JP7696226B2 - Method for producing polymerizable compound - Google Patents

Description

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

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 for selectively esterifying alcoholic hydroxyl groups by reacting a phenol derivative having an alcoholic hydroxyl group with an acid halide in the presence of N,N-diisopropylethylamine.

Patent No. 6090514 Patent No. 6191793

However, in the methods using aliphatic amines as described in the above patent documents, 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.

The present inventors have conducted extensive research to solve the above problems and have completed the present invention.
[1] Formula (A):
[In formula (A), R ¹ , R ² , R ³ and R ⁴ each independently represent 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]
and an alcohol compound (A) represented by the following formula (B):
[In formula (B), Y represents a hydrogen atom or a methyl group]
and an acid halide (B) represented by the following formula (C):
[In formula (C), R ⁶ , R ⁷ , R ⁸ , R ⁹ and R ¹⁰ each independently represent 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 represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms which may have a substituent]
In the presence of aniline (C) represented by the following formula (D):
(In formula (D), R ¹ to R ⁵ have the same meanings as R ¹ to R ⁵ in formula (A), respectively, and Y has the same meaning as Y in formula (B).)
A method for producing a polymerizable compound (D) represented by the following formula:
[2] The method according to [1], wherein the acid halide (B) is present in an amount of 1.0 molar equivalent or more and 15.0 molar equivalent or less per molar equivalent of the alcohol compound (A).
[3] The method according to [1] or [2], wherein the aniline (C) is present in an amount of 1.0 molar equivalent or more and 15.0 molar equivalent or less relative to 1 molar equivalent of the alcohol compound (A).
[4] The method according to any one of [1] to [3], wherein Y in formula (B) and formula (D) is a hydrogen atom.
[5] The method according to any one of [1] to [4], wherein R ⁵ in formula (A) and formula (D) is an alkanediyl group having 1 to 6 carbon atoms.
[6] The method according to any one of [1] to [5], wherein the reaction time in the reaction is 10 minutes to 24 hours.
[7] The method according to any one of [1] to [6], wherein the reaction is carried out at a temperature range of -10°C to 25°C.
[8] The method according to any one of [1] to [7], wherein the reaction is carried out in the presence of an aromatic solvent.
[9] The method according to any one of [1] to [8], wherein the reaction is carried out by adding the acid halide (B) dropwise to a mixture of the alcohol compound (A) and the aniline (C).
[10] The following formula (A):
[In formula (A), R ¹ , R ² , R ³ and R ⁴ each independently represent 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]
and an alcohol compound (A) represented by the following formula (B):
[In formula (B), Y represents a hydrogen atom or a methyl group]
and an acid halide (B) represented by the following formula (C):
[In formula (C), R ⁶ , R ⁷ , R ⁸ , R ⁹ and R ¹⁰ each independently represent 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 represent 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 (D):
(In formula (D), R ¹ to R ⁵ have the same meanings as R ¹ to R ⁵ in formula (A), respectively, and Y has the same meaning as Y in formula (B).)
A step of obtaining a polymerizable compound (D) represented by the formula:
The polymerizable compound (D) and a compound represented by the following formula (E):
[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 represent a divalent alicyclic hydrocarbon group or a divalent aromatic group, a hydrogen atom 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 a carbon atom 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 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 ₂ -S- or a single bond;
k and l each independently represent an integer of 0 or 1.
The present invention relates to a method for producing a compound represented by the following formula (X):
[In formula (X),
Ar, A ¹ , A ² , G ¹ , G ² , L ¹ , L ² , B ¹ , B ² , k and l each have the same meaning as Ar, A ¹ , ^{A 2 , G 1 , G 2 , L 1 , L 2 , B 1 , B 2 , k and l in formula} (E);
R ¹ to R ⁵ each have the same meaning as R ¹ to R ⁵ in formula (A);
Y has the same meaning as Y in the above formula (B).
A method for producing a polymerizable liquid crystal compound (X) represented by the following formula:
[11] The following formula (A):
[In formula (A), R ¹ , R ² , R ³ and R ⁴ each independently represent 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]
and an alcohol compound (A) represented by the following formula (B):
[In formula (B), Y represents a hydrogen atom or a methyl group]
and an acid halide (B) represented by the following formula (C):
[In formula (C), R ⁶ , R ⁷ , R ⁸ , R ⁹ and R ¹⁰ each independently represent 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 represent 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 (D):
(In formula (D), R ¹ to R ⁵ have the same meanings as R ¹ to R ⁵ in formula (A), respectively, and Y has the same meaning as Y in formula (B).)
A step of obtaining a polymerizable compound (D) represented by
The polymerizable compound (D) and a compound (F1) represented by the following formula (F1) and a compound (F2) represented by the following formula (F2):
[In formula (F1) and formula (F2),
A ¹ , A ² , G ¹ and G ² each independently represent a divalent alicyclic hydrocarbon group or a divalent aromatic group, a hydrogen atom 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 a carbon atom 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 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 ₂ -S- or a single bond;
k and l each independently represent an integer of 0 or 1;
^C1 represents a group which is converted into a substituent represented by ^L1 or ^L2 in the following formula (X) by reacting with a substituent represented by ^C2 in the following formula (H).
By reacting the above, a compound (G1) represented by the following formula (G1) and a compound (G2) represented by the following formula (G2):
[In formula (G1) and formula (G2),
A ¹ , A ² , G ¹ , G ² , B ¹ , B ² , k, l and C ¹ each have the same meaning as A ¹ , A ² , G ¹ , G ² , B ¹ , B ² , k, l and C ¹ in formula (F1) or formula (F2) above;
R ¹ to R ⁵ each have the same meaning as R ¹ to R ⁵ in formula (A);
Y has the same meaning as Y in the above formula (B).
and
The compound (G1) and the compound (G2) are reacted with a compound represented by the following formula (H):
[In formula (H),
Ar represents a divalent group having an aromatic group which may have a substituent;
^C2 represents a group which is converted into a substituent represented by ^L1 or ^L2 in the following formula (X) by reacting with a substituent represented by ^C1 in the formula (G1) and the formula (G2).
The method includes a step of reacting a compound represented by the following formula (X):
[In 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 ₂ -S- or a single bond;
A ¹ , A ² , G ¹ , G ² , B ¹ , B ² , k and l each have the same meaning as A ¹ , A ² , G ¹ , G ² , B ¹ , B ² , k and l in formula (G1) or formula (G2);
Ar has the same meaning as Ar in formula (H);
R ¹ to R ⁵ each have the same meaning as R ¹ to R ⁵ in formula (A);
Y has the same meaning as Y in the above formula (B).
A method for producing a polymerizable liquid crystal compound (X) represented by the following formula:

The present invention provides a method for selectively esterifying a phenol derivative having an alcoholic hydroxyl group in a sufficiently high yield.

The following describes in detail the embodiments of the present invention. Note that the scope of the present invention is not limited to the embodiments described here, and various modifications can be made without departing from the spirit of the present invention.

The present invention relates to a compound of formula (D):
The present invention relates to a method for producing a polymerizable compound (D) represented by the following formula (1):

In formula (D), R ¹ , R ² , R ³ and R ⁴ each independently represent 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, and a bromine atom. 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, and a butyl group, and an alkyl group in which a hydrogen atom contained in the alkyl group is substituted with a halogen atom, a nitro group, a cyano group, or the like. R ¹ , R ² , R ³ and R ⁴ each independently represent 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.

In formula (D), R ⁵ represents an alkanediyl group having 1 to 12 carbon atoms which may have a substituent. Specific examples include unsubstituted alkanediyl groups such as methylene, ethylene, propane-1,3-diyl, butane-1,3-diyl, butane-1,4-diyl, pentane-1,5-diyl, hexane-1,6-diyl, heptane-1,7-diyl, octane-1,8-diyl, and decane-1,10-diyl groups, and alkanediyl groups in which hydrogen atoms contained in the alkanediyl group are substituted with halogen atoms, alkoxy groups, nitro groups, cyano groups, or the like. 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 even more preferably an unsubstituted linear alkanediyl group having 1 to 6 carbon atoms.

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

In the present invention, the polymerizable compound (D) is represented by the formula (A):
and an alcohol compound (A) represented by the formula (B):
and an acid halide (B) represented by the following formula:

R ¹ to R ⁵ in formula (A) have the same meanings as R ¹ to R ⁵ in formula (D), respectively, and are determined depending on the structure of the intended polymerizable compound (D).

The alcohol compound (A) can be produced by 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 formula (A-1) with a halogenated alcohol compound (A-2) represented by formula (A-2).

In the above formulas (A-1) and (A-2), R ¹ to R ⁵ are structures corresponding to R ¹ to R ⁵ in the structure of the target alcohol compound (A), respectively, and X is a halogen atom.

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

Y in formula (B) has the same meaning as Y in formula (D) and is determined according to the structure of the desired polymerizable compound (D).

The acid halide (B) can be produced using a conventional organic synthesis method, but commercially available (meth)acrylic acid chloride may also be used.

In the production method of the present invention, an alcohol compound (A) and an acid halide (B) are reacted with a compound represented by the formula (C):
The reaction is carried out in the presence of aniline (C) represented by the formula: By carrying out the reaction of alcohol compound (A) with acid halide (B) in the presence of aniline (C), polymerizable compound (D) can be obtained in high yield. In addition, since the reaction tends to proceed in a shorter time than in the conventional method using an aliphatic amine, it is expected that polymerizable compound (D) can be produced more efficiently in high yield.

In formula (C), R ⁶ , R ⁷ , R ⁸ , R ⁹ and R ¹⁰ each independently represent 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 represent 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 as those exemplified as the alkyl group represented by R ¹ to R ⁴ in formula (A). R ⁶ , R ⁷ , R ⁸ , R ⁹ and R ¹⁰ each independently represent 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. In addition, R ¹¹ and R ¹² each independently represent a hydrogen atom or an unsubstituted alkyl group having 1 to 6 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms.

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

In the reaction between the alcohol compound (A) and the acid halide (B), the aniline (C) is preferably present in an amount of 1.0 molar equivalent or more and 15.0 molar equivalent or less relative to 1 molar equivalent of the alcohol compound (A). When the aniline (C) is present in an amount within 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, even more preferably 1.5 molar equivalents or more, and more preferably 10.0 molar equivalents or less, even more preferably 5.0 molar equivalents or less relative to 1 molar equivalent of the alcohol compound (A).

