) is more preferable, and the following general formula (I-A2-1-1-1) and general formula (I-A2-1-2) are preferred. -1)

(Wherein L ²¹¹¹ represents the same meaning as described above) is more preferable.

  Specifically, the compounds represented by general formula (I-A1) and general formula (I-A2) are preferably compounds represented by the following formulas (A-1) to (A-45).

  Specifically, compounds represented by general formula (I-B1) and general formula (I-B2) are preferably compounds represented by the following formulas (B-1) to (B-76).

  As the reaction of the compounds represented by the above formulas (I-A1) and (I-B1), respectively (I-A2) and (I-B2), respectively, (i) a method using an acid catalyst, Examples include (ii) a method using a dehydrating agent, (iii) a method for deriving a carboxylic acid into an acid anhydride, and (iv) a method for deriving a carboxylic acid into an acid halide.

  (I) When an acid catalyst is used, examples of the acid include Bronsted acid and Lewis acid. Examples thereof include sulfonic acid, sulfuric acid, boron compound, hafnium complex, zirconium complex, tin complex, diphenylammonium triflate, boric acid, polyphosphoric acid and the like. Examples of the reaction solvent include benzene, toluene, hexane, cyclohexane, xylene, mesitylene and the like. In order to improve the yield, for example, there is a method of azeotropic removal and separation of water using a Dean-Stark dehydrator.

  (Ii) When a dehydrating agent is used, examples of the dehydrating agent include N-cyclohexylcarbodiimide methylpolystyrene resin, N, N′-diisopropylcarbodiimide, N, N′-dicyclohexylcarbodiimide, 1- (3-dimethylaminopropyl) -3- Ethylcarbodiimide resin, 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide or its hydrochloride, 1-alkyl-2-halopyridinium salt, 1,1-carbonyldiimidazole, bis (2-oxo-3-oxazolidinyl ) Phosphinic acid chloride, di-2-pyridyl carbonate, 6-methyl-2-nitrobenzoic anhydride, diethyl azodicarboxylate, diisopropyl azodicarboxylate, p-toluenesulfonyl chloride and the like. When using carbodiimide, a method of adding 4- (dimethylamino) pyridine or the like can be mentioned. Examples of the solvent include dichloromethane, tetrahydrofuran, toluene and the like.

  (Iii) When the carboxylic acid is derived into an acid anhydride, the acid anhydride may be a mixed acid anhydride. In the case of mixed acid anhydrides, for example, mixed acid anhydrides with methanesulfonic acid, p-toluenesulfonic acid, 2,4,6-trichlorobenzoic acid, ethyl carbonate and the like can be mentioned. Examples include a method of adding a catalyst such as sodium acetate, pyridine, 4- (dimethylamino) pyridine, scandium (III) trifluoromethanesulfonic acid imide, TMSOTf, Amberlist 15, and iodine. Examples of the solvent include dichloromethane, tetrahydrofuran, toluene and the like.

  (Iv) When the carboxylic acid is derived into an acid halide, a method in which a base and an alkali are allowed to coexist is exemplified. Examples of the base and alkali include pyridine, triethylamine, N, N-dimethylaniline, sodium hydroxide, potassium hydroxide and the like. Examples of the solvent include dichloromethane, tetrahydrofuran, toluene and the like. When using an alkali, it may be a water solvent or a mixed solvent of water and an organic solvent.

  From the viewpoint of ease of synthesis and cost, the above method (i) or (ii) is preferable, and the method (i) is particularly preferable.

  The compound represented by the general formula (IC) is represented by the following general formula (ID):

(Wherein A ¹ , A ² and Z ¹ represent the same meaning as A ¹ , A ² and Z ¹ in formula (IC), provided that at least one of A ¹ and A ² is one of the above-mentioned substitutions Substituted by the group L, the L present may be the same or different,
R ¹ 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 adjacent. Two or more —CH ₂ — are each independently —O—, —S—, —CO—, —COO—, —OCO—, —CO—S—, —S—CO—, —O—CO. A straight chain having 1 to 20 carbon atoms which may be substituted by —O—, —CO—NH—, —NH—CO—, —CH═CH—, —CF═CF— or —C≡C—, or A branched alkyl group is represented, and any hydrogen atom in the alkyl group may be substituted with a fluorine atom, or R ¹ is a group represented by P ^1- (Sp ¹ -X ¹ ) _k1- ( wherein, P ¹ is a radical polymerization, by cationic polymerization or anionic polymerization It represents the total radicals, although Sp ¹ represents a spacer group, they if Sp ¹ there are a plurality may be different even in the same, ^{X 1} is -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 -, - N = N -, - CH = N-N = CH -, - CF = CF -, - C≡C- or represents a single bond, the same if they ^{where X 1} there are a plurality of Or P ^1- (Sp ¹ -X ¹ ) _k1 -does not include an -O-O- bond, and k1 represents an integer of 0 to 10. Represent,
R ² 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 adjacent. Two or more —CH ₂ — are each independently —O—, —S—, —CO—, —COO—, —OCO—, —CO—S—, —S—CO—, —O—CO. A straight chain having 1 to 20 carbon atoms which may be substituted by —O—, —CO—NH—, —NH—CO—, —CH═CH—, —CF═CF— or —C≡C—, or A branched alkyl group is represented, and any hydrogen atom in the alkyl group may be substituted with a fluorine atom, or R ² is a group represented by-(X ² -Sp ² ) _k2 -P ² ( wherein, P ² is a radical polymerization, by cationic polymerization or anionic polymerization Represents the total radicals, Sp ² each represents a spacer group, they if Sp ² there are a plurality may be different even in the same, ^{X 2} is -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 -, - N = N -, - CH = N-N = CH -, - CF = CF -, - C≡C- or represents a single bond, the same case ^{those X 2} there are a plurality even differ also good _{^{(although, - (X 2 -Sp 2)}} k2 in -P ² do not contain -O-O- bond.) the, k2 is an integer of 0 to 10). Represent,
A ³ and A ⁴ are each independently 1,4-phenylene group, 1,4-cyclohexylene group, bicyclo [2.2.2] octane-1,4-diyl group, pyridine-2,5-diyl group. , Pyrimidine-2,5-diyl group, naphthalene-2,6-diyl group, naphthalene-1,4-diyl group, tetrahydronaphthalene-2,6-diyl group, decahydronaphthalene-2,6-diyl group or 1 , 3-dioxane-2,5-diyl groups, these groups may be unsubstituted or substituted by one or more substituents L ³ , and they are identical when there are multiple A ³ Or when A ⁴ is present, they may be the same or different,
L ³ is fluorine atom, chlorine atom, bromine atom, iodine atom, pentafluorosulfuranyl group, nitro group, cyano group, isocyano group, amino group, hydroxyl group, mercapto group, methylamino group, dimethylamino group, diethylamino group , A diisopropylamino group, a trimethylsilyl group, a dimethylsilyl group, a thioisocyano group, an optionally substituted phenyl group, an optionally substituted phenylalkyl group, an optionally substituted cyclohexylalkyl group, or one- CH ₂ — or two or more non-adjacent —CH ₂ — are each independently —O—, —S—, —CO—, —COO—, —OCO—, —CO—S—, —S—. ^{CO -, - O-COO -} , - CO-NR 0 -, - NR 0 -CO -, - CH = CH-COO -, - CH = CH-OCO- -COO-CH = CH -, - OCO-CH = CH -, - CH = CH -, - N = N -, - CR 0 = N -, - N = CR 0 -, - CH = N-N = CH —, —CF═CF— or —C≡C— (wherein R ⁰ represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms) and is a straight chain having 1 to 20 carbon atoms which may be substituted. A chain or branched alkyl group is represented, and any hydrogen atom in the alkyl group may be substituted with a fluorine atom, or L ³ is represented by P ^L- (Sp ^L -X ^L ) _kL-. Wherein P ^L represents a group that is polymerized by radical polymerization, cationic polymerization, or anionic polymerization, and Sp ^L represents a spacer group or a single bond, but when there are a plurality of Sp ^L, they are the same. It may be different even, ^{X L} is -O -, - S -, - _{CH 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 -, - N = N -, - CH = N- N = CH -, - CF = CF -, - C≡C- or represents a single bond, they ^{if X L} there are multiple was in the same May have also different ^{(although, P L - (Sp L -X} L) kL - to contain no -O-O- bonds. ), KL represents an integer of 0 to 10, and when a plurality of L are present in the compound, they may be the same or different,
Z ² and Z ³ are each independently —O—, —S—, —OCH ₂ —, —CH ₂ O—, —CH ₂ CH ₂ —, —CO—, —COO—, —OCO—, —CO. -S-, -S-CO-, -O-CO-O-, -CO-NH-, -NH-CO-, -OCO-NH-, -NH-COO-, -NH-CO-NH-, _{-NH-O -, - O-} NH -, - 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 -OCO -, - CH = CH - , - N = N -, - CH = N -, - N = CH -, - CH = N-N = CH -, - CF = CF -, - C≡C- or represents a single bond, they if Z ² there are a plurality may be the same or different and they if Z ³ there are a plurality may be the same or different and one of Z ² Z ² directly bonded to A ¹ is —O—, —CH ₂ O—, —COO—, —O—CO—O—, —NH—COO—, —NH—O—, —CF ₂ O—, — Z = CH—COO—, —CH ₂ CH ₂ —COO— or —CH ₂ —COO—, wherein Z ³ directly bonded to A ² of Z ³ is —O—, —OCH ₂ —, —OCO—. , -O-CO-O -, - OCO-NH -, - O-NH -, - OCF 2 -, - OCO-CH = CH -, - OCO-CH 2 H ₂ - or -OCO-CH ₂ - represents,
m1 and m2 each independently represents an integer of 0 to 4, but m1 + m2 represents an integer of 0 to 4. It is preferable to be derived into a compound represented by

In the general formula (ID), R ¹ 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 Any hydrogen atom may be substituted with a fluorine atom, and one —CH ₂ — or two or more non-adjacent —CH ₂ — are each independently —O—, —S—, —CO—. , -COO-, -OCO-, -CO-S-, -S-CO-, -O-CO-O-, -CO-NH-, -NH-CO-, -CH = CH-, -CF = A linear or branched alkyl group having 1 to 20 carbon atoms which may be substituted by CF- or -C≡C-, or R ¹ is represented by P ^1- (Sp ¹ -X ¹ ) _k1-. Represents a group. When R ¹ represents a group other than the group represented by P ^1- (Sp ¹ -X ¹ ) _k1- , from the viewpoint of liquid crystallinity and ease of synthesis, R ¹ represents a hydrogen atom, a fluorine atom, a chlorine atom, A cyano group, or one —CH ₂ — or two or more non-adjacent —CH ₂ — are each independently —O—, —CO—, —COO—, —OCO—, —O—CO. Linear or branched having 1 to 12 carbon atoms which may be substituted by —O—, —CO—NH—, —NH—CO—, —CH═CH—, —CF═CF— or —C≡C— Preferably, it represents an alkyl group, and R ¹ is a hydrogen atom, a fluorine atom, a chlorine atom, or one —CH ₂ — or two or more non-adjacent —CH ₂ — are each independently —O—. , -CO-, -COO-, -OCO- or -O-CO-O- More preferably, it represents a linear or branched alkyl group having 1 to 12 elementary atoms, and R ¹ represents a hydrogen atom, a fluorine atom, a chlorine atom, or a linear alkyl group or linear alkoxy group having 1 to 12 carbon atoms. Is more preferable, and R ¹ particularly preferably represents a linear alkyl group having 1 to 12 carbon atoms or a linear alkoxy group.

When R ¹ represents a group represented by P ^1- (Sp ¹ -X ¹ ) _k1- , P ¹ represents a group that is polymerized by radical polymerization, cationic polymerization, or anionic polymerization, and the following formula (P-1 ) To formula (P-20)

It is preferable to represent a group selected from: 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-3), formula (P-8), formula (P-11) or formula (P-13) is more preferred, and formula (P-1), formula (P-2) or formula (P-3) is more preferred. More preferred is formula (P-1) or (P-2).

Sp ¹ represents a spacer group. When a plurality of Sp ¹ are present, they may be the same or different. From the viewpoint of liquid crystallinity, availability of raw materials, and ease of synthesis, Sp ¹ is a plurality. When present, they may be the same or different, and one —CH ₂ — or two or more non-adjacent —CH ₂ — may each independently represent —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 -, - _{CO-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-, -N = N-, -CH = N-N = CH-, -CF = CF- or -C≡C- preferably represents an alkylene group, Sp ¹ may be different even each identical in the presence of two or more, one -CH 2 _- or nonadjacent two or more -CH 2 _- are each May be independently replaced by —O—, —COO—, —OCO—, —OCO—O—, —CO—NH—, —NH—CO—, —CH═CH— or —C≡C—; more preferably represents an alkylene group having 1 to 20 carbon atoms, Sp ¹ is more exist When present, they may be the same or different, and one —CH ₂ — or two or more non-adjacent —CH ₂ — may each independently represent —O—, —COO—, — More preferably, it represents a linear alkylene group having 1 to 20 carbon atoms which may be replaced by OCO- or -OCO-O-, and when there are a plurality of Sp ^{1 s} , they may be the same or different. A linear alkylene group having 1 to 12 carbon atoms in which one —CH ₂ — or two or more non-adjacent —CH ₂ — may be independently replaced by —O—. It is even more preferable that, when a plurality of Sp ¹ are present, they may be the same or different, and it is particularly preferable to represent a linear alkylene group having 1 to 12 carbon atoms.

