Method for producing a congruent compound

Abstract

To provide a method for selective esterification of a phenol derivative having an alcoholic hydroxy group.SOLUTION: A method for producing a polymerizable compound represented by formula (D) includes reacting an alcohol compound represented by formula (A) with a methacrylic acid halide in the presence of an aniline [where R1-R4 each individually represent H, a halogen atom, or a C1-6 alkyl group; R5 represents a C1-12 alkanediyl group; Y represents H or a methyl group].SELECTED DRAWING: None

Description

Technical Field

[0001] The present invention relates to a method for producing a polymerizable compound and a method for producing a polymerizable liquid crystal compound.

Background Art

[0002] Conventionally, various methods for selectively esterifying alcoholic hydroxyl groups in phenol derivatives having alcoholic hydroxyl groups have been known. For example, Patent Documents 1 and 2 disclose a method of selectively esterifying an alcoholic hydroxyl group by reacting a phenol derivative having an alcoholic hydroxyl group with an acid halide in the presence of N,N-diisopropylethylamine.

Prior Art Documents

Patent Documents

[0003]

Patent Document 1

Patent Document 2

Summary of the Invention

Problems to be Solved by the Invention

[0004] However, in the method using an aliphatic amine as described in the above patent documents and the like, it has been difficult to produce the target compound in a high yield. An object of the present invention is to provide a method capable of realizing selective esterification of a phenol derivative having an alcoholic hydroxyl group in a sufficiently high yield.

Means for Solving the Problems

[0005] As a result of intensive studies to solve the above problems, the present inventors have completed the present invention. That is, the present invention includes the following aspects. [1] The following formula (A):

Chemical formula

[10] The following formula (A):

Chemical formula

Chemical formula

Chemical formula

Chemical formula

Chemical formula

Chemical formula

[11] The following formula (A):

Chemical formula

Chemical formula

Chemical formula

Chemical formula

Chemical formula

Chemical formula

Chemical formula

Chemical formula

Advantages of the Invention

[0006] According to the present invention, a method capable of realizing selective esterification of a phenol derivative having an alcoholic hydroxyl group in a sufficiently high yield can be provided.

Embodiments for Carrying Out the Invention

[0007] Hereinafter, embodiments of the present invention will be described in detail. It should be noted that the scope of the present invention is not limited to the embodiments described herein, and various modifications can be made without departing from the spirit of the present invention.

[0008] The present invention relates to a method for producing a polymerizable compound (D) represented by the formula (D):

Chemical Formula

[0009] In the formula (D), R 1 , R 2 , R 3 and R 4Each independently represents a hydrogen atom, a halogen atom, or an alkyl group having 1 to 6 carbon atoms which may have a substituent. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, etc. Examples of the alkyl group having 1 to 6 carbon atoms which may have a substituent include unsubstituted alkyl groups such as a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, etc., and alkyl groups in which a hydrogen atom contained in the alkyl group is substituted with a halogen atom, a nitro group, a cyano group, etc. R 1 R 2 R 3 and R 4 each independently preferably represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms which may have a substituent, more preferably a hydrogen atom or an unsubstituted alkyl group having 1 to 6 carbon atoms, and still more preferably a hydrogen atom.

[0010] In formula (D), R 5 represents an alkanediyl group having 1 to 12 carbon atoms which may have a substituent. Specifically, for example, unsubstituted alkanediyl groups such as a methylene group, an ethylene group, a propane-1,3-diyl group, a butane-1,3-diyl group, a butane-1,4-diyl group, a pentane-1,5-diyl group, a hexane-1,6-diyl group, a heptane-1,7-diyl group, an octane-1,8-diyl group, a decane-1,10-diyl group, etc., and alkanediyl groups in which a hydrogen atom contained in the alkanediyl group is substituted with a halogen atom, an alkoxy group, a nitro group, a cyano group, etc. R 5 is preferably an alkanediyl group having 1 to 6 carbon atoms which may have a substituent, more preferably an unsubstituted alkanediyl group having 1 to 6 carbon atoms, and still more preferably an unsubstituted linear alkanediyl group having 1 to 6 carbon atoms.

[0011] In formula (D), Y represents a hydrogen atom or a methyl group, and preferably a hydrogen atom.

[0012] In the present invention, the polymerizable compound (D) has the formula (A):

Chemical formula

[0013] R in the formula (A) 1 ~R 5 Each represents the same meaning as R in the formula (D) 1 ~R 5 and is determined according to the structure of the target polymerizable compound (D).

[0014] The alcohol compound (A) can be produced using a conventionally known organic synthesis method. For example, as shown in the following reaction formula, it can be prepared by reacting an alcohol compound (A-1) represented by the formula (A-1) with a halogenated alcohol compound (A-2) represented by the formula (A-2). [Chemical formula]

[0015] In the above formula (A-1) and formula (A-2), R 1 ~R 5 Each has a structure corresponding to R in the structure of the target alcohol compound (A) 1 ~R 5 and X is a halogen atom.

[0016] The reaction conditions for the alcohol compound (A-1) and the halogenated alcohol compound (A-2) are not particularly limited, but it is preferably carried out in a suitable solvent such as xylene in the presence of a basic compound such as sodium hydroxide.

[0017] Y in the formula (B) represents the same meaning as Y in the formula (D) and is determined according to the structure of the target polymerizable compound (D).

[0018] The acid halide (B) can be produced using a conventionally known organic synthesis method, or commercially available (meth)acrylic acid chloride may be used.

[0019] In the production method of the present invention, the alcohol compound (A) and the acid halide (B) are reacted in the presence of aniline (C) represented by the formula (C):

Chemical formula

[0020] In the formula (C), R 6 , R 7 , R 8 , R 9 and R 10 each independently represents a hydrogen atom, a halogen atom, or an alkyl group having 1 to 6 carbon atoms which may have a substituent, and R 11 and R 12 each independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms which may have a substituent. Examples of the alkyl group having 1 to 6 carbon atoms which may have a substituent include the same ones as exemplified for the alkyl group represented by R 1 ~R 4 in the formula (A). R 6 , R 7 , R 8 , R 9 and R 10 each independently is preferably a hydrogen atom or an alkyl group having 1 to 6 carbon atoms which may have a substituent, more preferably a hydrogen atom or an unsubstituted alkyl group having 1 to 6 carbon atoms, and even more preferably a hydrogen atom. Also, R 11 and R 12 each independently is preferably a hydrogen atom or an unsubstituted alkyl group having 1 to 6 carbon atoms, and more preferably an alkyl group having 1 to 6 carbon atoms.