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. Examples of such solvents include aromatic solvents such as toluene, xylene, benzene, dimethoxybenzene, chlorobenzene, dichlorobenzene, mesitylene, and ethylbenzene; ether solvents such as 1,4-dioxane, cyclopentyl methyl ether, tetrahydrofuran, tetrahydropyran, and 1,3-dioxolane; chlorine solvents such as chloroform and methylene chloride; amide solvents such as N-methylpyrrolidone, N,N-dimethylformamide, N,N-dimethylacetamide, and hexamethylphosphoric acid triamide; aliphatic hydrocarbon solvents such as pentane, hexane, and heptane; sulfur-containing solvents such as dimethyl sulfoxide and sulfolane; and polar solvents such as methanol, ethanol, and water. These solvents can be used alone or in combination of two or more. Among them, aromatic solvents are preferred from the viewpoint of the solubility of the product.

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

The reaction between the alcohol compound (A) and the acid halide (B) may be carried out using additives as necessary, for example, in the presence of a polymerization inhibitor to prevent polymerization. Examples of polymerization inhibitors include 2,6-di-tert-butyl-p-cresol (BHT), 2,2'-methylenebis(6-tert-butyl-p-cresol), triphenyl phosphite, tris(nonylphenyl phosphite), and phenothiazine. When a polymerization inhibitor is used, the amount added is preferably 0.01 molar equivalent or more, more preferably 0.05 molar equivalent or more, and preferably 0.5 molar equivalent or less, relative to 1 molar equivalent of the alcohol compound (A).

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 adding the acid halide (B) dropwise to a mixture containing the alcohol compound (A) and aniline (C), and optionally a solvent.

The conditions for the reaction can be appropriately determined depending on the types of the compounds used, the scale of the reaction, and the like.
In one embodiment of the production method of the present invention, the reaction temperature of 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 of the alcohol compound (A) and the acid halide (B) easily proceeds, and the target compound can be obtained more safely due to the mild conditions.

The reaction time may be determined according to the type, ratio, and temperature of the compounds used, and although it also depends on the scale of the reaction, it is preferably 10 minutes to 24 hours, and 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 when the alcohol compound (A) and the acid halide (B) begin to coexist, and ends when the reaction between the alcohol compound (A) and the acid halide (B) stops/comes to an end. The progress of the reaction can be confirmed by analytical means such as high-performance liquid chromatography, thin-layer chromatography, and gas chromatography.

When the reaction between the alcohol compound (A) and the acid halide (B) is carried out by adding the acid halide (B) dropwise to a mixture containing the alcohol compound (A) and aniline (C), the dropping rate may be, for example, 0.1 to 100 parts by mass/min, assuming that the total amount of the acid halide (B) used in the reaction is 100 parts by mass.

After the reaction is completed, the polymerizable compound (D) can be isolated, if necessary, by carrying out 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.

The structure of the obtained compound can be identified by measuring NMR spectrum, IR spectrum, mass spectrum, etc., elemental analysis, etc.

The present invention relates to a compound of formula (A):
[In formula (A), R ¹ , R ² , R ³ and R ⁴ each independently represent 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]
and an alcohol compound (A) represented by the formula (B):
[In formula (B), Y represents a hydrogen atom or a methyl group]
and an acid halide (B) represented by the formula (C):
[In formula (C), R ⁶ , R ⁷ , R ⁸ , R ⁹ and R ¹⁰ each independently represent 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 represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms which may have a substituent]
to obtain a compound represented by the formula (D):
(In formula (D), R ¹ to R ⁵ have the same meanings as R ¹ to R ⁵ in formula (A), respectively, and Y has the same meaning as Y in formula (B).)
A step of obtaining a polymerizable compound (D) represented by the formula:
The polymerizable compound (D) and a compound of the formula (E):
[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 represent a divalent alicyclic hydrocarbon group or a divalent aromatic group, a hydrogen atom 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 a carbon atom 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 represent a single bond or a divalent linking group;
k and l each independently represent an integer of 0 or 1.
With a compound (E) represented by formula (X):
[In formula (X),
Ar, A ¹ , A ² , G ¹ , G ² , L ¹ , L ² , B ¹ , B ² , k and l each have the same meaning as Ar, A ¹ , ^{A 2 , G 1 , G 2 , L 1 , L 2 , B 1 , B 2 , k and l in formula} (E);
R ¹ to R ⁵ each have the same meaning as R ¹ to R ⁵ in formula (A);
Y has the same meaning as Y in the above formula (B).
The present invention also covers a method for producing a polymerizable liquid crystal compound (X) represented by the following formula (hereinafter also referred to as "production method (X1)"). In this production method, the polymerizable compound (D) obtained by the above-described method for producing the polymerizable compound (D) is used as an intermediate, so that the final polymerizable liquid crystal compound (X) can be obtained more efficiently.

In the manufacturing method (X1) of the polymerizable liquid crystal compound (X), the step of reacting the alcohol compound (A) with the acid halide (B) in the presence of aniline (C) to obtain the polymerizable compound (D) is the same as in 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 the aniline (C), the method and conditions for reacting the alcohol compound (A) with the acid halide (B), etc. are the same as those described above as the manufacturing method of the polymerizable compound (D).

In the present invention, the production method (X1) comprises reacting an alcohol compound (A) with an acid halide (B) in the presence of aniline (C) to obtain a polymerizable compound (D) represented by the formula (E):
With a compound (E) represented by the following formula (1):

In formula (E), the divalent group represented by Ar may have two or more aromatic groups, and the aromatic groups may contain at least one of a nitrogen atom, an oxygen atom, and a sulfur atom. When Ar contains two or more aromatic groups, the two or more aromatic groups may be bonded to each other via a divalent bonding group such as a single bond, -CO-O-, or -O-.