X ¹ represents —O—, —S—, —OCH ₂ —, —CH ₂ O—, —CO—, —COO—, —OCO—, —CO—S—, —S—CO—, —O—CO. _{-O -, - CO-NH -} , - NH-CO -, - SCH 2 -, - CH 2 S -, - CF 2 O -, - OCF 2 -, - CF 2 S -, - SCF 2 -, - CH═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- , -N = N -, - CH = N-N = CH -, - CF = CF -, - C≡C- or represents a single bond, ^{X 1} is more present They may be different even in the same case that. From the viewpoint of easy availability of raw materials and ease of synthesis, when a plurality of X ¹ are present, they may be the same or different, and —O—, —S—, —OCH ₂ —, —CH ₂ O -, - COO -, - OCO -, - CO-S -, - S-CO -, - OCO-O -, - COO-CH 2 CH 2 -, - OCO-CH 2 CH 2 -, - It preferably represents CH ₂ CH ₂ —COO—, —CH ₂ CH ₂ —OCO— or a single bond, more preferably —O—, —COO—, —OCO— or a single bond, —O— or It is more preferable to represent a single bond, and it is particularly preferable to represent —O—.

  k1 represents an integer of 0 to 10. From the viewpoint of liquid crystallinity and availability of raw materials, it is preferable to represent an integer of 0 to 3. From the viewpoint of curing shrinkage when formed into a film, it is more preferably an integer of 1 to 3, and 1 is particularly preferable.

In general formula (ID), R ² represents 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 a group Any hydrogen atom may be substituted with a fluorine atom, and one —CH ₂ — or two or more non-adjacent —CH ₂ — are each independently —O—, —S—, —CO—. , -COO-, -OCO-, -CO-S-, -S-CO-, -O-CO-O-, -CO-NH-, -NH-CO-, -CH = CH-, -CF = CF- or a linear or branched alkyl group having 20 good 1 -C be replaced by -C≡C-, or, ^{R 2} is ^- is represented by _{^{(X 2 -Sp 2) k2 -P}} 2 Represents a group. When R ² represents a group other than the group represented by — (X ² —Sp ² ) _k ² —P ² , R ² represents a hydrogen atom, a fluorine atom, a chlorine atom, from the viewpoint of liquid crystallinity and ease of synthesis. A cyano group, or one —CH ₂ — or two or more non-adjacent —CH ₂ — are each independently —O—, —CO—, —COO—, —OCO—, —O—CO. Linear or branched having 1 to 12 carbon atoms which may be substituted by —O—, —CO—NH—, —NH—CO—, —CH═CH—, —CF═CF— or —C≡C— Preferably, it represents an alkyl group, and R ² is a hydrogen atom, a fluorine atom, a chlorine atom, or one —CH ₂ — or two or more non-adjacent —CH ₂ — are each independently —O—. , -CO-, -COO-, -OCO- or -O-CO-O- More preferably represents a straight-chain or branched alkyl group of atoms from 1 to 12, R ² is a hydrogen atom, a fluorine atom, a chlorine atom, or a straight-chain alkyl group or straight chain alkoxy group having 1 to 12 carbon atoms It is more preferable that R ² represents a linear alkyl group having 1 to 12 carbon atoms or a linear alkoxy group, and it is particularly preferable.

When R ² represents a group represented by-(X ² -Sp ² ) _k ² -P ² , preferred structures of P ² , Sp ² , X ² and k ² are P ¹ , Sp ¹ , X ¹ and k ¹ , respectively. This is the same as the preferred structure.

When the compound represented by formula (ID) is used for a polymer such as a film, both R ¹ and R ² are P ^1- (Sp ¹ -X ¹ ) _k1- and-(X ² -Sp ²⁾ _k2 -P ² in or a group represented, one of ^{R 1} and ^{R 2 _{P 1 - (Sp 1 -X 1}} ) k1 - , or ^- (Table with ^{X ₂} -Sp _²⁾ k2 -P ² the other represents a group is _{^{P 1 - (Sp 1 -X 1}} ) k1 - , or ^{- (X ₂} -Sp _²⁾ preferably represents a group other than a group represented by the in k2 -P ^2. When importance is attached to the flexibility of the film, ^one of R ¹ and R ² is a group represented by P ^1- (Sp ¹ -X ¹ ) _k1- or-(X ² -Sp ² ) _k2 -P ² It is preferable that the other represents a group other than the group represented by P ^1- (Sp ¹ -X ¹ ) _k1- or-(X ² -Sp ² ) _k2 -P ² , and the mechanical properties when formed into a film When importance is attached to strength, it is preferable that both R ¹ and R ² represent groups represented by P ^1- (Sp ¹ -X ¹ ) _k1- and-(X ² -Sp ² ) _k2 -P ² . In general formula when using the (I-D) a compound represented by the applications other than polymer, both of ^{R 1} and ^{R 2 _{P 1 - (Sp 1 -X 1}} ) k1 - and - ^{(X 2} -sp ²⁾ preferably represents a group other than a group represented by the in _k2 -P ^2. From the standpoint of preparation of the synthesis, both R ¹ and R ² represent groups represented by P ^1- (Sp ¹ -X ¹ ) _k1- and-(X ² -Sp ² ) _k2 -P ² , It is particularly preferred that both R ¹ and R ² represent groups other than those represented by P ^1- (Sp ¹ -X ¹ ) _k1- and-(X ² -Sp ² ) _k2 -P ² .

In the general formula (ID), A ³ and A ⁴ are each independently 1,4-phenylene group, 1,4-cyclohexylene group, bicyclo [2.2.2] octane-1,4-diyl group, Pyridine-2,5-diyl group, pyrimidine-2,5-diyl group, naphthalene-2,6-diyl group, naphthalene-1,4-diyl group, tetrahydronaphthalene-2,6-diyl group, decahydronaphthalene- Represents a 2,6-diyl group or a 1,3-dioxane-2,5-diyl group, these groups may be unsubstituted or substituted by one or more substituents L ³ , A ³ there they If there are multiple may be different even in the same, a ⁴ may be those when there are multiple different be the same. From the viewpoint of ease of synthesis, availability of raw materials, and liquid crystallinity, A ³ and A ⁴ are each independently unsubstituted or may be substituted with one or more substituents L ³ Represents 4-phenylene group, 1,4-cyclohexylene group, bicyclo [2.2.2] octane-1,4-diyl group, naphthalene-2,6-diyl group or naphthalene-1,4-diyl group Are preferably each independently represented by the following formulas (A-1) to (A-16):

And more preferably each independently represents a group selected from the above formulas (A-1) to (A-8), and each independently represents the above formula (A). It is even more preferable to represent a group selected from formula (A-4) and formula (A-8) to formula (A-4), and each independently selected from formula (A-1) or formula (A-2) above It is even more preferable that the group represented by formula (A-1) is particularly preferable. In the general formula (ID),-(A ³ -Z ² ) _{m1 -structural} unit and-(A ⁴ -Z ³ ) _m2 -structural unit represent the same structure from the viewpoint of simplicity in production. It is preferable. In this case, the general formula (I-C) and the compound represented by at _{^{- (A 3 -Z 2) m1}} - only one compound corresponding to the structural unit represented by general formula (I-D) Compound Can be derived in one step.

In the general formula (ID), L ³ represents a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a pentafluorosulfuranyl group, a nitro group, a cyano group, an isocyano group, an amino group, a hydroxyl group, a mercapto group, or methylamino. Group, dimethylamino group, diethylamino group, diisopropylamino group, trimethylsilyl group, dimethylsilyl group, thioisocyano group, optionally substituted phenyl group, optionally substituted phenylalkyl group, optionally substituted cyclohexylalkyl Group, or any hydrogen atom in the group may be substituted with a fluorine atom, and one —CH ₂ — or two or more non-adjacent —CH ₂ — may be independently —O—, -S-, -CO-, -COO-, -OCO-, -CO-S-, -S-CO-, -O-CO-O-, -CO- ^{R 0 -, - NR 0 -CO} -, - CH = CH-COO -, - CH = CH-OCO -, - COO-CH = CH -, - OCO-CH = CH -, - CH = CH -, - ^{N = N -, - CR 0} = N -, - N = CR 0 -, - CH = N-N = CH -, - CF = CF- or -C≡C- (wherein, ^{R 0} is a hydrogen atom or A linear or branched alkyl group having 1 to 20 carbon atoms which may be substituted, or L ³ is P ^L- (Sp ^L -X ^L ). _{kL -} group may represent represented by, but they may be the same or different if L ³ is more present in the compound. From the viewpoint of liquid crystallinity and ease of synthesis, the substituent L ³ is a fluorine atom, a chlorine atom, a pentafluorosulfuranyl group, a nitro group, a methylamino group, a dimethylamino group, a diethylamino group, a diisopropylamino group, or any Each of the hydrogen atoms may be replaced by a fluorine atom, and one —CH ₂ — or two or more non-adjacent —CH ₂ — may be independently —O—, —S—, —CO—, 1 to 20 carbon atoms which may be substituted by a group selected from —COO—, —OCO—, —O—CO—O—, —CH═CH—, —CF═CF— or —C≡C—. The substituent L ³ is preferably a fluorine atom, a chlorine atom, or an arbitrary hydrogen atom may be substituted with a fluorine atom, and one —CH ₂ — or 2 not adjacent -CH 2 above _- are each independently -O -, - COO- or a linear or branched alkyl group having 12 good 1 -C be substituted by a group selected from -OCO- More preferably, the substituent L ³ is a fluorine atom, a chlorine atom, or an arbitrary hydrogen atom is a linear or branched alkyl group having 1 to 12 carbon atoms or an alkoxy group, which may be substituted with a fluorine atom. More preferably, the substituent L ³ particularly preferably represents a fluorine atom, a chlorine atom, or a linear alkyl group or linear alkoxy group having 1 to 8 carbon atoms. Further, the substituent ^{L 3} is _{^{P L - (Sp L -X L}} ) kL - preferred structure of group may represent represented by ^{but, P L, Sp L, X} L and kL, respectively ^P 1, It is the same as the preferable structure of Sp ¹ , X ¹ and k ¹ .

In the general formula (ID), Z ² and Z ³ are each independently —O—, —S—, —OCH ₂ —, —CH ₂ O—, —CH ₂ CH ₂ —, —CO—, —COO. -, -OCO-, -CO-S-, -S-CO-, -O-CO-O-, -CO-NH-, -NH-CO-, -OCO-NH-, -NH-COO-, -NH-CO-NH -, - NH-O -, - O-NH -, - 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 -, - C _{2 -COO -, - CH 2 -OCO} -, - CH = CH -, - N = N -, - CH = N -, - N = CH -, - CH = N-N = CH -, - CF = CF —, —C≡C— or a single bond, but when there are a plurality of Z ^{2 s,} they may be the same or different, and when there are a plurality of Z ^{3 s,} they may be the same or different. At best, ^{Z 2} is bonded directly to ^{a 1} of the ^{Z 2} is _{-O -, - CH 2 O -} , - COO -, - O-COO -, - NH-COO -, - NH-O- _{, -CF 2 O -, - CH} = CH-COO -, - CH 2 CH 2 -COO- or _-CH 2 -COO- the stands, ^{Z 3} is directly bonded to ^{a 2} of ^{Z 3} is -O-, —OCH ₂ —, —OCO—, —O—CO—O—, —OCO—NH—, —O—NH—, —OCF ₂ —, —OCO—CH═C _{H -, - OCO-CH 2} CH 2 - or -OCO-CH ₂ - represents a. And ease of raw material availability and synthesis, liquid crystal, from the viewpoints of storage stability, Z ² and Z ³ are not directly bonded to A ¹ and A ² of Z ² and Z ³ present their case there are a plurality of May be the same or different and each independently represents —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 -, - C≡C- or a single bond _{preferably, -OCH 2 -, - CH 2} O -, - CH 2 CH 2 - _{, -COO -, - OCO -,} - COO-CH 2 CH 2 -, - OCO-CH 2 CH 2 -, - CH 2 CH 2 -COO -, - CH 2 CH 2 -OCO -, - CH = CH- , —C≡C— or a single bond is more preferable, —CH ₂ CH ₂ —, —COO—, —OCO—, —COO—CH ₂ CH ₂ —, —OCO—CH ₂ CH ₂ —, — It is more preferable to represent CH ₂ CH ₂ —COO—, —CH ₂ CH ₂ —OCO— or a single bond, and it is particularly preferable that each independently represents —COO— or —OCO—. Z ² directly bonded to A ¹ in Z ² represents —CH ₂ O—, —COO—, —CF ₂ O—, —CH═CH—COO— or —CH ₂ CH ₂ —COO—. _preferably, -CH 2 O _-, - COO- or more preferably representing a _-CH 2 _CH 2 -COO-, more preferably represent a -COO- -COO- or _-CH 2 _CH 2, -COO- Is particularly preferred. Z ³ directly bonded to A ² out of Z ³ preferably represents —OCH ₂ —, —OCO—, —OCF ₂ —, —OCO—CH═CH— or —OCO—CH ₂ CH ₂ —, OCH ₂ -, - OCO- or _{-OCO-CH 2 CH} 2 - and more preferably representing a -OCO- or _{-OCO-CH 2 CH} 2 - is more preferable to represent, in particular, may represent -OCO- preferable.

  In general formula (ID), m1 and m2 each independently represent an integer of 0 to 4, but m1 + m2 represents an integer of 0 to 4. From the viewpoint of liquid crystallinity, availability of raw materials, and ease of synthesis, m1 and m2 preferably each independently represent an integer of 0 to 2, more preferably each independently represent 0 or 1, m1 And m2 are more preferably the same integer, and m1 and m2 are particularly preferably 1.

  Examples of the compound represented by the general formula (ID) include the following general formula (ID-1) to general formula (ID-14).