[0021] In the reaction of the alcohol compound (A) and the acid halide (B), the acid halide (B) is preferably present in an amount of 1.0 to 15.0 molar equivalents relative to 1 molar equivalent of the alcohol compound (A). When the acid halide (B) is present in the above range, the reaction with the alcohol compound (A) easily proceeds, and the polymerizable compound (D) can be obtained in a high yield. The acid halide (B) is more preferably present in an amount of 1.2 molar equivalents or more, still more preferably 1.5 molar equivalents or more, and also more preferably 5.0 molar equivalents or less, still more preferably 4.0 molar equivalents or less, relative to 1 molar equivalent of the alcohol compound (A).

[0022] In the reaction of the alcohol compound (A) and the acid halide (B), the aniline (C) is preferably present in an amount of 1.0 to 15.0 molar equivalents relative to 1 molar equivalent of the alcohol compound (A). When the aniline (C) is present in the above range, the reaction between the alcohol compound (A) and the acid halide (B) is easily promoted, and the polymerizable compound (D) can be obtained in a sufficiently high yield. The aniline (C) is more preferably present in an amount of 1.2 molar equivalents or more, still more preferably 1.5 molar equivalents or more, and also more preferably 10.0 molar equivalents or less, still more preferably 5.0 molar equivalents or less, relative to 1 molar equivalent of the alcohol compound (A).

[0023] In the production method of the present invention, the reaction between the alcohol compound (A) and the acid halide (B) is preferably carried out in the presence of a solvent. For example, aromatic solvents such as toluene, xylene, benzene, dimethoxybenzene, chlorobenzene, dichlorobenzene, mesitylene, ethylbenzene, etc.; ether solvents such as 1,4-dioxane, cyclopentyl methyl ether, tetrahydrofuran, tetrahydropyran, 1,3-dioxolane, etc.; chlorine solvents such as chloroform, methylene chloride, etc.; amide solvents such as N-methylpyrrolidone, N,N-dimethylformamide, N,N-dimethylacetamide, hexamethylphosphoric triamide, etc.; aliphatic hydrocarbon solvents such as pentane, hexane, heptane, etc.; sulfur-containing solvents such as dimethyl sulfoxide, sulfolane, etc.; polar solvents such as methanol, ethanol, water, etc. These solvents can be used alone or in combination of two or more. Among them, from the viewpoint of the solubility of the product, aromatic solvents are preferred.

[0024] The amount of the solvent used is not particularly limited, but usually 2 parts by mass or more, preferably 3 parts by mass or more, more preferably 5 parts by mass or more with respect to 1 part by mass of the alcohol compound (A) so that each compound can be sufficiently dissolved and the reaction can proceed efficiently. To avoid the use of an excessive amount of the solvent, it is usually 100 parts by mass or less, preferably 70 parts by mass or less, more preferably 50 parts by mass or less.

[0025] In the reaction between the alcohol compound (A) and the acid halide (B), an additive may be used as necessary. For example, the reaction may be carried out in the presence of a polymerization inhibitor to prevent polymerization. Examples of the polymerization inhibitor include 2,6-di-tert-butyl-p-cresol (BHT), 2,2'-methylenebis(6-tert-butyl-p-cresol), triphenyl phosphite, tris(nonylphenyl) phosphite, phenothiazine, etc. When using a polymerization inhibitor, the addition amount is preferably 0.01 molar equivalent or more, more preferably 0.05 molar equivalent or more, and preferably 0.5 molar equivalent or less with respect to 1 molar equivalent of the alcohol compound (A).

[0026] In the production method of the present invention, the reaction between the alcohol compound (A) and the acid halide (B) can be carried out, for example, by dropping the acid halide (B) into a mixture containing the alcohol compound (A), aniline (C), and, if necessary, a solvent.

[0027] The conditions in the reaction can be appropriately determined according to the types of the respective compounds used, the reaction scale, and the like. In one embodiment of the production method of the present invention, the reaction temperature between the alcohol compound (A) and the acid halide (B) is preferably -10°C to 25°C, more preferably -5°C to 25°C. When the reaction temperature is within the above range, the reaction between the alcohol compound (A) and the acid halide (B) proceeds easily, and since the conditions are mild, it is easier to obtain the target compound more safely.

[0028] The reaction time may be determined according to the types, ratios, and temperature of the compounds used, etc. Although it also depends on the reaction scale, etc., it is preferably 10 minutes to 24 hours, more preferably 10 minutes to 12 hours. In the present invention, the reaction time between the alcohol compound (A) and the acid halide (B) starts from the point when the alcohol compound (A) and the acid halide (B) start to coexist, and ends at the point when the reaction between the alcohol compound (A) and the acid halide (B) stops / ends. The progress of the reaction can be confirmed by analytical means such as high performance liquid chromatography, thin layer chromatography, gas chromatography, etc.

[0029] When the reaction between the alcohol compound (A) and the acid halide (B) is carried out by dropping the acid halide (B) into a mixture containing the alcohol compound (A) and aniline (C), the dropping rate may be, for example, 0.1 to 100 parts by mass per minute with the total amount of the acid halide (B) used in the reaction being 100 parts by mass.

[0030] After the reaction is completed, if necessary, the polymerizable compound (D) can be isolated by performing post-treatments such as filtration, neutralization, extraction, washing with water, etc., and treatments and operations that can be employed in organic synthetic chemistry such as isolation treatments like distillation and crystallization.

[0031] The structure of the obtained compound can be identified by measurements such as NMR spectrum, IR spectrum, mass spectrum, elemental analysis, etc.

