Method for producing compound, method for producing polymerizable composition, method for producing polymer, method for producing optically anisotropic body, and compound

Abstract

SOLUTION: A method for producing a compound represented by the following general formula (III) from a compound represented by the following general formula (I), the method comprising no step of introducing substituents into hydroxy groups bonded to Sp2 in the following general formula (I): SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a method for producing a compound, and the compound. The present invention also relates to a method for producing a polymerizable composition, a method for producing a polymer, and a method for producing an optically anisotropic body using the compound. [Background technology]

[0002] Polymerizable compounds having an aliphatic hydrocarbon ring and an ester bond in the mesogen moiety and a long-chain alkylene group in the spacer moiety exhibit a wide smectic liquid crystal phase temperature range and are therefore used in polymerizable liquid crystal compositions for optical films (Patent Documents 1 to 3).

[0003] As a method for synthesizing the polymerizable compound, a method has been used in which the hydroxy group of a carboxylic acid having a hydroxy group is first protected with a tetrahydropyranyl group or the like, then an ester bond is formed at the carboxylic acid site, and finally the hydroxy group is deprotected to introduce a polymerizable group (Patent Documents 4 to 6). The synthesis method does not involve the intermediate of a carboxylic acid having a long-chain alkylene group and a cyclohexane ring, which has low solubility in both highly polar and low-polar organic solvents and is liable to be complicated to purify, and therefore was particularly useful in the synthesis of a compound having a long-chain alkylene group and a cyclohexane ring in the spacer moiety.

[0004] On the other hand, as a method for synthesizing the polymerizable compound without protecting the hydroxy group, a production method has been reported in which a polymerizable group is introduced into the hydroxy group of a carboxylic acid having a hydroxy group before forming an ester bond at the carboxylic acid site (Patent Document 7). [Prior art documents] [Patent documents]

[0005] [Patent Document 1] Japanese Patent Application Laid-Open No. 2017-167517 [Patent Document 2] Japanese Patent Application Laid-Open No. 2017-197630 [Patent Document 3] International Publication No. 2018 / 110530 [Patent Document 4] Japanese Patent Application Laid-Open No. 2013-224296 [Patent Document 5] Special Publication No. 2011-526321 [Patent Document 6] Special Publication No. 2011-526296 [Patent Document 7] Japanese Patent Publication No. 2020-158422 Summary of the Invention [Problem to be solved by the invention]

[0006] All of the methods reported in Patent Documents 4 to 6 have the problem of the generation of by-products due to the unintended introduction of a protecting group into the carboxylic acid in the step of protecting the hydroxy group with a tetrahydropyranyl group or the like, and the reduction in yield associated with the purification of the by-products. In the method described in Patent Document 7, it is essentially impossible to avoid the introduction of a polymerizable group into the carboxylic acid moiety, and there is a problem of a decrease in yield due to the generation of by-products and their removal.

[0007] The present invention aims to provide a method for producing an intermediate of a polymerizable liquid crystal compound via an ester bond formation reaction using a carboxylic acid having a hydroxy group in the molecule as a raw material, which can reduce the number of steps and does not cause the generation of by-products due to the step of protecting or chemically modifying the hydroxy group and the resulting decrease in yield. [Means for solving the problem]

[0008] The present inventors have found that the above problems can be solved by a specific manufacturing method, and have completed the present invention. The gist of the present invention is as follows.

[0009] [1] A method for producing a compound represented by the following general formula (III) from a compound represented by the following general formula (I), which does not include a step of introducing a substituent into the hydroxy group bonded to Sp2 in the following general formula (I):

[0010] [ka]

[0011] (In formula (I), A2, A 21 , A 22 , X2, X3, Sp2, R and a are represented by the formula (III) (This is the same as in

[0012] [ka]

[0013] In formula (III), A1 and A2 each independently represent a hydrocarbon ring group or a heterocyclic group, which may have a substituent. A 11 , A 12 , A 21 and A 22 each independently represents -CH2-CH2-, -CH=CH-, -C≡C-, or a direct bond. Sp1 and Sp2 each independently represent a linear or branched alkylene group, provided that any hydrogen atom in the alkylene group of Sp1 and Sp2 may be substituted with a fluorine atom, and one -CH2- or two or more non-adjacent -CH2- groups may each independently be replaced with -O-, -S-, -CO-, -COO-, -OCO-, -CO-S-, -S-CO-, -O-COO-, -CO-NH-, -NH-CO-, -CH=CH-, -CF=CF-, or -C≡C-. X1, X2 and X3 each independently represent -O-, -S-, -OCH2-, -CHO-, -CO-, -COO-, -OCO-, -CO-S-, -S-CO-, -O-CO-O-, -CO-NH-, -NH-CO-, -SCH2-, -CH2S-, -CF2O-, -OCF2-, -CF2S-, -SCF2-, -CH=CH-COO-, -CH=CH-OCO-, -C represents OO-CH=CH-, -OCO-CH=CH-, -COO-CH2CH2-, -OCO-CH2CH2-, -CH2CH2-COO-, -CH2CH2-OCO-, -COO-CH2-, -OCO-CH2-, -CH2-COO-, -CH2-OCO-, -CH=CH-, -N=N-, -CH=NN=CH-, -CF=CF-, -C≡C-, or a direct bond. R represents a hydrocarbon group having 1 to 4 carbon atoms which may have a substituent. a represents an integer of 0 to 4.

[0014] [2] A method for producing a compound represented by the following general formula (III), comprising a step of reacting a compound represented by the following general formula (I) with a compound represented by the following general formula (II):

[0015] [ka]

[0016] (In formula (I), A2, A 21 , A 22 , X2, X3, Sp2, R and a represent A2, A 21 , A 22 , X2, X3, Sp2, R and a are synonymous.)

[0017] [ka]

[0018] (In formula (II), A1, A 11 , A 12 , X1 and Sp1 are A1, A 11 , A 12, X1 and Sp1.)

[0019] [ka]

[0020] In formula (III), A1 and A2 each independently represent a hydrocarbon ring group or a heterocyclic group, which may have a substituent. A 11 , A 12 , A 21 and A 22 each independently represents -CH2-CH2-, -CH=CH-, -C≡C-, or a direct bond. Sp1 and Sp2 each independently represent a linear or branched alkylene group, provided that any hydrogen atom in the alkylene group of Sp1 and Sp2 may be substituted with a fluorine atom, and one -CH2- or two or more non-adjacent -CH2- groups may each independently be replaced with -O-, -S-, -CO-, -COO-, -OCO-, -CO-S-, -S-CO-, -O-COO-, -CO-NH-, -NH-CO-, -CH=CH-, -CF=CF-, or -C≡C-. X1, X2 and X3 each independently represent -O-, -S-, -OCH2-, -CHO-, -CO-, -COO-, -OCO-, -CO-S-, -S-CO-, -O-CO-O-, -CO-NH-, -NH-CO-, -SCH2-, -CH2S-, -CF2O-, -OCF2-, -CF2S-, -SCF2-, -CH=CH-COO-, -CH=CH-OCO-, -C represents OO-CH=CH-, -OCO-CH=CH-, -COO-CH2CH2-, -OCO-CH2CH2-, -CH2CH2-COO-, -CH2CH2-OCO-, -COO-CH2-, -OCO-CH2-, -CH2-COO-, -CH2-OCO-, -CH=CH-, -N=N-, -CH=NN=CH-, -CF=CF-, -C≡C-, or a direct bond. R represents a hydrocarbon group having 1 to 4 carbon atoms which may have a substituent. a represents an integer of 0 to 4.

[0021] [3] The method for producing the compound according to [1] or [2], wherein Sp1 and Sp2 in the general formula (III) are each independently a linear or branched alkylene group having 8 to 20 carbon atoms.

[0022] [4] In the general formula (III), A 11 and A 12 At least one of A is a direct bond, and 21 and A 22 The method for producing the compound according to any one of [1] to [3], wherein at least one of the following is a direct bond:

[0023] [5] In the general formula (III), A 11 , A 12 , A 21 and A 22 The method for producing the compound according to [4], wherein at least three of the above are direct bonds.

[0024] [6] A method for producing a compound represented by the following general formula (IV) from a compound represented by the general formula (III) obtained by the production method according to any one of [1] to [5].

[0025] [ka]

[0026] (In formula (IV), A1, A2, A 11 , A 12 , A 21 , A 22 , X1, X2, X3, Sp1, Sp2, R and a represent A1, A2, A 11 , A 12 , A 21 , A 22 , X1, X2, X3, Sp1, Sp2, R and a. P represents a group that is polymerizable by radical polymerization, cationic polymerization, or anionic polymerization.

[0027] [7] A method for producing a polymerizable composition comprising a compound represented by general formula (III) obtained by the production method according to any one of [1] to [5] and / or a compound represented by general formula (IV) obtained by the production method according to [6].

[0028] [8] A method for producing a polymer by polymerizing the polymerizable composition obtained by the method according to [7].

[0029] [9] A method for producing an optically anisotropic body by polymerizing the polymerizable composition obtained by the method according to [7].

[0030]

[10] A method for producing resins, resin additives, oils, filters, adhesives, pressure-sensitive adhesives, oils and fats, inks, pharmaceuticals, cosmetics, detergents, building materials, packaging materials, liquid crystal materials, organic electroluminescent materials, encapsulants, organic semiconductor materials, electronic materials, display elements, electronic devices, communication equipment, automobile parts, aircraft parts, machine parts, agricultural chemicals, and foods, and products using these, which are formulated with a compound represented by general formula (III) obtained by the production method described in any one of [1] to [5] and / or a compound represented by general formula (IV) obtained by the production method described in [6].