It is preferable that Ar has at least one selected from an aromatic hydrocarbon ring which may have a substituent, an aromatic heterocycle which may have a substituent, and an electron-withdrawing group. Examples of the aromatic hydrocarbon ring include a benzene ring, a naphthalene ring, and an anthracene ring, and a benzene ring and a naphthalene ring are preferable. Examples of the aromatic heterocycle 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.

Examples of aromatic groups contained in Ar include the following groups:

In formulae (Ar-1) to (Ar-23), * represents a linking portion, Z ⁰ , Z ¹ and Z ² each independently represent 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.

Q ¹ and Q ² each independently represent -CR ^2' R ^3' -, -S-, -NH-, -NR ^2' -, -CO- or -O-, and R ^2' and R ^3' each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.

J ¹ and J ² each independently represent a carbon atom or a nitrogen atom.

Y ¹ , Y ² and Y ³ each independently represent an aromatic hydrocarbon group or aromatic heterocyclic group which may be substituted. The aromatic hydrocarbon group in ^{Y 1} , Y ² and Y ³ may be an aromatic hydrocarbon group having 6 to 20 carbon atoms, such as a phenyl group, a naphthyl group, an anthryl group, a phenanthryl group, or a biphenyl group, and the aromatic heterocyclic group may be an aromatic heterocyclic group having 4 to 20 carbon atoms and containing at least one heteroatom, such as a nitrogen atom, an oxygen atom, or a sulfur atom, such as a furyl group, a pyrrolyl group, a thienyl group, a pyridinyl group, a thiazolyl group, or a benzothiazolyl group. Y ¹ , Y ² and Y ³ may each independently be a polycyclic aromatic hydrocarbon group or a polycyclic aromatic heterocyclic group which may be substituted.

W ¹ and W ² each independently represent a hydrogen atom, a cyano group, a methyl group or a halogen atom; m represents an integer of 0 to 6.

In formulae (Ar-16) to (Ar-23), Y ¹ may form an aromatic heterocyclic group together with the nitrogen atom to which it is bonded and Z ^0. Examples of the aromatic heterocyclic group include those described above as the aromatic heterocycle that Ar may have, and this aromatic heterocyclic group may have a substituent. Furthermore, Y ¹ may be, together with the nitrogen atom to which it is bonded and Z ⁰ , the aforementioned optionally substituted polycyclic aromatic hydrocarbon group or polycyclic aromatic heterocyclic group.

In formula (E), A ¹ , A ² , G ¹ and G ² are each independently preferably a 1,4-phenylenediyl group which may be substituted with at least one substituent selected from the group consisting of halogen atoms and alkyl groups having 1 to 4 carbon atoms, or a 1,4-cyclohexanediyl group which may be substituted with at least one substituent selected from the group consisting of halogen atoms and alkyl groups 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. It is preferable that at least one of A ¹ , A ² , G ¹ and G ² is 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.
G ¹ and G ² may be the same substituent, or may be different substituents.

In formula (E), examples of the divalent group represented by L ¹ and L ² include 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-, -CR ^c =CR ^d -, and -C≡C-. Here, R ^a1 to R ^a8 each independently represent a single bond or an alkylene group having 1 to 4 carbon atoms, and R ^c and R ^d each independently represent an alkyl group having 1 to 4 carbon atoms or a hydrogen atom. ^{L 1} and L ² each independently are preferably a single bond, -O-, -CH ₂ CH ₂ -, -COO-, -COOCH ₂ CH ₂ -, or -OCO-.

Ar, ^A1 , ^A2 , ^G1 , ^G2 , ^L1 , ^L2 , ^B1 , ^B2 , k and l in formula (E) are each determined according to the corresponding molecular structure of the desired polymerizable liquid crystal compound (X).

Compound (E) can be produced by appropriately combining known organic synthesis reactions (e.g., 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 the structure of the compound.

For example, a compound represented by the following formula (E-1) in which G ¹ and G ² are both 1,4-cyclohexanediyl groups, L ¹ and L ² are both -COO-, and k and l are both 0:
Compound (E-1) represented by the formula (E-1) can be produced, for example, in accordance with the method disclosed in JP-A-2014-123134 as follows. Note that Ar in the formula (E-1) has the same meaning as Ar in the formula (X) corresponding to the target polymerizable liquid crystal compound (X).

First, transcyclohexanedicarboxylic acid and benzyl bromide are reacted in the presence of potassium carbonate to produce intermediate (e1) represented by formula (e1).

Next, the obtained intermediate (e1) and an alcohol compound (F) represented by 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 formula (e2).

Furthermore, the benzyl group can be removed from the obtained intermediate (e2) using a catalyst such as palladium/carbon, followed by hydrogenation to obtain compound (E-1).

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

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 compound represented by the formula (X):
A polymerizable liquid crystal compound (X) represented by the following formula (1) is obtained.

In formula (X), Ar, ^A1 , ^A2 , ^G1 , ^G2 , ^L1 , ^L2 , ^B1 , ^B2 , k and l each have the same meaning as Ar, ^A1 , ^A2 , ^G1 , ^G2 , ^L1 , ^L2 , ^B1 , ^B2 , k and l in formula (E), ^R1 to ^R5 each have the same meaning as ^R1 to ^R5 in formula (A), and Y has the same meaning as Y in formula (B).