[0032] The present invention relates to a compound of formula (A):

Chemical formula

Chemical formula

Chemical formula

Chemical formula

Chemical formula

Chemical formula

[0033] In the production method (X1) of the polymerizable liquid crystal compound (X), the step of reacting the alcohol compound (A) and the acid halide (B) in the presence of aniline (C) to obtain the polymerizable compound (D) is the same as the production method of the polymerizable compound (D) of the present invention. Therefore, specific examples and preferred examples of the alcohol compound (A), the acid halide (B), and aniline (C), the method of reacting the alcohol compound (A) and the acid halide (B), and the conditions thereof are the same as those described above as the production method of the polymerizable compound (D).

[0034] In the present invention, the production method (X1) includes a step of reacting the polymerizable compound (D) obtained by reacting the alcohol compound (A) and the acid halide (B) in the presence of aniline (C) with a compound (E) represented by the formula (E):

Chemical formula

[0035]

[0036] Ar preferably has at least one selected from an aromatic hydrocarbon ring which may have a substituent, an aromatic heterocyclic ring which may have a substituent, and an electron-withdrawing group. Examples of the aromatic hydrocarbon ring include a benzene ring, a naphthalene ring, an anthracene ring, etc., and a benzene ring and a naphthalene ring are preferred. Examples of the aromatic heterocyclic ring include a furan ring, a benzofuran ring, a pyrrole ring, an indole ring, a thiophene ring, a benzothiophene ring, a pyridine ring, a pyrazine ring, a pyrimidine ring, a triazole ring, a triazine ring, a pyrroline ring, an imidazole ring, a pyrazole ring, a thiazole ring, a benzothiazole ring, a thienothiazole ring, an oxazole ring, a benzoxazole ring, and a phenanthroline ring, etc.

[0037] Examples of the aromatic group contained in Ar include the following groups.

[0038]

Chemical formula

[0039] In formulas (Ar-1) to (Ar-23), the * mark represents a linking portion, and Z 0 , Z 1 and Z 2 each independently represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 12 carbon atoms, a cyano group, a nitro group, an alkylsulfinyl group having 1 to 12 carbon atoms, an alkylsulfonyl group having 1 to 12 carbon atoms, a carboxyl group, a fluoroalkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an alkylthio group having 1 to 12 carbon atoms, an N-alkylamino group having 1 to 12 carbon atoms, an N,N-dialkylamino group having 2 to 12 carbon atoms, an N-alkylsulfamoyl group having 1 to 12 carbon atoms or an N,N-dialkylsulfamoyl group having 2 to 12 carbon atoms, and Z 0 , Z 1 and Z 2 may contain a polymerizable group.

[0040] Q 1 and Q 2 each independently represents -CR2’ R 3’ -、-S-、-NH-、-NR 2’ -、-CO- or -O-, where R 2’ and R 3’ each independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.

[0041] J 1 and J 2 each independently represents a carbon atom or a nitrogen atom.

[0042] Y 1 Y 2 and Y 3 each independently represents an optionally substituted aromatic hydrocarbon group or aromatic heterocyclic group. As the aromatic hydrocarbon group in Y 1 Y 2 and Y 3 examples include aromatic hydrocarbon groups having 6 to 20 carbon atoms such as phenyl group, naphthyl group, anthryl group, phenanthryl group, biphenyl group, etc., and as the aromatic heterocyclic group, examples include aromatic heterocyclic groups having 4 to 20 carbon atoms containing at least one hetero atom such as nitrogen atom, oxygen atom, sulfur atom, etc., such as furyl group, pyrrolyl group, thienyl group, pyridinyl group, thiazolyl group, benzothiazolyl group, etc. Y 1 Y 2 and Y 3 each independently may be an optionally substituted polycyclic aromatic hydrocarbon group or polycyclic aromatic heterocyclic group.

[0043] W 1 and W 2 each independently represents a hydrogen atom, a cyano group, a methyl group or a halogen atom, and m represents an integer from 0 to 6.

[0044] In formulas (Ar-16) to (Ar-23), Y 1 together with the nitrogen atom to which it is attached and Z 0 may form an aromatic heterocyclic group. Examples of the aromatic heterocyclic group include those described above as the aromatic heterocyclic group that Ar may have, and this aromatic heterocyclic group may have a substituent. Also, Y1 is, together with the nitrogen atom to which it binds and Z 0 may be an optionally substituted polycyclic aromatic hydrocarbon group or polycyclic aromatic heterocyclic group as described above.

[0045] In formula (E), A 1 , A 2 , G 1 and G 2 are each independently preferably a 1,4-phenylenediyl group optionally substituted with at least one substituent selected from the group consisting of a halogen atom and an alkyl group having 1 to 4 carbon atoms, or a 1,4-cyclohexanediyl group optionally substituted with at least one substituent selected from the group consisting of a halogen atom and an alkyl group having 1 to 4 carbon atoms, more preferably a 1,4-phenylenediyl group substituted with a methyl group, an unsubstituted 1,4-phenylenediyl group, or an unsubstituted 1,4-trans-cyclohexanediyl group, particularly preferably an unsubstituted 1,4-phenylenediyl group or an unsubstituted 1,4-trans-cyclohexanediyl group. A 1 , A 2 , G 1 and G 2 Among them, at least one is preferably a divalent alicyclic hydrocarbon group, and it is more preferable that at least one of A 1 and A 2 is a divalent alicyclic hydrocarbon group. Note that G 1 may be the same substituent as G 2 or may be different substituents from each other.

[0046] In formula (E), as the divalent groups represented by L 1 and L 2 , for example, an alkylene group having 1 to 4 carbon atoms, -O-, -S-, -R a1 OR a2 -, -R a3 COOR a4 -, -R a5 OCOR a6 -, -R a7 OC=OOR a8 -, -N=N-, -CRc =CR d - includes -C≡C-. Here, R a1 ~R a8 each independently represents a single bond or an alkylene group having 1 to 4 carbon atoms, and R c and R d each represents an alkyl group having 1 to 4 carbon atoms or a hydrogen atom. L 1 and L 2 each independently is preferably a single bond, -O-, -CH2CH2-, -COO-, -COOCH2CH2- or -OCO-.

[0047] Ar, A 1 in formula (E), A 2 , G 1 , G 2 , L 1 , L 2 , B 1 , B 2 , k and l are each determined according to the corresponding molecular structure of the desired polymerizable liquid crystal compound (X).