[0031]

[11] A compound represented by the following general formula (V):

[0032] [ka]

[0033] In formula (V), A3 and A4 each independently represent a hydrocarbon ring group or a heterocyclic group which may have a substituent, and A3 and A4 represent different groups. A 31 , A 32 , A 41 and A 42 each independently represents -CH2-CH2-, -CH=CH-, -C≡C-, or a direct bond. Sp3 and Sp4 each independently represent a linear or branched alkylene group having 8 to 20 carbon atoms, provided that any hydrogen atom in the alkylene group of Sp3 and Sp4 may be substituted with a fluorine atom, and one -CH2- or two or more non-adjacent -CH2- groups may each independently be replaced with -O-, -S-, -CO-, -COO-, -OCO-, -CO-S-, -S-CO-, -O-COO-, -CO-NH-, -NH-CO-, -CH=CH-, -CF=CF-, or -C≡C-. X4, X5 and X6 each independently represent -O-, -S-, -OCH2-, -CHO-, -CO-, -COO-, -OCO-, -CO-S-, -S-CO-, -O-CO-O-, -CO-NH-, -NH-CO-, -SCH2-, -CH2S-, -CF2O-, -OCF2-, -CF2S-, -SCF2-, -CH=CH-COO-, -CH=CH-OCO-, -C represents OO-CH=CH-, -OCO-CH=CH-, -COO-CH2CH2-, -OCO-CH2CH2-, -CH2CH2-COO-, -CH2CH2-OCO-, -COO-CH2-, -OCO-CH2-, -CH2-COO-, -CH2-OCO-, -CH=CH-, -N=N-, -CH=NN=CH-, -CF=CF-, -C≡C-, or a direct bond. R represents a hydrocarbon group having 1 to 4 carbon atoms which may have a substituent. a represents an integer of 0 to 4.

[0034]

[12] In the general formula (V), A 31 and A 32 At least one of A is a direct bond, and 41 and A 42 wherein at least one of the groups is a direct bond.

[0035]

[13] In the general formula (V), A 31 , A 32 , A 41 and A 42 The compound according to

[12] , wherein at least three of the above are direct bonds.

[0036]

[14] A compound represented by the following general formula (I):

[0037] [ka]

[0038] (In formula (I), each A2 independently represents a hydrocarbon ring group or a heterocyclic group, which may have a substituent. A 21 and A 22 each independently represents -CH2-CH2-, -CH=CH-, -C≡C-, or a direct bond. Each Sp2 independently represents a linear or branched alkylene group having 8 to 20 carbon atoms, provided that any hydrogen atom in the alkylene group of Sp2 may be substituted with a fluorine atom, and one -CH2- or two or more non-adjacent -CH2- groups may each independently be replaced with -O-, -S-, -CO-, -COO-, -OCO-, -CO-S-, -S-CO-, -O-COO-, -CO-NH-, -NH-CO-, -CH=CH-, -CF=CF-, or -C≡C-. X2 and X3 each independently represent -O-, -S-, -OCH2-, -CHO-, -CO-, -COO-, -OCO-, -CO-S-, -S-CO-, -O-CO-O-, -CO-NH-, -NH-CO-, -SCH2-, -CH2S-, -CF2O-, -OCF2-, -CF2S-, -SCF2-, -CH=CH-COO-, -CH=CH-OCO-, -CO O-CH=CH-, -OCO-CH=CH-, -COO-CH2CH2-, -OCO-CH2CH2-, -CH2CH2-COO-, -CH2CH2-OCO-, -COO-CH2-, -OCO-CH2-, -CH2-COO-, -CH2-OCO-, -CH=CH-, -N=N-, -CH=NN=CH-, -CF=CF-, -C≡C-, or a direct bond. R represents a hydrocarbon group having 1 to 4 carbon atoms which may have a substituent. a represents an integer of 0 to 4.

[0039]

[15] In the general formula (I), A 21 and A 22wherein at least one of the groups is a direct bond. [Effects of the Invention]

[0040] According to the method for producing a compound of the present invention, in producing a compound useful as an intermediate for a polymerizable liquid crystal compound, the number of steps can be reduced by not having a step of introducing a substituent into a hydroxy group, and the generation of by-products due to the step of protecting or chemically modifying the hydroxy group and the resulting decrease in yield can be suppressed. DETAILED DESCRIPTION OF THE INVENTION

[0041] The present invention will be described in detail below. The following description is an example of an embodiment of the present invention, and the present invention is not limited to these unless it exceeds the gist of the present invention.

[0042] <Compound represented by general formula (III)> The compound represented by the following general formula (III) (hereinafter, sometimes referred to as "compound (III)") produced by the method of the present invention is useful as an intermediate for a polymerizable liquid crystal compound.

[0043] [ka]

[0044] In formula (III), A1 and A2 each independently represent a hydrocarbon ring group or a heterocyclic group, which may have a substituent. A 11 , A 12 , A 21 and A 22 each independently represents -CH2-CH2-, -CH=CH-, -C≡C-, or a direct bond. Sp1 and Sp2 each independently represent a linear or branched alkylene group, provided that any hydrogen atom in the alkylene group of Sp1 and Sp2 may be substituted with a fluorine atom, and one -CH2- or two or more non-adjacent -CH2- groups may each independently be replaced with -O-, -S-, -CO-, -COO-, -OCO-, -CO-S-, -S-CO-, -O-COO-, -CO-NH-, -NH-CO-, -CH=CH-, -CF=CF-, or -C≡C-. X1, X2 and X3 each independently represent -O-, -S-, -OCH2-, -CHO-, -CO-, -COO-, -OCO-, -CO-S-, -S-CO-, -O-CO-O-, -CO-NH-, -NH-CO-, -SCH2-, -CH2S-, -CF2O-, -OCF2-, -CF2S-, -SCF2-, -CH=CH-COO-, -CH=CH-OCO-, -C represents OO-CH=CH-, -OCO-CH=CH-, -COO-CH2CH2-, -OCO-CH2CH2-, -CH2CH2-COO-, -CH2CH2-OCO-, -COO-CH2-, -OCO-CH2-, -CH2-COO-, -CH2-OCO-, -CH=CH-, -N=N-, -CH=NN=CH-, -CF=CF-, -C≡C-, or a direct bond. R represents a hydrocarbon group having 1 to 4 carbon atoms which may have a substituent. a represents an integer of 0 to 4.

[0045] In formula (III), A1 and A2 each independently represent a hydrocarbon ring group or a heterocyclic group which may have a substituent. When A1 and A2 are hydrocarbon ring groups or heterocyclic groups, a liquid crystal phase is exhibited and the temperature range in which the liquid crystal phase is exhibited tends to be broadened.

[0046] The hydrocarbon ring groups in A1 and A2 include aromatic hydrocarbon ring groups and non-aromatic hydrocarbon ring groups.

[0047] The aromatic hydrocarbon ring groups in A1 and A2 include unlinked aromatic hydrocarbon ring groups and linked aromatic hydrocarbon ring groups.

[0048] The non-linked aromatic hydrocarbon ring group is a divalent group of a monocyclic or condensed aromatic hydrocarbon ring, and the monocyclic or condensed ring preferably has 6 to 20 carbon atoms. Examples of aromatic hydrocarbon rings include a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, a perylene ring, a tetracene ring, a pyrene ring, a benzpyrene ring, a chrysene ring, a triphenylene ring, an acenaphthene ring, a fluoranthene ring, and a fluorene ring.

[0049] The linked aromatic hydrocarbon ring group is a divalent group in which a plurality of monocyclic or condensed aromatic hydrocarbon rings are directly bonded to each other and have a bond on an atom constituting the ring. The number of carbon atoms in the monocyclic or condensed ring is preferably 6 to 20. For example, it is a divalent group in which a first monocyclic or fused aromatic hydrocarbon ring having 6 to 20 carbon atoms and a second monocyclic or fused aromatic hydrocarbon ring having 6 to 20 carbon atoms are directly bonded, and which has a first bond on an atom constituting the first monocyclic or fused aromatic hydrocarbon ring having 6 to 20 carbon atoms, and a second bond on an atom constituting the second monocyclic or fused aromatic hydrocarbon ring having 6 to 20 carbon atoms. Examples of the linked aromatic hydrocarbon ring group include a biphenyl-4,4'-diyl group.

[0050] As the aromatic hydrocarbon ring group, a non-linked aromatic hydrocarbon ring group is preferred because it is easy to obtain an industrially applicable phase transition temperature (10° C. to 150° C.).

[0051] The aromatic hydrocarbon ring group is preferably a divalent group of a benzene ring or a divalent group of a naphthalene ring, and more preferably a divalent group of a benzene ring (phenylene group). As the phenylene group, a 1,4-phenylene group is preferred, and as the divalent group of a naphthalene ring, a naphthalene-2,6-diyl group, a naphthalene-1,4-diyl group, or a tetrahydronaphthalene-2,6-diyl group is preferred.

[0052] The non-aromatic hydrocarbon ring group in A1 and A2 is a divalent group of a monocyclic or condensed non-aromatic hydrocarbon ring, and preferably has 3 to 20 carbon atoms. Examples of non-aromatic hydrocarbon rings include a cyclopropane ring, a cyclobutane ring, a cyclopentane ring, a cyclohexane ring, a cycloheptane ring, a cyclooctane ring, a cyclohexene ring, a norbornane ring, a bornane ring, an adamantane ring, a tetrahydronaphthalene ring, and a bicyclo[2.2.2]octane ring.