For example, a polymerizable liquid crystal compound (X-1) represented by formula (X-1) is obtained by reacting the polymerizable compound (D) with the above-mentioned compound (E-1). R ¹ to R ⁵ and Y in formula (X-1) have the same meanings as R ¹ to R ⁵ and Y in formula (D) corresponding to the polymerizable compound (D), and Ar in formula (X-1) has the same meaning as Ar in formula (E-1) corresponding to compound (E-1).

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 quickly.

Condensation agents include, for example, 1-cyclohexyl-3-(2-morpholinoethyl)carbodiimide metho-para-toluenesulfonate, dicyclohexylcarbodiimide, diisopropylcarbodiimide, 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide, 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide hydrochloride (water-soluble carbodiimide: commercially available as WSC), bis(2,6-diisopropylphenyl)carbodiimide, Imides and carbodiimide compounds such as 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-yloxytripyrrolidinophosphonium hexafluorophosphate, 1H-benzyloxytriphenylphosphine ... N-(6-chlorobenzotriazol-1-yl)-N,N,N',N'-tetramethyluronium tetrafluoroborate, N-(1,2,2,2-tetrachloroethoxycarbonyloxy)succinimide, N-carbobenzoxysuccinimide, O-(6-chlorobenzotriazol-1-yl)-N,N,N',N'-tetramethyluronium tetrafluoroborate fluoroborate, 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 para-toluenesulfonate, 2-fluoro-1-methylpyridinium para-toluenesulfonate, and trichloroacetic acid pentachlorophenyl ester. From the viewpoints of reactivity, cost, and solvents that can be used, the condensation agent is preferably dicyclohexylcarbodiimide, 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide, 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide hydrochloride, bis(2,6-diisopropylphenyl)carbodiimide, bis(trimethylsilyl)carbodiimide, bisisopropylcarbodiimide, or 2,2'-carbonylbis-1H-imidazole.

The amount of the condensing agent used in the esterification reaction of the polymerizable compound (D) and the compound (E) can be appropriately determined depending on 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 mole of the compound (E).

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

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 those usable in the above-mentioned reactions for obtaining the intermediate (e1), the intermediate (e2), and the compound (E-1). From the viewpoint of reaction yield and productivity, non-polar organic solvents such as pentane, hexane, heptane, toluene, xylene, benzene, chlorobenzene, chloroform, and dichloromethane are preferred. The solvents may be used alone or in combination.

From the viewpoint of facilitating the production of 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 even more preferably 2 to 3 moles, per mole of the compound (E).

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, per 1 part by mass of the total of the polymerizable compound (D) and the compound (E).

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. 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.

After the reaction is completed, the polymerizable liquid crystal compound (X) can be isolated, if necessary, by carrying out 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.

The present invention relates to a compound of formula (A):
[In formula (A), R ¹ , R ² , R ³ and R ⁴ each independently represent 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]
and an alcohol compound (A) represented by the following formula (B):
[In formula (B), Y represents a hydrogen atom or a methyl group]
and an acid halide (B) represented by the following formula (C):
[In formula (C), R ⁶ , R ⁷ , R ⁸ , R ⁹ and R ¹⁰ each independently represent 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 represent 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 (D):
(In formula (D), R ¹ to R ⁵ have the same meanings as R ¹ to R ⁵ in formula (A), respectively, and Y has the same meaning as Y in formula (B).)
A step of obtaining a polymerizable compound (D) represented by
The polymerizable compound (D) and a compound (F1) represented by the following formula (F1) and a compound (F2) represented by the following formula (F2):
[In formula (F1) and formula (F2),
A ¹ , A ² , G ¹ and G ² each independently represent a divalent alicyclic hydrocarbon group or a divalent aromatic group, a hydrogen atom 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 a carbon atom 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 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 ₂ -S- or a single bond;
k and l each independently represent an integer of 0 or 1;
^C1 represents a group which is converted into a substituent represented by ^L1 or ^L2 in the following formula (X) by reacting with a substituent represented by ^C2 in the following formula (H).
By reacting the above, a compound (G1) represented by the following formula (G1) and a compound (G2) represented by the following formula (G2):
[In formula (G1) and formula (G2),
A ¹ , A ² , G ¹ , G ² , B ¹ , B ² , k, l and C ¹ each have the same meaning as A ¹ , A ² , G ¹ , G ² , B ¹ , B ² , k, l and C ¹ in formula (F1) or formula (F2) above;
R ¹ to R ⁵ each have the same meaning as R ¹ to R ⁵ in formula (A);
Y has the same meaning as Y in the above formula (B).
and
The compound (G1) and the compound (G2) are reacted with a compound represented by the following formula (H):
[In formula (H),
Ar represents a divalent group having an aromatic group which may have a substituent;
^C2 represents a group which is converted into a substituent represented by ^L1 or ^L2 in the following formula (X) by reacting with a substituent represented by ^C1 in the formula (G1) and the formula (G2).
The method includes a step of reacting a compound represented by the following formula (X):
[In 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 ₂ -S- or a single bond;
A ¹ , A ² , G ¹ , G ² , B ¹ , B ² , k and l each have the same meaning as A ¹ , A ² , G ¹ , G ² , B ¹ , B ² , k and l in formula (G1) or formula (G2);
Ar has the same meaning as Ar in formula (H);
R ¹ to R ⁵ each have the same meaning as R ¹ to R ⁵ in formula (A);
Y has the same meaning as Y in the above formula (B).
The present invention also covers a method for producing a polymerizable liquid crystal compound (X) represented by the following formula (hereinafter also referred to as "production method (X2)"). In the production method (X2), similarly to the production method (X1), the polymerizable compound (D) obtained by the above-described method for producing the polymerizable compound (D) is used as an intermediate, and therefore the final target polymerizable liquid crystal compound (X) can be obtained more efficiently.