[0048] Compound (E) can be produced by appropriately combining known organic synthesis reactions (for example, condensation reaction, esterification reaction, Williamson reaction, Ullmann reaction, Wittig reaction, Schiff base formation reaction, benzylation reaction, Sonogashira reaction, Suzuki-Miyaura reaction, Negishi reaction, Kumada reaction, Hiyama reaction, Buchwald-Hartwig reaction, Friedel-Crafts reaction, Heck reaction, aldol reaction, etc.) described in Methoden der Organischen Chemie, Organic Reactions, Organic Syntheses, Comprehensive Organic Synthesis, New Experimental Chemistry Course, etc. according to its structure.

[0049] For example, when both G 1 and G 2 are 1,4-cyclohexanediyl groups, both L 1 and L 2 are -COO-, and both k and l are 0, the following formula (E-1): [Chemical formula] The compound (E-1) represented by the formula can be produced as follows, for example, according to the method disclosed in JP-A-2014-123134. In the above formula (E-1), Ar has the same meaning as Ar in the formula (X) corresponding to the target polymerizable liquid crystal compound (X).

[0050] First, trans-cyclohexanedicarboxylic acid and benzyl bromide are reacted in the presence of potassium carbonate to produce an intermediate (e1) represented by the formula (e1).

[0051] [Chemical formula]

[0052] Next, the obtained intermediate (e1) and an alcohol compound (F) represented by the formula (F) are subjected to an esterification reaction in the presence of a condensing agent such as dicyclohexylcarbodiimide and a catalytic amount of a base such as N,N-dimethylaminopyridine to produce an intermediate (e2) represented by the formula (e2).

[0053] [Chemical formula]

[0054] Furthermore, the benzyl group is removed from the obtained intermediate (e2) and hydrogenated using a catalyst such as palladium / carbon to obtain the compound (E-1).

[0055] [Chemical formula]

[0056] Each of the above reactions for obtaining intermediate (e1), intermediate (e2), and compound (E-1) is usually carried out in a solvent. Examples of the solvent include ketone solvents such as acetone, methyl ethyl ketone, cyclopentanone, cyclohexanone, methyl amyl ketone, or methyl isobutyl ketone; aliphatic hydrocarbon solvents such as pentane, hexane, or heptane; aromatic hydrocarbon solvents such as toluene, xylene, benzene, or chlorobenzene; nitrile solvents such as acetonitrile; ether solvents such as tetrahydrofuran or dimethoxyethane; ester solvents such as ethyl lactate; halogenated hydrocarbon solvents such as chloroform or dichloromethane; aprotic polar solvents such as dimethyl sulfoxide, N-methyl-2-pyrrolidone, N,N-dimethylformamide, N,N-dimethylacetamide, or hexamethylphosphoric triamide; and the like. These organic solvents may be used alone or in combination of two or more.

[0057] The method (X1) for producing the polymerizable liquid crystal compound (X) of the present invention includes a step of reacting a polymerizable compound (D) with a compound (E), and by this step, a polymerizable liquid crystal compound (X) represented by the formula (X):

Chemical formula

[0058] In the formula (X), Ar, A 1 , A 2 , G 1 , G 2 , L 1 , L 2 , B 1 , B 2 , k and l have the same meanings as Ar, A 1 , A 2 , G 1 , G 2 , L 1 , L 2 , B 1 , B 2 in the formula (E) respectively, and R 1 ~R 5 have the same meanings as R 1 ~R 5Each represents the same meaning, and Y represents the same meaning as Y in the formula (B).

[0059] For example, by reacting the polymerizable compound (D) with the above-described compound (E-1), a polymerizable liquid crystal compound (X-1) represented by the formula (X-1) can be obtained. R in the formula (X-1) 1 ~R 5 and Y represent the same meaning as R in the formula (D) corresponding to the polymerizable compound (D) 1 ~R 5 and Y, and Ar in the formula (X-1) represents the same meaning as Ar in the formula (E-1) corresponding to the compound (E-1). [Chemical formula]

[0060] The reaction between the polymerizable compound (D) and the compound (E) is an esterification reaction, and is preferably carried out in the presence of a condensing agent. By carrying out the esterification reaction in the presence of a condensing agent, the esterification reaction can be carried out efficiently and rapidly.

[0061] Examples of the condensing agent include carbodiimide compounds such as 1-cyclohexyl-3-(2-morpholinoethyl)carbodiimide metho-p-toluenesulfonate, dicyclohexylcarbodiimide, diisopropylcarbodiimide, 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide, 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide hydrochloride (commercially available as water-soluble carbodiimide: WSC), bis(2,6-diisopropylphenyl)carbodiimide, and bis(trimethylsilyl)carbodiimide; 2-methyl-6-nitrobenzoic anhydride; 2,2'-carbonylbis-1H-imidazole; 1,1'-oxalyldiimidazole; diphenylphosphoryl azide; 1-(4-nitrobenzenesulfonyl)-1H-1,2,4-triazole; 1H-benzotriazol-1-yloxytris(pyrrolidino)phosphonium hexafluorophosphate; 1H-benzotriazol-1-yloxytris(dimethylamino)phosphonium hexafluorophosphate; N,N,N',N'-tetramethyl-O-(N-succinimidyl)uronium tetrafluoroborate; N-(1,2,2,2-tetrachloroethoxycarbonyloxy)succinimide; N-carbobenzoxysuccinimide; O-(6-chlorobenzotriazol-1-yl)-N,N,N',N'-tetramethyluronium tetrafluoroborate; O-(6-chlorobenzotriazol-1-yl)-N,N,N',N'-tetramethyluronium hexafluorophosphate; 2-bromo-1-ethylpyridinium tetrafluoroborate; 2-chloro-1,3-dimethylimidazolinium chloride; 2-chloro-1,3-dimethylimidazolinium hexafluorophosphate; 2-chloro-1-methylpyridinium iodide; 2-chloro-1-methylpyridinium p-toluenesulfonate; 2-fluoro-1-methylpyridinium p-toluenesulfonate; and pentachlorophenyl ester of trichloroacetic acid, etc.From the viewpoints of reactivity, cost, available solvents, etc., dicyclohexylcarbodiimide, 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide, 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide hydrochloride, bis(2,6-diisopropylphenyl)carbodiimide, bis(trimethylsilyl)carbodiimide, bisisopropylcarbodiimide, 2,2'-carbonylbis-1H-imidazole are preferred as the condensing agent.