(In the formula, each of L ¹¹ and L ²¹ is independently a fluorine atom, a chlorine atom, or an arbitrary hydrogen atom in the group may be substituted with a fluorine atom, and one —CH ₂ — or adjacent group. And two or more —CH ₂ — each independently represents a linear or branched alkyl group having 1 to 20 carbon atoms which may be substituted by —O—, and nL 1 and nL 2 are each independently 0 Or R ¹¹ represents a hydrogen atom, a fluorine atom, a chlorine atom, a cyano group, or one —CH ₂ — or two or more non-adjacent —CH ₂ — are each independently —O—. , —CO—, —COO—, —OCO—, —O—CO—O—, —CO—NH—, —NH—CO—, —CH═CH—, —CF═CF— or —C≡C—. A linear or branched alkyl having 1 to 12 carbon atoms which may be substituted by Group, ^{or, P 11 - (Sp 11 -X} 11) k11 - group (wherein represented ^{by, P 11} is the above 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) In the case where a plurality of Sp ¹¹ are present, they may be the same or different, and one —CH ₂ — or two or more —CH ₂ — that are not adjacent to each other may be independently represented. Carbon that may be replaced by -O-, -COO-, -OCO-, -OCO-O-, -CO-NH-, -NH-CO-, -CH = CH-, or -C≡C- from atoms 1 represents an alkylene group of ^{20, X 11} is them if there are a plurality may be different even in the same, -O -, - S -, - OCH 2 -, - C _{2 O -, - COO -,} - OCO -, - CO-S -, - S-CO -, - OCO-O -, - COO-CH 2 CH 2 -, - OCO-CH 2 CH 2 -, _{-CH 2 CH 2 -COO -, -} . CH 2 CH 2 -OCO- or a single bond, k11 represents a representative) an integer from 0 ^{3, R 21} is a hydrogen atom, a fluorine atom, a chlorine atom, a cyano A group, or one —CH ₂ — or two or more non-adjacent —CH ₂ — are each independently —O—, —CO—, —COO—, —OCO—, —O—CO—. C1-C12 linear or branched alkyl optionally substituted by O-, -CO-NH-, -NH-CO-, -CH = CH-, -CF = CF- or -C≡C- group, _{^{or, - (X 21 -Sp 21)}} k21 group (wherein represented by ^{-P 21, P 21} , Sp ²¹ , X ²¹ , k21 represent the same meaning as P ¹¹ , Sp ¹¹ , X ¹¹ , k11, respectively. A ³¹ and A ⁴¹ each independently represents a group selected from the above formulas (A-1) to (A-16), and Z ²¹ and Z ³¹ each independently represent —OCH ₂ —. _{, -CH 2 O -, - CH} 2 CH 2 -, - COO -, - OCO -, - COO-CH 2 CH 2 -, - OCO-CH 2 CH 2 -, - CH 2 CH 2 -COO -, - _{CH 2 CH 2 -OCO -, -} CH = CH -, - C≡C- or a single ^{bond, (rightmost Z 21} of ^{Z 21) Z} 21 bonded directly to ^{a 1} of the ^{Z 21} is - CH ₂ O -, - COO- or _-CH 2 _CH 2 -COO- the ^{stands, (Z 31} leftmost of ^{Z 31) Z} 31 bonded directly to ^{a 2} of ^{Z 31} is -OCH ₂ -, - OCO- or _{-OCO-CH 2 CH} 2 - represents, Germany each m11 and m21 Represent an integer from 0 to 2. The compounds represented by formula (ID-1-1) to formula (ID-12-2) are preferred:

(In the formula, each of L ¹¹¹ and L ²¹¹ independently represents that any hydrogen atom in the group may be substituted with a fluorine atom, and one —CH ₂ — or two or more —CH ₂ not adjacent to each other may be substituted. -Represents a linear or branched alkyl group having 1 to 10 carbon atoms, each of which may be independently substituted by -O-, and R ¹¹¹ represents a hydrogen atom, a fluorine atom, a chlorine atom, or one —CH ₂ — or two or more non-adjacent —CH ₂ — may be each independently substituted by —O—, —CO—, —COO—, —OCO— or —O—CO—O—. linear or branched alkyl group having from good 1 to 12 carbon atoms, ^{or, P 111 - (Sp 111 -X} 111) k111 - group represented by ^{(wherein, P 111} is above formula (P-1), Formula (P-2), Formula (P-3), Formula (P-8), Formula ( -11) or a group represented by the formula ^{(P-13), Sp 111} may be different even each identical in the presence of two or more, one -CH ₂ - not or adjacent Two or more —CH ₂ — each independently represents a linear alkylene group having 1 to 20 carbon atoms which may be replaced by —O—, —COO—, —OCO— or —OCO—O—. , X ¹¹¹ may be the same or different when a plurality of X ¹¹¹ are present, and represents —O—, —COO—, —OCO— or a single bond, and k111 represents an integer of 1 to 3. R ²¹¹ represents a hydrogen atom, a fluorine atom, a chlorine atom, or one —CH ₂ — or two or more non-adjacent —CH ₂ — each independently —O—, —CO—, — Substituted by COO-, -OCO- or -O-CO-O- Linear or branched alkyl group having from which may 1 to 12 carbon atoms, _{^{or, - (X 211 -Sp 211)}} k211 group (wherein represented by ^{-P 211, P 211, Sp 211} , X 211, k211 is Each represents the same meaning as P ¹¹¹ , Sp ¹¹¹ , X ¹¹¹ and k ¹¹¹ ), and A ³¹¹ and A ⁴¹¹ are each independently a group selected from the above formulas (A-1) to (A-8) the ^{stands, Z 211} and ^{Z 311} are _-CH 2 _CH 2 each independently _{-, - COO -, - OCO} -, - COO-CH 2 CH 2 -, - OCO-CH 2 CH 2 -, - CH 2 CH _{2 -COO -, - CH 2 CH} 2 -OCO- or a single ^{bond, (rightmost Z 211} of ^{Z 211) Z} 211 bonded directly to ^{a 1} of the ^{Z 211} is -COO- or -CH ₂ CH ₂ -COO- the ^{stands, Z Z} 311 attached directly to ^{A 2} of ^{311 (leftmost Z 311} of ^{Z 311)} is -OCO- or _{-OCO-CH 2 CH} 2 - represents, the m111 and m211 Each independently represents 0 or 1. The compounds represented by formula (II-1-1-1-1) to formula (ID-12-2-1) are more preferred.

( ^Wherein L ¹¹¹¹ and L ²¹¹¹ each independently represent a methyl group, an ethyl group, a propyl group, a methoxy group, a trifluoromethyl group or a trifluoromethoxy group, and R ¹¹¹¹ represents a hydrogen atom, a fluorine atom, a chlorine atom, or a linear alkyl or linear alkoxy group having 1 to 12 carbon atoms, ^{or, P 1111 - (Sp 1111 -X} 1111) k1111 - group (wherein represented ^{by, P 1111} is above formula (P -1) represents a group represented by formula (P-2) or formula (P-3), and when there are a plurality of Sp ^{1111 s} , they may be the same or different from each other, and one -CH ₂ or two or more non-adjacent —CH ₂ — each independently represents a linear alkylene group having 1 to 12 carbon atoms which may be replaced by —O—, and a plurality of X ¹¹¹¹ are present. Place They may be the same or different and represents -O- or a single bond, K1111 represents represents.) An integer from 1 ^{3, R 2111} represents a hydrogen atom, a fluorine atom, a chlorine atom, or, linear alkyl or linear alkoxy groups of from 1 to 12 carbon atoms, ^or, - ^(X _{2111 -Sp 2111)} group (wherein represented by ^{k2111 -P 2111, P 2111, Sp} 2111, X 2111, k2111 Each represents the same meaning as P ¹¹¹¹ , Sp ¹¹¹¹ , X ¹¹¹¹ , and k1111.), A ³¹¹¹ and A ⁴¹¹¹ are each independently selected from the above formula (A-1) or formula (A-2). A compound represented by the following formula: is more preferred.

  From the viewpoint of liquid crystallinity, general formula (I-A1), general formula (I-B1), general formula (I-A2), general formula (I-B2), general formula (IC), and general formula 1,4-cyclohexylene group, tetrahydropyran-2,5-diyl group, 1,3-dioxane-2,5-diyl group and decahydronaphthalene-2, contained in the compound represented by (ID) The 6-diyl group may be either a cis isomer or a trans isomer, or a mixture of both. However, from the viewpoint of liquid crystallinity, the trans isomer is preferably the main component, and the trans isomer only It is particularly preferred.

A compound represented by general formula (IC) is used as a production intermediate, and A ⁴ , Z ³ , R ² and m2 in general formula (ID) are A ³ , Z ² , R ¹ and m 1, respectively. A method for producing the same compound represented by formula (ID) is also one embodiment of the present invention. According to this production method, the compound represented by the general formula (ID) having a polymerizable group can be obtained easily and with high purity.

  In the conventional production method of the compound represented by formula (ID) having a polymerizable group, a relatively high molecular weight polymerizable production intermediate is used in the production process. For this reason, it is inevitable that the compound contains a high molecular weight oligomer derived from the polymerizable production intermediate as an impurity. The presence of such a high molecular weight oligomer is not preferable because it causes alignment failure during the production of the optical anisotropic body. On the other hand, according to this production method, the compound represented by the general formula (IC) is used as a production intermediate, so that the compound can be obtained in one step without going through the polymerizable production intermediate as described above. Can be manufactured. For this reason, the production | generation of a high molecular weight oligomer can be suppressed.

According to this production method, the compound represented by formula (ID) is obtained as a mixture containing a small amount of an unreacted intermediate and a derivative of the intermediate. That is, the mixture has the following general formula (ID)

(Wherein A ¹ , A ² , A ³ , A ⁴ , Z ¹ , Z ² , Z ³ , R ¹ , R ² , m 1 and m ² represent the same meaning as in the general formula (ID), provided that , At least one of A ¹ and A ² is substituted by one said substituent L, and the existing L may be the same or different.)
And a compound represented by the following general formula (IC)

(In the formula, A ¹ , A ² , Z ¹ represent the same meaning as in the general formula (IC), provided that at least one of A ¹ and A ² is substituted with one of the substituents L, L present may be the same or different.)
A compound represented by the following general formula (I-F1)

(In the formula, A ¹ , A ² , A ³ , Z ¹ , Z ² , R ¹ and m 1 are A ¹ , A ² , A ³ , Z ¹ , Z ² , m ^{1 in} the general formula (ID)). It represents the same meaning, provided that at least one of A ¹ and A ² is substituted by one said substituent L, and L present may be the same or different.) Or the following general formula (I-F2 )

(In the formula, A ¹ , A ² , A ⁴ , Z ¹ , Z ³ , R ² and m ² are A ¹ , A ² , A ⁴ , Z ¹ , Z ³ , R ^{2 in the} general formula (ID)). And m2 have the same meanings, provided that at least one of A ¹ and A ² is substituted by one of the substituents L, and the existing L may be the same or different.
And a compound represented by the general formula (I-C), a compound represented by the general formula (I-F1), and a compound represented by the general formula (I-F2) The amount is 0.001 wt% or more and 5 wt% or less. Here, in each _{^{formula, - (A 3 -Z 2)}} m1 - structural unit _{^{- (A 4 -Z 3) m2}} - represent the same structure as the structural unit, tables in the general formula (I-F1) The compound represented by formula (I-F2) is preferably the same.

  The total content of the compound represented by formula (IC) and the compound represented by formula (IF) in the mixture is 0.003% by weight from the viewpoint of simplifying the purification step. Preferably, it is 0.005% by weight or more, more preferably 0.01% by weight or more, and 3% by weight or less from the viewpoint of suppressing unevenness and discoloration in the resulting film. Preferably, it is 2% by weight or less, more preferably 1% by weight or less.

The method for producing the compound represented by the general formula (ID) uses the compound represented by the general formula (IC) as a production intermediate and is represented by the general formula (IE) described later. It is preferable to use a compound. Specifically, the method for producing the compound represented by the general formula (ID) includes the general formula (IC).

(In the formula, A ¹ , A ² , and Z ¹ represent the same meaning as described above, provided that at least one of A ¹ and A ² is substituted with one of the substituents L, and the existing L may be the same. May be different.)
And a compound represented by the general formula (IE)

^{(Wherein, R 1, A 3, Z} 2, m1 have the same meanings as ^{R 1, A 3, Z 2} , m1 in formula (I-D), the ^{A 3} present be the same or different May be.)
It is preferable to make it react with the compound represented by these. In this reaction, it is preferable to use 1.5 equivalents or more, and 1.8 equivalents or more of the compound represented by the general formula (IE) to 1 equivalent of the compound represented by the general formula (IC). It is more preferable to use 1.9 equivalents or more. The reaction method is not particularly limited, but conventional dehydration condensation may be used.

  In general formula (IE), m1 preferably represents 0. By using the compound represented by the general formula (IE) in which m1 represents 0, the molecular weight of impurities such as oligomers derived from the compound can be reduced. As a result, a high-purity compound represented by the formula (ID) with few high molecular weight impurities is obtained.