[0053] The non-aromatic hydrocarbon ring group includes an alicyclic hydrocarbon ring group that does not have an unsaturated bond between atoms constituting the non-aromatic hydrocarbon ring, and an unsaturated non-aromatic hydrocarbon ring group that has an unsaturated bond between atoms constituting the non-aromatic hydrocarbon ring. The non-aromatic hydrocarbon ring group is preferably an alicyclic hydrocarbon ring group.

[0054] As the non-aromatic hydrocarbon ring group, specifically, a divalent group of a ring having a 6-membered carbon ring is preferred, and a divalent group of cyclohexane (cyclohexylene group) and a divalent group of bicyclo[2.2.2]octane are particularly preferred. As the cyclohexylene group, a 1,4-cyclohexylene group is preferred, and as the divalent group of bicyclo[2.2.2]octane-1,4-diyl group is preferred.

[0055] The heterocyclic groups in A1 and A2 include aromatic heterocyclic groups and non-aromatic heterocyclic groups, and aromatic heterocyclic groups include non-linked aromatic heterocyclic groups and linked aromatic heterocyclic groups.

[0056] The non-linked aromatic heterocyclic group is a divalent group of a monocyclic or condensed aromatic heterocyclic ring, and preferably has 4 to 20 carbon atoms. Examples of aromatic heterocycles include a furan ring, a benzofuran ring, a thiophene ring, a benzothiophene ring, a pyrrole ring, a pyrazole ring, an imidazole ring, an oxadiazole ring, an indole ring, a carbazole ring, a pyrroloimidazole ring, a pyrrolopyrazole ring, a pyrrolopyrrole ring, a thienopyrrole ring, a thienothiophene ring, a furopyrrole ring, a furofuran ring, a thienofuran ring, a thienothiazole ring, a benzisoxazole ring, a benzisothiazole ring, a benzimidazole ring, a pyridine ring, a pyrazine ring, a pyridazine ring, a pyrimidine ring, a triazine ring, a quinoline ring, an isoquinoline ring, a cinnoline ring, a quinoxaline ring, a phenanthridine ring, a benzimidazole ring, a pyrimidine ring, a quinazoline ring, a quinazolinone ring, and an azulene ring. The linked aromatic heterocyclic group is a divalent group in which a plurality of monocyclic or fused aromatic heterocyclic rings are bonded together by single bonds and which has a bond on an atom constituting the ring. The number of carbon atoms in the monocyclic or fused ring is preferably 4 to 20. For example, it is a divalent group in which a first monocyclic or fused aromatic heterocyclic ring having 4 to 20 carbon atoms is bonded to a second monocyclic or fused aromatic heterocyclic ring having 4 to 20 carbon atoms by a single bond, which has a first bond on an atom constituting the first monocyclic or fused aromatic heterocyclic ring having 4 to 20 carbon atoms and a second bond on an atom constituting the second monocyclic or fused aromatic heterocyclic ring having 4 to 20 carbon atoms. Specific examples of the aromatic heterocyclic group include a pyridine-2,5-diyl group and a pyrimidine-2,5-diyl group.

[0057] Non-aromatic heterocyclic groups include unlinked non-aromatic heterocyclic groups and linked non-aromatic heterocyclic groups. The unlinked non-aromatic heterocyclic group is a divalent group of a monocyclic or condensed non-aromatic heterocyclic ring, and preferably has 4 to 20 carbon atoms. Examples of non-aromatic heterocycles include a tetrahydrofuran ring, a tetrahydropyran ring, a dioxane ring, a tetrahydrothiophene ring, a tetrahydrothiopyran ring, a pyrrolidine ring, a piperidine ring, a dihydropyridine ring, a piperazine ring, a tetrahydrothiazole ring, a tetrahydrooxazole ring, an octahydroquinoline ring, a tetrahydroquinoline ring, an octahydroquinazoline ring, a tetrahydroquinazoline ring, a tetrahydroimidazole ring, a tetrahydrobenzimidazole ring, and a quinuclidine ring. The linked non-aromatic heterocyclic group is a divalent group in which a plurality of monocyclic or fused non-aromatic heterocyclic rings are bonded together by single bonds and which has a bond on an atom constituting the ring. The monocyclic or fused ring preferably has 4 to 20 carbon atoms. For example, it is a divalent group in which a first monocyclic or fused non-aromatic heterocyclic ring having 4 to 20 carbon atoms is bonded to a second monocyclic or fused non-aromatic heterocyclic ring having 4 to 20 carbon atoms by a single bond, which has a first bond on an atom constituting the first monocyclic or fused non-aromatic heterocyclic ring having 4 to 20 carbon atoms and a second bond on an atom constituting the second monocyclic or fused non-aromatic heterocyclic ring having 4 to 20 carbon atoms.

[0058] Specifically, the non-aromatic heterocyclic group is preferably a tetrahydropyran-2,5-diyl group or a 1,3-dioxane-2,5-diyl group.

[0059] The heterocyclic group in A1 and A2 is preferably an aromatic heterocyclic group from the viewpoint of the stability of the compound.

[0060] Specific examples of A1 and A2 that are preferred are a 1,4-phenylene group, a 1,4-cyclohexylene group, a bicyclo[2.2.2]octane-1,4-diyl group, a pyridine-2,5-diyl group, a pyrimidine-2,5-diyl group, a naphthalene-2,6-diyl group, a naphthalene-1,4-diyl group, a tetrahydronaphthalene-2,6-diyl group, a decahydronaphthalene-2,6-diyl group, a tetrahydropyran-2,5-diyl group, and a 1,3-dioxane-2,5-diyl group.

[0061] When an anisotropic dye film is formed using a polymerizable liquid crystal compound, a highly linear substituent is preferred from the viewpoint of increasing the dichroic ratio of the anisotropic dye film. Therefore, as A1 and A2 in compound (III), which is an intermediate of the polymerizable liquid crystal compound, a 1,4-cyclohexylene group and a 1,4-phenylene group are more preferred.

[0062] A1 and A2 may be the same or different, but from the viewpoint of the physical properties of the resulting polymerizable liquid crystal compound, it is preferable that A1 and A2 are different groups.

[0063] The hydrocarbon ring group or heterocyclic group of A1 and A2 may be unsubstituted or substituted with one or more substituents L.

[0064] The substituent L includes the following. fluorine atoms, chlorine atoms, bromine atoms, iodine atoms; pentafluorosulfanyl group, nitro group, cyano group, isocyano group, amino group, hydroxy group, mercapto group, methylamino group, dimethylamino group, diethylamino group, diisopropylamino group, trimethylsilyl group, dimethylsilyl group, thioisocyano group; a linear or branched alkyl group having 1 to 20 carbon atoms, in which one -CH2- or two or more non-adjacent -CH2- groups are each independently replaced by -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- (any hydrogen atom in the alkyl group is optionally substituted by a fluorine atom); -(X L -Sp L -) kL A group represented by -OH. where Sp Lrepresents a linear or branched alkylene group having 8 to 20 carbon atoms in which any hydrogen atom may be substituted with a fluorine atom, and one -CH2- or two or more non-adjacent -CH2- groups may each independently be substituted with -O-, -S-, -CO-, -COO-, -OCO-, -CO-S-, -S-CO-, -O-CO-O-, -CO-NH-, -NH-CO-, -CH=CH-, -CF=CF-, or -C≡C-. However, Sp L When there are multiple, they may be the same or different. X L -O-, -S-, -OCH2-, -CH2O-, -CO-, -COO-, -OCO-, -CO-S-, -S-CO-, -O-CO-O-, -CO-NH-, -NH-CO -, -SCH2-, -CH2S-, -CF2O-, -OCF2-, -CF2S-, -SCF2-, -CH=CH-COO-, -CH=CH-OCO-, -COO-CH=CH X represents -, -OCO-CH=CH-, -COO-CH2CH2-, -OCO-CH2CH2-, -CH2CH2-COO-, -CH2CH2-OCO-, -COO-CH2-, -OCO-CH2-, -CH2-COO-, -CH2-OCO-, -CH=CH-, -N=N-, -CH=NN=CH-, -CF=CF-, -C≡C-, or a direct bond. L When there are multiple, they may be the same or different. However, -(X L -Sp L -) kL -OH does not include an -OO- bond. kL represents an integer of 1 to 5.

[0065] When a plurality of substituents L are present in A1 and A2, they may be the same or different.

[0066] In order to ensure the linearity of compound (III), A1 and A2 are preferably unsubstituted.

[0067] In the general formula (III), A 11 , A 12 , A 21 and A 22each independently represents -CH2-CH2-, -CH=CH-, -C≡C-, or a direct bond. The high linearity of the molecules makes it easier to develop a liquid crystal phase and widens the temperature range in which the liquid crystal phase is developed. 11 and A 12 At least one of A is a direct bond, and 21 and A 22 Preferably, at least one of A is a direct bond, 11 , A 12 , A 21 and A 22 More preferably, at least three of A are direct bonds, 11 , A 12 , A 21 and A 22 It is more preferred that three of A are direct bonds and one is -C≡C- or a direct bond; 11 , A 12 , A 21 and A 22 Three of the bonds are direct bonds, and A 11 and A 22 It is particularly preferred that either of is -C≡C- or a direct bond.

[0068] In general formula (III), Sp1 and Sp2 each independently represent a linear or branched alkylene group, provided that any hydrogen atom in the alkylene group of Sp1 and Sp2 may be substituted with a fluorine atom, and one -CH2- or two or more non-adjacent -CH2- groups may each independently be replaced with -O-, -S-, -CO-, -COO-, -OCO-, -CO-S-, -S-CO-, -O-COO-, -CO-NH-, -NH-CO-, -CH=CH-, -CF=CF-, or -C≡C-.

[0069] From the viewpoint of allowing the polymerizable liquid crystal compound obtained from compound (III) to exhibit sufficient liquid crystallinity and increasing the dichroic ratio of an anisotropic dye film formed using the polymerizable liquid crystal compound, Sp1 and Sp2 are preferably alkylene groups having a specific length. Specifically, Sp1 and Sp2 are each independently preferably a linear or branched alkylene group having 8 to 20 carbon atoms, more preferably a linear alkylene group having 8 to 20 carbon atoms, and even more preferably a linear alkylene group having 8 to 12 carbon atoms.

[0070] In the general formula (III), X1, X2 and X3 each independently represent -O-, -S-, -OCH2-, -CHO-, -CO-, -COO-, -OCO-, -CO-S-, -S-CO-, -O-CO-O-, -CO-NH-, -NH-CO-, -SCH2-, -CH2S-, -CF2O-, -OCF2-, -CF2S-, -SCF2-, -CH=CH-COO-, -CH=CH- represents OCO-, -COO-CH=CH-, -OCO-CH=CH-, -COO-CH2CH2-, -OCO-CH2CH2-, -CH2CH2-COO-, -CH2CH2-OCO-, -COO-CH2-, -OCO-CH2-, -CH2-COO-, -CH2-OCO-, -CH=CH-, -N=N-, -CH=NN=CH-, -CF=CF-, -C≡C-, or a direct bond. When an anisotropic dye film is formed using the polymerizable liquid crystal compound obtained from compound (III), X1, X2, and X3 are preferably each independently -O-, -COO-, or -C≡C-, from the viewpoint of increasing the dichroic ratio of the anisotropic dye film.

[0071] In general formula (III), R represents a hydrocarbon group having 1 to 4 carbon atoms which may have a substituent, and a represents an integer of 0 to 4. When a is 2 or more, multiple Rs may be the same or different. When an anisotropic dye film is formed using a polymerizable liquid crystal compound obtained from compound (III), the polymerizable liquid crystal compound preferably has high crystallinity, and a=0 is preferred, from the viewpoint of increasing the dichroic ratio of the anisotropic dye film.

[0072] Specific examples of the compound (III) include compounds represented by the following formulae (III-1) to (III-25).

[0073] [ka]

[0074] [ka]

[0075] [ka]

[0076] <Compound represented by general formula (V)> Among the compounds (III), the compound of the present invention represented by the following general formula (V) (hereinafter, sometimes referred to as "compound (V)") is useful as an intermediate for a polymerizable liquid crystal compound.

[0077] [ka]

[0078] In formula (V), A3 and A4 have the same meanings as A1 and A2 in general formula (III), and the preferred ranges are also the same, provided that A3 and A4 represent different groups from the viewpoint of the physical properties of the resulting polymerizable liquid crystal compound. A 31 , A 32 , A 41 and A 42 is A in the general formula (III). 11 , A 12 , A 21 , A 22 The same applies to the preferred ranges. In formula (V), Sp3 and Sp4 have the same meanings as Sp1 and Sp2 in general formula (III), and the preferred ranges are also the same. In formula (V), X4, X5, and X6 have the same meanings as X1, X2, and X3 in general formula (III), and the preferred ranges are also the same. In formula (V), R and a have the same meanings as R and a in general formula (III), and the preferred ranges are also the same.

[0079] Specific examples of compound (V) include the same compounds as those given as specific examples of compound (III).

[0080] <Method for producing the compound represented by general formula (III)> The method for producing a compound according to the first aspect of the present invention is a method for producing compound (III) using a compound represented by the following general formula (I) (hereinafter, sometimes referred to as "compound (I)") as a starting material, without going through a step of introducing a substituent into the hydroxy group bonded to Sp2 in general formula (I).

[0081] [ka]

[0082] (In formula (I), A2, A 21 , A 22 , X2, X3, Sp2, R and a represent A2, A 21 , A 22 , X2, X3, Sp2, R and a are synonymous.)

[0083] In the present invention, the number of steps for producing compound (III) can be reduced by eliminating the step of introducing a substituent into the hydroxy group bonded to Sp2 in general formula (I).Furthermore, the generation of by-products due to the step of introducing a substituent into the hydroxy group and the resulting decrease in yield can be suppressed.

[0084] Furthermore, the method for producing a compound according to the second aspect of the present invention is a method for producing compound (III) by reacting a compound represented by the general formula (I) (compound (I)) with a compound represented by the following general formula (II) (hereinafter, sometimes referred to as "compound (II)"), as shown in the following reaction scheme. This method also makes it possible to reduce the number of steps for producing compound (III), and to suppress the generation of by-products in the step of introducing a substituent into a hydroxy group and the resulting decrease in yield. The second embodiment can be cited as a preferred embodiment of the first embodiment.

[0085] [ka]

[0086] [ka]

[0087] (In formula (II), A1, A 11 , A 12 , X1 and Sp1 are A1, A 11 , A 12 , X1 and Sp1.)

[0088] As in the second embodiment, compound (III) can be obtained by reacting compound (I) with compound (II). Examples of the reaction method include a method using a condensing agent (hereinafter, sometimes referred to as "Method (1)"), and a method in which compound (II) is reacted with compound (I) together with an acid chloride, a mixed acid anhydride, or a carboxylic acid anhydride in the presence of a base and a salt (hereinafter, sometimes referred to as "Method (2)").

[0089] Examples of the condensing agent in the method (1) include N,N'-dicyclohexylcarbodiimide, N,N'-diisopropylcarbodiimide, 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide hydrochloride, and dimethylsulfamoyl chloride. Examples of the base used in the method (2) include triethylamine, diisopropylethylamine, N,N-dimethylaniline, and 4-dimethylaminopyridine. Examples of the salt include trimethylamine hydrochloride and triethylamine hydrochloride.

[0090] Depending on the structure of X3, the starting material compound (I) may be obtained by reacting a compound containing X3 with another compound, or by reacting two compounds to form X3.

[0091] When compound (I) is obtained by reacting a compound containing X3 with a compound other than X3, for example, when X3 is -O-, it can be produced according to the following reaction scheme.

[0092] [ka]

[0093] When compound (I) is obtained by reacting two compounds to form X3, for example, when X3 is -OCO-, it can be produced according to the following reaction scheme.

[0094] [ka]

[0095] According to the above reaction scheme, compound (Ib) can be obtained by reacting a compound represented by general formula (S-1b) with a compound represented by general formula (S-2b). Examples of the reaction method include a method using a condensing agent (hereinafter, sometimes referred to as "method (1-1)"), or a method in which a compound represented by general formula (S-1b) is reacted with an acid chloride, a mixed acid anhydride, or a carboxylic acid anhydride in the presence of a base and a salt (hereinafter, sometimes referred to as "method (1-2)"). Examples of the condensing agent in the method (1-1) include N,N'-dicyclohexylcarbodiimide, N,N'-diisopropylcarbodiimide, 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide hydrochloride, and dimethylsulfamoyl chloride. Examples of the base in the method (1-2) include triethylamine, diisopropylethylamine, N,N-dimethylaniline, and 4-dimethylaminopyridine. Examples of the salt include trimethylamine hydrochloride and triethylamine hydrochloride.

[0096] Compound (II) can be produced, for example, according to the following reaction scheme.

[0097] [ka]

[0098] In the above reaction scheme, LG represents a leaving group and PG represents a protecting group.

[0099] According to the above reaction scheme, a compound represented by general formula (S-3) can be reacted with a compound represented by general formula (S-4) in the presence of a base to obtain a compound represented by general formula (S-5). Examples of the base include potassium carbonate, cesium carbonate, and sodium carbonate.

[0100] Examples of the leaving group LG in the compound represented by general formula (S-4) include a chlorine atom, a bromine atom, an iodine atom, a methanesulfonyloxy group, and a p-toluenesulfonyloxy group.

[0101] As the protecting group PG in the compounds represented by general formulae (S-3) and (S-5), for example, those listed in GREENE'S PROTECTIVE GROUPS IN ORGANIC SYNTHESIS ((Fourth Edition), co-authored by PETER GMWUTS and THEODORA W. GREENE, A John Wiley & Sons, Inc., Publication) are preferred. Specific examples of the protecting group PG include a methyl group and an ethyl group.

[0102] Compound (II) can be obtained by deprotecting the protecting group PG of the compound represented by general formula (S-5). The deprotection reaction method is preferably, for example, the method described in the above-mentioned non-patent document. Specifically, a method of deprotection in the presence of a base such as sodium hydroxide or potassium hydroxide can be mentioned.

[0103] <Compound represented by general formula (I)> Compound (I), which is a raw material for compound (III) and is represented by the following general formula (I), is a useful compound that can be used as a raw material for compound (III) to produce compound (III), which is an intermediate for a polymerizable liquid crystal compound, according to the compound production method of the present invention.

[0104] [ka]

[0105] In formula (I), A2 has the same meaning as A2 in general formula (III), and the preferred range is also the same. A 21 and A 22 is A in the general formula (III). 21 , A 22 The same applies to the preferred ranges. In formula (I), Sp2 has the same meaning as Sp2 in general formula (III), and the preferred range is also the same. In formula (I), X2 and X3 have the same meanings as X2 and X3 in general formula (III), and the preferred ranges are also the same. In formula (I), R and a have the same meanings as R and a in general formula (III), and the preferred ranges are also the same.

[0106] The method for producing compound (I) is as described above.

[0107] <Compound represented by general formula (IV)> Using compound (III), preferably compound (V), as an intermediate, a compound represented by the following general formula (IV), which is a polymerizable liquid crystal compound (hereinafter, sometimes referred to as "compound (IV)"): can be manufactured.

[0108] [ka]

[0109] (In formula (IV), A1, A2, A 11 , A 12 , A 21 , A 22 , X1, X2, X3, Sp1, Sp2, R and a represent A1, A2, A 11 , A 12 , A 21 , A 22 , X1, X2, X3, Sp1, Sp2, R and a. P represents a group that is polymerizable by radical polymerization, cationic polymerization, or anionic polymerization.

[0110] In the general formula (IV), P represents a group that can be polymerized by radical polymerization, cationic polymerization, or anionic polymerization. Specific examples include an acryloyl group, a methacryloyl group, an acryloyloxy group, a methacryloyloxy group, an acryloylamino group, a methacryloylamino group, a vinyl group, a vinyloxy group, an ethynyl group, an ethynyloxy group, a 1,3-butadienyl group, a 1,3-butadienyloxy group, an oxiranyl group, an oxetanyl group, a glycidyl group, a glycidyloxy group, a styryl group, and a styryloxy group. Of these, an acryloyl group, a methacryloyl group, an acryloyloxy group, a methacryloyloxy group, an acryloylamino group, a methacryloylamino group, an oxiranyl group, a glycidyl group, and a glycidyloxy group are preferred, an acryloyl group, a methacryloyloxy group, a methacryloylamino group, a methacryloylamino group, a glycidyl group, and a glycidyloxy group are more preferred, and an acryloyloxy group, a methacryloyloxy group, and a glycidyloxy group are even more preferred.

[0111] The two Ps in general formula (IV) may be the same or different, but when they are the same, both ends can be polymerized under similar conditions when polymerizing compound (IV), and the resulting polymer tends to have excellent solvent resistance and thermal stability, which is preferable.

[0112] Compound (IV) can be produced using compound (III) by the following method. For example, compound (IV-1), which is compound (IV) in which P is an acryloyloxy group, can be produced by the following method.

[0113] [ka]

[0114] In the above reaction scheme, LG represents a leaving group.

[0115] According to the above reaction scheme, compound (IV-1) can be obtained by reacting a compound represented by general formula (III) with a compound represented by general formula (S-6). Examples of the reaction method include a method using a condensing agent (hereinafter, sometimes referred to as "method (3-1)"), or a method in which a compound represented by general formula (III) is reacted with an acid chloride, mixed acid anhydride, or carboxylic acid anhydride represented by general formula (S-6) in the presence of a base and a salt (hereinafter, sometimes referred to as "method (3-2)"). Examples of the condensing agent in the method (3-1) include N,N'-dicyclohexylcarbodiimide, N,N'-diisopropylcarbodiimide, 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide hydrochloride, and dimethylsulfamoyl chloride. In the method (3-2), examples of the base include triethylamine, diisopropylethylamine, N,N-dimethylaniline, and 4-dimethylaminopyridine. Examples of the salt include trimethylamine hydrochloride and triethylamine hydrochloride.

[0116] Examples of the leaving group LG in the compound represented by general formula (S-6) include a chlorine atom, a bromine atom, an iodine atom, a methanesulfonyloxy group, and a p-toluenesulfonyloxy group.

[0117] Compound (IV-2), which is compound (IV) where P is a methacryloyloxy group, can be produced, for example, by the following method.

[0118] [ka]

[0119] In the above reaction scheme, LG represents a leaving group.

[0120] According to the above reaction scheme, compound (IV-2) can be obtained by reacting a compound represented by general formula (III) with a compound represented by general formula (S-7). Examples of the reaction method include a method using a condensing agent (hereinafter, sometimes referred to as "method (4-1)"), or a method in which a compound represented by general formula (III) is reacted with an acid chloride, mixed acid anhydride, or carboxylic acid anhydride represented by general formula (S-7) in the presence of a base and a salt (hereinafter, sometimes referred to as "method (4-2)"). Examples of the condensing agent in the method (4-1) include N,N'-dicyclohexylcarbodiimide, N,N'-diisopropylcarbodiimide, 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide hydrochloride, and dimethylsulfamoyl chloride. In the method (4-2), examples of the base include triethylamine, diisopropylethylamine, N,N-dimethylaniline, and 4-dimethylaminopyridine. Examples of the salt include trimethylamine hydrochloride and triethylamine hydrochloride.

[0121] Examples of the leaving group LG in the compound represented by general formula (S-7) include a chlorine atom, a bromine atom, an iodine atom, a methanesulfonyloxy group, and a p-toluenesulfonyloxy group.

[0122] Compound (IV-3), in which P is a glycidyloxy group in compound (IV), can be produced by the following method.

[0123] [ka]

[0124] In the above reaction scheme, LG represents a leaving group.

[0125] According to the above reaction scheme, compound (IV-3) can be obtained by reacting a compound represented by general formula (III) with a compound represented by general formula (S-8). Examples of the reaction method include a method using a condensing agent (hereinafter, sometimes referred to as "method (5-1)"), or a method in which a compound represented by general formula (III) is reacted with a compound represented by general formula (S-8) in the presence of a base and a salt (hereinafter, sometimes referred to as "method (5-2)"). Examples of the condensing agent in the method (5-1) include N,N'-dicyclohexylcarbodiimide, N,N'-diisopropylcarbodiimide, 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide hydrochloride, and dimethylsulfamoyl chloride. Examples of the base in the method (5-2) include sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, triethylamine, diisopropylethylamine, N,N-dimethylaniline, and 4-dimethylaminopyridine. Examples of the salt include trimethylamine hydrochloride and triethylamine hydrochloride.

[0126] Examples of the leaving group LG in the compound represented by general formula (S-8) include a chlorine atom, a bromine atom, an iodine atom, a methanesulfonyloxy group, and a p-toluenesulfonyloxy group.

[0127] <Polymerizable composition> A polymerizable composition (hereinafter, sometimes referred to as the "polymerizable composition of the present invention") can be prepared by blending compound (III) and / or compound (IV). The prepared polymerizable composition can be used, for example, as a nematic liquid crystal composition, a smectic liquid crystal composition, a chiral smectic liquid crystal composition, or a cholesteric liquid crystal composition.

[0128] The polymerizable composition of the present invention preferably contains compound (IV), which is a polymerizable liquid crystal compound.

[0129] The polymerizable composition of the present invention may contain other additives, as needed, such as a solvent, a polymerizable liquid crystal compound other than compound (IV), a non-polymerizable liquid crystal compound, a polymerization initiator, a polymerization inhibitor, a polymerization aid, a polymerizable non-liquid crystal compound, a surfactant, a leveling agent, a coupling agent, a pH adjuster, a dispersant, an antioxidant, an organic or inorganic filler, an organic or inorganic nanosheet, an organic or inorganic nanofiber, or a metal oxide.

[0130] <Polymers / Optical Anisotropic Materials> A polymer (hereinafter, sometimes referred to as "the polymer of the present invention") can be produced by polymerizing the polymerizable composition of the present invention. The produced polymer can be used for various purposes.

[0131] For example, polymers obtained by polymerizing the polymerizable composition of the present invention without orientation can be used as light-scattering plates, depolarizing plates, and anti-moiré plates. Furthermore, polymers obtained by polymerizing the composition after orientation have optical anisotropy and are useful. That is, an optically anisotropic body (hereinafter sometimes referred to as the "optically anisotropic body of the present invention") can be produced using the polymer of the present invention. The optically anisotropic body of the present invention can be produced, for example, by supporting the polymerizable composition of the present invention on a substrate that has been rubbed with a cloth or the like, a substrate on which an organic thin film has been formed, or a substrate on which an orientation film formed by obliquely vapor-depositing SiO2 has been formed, or by sandwiching the polymerizable composition between such substrates, and then polymerizing the polymerizable composition.

[0132] Examples of methods for supporting the polymerizable composition of the present invention on a substrate include spin coating, die coating, extrusion coating, roll coating, wire bar coating, gravure coating, spray coating, dipping, and printing.

[0133] In addition, an organic solvent may be added to the polymerizable composition during coating. Examples of the organic solvent that can be used include hydrocarbon solvents, halogenated hydrocarbon solvents, ether solvents, alcohol solvents, ketone solvents, ester solvents, and aprotic solvents. For example, hydrocarbon solvents include toluene or hexane. Halogenated hydrocarbon solvents include methylene chloride. Ether solvents include tetrahydrofuran, acetoxy-2-ethoxyethane, or propylene glycol monomethyl ether acetate. Alcohol solvents include methanol, ethanol, or isopropanol. Ketone solvents include acetone, methyl ethyl ketone, cyclohexanone, γ-butyl lactone, or N-methylpyrrolidinones. Ester solvents include ethyl acetate or cellosol. Aprotic solvents include dimethylformamide or acetonitrile. These may be used alone or in combination, and may be appropriately selected taking into consideration their vapor pressure and the solubility of the polymerizable composition.

[0134] Examples of methods that can be used to volatilize the added organic solvent include natural drying, heat drying, reduced-pressure drying, and reduced-pressure heat drying. In order to further improve the coatability of the polymerizable composition, 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 composition. The method of providing an intermediate layer such as a polyimide thin film on the substrate is effective for improving the adhesion between the polymer obtained by polymerizing the polymerizable composition and the substrate.

[0135] Other alignment treatments include the use of flow alignment of liquid crystal compounds and the use of electric or magnetic fields. These alignment means may be used alone or in combination. Furthermore, a photoalignment method may be used as an alignment treatment method instead of rubbing.

[0136] The substrate may be in the form of a flat plate or may have a curved surface as a constituent part. The material constituting the substrate can be either organic or inorganic.