In the manufacturing method (X2), the step of reacting the alcohol compound (A) with the acid halide (B) in the presence of aniline (C) to obtain the polymerizable compound (D) is the same as in 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 the aniline (C), the method and conditions for reacting the alcohol compound (A) with the acid halide (B), etc. are the same as those described above as the manufacturing method of the polymerizable compound (D).

The production method (X2) comprises reacting an alcohol compound (A) with an acid halide (B) in the presence of aniline (C) to obtain a polymerizable compound (D), and then reacting the resulting polymerizable compound with a compound (F1) represented by formula (F1) and a compound (F2) represented by formula (F2):
By reacting with the above, a compound (G1) represented by formula (G1) and a compound (G2) represented by formula (G2):
The method includes the step of obtaining

A ¹ , A ² , G ¹ , G ^{2 , B 1 , B 2 , k and l in formula (F1), formula (F2), formula (G1) and formula (G2) are groups (structures) corresponding to A 1 , A 2 , G 1 , G 2 , B 1 ,} B ² , k and l in formula (X) corresponding to the finally obtained compound (X), respectively. Examples of ^{A 1} , A ² , G ¹ , G ² , B ¹ , B ² , k and l include the same groups (structures) as A ¹ , A ² , G ¹ , G ² , B ¹ , B ² , k and l in formula (E) corresponding to the compound (E) used in the above-mentioned production method (X1), and are determined according to the molecular structure of the desired polymerizable liquid crystal compound (X).

C ¹ in formula (F1), formula (F2), formula (G1) and formula (G2) is a group which becomes a substituent represented by L ¹ or L ² in formula (X) by reacting with a substituent represented by C ² in formula (H) corresponding to compound (H) described later. For example, when C ¹ is -COOH and C ² is -OH, compound (X) in which L ¹ and L ² are each *-OCO- (* indicates the bond position with Ar) is obtained by ester condensation reaction of compound (G1) and compound (G2) with compound (H). Specific examples of C ¹ include -COOH, -COCl, -COOCH ₃ , -COSH, -CSOH, -NH ₂ , -NR ₁ H, -OH, -SH, CH ₂ X, etc. Among them, -COOH and -OH are preferable from the viewpoint of reactivity.
G ¹ in formula (F1) and formula (G1) may be the same substituent as G ² in formula (F2) and formula (G2), or may be different substituents.

R ¹ to R ⁵ in formula (G1) and formula (G2) have the same meanings as R ¹ to R ⁵ in formula (A), respectively, and Y has the same meaning as Y in formula (B).

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

Examples of the solvent in the above reaction include the same ones that can be used in the reaction of 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 even more preferably 1 to 10 parts by mass, per part by mass of the total of polymerizable compound (D) and compound (E).

The amount of polymerizable compound (D) used in the above reaction is preferably 0.1 to 1 mol, more preferably 0.2 to 0.8 mol, and even more preferably 0.3 to 0.6 mol per 1 mol of the total of compounds (F1) and (F2), from the viewpoint of facilitating the production of polymerizable liquid crystal compound (X).

The conditions for the reaction of compound (F1) and compound (F2) with polymerizable compound (D) may be appropriately determined. From the viewpoints of reaction yield and productivity, the reaction temperature is, for example, −20 to 60° C., preferably −20 to 40° C., and more preferably −20 to 10° C. In addition, from the viewpoints of reaction yield and productivity, the reaction time may be, for example, 1 minute to 72 hours, preferably 1 minute to 48 hours, and more preferably 1 minute to 24 hours.

Compound (F1) and compound (F2) used in the above reaction can be produced by appropriately combining various known organic synthesis reactions described in relation to production method (X1) according to their structures.

Compound (G1) and compound (G2) can also be obtained by esterification of compound (F1) and compound (F2) with polymerizable compound (D). The esterification can be carried out in the presence of a suitable condensing agent, catalyst, solvent, etc. The types and amounts of condensing agents, catalysts, and solvents that can be used, as well as the conditions for the esterification, etc., are the same as those for the esterification of polymerizable compound (D) and compound (E) in the above-mentioned production method (X1).

In the production method (X2), the compound (G1) and the compound (G2) obtained in the above steps are reacted with a compound represented by the formula (H):
With a compound (H) represented by the formula (X):
A polymerizable liquid crystal compound (X) represented by the following formula (1) is obtained.

Ar in formula (H) is a group (structure) corresponding to Ar in formula (X) corresponding to the finally obtained compound (X). Ar can be exemplified by the same group (structure) as Ar in formula (E) corresponding to compound (E) used in production method (X1), and is determined according to the molecular structure of the desired polymerizable liquid crystal compound (X).