Hereinafter, along with the production method of the present invention, an example of a series of steps for obtaining the compound of the present invention and derivatives thereof will be shown.
(Production method 1) Production of a compound represented by the following formula (S-3)

(In the formula, L ² represents the same meaning as L in formula (IC).)
A compound represented by the formula (S-3) is obtained by reacting a compound represented by the formula (S-1) with a compound represented by the formula (S-2). The reaction includes (i) a method using an acid catalyst, (ii) a method using a dehydrating agent, (iii) a method for inducing a carboxylic acid into an acid anhydride, and (iv) inducing a carboxylic acid into an acid halide. Methods and the like. Further, one hydroxyl group of the compound represented by the formula (S-1) may be protected by a protecting group, or the hydroxyl group of the compound represented by the formula (S-2) may be protected by a protecting group. good. In this case, the protecting group is not particularly limited as long as it can be stably protected until the deprotection step. For example, GREEN'S PROTECTIVE GROUPS IN ORGANIC SYNTHESIS ((Fourth Edition), PETER GM. Protecting groups (PG) mentioned in WUTS, THEODORA W. GREENE, John Wiley & Sons, Inc., Publication) and the like are preferred. Specific examples of the protecting group include a tetrahydropyranyl group, a methoxymethyl group, an ethoxymethyl group, an acetyl group, and a benzyl group. Examples of the deprotection method include the methods described in the above documents.
(Production Method 2) Production of a compound (mixture) represented by the following formula (S-6)

(In the formula, L ¹ represents the same meaning as L in formula (IC).)
It can be produced by the same method as production method 1.
(Manufacturing method 3) Production of a compound represented by the following formula (S-8) using a compound represented by the formula (S-3)

(In the formula, L ² represents the same meaning as L in the general formula (IC), and P, Sp, X and L are the same as P ¹ , Sp ¹ , X ¹ and L in the general formula (ID). And r represents an integer from 0 to 4.)
The compound represented by the formula (S-8) can be obtained by reacting the compound represented by the formula (S-3) with the compound represented by the formula (S-7). As the reaction conditions, for example, a method using a condensing agent or a compound represented by the formula (S-7) is converted to an acid chloride, mixed acid anhydride or carboxylic acid anhydride and then represented by the general formula (S-3). The method of making it react with a compound in base presence is mentioned. When a condensing agent is used, examples of the condensing agent include N, N′-dicyclohexylcarbodiimide, N, N′-diisopropylcarbodiimide, and 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide hydrochloride. Examples of the base include triethylamine and diisopropylethylamine.
(Manufacturing method 4) Manufacture of the compound (mixture) represented by the following formula (S-10) using the compound (mixture) represented by the formula (S-6)

(In the formula, L ¹ represents the same meaning as L in the general formula (IC), and P, Sp, X and L ³ represent P ¹ , Sp ¹ , X ¹ and L ^{3 in the} general formula (ID). And r represents an integer of 0 to 4.)
It can be produced by the same method as production method 3.

  As reaction conditions other than those described in each step of production method 1 to production method 4, for example, Experimental Chemistry Course (edited by Chemical Society of Japan, published by Maruzen Co., Ltd.), Organic Synthesis (John Wiley & Sons, Inc., Publication), Beilstein Handbook of Organic Chemistry (Beilstein-Institut fuer Literatur der Organischen Chemie, Springer-Verlag Berlin and Heidelberg GmbH & Co.K), Fiesers' Reagents for Organic Synthesis (John Wiley & Sons, Inc.) conditions or SciFind described in the literature such as r (Chemical Abstracts Service, American Chemical Society) or Reaxys conditions provided from 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, isopropyl alcohol, ethylene glycol, methanol, ethanol, chloroform, dichloromethane, 1,2-dichloroethane, acetone, acetonitrile, N, N-dimethylformamide, N , N-dimethylacetamide, dimethyl sulfoxide, diethyl ether, ethylene glycol monoethyl ether, xylene, ethyl acetate, 1,4-dioxane, tetrahydrofuran, pyridine, 1-methyl-2-pyrrolidinone, toluene, hexane, cyclohexane, heptane, methyl Examples include isobutyl ketone, tert-butyl methyl ether, and methyl ethyl ketone. 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.

  The compound represented by formula (ID) is preferably used for nematic liquid crystal compositions, smectic liquid crystal compositions, chiral smectic liquid crystal compositions, and cholesteric liquid crystal compositions. In the liquid crystal composition using the compound represented by formula (ID), a compound other than the present invention may be added.

  Specific examples of the other polymerizable compound used by mixing with the compound represented by formula (ID) include those represented by formula (X-11).

And / or general formula (X-12)

(In the formula, P ¹¹ , P ¹² and P ¹³ each independently represent a polymerizable group, and Sp ¹¹ , Sp ¹² and Sp ¹³ each independently represent a single bond or an alkylene group having 1 to 20 carbon atoms. represents but one -CH ₂ - or nonadjacent two or more _-CH 2 - is -O -, - COO -, - OCO -, - OCOO- may be replaced ^{by, X} 11, X ¹² and X ¹³ are each independently —O—, —S—, —OCH ₂ —, —CH ₂ O—, —CO—, —COO—, —OCO—, —CO—S—, —S—CO. -, - O-CO-O -, - CO-NH -, - NH-CO -, - SCH 2 -, - CH 2 S -, - CF 2 O -, - OCF 2 -, - CF 2 S-, _{-SCF 2 -, - CH = CH} -COO -, - CH = CH-OCO -, - COO-CH = CH -, - OCO- _{H = 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, Z 11} and ^{Z 12} are each independently _, - - S _-, - _-O and 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 -, - C = 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 Represents ≡C— or a single bond, and A ¹¹ , A ¹² , A ¹³ and A ¹⁴ each independently represents a 1,4-phenylene group, a 1,4-cyclohexylene group, a pyridine-2,5-diyl group, Pyrimidine-2,5-diyl group, naphthalene-2,6-diyl group, naphthalene-1,4-diyl group, tetrahydronaphthalene-2,6-diyl group or 1,3-dioxane-2,5-diyl group It represents ^{but, A 11, A 12, A} 13 and ¹⁴ are each independently unsubstituted or substituted by an alkyl group, a halogenated alkyl group, alkoxy group, halogenated alkoxy group, a halogen atom, may be substituted with a cyano group or a nitro group, R ¹¹ 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 two or more non-adjacent — CH ₂ — is 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═CH—, —CF = CF- or -C≡C- Represents a linear or branched alkyl group having 1 to 20 carbon atoms which may be substituted, and m11 and m12 represent 0, 1, 2 or 3, but when m11 and / or m12 represents 2 or 3, Two or three A ¹¹ , A ¹³ , Z ¹¹ and / or Z ¹² may be the same or different. ) Is preferred, and the case where P ¹¹ , P ¹² and P ¹³ are acrylic groups or methacrylic groups is particularly preferred. Specifically, the compound represented by the general formula (X-11) is represented by the general formula (X-11a).

Wherein W ¹¹ and W ¹² each independently represent a hydrogen atom or a methyl group, Sp ¹⁴ and Sp ¹⁵ each independently represent an alkylene group having 2 to 18 carbon atoms, and X ¹⁴ and X ¹⁵ each independently to -O -, - COO -, - OCO- or a single ^{bond, Z 13} and ^{Z 14} are each independently represents a -COO- or ^{-OCO-, a 15,} a ¹⁶ and ^{a 17} are each independently And may be unsubstituted or substituted by a fluorine atom, a chlorine atom, a linear or branched alkyl group having 1 to 4 carbon atoms, or a linear or branched alkoxy group having 1 to 4 carbon atoms. , A 4-phenylene group) is preferable, and the following formulas (X-11a-1) to (X-11a-4)

(Wherein, W ¹¹ , W ¹² , Sp ¹⁴ and Sp ¹⁵ represent the same meaning as in the general formula (X-11a)) are particularly preferable. In the above formulas (X-11a-1) to (X-11a-4), compounds in which Sp ¹⁴ and Sp ¹⁵ are each independently an alkylene group having 2 to 8 carbon atoms are particularly preferable.

  In addition, preferable bifunctional polymerizable compounds include those represented by the following general formulas (X-11b-1) to (X-11b-3):

(Wherein W ¹³ and W ¹⁴ each independently represent a hydrogen atom or a methyl group, and Sp ¹⁶ and Sp ¹⁷ each independently represent an alkylene group having 2 to 18 carbon atoms). Is mentioned. In the above formulas (X-11b-1) to (X-11b-3), compounds in which Sp ¹⁶ and Sp ¹⁷ are each independently an alkylene group having 2 to 8 carbon atoms are particularly preferable.

  Specific examples of the compound represented by the general formula (X-12) include the following general formula (X-12-1) to formula (X-12-7).

(Wherein P ¹⁴ represents a polymerizable group, and Sp ¹⁸ represents a single bond or an alkylene group having 1 to 20 carbon atoms, but one —CH ₂ — or two or more non-adjacent — CH ₂ — may be replaced by —O—, —COO—, —OCO—, —O—CO—O—, and X ¹⁶ represents a single bond, —O—, —COO—, or —OCO—. , Z ¹⁵ represents a single bond, —COO— or —OCO—, and L ¹¹ is independently a fluorine atom, a chlorine atom, one —CH ₂ — or two or more —CH ₂ — that are not adjacent to each other. Te -O -, - COO -, - OCO- the replaced represents a linear or branched alkyl group from a good 1 -C even of 10, s11 represents an integer from 0 ^{4, R 12} represents hydrogen Atom, fluorine atom, chlorine atom, cyano group, nitro group, one —CH ₂ — or Two or more non-adjacent —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 = CH-, -CF = CF- or -C≡C- represents a linear or branched alkyl group having 1 to 20 carbon atoms which may be substituted. It is done.

  The compound represented by the general formula (ID) obtained by the production method of the present invention contains a polymerizable liquid crystal composition having liquid crystallinity to such an extent that the liquid crystallinity of the composition is not significantly impaired. It is also possible to add polymerizable compounds not shown. 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 represented by the general formula (ID) obtained by the production method of the present invention can be polymerized without using a photopolymerization initiator. You may add. 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 with respect to the compound represented by the general formula (ID). 0.4 mass% to 8 mass% 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), benzoic acid [1- [4- (phenylthio) benzoyl] heptylidene]. Amino (IRGACURE OXE 01) etc. are mentioned. Examples of the thermal polymerization initiator include azo compounds and peroxides. Specific examples of the thermal polymerization initiator include 2,2'-azobis (4-methoxy-2,4-dimethylvaleronitrile), 2,2'-azobis (isobutyronitrile) and the like. 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 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 (X-13-1) to the formula (X-13-35)

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

  In addition, the polymerizable liquid crystal composition containing the compound represented by the general formula (ID) obtained by the production method of the present invention is converted into films, optical elements, functional pigments, pharmaceuticals, cosmetics, When used for applications such as coating agents and synthetic resins, metals, metal complexes, dyes, pigments, pigments, fluorescent materials, phosphorescent materials, surfactants, leveling agents, thixotropic agents, gels are used depending on the purpose. Agents, polysaccharides, ultraviolet absorbers, infrared absorbers, antioxidants, ion exchange resins, metal oxides such as titanium oxide, and the like can also be added.

The polymer obtained by polymerizing the polymerizable liquid crystal composition containing the compound represented by formula (ID) obtained by the production method of the present invention can be used for various applications. For example, the polymer obtained by polymerizing the polymerizable liquid crystal composition containing the compound represented by the general formula (ID) without being oriented is a light scattering plate, a depolarizing plate, a moire fringe prevention plate. Is available as 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 represented by the general formula (ID) with a cloth, a substrate on which an organic thin film is formed, or SiO ₂ can be produced by polymerizing the polymerizable liquid crystal composition after it is supported on a substrate having an orientation film obliquely deposited or sandwiched between the 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 represented by the general formula (ID) is polymerized, it is desirable that the polymerization proceeds rapidly. Therefore, by irradiating active energy rays such as ultraviolet rays or electron beams A polymerization method is preferred. 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”. When handling a substance unstable to oxygen and / or moisture in each step, it is preferable to work in an inert gas such as nitrogen gas or argon gas. In addition to the operations specifically described below, as necessary, operations such as quenching, separation / extraction, neutralization, washing, separation, purification, drying, concentration, etc. that are commonly performed among those skilled in the art May be performed.
(GC analysis conditions)
Column: Agilent Technologies, J & W Column DB-1HT, 15 m × 0.25 mm × 0.10 μm
Temperature program: 100 ° C (1 minute)-(20 ° C / minute)-250 ° C-(10 ° C / minute)-380 ° C-(7 ° C / minute)-400 ° C (2.64 minutes)
Inlet temperature: 350 ° C
Detector temperature: 400 ° C
(UPLC analysis conditions)
Column: Waters ACQUITY UPLC BEH C18, 2.1 × 100 mm, 1.7 μm
Elution solvent: acetonitrile / water (90:10), acetonitrile / water (85:15), 0.1% formic acid-acetonitrile / water (90:10) or 0.1% formic acid-acetonitrile / water (70:30)
Flow rate: 0.4 mL / min
Detector: UV (PDA)
Column oven: 40 ° C
Example 1-1 Production of Compound Represented by Formula (C-1)

In a reaction vessel equipped with a Dean-Stark apparatus and a condenser, 10.0 g of the compound represented by the formula (C-1-1), 15.3 g of the compound represented by the formula (C-1-2), 200 mL of toluene, concentrated 1 mL of sulfuric acid was added, and the mixture was heated to reflux for 30 hours while removing water. After the solvent was distilled off, the obtained solid was dispersed and washed with acetonitrile. By drying, 21.2 g of a compound represented by the formula (C-1) was obtained.
LC-MS: 261 [M + 1]
Example 1-2 Production of Compound Represented by Formula (C-2A)

10.0 g of the compound represented by the formula (C-2A-1), 11.1 g of the compound represented by the formula (C-2A-2), p-toluenesulfone, in a reaction vessel equipped with a Dean-Stark apparatus and a condenser. 3.1 g of acid monohydrate and 200 mL of xylene were added, and the mixture was heated to reflux for 30 hours while removing water. After cooling, the solid was filtered and washed with cooled methanol. By drying, 18.1 g of a compound represented by the formula (C-2A) was obtained.
LC-MS: 245 [M + 1]
(Example 1-3) Production of compound represented by formula (C-2B)

  Under a nitrogen atmosphere, 10.0 g of the compound represented by the formula (C-2B-2) and 50 mL of thionyl chloride were added to the reaction vessel, and the mixture was heated and stirred at 60 ° C. for 5 hours. By distilling off thionyl chloride, an acid chloride of the compound represented by the formula (C-2B-2) was obtained. Under a nitrogen atmosphere, 6.9 g of a compound represented by the formula (C-2B-1), 60 mL of dichloromethane, and 5.3 g of pyridine were added to the reaction vessel. A solution prepared by dissolving the acid chloride of the compound represented by the formula (C-2B-2) in 20 mL of dichloromethane was added dropwise with ice cooling, and the mixture was stirred at room temperature for 5 hours. The reaction solution was washed with 5% hydrochloric acid, water and brine. By distilling off the solvent and drying, 15.1 g of a compound represented by the formula (C-2B-3) was obtained.