[0137] Examples of organic materials that can be used for the substrate include polyethylene terephthalate, polycarbonate, polyimide, polyamide, polymethyl methacrylate, polystyrene, polyvinyl chloride, polytetrafluoroethylene, polychlorotrifluoroethylene, polyarylate, polysulfone, triacetyl cellulose, cellulose, and polyether ether ketone. Examples of inorganic materials that can be used for the substrate include silicon, glass, and calcite.

[0138] When polymerizing the polymerizable composition of the present invention, it is desirable that the polymerization proceeds quickly, and therefore a method of polymerizing by irradiation with active energy rays such as ultraviolet rays or electron beams is preferred.

[0139] When ultraviolet light is used, either a polarized light source or a non-polarized light source may be used. When polymerizing a polymerizable composition sandwiched between two substrates, at least the substrate on the irradiation side must have appropriate transparency to actinic energy rays. A method may be used in which only specific parts are polymerized using a mask during light irradiation, and then the orientation state of the unpolymerized parts is changed by changing conditions such as an electric field, a magnetic field, or temperature, and then further polymerized by irradiating with actinic energy rays.

[0140] The temperature during irradiation with active energy rays is preferably within a temperature range in which the liquid crystal state of the polymerizable composition is maintained. In particular, when an optically anisotropic material is to be produced by irradiation with active energy rays, in order to avoid unintended thermal polymerization, the polymerization can be carried out at a temperature as close to room temperature as possible, i.e., typically in the range of 10 to 100°C, preferably 15 to 60°C, more preferably 20 to 50°C, and for example, it is preferable to carry out the polymerization at a temperature of 25°C. The intensity of the active energy rays is 0.1 mW / cm 2 ~2W / cm 2 When the strength is in this range, it is possible to increase productivity while suppressing deterioration of the polymerizable composition, which is preferable.

[0141] The optically anisotropic material obtained by polymerization may be subjected to a heat treatment in order to reduce initial changes in properties and ensure stable property development. 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.

[0142] The optically anisotropic body produced by such a method may be used alone after being peeled off from the substrate, or may be used without being peeled off. The obtained optically anisotropic body may be laminated or may be attached to another substrate for use.

[0143] <Various products> In addition to the polymerizable composition of the present invention, various products can be produced by blending Compound (III) and / or Compound (IV). Examples of the products that can be produced include resins, resin additives, oils, filters, adhesives, pressure-sensitive adhesives, oils and fats, inks, pharmaceuticals, cosmetics, detergents, building materials, packaging materials, liquid crystal materials, organic electroluminescent materials, encapsulants, organic semiconductor materials, electronic materials, display elements, electronic devices, communication equipment, automobile parts, aircraft parts, machine parts, agricultural chemicals, and foods, as well as products using them. [Example]

[0144] The present invention will be described in more detail below with reference to examples, but the present invention is not limited to the following examples as long as it does not depart from the gist of the invention. In the following description, "parts" means "parts by weight."

[0145] [Example 1] Compound (I-1-e) and compound (I-1) were synthesized according to the synthesis method described below.

[0146] [ka]

[0147] Synthesis of compound (I-1-a): Ethyl propiolate (9.7 g, 99 mmol) and copper(I) oxide (7.5 g, 94 mmol) were added to a solution of p-iodophenol (11.0 g, 50 mmol) in N,N-dimethylformamide (150 mL), and the mixture was stirred at 110°C for 9 hours and allowed to cool to room temperature. The precipitate was filtered off, and then ethyl acetate was added. The mixture was washed with water and then saturated brine. Purification was performed by silica gel column chromatography (hexane / ethyl acetate) to obtain 7.3 g of compound (I-1-a) as brown crystals.

[0148] Synthesis of compound (I-1-b): Compound (I-1-a) (4.20 g, 22.1 mmol), 11-bromo-1-undecanol (5.55 g, 22.1 mmol), potassium carbonate (6.10 g, 44.2 mmol), and N,N-dimethylformamide (30 mL) were mixed and stirred at 80°C for 4 hours. The precipitate was filtered off, and then diethyl ether was added. The mixture was washed with water and then saturated brine. Purification was performed by silica gel column chromatography (hexane / ethyl acetate), yielding 5.5 g of compound (I-1-b) as an orange solid.

[0149] Synthesis of compound (I-1-c): Compound (I-1-b) (3.6 g, 10 mmol), potassium hydroxide (1.7 g, 30 mmol), and water (20 mL) were mixed and stirred at 100°C for 2 hours. Water (20 mL) was added, and the mixture was acidified with concentrated hydrochloric acid. The precipitate was then filtered off. The resulting precipitate was washed by suspending in acetonitrile, yielding 3.2 g of compound (I-1-c) as a milky white solid.

[0150] Compound (I-1-d) was synthesized according to the synthesis method described below.

[0151] [ka]

[0152] Synthesis of compound (I-1-g): Compound (I-1-f) was synthesized according to the method described in Lub et al., Recl. Trav. ChIm. Pays-Bas, 115, 321-328 (1996). Next, compound (I-1-f) (trans isomer only) (42.9 g, 107.6 mmol), p-toluenesulfonic acid pyridinium salt (2.6 g, 10.8 mmol), and ethanol (430 mL) were mixed and stirred at 78 °C for 2 hours. The solvent was distilled off, and the mixture was dissolved in ethyl acetate (150 mL), and hexane (750 mL) was added and cooled. The precipitate was filtered, washed with hexane, and then dried to obtain 29.2 g of compound (I-1-g) as a white solid.

[0153] Synthesis of compound (I-1-d): Hydroquinone (17.5 g, 159 mmol), 4-dimethylaminopyridine (0.60 g, 5.33 mmol), 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride (4.52 g, 23.6 mmol), and acetonitrile (50 mL) were mixed and cooled in an ice bath. Compound (I-1-g) (5.00 g, 15.9 mmol) was added to the mixture, followed by stirring at 25°C for 12 hours. The resulting precipitate was filtered, washed with acetonitrile and then with water, and dried to obtain 4.40 g of compound (I-1-d) as a white solid.

[0154] The results of structural confirmation of compound (I-1-d) by NMR are shown below. 1 H NMR(CDCl3,400MHz)δ1.20-1.70(m,22H),2. 09-2.20(m,4H),2.45-2.55(m,1H),3.21-3.29(m,1H),3.46(t,2H,J=6.7Hz),3.64(t,2H,J=6.7Hz),6.80(d,2H,J=9.0Hz),6.91(d,2H,J=9.0Hz)

[0155] Synthesis of compound (I-1-e) using compound (I-1-c) and compound (I-1-d): Compound (I-1-d) (2.60 g, 6.40 mmol), compound (I-1-c) (2.03 g, 6.11 mmol), 4-dimethylaminopyridine (0.23 g, 0.90 mmol), triethylamine (1.86 g, 18.4 mmol), trimethylamine hydrochloride (1.19 g, 12.4 mmol), and acetonitrile were mixed and cooled on ice. Dimethylsulfamoyl chloride (1.78 g, 12.4 mmol) was added. After stirring at 25 °C for 15 hours, the reaction mixture was filtered, and the solid was washed with acetonitrile and then with water. The resulting solid was dried under reduced pressure, dissolved in 3.5 mL of dichloromethane, and 3.5 mL of hexane was added. The precipitate was filtered off. The mixture was washed with dichloromethane and then with hexane, and then dried to obtain 1.72 g of compound (I-1-e) as a pale yellow solid.

[0156] The results of liquid chromatography-mass spectrometry of compound (I-1-e) are shown below. LC-MS(APCI)m / z 720.54(M+NH4) + The results of structural confirmation by NMR are shown below. 1 H NMR(CDCl3,400MHz)δ1.20-1.70(m,38H),1.74-1.85(m,2H),2.05-2.25(m,4H),2.49-2.58(m,1H),3.21-3.29(m,1H),3.46(t,2H,J= 6.7Hz),3.64(m,4H),3.99(t,2H,J=6.6Hz),6.89(d,2H,J=9.0Hz),7.10(d,2H,J=9.0Hz),7.19(d,2H,J=9.0Hz),7.55(d,2H,J=9.0Hz)

[0157] Synthesis of compound (I-1): Compound (I-1-e) (2.20 g, 3.05 mmol), N,N-dimethylaniline (1.08 g, 8.94 mmol), 2,5-di-t-butylphenol (0.026 g, 0.12 mmol), and dichloromethane (20 mL) were mixed. After cooling in an ice bath, acryloyl chloride (0.71 g, 7.80 mmol) was slowly added. After the dropwise addition, the mixture was stirred at 5°C for 6 hours, and the dichloromethane layer was washed with water. After distilling off the dichloromethane, the mixture was purified by silica gel column chromatography (hexane / ethyl acetate) to obtain 1.10 g of compound (I-1) as a white solid.

[0158] [Example 2] Compound (I-1-e) and compound (I-1) were synthesized according to the synthesis method described below.

[0159] [ka]

[0160] Synthesis of compound (I-1-h): Hydroquinone (3.31 g, 30.1 mmol), 4-dimethylaminopyridine (0.10 g, 0.89 mmol), 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride (0.86 g, 4.50 mmol), and acetonitrile (10 mL) were mixed and cooled in an ice bath. Compound (I-1-c) (1.00 g, 3.01 mmol), synthesized in the same manner as in Example 1, was added to the mixture, and the mixture was stirred at 25°C for 12 hours. The resulting precipitate was filtered, washed with acetonitrile and then with water, and then dried to obtain 0.98 g of compound (I-1-h) as a pale yellow solid.