C ² in formula (H) is a group that is converted to a substituent represented by L 1 or L ² in formula (X) by reacting with a substituent represented by C ¹ in formula (G1) and formula (G2) corresponding to the compound (G1) and compound (G2). For example, when C ² is -OH and C ¹ is -COOH, ^a compound (X) in which L ¹ and L ² are each *-OCO- (* indicates the bond position with Ar) is obtained by an ester condensation reaction between compound (G1) and compound (G2) and compound (H). Specific examples of C ² include -OH, -SH, CH ₂ X, -COOH, -COCl, -COOCH ₃ , -COSH, -CSOH, -NH ₂ , -NR ₁ H, and -OH. Among them, -OH and -COOH are preferable from the viewpoint of reactivity.

For example, a compound (G1-1) and a compound (G2-1) in which C ¹ in the formulas (G1) and (G2) is -COOH are reacted with a compound (H-1) in which C ² in the formula (H) is -OH to obtain a polymerizable liquid crystal compound (X-2) represented by the formula (X-2). In addition, A ¹ , A ² , B ¹ , B ² , G ¹ , G ² , k and l in formula (X-2) 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 (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 to R ⁵ and Y have the same meanings as R ¹ to R ⁵ and Y in formula (D) corresponding to polymerizable compound (D).

The reaction between compound (G1) and compound (G2) and compound (H) 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 quickly. Examples of condensing agents that can be used include those similar to those used in the esterification reaction between polymerizable compound (D) and compound (E) in the above-mentioned production method (X1).

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

The esterification reaction may be carried out in the presence of a catalyst. Examples of catalysts that can be used include those similar to those used in the esterification reaction of the polymerizable compound (D) and the compound (E) in the production method (X1). The amount of catalyst used is preferably 0.01 to 0.5 mol per mol of the compound (H), for example.

The esterification reaction of compound (G1) and compound (G2) with compound (H) is usually carried out in a solvent. Examples of solvents that can be used include those similar to those used in the esterification reaction of polymerizable compound (D) with compound (E) in 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 even more preferably 2 to 10 parts by mass, per part by mass of the total of compound (G1), compound (G2), and compound (H).

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. 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.

After the reaction is completed, the polymerizable liquid crystal compound (X) can be isolated, if necessary, by carrying out 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.

The reaction of compound (G1) and compound (G2) with compound (H) can be carried out based on various known organic synthesis reactions depending on the structure of ^C1 in formula (G1) or (G2) and the structure represented by ^C2 in formula (H). The conditions and the like can also be appropriately determined depending on the type of organic synthesis reaction used, the types of compound (G1), compound (G2) and compound (H), and the like.

The structure of the obtained compound can be identified by measuring NMR spectrum, IR spectrum, mass spectrum, etc., elemental analysis, etc.

The polymerizable liquid crystal compound (X) generally exhibits reverse wavelength dispersion in the birefringence of the polymer when polymerized in a unidirectionally oriented state, and such a polymerizable liquid crystal compound can be used to produce an optical film capable of uniform polarization conversion over a wide wavelength range.

The present invention will be explained in more detail below with reference to the following examples. In the examples, "%" and "parts" refer to mass % and mass parts, respectively, unless otherwise specified.

1. Example 1
<Preparation of polymerizable compound (D1)>
Formula (A1):
In a 50 mL four-neck flask equipped with a stirrer, a Dimroth condenser, and a thermometer, 1.00 g of the alcohol compound (A1) represented by the formula (1) was added, and 6.57 g of toluene (6.6 parts by mass relative to the alcohol compound (A1)) was added and stirred. Next, 1.50 g of N,N-dimethylaniline (1.5 molar equivalent relative to the alcohol compound (A1)) and 0.09 g of 2,6-di-tert-butyl-p-cresol [BHT] (0.1 molar equivalent relative to the alcohol compound (A1)) were added, and the mixture was stirred and cooled to 0°C.
Next, 0.93 g of acrylic acid chloride (2.5 molar equivalents relative to the alcohol compound (A1)) was added dropwise over 10 minutes. Thirty minutes after the addition, the mixture was analyzed by HPLC under the following measurement conditions, and the product was found to have the formula (D1):
The polymerizable compound (D1) obtained according to this method had an area percentage of 95.6% calculated based on the peak area measured by liquid chromatography.

[HPLC Measurement]
The HPLC measurement was carried out under the following conditions.
(Measurement conditions)
Measurement device: HPLC LC-10AT (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
20min 65.3%-B
40min 100%-B
50min 100%-B
50.1min 2%-B
60min STOP
Flow rate: 1.0mL/min
Injection volume: 5μL
Detection wavelength: UV 220 nm

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

Claims (10)