To the reaction vessel were added 15.1 g of the compound represented by the formula (C-2B-3), 150 mL of methanol, 50 mL of water, and 17 mL of 25% aqueous sodium hydroxide solution, and the mixture was stirred at room temperature for 8 hours. The reaction mixture was poured into 5% hydrochloric acid and extracted with ethyl acetate. The solvent was distilled off and dried to obtain 11.8 g of a compound represented by the formula (C-2B).
LC-MS: 245 [M + 1]
(Example 1-4) Production of compound represented by formula (C-2C)

  10.0 g of the compound represented by the formula (C-2C-1), 18.4 g of the compound represented by the formula (C-2C-2), p-toluenesulfone, in a reaction vessel equipped with a Dean-Stark apparatus and a condenser. 3.1 g of acid monohydrate and 200 mL of xylene were added, and the mixture was heated to reflux for 30 hours while removing water. After cooling, the solid was filtered and washed with cooled methanol. By drying, 25.6 g of a compound represented by the formula (C-2C-3) was obtained.

To the autoclave were added 25.6 g of the compound represented by the formula (C-2C-3), 300 mL of tetrahydrofuran, 150 mL of ethanol, and 0.3 g of 5% palladium carbon, and the mixture was heated and stirred at a hydrogen pressure of 0.5 MPa and 50 ° C. for 5 hours. After removing the palladium carbon, the solvent was distilled off and dried to obtain 17.8 g of a compound represented by the formula (C-2C).
LC-MS: 245 [M + 1]
(Example 1-5) Production of compound represented by formula (C-2D)

  Under a nitrogen atmosphere, 10.0 g of the compound represented by the formula (C-2D-1), 0.2 g of pyridinium p-toluenesulfonate, and 100 mL of dichloromethane were added to the reaction vessel. While cooling with ice, 6.6 g of 3,4-dihydro-2H-pyran was added dropwise and stirred at room temperature for 8 hours. After sequentially washing with a saturated aqueous sodium hydrogen carbonate solution and brine, the solvent was distilled off to obtain 14.8 g of a compound represented by the formula (C-2D-2).

  To the reaction vessel were added 14.8 g of the compound represented by the formula (C-2D-2), 150 mL of methanol, 50 mL of water, and 20 mL of 25% aqueous sodium hydroxide solution, and the mixture was stirred at room temperature for 3 hours. The pH of the reaction solution was adjusted to 4.0, and extracted with ethyl acetate. By distilling off the solvent and drying, 13.2 g of a compound represented by the formula (C-2D-3) was obtained.

  Under a nitrogen atmosphere, 13.6 g of methanesulfonyl chloride and 30 mL of tetrahydrofuran were added to the reaction vessel. A solution prepared by dissolving 13.2 g of the compound represented by the formula (C-2D-3) and 15.3 g of diisopropylethylamine in 50 mL of tetrahydrofuran was added dropwise with ice cooling, and the mixture was stirred at room temperature for 1 hour. A solution prepared by dissolving 15.3 g of diisopropylethylamine and 7.4 g of the compound represented by the formula (C-2D-4) in 50 mL of tetrahydrofuran and 0.7 g of 4-dimethylaminopyridine were added, and the mixture was stirred at room temperature for 5 hours. The reaction mixture was poured into water and extracted with ethyl acetate. By distilling off the solvent and drying, 18.3 g of a compound represented by the formula (C-2D-5) was obtained.

To the reaction vessel, 18.3 g of the compound represented by the formula (C-2D-5), 180 mL of methanol, and 1 mL of concentrated hydrochloric acid were added and stirred at room temperature for 5 hours. Water was added and extracted with ethyl acetate. By distilling off the solvent and drying, 13.2 g of a compound represented by the formula (C-2D) was obtained.
LC-MS: 245 [M + 1]
(Example 1-6) Production of compound represented by formula (C-3)

10.0 g of the compound represented by the formula (C-3-1), 13.8 g of the compound represented by the formula (C-3-2), and p-toluenesulfone in a reaction vessel equipped with a Dean-Stark apparatus and a condenser. Pyridinium acid 2.3 g and xylene 200 mL were added, and the mixture was heated to reflux for 30 hours while removing water. After cooling, the solid was filtered and washed with cooled methanol. By drying, 21.1 g of a compound represented by the formula (C-3) was obtained.
LC-MS: 245 [M + 1]
(Example 1-7) Production of compound represented by formula (C-4)

In a reaction vessel equipped with a Dean-Stark apparatus and a condenser, 10.0 g of the compound represented by the formula (C-4-1), 15.2 g of the compound represented by the formula (C-4-2), and 0.1% phosphoric acid. 8 g and 150 mL of mesitylene were added, and the mixture was heated to reflux for 20 hours while removing water. After cooling, the solid was filtered and dispersed and washed with water. By drying, 21.8 g of a compound represented by the formula (C-4) was obtained.
LC-MS: 295 [M + 1]
(Example 1-8) Production of compound represented by formula (C-5)

In a reaction vessel equipped with a Dean-Stark apparatus and a condenser, 10.0 g of the compound represented by the formula (C-5-1), 3.8 g of the compound represented by the formula (C-5-2), 200 mL of toluene, concentrated 1.0 g of sulfuric acid was added, and the mixture was heated to reflux for 40 hours while removing water. After cooling, the solid was filtered and washed with cooled methanol. By drying, 12.4 g of a compound represented by the formula (C-5) was obtained.
LC-MS: 483 [M + 1]
(Example 1-9) Production of compound represented by formula (C-6)

Under a nitrogen atmosphere, 10.0 g of a compound represented by the formula (C-6-2) and 50 mL of thionyl chloride were added to the reaction vessel, and the mixture was heated and stirred at 60 ° C. for 3 hours. By distilling off thionyl chloride, an acid chloride of the compound represented by the formula (C-6-2) was obtained. Under a nitrogen atmosphere, 9.4 g of the compound represented by the formula (C-6-1), 8.1 g of pyridine, and 100 mL of dichloromethane were added to the reaction vessel. A solution prepared by dissolving the acid chloride of the compound represented by the formula (C-6-2) in 30 mL of dichloromethane was added dropwise with ice cooling, and the mixture was stirred at room temperature for 5 hours. The reaction mixture was poured into water and extracted with ethyl acetate. By purification by column chromatography (silica gel, dichloromethane / ethyl acetate), 11.0 g of the compound represented by the formula (C-6) was obtained.
LC-MS: 359 [M + 1]
(Example 1-10) Production of compound represented by formula (C-7)

In a reaction vessel equipped with a Dean-Stark apparatus and a condenser, 10.0 g of the compound represented by the formula (C-7-1), 9.5 g of the compound represented by the formula (C-7-2), 200 mL of cyclohexane, concentrated 0.4 g of sulfuric acid was added, and the mixture was heated to reflux for 60 hours while removing water. After cooling, the solid was filtered and dispersed and washed with water. By drying, 14.6 g of a compound represented by the formula (C-7) was obtained.
LC-MS: 279 [M + 1]
(Example 1-11) Production of compound represented by formula (C-8)

In a reaction vessel equipped with a Dean-Stark apparatus and a condenser, 10.0 g of the compound represented by the formula (C-8-1), 13.9 g of the compound represented by the formula (C-8-2), 200 mL of mesitylene, concentrated 1.0 g of sulfuric acid was added, and the mixture was heated to reflux for 60 hours while removing water. After cooling, the solid was filtered and dispersed and washed with water. By drying, 20.5 g of a compound represented by the formula (C-8) was obtained.
LC-MS: 365 [M + 1]
(Example 1-12) Production of compound represented by formula (C-9)

Under a nitrogen atmosphere, 10.0 g of the compound represented by the formula (C-9-1), 13.3 g of the compound represented by the formula (C-9-2), 0.8 g of 4-dimethylaminopyridine, 100 mL of dichloromethane was added. Diisopropylcarbodiimide (13.1 g) was added dropwise and stirred at room temperature for 6 hours. After sequentially washing with 5% hydrochloric acid, water and brine, purification by column chromatography (silica gel, dichloromethane / ethyl acetate) gave 15.4 g of the compound represented by the formula (C-9).
LC-MS: 319 [M + 1]
(Example 1-13) Production of compound represented by formula (C-10)

  Under a nitrogen atmosphere, 10.0 g of the compound represented by the formula (C-10-1), 0.7 g of pyridinium p-toluenesulfonate, and 100 mL of dichloromethane were added to the reaction vessel. While cooling with ice, 5.1 g of 3,4-dihydro-2H-pyran was added dropwise and stirred at room temperature for 8 hours. After sequentially washing with a saturated aqueous sodium hydrogen carbonate solution and brine, the solvent was distilled off to obtain 14.1 g of a compound represented by the formula (C-10-2).

  To the reaction vessel, 14.1 g of the compound represented by the formula (C-10-2), 150 mL of methanol, 50 mL of water, and 17 mL of 25% aqueous sodium hydroxide solution were added and stirred at room temperature for 3 hours. The pH of the reaction solution was adjusted to 4.0, and extracted with ethyl acetate. By distilling off the solvent and drying, 12.8 g of a compound represented by the formula (C-10-3) was obtained.

  Under a nitrogen atmosphere, 8.8 g of methanesulfonyl chloride and 30 mL of tetrahydrofuran were added to the reaction vessel. A solution prepared by dissolving 12.8 g of the compound represented by the formula (C-10-3) and 13.2 g of diisopropylethylamine in 50 mL of tetrahydrofuran was added dropwise with ice cooling, and the mixture was stirred at room temperature for 1 hour. A solution prepared by dissolving 13.2 g of diisopropylethylamine and 8.7 g of the compound represented by the formula (C-10-4) in 50 mL of tetrahydrofuran and 0.6 g of 4-dimethylaminopyridine were added, and the mixture was stirred at room temperature for 5 hours. The reaction mixture was poured into water and extracted with ethyl acetate. By distilling off the solvent and drying, 19.6 g of a compound represented by the formula (C-10-5) was obtained.

To the reaction vessel were added 19.6 g of the compound represented by the formula (C-10-5), 200 mL of methanol, and 0.5 mL of concentrated hydrochloric acid, and the mixture was stirred at room temperature for 5 hours. Water was added and extracted with ethyl acetate. The solvent was distilled off and dried to obtain 14.7 g of a compound represented by the formula (C-10).
LC-MS: 319 [M + 1]
By a method similar to that of Example 1-1, the compound represented by the general formula (IC) from the compound represented by the general formula (IA) and the compound represented by the general formula (IB) in the following table is used. The resulting compound was prepared.

(Example 2-1) Production of compound represented by formula (D-1)

  Under a nitrogen atmosphere, 20.0 g of the compound represented by the formula (D-1-1), 8.8 g of tert-butyl alcohol, 1.3 g of 4-dimethylaminopyridine, and 100 mL of dichloromethane were added to the reaction vessel. While cooling with ice, 16.3 g of diisopropylcarbodiimide was added dropwise and stirred at room temperature for 8 hours. The precipitate was removed by filtration, and the filtrate was washed successively with 5% hydrochloric acid and brine. Purification was performed by column chromatography (silica gel, dichloromethane) to obtain 20.8 g of a compound represented by the formula (D-1-2).

  20.8 g of the compound represented by the formula (D-1-2), 200 mL of methanol, and 30 mL of 25% aqueous sodium hydroxide solution were added to the reaction vessel, and the mixture was heated and stirred at 60 ° C. Cool and add chloroform. 10% hydrochloric acid was added to adjust the pH of the aqueous layer to 4 to 5, followed by liquid separation treatment. The organic layer was washed with brine and dried over sodium sulfate. The insoluble material was filtered through celite, and the solvent was evaporated and dried to obtain 17.7 g of a compound represented by the formula (D-1-3).

  In a reaction vessel, 5.0 g of the compound represented by the formula (D-1-3), 4.2 g of the compound represented by the formula (D-1-4), 4.5 g of potassium carbonate, 20 mL of N, N-dimethylformamide. And heated and stirred at 90 ° C. for 8 hours. Dilute with dichloromethane and wash with water. Purification was performed by column chromatography (silica gel, dichloromethane / hexane) to obtain 6.7 g of a compound represented by the formula (D-1-5).

  To the reaction vessel was added 6.7 g of the compound represented by the formula (D-1-5), 25 mL of dichloromethane, and 15 mL of formic acid, and the mixture was heated at 40 ° C. for 8 hours. After the solvent was distilled off, it was diluted with ethyl acetate and washed with water and brine. Purification was performed by column chromatography (alumina, ethyl acetate) to obtain 4.6 g of a compound represented by the formula (D-1-6).

Under a nitrogen atmosphere, 3.0 g of the compound represented by the formula (D-1-6) in a reaction vessel, 1.2 g of the compound represented by the formula (C-1) produced in Example 1-1, 4-dimethyl 0.1 g of aminopyridine and 40 mL of dichloromethane were added. While cooling with ice, 1.4 g of diisopropylcarbodiimide was added dropwise and stirred at room temperature for 10 hours. The precipitate was removed by filtration, and the filtrate was washed successively with 1% hydrochloric acid, water and brine. After recrystallization (dichloromethane / methanol), purification was performed by column chromatography (silica gel, dichloromethane) and recrystallization (dichloromethane / methanol) to obtain 3.2 g of a compound represented by the formula (D-1). . The obtained compound had a purity of 99.631% (impurity content represented by formula (C-1) 0.001%, impurity content represented by formula (F1-1) and formula (F2-1)) 0.020%).
LC-MS: 877 [M + 1]
(Example 2-2) Production of compound represented by formula (D-2)

Under a nitrogen atmosphere, in a reaction vessel, 2.0 g of the compound represented by the formula (C-4) produced in Example 1-7, 4.0 g of the compound represented by the formula (D-2-1), 4-dimethyl 0.1 g of aminopyridine and 40 mL of dichloromethane were added. While cooling with ice, 2.1 g of diisopropylcarbodiimide was added dropwise and stirred at room temperature for 10 hours. The precipitate was removed by filtration, and the filtrate was washed successively with 1% hydrochloric acid, water and brine. After recrystallization (dichloromethane / methanol), purification was performed by column chromatography (silica gel, dichloromethane) and recrystallization (dichloromethane / methanol) to obtain 4.6 g of a compound represented by the formula (D-2). . The resulting compound has a purity of 98.644% (impurity content represented by formula (C-4) 0.006%, impurity content represented by formula (F1-2) and formula (F2-2)) 0.120%).
LC-MS: 843 [M + 1]
(Example 2-3) Production of a compound represented by the formula (D-3)

Under a nitrogen atmosphere, in a reaction vessel, 2.0 g of the compound represented by the formula (C-3) produced in Example 1-6, 4.1 g of the compound represented by the formula (D-3-1), 4-dimethyl 0.1 g of aminopyridine and 30 mL of dichloromethane were added. While cooling with ice, 2.3 g of diisopropylcarbodiimide was added dropwise and stirred at room temperature for 10 hours. The precipitate was removed by filtration, and the filtrate was washed successively with 1% hydrochloric acid, water and brine. After recrystallization (dichloromethane / methanol), purification was performed by column chromatography (silica gel, dichloromethane) and recrystallization (dichloromethane / methanol) to obtain 4.6 g of a compound represented by the formula (D-3). .
LC-MS: 709 [M + 1]
(Example 2-4) Production of compound represented by formula (D-4)

In a reaction vessel, 4.0 g of the compound represented by the formula (C-5) produced in Example 1-8, 3.6 g of the compound represented by the formula (D-4-1), 8.1 g of cesium carbonate, dimethyl 40 mL of sulfoxide was added, and the mixture was heated and stirred at 80 ° C. for 8 hours. Diluted with dichloromethane and washed sequentially with water and brine. By purification by column chromatography (silica gel, dichloromethane), 5.2 g of the compound represented by the formula (D-4) was obtained.
LC-MS: 791 [M + 1]
(Example 2-5) Production of compound represented by formula (D-5)

  10.0 g of the compound represented by the formula (D-5-1), 7.9 g of 2-fluoroacrylic acid, 0.8 g of p-toluenesulfonic acid monohydrate in a reaction vessel equipped with a Dean-Stark apparatus and a condenser. Then, 150 mL of toluene was added, and the mixture was heated to reflux for 8 hours while removing water. After washing with a saturated aqueous sodium hydrogen carbonate solution and brine, the solvent was distilled off to obtain 15.2 g of a compound represented by the formula (D-5-2).

  In a reaction vessel, 5.3 g of the compound represented by the formula (D-5-2), 3.0 g of the compound represented by the formula (D-5-3), 5.1 g of potassium carbonate, 30 mL of N, N-dimethylformamide And heated and stirred at 90 ° C. for 10 hours. Diluted with dichloromethane and washed with water and brine. Purification was performed by column chromatography (silica gel, dichloromethane / hexane) to obtain 6.2 g of a compound represented by the formula (D-5-4).

  An aqueous solution in which 6.2 g of the compound represented by the formula (D-5-4), 80 mL of methanol, and 2.5 g of sodium dihydrogen phosphate dihydrate are dissolved in 30 mL of water in a reaction vessel, 30% aqueous hydrogen peroxide 5.0 g was added. An aqueous solution in which 5.0 g of sodium chlorite was dissolved in 50 mL of water was dropped, and the mixture was heated and stirred at 45 ° C. for 5 hours. Water was added and the precipitated solid was filtered and washed with water. By drying, 5.9 g of a compound represented by the formula (D-5-5) was obtained.

Under a nitrogen atmosphere, 5.9 g of the compound represented by the formula (D-5-5), 100 mL of dichloromethane, and 0.1 g of N, N-dimethylformamide were added to the reaction vessel. 3.8 g of oxalyl chloride was added dropwise and stirred with heating at 40 ° C. for 5 hours. After the solvent was distilled off, 3.1 g of pyridine and 20 mL of dichloromethane were added. While cooling with ice, 3.6 g of the compound represented by (C-6) produced in Example 1-9 was added, and the mixture was stirred at room temperature for 8 hours. The reaction mixture was poured into 5% hydrochloric acid and extracted with dichloromethane. By purification by column chromatography (silica gel, dichloromethane) and recrystallization (dichloromethane / methanol), 7.3 g of a compound represented by the formula (D-5) was obtained.
LC-MS: 919 [M + 1]
(Example 2-6) Production of compound represented by formula (D-6)

  Under a nitrogen atmosphere, 10.0 g of the compound represented by the formula (D-6-1), 7.4 g of propiolic acid, 1.3 g of 4-dimethylaminopyridine, and 100 mL of dichloromethane were added to the reaction vessel. While cooling with ice, 14.7 g of diisopropylcarbodiimide was added dropwise and stirred at room temperature for 10 hours. The precipitate was removed by filtration, and the filtrate was washed successively with 1% hydrochloric acid, water and brine. Purification was performed by distillation under reduced pressure to obtain 10.9 g of a compound represented by the formula (D-6-2).

  In a reaction vessel, 2.0 g of the compound represented by the formula (D-6-2), 3.8 g of the compound represented by (C-7) produced in Example 1-10, 2.8 g of potassium carbonate, N, 30 mL of N-dimethylformamide was added and the mixture was heated and stirred at 90 ° C. for 10 hours. Diluted with dichloromethane and washed with water and brine. Purification was performed by column chromatography (silica gel, dichloromethane / hexane) to obtain 3.7 g of a compound represented by the formula (D-6-3).

  In a reaction vessel equipped with a Dean-Stark apparatus, 20.0 g of the compound represented by the formula (D-6-4), 28.4 g of 2-trifluoromethylacrylic acid, 1.8 g of p-toluenesulfonic acid monohydrate, Cyclohexane 300 mL and diisopropyl ether 150 mL were added. The mixture was heated to reflux for 12 hours while removing water. Diluted with dichloromethane and washed successively with 5% aqueous sodium bicarbonate and brine. Purification was performed by column chromatography (silica gel, dichloromethane) to obtain 34.0 g of a compound represented by the formula (D-6-5).

  11.3 g of a compound represented by the formula (D-6-5), 5.0 g of a compound represented by the formula (D-6-6), 8.5 g of potassium carbonate, 200 mL of N, N-dimethylformamide in a reaction vessel And heated to reflux for 12 hours. After pouring into 5% hydrochloric acid, the mixture was extracted with dichloromethane and washed with brine. Purification was performed by column chromatography (silica gel, dichloromethane) to obtain 10.4 g of a compound represented by the formula (D-6-7).

  10.4 g of a compound represented by the formula (D-6-7), 5.1 g of sodium dihydrogen phosphate dihydrate, 100 mL of methanol, 50 mL of water, and 5.4 mL of 35% hydrogen peroxide water are added to the reaction vessel. It was. A solution prepared by dissolving 4.4 g of sodium chlorite in 20 mL of water was added dropwise, and the mixture was heated and stirred at 60 ° C. for 3 hours. Water was added and cooled, and the precipitate was filtered. The obtained solid was dried to obtain 8.7 g of a compound represented by the formula (D-6-8).

  Under a nitrogen atmosphere, 8.7 g of a compound represented by the formula (D-6-8), 3.2 g of a compound represented by the formula (D-6-9), N, N-dimethylaminopyridine 1 g and 60 mL dichloromethane were added. While cooling with ice, 4.0 g of diisopropylcarbodiimide was added dropwise and stirred at room temperature for 6 hours. The precipitate was removed by filtration, and the filtrate was washed successively with 1% hydrochloric acid, water and brine. Purification was performed by column chromatography (silica gel, dichloromethane) and recrystallization (dichloromethane / methanol) to obtain 9.1 g of a compound represented by the formula (D-6-10).

  9.1 g of the compound represented by the formula (D-6-10), 5.1 g of sodium dihydrogen phosphate dihydrate, 100 mL of methanol, 50 mL of water, and 3.5 mL of 35% hydrogen peroxide water were added to the reaction vessel. It was. A solution prepared by dissolving 3.4 g of sodium chlorite in 15 mL of water was added dropwise, and the mixture was heated and stirred at 60 ° C. for 3 hours. Water was added and cooled, and the precipitate was filtered. The obtained solid was dried to obtain 7.6 g of a compound represented by the formula (D-6-11).

Under a nitrogen atmosphere, 2.0 g of the compound represented by the formula (D-6-11), 1.7 g of the compound represented by the formula (D-6-3), 0.1 g of 4-dimethylaminopyridine, and 30 mL of dichloromethane. added. While cooling with ice, 0.7 g of diisopropylcarbodiimide was added dropwise and stirred at room temperature for 10 hours. The precipitate was removed by filtration, and the filtrate was washed successively with 1% hydrochloric acid, water and brine. After recrystallization (dichloromethane / methanol), purification was performed by column chromatography (silica gel, dichloromethane) and recrystallization (dichloromethane / methanol) to obtain 2.5 g of a compound represented by the formula (D-6). .
LC-MS: 823 [M + 1]
(Example 2-7) Production of compound represented by formula (D-7)

Under a nitrogen atmosphere, in a reaction vessel, 2.0 g of the compound represented by the formula (C-10) produced in Example 1-13, 3.8 g of the compound represented by the formula (D-7-1), 4-dimethyl 0.1 g of aminopyridine and 30 mL of dichloromethane were added. While cooling with ice, 2.0 g of diisopropylcarbodiimide was added dropwise and stirred at room temperature for 10 hours. The precipitate was removed by filtration, and the filtrate was washed successively with 1% hydrochloric acid, water and brine. After recrystallization (dichloromethane / methanol), purification was performed by column chromatography (silica gel, dichloromethane) and recrystallization (dichloromethane / methanol) to obtain 3.9 g of a compound represented by the formula (D-7). .
LC-MS: 895 [M + 1]
(Example 2-8) Production of compound represented by formula (D-8)

To the reaction vessel, 8.4 g of a compound represented by the formula (D-8-1), 42 mg of 2,6-di-tert-butyl-4-methylphenol, 24 mL of ethyl acetate, and 8 mL of N, N-dimethylacetamide were added. . After cooling to 5 ° C., 4.6 g of thionyl chloride was added dropwise, and the mixture was stirred at 5 ° C. for 1 hour. A solution prepared by dissolving 5.0 g of the compound represented by (C-8) produced in Example 1-11 in 25 mL of N, N-dimethylacetamide was added dropwise and stirred at room temperature for 12 hours. The reaction solution was poured into water, extracted with ethyl acetate, and then washed sequentially with 5% hydrochloric acid, water and brine. After drying with sodium sulfate, the solvent was distilled off to obtain 7.3 g of a compound represented by the formula (D-8).
LC-MS: 761 [M + 1]
(Example 2-9) Production of compound represented by formula (D-9)

  A compound represented by the formula (D-9-2) was produced by the method described in Macromolecular Chemistry and Physics, 2009, Vol. 210, No. 7, pp. 531-541. Under a nitrogen atmosphere, 5.0 g of a compound represented by the formula (D-9-1), 7.1 g of a compound represented by the formula (D-9-2), 11.2 g of triphenylphosphine, and 30 mL of tetrahydrofuran were added. . While cooling with ice, 8.0 g of diisopropyl azodicarboxylate was added and stirred at room temperature for 3 hours. After adding water, the mixture was extracted with dichloromethane and washed with brine. Purification was performed by column chromatography (silica gel, dichloromethane) to obtain 8.1 g of a compound represented by the formula (D-9-3).

  To the reaction vessel, 8.1 g of the compound represented by the formula (D-9-3), 5.5 g of sodium dihydrogen phosphate dihydrate, 100 mL of methanol, 50 mL of water, and 5.0 mL of 35% hydrogen peroxide water were added. It was. A solution prepared by dissolving 4.7 g of sodium chlorite in 20 mL of water was added dropwise, and the mixture was stirred with heating at 60 ° C. for 2 hours. Water was added and cooled, and the precipitate was filtered. The obtained solid was dried to obtain 6.7 g of a compound represented by the formula (D-9-4).

  Under a nitrogen atmosphere, 2.0 g of the compound represented by the formula (C-9) produced in Example 1-12, 2.3 g of the compound represented by the formula (D-9-4), and 4-dimethyl were produced in a reaction vessel. 0.1 g of aminopyridine and 30 mL of dichloromethane were added. While cooling with ice, 2.0 g of diisopropylcarbodiimide was added dropwise and stirred at room temperature for 10 hours. The precipitate was removed by filtration, and the filtrate was washed successively with 1% hydrochloric acid, water and brine. Purification was performed by column chromatography (silica gel, dichloromethane / ethyl acetate) and recrystallization (dichloromethane / hexane) to obtain 1.7 g of a compound represented by the formula (D-9-5).

  Under a nitrogen atmosphere, 7.0 g of the compound represented by the formula (D-9-6), 0.7 g of pyridinium p-toluenesulfonate, and 70 mL of dichloromethane were added to the reaction vessel. While cooling with ice, 5.8 g of 3,4-dihydro-2H-pyran was added dropwise and stirred at room temperature for 8 hours. After sequentially washing with 5% aqueous sodium hydrogen carbonate solution and brine, purification was performed by column chromatography (silica gel, dichloromethane) to obtain 10.6 g of a compound represented by the formula (D-9-7).

  Under a nitrogen atmosphere, 6.3 g of the compound represented by the formula (D-9-8), 30 mL of tetrahydrofuran and 1.9 g of sodium hydride were added to the reaction vessel and stirred. A solution prepared by dissolving 10.6 g of the compound represented by the formula (D-9-7) in 20 mL of tetrahydrofuran was added dropwise with ice cooling, and the mixture was heated and stirred at 50 ° C. for 8 hours. After pouring into water, the mixture was extracted with dichloromethane and washed with brine. Purification was performed by column chromatography (silica gel, dichloromethane) to obtain 8.1 g of a compound represented by the formula (D-9-9).

  To the reaction vessel, 80 mL of formic acid, 80 mL of dichloromethane, and 10 mL of 35% hydrogen peroxide were added and stirred. While cooling with ice, a solution prepared by dissolving 8.1 g of the compound represented by the formula (D-9-9) in 16 mL of dichloromethane was dropped, and the mixture was heated and stirred at 40 ° C. for 10 hours. After adding an aqueous sodium sulfite solution, the mixture was extracted with dichloromethane and washed successively with water and brine. Purification was performed by column chromatography (silica gel, dichloromethane) to obtain 7.7 g of a compound represented by the formula (D-9-10).

  7.7 g of the compound represented by the formula (D-9-10), 30 mL of methanol, 30 mL of tetrahydrofuran, and 5 mL of concentrated hydrochloric acid were added to the reaction vessel, and the mixture was heated and stirred at 50 ° C. for 8 hours. After dilution with ethyl acetate, the mixture was washed successively with water and brine. Purification was performed by column chromatography (silica gel, hexane / ethyl acetate) to obtain 4.4 g of a compound represented by the formula (D-9-11).

Under a nitrogen atmosphere, 1.7 g of the compound represented by the formula (D-9-5), 0.5 g of the compound represented by the formula (D-9-11), 0.9 g of triphenylphosphine, and 20 mL of tetrahydrofuran were added. . While cooling with ice, 0.6 g of diisopropyl azodicarboxylate was added and stirred at room temperature for 3 hours. After adding water, the mixture was extracted with dichloromethane and washed with brine. Purification was performed by column chromatography (silica gel, dichloromethane) to obtain 1.5 g of a compound represented by the formula (D-9).
LC-MS: 863 [M + 1]
(Example 2-10) Production of compound represented by formula (D-10A)

Under a nitrogen atmosphere, 1.0 g of methanesulfonyl chloride, 5 mL of tetrahydrofuran, and 10 mg of 2,6-di-tert-butyl-4-methylphenol were added to the reaction vessel. The solution was cooled to −5 ° C., a solution of 2.0 g of the compound represented by the formula (D-10A-1) dissolved in 10 mL of tetrahydrofuran and 1.3 g of diisopropylethylamine were added dropwise, and the mixture was stirred at −5 ° C. for 1 hour. 9 mL of a tetrahydrofuran solution of 1.8 g of the compound represented by the formula (C-2A) produced in Example 1-2, 1.3 g of diisopropylethylamine and 10 mg of 4-dimethylaminopyridine were added, and the mixture was stirred at room temperature for 2 hours. The reaction mixture was poured into water and extracted with dichloromethane. Purification was performed by column chromatography (silica gel, dichloromethane) and recrystallization (dichloromethane / methanol) to obtain 4.5 g of a compound represented by the formula (D-10A). The resulting multi-compound has a purity of 99.431% (impurity content represented by the formula (C-2A) 0.002%, impurity content represented by the formulas (F1-10) and (F2-10)) 0.012%).
¹ H NMR (CDCl ₃ ) δ 1.8-2.0 (m, 8H), 2.3 (s, 3H), 4.2-4.5 (m, 8H), 5.8 (m, 2H) ), 6.1 (m, 2H), 6.4 (m, 2H), 6.9-7.0 (m, 4H), 7.1-7.2 (m, 3H), 7.3 7.4 (m, 2H), 8.1-8.2 (m, 4H), 8.2-8.3 (m, 2H) ppm.
LC-MS: 737 [M + 1]
(Example 2-11) Production of compound represented by formula (D-10B)

In Example 2-10, the compound represented by formula (C-2A) is represented by formula (D-10A-1) to the compound represented by formula (C-2B) produced in Example 1-3. The compound represented by the formula (D-10B) was produced by the same method except that the compound represented by the formula (D-10B-1) was replaced. The resulting compound had a purity of 99.211% (impurity content of 0.004% represented by formula (C-2B), impurity content represented by formula (F1-10) and formula (F2-10)) 0.030%).
(Example 2-12) Production of compound represented by formula (D-10C)

In Example 2-10, the compound represented by the formula (C-2A) produced in Example 1-4 was represented by the formula (D-10A-1). The compound represented by the formula (D-10C) was produced by the same method except that the compound represented by the formula (D-10C-1) was replaced. The resulting compound had a purity of 98.735% (impurity content represented by formula (C-2C) 0.005%, impurity content represented by formula (F1-10) and formula (F2-10)) 0.054%).
(Example 2-13) Production of compound represented by formula (D-10D)

The compound represented by the formula (C-2A) produced in Example 1-5 in the compound represented by the formula (C-2A) in Example 2-10 is represented by the formula (D-10A-1). The compound represented by the formula (D-10D) was produced by the same method except that the compound represented by the formula (D-10D-1) was replaced. The resulting compound had a purity of 97.892% (impurity content of 0.011% represented by formula (C-2D), impurity content represented by formula (F1-10) and formula (F2-10)) 0.034%).
(Comparative Example 2-1) Production of compound represented by formula (D-1R)

  Under a nitrogen atmosphere, 2.0 g of the compound represented by the formula (D-1R-1), 1.2 g of the compound represented by the formula (D-1R-2), 0.1 g of 4-dimethylaminopyridine, 30 mL of dichloromethane was added. While cooling with ice, 1.0 g of diisopropylcarbodiimide was added dropwise and stirred at room temperature for 10 hours. The precipitate was removed by filtration, and the filtrate was washed successively with 1% hydrochloric acid, water and brine. Purification was performed by column chromatography (alumina, dichloromethane / hexane) to obtain 2.5 g of a compound represented by the formula (D-1R-3).

  To the reaction vessel were added 2.5 g of the compound represented by the formula (D-1R-3), 8 mL of tetrahydrofuran, 8 mL of methanol, and 0.1 mL of concentrated hydrochloric acid, and the mixture was stirred at room temperature for 5 hours. Water was added to the reaction mixture, and the mixture was extracted with ethyl acetate. Purification was performed by column chromatography (silica gel, dichloromethane / ethyl acetate) to obtain 1.8 g of a compound represented by the formula (D-1R-4).

  Under a nitrogen atmosphere, 1.0 g of methanesulfonyl chloride, 5 mL of tetrahydrofuran, and 10 mg of 2,6-di-tert-butyl-4-methylphenol were added to the reaction vessel. The mixture was cooled to −5 ° C., a solution of 2.2 g of the compound represented by the formula (D-1R-5) dissolved in 10 mL of tetrahydrofuran and 1.3 g of diisopropylethylamine were added dropwise, and the mixture was stirred at −5 ° C. for 1 hour. A tetrahydrofuran solution (9 mL) containing 1.0 g of the compound represented by the formula (D-1R-6), diisopropylethylamine (1.3 g) and 4-dimethylaminopyridine (10 mg) were added, and the mixture was stirred at room temperature for 2 hours. The reaction mixture was poured into water and extracted with dichloromethane. Purification was performed by column chromatography (silica gel, dichloromethane) and recrystallization (dichloromethane / methanol) to obtain 2.5 g of a compound represented by the formula (D-1R-7).

  To the reaction vessel was added 2.5 g of the compound represented by the formula (D-1R-7), 2.0 g of sodium dihydrogen phosphate dihydrate, 25 mL of methanol, 20 mL of water, and 2.5 mL of 35% hydrogen peroxide solution. It was. A solution prepared by dissolving 4.7 g of sodium chlorite in 20 mL of water was added dropwise, and the mixture was stirred with heating at 60 ° C. for 2 hours. Water was added and cooled, and the precipitate was filtered. The obtained solid was dried to obtain 2.3 g of a compound represented by the formula (D-1R-8).

Under a nitrogen atmosphere, 1.0 g of methanesulfonyl chloride, 5 mL of tetrahydrofuran, and 10 mg of 2,6-di-tert-butyl-4-methylphenol were added to the reaction vessel. The solution was cooled to −5 ° C., a solution obtained by dissolving 2.3 g of the compound represented by the formula (D-1R-8) in 10 mL of tetrahydrofuran and 1.3 g of diisopropylethylamine were added dropwise, and the mixture was stirred at −5 ° C. for 1 hour. 9 mL of a tetrahydrofuran solution of 2.0 g of the compound represented by the formula (D-1R-4), 1.3 g of diisopropylethylamine, and 10 mg of 4-dimethylaminopyridine were added, and the mixture was stirred at room temperature for 2 hours. The reaction mixture was poured into water and extracted with dichloromethane. Purification was performed by column chromatography (silica gel, dichloromethane) and recrystallization (dichloromethane / methanol) to obtain 2.5 g of a compound represented by the formula (D-1R). Purity 94.322%
(Comparative Example 2-2) Production of compound represented by formula (D-2R)

  Under a nitrogen atmosphere, 1.0 g of methanesulfonyl chloride, 5 mL of tetrahydrofuran, and 10 mg of 2,6-di-tert-butyl-4-methylphenol were added to the reaction vessel. The solution was cooled to −5 ° C., a solution prepared by dissolving 2.0 g of the compound represented by the formula (D-2R-1) in 10 mL of tetrahydrofuran and 1.3 g of diisopropylethylamine were added dropwise, and the mixture was stirred at −5 ° C. for 1 hour. 4 mL of a tetrahydrofuran solution of 0.8 g of the compound represented by the formula (D-2R-2), 1.3 g of diisopropylethylamine, and 10 mg of 4-dimethylaminopyridine were added, and the mixture was stirred at room temperature for 2 hours. The reaction mixture was poured into 5% hydrochloric acid and extracted with ethyl acetate. Purification was performed by column chromatography (silica gel, ethyl acetate) to obtain 2.1 g of a compound represented by the formula (D-2R-3).

  Under a nitrogen atmosphere, 1.0 g of methanesulfonyl chloride, 5 mL of tetrahydrofuran, and 10 mg of 2,6-di-tert-butyl-4-methylphenol were added to the reaction vessel. The solution was cooled to −5 ° C., a solution of 2.0 g of the compound represented by the formula (D-2R-4) dissolved in 10 mL of tetrahydrofuran and 1.3 g of diisopropylethylamine were added dropwise and stirred at −5 ° C. for 1 hour. 9 mL of a tetrahydrofuran solution of 1.2 g of the compound represented by the formula (D-2R-5), 1.3 g of diisopropylethylamine and 10 mg of 4-dimethylaminopyridine were added, and the mixture was stirred at room temperature for 2 hours. The reaction mixture was poured into water and extracted with dichloromethane. Purification was performed by column chromatography (silica gel, dichloromethane) and recrystallization (dichloromethane / methanol) to obtain 2.4 g of a compound represented by the formula (D-2R-6).

  To the reaction vessel, 2.4 g of the compound represented by the formula (D-2R-6), 3.0 g of sodium dihydrogen phosphate dihydrate, 30 mL of methanol, 20 mL of water, and 3.0 mL of 35% hydrogen peroxide water were added. It was. A solution prepared by dissolving 3.0 g of sodium chlorite in 10 mL of water was added dropwise, and the mixture was heated and stirred at 60 ° C. for 2 hours. Water was added and cooled, and the precipitate was filtered. The obtained solid was dried to obtain 2.3 g of a compound represented by the formula (D-2R-7).

Under a nitrogen atmosphere, 0.8 g of methanesulfonyl chloride, 5 mL of tetrahydrofuran, and 10 mg of 2,6-di-tert-butyl-4-methylphenol were added to the reaction vessel. The solution was cooled to −5 ° C., a solution of 1.8 g of the compound represented by the formula (D-2R-7) dissolved in 10 mL of tetrahydrofuran and 0.8 g of diisopropylethylamine were added dropwise, and the mixture was stirred at −5 ° C. for 1 hour. 8 mL of a tetrahydrofuran solution of 1.6 g of the compound represented by the formula (D-2R-3), 0.8 g of diisopropylethylamine, and 10 mg of 4-dimethylaminopyridine were added, and the mixture was stirred at room temperature for 2 hours. The reaction mixture was poured into water and extracted with dichloromethane. Purification was performed by column chromatography (silica gel, dichloromethane) and recrystallization (dichloromethane / methanol) to obtain 2.3 g of a compound represented by the formula (D-2R). Purity 95.186%
LC-MS: 843 [M + 1]
(Comparative Example 2-3) Production of compound represented by formula (D-10R)

  A compound represented by the formula (D-10R-1) was produced by the method described in Patent Document 1. A compound represented by the formula (D-10R-2) was produced by the method described in JP2013-0667603A.

Under a nitrogen atmosphere, 0.8 g of methanesulfonyl chloride, 5 mL of tetrahydrofuran, and 10 mg of 2,6-di-tert-butyl-4-methylphenol were added to the reaction vessel. The solution was cooled to −5 ° C., a solution of 2.0 g of the compound represented by the formula (D-10R-2) dissolved in 10 mL of tetrahydrofuran and 1.3 g of diisopropylethylamine were added dropwise, and the mixture was stirred at −5 ° C. for 1 hour. 10 mL of a tetrahydrofuran solution of 1.9 g of the compound represented by the formula (D-10R-1), 1.3 g of diisopropylethylamine and 10 mg of 4-dimethylaminopyridine were added, and the mixture was stirred at room temperature for 2 hours. The reaction mixture was poured into water and extracted with dichloromethane. Purification was performed by column chromatography (silica gel, dichloromethane) and recrystallization (dichloromethane / methanol) to obtain 3.1 g of a compound represented by the formula (D-10R). 95.038% purity
(Examples 3-1 to 3-13, Comparative examples 3-1 to 3-3)
Compounds represented by formula (D-1) to formula (D-10D) described in Example 2-1 to Example 2-13 and formula (D) described in comparative example 2-1 to comparative example 2-3 -1R), the compound represented by the formula (D-2R) and the formula (D-10R) were used as the compounds to be evaluated.