[0161] Synthesis of compound (I-1-e) using compound (I-1-h) and compound (I-1-g): Compound (I-1-h) (0.100 g, 0.24 mmol), 4-dimethylaminopyridine (0.010 g, 0.90 mmol), 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride (0.076 g, 0.40 mmol), and dichloromethane (4 mL) were mixed and cooled on ice. Compound (I-1-g) (0.073 g, 0.23 mmol), synthesized in the same manner as in Example 1, was then added. After stirring at 25°C for 15 hours, the dichloromethane layer was washed with 1N hydrochloric acid and then with water. The dichloromethane was distilled off, the reaction solution was filtered, and the solid was washed with acetonitrile and then with water. The resulting solid was dried under reduced pressure, dissolved in 3.5 mL of dichloromethane, and 3.5 mL of hexane was added. The resulting precipitate was filtered off. After distilling off dichloromethane, the residue was purified by silica gel column chromatography (hexane / ethyl acetate) to obtain 0.07 g of compound (I-1-e) as a white solid.

[0162] The results of structural confirmation of compound (I-1-e) by NMR are shown below. 1 H NMR(CDCl3,400MHz)δ1.20-1.60(m,16H),1.74-1.83(m,2H),3.65(t,2H,J=6.6Hz),3.99(t,2H,J= 6.6Hz),6.85(d,2H,J=9.0Hz),6.88(d,2H,J=9.0Hz),7.05(d,2H,J=9.0Hz),7.55(d,2H,J=9.0Hz)

[0163] Synthesis of compound (I-1): Using the compound (I-1-e), 0.06 g of a white solid compound (I-1) was obtained in the same manner as in Example 1.

[0164] [Comparative Example 1] Compound (I-1) was synthesized according to the synthesis method described below.

[0165] [ka]

[0166] Synthesis of compound (I-1-i): Compound (I-1-c) (2.33 g, 7.0 mmol), synthesized in the same manner as in Example 1, was mixed with tetrahydrofuran (20 mL), followed by the addition of N,N-dimethylaniline (1.02 g, 8.4 mmol) and 2,5-di-t-butylphenol (54 mg). After cooling in an ice bath, acryloyl chloride (0.76 g, 8.4 mmol) was slowly added. After stirring for 6 hours in an ice bath, methylene chloride was added, and the mixture was washed with 1 mol / L hydrochloric acid, saturated aqueous sodium bicarbonate, and then saturated saline. The mixture was purified by silica gel column chromatography (chloroform / methanol) to obtain 2.0 g of compound (I-1-i) as a white solid.

[0167] Synthesis of compound (I-1-j): Compound (I-1-j) was synthesized by the synthesis method described in WO 2019 / 181888.

[0168] Synthesis of compound (I-1-k): Compound (I-1-i) (2.00 g, 5.17 mmol), compound (I-1-j) (1.01 g, 5.17 mmol), 4-dimethylaminopyridine (0.13 g, 1.03 mmol), 2,5-di-t-butylphenol (58 mg), and methylene chloride (30 mL) were mixed and cooled in an ice bath. 1-Ethyl-3-(3-dimethylaminopropyl)carbodiimide hydrochloride (1.09 g, 5.69 mmol) was then added. After standing overnight, the mixture was washed with saturated aqueous ammonium chloride and then saturated saline. The mixture was purified by silica gel column chromatography (hexane / ethyl acetate) to obtain 1.9 g of compound (I-1-k) as a white solid. Ta.

[0169] Synthesis of compound (I-1-l): Compound (I-1-k) (2.6 g, 4.62 mmol), p-toluenesulfonic acid pyridinium salt (0.23 g, 0.92 mmol), 2,5-di-t-butylphenol (44 mg), and ethanol (20 mL) were mixed and stirred for 2 hours at 50° C. The reaction solution was poured into water, and the resulting precipitate was filtered and dried to obtain 2.0 g of compound (I-1-l) as a white solid.

[0170] Synthesis of Compound (I-1-n): Compound (I-1-n) was synthesized according to the synthesis method described below.

[0171] [ka]

[0172] Compound (I-1-f) was synthesized according to the method described in Lub et al., Recl. Trav. ChIm. Pays-Bas, 115, 321-328 (1996).

[0173] Next, compound (I-1-f) (trans isomer only) (42.9 g, 107.6 mmol), p-toluenesulfonic acid pyridinium salt (2.6 g, 10.8 mmol), and ethanol (430 mL) were mixed and stirred at 78 °C for 2 hours. The solvent was distilled off, and the mixture was dissolved in ethyl acetate (150 mL), and hexane (750 mL) was added and cooled. The precipitate was filtered, washed with hexane, and then dried to obtain 29.2 g of compound (I-1-m) as a white solid.

[0174] Compound (I-1-m) (37.2 g, 118.3 mmol), N,N-dimethylaniline (21.5 g, 177.5 mmol), 2,5-di-t-butylphenol (0.24 g), and tetrahydrofuran (380 mL) were mixed. After cooling in an ice bath, acryloyl chloride (16.1 g, 177.5 mmol) was slowly added. After the dropwise addition, the mixture was stirred at 50°C for 2 hours. The solvent was distilled off until the liquid volume reached 190 mL, and the mixture was poured into 1 mol / L hydrochloric acid under ice cooling. The precipitate was filtered and washed with water and then hexane. The mixture was purified by silica gel column chromatography (hexane / ethyl acetate) to obtain 39.4 g of compound (I-1-n) as a white solid.

[0175] Synthesis of compound (I-1): Compound (I-1-l) (494 mg, 1.03 mmol), compound (I-1-n) (400 mg, 1.09 mmol), 4-dimethylaminopyridine (27 mg, 0.22 mmol), 2,5-di-t-butylphenol (2 mg), and methylene chloride (10 mL) were mixed and cooled in an ice bath. 1-Ethyl-3-(3-dimethylaminopropyl)carbodiimide hydrochloride (230 mg, 1.19 mmol) was then added. After stirring for 4 hours in an ice bath, the mixture was washed with saturated aqueous ammonium chloride and then with saturated saline. Purification by silica gel column chromatography (hexane / ethyl acetate) afforded 530 mg of compound (I-1) as a white solid.

[0176] [Example 3] Compound (I-2-b) and compound (I-2) were synthesized according to the synthesis method described below.

[0177] [ka]

[0178] Synthesis of compound (I-2-a): Under an argon atmosphere, 11-bromo-1-undecanol (375 g, 1.49 mol), N,N-dimethylacetamide (500 mL), potassium carbonate (435 g, 3.14 mol), and ethyl 1-hydroxybenzoate (250 g, 1.50 mol) were added to a 10 L four-neck flask and stirred at 100 °C for 3 hours. After cooling to room temperature, the reaction mixture was added to 2.5 L of distilled water, and the precipitated solid was filtered and washed with water to obtain 933 g of a white solid. Next, under an argon atmosphere, 933 g of the resulting white solid and 2 L of distilled water were added to a four-neck flask, and potassium hydroxide (250 g, 4.47 mol) was added. The mixture was stirred at 90 °C for 3 hours and cooled to room temperature. Concentrated hydrochloric acid (420 mL) was added dropwise to the reaction mixture, and the precipitated solid was filtered and washed with water. The product was purified by crystallization from acetonitrile to obtain 425 g of compound (I-2-a) as a white solid.

[0179] Compound (I-2-c) was synthesized according to the synthesis method described below.

[0180] [ka]

[0181] Synthesis of compound (I-2-e): Compound (I-2-d) was synthesized according to the method described in Lub et al., Recl. Trav. ChIm. Pays-Bas, 115, 321-328 (1996). Next, compound (I-2-d) (trans isomer only) (42.9 g, 107.6 mmol), p-toluenesulfonic acid pyridinium salt (2.6 g, 10.8 mmol), and ethanol (430 mL) were mixed and stirred at 78 °C for 2 hours. The solvent was distilled off, and the mixture was dissolved in ethyl acetate (150 mL), and hexane (750 mL) was added and cooled. The precipitate was filtered, washed with hexane, and then dried to obtain 29.2 g of compound (I-2-e) as a white solid.

[0182] Synthesis of compound (I-2-c): Hydroquinone (17.5 g, 159 mmol), 4-dimethylaminopyridine (0.60 g, 5.33 mmol), 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride (4.52 g, 23.6 mmol), and acetonitrile (50 mL) were mixed and cooled in an ice bath. Compound (I-2-e) (5.00 g, 15.9 mmol) was added, and the mixture was stirred at 25°C for 12 hours. The precipitate was filtered, washed with acetonitrile and then with water, and then dried to obtain 4.40 g of compound (I-2-c) as a white solid.

[0183] The results of structural confirmation of compound (I-2-c) by NMR are shown below. 1 H NMR(CDCl3,400MHz)δ1.20-1.70(m,22H),2.09-2.20(m,4H),2.45-2.55(m,1H),3.21-3.29(m, 1H),3.46(t,2H,J=6.7Hz),3.64(t,2H,J=6.7Hz),6.80(d,2H,J=9.0Hz),6.91(d,2H,J=9.0Hz)

[0184] Synthesis of compound (I-2-b) using compound (I-2-a) and compound (I-2-c): Compound (I-2-a) (1.51 g, 4.89 mmol), compound (I-2-c) (2.03 g, 4.89 mmol), 4-dimethylaminopyridine (0.18 g, 1.43 mmol), triethylamine (1.46 g, 1.43 mmol), trimethylamine hydrochloride (0.91 g, 9.55 mmol), and acetonitrile (40 mL) were mixed and cooled on ice. Dimethylsulfamoyl chloride (1.38 g, 9.60 mmol) was added and stirred for 3 hours. After stirring at 25 °C for 3 hours, the reaction mixture was filtered, and the solid was washed with acetonitrile and then with water. The resulting solid was dried to obtain 2.05 g of compound (I-2-b) as a white solid.

[0185] The results of structural confirmation of compound (I-2-b) by NMR are shown below. 1 H NMR(CDCl3,400MHz)δ1.22-1.66(m,38H),1.78-1.85(m,2H),2.12-2.20(m,4H),2.50-2.56(m,1H),3.23-3.29(m,1H),3.47(t,2H,J= 6.7Hz),3.64(m,4H),4.04(t,2H,J=6.8Hz),6.96(d,2H,J=8.0Hz),7.10(d,2H,J=6.8Hz),7.19(d,2H,J=8.0Hz),8.12(d,2H,J=6.8Hz)

[0186] Synthesis of compound (I-2): Compound (I-2-b) (1.05 g, 1.46 mmol), N,N-dimethylaniline (0.51 g, 4.22 mmol), 2,5-di-t-butylphenol (0.6 mg, 0.2 mol%), and dichloromethane (10 mL) were mixed. After cooling in an ice bath, acryloyl chloride (0.35 g, 3.89 mmol) was slowly added. After stirring at room temperature for 5 hours, the dichloromethane layer was washed with 1 M hydrochloric acid (2 mL). After distilling off the dichloromethane, the mixture was purified by silica gel column chromatography (hexane / dichloromethane / ethyl acetate) to obtain 0.46 g of compound (I-2) as a white solid.

[0187] Comparative Example 2 Compound (I-2) was synthesized according to the synthesis method described below.

[0188] [ka]

[0189] Synthesis of compound (I-2-f): Compound (I-2-a) (2.01 g, 6.52 mmol), synthesized in a similar manner to Example 3, 1-hydroxy-2,6-di-tert-butyltoluene (15.9 mg, 1 mol%), N,N-dimethylaniline (1.74 g, 14.3 mmol), and tetrahydrofuran (16 mL) were mixed and cooled in an ice bath. Acryloyl chloride (1.30 g, 14.3 mmol) was added dropwise, and the mixture was allowed to react at room temperature overnight. 1 mol / L hydrochloric acid (10 mL) was added, and the mixture was extracted with ethyl acetate, followed by distillation of the solvent. Toluene / heptane was added to the resulting crude product, and the precipitate was filtered and dried to obtain 1.90 g of compound (I-2-f) as a white solid.

[0190] Compound (I-2-g) was synthesized according to the synthesis method described below.

[0191] [ka]

[0192] Synthesis of compound (I-2-e): Compound (I-2-d) was synthesized according to the method described in Lub et al., Recl. Trav. ChIm. Pays-Bas, 115, 321-328 (1996). Next, compound (I-2-d) (trans isomer only) (42.9 g, 107.6 mmol), p-toluenesulfonic acid pyridinium salt (2.6 g, 10.8 mmol), and ethanol (430 mL) were mixed and stirred at 78 °C for 2 hours. The solvent was distilled off, and the mixture was dissolved in ethyl acetate (150 mL), and hexane (750 mL) was added and cooled. The precipitate was filtered, washed with hexane, and then dried to obtain 29.2 g of compound (I-2-e) as a white solid.

[0193] Synthesis of compound (I-2-h): Compound (I-2-e) (37.2 g, 118.3 mmol), N,N-dimethylaniline (21.5 g, 177.5 mmol), 2,5-di-tert-butylphenol (0.24 g), and tetrahydrofuran (380 mL) were mixed. After cooling in an ice bath, acryloyl chloride (16.1 g, 177.5 mmol) was slowly added. After the dropwise addition, the mixture was stirred at 50 °C for 2 hours. The solvent was distilled off until the liquid volume reached 190 mL, and the mixture was poured into 1 mol / L hydrochloric acid under ice cooling. The precipitate was filtered and washed with water and then hexane. The mixture was purified by silica gel column chromatography (hexane / ethyl acetate) to obtain 39.4 g of compound (I-2-h) as a white solid.

[0194] Synthesis of compound (I-2-g): Hydroquinone (17.5 g, 159 mmol), 4-dimethylaminopyridine (0.60 g, 5.33 mmol), 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride (4.52 g, 23.6 mmol), and acetonitrile (50 mL) were mixed and cooled in an ice bath. Compound (I-2-h) (5.00 g, 15.9 mmol) was added, and the mixture was stirred at 25°C for 12 hours. The precipitate was filtered, washed with acetonitrile and then with water, and then dried to obtain 4.40 g of compound (I-2-g) as a white solid.

[0195] The results of structural confirmation of compound (I-2-g) by NMR are shown below. 1H NMR(CDCl3,400MHz)δ1.20-1.70(m,22H),2.09-2.20(m,4H),2.45-2.55(m,1H),3.21-3.29(m, 1H),3.46(t,2H,J=6.7Hz),3.64(t,2H,J=6.7Hz),6.80(d,2H,J=9.0Hz),6.91(d,2H,J=9.0Hz)

[0196] Synthesis of compound (I-2): Under a nitrogen atmosphere, compound (I-2-f) (1.53 g, 4.22 mmol) and 1-hydroxy-2,6-di-tert-butyl-toluene (9.1 mg, 1 mol%) were dissolved in dichloromethane (47 mL), and compound (I-2-g) (2.05 g, 4.22 mmol), triethylamine (1.27 g, 12.4 mmol), and 4-dimethylaminopyridine (50.5 mg, 10 mol%) were added and stirred. Under ice cooling, trimethylamine hydrochloride (0.74 g, 82.8 mmol) was added, followed by dropwise addition of a dichloromethane solution (5 mL) of dimethylsulfamoyl chloride (1.20 g, 82.8 mmol). The mixture was stirred for 3 hours. Water (52 mL) and 1 mol / L hydrochloric acid were added dropwise to adjust the pH to 1, and the oil was separated. After washing with saturated saline, the solution was concentrated and then purified by silica gel column chromatography (hexane / ethyl acetate / dichloromethane) to obtain 0.82 g of compound (I-2) as a white solid.

[0197] Table 1 below shows the total number of steps for synthesizing compound (I-1) using p-iodophenol and compound (I-1-f) as starting materials in Example 1, Example 2, and Comparative Example 1, as well as the yield of compound (I-1) relative to compound (I-1-c), and the number of purification steps by column chromatography (column run number).

[0198] [Table 1]

[0199] Table 2 below shows the total number of steps for synthesizing compound (I-2) using ethyl 1-hydroxybenzoate and compound (I-2-d) as starting materials in Example 3 and Comparative Example 2, as well as the yield of compound (I-2) relative to compound (I-2-a) and the number of purification steps by column chromatography (column run number).

[0200] [Table 2]

[0201] As can be seen from the results in Tables 1 and 2, comparing Comparative Example 1 with Examples 1 and 2, and further, Comparative Example 2 with Example 3, it was found that the total number of steps can be reduced by eliminating the step of introducing a substituent into the hydroxy group bonded to Sp2 in general formula (I) or by reacting the compound represented by general formula (1) with the compound represented by general formula (II), and that the generation of by-products due to the step of protecting or chemically modifying the hydroxy group and the resulting decrease in yield can be suppressed. Furthermore, by reducing the number of steps, it is possible to avoid the associated decrease in yield due to each purification operation. The reduction in the number of purification steps by column chromatography can significantly reduce the amount of organic solvent used. Furthermore, by suppressing the production of by-products such as acrylic group adducts at the carboxylic acid end, it is expected that the deterioration of polymer performance due to the inclusion of low-molecular-weight substances can be suppressed.

[0202] Although the present invention has been described in detail with reference to specific embodiments, it will be apparent to those skilled in the art that various modifications can be made without departing from the spirit and scope of the invention. This application is based on Japanese Patent Application No. 2021-090324, filed on May 28, 2021, the entire contents of which are incorporated by reference.

Claims

1. A compound represented by the following general formula (V): 【Chemistry 1】 (In formula (V), A ３ and A ４ each independently represents a hydrocarbon ring group or a heterocyclic group which may have a substituent; A ３ and A ４ represents a different group. A ３ and A ４ When the hydrocarbon ring group used in is an aromatic hydrocarbon ring group, it is a divalent group of a benzene ring (phenylene group). A ３１ , A ３２ , A ４１ and A ４２ are each independently —CH ２ -CH ２ represents -, -CH=CH-, -C≡C-, or a direct bond. Sp ３ and Sp ４ Each independently represents a linear or branched alkylene group having 8 to 20 carbon atoms. ３ and Sp ４ Any hydrogen atom in the alkylene group may be substituted with a fluorine atom, and one —CH ２ - or two or more non-adjacent -CH ２ Each - may independently be replaced by -O-, -S-, -CO-, -COO-, -OCO-, -CO-S-, -S-CO-, -O-COO-, -CO-NH-, -NH-CO-, -CH=CH-, -CF=CF-, or -C≡C-. X ４ , X ５ and X ６ are each independently —O—, —S—, or —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 represents —OCO—, —CH═CH—, —N═N—, —CH═N—N═CH—, —CF═CF—, —C≡C—, or a direct bond. R represents a hydrocarbon group having 1 to 4 carbon atoms which may have a substituent. a represents an integer of 0 to 4.

2. In the general formula (V), A ３１ and A ３２ At least one of A is a direct bond, and ４１ and A ４２ The compound of claim 1 , wherein at least one of is a direct bond.

3. In the general formula (V), A ３１ , A ３２ , A ４１ and A ４２ The compound of claim 2, wherein at least three of the following are direct bonds:

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