[0062] The amount of the condensing agent used in the esterification reaction between the polymerizable compound (D) and the compound (E) can be appropriately determined according to the types of the polymerizable compound (D) and the compound (E) used, the type of the condensing agent, etc. For example, it is usually 2 to 4 moles per 1 mole of the compound (E).

[0063] Also, the esterification reaction may be carried out in the presence of a catalyst. Examples of the catalyst include N,N-dimethylaminopyridine, N,N-dimethylaniline, dimethylammonium pentafluorobenzenesulfonate, etc. The amount of the catalyst used is, for example, preferably 0.01 to 0.5 moles per 1 mole of the compound (E).

[0064] The esterification reaction between the polymerizable compound (D) and the compound (E) is usually carried out in a solvent. Examples of the solvent include the same solvents as those exemplified as the solvents that can be used in each of the above-mentioned reactions for obtaining the intermediate (e1), the intermediate (e2), and the compound (E-1). From the viewpoints of reaction yield and productivity, nonpolar organic solvents such as pentane, hexane, heptane, toluene, xylene, benzene, chlorobenzene, chloroform, dichloromethane are preferred. The solvents may be used alone or in combination of a plurality.

[0065] From the viewpoint of easily obtaining the polymerizable liquid crystal compound (X), the amount of the polymerizable compound (D) used is preferably 2 to 10 moles, more preferably 2 to 5 moles, and still more preferably 2 to 3 moles per 1 mole of the compound (E).

[0066] The amount of the solvent used is not particularly limited, but is preferably 0.5 to 50 parts by mass, more preferably 1 to 20 parts by mass, and even more preferably 2 to 10 parts by mass with respect to 1 part by mass in total of the polymerizable compound (D) and the compound (E).

[0067] From the viewpoints of reaction yield and productivity, the temperature of the esterification reaction is preferably -20 to 120°C, more preferably -20 to 60°C, and even more preferably -10 to 20°C. Also, from the viewpoints of reaction yield and productivity, the time of the esterification reaction is preferably 1 minute to 72 hours, more preferably 1 to 48 hours, and even more preferably 1 to 24 hours.

[0068] After completion of the reaction, if necessary, the polymerizable liquid crystal compound (X) can be isolated by performing treatments and operations that can be employed in organic synthetic chemistry, such as post-treatments such as filtration, neutralization, extraction, and washing with water, and isolation treatments such as distillation and crystallization.

[0069] The present invention relates to an alcohol compound (A) represented by the formula (A):

Chemical formula

Chemical formula

Chemical formula

Chemical formula

Chemical formula

Chemical formula

Chemical formula

Chemical formula

[0070] In the manufacturing method (X2), the step of reacting the alcohol compound (A) and the acid halide (B) in the presence of aniline (C) to obtain the polymerizable compound (D) is the same as the manufacturing method of the polymerizable compound (D) of the present invention. Therefore, specific examples and preferred examples of the alcohol compound (A), the acid halide (B), and aniline (C), the method of reacting the alcohol compound (A) and the acid halide (B), and the conditions thereof are the same as those described above as the manufacturing method of the polymerizable compound (D).

[0071] The manufacturing method (X2) reacts the polymerizable compound (D) obtained by reacting the alcohol compound (A) and the acid halide (B) in the presence of aniline (C) with the compound (F1) represented by the formula (F1) and the compound (F2) represented by the formula (F2):

Chemical formula

Chemical formula

[0072] A in the formula (F1), the formula (F2), the formula (G1), and the formula (G2) 1 , A 2 , G 1 , G 2 , B 1 , B 2 , k and l respectively correspond to A in the formula (X) of the finally obtained compound (X) 1 , A 2 , G 1 , G 2, B 1 , B 2 are groups (structures) corresponding to k and l. A 1 , A 2 , G 1 , G 2 , B 1 , B 2 As k and l, the A in formula (E) corresponding to compound (E) used in the above production method (X1) 1 , A 2 , G 1 , G 2 , B 1 , B 2 Groups (structures) the same as k and l can be exemplified and are determined according to the molecular structure of the desired polymerizable liquid crystal compound (X).

[0073] C in formula (F1), formula (F2), formula (G1) and formula (G2) 1 is a group that reacts with the substituent represented by C in formula (H) described later to form the substituent represented by L 2 or L 1 in formula (X). For example, when C 2 is -COOH and C 1 is -OH, by the ester condensation reaction of compound (G1) and compound (G2) with compound (H), a compound (X) in which L 2 and L 1 are each *-OCO- (* indicates the bonding position to Ar) is obtained. As C 2 , specifically, -COOH, -COCl, -COOCH3, -COSH, -CSOH, -NH2, -NR1H, -OH, -SH, CH2X, etc. can be mentioned. Among them, from the viewpoint of reactivity, -COOH and -OH are preferable. 1 Note that G in formula (F1) and formula (G1) 1 may be the same substituent as G 2 in formula (F2) and formula (G2), or may be different substituents from each other.

[0074] R 1 ~R 5 in formula (G1) and formula (G2) are the R in the above formula (A)1 ~R 5 respectively represent the same meaning, and Y represents the same meaning as Y in the formula (B).

[0075] For example, in the presence of a base and a solvent, by reacting compound (F1) and compound (F2) with a polymerizable compound (D), compounds (G1) and (G2) can be obtained. Examples of the base in the reaction include pyridine, aniline, dimethylaniline, triethylamine, etc. The amount used can be appropriately determined according to the types of the polymerizable compound (D), compounds (F1) and (F2), and the type of the base, etc. For example, it may be 2 to 20 moles, preferably 2 to 4 moles, per 1 mole in total of compounds (F1) and (F2).

[0076] Examples of the solvent in the above reaction include the same ones as those that can be used in the reaction between compound (D) and compound (E) in production method (X1). The amount of the solvent used is not particularly limited, but is preferably 1 to 100 parts by mass, more preferably 1 to 20 parts by mass, and still more preferably 1 to 10 parts by mass, per 1 part by mass in total of the polymerizable compound (D) and compound (E).

[0077] From the viewpoint of easily obtaining the polymerizable liquid crystal compound (X), the amount of the polymerizable compound (D) used in the above reaction is preferably 0.1 to 1 mole, more preferably 0.2 to 0.8 mole, and still more preferably 0.3 to 0.6 mole, per 1 mole in total of compounds (F1) and (F2).

[0078] The conditions of the reaction between compound (F1) and compound (F2) and the polymerizable compound (D) may be appropriately determined. The reaction temperature is, from the viewpoints of reaction yield and productivity, for example, -20 to 60 °C, preferably -20 to 40 °C, and more preferably -20 to 10 °C. Also, the reaction time is, from the viewpoints of reaction yield and productivity, for example, 1 minute to 72 hours, preferably 1 minute to 48 hours, and more preferably 1 minute to 24 hours.

[0079] The compounds (F1) and (F2) used in the above reaction can be produced by appropriately combining various known organic synthesis reactions described with respect to the production method (X1) according to their structures.

[0080] Also, the compounds (G1) and (G2) can be obtained by subjecting the compounds (F1) and (F2) and the polymerizable compound (D) to an esterification reaction. The esterification reaction can be carried out in the presence of a suitable condensing agent, catalyst, solvent, etc. Examples of the types and amounts of the condensing agent, catalyst, and solvent that can be used, as well as the conditions of the esterification reaction, are the same as those in the esterification reaction between the polymerizable compound (D) and the compound (E) in the production method (X1).

[0081] The production method (X2) includes a step of reacting the compounds (G1) and (G2) obtained in the above step with a compound (H) represented by the formula (H):

Chemical formula

Chemical formula

[0082] Ar in the formula (H) is a group (structure) corresponding to Ar in the formula (X) of the finally obtained compound (X). Examples of Ar include the same group (structure) as Ar in the formula (E) corresponding to the compound (E) used in the production method (X1), and it is determined according to the molecular structure of the desired polymerizable liquid crystal compound (X).

[0083] C in the formula (H) 2 reacts with the substituent represented by C 1 in the formulas (G1) and (G2) corresponding to the compounds (G1) and (G2) to be converted into a substituent represented by L 1 or L 2 in the formula (X). For example, C 2is -OH, C 1 When is -COOH, by the ester condensation reaction of compound (G1) and compound (G2) with compound (H), L 1 and L 2 each represent *-OCO- (* indicates the bonding position with Ar), and compound (X) is obtained. C 2 Specific examples of include -OH, -SH, CH2X, -COOH, -COCl, -COOCH3, -COSH, -CSOH, -NH2, -NR1H, -OH, etc. Among them, from the perspective of reactivity, -OH and -COOH are preferred.

[0084] For example, when C 1 in formula (G1) and formula (G2) is -COOH in compound (G1-1) and compound (G2-1), and C 2 in formula (H) is -OH in compound (H-1), by reacting them, a polymerizable liquid crystal compound (X-2) represented by formula (X-2) is obtained. In formula (X-2), A 1 , A 2 , B 1 , B 2 , G 1 , G 2 , k and l have the same meanings as A 1 , A 2 , B 1 , B 2 , G 1 , G 2 , k and l in formula (G1-1) or formula (G2-1) corresponding to compound (G1-1) or compound (G2-1), Ar has the same meaning as Ar in formula (H-1) corresponding to compound (H-1), and R 1 ~R 5 and Y have the same meanings as R 1 ~R 5 and Y in formula (D) corresponding to the polymerizable compound (D).

Chemical formula

[0085] The reaction of compound (G1) and compound (G2) with compound (H) is an esterification reaction, preferably carried out in the presence of a condensing agent. By carrying out the esterification reaction in the presence of a condensing agent, the esterification reaction can be carried out efficiently and rapidly. Examples of the condensing agent that can be used include the same ones as those in the esterification reaction of the polymerizable compound (D) and compound (E) in the production method (X1).

[0086] The amount of the condensing agent used in the esterification reaction of compound (G1) and compound (G2) with compound (H) can be appropriately determined according to the types of compound (G1) and compound (G2) and compound (H) used, the type of the condensing agent, etc. For example, it is usually 2 to 4 moles per 1 mole of compound (H).

[0087] Also, the esterification reaction may be carried out in the presence of a catalyst. Examples of the catalyst that can be used include the same ones as those in the esterification reaction of the polymerizable compound (D) and compound (E) in the production method (X1). The amount of the catalyst used is, for example, preferably 0.01 to 0.5 moles per 1 mole of compound (H).

[0088] The esterification reaction of compound (G1) and compound (G2) with compound (H) is usually carried out in a solvent. Examples of the solvent that can be used include the same ones as those in the esterification reaction of the polymerizable compound (D) and compound (E) in the production method (X1). The amount of the solvent used is not particularly limited, but is preferably 0.5 to 50 parts by mass, more preferably 1 to 20 parts by mass, and still more preferably 2 to 10 parts by mass, based on 1 part by mass in total of compound (G1) and compound (G2) and compound (H).

[0089] From the viewpoints of reaction yield and productivity, the temperature of the esterification reaction is preferably -20 to 120 °C, more preferably -20 to 60 °C, and still more preferably -10 to 20 °C. Also, from the viewpoints of reaction yield and productivity, the time of the esterification reaction is preferably 1 minute to 72 hours, more preferably 1 to 48 hours, and still more preferably 1 to 24 hours.

[0090] After the reaction is completed, if necessary, post-treatments such as filtration, neutralization, extraction, and water washing, and treatments and operations that can be employed in organic synthetic chemistry such as isolation treatments like distillation and crystallization are performed, whereby the polymerizable liquid crystal compound (X) can be isolated.

[0091] The reaction of compound (G1) and compound (G2) with compound (H) can be carried out based on various known organic synthetic reactions according to the structure of C in formula (G1) and (G2) 1 and the structure represented by C in formula (H). 2 The conditions and the like can also be appropriately determined according to the type of the organic synthetic reaction used, the types of compound (G1), compound (G2), and compound (H), and the like.

[0092] The structure of the obtained compound can be identified by measurements such as NMR spectrum, IR spectrum, mass spectrum, and elemental analysis.

[0093] The polymerizable liquid crystal compound (X) generally has a polymer with a reverse wavelength dispersion property of birefringence when polymerized in an oriented state in one direction. An optical film capable of uniform polarization conversion in a wide wavelength range can be produced using such a polymerizable liquid crystal compound.

Examples

[0094] Hereinafter, the present invention will be described more specifically with reference to examples. In the examples, “%” and “parts” mean mass % and parts by mass, respectively, unless otherwise specified.

[0095] 1. Example 1 <Preparation of Polymerizable Compound (D1)> Formula (A1):

Chemical formula

[0096] [HPLC measurement] The HPLC measurement was performed under the following conditions. (Measurement conditions) Measuring device: HPLC LC-10AT (manufactured by Shimadzu Corporation) Column used: Kinetex 2.6 μm C18, 100 Å, 100 × 4.6 mm Column temperature: 40 °C Solution A: 0.1 mM PIC TBA-HS / water Solution B: 0.1 mM PIC TBA-HS / acetonitrile Gradient conditions 0 min 2%-B 20 min 65.3%-B 40 min 100%-B 50 min 100%-B 50.1 min 2%-B 60 min STOP Flow rate: 1.0 mL / min Injection volume: 5 μL Detection wavelength: UV 220 nm

[0097] 2. Example 2 and Comparative Examples 1 to 3 According to the description in Table 1, the polymerizable compound (D1) was synthesized in the same manner as in Example 1, except that the blending amount of acrylic acid chloride, the solvent, the base, and the type or blending amount of the additive, the reaction temperature, and / or the reaction time were changed. After completion of the reaction, analysis was performed by HPLC, and the yield (area percentage value) of the polymerizable compound (D1) was calculated based on the peak area measured by liquid chromatography. The results are shown in Table 1. In addition, in Table 1, the blending amounts of the acid halide (B), the base, and the additive are in molar equivalents relative to 1 mol of the alcohol compound (A1), and the blending amount of the solvent is in parts by mass relative to 1 part by mass of the alcohol compound (A1).

[0098] [Table 1]

Claims

1. The following formula (A): 【Chemical Formula 1】 〔In formula (A), R １ , R ２ , R ３ and R ４ each independently represents a hydrogen atom, a halogen atom, or an alkyl group having 1 to 6 carbon atoms which may have a substituent, and R ５ represents an alkanediyl group having 1 to 12 carbon atoms which may have a substituent〕 An alcohol compound (A) represented by the formula and an acid halide (B) represented by the following formula (B): 【Chemical Formula 2】 〔In formula (B), Y represents a hydrogen atom or a methyl group〕 Reacting in the presence of an aniline (C) represented by the following formula (C) and a polymerization inhibitor, wherein in the reaction, the acid halide (B) is present in an amount of 1.0 molar equivalent or more and 15.0 molar equivalents or less based on 1 molar equivalent of the alcohol compound (A). The following formula (D): 【Chemical Formula 3】 〔In formula (C), R ６ , R ７ , R ８ , R ９ and R １０ each independently represents a hydrogen atom, a halogen atom, or an alkyl group having 1 to 6 carbon atoms which may have a substituent, and R １１ and R １２ each independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms which may have a substituent〕 A method for producing a polymerizable compound (D) represented by the formula, comprising reacting in the presence of an aniline (C) represented by the formula and a polymerization inhibitor, wherein in the reaction, the acid halide (B) is present in an amount of 1.0 molar equivalent or more and 15.0 molar equivalents or less based on 1 molar equivalent of the alcohol compound (A). The following formula (D): 【Chemical Formula 4】 〔In formula (D), R １ to R ５ have the same meanings as R １ to R ５ in the formula (A) respectively, and Y has the same meaning as Y in the formula (B)〕 A method for producing a polymerizable compound (D) represented by the formula.

2. The method according to claim 1, wherein aniline (C) is present in an amount of 1.0 to 15.0 molar equivalents relative to 1 molar equivalent of the alcohol compound (A).

3. The method according to claim 1 or 2, wherein Y in formula (B) and formula (D) is a hydrogen atom.

4. R in formula (A) and formula (D) ５ is an alkanediyl group having 1 to 6 carbon atoms, and the method according to any one of claims 1 to 3.

5. The method according to any one of claims 1 to 4, wherein the reaction time in the reaction is 10 minutes to 24 hours.

6. The method according to any one of claims 1 to 5, wherein the reaction is carried out in a temperature range of -10°C to 25°C.

7. The method according to any one of claims 1 to 6, wherein the reaction is carried out in the presence of an aromatic solvent.

8. The method according to any one of claims 1 to 7, wherein the reaction is carried out by dropping acid halide (B) into a mixture of alcohol compound (A) and aniline (C).

9. The following formula (A): 【Chemical formula 5】 [In formula (A), R １ , R ２ , R ３ and R ４ each independently represents a hydrogen atom, a halogen atom, or an alkyl group having 1 to 6 carbon atoms which may have a substituent, and R ５ represents an alkanediyl group having 1 to 12 carbon atoms which may have a substituent] An alcohol compound (A) represented by the following formula (B): 【Chemical formula 6】 [In formula (B), Y represents a hydrogen atom or a methyl group] An acid halide (B) represented by the following formula (C): 【Chemical formula 7】 (In formula (C), R ６ , R ７ , R ８ , R ９ , and R １０ each independently represents a hydrogen atom, a halogen atom, or an alkyl group having 1 to 6 carbon atoms which may have a substituent, and R １１ and R １２ each independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms which may have a substituent) React in the presence of aniline (C) represented by the following formula (D): [Chemical formula 8] (In formula (D), R １ to R ５ have the same meanings as R １ to R ５ in the above formula (A), respectively, and Y has the same meaning as Y in the above formula (B)) to obtain a polymerizable compound (D) represented by the following formula, and the polymerizable compound (D) and the following formula (E): [Chemical formula 9] (In formula (E), Ar represents a divalent group having an aromatic group which may have a substituent; A １ , A ２ , G １ and G ２ each independently represents a divalent alicyclic hydrocarbon group or a divalent aromatic group, and the hydrogen atoms contained in the divalent alicyclic hydrocarbon group or the divalent aromatic group may be substituted with a halogen atom, an alkyl group having 1 to 4 carbon atoms, a fluoroalkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a cyano group or a nitro group, and the carbon atoms constituting the divalent alicyclic hydrocarbon group or the divalent aromatic group may be substituted with an oxygen atom, a sulfur atom or a nitrogen atom; L １ , L ２ , B １ and B ２ each independently represents -CR １ R ２ -, -CH ２-CH ２ -、-O-、-S-、-CO-O-、-O-CO-、-O-CO-O-、-C(=S)-O-、-O-C(=S)-、-O-C(=S)-O-、-CO-NR １ -、-NR ２ -CO-、-O-CH ２ -、-CH ２ -O-、-S-CH ２ -、-CH ２ -S- or a single bond, and R １ and R ２ each independently represents a hydrogen atom, a halogen atom, or an alkyl group having 1 to 6 carbon atoms which may have a substituent; k and l each independently represent an integer of 0 or 1] A process comprising reacting with a compound (E) represented by the following formula (X): [Chemical Formula 10] [In formula (X), Ar, A １ , A ２ , G １ , G ２ , L １ , L ２ , B １ , B ２ , k and l have the same meanings as Ar, A １ , A ２ , G １ , G ２ , L １ , L ２ , B １ , B ２ , k and l; R １ ~R ５ have the same meanings as R １ ~R ５ in formula (A) respectively; Y has the same meaning as Y in formula (B)] A method for producing a polymerizable liquid crystal compound (X) represented by.

10. The following formula (A): [Chemical Formula 11] [In formula (A), R １ , R ２ , R ３ and R ４ each independently represents a hydrogen atom, a halogen atom, or an alkyl group having 1 to 6 carbon atoms which may have a substituent, and R ５ represents an alkanediyl group having 1 to 12 carbon atoms which may have a substituent. The alcohol compound (A) represented by the following formula is reacted with the acid halide (B) represented by the following formula (B): 【Chemical formula 12】 〔In formula (B), Y represents a hydrogen atom or a methyl group.〕 in the presence of aniline (C) represented by the following formula (C): 【Chemical formula 13】 〔In formula (C), R ６ , R ７ , R ８ , R ９ and R １０ each independently represents a hydrogen atom, a halogen atom, or an alkyl group having 1 to 6 carbon atoms which may have a substituent, and R １１ and R １２ each independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms which may have a substituent.〕 The reaction is carried out in the presence of aniline (C) represented by the following formula (C) to obtain a polymerizable compound (D) represented by the following formula (D): 【Chemical formula 14】 〔In formula (D), R １ to R ５ have the same meanings as R １ to R ５ in the above formula (A), respectively, and Y has the same meaning as Y in the above formula (B).〕 A step of obtaining a polymerizable compound (D) represented by the following formula: The polymerizable compound (D) is reacted with a compound (F1) represented by the following formula (F1) and a compound (F2) represented by the following formula (F2): 【Chemical formula 15】 〔In formula (F1) and formula (F2), A １ , A ２ , G １ and G ２each independently represents a divalent alicyclic hydrocarbon group or a divalent aromatic group, and the hydrogen atoms contained in the divalent alicyclic hydrocarbon group or the divalent aromatic group may be substituted with a halogen atom, an alkyl group having 1 to 4 carbon atoms, a fluoroalkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a cyano group or a nitro group, and the carbon atoms constituting the divalent alicyclic hydrocarbon group or the divalent aromatic group may be substituted with an oxygen atom, a sulfur atom or a nitrogen atom; B １ and B ２ each independently represents -CR １ R ２ -, -CH ２ -CH ２ -, -O-, -S-, -CO-O-, -O-CO-, -O-CO-O-, -C(=S)-O-, -O-C(=S)-, -O-C(=S)-O-, -CO-NR １ -, -NR ２ -CO-, -O-CH ２ -, -CH ２ -O-, -S-CH ２ -, -CH ２ -S- or a single bond, and R １ and R ２ each independently represents a hydrogen atom, a halogen atom, or an alkyl group having 1 to 6 carbon atoms which may have a substituent; k and l each independently represent an integer of 0 or 1; C １ is a group that reacts with the substituent represented by C in the following formula (H) to be converted into the substituent represented by L in the following formula (X) ２ or L １ or L ２ represented by; By reacting, a compound (G1) represented by the following formula (G1) and a compound (G2) represented by formula (G2): [Chemical 16] [In formula (G1) and formula (G2), A １ 、A ２ 、G １ 、G ２ 、B １ 、B ２, k, l, and C １ each represent the same meaning as A in the formula (F1) or formula (F2); １ A ２ G １ G ２ B １ B ２ , k, l, and C １ represent the same meaning as; R １ ~R ５ each represent the same meaning as R in the formula (A); １ ~R ５ represent the same meaning as; Y represents the same meaning as Y in the formula (B). A step of obtaining, and reacting the compound (G1) and compound (G2) with the following formula (H): [Chemical 17] (In the formula (H), Ar represents a divalent group having an optionally substituted aromatic group; C ２ represents a group that reacts with the substituent represented by C in the formula (G1) and formula (G2) to be converted into the substituent represented by L in the following formula (X): １ L １ or L ２ represented by) A step of reacting with the compound (H) represented by the following formula (X): [Chemical 18] (In the formula (X), L １ and L ２ each independently represent -CR １ R ２ -, -CH ２ -CH ２ -, -O-, -S-, -CO-O-, -O-CO-, -O-CO-O-, -C(=S)-O-, -O-C(=S)-, -O-C(=S)-O-, -CO-NR １ -, -NR ２ -CO-, -O-CH ２ -, -CH ２ -O-, -S-CH ２ -, -CH ２represents -S- or a single bond; A １ , A ２ , G １ , G ２ , B １ , B ２ , k and l each represent the same meaning as A, A, G, G, B, B in the formula (G1) or formula (G2); １ , A ２ , G １ , G ２ , B １ , B ２ , k and l represent the same meaning as themselves, and R1 and R2 each independently represent a hydrogen atom, a halogen atom, or an alkyl group having 1 to 6 carbon atoms which may have a substituent; Ar represents the same meaning as Ar in the formula (H); R １ ~R ５ represents the same meaning as R~R in the formula (A); １ ~R ５ respectively; Y represents the same meaning as Y in the formula (B); Process for producing a polymerizable liquid crystal compound (X) represented by the formula.

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