  Further, a chiral liquid crystal composition composed of the following polymerizable compound (X-1): 20%, polymerizable compound (X-2): 75%, and chiral compound LC756 (manufactured by BASF): 5% is used as a base liquid crystal (X ).

  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.

11.87% of the base liquid crystal (X), 7.91% of the compound to be evaluated (40% based on the total content of the base liquid crystal (X) and the compound), photopolymerization initiator Irgacure 907 (manufactured by BASF) Was mixed with 0.20%, 4-methoxyphenol 0.02% and cyclohexanone 80.00%. This coating solution was applied to a rubbed glass substrate using a bar coater (No. 9), and then placed on a hot plate at 100 ° C. to evaporate the solvent. Then, the film was produced by irradiating ultraviolet rays with the intensity | strength of 40 mW / cm < ² > for 25 second using a high pressure mercury lamp.

Next, the obtained film was irradiated with light of 60 mW for 800 hours with an LED lamp (365 nm). The degree of unevenness was evaluated by observing the film after irradiation with a polarizing microscope. The film was divided into 10 squares × 10 squares, for a total of 100 squares, and the number of squares with unevenness was counted. The evaluation result is expressed in five levels, and the smaller the value, the less the unevenness. Moreover, the degree of discoloration was evaluated about the film after irradiation. The difference between the yellowness (YI ₀ ) of the film before light irradiation by the LED lamp and the yellowness (YI) of the film after light irradiation, and the yellowing degree (ΔYI = YI−YI ₀ ) were measured. The yellowness was calculated by measuring the absorption spectrum of the film with JASCO UV / VIS Spectrophotometer V-560 and using the attached color diagnostic program. The formula is
Yellowness = 100 (1.28X-1.06Z) / Y
(JIS K7373). The results are shown in the table below.

  From the above results, the compounds represented by the formulas (D-1) to (D-10D) are represented by the formulas (D-1R), (D-2R) and (D-10R) of Comparative Examples. It can be seen that unevenness and discoloration are less likely to occur compared to the compound to be produced. In the method for producing a comparative compound, an intermediate having a relatively high molecular weight polymerizable group having a large number of ring structures is used. For this reason, the molecular weight of the very small amount of oligomer component by-produced during the manufacturing process is also relatively large. These oligomer components having a relatively large molecular weight are considered to have an effect on unevenness and discoloration when formed into a film.

  From the above results, the compound represented by the general formula (IC) of the present invention is useful as a production intermediate for obtaining a compound having an ester bond with high yield and high purity in a short production process. In addition, the compound represented by the general formula (ID) produced using the compound represented by the general formula (IC) of the present invention as an intermediate is added to the polymerizable composition to form a film-like polymer. This is useful as a constituent member of the polymerizable composition because it is less likely to cause unevenness and discoloration when prepared. Moreover, the said polymeric composition is useful for the use of optical materials, such as a phase difference film and a selective reflection film.

Claims (11)

The following general formula (IC)

(In the formula, A ¹ and A ² are each independently 1,4-phenylene group, 1,4-cyclohexylene group, naphthalene-2,6-diyl group, naphthalene-1,4-diyl group, tetrahydronaphthalene- 2,6-diyl group or decahydronaphthalene-2,6-diyl group, Z ¹ represents —COO— or —OCO—, wherein at least one of A ¹ and A ² is represented by one substituent L; Each substituted L is independently a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a pentafluorosulfuranyl group, a cyano group, an optionally substituted phenyl group, or one — CH ₂ — or two or more non-adjacent —CH ₂ — are each independently —O—, —S—, —CO—, —COO—, —OCO—, —CO—S—, —S—. CO-, -O-CO-O- ^{-CO-NR 0 -, - NR} 0 -CO -, - CH = CH-COO -, - CH = CH-OCO -, - COO-CH = CH -, - OCO-CH = CH -, - CH = CH ^{-, - N = N -,} - CR 0 = N -, - N = CR 0 -, - CH = N-N = CH -, - CF = CF- or -C≡C- (wherein, ^{R 0} is Represents a hydrogen atom or a linear or branched alkyl group having 1 to 20 carbon atoms which may be substituted by a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, but any hydrogen atom in the alkyl group May be substituted with a fluorine atom.) The compound according to claim 1, wherein in formula (IC), only one of A ^{1 and} A ² is substituted with one substituent L. Each of the following formulas (I-A1) and (I-B1)

(In the formula, A ¹ and A ² represent the same meaning as A ¹ and A ² in the general formula (IC), provided that at least one of A ¹ and A ² is substituted with one substituent L. And L present may be the same or different.) Or each of the following formulas (I-B2) and (I-A2):

(In the formula, A ¹ and A ² represent the same meaning as A ¹ and A ² in the general formula (IC), provided that at least one of A ¹ and A ² is substituted with one substituent L. And the existing L may be the same or different.) A method for producing a compound represented by the general formula (IC) according to claim 1 or 2, wherein the compound represented by formula (I-C) is reacted. The compound represented by the general formula (IC) according to claim 1 or 2, wherein the compound represented by the following general formula (ID) is used as a production intermediate.

^(Wherein, A ^1, A 2, ^{Z 1} has the same meaning as ^{A 1,} A 2, ^{Z 1} in the general formula (I-C), provided that at least one of one of the ^{A 1} and ^{A 2} Substituted by the substituent L, the L present may be the same or different,
R ¹ 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 adjacent. Two or more —CH ₂ — are each independently —O—, —S—, —CO—, —COO—, —OCO—, —CO—S—, —S—CO—, —O—CO. A straight chain having 1 to 20 carbon atoms which may be substituted by —O—, —CO—NH—, —NH—CO—, —CH═CH—, —CF═CF— or —C≡C—, or A branched alkyl group is represented, and any hydrogen atom in the alkyl group may be substituted with a fluorine atom, or R ¹ is a group represented by P ^1- (Sp ¹ -X ¹ ) _k1- ( wherein, P ¹ is a radical polymerization, by cationic polymerization or anionic polymerization It represents the total radicals, although Sp ¹ represents a spacer group, they if Sp ¹ there are a plurality may be different even in the same, ^{X 1} is -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 -, - N = N -, - CH = N-N = CH -, - CF = CF -, - C≡C- or represents a single bond, the same if they ^{where X 1} there are a plurality of Or P ^1- (Sp ¹ -X ¹ ) _k1 -does not include an -O-O- bond, and k1 represents an integer of 0 to 10. Represent,
R ² 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 adjacent. Two or more —CH ₂ — are each independently —O—, —S—, —CO—, —COO—, —OCO—, —CO—S—, —S—CO—, —O—CO. A straight chain having 1 to 20 carbon atoms which may be substituted by —O—, —CO—NH—, —NH—CO—, —CH═CH—, —CF═CF— or —C≡C—, or A branched alkyl group is represented, and any hydrogen atom in the alkyl group may be substituted with a fluorine atom, or R ² is a group represented by-(X ² -Sp ² ) _k2 -P ² ( wherein, P ² is a radical polymerization, by cationic polymerization or anionic polymerization Represents the total radicals, Sp ² each represents a spacer group, they if Sp ² there are a plurality may be different even in the same, ^{X 2} is -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 -, - N = N -, - CH = N-N = CH -, - CF = CF -, - C≡C- or represents a single bond, the same case ^{those X 2} there are a plurality even differ also good _{^{(although, - (X 2 -Sp 2)}} k2 in -P ² do not contain -O-O- bond.) the, k2 is an integer of 0 to 10). Represent,
A ³ and A ⁴ are each independently 1,4-phenylene group, 1,4-cyclohexylene group, bicyclo [2.2.2] octane-1,4-diyl group, pyridine-2,5-diyl group. , Pyrimidine-2,5-diyl group, naphthalene-2,6-diyl group, naphthalene-1,4-diyl group, tetrahydronaphthalene-2,6-diyl group, decahydronaphthalene-2,6-diyl group or 1 , 3-dioxane-2,5-diyl groups, these groups may be unsubstituted or substituted by one or more substituents L ³ , and they are identical when there are multiple A ³ Or when A ⁴ is present, they may be the same or different,
L ³ is fluorine atom, chlorine atom, bromine atom, iodine atom, pentafluorosulfuranyl group, nitro group, cyano group, isocyano group, amino group, hydroxyl group, mercapto group, methylamino group, dimethylamino group, diethylamino group , A diisopropylamino group, a trimethylsilyl group, a dimethylsilyl group, a thioisocyano group, an optionally substituted phenyl group, an optionally substituted phenylalkyl group, an optionally substituted cyclohexylalkyl group, or one- CH ₂ —two or more non-adjacent —CH ₂ — are each independently —O—, —S—, —CO—, —COO—, —OCO—, —CO—S—, —S—CO. ^{-, - OCO-O -,} - CO-NR 0 -, - NR 0 -CO -, - CH = CH-COO -, - CH = CH-OCO -, - CO -CH = CH -, - OCO- CH = CH -, - CH = CH -, - N = N -, - CR 0 = N -, - N = CR 0 -, - CH = N-N = CH-, A straight chain having 1 to 20 carbon atoms which may be substituted by —CF═CF— or —C≡C— (wherein R ⁰ represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms) A branched alkyl group is represented, and any hydrogen atom in the alkyl group may be substituted with a fluorine atom, or L ³ represents a group represented by P ^L- (Sp ^L -X ^L ) _kL-. Here, P ^L represents a group that is polymerized by radical polymerization, cationic polymerization, or anionic polymerization, and Sp ^L represents a spacer group or a single bond, but when there are a plurality of Sp ^L, they are the same. It may be the or different, ^{X L} is -O -, - S -, - OCH 2 -, - C H 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 -, - N = N -, - CH = N-N = CH-, -CF = CF -, - C≡C- or represents a single bond, they if X ^L there are a plurality optionally be the same or different Well ^{(however, P L - (Sp L -X} L) kL - to contain no -O-O- bonds. ), KL represents an integer of 0 to 10, and when a plurality of L ³ are present in the compound, they may be the same or different,
Z ² and Z ³ are each independently —O—, —S—, —OCH ₂ —, —CH ₂ O—, —CH ₂ CH ₂ —, —CO—, —COO—, —OCO—, —CO. -S-, -S-CO-, -O-CO-O-, -CO-NH-, -NH-CO-, -OCO-NH-, -NH-COO-, -NH-CO-NH-, _{-NH-O -, - O-} NH -, - 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 -OCO -, - CH = CH - , - N = N -, - CH = N -, - N = CH -, - CH = N-N = CH -, - CF = CF -, - C≡C- or represents a single bond, they if Z ² there are a plurality may be the same or different and they if Z ³ there are a plurality may be the same or different and one of Z ² Z ² directly bonded to A ¹ is —O—, —CH ₂ O—, —COO—, —O—CO—O—, —NH—COO—, —NH—O—, —CF ₂ O—, — Z = CH—COO—, —CH ₂ CH ₂ —COO— or —CH ₂ —COO—, wherein Z ³ directly bonded to A ² of Z ³ is —O—, —OCH ₂ —, —OCO—. , -O-CO-O -, - OCO-NH -, - O-NH -, - OCF 2 -, - OCO-CH = CH -, - OCO-CH 2 H ₂ - or -OCO-CH ₂ - represents,
m1 and m2 each independently represents an integer of 0 to 4, but m1 + m2 represents an integer of 0 to 4. The manufacturing method of the compound represented by this. The compound represented by the general formula (IC) according to claim 1 or 2, and the following general formula (IE)

^(Wherein, R ^1, A ^{3, Z} is ² and m1 represents the same meaning as ^{R 1,} A 3, ^{Z 2} and m1 in formula (I-D), the ^{A 3} present is also the same May be different.)
In general formula (ID), A ⁴ , Z ³ , R ² and m ² are the same as A ³ , Z ² , R ¹ and m 1, respectively. The manufacturing method of Claim 4 which obtains the compound represented by D). The following general formula (ID)

(Wherein A ¹ , A ² , A ³ , A ⁴ , Z ¹ , Z ² , Z ³ , R ¹ , R ² , m 1 and m ² represent the same meaning as in the general formula (ID), provided that , At least one of A ¹ and A ² is substituted by one said substituent L, and the existing L may be the same or different.)
And a compound represented by the following general formula (IC)

(In the formula, A ¹ , A ² , Z ¹ represent the same meaning as in the general formula (IC), provided that at least one of A ¹ and A ² is substituted by one substituent L. The L present may be the same or different.)
A compound represented by the following general formula (I-F1)

^{(Wherein, A 1, A 2, A} 3, Z 1, Z 2, A 1 R 1 and m1 is in the general formula ^{(I-D), A 2} , A 3, Z 1, Z 2, R 1 And at least one of A ¹ and A ² is substituted by one said substituent L, and the existing L may be the same or different, or a compound represented by: The following general formula (I-F2)

(In the formula, A ¹ , A ² , A ⁴ , Z ¹ , Z ³ , R ² and m ² are A ¹ , A ² , A ⁴ , Z ¹ , Z ³ , R ^{2 in the} general formula (ID)). And at least one of A ¹ and A ² is substituted with one said substituent L, and the existing L may be the same or different.) Including
The total content of the compound represented by the general formula (IC), the compound represented by the general formula (I-F1) and the compound represented by the general formula (I-F2) is 0.001% by weight or more 5 A mixture that is less than or equal to weight percent.   A composition comprising the mixture according to claim 6.   A liquid crystal composition containing the mixture according to claim 6.   A polymer obtained by polymerizing the composition according to claim 7 or 8.   An optical anisotropic body using the polymer according to claim 9.   Resin, resin additive, oil, filter, adhesive, pressure-sensitive adhesive, oil, ink, medicine, cosmetics, detergent, building material, packaging material, liquid crystal material, organic EL material, organic using the mixture according to claim 6 Semiconductor materials, electronic materials, display elements, electronic devices, communication equipment, automobile parts, aircraft parts, machine parts, agricultural chemicals and foods, and products using them.