The following formula (A):
[In formula (A), R ¹ , R ² , R ³ and R ⁴ each independently represent 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]
and an alcohol compound (A) represented by the following formula (B):
[In formula (B), Y represents a hydrogen atom or a methyl group]
and an acid halide (B) represented by the following formula (C):
[In formula (C), R ⁶ , R ⁷ , R ⁸ , R ⁹ and R ¹⁰ each independently represent 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 represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms which may have a substituent]
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 equivalent or less relative to 1 molar equivalent of the alcohol compound (A), and a reaction product represented by the following formula (D):
(In formula (D), R ¹ to R ⁵ have the same meanings as R ¹ to R ⁵ in formula (A), respectively, and Y has the same meaning as Y in formula (B).)
A method for producing a polymerizable compound (D) represented by the following formula: The method according to claim 1, wherein the aniline (C) is present in an amount of 1.0 molar equivalent or more and 15.0 molar equivalent or less per molar equivalent of the alcohol compound (A). The method according to claim 1 or 2, wherein Y in formula (B) and formula (D) is a hydrogen atom. The method according to any one of claims 1 to 3, wherein R ⁵ in formula (A) and formula (D) is an alkanediyl group having 1 to 6 carbon atoms. The method according to any one of claims 1 to 4, wherein the reaction time in the reaction is 10 minutes to 24 hours. The method according to any one of claims 1 to 5, wherein the reaction is carried out at a temperature range of -10°C to 25°C. The method according to any one of claims 1 to 6, wherein the reaction is carried out in the presence of an aromatic solvent. The method according to any one of claims 1 to 7, wherein the reaction is carried out by adding an acid halide (B) dropwise to a mixture of an alcohol compound (A) and an aniline (C). The following formula (A):
[In formula (A), R ¹ , R ² , R ³ and R ⁴ each independently represent 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]
and an alcohol compound (A) represented by the following formula (B):
[In formula (B), Y represents a hydrogen atom or a methyl group]
and an acid halide (B) represented by the following formula (C):
[In formula (C), R ⁶ , R ⁷ , R ⁸ , R ⁹ and R ¹⁰ each independently represent 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 represent 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 (D):
(In formula (D), R ¹ to R ⁵ have the same meanings as R ¹ to R ⁵ in formula (A), respectively, and Y has the same meaning as Y in formula (B).)
A step of obtaining a polymerizable compound (D) represented by the formula:
The polymerizable compound (D) and a compound represented by the following formula (E):
[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 represent a divalent alicyclic hydrocarbon group or a divalent aromatic group, a hydrogen atom 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 a carbon atom 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 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 ₂ -S- or a single bond, and R ¹ and R ² each independently represent 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.
The present invention relates to a method for producing a compound represented by the following formula (X):
[In formula (X),
Ar, A ¹ , A ² , G ¹ , G ² , L ¹ , L ² , B ¹ , B ² , k and l each have the same meaning as Ar, A ¹ , ^{A 2 , G 1 , G 2 , L 1 , L 2 , B 1 , B 2 , k and l in formula} (E);
R ¹ to R ⁵ each have the same meaning as R ¹ to R ⁵ in formula (A);
Y has the same meaning as Y in the above formula (B).
A method for producing a polymerizable liquid crystal compound (X) represented by the following formula: The following formula (A):
[In formula (A), R ¹ , R ² , R ³ and R ⁴ each independently represent 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]
and an alcohol compound (A) represented by the following formula (B):
[In formula (B), Y represents a hydrogen atom or a methyl group]
and an acid halide (B) represented by the following formula (C):
[In formula (C), R ⁶ , R ⁷ , R ⁸ , R ⁹ and R ¹⁰ each independently represent 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 represent 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 (D):
(In formula (D), R ¹ to R ⁵ have the same meanings as R ¹ to R ⁵ in formula (A), respectively, and Y has the same meaning as Y in formula (B).)
A step of obtaining a polymerizable compound (D) represented by
The polymerizable compound (D) and a compound (F1) represented by the following formula (F1) and a compound (F2) represented by the following formula (F2):
[In formula (F1) and formula (F2),
A ¹ , A ² , G ¹ and G ² each independently represent a divalent alicyclic hydrocarbon group or a divalent aromatic group, a hydrogen atom 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 a carbon atom 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 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 ₂ -S- or a single bond, and R ¹ and R ² each independently represent 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;
^C1 represents a group which is converted into a substituent represented by ^L1 or ^L2 in the following formula (X) by reacting with a substituent represented by ^C2 in the following formula (H).
By reacting the above, a compound (G1) represented by the following formula (G1) and a compound (G2) represented by the following formula (G2):
[In formula (G1) and formula (G2),
A ¹ , A ² , G ¹ , G ² , B ¹ , B ² , k, l and C ¹ each have the same meaning as A ¹ , A ² , G ¹ , G ² , B ¹ , B ² , k, l and C ¹ in formula (F1) or formula (F2) above;
R ¹ to R ⁵ each have the same meaning as R ¹ to R ⁵ in formula (A);
Y has the same meaning as Y in the above formula (B).
and
The compound (G1) and the compound (G2) are reacted with a compound represented by the following formula (H):
[In formula (H),
Ar represents a divalent group having an aromatic group which may have a substituent;
^C2 represents a group which is converted into a substituent represented by ^L1 or ^L2 in the following formula (X) by reacting with a substituent represented by ^C1 in the formula (G1) and the formula (G2).
The method includes a step of reacting a compound represented by the following formula (X):
[In 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 ₂ -S- or a single bond;
A ¹ , A ² , G ¹ , G ² , B ¹ , B ² , k and l each have the same meaning as A ¹ , A ² , G ¹ , G ² , B ¹ , B ² , k and l in formula (G1) or formula (G2) , and R ¹ and R ² 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 has the same meaning as Ar in formula (H);
R ¹ to R ⁵ each have the same meaning as R ¹ to R ⁵ in formula (A);
Y has the same meaning as Y in the above formula (B).
A method for producing a polymerizable liquid crystal compound (X) represented by the following formula: