CN112166108A - Method for producing polymerizable compound - Google Patents

Abstract

The method for producing a polymerizable compound of the present invention comprises the steps of: a step (1) in which a compound represented by the formula (I) and a compound represented by the formula (II) are reacted in an organic solvent in the presence of a base and/or a dehydration condensation agent to obtain a reaction solution containing a compound represented by the formula (III); a step (2) for hydrolyzing the compound represented by the formula (II) or the dehydration condensation agent contained in the reaction solution; and a step (3) in which a compound represented by the formula (IV) is added to react with a compound represented by the formula (III). Wherein Q represents a hydrogen atom or the like, Fg¹、Fg²Represents a hydroxyl group or the like, A represents a hydrogen atom, a methyl group or the like, L represents a hydroxyl group or a leaving group, n represents an integer of 1 to 20, Y represents¹、Y²represents-C (═ O) -O-, -O-C (═ O) -or the like, X represents an oxygen atom, a sulfur atom or the like, R represents a hydrogen atom, an organic group or the like^XRepresents a hydrogen atom, a halogen atom or the like.

Description

Method for producing polymerizable compound

Technical Field

The present invention relates to a method for producing a polymerizable compound which can be used for producing an optical film or the like in high yield.

Background

In recent years, as a technique for making a retardation plate, particularly a retardation plate having reverse wavelength dispersibility thinner, a method for producing a retardation plate by applying a polymerizable composition containing a low-molecular polymerizable compound to a film base material has been attracting attention.

Further, for example, patent document 1 discloses a polymerizable compound represented by the following formula (α) as a polymerizable compound which has a practical low melting point and high solubility in a general-purpose solvent and can be preferably used for producing a polymerizable composition and which can form an optical film capable of performing the same polarization conversion in a wide wavelength range.

[ chemical formula 1]

(wherein A independently represents a hydrogen atom, a methyl group or a chlorine atom, R represents a hydrogen atom or an organic group having 1 to 60 carbon atoms which may have a substituent, and X represents an oxygen atom, a sulfur atom or-C (R)¹)(R²) -or-N-R¹-, where R¹And R²Each independently represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms which may have a substituent, R^XRepresents a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, a cyano group, a nitro group, an alkyl group having 1 to 6 carbon atoms in which at least 1 hydrogen atom is substituted by a halogen atom, an alkoxy group having 1 to 6 carbon atoms, an alkylthio group having 1 to 6 carbon atoms, a mono-substituted amino group, a di-substituted amino groupBase, -OCF₃、-C(＝O)-O-R³or-O-C (═ O) -R³Where R is³Is represented by the above-mentioned R¹、R²Same meaning, a plurality of R^XCan be the same or different from each other, and form an arbitrary C-R ring^XCan be substituted by a nitrogen atom, and n represents an integer of 1 to 20. )

Further, patent document 1 proposes the following method for producing a polymerizable compound represented by the above formula (α) with high purity and good yield: in an organic solvent, reacting a compound of the following formula (II):

[ chemical formula 2]

(wherein A and n represent the same meanings as described above, and L represents a leaving group.)

The compound represented is reacted with 2, 5-dihydroxybenzaldehyde in the presence of a base (esterification reaction) to obtain a compound comprising the following formula (β):

[ chemical formula 3]

(wherein A and n represent the same meanings as described above.)

After the reaction solution of the compound represented by the formula (IV), the following formula (IV) is added to the obtained reaction solution:

[ chemical formula 4]

(wherein, X, R and R^XThe same meanings as described above are indicated. )

The compound represented by the formula (a) and an acidic aqueous solution are prepared by dissolving an ester produced by the esterification reaction in the acidic aqueous solution to synthesize a polymerizable compound represented by the formula (a).

Documents of the prior art

Patent document

Patent document 1: international publication No. 2015/141784.

Disclosure of Invention

Problems to be solved by the invention

However, in the conventional method for producing a polymerizable compound by adding the compound represented by the formula (IV) and an acidic aqueous solution together, there is still room for improvement in terms of further improving the yield of the polymerizable compound.

Accordingly, an object of the present invention is to provide a method for producing a polymerizable compound which can be used for producing an optical film or the like in high yield.

Means for solving the problems

The present inventors have conducted intensive studies in order to solve the above-mentioned problems, and as a result, have found that a polymerizable compound represented by the following formula (a) can be obtained in a high yield by reacting a compound represented by the following formula (I) with a compound represented by the following formula (II) in an organic solvent in the presence of a base and/or a dehydration condensation agent to obtain a reaction solution containing a compound represented by the following formula (III), then hydrolyzing predetermined components contained in the obtained reaction solution, and then adding a compound represented by the following formula (IV) to react the compound represented by the formula (IV) with the compound represented by the formula (III), thereby completing the present invention.

Thus, the present invention provides a method for producing polymerizable compounds described in the following <1> to <9 >.

<1> a method for producing a polymerizable compound, comprising the steps of:

a step (1) in which a compound represented by the following formula (I) and a compound represented by the following formula (II) are esterified in an organic solvent in the presence of a base and/or a dehydration condensation agent to obtain a reaction solution containing a compound represented by the following formula (III);

[ chemical formula 5]

(wherein Q represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms; Fg)¹And Fg²Each independently represents a hydroxyl group, -CH₂OH or-CH₂CH₂OH。)

[ chemical formula 6]

(wherein A represents a hydrogen atom, a methyl group or a chlorine atom, L represents a hydroxyl group or a leaving group, and n represents an integer of 1 to 20.)

[ chemical formula 7]

(in the formula, Y¹And Y²Each independently represents-C (═ O) -O-, -O-C (═ O) -, -CH₂-O-C(＝O)-、-C(＝O)-O-CH₂-、-CH₂-CH₂-O-C (═ O) -or-C (═ O) -O-CH₂-CH₂-, Q, A and n are as defined above. )

A step (2) of hydrolyzing the compound represented by the formula (II) or the dehydration condensation agent contained in the reaction solution obtained in the step (1); and

and (3) adding a compound represented by the following formula (IV) after the step (2), and reacting the compound with a compound represented by the formula (III).

[ chemical formula 8]

(wherein X represents an oxygen atom, a sulfur atom, or-C (R)¹)(R²) -or-N-R¹-, where R¹And R²Each independently represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms which may have a substituent, R represents a hydrogen atomOr an organic group having 1 to 60 carbon atoms which may have a substituent, R^XRepresents a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, a cyano group, a nitro group, an alkyl group having 1 to 6 carbon atoms in which at least 1 hydrogen atom is substituted by a halogen atom, an alkoxy group having 1 to 6 carbon atoms, an alkylthio group having 1 to 6 carbon atoms, a mono-substituted amino group, a di-substituted amino group, or a-OCF group₃、-C(＝O)-O-R³or-O-C (═ O) -R³Where R is³Is represented by the above-mentioned R¹、R²Same meaning, a plurality of R^XMay or may not be identical to each other, and may form an arbitrary C-R ring^XCan be substituted by nitrogen atoms. )

The polymerizable compound is represented by the following formula (a).

[ chemical formula 9]

(in the formula, Y¹、Y²、A、R、R^XX, Q and n are as defined above. )

<2> the method for producing a polymerizable compound according to <1>, wherein in the step (2), water or an aqueous solution is added to the reaction solution to carry out the hydrolysis.

<3> the method for producing a polymerizable compound according to <2>, wherein in the step (2), an acidic aqueous solution is added to the reaction solution.

<4> the method for producing a polymerizable compound according to <3>, wherein the acid component of the acidic aqueous solution is an inorganic acid and/or an organic acid having 1 to 20 carbon atoms.

<5> the method for producing a polymerizable compound according to <3> or <4>, wherein the acid component of the acidic aqueous solution is at least one selected from the group consisting of hydrochloric acid, sulfuric acid, phosphoric acid, boric acid, sulfonic acids, sulfinic acids, formic acid, acetic acid, oxalic acid, citric acid, ascorbic acid, tartaric acid and malic acid.

<6>According to<1>～<5>The method for producing a polymerizable compound according to any one of the above processes, wherein R represents an alkyl group having 1 to 60 carbon atoms which may have a substituent, an alkenyl group having 2 to 60 carbon atoms which may have a substituent, an alkynyl group having 2 to 60 carbon atoms which may have a substituent, an aromatic hydrocarbon ring group having 6 to 18 carbon atoms which may have a substituent, an aromatic heterocyclic group having 2 to 18 carbon atoms which may have a substituent, or Ra-Y-G- (wherein Ra represents a cyclic group having at least one of an aromatic hydrocarbon ring and an aromatic heterocyclic ring), y represents a single chemical bond, -O-, -S-, -C (═ O) -, -O-C (Rb) (-) -, -O-CH.₂-CH₂-、-CH₂-CH₂-O-、-C(＝O)-O-、-O-C(＝O)-、-C(＝O)-S-、-S-C(＝O)-、-NR⁴-C(＝O)-、-C(＝O)-NR⁴-、-CH＝CH-C(＝O)-O-、-O-C(＝O)-CH＝CH-、-CH₂-CH₂-C(＝O)-O-、-O-C(＝O)-CH₂-CH₂-、-CH₂-CH₂-O-C(＝O)-、-C(＝O)-O-CH₂-CH₂-、-C(＝O)-O-C(Rb)(Rc)-、-C(Rb)(Rc)-O-C(＝O)-、-O-C(＝O)-C(Rb)(Rc)-、-C(Rb)(Rc)-C(＝O)-O-、-O-C(＝O)-NR⁴-、-NR⁴-C(＝O)-O-、-O-C(＝O)-CH₂-S-、-S-CH₂-C (═ O) -O-or-O-C (═ O) -O-, where R is⁴Represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, Rc and Rb each independently represents a hydrogen atom, an optionally substituted aromatic hydrocarbon ring group having 6 to 18 carbon atoms or an optionally substituted aromatic heterocyclic group having 2 to 18 carbon atoms, and G is-CH which is at least one of (i) an aliphatic hydrocarbon group having 2 carbon atoms and (ii) an aliphatic hydrocarbon group having 2 carbon atoms and having 2 carbon atoms₂-by-O-, -S-, -O-C (═ O) -, -C (═ O) -O-, -O-C (═ O) -O-, -NR⁵-C(＝O)-、-C(＝O)-NR⁵-、-NR⁵Any one of organic groups of-or-C (═ O) -substituted groups (except for the case where 2 or more of each of-O-or-S-are present adjacent thereto), here, R⁵Represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. ).

<7>According to<1>～<6>Any one ofThe process for producing a polymerizable compound of (1), wherein R is^XAll are hydrogen atoms.

<8> the method for producing a polymerizable compound according to any one of <1> to <7>, wherein in the step (3), an acidic aqueous solution is further added to perform the reaction.

<9> the method for producing a polymerizable compound according to any one of <1> to <8>, wherein the compound represented by the formula (II) is a compound represented by the following formula (IIa).

[ chemical formula 10]

(wherein A, L and n represent the same meanings as described above.)

Effects of the invention

According to the production method of the present invention, the polymerizable compound represented by the formula (a) can be obtained in high yield, which can be used for producing an optical film or the like.

Detailed Description

The present invention is described in detail below. In the present invention, "may have a substituent" means "unsubstituted or substituted". When an organic group such as an alkyl group or an aromatic hydrocarbon ring group included in the general formula has a substituent, the number of carbon atoms of the organic group having a substituent does not include the number of carbon atoms of the substituent. For example, when an aromatic hydrocarbon ring group having 6 to 18 carbon atoms has a substituent, the number of carbon atoms of such substituent is not included in the number of carbon atoms of the aromatic hydrocarbon ring group having 6 to 18 carbon atoms. On the other hand, the "pi electron number in the ring structure in Ra" also includes pi electrons in the ring structure in the substituent. In the present invention, "alkyl" refers to a chain (straight-chain or branched) saturated hydrocarbon group, and "alkyl" does not include a "cycloalkyl" as a cyclic saturated hydrocarbon group.

The present invention is a method for producing a polymerizable compound represented by the following formula (a) (hereinafter, sometimes referred to as "polymerizable compound (a)"), characterized by comprising the steps of: a step (1) of esterifying a compound represented by the following formula (I) (hereinafter, sometimes referred to as "compound (I)") with a compound represented by the following formula (II) (hereinafter, sometimes referred to as "compound (II)") in an organic solvent in the presence of a base and/or a dehydration condensation agent to obtain a reaction solution containing a compound represented by the following formula (III) (hereinafter, sometimes referred to as "compound (III)"); a step (2) of adding, for example, water or an aqueous solution to hydrolyze the compound (II) or dehydration condensation agent contained in the reaction solution obtained in the step (1); and a step (3) of adding a compound represented by the following formula (IV) (hereinafter, sometimes referred to as "compound (IV)") after the step (2) and reacting the compound with the compound (III).

[ chemical formula 11]

In the production method of the present invention, after the compound (III) is obtained by reacting the compound (I) and the compound (II) in the step (1), the compound (II) or the dehydration condensation agent is hydrolyzed in the step (2), so that the compound (II) (when L of the compound (II) is a leaving group (for example, a halogen atom, an organic sulfonyloxy group, or the like)) remaining when the compound (I) is reacted with the compound (II) in the step (1) or the dehydration condensation agent (when L of the compound (II) is a hydroxyl group) that can be used in the step (1) can be hydrolyzed in the step (2). Therefore, according to the production method of the present invention, when the compound (III) is reacted with the compound (IV) in the step (3), the compound (II) or dehydration condensation agent remaining in the step (1) can be prevented from reacting with the compound (IV), and the polymerizable compound represented by the formula (a) can be obtained in high yield.

(step (1))

The step (1) is a step of reacting (esterifying) the compound (I) with the compound (II) in an organic solvent to obtain a reaction solution containing the compound (III). The reaction in step (1) of the present invention is carried out in the presence of a base and/or a dehydration condensation agent.

In the compound (I) represented by the formula (I), Q represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. Examples of the alkyl group having 1 to 6 carbon atoms include a methyl group, an ethyl group, a n-propyl group, an isopropyl group, a n-butyl group, a sec-butyl group, a tert-butyl group, a n-pentyl group, an isopentyl group, a neopentyl group, a n-hexyl group, and an isohexyl group. Among them, Q is preferably a hydrogen atom.

Further, in the compound (I), Fg¹And Fg²Each independently represents a hydroxyl group, -CH₂OH or-CH₂CH₂OH, preferably hydroxy or-CH₂OH, more preferably hydroxyl.

In the compound (II) represented by the formula (II), a represents a hydrogen atom, a methyl group or a chlorine atom, and is preferably a hydrogen atom.

Further, in the compound (II), L represents a hydroxyl group or a leaving group. Examples of the leaving group include: halogen atoms such as chlorine atom, bromine atom, and iodine atom; and organic sulfonyloxy groups such as methanesulfonyloxy, p-toluenesulfonyloxy, trifluoromethanesulfonyloxy, camphorsulfonyloxy, and benzenesulfonyloxy. Among these, from the viewpoint of obtaining the target product at low cost and in good yield, a halogen atom is preferable, and a chlorine atom is more preferable.

In the compound (II), n represents an integer of 1 to 20. N is preferably an integer of 2 to 8, more preferably 6.

In addition, the compound (II) is preferably a compound represented by the following formula (IIa) from the viewpoint of improving the characteristics of an optical film or the like produced using the obtained polymerizable compound.

[ chemical formula 12]

(wherein A, L and n represent the same meanings as described above.)

The ratio of the compound (I) to the compound (II) in the step (1) is 1: 2 to 1: 4, preferably 1: 2 to 1: 3, more preferably 1: 2 to 1: 2.5, and still more preferably 1: 2.01 to 1: 2.5, in terms of the molar ratio of the compound (I) to the compound (II).

In the step (1), if 2 different compounds (compound (II-1) and compound (II-2)) are used as the compound (II) and the reaction is carried out in stages, a compound (III) having different groups on the left and right sides can be obtained. That is, compound (III) having different groups on the left and right can be obtained by reacting 1 mole of compound (I) with 1 mole of compound (II-1) and then further reacting 1 mole of compound (II-2).

Examples of the base that can be used in step (1) include: organic bases such as triethylamine, diisopropylethylamine, pyridine, 4- (dimethylamino) pyridine (N, N-dimethyl-4-aminopyridine), and 2, 6-dimethylpyridine; inorganic bases such as sodium hydroxide, sodium carbonate, and sodium bicarbonate.

The amount of the base used is usually 1 to 3 moles based on 1 mole of the compound (II).

In addition, in the case where L of the compound (II) represented by the formula (II) is a leaving group (for example, a halogen atom, an organic sulfonyloxy group, or the like), the reaction of the step (1) is usually carried out in the presence of a base. In the case where L of the compound (II) represented by the formula (II) is a hydroxyl group, the reaction in the step (1) may be carried out in the presence or absence of a base.

Examples of the dehydration condensation agent that can be used in step (1) include N, N-dicyclohexylcarbodiimide, 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide hydrochloride, and N, N-diisopropylcarbodiimide.

In addition, when L of the compound (II) represented by the formula (II) is a hydroxyl group, the reaction of the step (1) is usually carried out in the presence of a dehydration condensation agent.

The reaction is carried out in an organic solvent. The organic solvent used is not particularly limited as long as it is an organic solvent inactive to the reaction. Examples thereof include: chlorine-based solvents such as chloroform and methylene chloride; amide solvents such as N-methylpyrrolidone, N-dimethylformamide, N-dimethylacetamide, hexamethylphosphoric triamide, and the like; 1, 4-di

Ether solvents such as alkane, cyclopentylmethyl ether, tetrahydrofuran, tetrahydropyran, and 1, 3-dioxolane; sulfur-containing solvents such as dimethyl sulfoxide and sulfolane; nitrile solvents such as acetonitrile; ester solvents such as ethyl acetate and propyl acetate; aromatic hydrocarbon solvents such as benzene, toluene and xylene; aliphatic hydrocarbon solvents such as n-pentane, n-hexane, and n-octane; alicyclic hydrocarbon solvents such as cyclopentane and cyclohexane; and a mixed solvent composed of 2 or more of these solvents.

Among these, organic solvents such as chlorine-based solvents, amide-based solvents, ether-based solvents, and aromatic hydrocarbon-based solvents are preferable from the viewpoint of obtaining the target product in good yield.

The amount of the organic solvent used is not particularly limited, and may be suitably determined in consideration of the kind of the compound to be used, the scale of the reaction, and the like, and is usually 1 to 50g per 1g of the compound (II).

Examples of the reaction method include: (a) a method in which compound (II) or an organic solvent solution of compound (II) is added to an organic solvent solution containing compound (I) and a base and/or a dehydration condensation agent; (b) a method in which compound (I) or an organic solvent solution of compound (I) is added to an organic solvent solution containing compound (II) and a base and/or a dehydration condensation agent; (c) a method of adding a base and/or a dehydration condensation agent to an organic solvent solution of the compound (I) and the compound (II), and the like, the method (a) is preferred from the viewpoint of obtaining the target product in a good yield.

The reaction temperature is in the range from-20 ℃ to the boiling point of the solvent used, and is preferably from-15 ℃ to +30 ℃.

The reaction time also depends on the scale of the reaction and is usually from a few minutes to a few hours.

The obtained reaction solution was supplied to the next step (2) without washing, extraction or the like while maintaining the above temperature.

Many compounds (I) and (II) are known substances and can be produced and obtained by a known method (for example, the method described in international publication No. 2014/010325). The compound (I) can be used as it is or after purification as desired.

For example, among the compounds (II), a compound in which L is a halogen atom can be produced by the method described in international publication No. 2015/141784.

In the compound (III) represented by the formula (III) obtained in the step (1), Q, A and n represent the same meanings as those of the compounds (I) and (II).

Further, in the compound (III), Y¹And Y²Each independently represents-C (═ O) -O-, -O-C (═ O) -, -CH₂-O-C(＝O)-、-C(＝O)-O-CH₂-、-CH₂-CH₂-O-C (═ O) -, or-C (═ O) -O-CH₂-CH₂-, preferably-C (═ O) -O-, -O-C (═ O) -.

In the step (1), it is preferable to use the compound represented by the above formula (IIa) as the compound (II) and obtain the compound represented by the following formula (IIIa) as the compound (III).

[ chemical formula 13]

(in the formula, Q, A, Y¹、Y²And n represents the same meaning as described above. )

(step (2))

In the step (2), a reaction is performed in which the compound (II) remaining after the reaction of the compound (I) and the compound (II) in the step (1) or the dehydration condensation agent used in the step (1) is hydrolyzed. Specifically, in the step (2), when L of the compound (II) used in the step (1) is a leaving group (for example, a halogen atom, an organic sulfonyloxy group, or the like), the remaining compound (II) is hydrolyzed, and when L of the compound (II) used in the step (1) is a hydroxyl group, the remaining dehydration condensation agent is hydrolyzed.

The hydrolysis in step (2) is performed by, for example, adding water or an aqueous solution to the reaction solution obtained in step (1). The amount of water to be added in the step (2) is not particularly limited as long as it is an amount capable of hydrolyzing the residual compound (II) or dehydration condensation agent, and may be equal to or more than the reaction equivalent, and is preferably 1.05 to 500 times the reaction equivalent, more preferably 1.5 to 300 times the reaction equivalent, and still more preferably 1.5 to 200 times the reaction equivalent.

In the step (2), an aqueous solution is preferably added. Here, the aqueous solution includes an alkaline aqueous solution and an acidic aqueous solution, and an acidic aqueous solution is preferable.

Here, the acidic aqueous solution is not particularly limited, but an acidic aqueous solution having a pH of 6 or less is preferable, and an acidic aqueous solution having a pH of 2 or less is more preferable.

Further, as the acid component of the acidic aqueous solution, there may be mentioned: inorganic acids such as hydrochloric acid, sulfuric acid, phosphoric acid, carbonic acid, boric acid, perchloric acid, and nitric acid; carboxylic acids such as formic acid, acetic acid, butyric acid and trifluoroacetic acid; hydroxy acids such as oxalic acid, citric acid, ascorbic acid, tartaric acid, malic acid, and lactic acid; sulfonic acids such as p-toluenesulfonic acid, methanesulfonic acid, trifluoromethanesulfonic acid, and 10-camphorsulfonic acid; sulfinic acids such as benzenesulfinic acid, and the like. These can be used alone or in combination of two or more.

Among these, from the viewpoint of favorably hydrolyzing the compound (II), an inorganic acid and/or an organic acid having 1 to 20 carbon atoms is preferable, and at least one selected from the group consisting of hydrochloric acid, sulfuric acid, phosphoric acid, boric acid, sulfonic acids, sulfinic acids, formic acid, acetic acid, oxalic acid, citric acid, ascorbic acid, tartaric acid, and malic acid is more preferable, and hydrochloric acid and sulfonic acids are even more preferable.

The concentration of the acidic aqueous solution is preferably 0.1 to 2mol/L, and more preferably 0.5 to 1.5 mol/L. When the concentration of the acidic aqueous solution is not less than the lower limit, the compound (II) or the dehydration condensation agent can be hydrolyzed well. Further, if the concentration of the acidic aqueous solution is not more than the above upper limit, side reactions such as decomposition of the compound (III) produced in the step (1) can be suppressed.

The amount of the acidic aqueous solution to be used is preferably an amount capable of hydrolyzing the remaining compound (II) or dehydration condensation agent and possibly catalyzing the reaction in the step (3) described later. For example, if the concentration is 1.0 equivalent of the acidic aqueous solution, the amount of the acidic aqueous solution to be used is 1 to 50 parts by mass, preferably 5 to 50 parts by mass, relative to 10 parts by mass of the compound (II). If the amount of the acidic aqueous solution used is not less than the lower limit, the compound (II) or the dehydration condensation agent can be hydrolyzed well and the reaction can be catalyzed in the step (3). Further, if the amount of the acidic aqueous solution used is not more than the above upper limit, side reactions such as decomposition of the compound (III) produced in the step (1) can be suppressed.

The acidic aqueous solution required for the catalytic reaction in step (3) described later may be further added after hydrolyzing compound (II) or the dehydration condensation agent.

Here, the hydrolysis reaction in the step (2) can be carried out with stirring as desired. The reaction time in the step (2) is not particularly limited as long as the compound (II) or the dehydration condensation agent is sufficiently hydrolyzed, and may be, for example, 1 minute to 5 hours, preferably 15 minutes to 1 hour. When the reaction time is not less than the lower limit, the compound (II) or the dehydration condensation agent can be hydrolyzed well. If the reaction time is not more than the upper limit, side reactions such as decomposition of the compound (III) produced in the step (1) can be suppressed.

The reaction temperature in the step (2) is not particularly limited as long as the compound (II) or the dehydration condensation agent is sufficiently hydrolyzed, and may be, for example, -5 ℃ or more and 50 ℃ or less, preferably 0 ℃ or more and 50 ℃ or less. When the reaction temperature is not lower than the lower limit, the compound (II) or the dehydration condensation agent can be hydrolyzed well. Further, if the reaction temperature is not higher than the upper limit, side reactions such as decomposition of the compound (III) produced in the step (1) can be suppressed.

In the step (2), when L is a leaving group (for example, a halogen atom, an organic sulfonyloxy group, or the like), the remaining compound (II) is hydrolyzed to be a compound represented by the formula (II) in which L is a hydroxyl group. Alternatively, in the step (2), when L is a hydroxyl group, for example, a carbodiimide compound used as a dehydration condensation agent is converted into a urea compound.

The reaction solution after the step (2) may be supplied to the next step (3) without any post-treatment operation such as washing or extraction.

(step (3))

The step (3) is a step of adding the compound (IV) after the step (2) and reacting the compound (III) with the compound (IV).

In the production method of the present invention, since the step (3) is performed after the step (2), the compound (II) or dehydration condensation agent remaining in the step (1) can be prevented from reacting with the compound (IV), and the polymerizable compound represented by the formula (a) can be obtained in a high yield even if the amount of the compound (IV) used is small.

Wherein, in the compound (IV) represented by the formula (IV), X represents an oxygen atom, a sulfur atom, -C (R)¹)(R²) -or-N-R¹-. Herein, R is¹And R²Each independently represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms which may have a substituent.

As R¹、R²Examples of the alkyl group having 1 to 10 carbon atoms which may have a substituent(s) include methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, neopentyl, n-hexyl, isohexyl, 3-heptyl, n-octyl, n-nonyl, and n-decyl.

Examples of the substituent of the alkyl group having 1 to 10 carbon atoms include: halogen atoms such as fluorine atom and chlorine atom; a cyano group; substituted amino groups such as dimethylamino group; alkoxy groups having 1 to 6 carbon atoms such as methoxy and ethoxy; a nitro group; aryl groups such as phenyl; cycloalkyl groups having 3 to 8 carbon atoms such as cyclopropyl groups and cyclopentyl groups; hydroxyl groups, and the like.

Among these, X is preferably an oxygen atom, a sulfur atom or-CH from the viewpoint of more easily obtaining the effect of the present invention₂The oxygen atom or the sulfur atom is more preferable, and the sulfur atom is particularly preferable.

In the compound (IV), R represents a hydrogen atom or an organic group having 1 to 60 carbon atoms which may have a substituent.

Examples of the organic group having 1 to 60 carbon atoms include an alkyl group having 1 to 60 carbon atoms, an alkenyl group having 2 to 60 carbon atoms, an alkynyl group having 2 to 60 carbon atoms, an aromatic hydrocarbon ring group having 6 to 18 carbon atoms, and an aromatic heterocyclic group having 2 to 18 carbon atoms.

Examples of the alkyl group having 1 to 60 carbon atoms include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, a tert-butyl group, an n-pentyl group, an n-hexyl group, an n-heptyl group, an n-undecyl group, an n-dodecyl group, a 1-methylpentyl group, and a 1-ethylpentyl group. Among these, an alkyl group having 1 to 12 carbon atoms is preferable, and n-butyl, n-hexyl, and n-octyl are more preferable, and n-hexyl is particularly preferable, from the viewpoint of more easily obtaining the effects of the present invention.

Examples of the alkenyl group having 2 to 60 carbon atoms include a vinyl group, an allyl group, an isopropenyl group, a butenyl group, and the like, and an alkenyl group having 2 to 12 carbon atoms is preferable.

Examples of the alkynyl group having 2 to 60 carbon atoms include propynyl group, propargyl group, butynyl group and the like, and an alkynyl group having 2 to 12 carbon atoms is preferable.

Examples of the aromatic hydrocarbon ring group having 6 to 18 carbon atoms include a phenyl group, a 1-naphthyl group, and a 2-naphthyl group.

Examples of the aromatic heterocyclic group having 2 to 18 carbon atoms include thienyl, pyrrolyl, furyl, pyridyl, piperidyl, quinolyl, isoquinolyl, pyrimidinyl, triazinyl, benzothiazolyl and the like.

Examples of the substituent for the organic group having 1 to 60 carbon atoms for R include: a cyano group; a nitro group; a hydroxyl group; halogen atoms such as fluorine atom, chlorine atom, and bromine atom; alkyl groups having 1 to 6 carbon atoms such as methyl and ethyl; an alkoxy group having 1 to 6 carbon atoms such as a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, an n-butoxy group, and a tert-butoxy group; an alkoxy group having 1 to 6 carbon atoms which is substituted with an alkoxy group having 1 to 6 carbon atoms such as a methoxymethoxy group, a methoxyethoxy group, or an ethoxyethoxy group; cycloalkyl groups having 3 to 8 carbon atoms such as cyclopropyl, cyclopentyl, cyclohexyl, cycloheptyl and the like; and substituted amino groups such as methylamino, ethylamino, acetylamino, and dimethylamino.

Further, as the organic group having 1 to 60 carbon atoms, the following formula may be mentioned: Ra-Y-G-represents a group.

Here, Ra represents a cyclic group having at least one of an aromatic hydrocarbon ring and an aromatic hetero ring.

Among these, an aromatic hydrocarbon ring group having 6 to 30 carbon atoms is more preferable in that the effects of the present invention can be more easily obtained.

Examples of the aromatic hydrocarbon ring include a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, a pyrene ring, a fluorene ring, and the like. Among these, benzene rings, naphthalene rings, anthracene rings, fluorene rings are preferable, and benzene rings and naphthalene rings are more preferable, from the viewpoint of more easily obtaining the effects of the present invention.

Examples of the aromatic heterocyclic ring include a 1H-isoindole-1, 3(2H) -dione ring, 1-benzofuran ring, 2-benzofuran ring, acridine ring, isoquinoline ring, imidazole ring, indole ring, and the like,

A diazole ring,

An azolyl ring,

An azolo pyrazine ring,

A pyrazolopyridine ring,

An oxazolopyridazine ring,

An oxazolopyrimidine ring, a quinazoline ring, a quinoxaline ring, a quinoline ring, a cinnoline ring, a thiadiazole ring, a thiazole ring, a thiazolopyridine ring, a thiazolopyridazine ring, a thiazolopyrimidine ring, a thiophene ring, a triazine ring, a triazole ring, a naphthyridine ring, a pyrazine ring, a pyrazole ring, a pyrone ring, a pyran ring, a pyridine ring, a pyridazine ring, a pyrimidine ringRing, pyrrole ring, phenanthridine ring, phthalazine ring, furan ring, benzo [ b ]]Thiophene ring, benzo [ c ]]Thiophene ring, benzisoxazines

Azole ring, benzisothiazole ring, benzimidazole ring, benzo

Diazole ring, benzo

An azole ring, a benzothiadiazole ring, a benzothiazole ring, a benzothiophene ring, a benzotriazine ring, a benzotriazole ring, a benzopyran ring, a xanthene ring, etc.

Among these, as the aromatic heterocyclic ring, preferred are: furan ring, pyran ring, thiophene ring,

An azolyl ring,

-ring aromatic heterocycles such as a diazole ring, a thiazole ring and a thiadiazole ring; and a benzothiazole ring, a benzo

Azole ring, quinoline ring, 1-benzofuran ring, 2-benzofuran ring, benzo [ b ]]Thiophene ring, 1H-isoindole-1, 3(2H) -dione ring, benzo [ c]Thiophene ring, thiazolopyridine ring, benzisoxazole

Azolyl ring, benzo

Fused aromatic heterocycles such as a diazole ring, a benzothiadiazole ring, and a xanthene ring.

The aromatic hydrocarbon ring and the aromatic heterocyclic ring of Ra may have a substituent. Examples of the substituent include: halogen atom such as fluorine atom and chlorine atom(ii) a A cyano group; alkyl groups having 1 to 6 carbon atoms such as methyl, ethyl and propyl; alkenyl groups having 2 to 6 carbon atoms such as vinyl groups and allyl groups; an alkyl group having 1 to 6 carbon atoms, wherein at least 1 hydrogen atom is substituted with a halogen atom, such as a trifluoromethyl group or a pentafluoroethyl group; an N, N-dialkylamino group having 2 to 12 carbon atoms such as a dimethylamino group; alkoxy groups having 1 to 6 carbon atoms such as methoxy, ethoxy, and isopropoxy; a nitro group; an aromatic hydrocarbon ring group having 6 to 18 carbon atoms such as a phenyl group and a naphthyl group; -OCF₃；-C(＝O)-R^Y；-C(＝O)-O-R^Y；-O-C(＝O)-R^Yand-SO₂R^bAnd the like. Herein, R is^YThe aromatic hydrocarbon ring group is characterized by being represented by (i) an alkyl group having 1 to 20 carbon atoms and being capable of having a substituent, (ii) an alkenyl group having 2 to 20 carbon atoms and being capable of having a substituent, (iii) a cycloalkyl group having 3 to 12 carbon atoms and being capable of having a substituent, or (iv) an aromatic hydrocarbon ring group having 6 to 18 carbon atoms and being capable of having a substituent. Furthermore, R^bAn alkyl group having 1 to 6 carbon atoms such as a methyl group or an ethyl group; or an aromatic hydrocarbon ring group having 6 to 18 carbon atoms which may have, as a substituent, an alkyl group having 1 to 6 carbon atoms or an alkoxy group having 1 to 6 carbon atoms, such as a phenyl group, a 4-methylphenyl group, or a 4-methoxyphenyl group.

Among these, as the substituents of the aromatic hydrocarbon ring and the aromatic heterocyclic ring of Ra, a halogen atom, a cyano group, an alkyl group having 1 to 6 carbon atoms, and an alkoxy group having 1 to 6 carbon atoms are preferable.

In addition, Ra may have a plurality of substituents selected from the above substituents. In the case where Ra has a plurality of substituents, the substituents may be the same or different.

As R^YExamples of the alkyl group having 1 to 20 carbon atoms which may have a substituent (i) include a methyl group, an ethyl group, a n-propyl group, an isopropyl group, a n-butyl group, an isobutyl group, a 1-methylpentyl group, a 1-ethylpentyl group, a sec-butyl group, a tert-butyl group, a n-pentyl group, an isopentyl group, a neopentyl group, a n-hexyl group, an isohexyl group, a n-heptyl group, a n-octyl group, a n-nonyl group, a n-decyl group, a n-undecyl group, a n-dodecyl group, a n-tridecyl group, a n-tetradecyl group, a n-pentadecyl group, a n,N-octadecyl, n-nonadecyl, n-eicosyl, and the like.

The alkyl group having 1 to 20 carbon atoms which may have a substituent (i) preferably has 1 to 12 carbon atoms, more preferably 1 to 10 carbon atoms.

As R^YThe alkenyl group having 2 to 20 carbon atoms of the alkenyl group having 2 to 20 carbon atoms which may have a substituent (ii) includes vinyl, propenyl, isopropenyl, butenyl, isobutenyl, pentenyl, hexenyl, heptenyl, octenyl, nonenyl, decenyl, undecenyl, dodecenyl, tridecenyl, tetradecenyl, pentadecenyl, hexadecenyl, heptadecenyl, octadecenyl, nonadecenyl, eicosenyl and the like.

In addition, the number of carbon atoms of the (ii) alkenyl group having 2 to 20 carbon atoms which may have a substituent is preferably 2 to 12.

As R^YThe substituent for (i) an alkyl group having 1 to 20 carbon atoms which may have a substituted alkyl group having 1 to 20 carbon atoms and (ii) an alkenyl group having 2 to 20 carbon atoms which may have a substituted alkenyl group having 2 to 20 carbon atoms includes: halogen atoms such as fluorine atom and chlorine atom; a cyano group; an N, N-dialkylamino group having 2 to 12 carbon atoms such as a dimethylamino group; alkoxy groups having 1 to 20 carbon atoms such as methoxy, ethoxy, isopropoxy, butoxy, and the like; an alkoxy group having 1 to 12 carbon atoms, such as a methoxymethoxy group or a methoxyethoxy group, which is substituted with an alkoxy group having 1 to 12 carbon atoms; a nitro group; an aromatic hydrocarbon ring group having 6 to 18 carbon atoms such as a phenyl group and a naphthyl group; an aromatic heterocyclic group having 2 to 18 carbon atoms such as a triazolyl group, a pyrrolyl group, a furyl group, a thienyl group, a benzothiazol-2-ylthio group and the like; cycloalkyl groups having 3 to 8 carbon atoms such as cyclopropyl, cyclopentyl, cyclohexyl and the like; a cycloalkoxy group having 3 to 8 carbon atoms such as a cyclopentyloxy group, a cyclohexyloxy group, or the like; tetrahydrofuryl, tetrahydropyranyl, dioxolanyl, diyl

A cyclic ether group having 2 to 12 carbon atoms such as an alkyl group; aryloxy group having 6 to 14 carbon atoms such as phenoxy group, naphthoxy group and the like(ii) a Trifluoromethyl, pentafluoroethyl, -CH₂CF₃Fluoroalkyl groups having 1 to 12 carbon atoms in which at least 1 hydrogen atom is substituted with a fluorine atom; a benzofuranyl group; a benzopyranyl group; benzodioxolyl group; benzodi (benzo-b)

Alkyl groups, and the like. Among these, as R^YThe substituent (i) which may have a C1-20 alkyl group of a C1-20 alkyl group and (ii) which may have a C2-20 alkenyl group of a C2-20 alkenyl group, preferably: halogen atoms such as fluorine atom and chlorine atom; a cyano group; alkoxy groups having 1 to 20 carbon atoms such as methoxy, ethoxy, isopropoxy, butoxy, and the like; a nitro group; an aromatic hydrocarbon ring group having 6 to 18 carbon atoms such as a phenyl group and a naphthyl group; an aromatic heterocyclic group having 2 to 18 carbon atoms such as furyl, thienyl, benzothiazol-2-ylthio and the like; cycloalkyl groups having 3 to 8 carbon atoms such as cyclopropyl, cyclopentyl, cyclohexyl and the like; trifluoromethyl, pentafluoroethyl, -CH₂CF₃And fluoroalkyl groups having 1 to 12 carbon atoms in which at least 1 hydrogen atom is substituted with a fluorine atom.

In addition, R^YThe (i) C1-20 alkyl group of C1-20 alkyl group which may have a substituent and (ii) C2-20 alkenyl group which may have a substituent and may have a C2-20 alkenyl group may have a plurality of substituents selected from the above substituents. At R^YWhen (i) an alkyl group having 1 to 20 carbon atoms which may have a C1 to C20 alkyl group as a substituent and (ii) an alkenyl group having 2 to C20 carbon atoms which may have a C2 to C20 alkenyl group as a substituent have a plurality of substituents, the plurality of substituents may be the same or different from each other.

As R^YThe cycloalkyl group having 3 to 12 carbon atoms which may have a substituent (iii) includes cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl and cyclooctyl. Among these, cyclopentyl and cyclohexyl are preferable.

As R^Y(iii) of) Examples of the substituent for the cycloalkyl group having 3 to 12 carbon atoms which may have a substituent include: halogen atoms such as fluorine atom and chlorine atom; a cyano group; an N, N-dialkylamino group having 2 to 12 carbon atoms such as a dimethylamino group; alkyl groups having 1 to 6 carbon atoms such as methyl, ethyl and propyl; alkoxy groups having 1 to 6 carbon atoms such as methoxy, ethoxy, and isopropoxy; a nitro group; and an aromatic hydrocarbon ring group having 6 to 18 carbon atoms such as a phenyl group and a naphthyl group. Among these, as R^Y(iii) a substituent of a cycloalkyl group having 3 to 12 carbon atoms, which may have a substituent, preferably: halogen atoms such as fluorine atom and chlorine atom; a cyano group; alkyl groups having 1 to 6 carbon atoms such as methyl, ethyl and propyl; alkoxy groups having 1 to 6 carbon atoms such as methoxy, ethoxy, and isopropoxy; a nitro group; an aromatic hydrocarbon ring group having 6 to 18 carbon atoms such as a phenyl group and a naphthyl group.

In addition, R^Y(iii) the cycloalkyl group having 3 to 12 carbon atoms which may have a substituent(s) may have a plurality of substituents. At R^YIn the case where the cycloalkyl group having 3 to 12 carbon atoms which may have a substituent (iii) has a plurality of substituents, the plurality of substituents may be the same or different from each other.

As R^YThe aromatic hydrocarbon ring group having 6 to 18 carbon atoms of the aromatic hydrocarbon ring group having 6 to 18 carbon atoms which may have a substituent(s) includes phenyl, 1-naphthyl, 2-naphthyl and the like. Among these, phenyl and naphthyl are preferable, and phenyl, 1-naphthyl and 2-naphthyl are more preferable.

As R^YThe substituent of the aromatic hydrocarbon ring group having 6 to 18 carbon atoms which may have a substituent (iv) includes: halogen atoms such as fluorine atom and chlorine atom; a cyano group; an N, N-dialkylamino group having 2 to 12 carbon atoms such as a dimethylamino group; alkoxy groups having 1 to 20 carbon atoms such as methoxy, ethoxy, isopropoxy, butoxy, and the like; an alkoxy group having 1 to 12 carbon atoms, such as a methoxymethoxy group or a methoxyethoxy group, which is substituted with an alkoxy group having 1 to 12 carbon atoms; a nitro group; triazolyl, pyrindineAn aromatic heterocyclic group having 2 to 18 carbon atoms such as a pyrrolyl group, a furyl group, a thienyl group and the like; cycloalkyl groups having 3 to 8 carbon atoms such as cyclopropyl, cyclopentyl, cyclohexyl and the like; a cycloalkoxy group having 3 to 8 carbon atoms such as a cyclopentyloxy group, a cyclohexyloxy group, or the like; tetrahydrofuryl, tetrahydropyranyl, dioxolanyl, diyl

A cyclic ether group having 2 to 12 carbon atoms such as an alkyl group; aryloxy groups having 6 to 14 carbon atoms such as phenoxy groups and naphthoxy groups; trifluoromethyl, pentafluoroethyl, -CH₂CF₃Fluoroalkyl groups having 1 to 12 carbon atoms in which at least 1 hydrogen atom is substituted with a fluorine atom; -OCF₃(ii) a A benzofuranyl group; a benzopyranyl group; benzodioxolyl group; benzodi (benzo-b)

Alkyl groups, and the like. Among these, as R^Y(iv) a substituent which may have a substituted aromatic hydrocarbon ring group having 6 to 18 carbon atoms, and is preferably selected from the group consisting of: halogen atoms such as fluorine atom and chlorine atom; a cyano group; alkoxy groups having 1 to 20 carbon atoms such as methoxy, ethoxy, isopropoxy, butoxy, and the like; a nitro group; an aromatic heterocyclic group having 2 to 18 carbon atoms such as a triazolyl group, a pyrrolyl group, a furyl group, a thienyl group and the like; cycloalkyl groups having 3 to 8 carbon atoms such as cyclopropyl, cyclopentyl, cyclohexyl and the like; trifluoromethyl, pentafluoroethyl, -CH₂CF₃Fluoroalkyl groups having 1 to 12 carbon atoms in which at least 1 hydrogen atom is substituted with a fluorine atom; -OCF₃(ii) a At least 1 substituent in (a).

In addition, R^Y(iv) the aromatic hydrocarbon ring group having 6 to 18 carbon atoms which may have a substituent(s) may have a plurality of substituents. At R^YWhen the aromatic hydrocarbon ring group having 6 to 18 carbon atoms of the aromatic hydrocarbon ring group having 6 to 18 carbon atoms which may have a substituent has a plurality of substituents, the substituents may be the same or different.

Here, the "number of carbon atoms" of the cyclic group having at least one of an aromatic hydrocarbon ring and an aromatic heterocycle in Ra means: the number of carbon atoms of the organic group itself having at least one of an aromatic hydrocarbon ring and an aromatic hetero ring, which does not include a carbon atom of a substituent.

When Ra has a plurality of aromatic hydrocarbon rings and/or a plurality of aromatic heterocyclic rings, they may be the same or different.

The Ra is preferably a cyclic group having at least one of an aromatic hydrocarbon ring having 6 to 30 carbon atoms and an aromatic heterocycle having 2 to 30 carbon atoms.

Preferred specific examples of the cyclic group having at least one of an aromatic hydrocarbon ring having 6 to 30 carbon atoms and an aromatic heterocycle having 2 to 30 carbon atoms in Ra are as follows. However, the present invention is not limited to the specific examples shown below. In the following formula, "-" represents a bonding position with Y extending from an arbitrary position of the ring.

1) Specific examples of the hydrocarbon ring group which may have a substituent and has at least one aromatic hydrocarbon ring having 6 to 30 carbon atoms include those represented by the following formulas (1-1) to (1-21), and those represented by the formulas (1-8) to (1-21) and the like are preferable. The groups represented by the following formulae (1-1) to (1-21) may have a substituent.

[ chemical formula 14]

[ chemical formula 15]

2) Specific examples of the heterocyclic group which may have a substituent and has at least one aromatic ring selected from an aromatic hydrocarbon ring having 6 to 30 carbon atoms and an aromatic heterocycle having 2 to 30 carbon atoms include structures represented by the following formulae (2-1) to (2-51), and the like, and heterocyclic groups having 2 to 16 carbon atoms represented by the formulae (2-11) to (2-51) and the like are preferable. The groups represented by the following formulae (2-1) to (2-51) may have a substituent.

[ chemical formula 16]

[ chemical formula 17]

[ chemical formula 18]

[ chemical formula 19]

(in the formulae, A represents-CH₂-、-NR^c-, oxygen atom, sulfur atom, -SO-or-SO₂-，

B and D each independently represent-NR^c-, oxygen atom, sulfur atom, -SO-or-SO₂-，

E represents-NR^c-, oxygen atom or sulfur atom.

Herein, R is^cRepresents: a hydrogen atom; or an alkyl group having 1 to 6 carbon atoms such as a methyl group, an ethyl group, a propyl group, etc. (wherein, in each formula, an oxygen atom, a sulfur atom, -SO-, -SO₂Respectively, not adjacent. ))

Among the above, Ra is preferably any one of the groups represented by the above formulae (1-8), (1-11), (1-12), (1-13), (1-14), (1-15), (1-20), (2-9) to (2-11), (2-24) to (2-33), (2-35) to (2-43), (2-47) and (2-49) to (2-51).

The total number of pi electrons included in the ring structure in Ra is preferably 4 or more, more preferably 6 or more, further preferably 8 or more, particularly preferably 10 or more, preferably 20 or less, and more preferably 18 or less.

Further, Ra is preferably any of the following (i-1) to (i-6). The groups represented by the following formulas (i-1) to (i-6) may have a substituent.

[ chemical formula 20]

(in the formula (i-4), J represents-CH₂-、-NR^d-, oxygen atom, sulfur atom, -SO-or-SO₂-，R^dRepresents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. )

In addition, the cyclic group of at least one of the aromatic hydrocarbon ring having 6 to 30 carbon atoms and the aromatic heterocyclic ring having 2 to 30 carbon atoms in Ra may have 1 or more substituents. In the case of having a plurality of substituents, the plurality of substituents may be the same as or different from each other.

Examples of the substituent of the cyclic group of Ra having at least one of an aromatic hydrocarbon ring having 6 to 30 carbon atoms and an aromatic heterocycle having 2 to 30 carbon atoms include: halogen atoms such as fluorine atom and chlorine atom; a cyano group; alkyl groups having 1 to 6 carbon atoms such as methyl, ethyl and propyl; alkenyl groups having 2 to 6 carbon atoms such as vinyl groups and allyl groups; an alkyl group having 1 to 6 carbon atoms, wherein at least 1 hydrogen atom is substituted with a halogen atom, such as a trifluoromethyl group or a pentafluoroethyl group; an N, N-dialkylamino group having 2 to 12 carbon atoms such as a dimethylamino group; alkoxy groups having 1 to 6 carbon atoms such as methoxy, ethoxy, and isopropoxy; a nitro group; an aromatic hydrocarbon ring group having 6 to 18 carbon atoms such as a phenyl group and a naphthyl group; -OCF₃；-C(＝O)-R^Y；-C(＝O)-O-R^Y；-O-C(＝O)-R^Y；-SO₂R^bAnd the like. Herein, R is^YAnd R^bThe same meanings as above are given, and preferred examples thereof are also the same as above. In the case of having a plurality of substituents, the plurality of substituents may be the same as or different from each other.

Among these, at least 1 substituent selected from the group consisting of a halogen atom, a cyano group, an alkyl group having 1 to 6 carbon atoms and an alkoxy group having 1 to 6 carbon atoms is preferable.

Y represents a single chemical bond, -O-, -S-, -C (-O) -, -O-C (Rb) (Rc) -, -C (Rb) ((Rc) -O-, -O-CH)₂-CH₂-、-CH₂-CH₂-O-、-C(＝O)-O-、-O-C(＝O)-、-C(＝O)-S-、-S-C(＝O)-、-NR⁴-C(＝O)-、-C(＝O)-NR⁴-、-CH＝CH-C(＝O)-O-、-O-C(＝O)-CH＝CH-、-CH₂-CH₂-C(＝O)-O-、-O-C(＝O)-CH₂-CH₂-、-CH₂-CH₂-O-C(＝O)-、-C(＝O)-O-CH₂-CH₂-、-C(＝O)-O-C(Rb)(Rc)-、-C(Rb)(Rc)-O-C(＝O)-、-O-C(＝O)-C(Rb)(Rc)-、-C(Rb)(Rc)-C(＝O)-O-、-O-C(＝O)-NR⁴-、-NR⁴-C(＝O)-O-、-O-C(＝O)-CH₂-S-、-S-CH₂-C (═ O) -O-or-O-C (═ O) -O-. Herein, R is⁴Represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and Rc and Rb each independently represents a hydrogen atom, an optionally substituted aromatic hydrocarbon ring group having 6 to 18 carbon atoms, or an optionally substituted aromatic heterocyclic group having 2 to 18 carbon atoms.

Among these, the Y is preferably a single chemical bond, -O-C (Rb) (Rc) -, -C (Rb) ((Rc) -O-, -O-CH) in order to more easily obtain the effects of the present invention₂-CH₂-、-CH₂-CH₂-O-、-C(＝O)-O-、-O-C(＝O)-、-CH₂-CH₂-C(＝O)-O-、-O-C(＝O)-CH₂-CH₂-、-CH₂-CH₂-O-C(＝O)-、-C(＝O)-O-CH₂-CH₂-、-C(＝O)-O-C(Rb)(Rc)-、-C(Rb)(Rc)-O-C(＝O)-、-O-C(＝O)-C(Rb)(Rc)-、-C(Rb)(Rc)-C(＝O)-O-、-O-C(＝O)-NR⁴-、-NR⁴-C(＝O)-O-、-O-C(＝O)-CH₂-S-、-S-CH₂-C (═ O) -O-, -O-C (═ O) -O-, more preferably a single chemical bond, -O-C (rb) (rc) -, -C (rb) (rc) -O-, -O-CH-, -C (rb) ((rc) — O-)₂-CH₂-、-CH₂-CH₂-O-、-C(＝O)-O-、-O-C(＝O)-、-CH₂-CH₂-C(＝O)-O-、-O-C(＝O)-CH₂-CH₂-、-CH₂-CH₂-O-C(＝O)-、-C(＝O)-O-CH₂-CH₂-、-C(＝O)-O-C(Rb)(Rc)-、-C(Rb)(Rc)-O-C(＝O)-、-O-C(＝O)-C(Rb)(Rc)-、-C(Rb)(Rc)-C(＝O)-O-、-O-C(＝O)-NR⁴-、-NR⁴-C(＝O)-O-、-S-CH₂-C(＝O)-O-、-O-C(＝O)-CH₂-S-, particularly preferably a single chemical bond, -O-C (Rb) (Rc) -, -C (Rb) ((Rc)) O-, -O-CH₂-CH₂-、-CH₂-CH₂-O-、-C(＝O)-O-、-O-C(＝O)-、-CH₂-CH₂-C(＝O)-O-、-O-C(＝O)-CH₂-CH₂-、-C(＝O)-O-C(Rb)(Rc)-、-C(Rb)(Rc)-O-C(＝O)-、-O-C(＝O)-C(Rb)(Rc)-、-C(Rb)(Rc)-C(＝O)-O-、-O-C(＝O)-NR⁴-、-NR⁴-C(＝O)-O-、-S-CH₂-C(＝O)-O-、-O-C(＝O)-CH₂-S-。

Herein, R is⁴Represents (i) a hydrogen atom or (ii) an alkyl group having 1 to 6 carbon atoms such as a methyl group or an ethyl group, wherein R is⁴Preferably a hydrogen atom.

Rc and Rb each independently represent a hydrogen atom, an optionally substituted aromatic hydrocarbon ring group having 6 to 18 carbon atoms, or an optionally substituted aromatic heterocyclic group having 2 to 18 carbon atoms. Rc and Rb may be the same or different.

Specific examples of the optionally substituted aromatic hydrocarbon ring group having 6 to 18 carbon atoms or the optionally substituted aromatic heterocyclic group having 2 to 18 carbon atoms of Rb and Rc include those having a predetermined carbon number among the same groups as Ra. Examples of the substituent group of Rb and Rc include the same substituent groups as those of Ra, and preferred substituent groups thereof are also the same. When a plurality of substituents are present, they may be the same or different.

Each of Rc and Rb is independently preferably a hydrogen atom, an optionally substituted aromatic hydrocarbon ring group having 6 to 18 carbon atoms, more preferably a hydrogen atom, a phenyl group or a naphthyl group, and particularly preferably a combination of both Rc and Rb are a hydrogen atom, a combination of a hydrogen atom and a phenyl group or a combination of a hydrogen atom and a naphthyl group.

As a preferred combination of Ra-Y-,

preferably, Ra is selected from the above formulae (i-1) to (i-6), Y is selected from the group consisting of a single chemical bond, -O-Z, -O-C (Rb) (Rc) -Z, -C (Rb) ((Rc) -O-Z, -O-CH)₂-CH₂-Z、-CH₂-CH₂-O-Z、-C(＝O)-O-Z、-O-C(＝O)-Z、-CH₂-CH₂-C(＝O)-O-Z、-O-C(＝O)-CH₂-CH₂-Z、-C(＝O)-O-C(Rb)(Rc)-Z、-C(Rb)(Rc)-O-C(＝O)-Z、-O-C(＝O)-C(Rb)(Rc)-Z、-C(Rb)(Rc)-C(＝O)-O-Z、-NR⁴-C(＝O)-O-Z、-S-CH₂-a combination of-C (═ O) -O-Z.

More preferably, Ra is selected from the above formulae (i-1) to (i-6), Y is selected from the group consisting of a single chemical bond, -O-Z, -C (Rb) (Rc) — O-Z, -CH₂-CH₂-O-Z、-C(＝O)-O-Z、-O-C(＝O)-Z、-CH₂-CH₂-C(＝O)-O-Z、-C(Rb)(Rc)-O-C(＝O)-Z、-C(Rb)(Rc)-C(＝O)-O-Z、-NR⁴-C(＝O)-O-Z、-S-CH₂-a combination of-C (═ O) -O-Z.

Further, Ra-Y-is particularly preferably any one of the following formulae (ii-1) to (ii-45), and most preferably any one of (iii-1) to (iii-46). Rb and Rc are the same as defined above, and Z is the direction in which G is bonded. Further, "●" in the groups represented by the following formulas (ii-1) to (ii-45) and the groups represented by the following formulas (iii-1) to (iii-46) represents a bonding site to G.

The groups represented by the following formulae (ii-1) to (ii-45) and the groups represented by the following formulae (iii-1) to (iii-46) may have a substituent.

In the following formulae (ii-26) to (ii-32) and the following formulae (iii-26) to (iii-32), J represents-CH₂-、-NR^d-, oxygen atom, sulfur atom, -SO-or-SO₂-，R^dRepresents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.

[ chemical formula 21]

[ chemical formula 22]

G is a 2-valent organic group having 1 to 20 carbon atoms which may have a substituent, and preferably a 2-valent organic group having 3 to 20 carbon atoms which may have a substituent.

G is more preferably (i) a 2-valent aliphatic hydrocarbon group having 1 to 20 carbon atoms which may have a substituent; and (ii) a 2-valent aliphatic hydrocarbon group having 3 to 20 carbon atoms and optionally having a substituent₂At least one of-is-O-, -S-, -O-C (═ O) -, -C (═ O) -O-, -O-C (═ O) -O-, -NR⁵-C(＝O)-、-C(＝O)-NR⁵-、-NR⁵-or-C (═ O) -substituted group; any one of (1) an organic group. Wherein the case where 2 or more of each of-O-and-S-are present adjacently is not included (i.e., the structure of-O-and-S-is not formed).

Herein, R is⁵Represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. Among these, a hydrogen atom or a methyl group is preferable. Examples of the substituent of the organic group of G include: alkyl groups having 1 to 5 carbon atoms such as methyl, ethyl and propyl; alkoxy groups having 1 to 5 carbon atoms such as methoxy, ethoxy, propoxy and the like; a cyano group; a halogen atom such as a fluorine atom or a chlorine atom.

Here, the "aliphatic hydrocarbon group having a valence of 2" as G is preferably a chain aliphatic hydrocarbon group having a valence of 2, and more preferably an alkylene group. The number of carbon atoms of the "aliphatic hydrocarbon group having a valence of 2" is preferably 3 to 20, more preferably 3 to 18. The "aliphatic hydrocarbon group having a valence of 2" is preferably an aliphatic hydrocarbon group having a valence of 2 to 20 carbon atoms, more preferably a chain-like aliphatic hydrocarbon group having a valence of 2 to 18 carbon atoms, and still more preferably an alkylene group having a carbon number of 3 to 18.

The number of carbon atoms of G is preferably 4 to 16, more preferably 5 to 14, particularly preferably 6 to 12, and most preferably 6 to 10.

The structure of G is preferably an unsubstituted alkylene group having 4 to 16 carbon atoms, more preferably an unsubstituted alkylene group having 5 to 14 carbon atoms, still more preferably an unsubstituted alkylene group having 6 to 12 carbon atoms, particularly preferably an unsubstituted alkylene group having 6 to 10 carbon atoms, and most preferably a n-hexylene group or a n-octylene group.

When the number of carbon atoms of G is 3 or more, both ends of G are preferably-CH₂- (G having no substitution at both ends). In addition, in the "(ii) carbon number is 3 ~ 20 of 2 valence aliphatic hydrocarbyl containing-CH₂At least one of-is-O-, -S-, -O-C (═ O) -, -C (═ O) -O-, -O-C (═ O) -O-, -NR⁵-C(＝O)-、-C(＝O)-NR⁵-、-NR⁵In the group "substituted with — O" or — C (═ O), "continuous — CH in the group" unsubstituted aliphatic hydrocarbon group with — C (═ O) — is preferable₂- (i.e. structures which do not form-C (═ O) -).

a-CH contained in a 2-valent aliphatic hydrocarbon group having 3 to 20 carbon atoms₂At least one of-is-O-, -S-, -O-C (═ O) -, -C (═ O) -O-, -O-C (═ O) -O-, -NR⁵-C(＝O)-、-C(＝O)-NR⁵-、-NR⁵In the case of substitution with-or-C (═ O) -, most preferred is substitution with-O-, preferably a so-called ethyleneoxy group substituted with-O-every 2 carbon atoms as a repeating unit and both ends of G are-CH₂-。

The G is preferably (i) "CH contained in a 2-valent chain aliphatic hydrocarbon group having 1 to 18, preferably 3 to 18, carbon atoms which may have a substituent, and a 2-valent chain aliphatic hydrocarbon group having 3 to 18 carbon atoms which may have a substituent₂Any organic group of at least one group substituted with-O-, -S-, -O-C (-O) -, -C (-O) -O-or-C (-O) -, wherein 2 or more of each of-O-and-S-are not present adjacent to each other ", more preferably (ii)" a 2-valent chain aliphatic hydrocarbon group having 3 to 18 carbon atoms which may have a substituent ", still more preferably (iii)" an alkylene group having 3 to 18 carbon atoms which may have a substituent ", still more preferably (iv)" an unsubstituted alkylene group having 4 to 16 carbon atoms ", still more preferably (v)" an unsubstituted alkylene group having 5 to 14 carbon atoms ", still more preferably (vi)" an unsubstituted alkylene group having 6 to 12 carbon atoms ", in particular(vii) preferably represents an "unsubstituted alkylene group having 6 to 10 carbon atoms", and most preferably a "n-hexylene group or a" n-octylene group ". Examples of the substituent for G include: alkyl groups having 1 to 5 carbon atoms such as methyl, ethyl and propyl; alkoxy groups having 1 to 5 carbon atoms such as methoxy, ethoxy, and isopropoxy; a cyano group; a halogen atom such as a fluorine atom or a chlorine atom.

R^XRepresents: a hydrogen atom; halogen atoms such as fluorine atom, chlorine atom, and bromine atom; alkyl groups having 1 to 6 carbon atoms such as methyl, ethyl and propyl; a cyano group; a nitro group; an alkyl group having 1 to 6 carbon atoms, wherein at least 1 hydrogen atom is substituted with a halogen atom, such as a trifluoromethyl group or a pentafluoroethyl group; alkoxy groups having 1 to 6 carbon atoms such as methoxy, ethoxy, isopropoxy, butoxy, and the like; alkylthio groups having 1 to 6 carbon atoms in which at least 1 hydrogen atom is replaced by a sulfur atom, such as methylthio group and ethylthio group; a mono-substituted amino group such as methylamino, ethylamino, acetylamino, etc.; a disubstituted amino group such as a dimethylamino group, a diethylamino group, or a phenylmethylamino group; -OCF₃；-C(＝O)-O-R³(ii) a or-O-C (═ O) -R³. Herein, R is³Represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms which may have a substituent, and is preferably a methyl group or an ethyl group. As R³The alkyl group having 1 to 10 carbon atoms which may have a substituent(s) is represented by¹、R²The alkyl group having 1 to 10 carbon atoms which may have a substituent(s) is the same, and preferred examples thereof are the same.

Among these, R^XEach independently preferably represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, more preferably R^XAll are hydrogen atoms.

R^XCan all be the same or different and form at least 1C-R of a ring^XCan be substituted by nitrogen atoms. C-R^XSpecific examples of the group in which at least 1 is substituted with a nitrogen atom are shown below. However, C-R^XThe group in which at least 1 is substituted with a nitrogen atom is not limited thereto.

[ chemical formula 23]

(wherein, R, X and R^XThe same meanings as described above are indicated. )

The amount of the compound (IV) used in the step (3) is preferably such that the ratio of the compound (III) to the compound (IV) is 1: 1 to 1: 2, more preferably 1: 1 to 1: 1.5, in terms of the molar ratio of the compound (III) to the compound (IV).

When water or an aqueous solution is added to the reaction solution to hydrolyze in step (2), the reaction in step (3) is usually carried out by adding compound (IV) to a mixed solution obtained by adding water or an aqueous solution to the reaction solution in step (2), and the reaction in step (3) may be carried out by adding compound (IV) after separating the water or the aqueous solution added in step (2). In the step (3), an acidic aqueous solution for catalytic reaction may be newly added, and particularly, when the water or aqueous solution added in the step (2) is separated, it is preferable to newly add an acidic aqueous solution for catalytic reaction. As the newly added acidic aqueous solution, the same acidic aqueous solution as the acidic aqueous solution listed as the acidic aqueous solution that can be used in step (2) can be used.

Among the above, in the step (3), it is preferable to use the reaction solution obtained in the step (2) as it is without performing post-treatment operations such as washing and extraction (that is, to add the compound (IV) to the mixed solution obtained in the step (2)), because the cost can be reduced. In this case, in the step (2), an acidic aqueous solution is particularly preferably used. This is because the acidic aqueous solution added in step (2) can be efficiently used as a catalyst for the reaction in step (3).

The compound (IV) may be dissolved in an appropriate organic solvent and added as desired. As the organic solvent to be used, the same organic solvents as those exemplified in the above step (1) can be used.

The compound (IV) can be produced, for example, by the method described in International publication No. 2015/141784 and Japanese patent application laid-open No. 2016 and 190818.

Here, in the present invention, it is preferable that at least one of the organic solvent (1 st organic solvent) used in the step (1) and the organic solvent (2 nd organic solvent) used in the case where the compound (IV) is added as an organic solvent solution in the step (3) is a water-immiscible organic solvent. By using a water-immiscible organic solvent as the 1 st organic solvent and/or the 2 nd organic solvent, the polymerizable compound (a) with high purity can be obtained in higher yield.

Here, the "water-immiscible organic solvent" is an organic solvent as described below: the solubility in water at 20 ℃ is 10g (organic solvent)/100 mL (water) or less, preferably 1g (organic solvent)/100 mL (water) or less, and more preferably 0.1g (organic solvent)/100 mL (water) or less.

Examples of the water-immiscible organic solvent include: esters such as ethyl acetate, isopropyl acetate, butyl acetate, dimethyl carbonate, and diethyl carbonate; halogenated hydrocarbons such as dichloromethane, chloroform, and 1, 2-dichloroethane; aromatic hydrocarbons such as benzene, toluene, and xylene; saturated hydrocarbons such as pentane, hexane, and heptane; ethers such as diethyl ether and cyclopentyl methyl ether; alicyclic hydrocarbons such as cyclopentane and cyclohexane.

The reaction temperature in the step (3) is from-20 ℃ to the boiling point of the solvent used, and is preferably from 0 ℃ to 80 ℃. The reaction time depends on the scale of the reaction and is usually several minutes to 10 hours.

After the reaction is completed, when the reaction solution is separated into 2 layers of an organic layer and an aqueous layer, water (saline solution) and a water-immiscible organic solvent are added as necessary, liquid separation is performed, and the organic layer is separated and taken out.

In addition, in the case where the reaction solution is not separated into 2 layers, water (saline solution) and a water-immiscible organic solvent are added as necessary, liquid separation is performed, and the organic layer is separated and taken out.

In either case, the obtained organic layer can be subjected to a usual post-treatment operation in organic synthetic chemistry, and a known separation and purification method such as a precipitation method, a recrystallization method, a distillation method, a chromatography column, or the like is carried out as desired, thereby isolating the intended polymerizable compound (a) alone.

In the step (3), an adsorbent or a filter aid, or both of them may be used in combination for the purpose of reducing ionic impurities and removing insoluble components (high molecular weight substances).

Examples of the adsorbent used herein include activated carbon and silica gel (main component SiO)₂) And synthetic adsorbent (main components MgO and Al)₂O₃、SiO₂) Activated clay, alumina, ion exchange resin, adsorption resin, and the like.

Examples of the filter aid include diatomaceous earth and silica gel (main component SiO)₂) Synthetic zeolites, perlite, Radiolite, and the like.

Among these, in the present invention, from the viewpoint of obtaining a high-purity target product in a high yield by a simple operation, a method of concentrating the obtained organic layer and precipitating crystals of the target product from the concentrated solution is preferable; or a method of concentrating the obtained organic layer, adding a poor solvent to the concentrated solution, and precipitating crystals of the target product.

Examples of the poor solvent used in the latter method include: water; alcohols such as methanol and ethanol.

Furthermore, the crystals obtained are preferably purified by recrystallization.

The recrystallization method is as follows: the obtained (crude) crystals were dissolved in a small amount of a solvent (to make the crystals have an undissolved portion), heated to be completely dissolved, filtered while hot to remove insoluble matter, and then the filtrate was cooled to precipitate the crystals.

Examples of the solvent used for recrystallization include a poor solvent exemplified in the precipitation method and ethers such as tetrahydrofuran.

In addition, from the viewpoint of obtaining a high-purity product, it is preferable to add an antioxidant such as 2, 6-di-t-butyl-4-cresol to the recrystallization solvent. The amount of the antioxidant added is 1 to 500mg per 100g of crystals of the objective product.

The structure of the target product can be identified by measurement such as NMR spectrum, IR spectrum, mass spectrum, elemental analysis, or the like.

According to the present invention, the polymerizable compound (a) represented by the formula (a) can be obtained in high yield in the step (3). In addition, in the polymerizationIn the compound (A), Y¹、Y²、A、R、R^XX, Q and n are as defined above.

Further, if the polymerizable compound (a) obtained by the present invention is used, a high-quality liquid crystal layer free from alignment defects, for example, can be formed.

In the present invention, it is preferable to use the compound represented by the above formula (IIa) as the compound (II) and obtain a polymerizable compound represented by the following formula (Aa) as the polymerizable compound (a).

[ chemical formula 24]

(in the formula, Y¹、Y²、A、R、R^XX, Q and n are as defined above. )

Examples

The present invention will be described in further detail below with reference to examples. However, the present invention is not limited to the following examples.

Example 1 Synthesis of polymerizable Compound 1

[ chemical formula 25]

Step 1: synthesis of intermediate A

[ chemical formula 26]

In a nitrogen stream, 90g (0.52mol) of trans-1, 4-cyclohexanedicarboxylic acid and 800ml of Tetrahydrofuran (THF) were introduced into a 3-port reactor having a thermometer. To this was added 33g (0.29mol) of methanesulfonyl chloride, and the reactor was immersed in a water bath to make the reactor internal temperature 20 ℃. Then, 31.7g (0.31mol) of triethylamine was added dropwise over 30 minutes while maintaining the reactor internal temperature at 20 to 30 ℃. After the end of the dropwise addition, the entire contents were further stirred at 25 ℃ for 2 hours. To the obtained reaction solution were added 3.2g (26.2mmol) of 4- (dimethylamino) pyridine and 69g (0.26mol) of 4- (6-acryloyloxy-hex-1-yloxy) phenol synthesized in Japanese patent application laid-open No. 2015-140302, and the reactor was again immersed in water so that the reactor internal temperature became 15 ℃. While the reactor internal temperature was maintained at 20 to 30 ℃, 31.7g (0.31mol) of triethylamine was added dropwise thereto over 30 minutes, and after completion of the dropwise addition, the entire contents were further stirred at 25 ℃ for 2 hours. After completion of the reaction, 4000ml of distilled water and 500ml of saturated saline were added to the reaction mixture, and the mixture was extracted 2 times with 1000ml of ethyl acetate. The organic layer was collected, dried over anhydrous sodium sulfate, and the sodium sulfate was filtered off. After the solvent was evaporated from the filtrate by a rotary evaporator, the obtained residue was purified by silica gel column chromatography (THF: toluene 1: 9 (volume ratio, the same applies hereinafter)), to obtain 70.6g of intermediate a as a white solid. The yield thereof was found to be 65%.

Structural use of the target product¹And H-NMR identification.

¹H-NMR(500MHz，DMSO-d₆，TMS，ppm)：12.12(s，1H)、6.99(d，2H，J＝9.0Hz)、6.92(d，2H，J＝9.0Hz)、6.32(dd，1H，J＝1.5Hz，17.5Hz)、6.17(dd，1H，J＝10.0Hz，17.5Hz)、5.93(dd，1H，J＝1.5Hz，10.0Hz)、4.11(t，2H，J＝6.5Hz)、3.94(t，2H，J＝6.5Hz)、2.48-2.56(m，1H)、2.18-2.26(m，1H)、2.04-2.10(m，2H)、1.93-2.00(m，2H)、1.59-1.75(m，4H)、1.35-1.52(m，8H)。

Step 2: synthesis of intermediate B

[ chemical formula 27]

Intermediate B was synthesized with reference to Japanese patent application laid-open No. 2016-190818.

Structural use of the target product¹And H-NMR identification.

¹H-NMR(500MHz，CDCl₃，TMS，ppm)：7.60(dd，1H，J＝1.0Hz，8.0Hz)、7.53(dd，1H，J＝1.0Hz，8.0Hz)、7.27(ddd，1H，J＝1.0Hz，8.0Hz，8.0Hz)、7.06(ddd，1H，J＝1.0Hz，8.0Hz，8.0Hz)、4.22(s，2H)、3.74(t，2H，J＝7.5Hz)、1.69-1.76(m，2H)、1.29-1.42(m，6H)、0.89(t，3H，J＝7.0Hz)。

And step 3: synthesis of intermediate C

[ chemical formula 28]

30g (71.7mmol) of the intermediate A synthesized in the above step 1, 300g of chloroform and 10.5g (143.4mmol) of N, N-dimethylformamide were charged into a 3-port reactor equipped with a thermometer under a nitrogen flow, and cooled to 10 ℃ or lower. 9.81g (82.44mmol) of thionyl chloride was added dropwise thereto while keeping the reaction temperature at 10 ℃ or lower. After the completion of the dropwise addition, the reaction solution was returned to 25 ℃ and stirred for 1 hour. After completion of the reaction, 225g of chloroform was separated by a rotary evaporator and concentrated to prepare a chloroform solution.

And 4, step 4: synthesis of polymerizable Compound 1

In a 3-port reactor equipped with a thermometer, 4.5g (32.58mmol) of 2, 5-dihydroxybenzaldehyde and 19.78g (195.5mmol) of triethylamine were dissolved in 150g of chloroform under a nitrogen flow, and the resulting solution was cooled to 10 ℃ or lower. The entire amount of the chloroform solution of intermediate C synthesized in step 3 was slowly added dropwise to the solution while keeping the reaction temperature at 10 ℃ or lower. After completion of the dropwise addition, the entire contents were further stirred at 5 to 10 ℃ for 1 hour (step (1)).

After the reaction, 120g of a 1.0N aqueous hydrochloric acid solution was added to the reaction mixture while keeping the temperature at 10 ℃ or lower. Thereafter, the reaction mixture was stirred at 10 ℃ or lower for 30 minutes to effect a reaction (step (2)).

After the reaction was completed, 10.58g (42.4mmol) of intermediate B synthesized in the above step 2 and 0.3g of 2, 6-di-t-butyl-p-cresol were added. Thereafter, the reaction solution was heated to 40 ℃ to carry out a reaction for 4 hours (step (3)).

After the reaction was completed, the aqueous layer was separated. Further, 105g of distilled water was put into the organic layer, and the organic layer was stirred at 40 ℃ for 30 minutes to clean the organic layer. After separating the aqueous layer, the organic layer was cooled to 25 ℃ and 1.5g of Rokahelp #479 was added and stirred for 30 minutes. Thereafter, Rokahelp #479 was removed by filtration using a Tung mountain funnel paved with 1g of Rokahelp # 479. From the obtained organic layer, 180g of chloroform was separated by a rotary evaporator and concentrated. To the obtained organic layer was added 210g of hexane over 1 hour to precipitate a solid, which was then filtered to obtain a pale yellow solid. The resulting pale yellow solid was dissolved in 120g of tetrahydrofuran at 25 ℃ and 1.5g of Rokahelp #479 was added thereto and stirred for 30 minutes. Thereafter, Rokahelp #479 was removed by filtration using a Tung mountain funnel paved with 1g of Rokahelp # 479. To the obtained organic layer, 165g of methanol was slowly dropped at 15 ℃ to precipitate a solid, which was then filtered to obtain a solid. The obtained solid was dried by a vacuum dryer to obtain 32.4g of polymerizable compound 1 as a pale yellow solid. The yield was 85% (based on 2, 5-dihydroxybenzaldehyde).

Structural use of the target product¹And H-NMR identification.

¹H-NMR(400MHz，CDCl₃，TMS，ppm)：7.75(d，1H，J＝2.5Hz)、7.67-7.70(m，3H)、7.34(ddd，1H，J＝1.0Hz，7.0Hz，7.5Hz)、7.17(ddd，1H，J＝1.0Hz，7.5Hz，7.5Hz)、7.12(d，1H，J＝9.0Hz)、7.10(dd，1H，J＝2.5Hz，9.0Hz)、6.99(d，2H，J＝9.0Hz)、6.98(d，2H，J＝9.0Hz)、6.88(d，4H，J＝9.0Hz)、6.40(dd，2H，J＝1.5Hz，17.0Hz)、6.13(dd，2H，J＝10.5Hz，17.5Hz)、5.82(dd，2H，J＝1.5Hz，10.5Hz)、4.30(t，2H，J＝8.0Hz)、4.18(t，4H，J＝6.5Hz)、3.95(t，4H，J＝6.5Hz)、2.58-2.70(m，4H)、2.31-2.35(m，8H)、1.66-1.82(m，18H)、1.31-1.54(m，14H)、0.90(t，3H，J＝7.0Hz)。

Example 2 Synthesis of polymerizable Compound 1

Step 1: synthesis of intermediate C

30g (71.7mmol) of the intermediate A synthesized in the step 1 of the above example 1, 300g of toluene and 5.5g of N, N-dimethylformamide were charged in a 3-port reactor having a thermometer under a nitrogen flow, and cooled to 10 ℃ or lower. While the reaction temperature was kept at 10 ℃ or lower, 8.96g (75.3mmol) of thionyl chloride was added dropwise thereto. After the completion of the dropwise addition, the reaction solution was returned to 25 ℃ and stirred for 1 hour. After the reaction, the reaction mixture was concentrated by a rotary evaporator until the amount of the reaction mixture became half. Thereafter, toluene was added in an amount equal to the amount separated, and the reaction solution was concentrated by a rotary evaporator until the amount of the reaction solution became half. This operation was repeated 3 times, and the synthesis was performed as a toluene solution.

Step 2: synthesis of polymerizable Compound 1

In a 3-port reactor equipped with a thermometer, 4.13g (29.9mmol) of 2, 5-dihydroxybenzaldehyde and 7.62g (75.4mmol) of triethylamine were dissolved in 150g of tetrahydrofuran in a nitrogen stream, and the resulting solution was cooled to 10 ℃ or lower. While the reaction temperature was kept at 10 ℃ or lower, 150g of a toluene solution of intermediate C synthesized in step 1 was slowly added dropwise to the solution. After completion of the dropwise addition, the entire contents were further stirred at 5 to 10 ℃ for 1 hour (step (1)).

After the reaction, 30g of a 1.0-equivalent hydrochloric acid aqueous solution was added to the reaction mixture while keeping the temperature at 10 ℃ or lower, and the mixture was stirred at 10 ℃ or lower for 30 minutes (step (2)).

Thereafter, 9.7g (38.9mmol) of intermediate B synthesized in step 2 of example 1 was added, and the temperature was raised to 40 ℃ to conduct a reaction for 4 hours (step (3)).

After completion of the reaction, the reaction mixture was cooled to 25 ℃ and 300g of ethyl acetate and 300g of 10 mass% saline were added to conduct a liquid separation operation. The obtained organic layer was further washed 2 times with 300g of 2 mass% saline solution.

About 15% of the total mass was separated from the obtained organic layer by a rotary evaporator, and concentrated. After the temperature of the solution was set to 25 ℃, a mixed solvent of 300g of methanol and 60g of water was slowly dropped thereinto. Thereafter, the mixture was cooled to 10 ℃ to precipitate a solid, and the solid was obtained by filtration. To the resulting solid were added 240g of tetrahydrofuran, 240g of methanol and 20mg of 2, 6-di-t-butyl-4-methylphenol, and the whole was heated to 50 ℃ to prepare a uniform solution. The solution was filtered hot at 50 ℃ and the filtrate obtained was slowly cooled to 10 ℃ for recrystallization. Crystals were obtained by filtration and dried by a vacuum drier to obtain 28.3g of polymerizable compound 1 as a pale yellow solid. The yield was 81% (based on 2, 5-dihydroxybenzaldehyde).

Example 3 Synthesis of polymerizable Compound 1

Step 1: synthesis of mixture 1

[ chemical formula 29]

16.6g (79.40mmol) of trans-1, 4-cyclohexanedicarboxylic acid dichloride, 120g of cyclopentylmethyl ether (CPME) and 46g of tetrahydrofuran are introduced into a 3-port reactor with a thermometer in a nitrogen stream. To this was added 20g (75.67mmol) of 4- (6-acryloyloxy-hex-1-yloxy) phenol synthesized in Japanese patent application laid-open No. 2015-140302 and 0.33g of 2, 6-di-t-butyl-p-cresol, and the reactor was immersed in an ice bath to adjust the reactor internal temperature to 0 ℃. Then, while the reactor internal temperature was kept at 10 ℃ or lower, 8.0g (79.45mmol) of triethylamine was slowly added dropwise over 30 minutes. After completion of the dropwise addition, the entire contents were further stirred for 1 hour while being kept at 10 ℃ or lower.

To the obtained reaction solution, 50g of distilled water was added. The reaction mixture was heated to 50 ℃ and washed for 2 hours (hydrolysis reaction), and then the aqueous layer was separated. The washing with water (hydrolysis reaction) was performed 3 times in total, and the washing was performed for 6 hours in total. The obtained organic layer was cooled to 40 ℃ and then 83.2g of a 1mol/L buffer solution (pH: 5.5) composed of acetic acid and sodium acetate was further added thereto and stirred, thereby washing was performed. Thereafter, the buffer solution layer (aqueous layer) was separated to obtain an organic layer. The washing operation with the buffer solution was performed 5 times in total. The obtained organic layer was further washed with 50g of distilled water, and then the aqueous layer was separated. The washing with distilled water was performed 2 times in total. 240g of n-hexane was added to the obtained organic layer at 40 ℃ and then cooled to 0 ℃ to precipitate crystals. Thereafter, the precipitated crystals were collected by filtration. The filtrate was washed with n-hexane and then dried under vacuum to obtain 26.91g of mixture 1 as a white solid.

The crystals obtained were analyzed by HPLC, and the monoesters and diesters were quantified from a calibration curve, whereby it was found that 68.34 mass% (43.95mmol) of the monoester was contained as the target product. In addition, use¹³C-NMR

Alkane-d₈) The crystals obtained were analyzed to calculate the content of cyclohexanedicarboxylic acid, and the results were below the detection limit.

Step 2: synthesis of polymerizable Compound 1

26.91g of the mixture 1 synthesized in the above step 1, 183.9g of chloroform and 6.4g of N, N-dimethylformamide were charged in a 3-port reactor equipped with a thermometer under a nitrogen stream, and cooled to 10 ℃ or lower. The reaction temperature was controlled to 10 ℃ or lower, and 6.0g (50.54mmol) of thionyl chloride was added dropwise thereto. After the completion of the dropwise addition, the reaction solution was returned to 25 ℃ and stirred for 1 hour. After the reaction was completed, 138g of chloroform was separated under reduced pressure using a rotary evaporator. Thereafter, 46g of fresh chloroform was added to obtain a chloroform solution (1). In a 3-port reactor equipped with a thermometer, 2.76g (20.0mmol) of 2, 5-dihydroxybenzaldehyde and 12.13g (119.8mmol) of triethylamine were dissolved in 92g of chloroform in a nitrogen stream, and the mixture was cooled to 10 ℃ or lower. The chloroform solution (1) was slowly added dropwise to the reactor while keeping the reactor internal temperature at 10 ℃ or lower. After completion of the dropwise addition, the reaction solution was kept at 10 ℃ or lower for 1 hour to conduct the reaction (step (1)).

After the reaction, the temperature was maintained at 10 ℃ or lower, 725g of a 1.0-equivalent hydrochloric acid aqueous solution was added to the reaction mixture, and the mixture was stirred at 10 ℃ or lower for 30 minutes (step (2)).

Thereafter, 6.48g (26.0mmol) of the intermediate B synthesized in step 2 of example 1 and 0.33g of 2, 6-di-t-butyl-p-cresol were added, and the reaction mixture was heated to 40 ℃ to conduct a reaction for 4 hours (step (3)).

After completion of the reaction, the aqueous layer was separated at 40 ℃ and subjected to a liquid separation operation. To the obtained organic layer was added 0.92g of Rokahelp #479 (manufactured by Mitsui Metal mining Co., Ltd.), and after stirring at 25 ℃ for 30 minutes, it was filtered off with a filter equipped with 0.6g of Rokahelp # 479. The filter was washed with 9.2g of chloroform and combined with the filtrate obtained previously. Then, 110g of chloroform was separated from the obtained organic layer under reduced pressure by a rotary evaporator, and the resulting mixture was concentrated. After adding 33g of tetrahydrofuran to the solution, the mixture was cooled to 15 ℃ with stirring. Then, 129g of 60% hexane (made by Godo co., ltd.) was slowly added dropwise to the solution. The mixture was stirred at the current temperature for 30 minutes to precipitate a solid. Thereafter, the precipitated solid was collected by filtration.

88.3g of tetrahydrofuran, 1.1g of Rokahelp #479 and 0.33g of 2, 6-di-t-butyl-p-cresol were added to the obtained solid, and after stirring at 25 ℃ for 30 minutes, it was filtered off with a filter fitted with 0.66g of Rokahelp # 479. The filter was washed with 44g of tetrahydrofuran and combined with the filtrate obtained previously. Next, 110g of tetrahydrofuran was distilled off from the resulting organic layer by a rotary evaporator. The resulting solution was brought to 15 ℃ and 121g of methanol was slowly added dropwise. The mixture was stirred for 30 minutes while maintaining the current temperature, and a solid was precipitated. Thereafter, the precipitated solid was collected by filtration. The filtrate was washed with methanol and then dried under vacuum to obtain 19.4g of polymerizable compound 1 as a pale yellow solid. The yield was 83% (based on 2, 5-dihydroxybenzaldehyde).

Example 4 Synthesis of polymerizable Compound 1

The same operation as in example 1 was carried out, except that 19.78g (195.5mmol) of triethylamine was changed to 20.97g (195.7mmol) of 2, 6-lutidine in step 4 of example 1. As a result, 34.7g of the polymerizable compound 1 was obtained as a pale yellow solid. The yield was 91% (based on 2, 5-dihydroxybenzaldehyde).

Example 5 Synthesis of polymerizable Compound 1

The same operation as in example 3 was carried out except that 12.13g (119.8mmol) of triethylamine in step 2 of example 3 was changed to 12.8g (120.0mmol) of 2, 6-lutidine. As a result, 21.1g of the polymerizable compound 1 was obtained as a pale yellow solid. The yield was 90% (based on 2, 5-dihydroxybenzaldehyde).

Example 6 Synthesis of polymerizable Compound 1

The same operation as in example 3 was carried out except that 725g of a 1.0N hydrochloric acid aqueous solution was changed to 700g of a 1.0N methanesulfonic acid aqueous solution in step 2 of example 3. As a result, 19.9g of the polymerizable compound 1 was obtained as a pale yellow solid. The yield was 85% (based on 2, 5-dihydroxybenzaldehyde).

Example 7 Synthesis of polymerizable Compound 1

The same operation as in example 3 was carried out except that in step 2 of example 3, 12.13g (119.8mmol) of triethylamine was changed to 12.8g (120.0mmol) of 2, 6-lutidine, and 725g of a 1.0-normality aqueous hydrochloric acid solution was changed to 700g of a 1.0-normality aqueous methanesulfonic acid solution. As a result, 20.6g of the polymerizable compound 1 was obtained as a pale yellow solid. The yield was 88% (based on 2, 5-dihydroxybenzaldehyde).

Comparative example 1 Synthesis of polymerizable Compound 1

Step 1-3: the same operations as in steps 1 to 3 of example 1 were carried out.

And 4, step 4: synthesis of polymerizable Compound 1

In a 3-port reactor equipped with a thermometer, 4.5g (32.58mmol) of 2, 5-dihydroxybenzaldehyde and 19.78g (195.5mmol) of triethylamine were dissolved in 150g of chloroform under a nitrogen flow, and the resulting solution was cooled to 10 ℃ or lower. The entire amount of the chloroform solution of intermediate C synthesized in step 3 was slowly added dropwise to the solution while keeping the reaction temperature at 10 ℃ or lower. After completion of the dropwise addition, the entire contents were further stirred at 5 to 10 ℃ for 1 hour (step (1)).

After the reaction was completed, 120g of a 1.0N aqueous hydrochloric acid solution, 10.58g (42.4mmol) of intermediate B synthesized in step 2, and 0.3g of 2, 6-di-t-butyl-p-cresol were added to the reaction mixture while maintaining the temperature at 10 ℃ or lower. Thereafter, the reaction solution was heated to 40 ℃ to carry out a reaction for 4 hours (step (3)).

After the reaction was completed, the aqueous layer was separated. Further, 105g of distilled water was put into the organic layer, and the organic layer was stirred at 40 ℃ for 30 minutes to clean the organic layer. After separating the aqueous layer, the organic layer was cooled to 25 ℃ and 1.5g of Rokahelp #479 was added and stirred for 30 minutes. Thereafter, Rokahelp #479 was removed by filtration using a Tung mountain funnel paved with 1g of Rokahelp # 479. From the obtained organic layer, 180g of chloroform was separated by a rotary evaporator and concentrated. To the obtained organic layer was added 210g of hexane over 1 hour to precipitate a solid, which was then filtered to obtain a pale yellow solid. The resulting pale yellow solid was dissolved in 120g of tetrahydrofuran at 25 ℃ and 1.5g of Rokahelp #479 was added thereto and stirred for 30 minutes. Thereafter, Rokahelp #479 was removed by filtration using a Tung mountain funnel paved with 1g of Rokahelp # 479. To the obtained organic layer, 165g of methanol was slowly dropped at 15 ℃ to precipitate a solid, which was then filtered to obtain a solid. The obtained solid was dried by a vacuum dryer to obtain 27.5g of polymerizable compound 1 as a pale yellow solid. The yield was 72% (based on 2, 5-dihydroxybenzaldehyde).

Comparative example 2 Synthesis of polymerizable Compound 1

Step 1: the same operation as in step 1 of example 3 was carried out.

Step 2: synthesis of polymerizable Compound 1

26.91g of the mixture 1 synthesized in step 1, 183.9g of chloroform and 6.4g of N, N-dimethylformamide were charged in a 3-port reactor equipped with a thermometer under a nitrogen stream, and cooled to 10 ℃ or lower. The reaction temperature was controlled to 10 ℃ or lower, and 6.0g (50.54mmol) of thionyl chloride was added dropwise thereto. After the completion of the dropwise addition, the reaction solution was returned to 25 ℃ and stirred for 1 hour. After the reaction was completed, 138g of chloroform was separated under reduced pressure using a rotary evaporator. Thereafter, 46g of fresh chloroform was added to obtain a chloroform solution (2). In a 3-port reactor equipped with a thermometer, 2.76g (20.0mmol) of 2, 5-dihydroxybenzaldehyde and 12.13g (119.8mmol) of triethylamine were dissolved in 92g of chloroform in a nitrogen stream, and the mixture was cooled to 10 ℃ or lower. The chloroform solution (2) was slowly added dropwise to the reactor while keeping the reactor internal temperature at 10 ℃ or lower. After completion of the dropwise addition, the reaction solution was allowed to stand at 10 ℃ or lower for 1 hour to perform a further reaction (step (1)).

After the reaction was completed, 725g of a 1.0 equivalent hydrochloric acid aqueous solution, 6.48g (26.0mmol) of intermediate B synthesized in step 2 of example 1, and 0.33g of 2, 6-di-t-butyl-p-cresol were added to the reaction mixture while keeping the temperature at 10 ℃ or lower, and the reaction mixture was heated to 40 ℃ to conduct a reaction for 4 hours (step (3)).

After completion of the reaction, the aqueous layer was separated at 40 ℃ and subjected to a liquid separation operation. To the obtained organic layer was added 0.92g of Rokahelp #479 (manufactured by Mitsui Metal mining Co., Ltd.), and after stirring at 25 ℃ for 30 minutes, it was filtered off with a filter equipped with 0.6g of Rokahelp # 479. The filter was washed with 9.2g of chloroform and combined with the filtrate obtained previously. Then, 110g of chloroform was separated from the obtained organic layer under reduced pressure by a rotary evaporator, and the resulting mixture was concentrated. After adding 33g of tetrahydrofuran to the solution, the mixture was cooled to 15 ℃ with stirring. Then, 129g of 60% hexane (made by Godo co., ltd.) was slowly added dropwise to the solution. The mixture was stirred at the current temperature for 30 minutes to precipitate a solid. Thereafter, the precipitated solid was collected by filtration.

88.3g of tetrahydrofuran, 1.1g of Rokahelp #479 and 0.33g of 2, 6-di-t-butyl-p-cresol were added to the obtained solid, and after stirring at 25 ℃ for 30 minutes, it was filtered off with a filter fitted with 0.66g of Rokahelp # 479. The filter was washed with 44g of tetrahydrofuran and combined with the filtrate obtained previously. Next, 110g of tetrahydrofuran was distilled off from the resulting organic layer by a rotary evaporator. The resulting solution was brought to 15 ℃ and 121g of methanol was slowly added dropwise. The mixture was stirred at the current temperature for 30 minutes to precipitate a solid. Thereafter, the precipitated solid was collected by filtration. The filtrate was washed with methanol and then dried under vacuum to obtain 16.6g of polymerizable compound 1 as a pale yellow solid. The yield was 71% (based on 2, 5-dihydroxybenzaldehyde).

Comparative example 3 Synthesis of polymerizable Compound 1

Step 1-3: the same operations as in steps 1 to 3 of example 1 were carried out.

And 4, step 4: synthesis of polymerizable Compound 1

In a 3-port reactor equipped with a thermometer, 4.5g (32.58mmol) of 2, 5-dihydroxybenzaldehyde and 20.97g (195.7mmol) of 2, 6-lutidine were dissolved in 150g of chloroform in a nitrogen stream, and the resulting solution was cooled to 10 ℃ or lower. The entire amount of the chloroform solution of intermediate C synthesized in step 3 was slowly added dropwise to the solution while keeping the reaction temperature at 10 ℃ or lower. After completion of the dropwise addition, the entire contents were further stirred at 5 to 10 ℃ for 1 hour (step (1)).

After the reaction was completed, 120g of a 1.0N aqueous hydrochloric acid solution, 10.58g (42.4mmol) of intermediate B synthesized in step 2, and 0.3g of 2, 6-di-t-butyl-p-cresol were added to the reaction mixture while maintaining the temperature at 10 ℃ or lower. Thereafter, the reaction solution was heated to 40 ℃ to carry out a reaction for 4 hours (step (3)).

After the reaction was completed, the aqueous layer was separated. Further, 105g of distilled water was put into the organic layer, and the organic layer was stirred at 40 ℃ for 30 minutes to clean the organic layer. After separating the aqueous layer, the organic layer was cooled to 25 ℃ and 1.5g of Rokahelp #479 was added and stirred for 30 minutes. Thereafter, Rokahelp #479 was removed by filtration using a Tung mountain funnel paved with 1g of Rokahelp # 479. From the obtained organic layer, 180g of chloroform was separated by a rotary evaporator and concentrated. To the obtained organic layer was added 210g of hexane over 1 hour to precipitate a solid, which was then filtered to obtain a pale yellow solid. The resulting pale yellow solid was dissolved in 120g of tetrahydrofuran at 25 ℃ and 1.5g of Rokahelp #479 was added thereto and stirred for 30 minutes. Thereafter, Rokahelp #479 was removed by filtration using a Tung mountain funnel paved with 1g of Rokahelp # 479. To the obtained organic layer, 165g of methanol was slowly dropped at 15 ℃ to precipitate a solid, which was then filtered to obtain a solid. The obtained solid was dried by a vacuum dryer to obtain 29.4g of polymerizable compound 1 as a pale yellow solid. The yield was 77% (based on 2, 5-dihydroxybenzaldehyde).

Comparative example 4 Synthesis of polymerizable Compound 1

Step 1: the same operation as in step 1 of example 3 was carried out.

Step 2: synthesis of polymerizable Compound 1

26.91g of the mixture 1 synthesized in step 1, 183.9g of chloroform and 6.4g of N, N-dimethylformamide were charged in a 3-port reactor equipped with a thermometer under a nitrogen stream, and cooled to 10 ℃ or lower. The reaction temperature was controlled to 10 ℃ or lower, and 6.0g (50.54mmol) of thionyl chloride was added dropwise thereto. After the completion of the dropwise addition, the reaction solution was returned to 25 ℃ and stirred for 1 hour. After the reaction was completed, 138g of chloroform was separated under reduced pressure using a rotary evaporator. Thereafter, 46g of fresh chloroform was added to obtain a chloroform solution (3). In a nitrogen stream, 2.76g (20.0mmol) of 2, 5-dihydroxybenzaldehyde and 12.8g (120.0mmol) of 2, 6-lutidine were dissolved in 92g of chloroform in a 3-port reactor equipped with a thermometer, and the mixture was cooled to 10 ℃ or lower. The chloroform solution (3) was slowly added dropwise to the reactor while keeping the reactor internal temperature at 10 ℃ or lower. After completion of the dropwise addition, the reaction solution was allowed to stand at 10 ℃ or lower for 1 hour to perform a further reaction (step (1)).

After the reaction was completed, 725g of a 1.0 equivalent hydrochloric acid aqueous solution, 6.48g (26.0mmol) of intermediate B synthesized in step 2 of example 1, and 0.33g of 2, 6-di-t-butyl-p-cresol were added to the reaction solution while maintaining the temperature at 10 ℃ or lower, and the reaction solution was heated to 40 ℃ to conduct the reaction for 4 hours (step (3)).

After completion of the reaction, the aqueous layer was separated at 40 ℃ and subjected to a liquid separation operation. To the obtained organic layer was added 0.92g of Rokahelp #479 (manufactured by Mitsui Metal mining Co., Ltd.), and after stirring at 25 ℃ for 30 minutes, it was filtered off with a filter equipped with 0.6g of Rokahelp # 479. The filter was washed with 9.2g of chloroform and combined with the filtrate obtained previously. Then, 110g of chloroform was separated from the obtained organic layer under reduced pressure by a rotary evaporator, and the resulting mixture was concentrated. After adding 33g of tetrahydrofuran to the solution, the mixture was cooled to 15 ℃ with stirring. Then, 129g of 60% hexane (made by Godo co., ltd.) was slowly added dropwise to the solution. The mixture was stirred for 30 minutes while maintaining the current temperature, and a solid was precipitated. Thereafter, the precipitated solid was collected by filtration. 88.3g of tetrahydrofuran, 1.1g of Rokahelp #479 and 0.33g of 2, 6-di-t-butyl-p-cresol were added to the obtained solid, and after stirring at 25 ℃ for 30 minutes, it was filtered off with a filter fitted with 0.66g of Rokahelp # 479. The filter was washed with 44g of tetrahydrofuran and combined with the filtrate obtained previously. Next, 110g of tetrahydrofuran was distilled off from the resulting organic layer by a rotary evaporator. The resulting solution was brought to 15 ℃ and 121g of methanol was slowly added dropwise. The mixture was stirred for 30 minutes while maintaining the current temperature, and a solid was precipitated. Thereafter, the precipitated solid was collected by filtration. The filtrate was washed with methanol and then dried under vacuum to obtain 17.8g of polymerizable compound 1 as a pale yellow solid. The yield was 76% (based on 2, 5-dihydroxybenzaldehyde).

Comparative example 5 Synthesis of polymerizable Compound 1

Step 1: the same operation as in step 1 of example 3 was carried out.

Step 2: synthesis of polymerizable Compound 1

26.91g of the mixture 1 synthesized in step 1, 183.9g of chloroform and 6.4g of N, N-dimethylformamide were charged in a 3-port reactor equipped with a thermometer under a nitrogen stream, and cooled to 10 ℃ or lower. The reaction temperature was controlled to 10 ℃ or lower, and 6.0g (50.54mmol) of thionyl chloride was added dropwise thereto. After the completion of the dropwise addition, the reaction solution was returned to 25 ℃ and stirred for 1 hour. After the reaction was completed, 138g of chloroform was separated under reduced pressure using a rotary evaporator. Thereafter, 46g of fresh chloroform was added to obtain a chloroform solution (4). In a 3-port reactor equipped with a thermometer, 2.76g (20.0mmol) of 2, 5-dihydroxybenzaldehyde and 12.8g (120.0mmol) of 2, 6-lutidine were dissolved in 92g of chloroform in a nitrogen stream, and the mixture was cooled to 10 ℃ or lower. The chloroform solution (4) was slowly added dropwise to the reactor while keeping the reactor internal temperature at 10 ℃ or lower. After completion of the dropwise addition, the reaction solution was kept at 10 ℃ or lower for 1 hour to conduct the reaction (step (1)).

After the reaction was completed, 700g of a 1.0-equivalent-concentration methanesulfonic acid aqueous solution, 6.48g (26.0mmol) of intermediate B synthesized in step 2 of example 1, and 0.33g of 2, 6-di-t-butyl-p-cresol were added to the reaction solution while maintaining the temperature at 10 ℃ or lower, and the reaction solution was heated to 40 ℃ to carry out a reaction for 4 hours (step (3)).

After completion of the reaction, the aqueous layer was separated at 40 ℃ and subjected to a liquid separation operation. To the obtained organic layer was added 0.92g of Rokahelp #479 (manufactured by Mitsui Metal mining Co., Ltd.), and after stirring at 25 ℃ for 30 minutes, it was filtered off with a filter equipped with 0.6g of Rokahelp # 479. The filter was washed with 9.2g of chloroform and combined with the filtrate obtained previously. Then, 110g of chloroform was separated from the obtained organic layer under reduced pressure by a rotary evaporator, and the resulting mixture was concentrated. After adding 33g of tetrahydrofuran to the solution, the mixture was cooled to 15 ℃ with stirring. Then, 129g of 60% hexane (made by Godo co., ltd.) was slowly added dropwise to the solution. The mixture was stirred at the current temperature for 30 minutes to precipitate a solid. Thereafter, the precipitated solid was collected by filtration. 88.3g of tetrahydrofuran, 1.1g of Rokahelp #479 and 0.33g of 2, 6-di-t-butyl-p-cresol were added to the obtained solid, and after stirring at 25 ℃ for 30 minutes, it was filtered off with a filter fitted with 0.66g of Rokahelp # 479. The filter was washed with 44g of tetrahydrofuran and combined with the filtrate obtained previously. Next, 110g of tetrahydrofuran was distilled off from the resulting organic layer by a rotary evaporator. The resulting solution was brought to 15 ℃ and 121g of methanol was slowly added dropwise. The mixture was stirred for 30 minutes while maintaining the current temperature, and a solid was precipitated. Thereafter, the precipitated solid was collected by filtration. The filtrate was washed with methanol and then dried under vacuum to obtain 17.6g of polymerizable compound 1 as a pale yellow solid. The yield was 75% (based on 2, 5-dihydroxybenzaldehyde).

Comparative example 6 Synthesis of polymerizable Compound 1

The same operation as in comparative example 1 was performed except that the reaction time in step (3) in step 4 of comparative example 1 was changed from 4 hours to 8 hours. As a result, 28.6g of the polymerizable compound 1 was obtained as a pale yellow solid. The yield was 75% (based on 2, 5-dihydroxybenzaldehyde).

Comparative example 7 Synthesis of polymerizable Compound 1

The same operation as in comparative example 2 was performed except that the reaction time in step (3) in step 2 of comparative example 2 was changed from 4 hours to 8 hours. As a result, 17.1g of polymerizable compound 1 was obtained as a pale yellow solid. The yield was 73% (based on 2, 5-dihydroxybenzaldehyde).

Comparative example 8 Synthesis of polymerizable Compound 1

The same operation as in comparative example 3 was performed except that the reaction time in step (3) in step 4 of comparative example 3 was changed from 4 hours to 8 hours. As a result, 30.5g of polymerizable compound 1 was obtained as a pale yellow solid. The yield was 80% (based on 2, 5-dihydroxybenzaldehyde).

Comparative example 9 Synthesis of polymerizable Compound 1

The same operation as in comparative example 4 was performed except that the reaction time in step (3) in step 2 of comparative example 4 was changed from 4 hours to 8 hours. As a result, 18.5g of the polymerizable compound 1 was obtained as a pale yellow solid. The yield was 79% (based on 2, 5-dihydroxybenzaldehyde).

Comparative example 10 Synthesis of polymerizable Compound 1

The same operation as in comparative example 5 was performed except that the reaction time in step (3) in step 2 of comparative example 5 was changed from 4 hours to 8 hours. As a result, 18.0g of the polymerizable compound 1 was obtained as a pale yellow solid. The yield was 77% (based on 2, 5-dihydroxybenzaldehyde).

The results of examples 1 to 7 and comparative examples 1 to 10 are summarized in Table 1.

[ Table 1]

Example 8 Synthesis of polymerizable Compound 2

[ chemical formula 30]

Step 1: synthesis of intermediate D

[ chemical formula 31]

500.5g (2.69mol) of 1-naphthylacetic acid and 1049g of toluene are introduced into a 3-port reactor having a thermometer in a nitrogen stream. 349.5g (2.56mol) of 6-chloro-1-hexanol and 48.6g (0.26mol) of p-toluenesulfonic acid monohydrate were further added. The solution was heated using Dean-Stark, and azeotropic dehydration was carried out for 2 hours while removing the produced water from the reaction system (inner temperature: about 95 ℃ C.). After completion of the reaction, the reaction mixture was cooled to 25 ℃ and washed with 742g of a 5.8 mass% aqueous sodium bicarbonate solution. After the liquid separation, the organic layer was further washed with 500g of water. Then, 7g of Rokahelp #479 was added to the organic layer, and after stirring at room temperature for 30 minutes, the mixture was filtered to remove Rokahelp # 479. The solvent was distilled off from the organic layer using a rotary evaporator to give 755g of a pale brown oil containing intermediate D. The pale brown oil containing intermediate D contained 93.0 mass% of intermediate D as seen by quantitative analysis using high performance liquid chromatography. The pale brown oil was not purified and used directly in the next reaction.

Step 2: synthesis of intermediate E

[ chemical formula 32]

59.52g (55.35 g (0.182mol) of a pale brown oil comprising intermediate D synthesized in the preceding step 1 and 235g of N-methyl-2-pyrrolidone were charged into a 3-port reactor with a thermometer under a nitrogen flow to prepare a homogeneous solution. To this was added 25.0g (0.151mol) of 2-hydrazinobenzothiazole. Next, 48.18g (0.227mol) of tripotassium phosphate was added, and the whole content was stirred at 100 ℃ for 3 hours. After completion of the reaction, 312.5g of ethyl acetate was added to the reaction mixture cooled to 60 ℃ and then the mixture was filtered while maintaining the temperature at 60 ℃. The organic layer as a filtrate was slowly dropped into 250g of a 0.5N aqueous solution of citric acid, and stirred at an internal temperature of 60 ℃ for 30 minutes, followed by separation of an aqueous layer. Further, 275g of a 9.1 mass% aqueous solution of sodium chloride was added to the organic layer, and after stirring at an internal temperature of 60 ℃ for 30 minutes, the mixture was allowed to stand for 30 minutes, and the aqueous layer was separated. Then, 262.5g of a 4.76 mass% aqueous solution of sodium hydrogencarbonate was added to the organic layer, and the mixture was stirred at an internal temperature of 60 ℃ for 30 minutes, and then allowed to stand for 30 minutes to separate an aqueous layer. Further, 250g of water was added to the organic layer, and after stirring at an internal temperature of 60 ℃ for 30 minutes, the mixture was allowed to stand for 30 minutes, and the aqueous layer was separated. The resulting organic layer was slowly cooled to 0 ℃ and stirred at 0 ℃ for 30 minutes. The resulting solid was taken up by filtration. Thereafter, 150g of ethyl acetate was added to the obtained solid, and the mixture was heated to 60 ℃ to prepare a uniform solution, and stirred for 30 minutes. Thereafter, the ethyl acetate solution was slowly cooled to 0 ℃ and stirred at 0 ℃ for 1 hour. The resulting solid was collected by filtration and dried under reduced pressure, whereby 36.9g of intermediate E was obtained as a white solid. The yield thereof was found to be 56.4 mol%.

Structural use of the target product¹And H-NMR identification.

¹H-NMR(500MHz，CDCl₃，TMS，ppm)：8.00(d，1H，J＝8.5Hz)、7.85(dd，1H、J＝1.0Hz、8.0Hz)、7.78(dd，1H，J＝1.5Hz，7.5Hz)、7.60(dd，1H，J＝1.0Hz，7.5Hz)、7.54-7.51(m，2H)、7.49-7.40(m，3H)、7.28(ddd，1H，J＝1.0Hz，7.5Hz，7.5Hz)、7.07(ddd，1H，J＝1.0Hz，7.5Hz，7.5Hz)、4.16(br，2H)、4.08(t，2H，J＝6.5Hz)、4.06(s，2H)、3.66(t，2H，J＝7.0Hz)、1.63-1.54(m，4H)、1.32-1.22(m，4H)。

And step 3: synthesis of polymerizable Compound 2

26.91g of the mixture 1 synthesized in step 1 of example 3, 183.9g of chloroform and 6.4g of N, N-dimethylformamide were charged into a 3-port reactor equipped with a thermometer under a nitrogen stream, and cooled to 10 ℃ or lower. The reaction temperature was controlled to 10 ℃ or lower, and 6.0g (50.54mmol) of thionyl chloride was added dropwise thereto. After the completion of the dropwise addition, the reaction solution was returned to 25 ℃ and stirred for 1 hour. After the reaction was completed, 138g of chloroform was separated under reduced pressure using a rotary evaporator. Thereafter, 46g of fresh chloroform was added to obtain a chloroform solution (5). In a 3-port reactor equipped with a thermometer, 2.76g (20.0mmol) of 2, 5-dihydroxybenzaldehyde and 12.13g (119.8mmol) of triethylamine were dissolved in 92g of chloroform in a nitrogen stream, and the mixture was cooled to 10 ℃ or lower. The chloroform solution (5) was slowly added dropwise to the reactor while keeping the reactor internal temperature at 10 ℃ or lower. After completion of the dropwise addition, the reaction solution was kept at 10 ℃ or lower for 1 hour to conduct the reaction (step (1)).

After the reaction, the temperature was maintained at 10 ℃ or lower, 725g of a 1.0-equivalent hydrochloric acid aqueous solution was added to the reaction mixture, and the mixture was stirred at 10 ℃ or lower for 30 minutes (step (2)).

Thereafter, 10.38g (23.9mmol) of the intermediate E synthesized in the above step 2 and 0.33g of 2, 6-di-t-butyl-p-cresol were added, and the reaction mixture was heated to 40 ℃ to conduct a reaction for 4 hours (step (3)).

After completion of the reaction, the aqueous layer was separated at 40 ℃ and subjected to a liquid separation operation. To the obtained organic layer was added 0.92g of Rokahelp #479 (manufactured by Mitsui Metal mining Co., Ltd.), and after stirring at 25 ℃ for 30 minutes, it was filtered off with a filter equipped with 0.6g of Rokahelp # 479. The filter was washed with 9.2g of chloroform and combined with the filtrate obtained previously. The chloroform solution was slowly added dropwise to 367.8g of methanol at 25 ℃ to precipitate a solid. After aging for 30 minutes while keeping the current temperature under slow stirring, the precipitated solid was collected by filtration. The obtained solid was dissolved in 147g of chloroform, and 0.92g of Rokahelp #479 (manufactured by Mitsui Metal mining Co., Ltd.) was added thereto, and after stirring at 25 ℃ for 30 minutes, the mixture was filtered off through a filter equipped with 0.6g of Rokahelp # 479. The filter was washed with 36.8g of chloroform and combined with the filtrate obtained previously. The chloroform solution was slowly added dropwise to 184g of methanol at 25 ℃ to precipitate a solid. After aging for 30 minutes while keeping the current temperature under slow stirring, the precipitated solid was collected by filtration. The filtrate was washed with methanol and then dried under vacuum to obtain 22.2g of polymerizable compound 2 as a pale yellow solid. The yield was 82% (based on 2, 5-dihydroxybenzaldehyde).

Structural use of the target product¹And H-NMR identification.

¹H-NMR(500MHz，CDCl₃，TMS，ppm)：7.97(dd，1H，J＝0.5Hz，8.5Hz)、7.80(ddd，1H，J＝0.5Hz，0.5Hz，8.0Hz)、7.73-7.76(m，2H)、7.67-7.71(m，2H)、7.61(s，1H)、7.49(ddd，1H，J＝1.0Hz，6.5Hz，8.5Hz)、7.42(ddd，1H，J＝1.5Hz，7.0Hz，7.0Hz)、7.33-7.39(m，3H)、7.18(ddd，1H，J＝1.0Hz，7.5Hz，8.0Hz)、7.10-7.14(m，2H)、6.95-7.01(m，4H)、6.85-6.90(m，4H)、6.405(dd，1H，J＝1.5Hz，17.5Hz)、6.402(dd，1H，J＝1.5Hz，17.5Hz)、6.127(dd，1H，J＝10.5Hz，17.5Hz)、6.124(dd，1H，J＝10.5Hz，17.5Hz)、5.822(dd，1H，J＝1.5Hz，10.5Hz)、5.819(dd，1H，J＝1.5Hz，10.5Hz)、4.16-4.22(m，6H)、4.08(t，2H，J＝6.5Hz)、4.03(s，2H)、3.95(t，2H，J＝6.5Hz)、3.93(t，2H，J＝6.5Hz)、2.56-2.67(m，4H)、2.28-2.36(m，8H)、1.59-1.83(m，20H)、1.42-1.56(m，8H)、1.24-1.36(m，4H)。

Example 9 Synthesis of polymerizable Compound 2

Step 1: the same operation as in step 1 of example 1 was performed.

Step 2: synthesis of polymerizable Compound 2

18.39g of intermediate A synthesized in step 1 of example 1, 183.9g of chloroform and 6.4g of N, N-dimethylformamide were charged into a 3-port reactor equipped with a thermometer under a nitrogen flow, and cooled to 10 ℃ or lower. The reaction temperature was controlled to 10 ℃ or lower, and 6.0g (50.54mmol) of thionyl chloride was added dropwise thereto. After the completion of the dropwise addition, the reaction solution was returned to 25 ℃ and stirred for 1 hour. After the reaction was completed, 138g of chloroform was separated under reduced pressure using a rotary evaporator. Thereafter, 46g of fresh chloroform was added to obtain a chloroform solution (6). In a 3-port reactor equipped with a thermometer, 2.76g (20.0mmol) of 2, 5-dihydroxybenzaldehyde and 12.84g (119.8mmol) of 2, 6-lutidine were dissolved in 92g of chloroform in a nitrogen stream, and the mixture was cooled to 10 ℃ or lower. The chloroform solution (6) was slowly added dropwise to the reactor while keeping the reactor internal temperature at 10 ℃ or lower. After completion of the dropwise addition, the reaction solution was kept at 10 ℃ or lower for 1 hour to conduct the reaction (step (1)).

After the reaction, the temperature was maintained at 10 ℃ or lower, 725g of a 1.0-equivalent hydrochloric acid aqueous solution was added to the reaction mixture, and the mixture was stirred at 10 ℃ or lower for 30 minutes (step (2)).

Thereafter, 10.38g (23.9mmol) of the intermediate E synthesized in the step 2 of the above example 8 and 0.33g of 2, 6-di-t-butyl-p-cresol were added, and the reaction solution was heated to 40 ℃ to carry out a reaction for 4 hours (step (3)).

After completion of the reaction, the aqueous layer was separated at 40 ℃ and subjected to a liquid separation operation. To the obtained organic layer was added 0.92g of Rokahelp #479 (manufactured by Mitsui Metal mining Co., Ltd.), and after stirring at 25 ℃ for 30 minutes, it was filtered off with a filter equipped with 0.6g of Rokahelp # 479. The filter was washed with 9.2g of chloroform and combined with the filtrate obtained previously. The chloroform solution was slowly added dropwise to 367.8g of methanol at 25 ℃ to precipitate a solid. After aging for 30 minutes while keeping the current temperature under slow stirring, the precipitated solid was collected by filtration. The obtained solid was dissolved in 147g of chloroform, and 0.92g of Rokahelp #479 (manufactured by Mitsui Metal mining Co., Ltd.) was added thereto, and after stirring at 25 ℃ for 30 minutes, the mixture was filtered off through a filter equipped with 0.6g of Rokahelp # 479. The filter was washed with 36.8g of chloroform and combined with the filtrate obtained previously. The chloroform solution was slowly added dropwise to 184g of methanol at 25 ℃ to precipitate a solid. After aging for 30 minutes while keeping the current temperature under slow stirring, the precipitated solid was collected by filtration. The filtrate was washed with methanol and then dried under vacuum to obtain 24.9g of polymerizable compound 2 as a pale yellow solid. The yield was 92% (based on 2, 5-dihydroxybenzaldehyde).

Example 10 Synthesis of polymerizable Compound 2

The same operation as in example 8 was carried out except that 12.13g (119.8mmol) of triethylamine in step 3 of example 8 was changed to 12.84g (119.8mmol) of 2, 6-lutidine. As a result, 24.9g of polymerizable compound 2 was obtained as a pale yellow solid. The yield was 92% (based on 2, 5-dihydroxybenzaldehyde).

Comparative example 11 Synthesis of polymerizable Compound 2

Step 1-3: the same operations as in steps 1 to 3 of example 8 were carried out.

Step 2: synthesis of polymerizable Compound 2

26.91g of the mixture 1 synthesized in step 1 of example 3, 183.9g of chloroform and 6.4g of N, N-dimethylformamide were charged into a 3-port reactor equipped with a thermometer under a nitrogen stream, and cooled to 10 ℃ or lower. The reaction temperature was controlled to 10 ℃ or lower, and 6.0g (50.54mmol) of thionyl chloride was added dropwise thereto. After the completion of the dropwise addition, the reaction solution was returned to 25 ℃ and stirred for 1 hour. After the reaction was completed, 138g of chloroform was separated under reduced pressure using a rotary evaporator. Thereafter, 46g of fresh chloroform was added to obtain a chloroform solution (7). In a 3-port reactor equipped with a thermometer, 2.76g (20.0mmol) of 2, 5-dihydroxybenzaldehyde and 12.13g (119.8mmol) of triethylamine were dissolved in 92g of chloroform in a nitrogen stream, and the mixture was cooled to 10 ℃ or lower. The chloroform solution (7) was slowly added dropwise to the reactor while keeping the reactor internal temperature at 10 ℃ or lower. After completion of the dropwise addition, the reaction solution was kept at 10 ℃ or lower for 1 hour to conduct the reaction (step (1)).

After the reaction was completed, the temperature was maintained at 10 ℃ or lower, 725g of a 1.0 equivalent hydrochloric acid aqueous solution, 10.38g (23.9mmol) of the intermediate E synthesized in step 2, and 0.33g of 2, 6-di-t-butyl-p-cresol were added to the reaction solution, and the reaction solution was heated to 40 ℃ for 4 hours to effect a reaction (step (3)).

After completion of the reaction, the aqueous layer was separated at 40 ℃ and subjected to a liquid separation operation. To the obtained organic layer was added 0.92g of Rokahelp #479 (manufactured by Mitsui Metal mining Co., Ltd.), and after stirring at 25 ℃ for 30 minutes, it was filtered off with a filter equipped with 0.6g of Rokahelp # 479. The filter was washed with 9.2g of chloroform and combined with the filtrate obtained previously. The chloroform solution was slowly added dropwise to 367.8g of methanol at 25 ℃ to precipitate a solid. After aging for 30 minutes while keeping the current temperature under slow stirring, the precipitated solid was collected by filtration. The obtained solid was dissolved in 147g of chloroform, and 0.92g of Rokahelp #479 (manufactured by Mitsui Metal mining Co., Ltd.) was added thereto, and after stirring at 25 ℃ for 30 minutes, the mixture was filtered off through a filter equipped with 0.6g of Rokahelp # 479. The filter was washed with 36.8g of chloroform and combined with the filtrate obtained previously. The chloroform solution was slowly added dropwise to 184g of methanol at 25 ℃ to precipitate a solid. After aging for 30 minutes while keeping the current temperature under slow stirring, the precipitated solid was collected by filtration. The filtrate was washed with methanol and then dried under vacuum to obtain 18.69g of polymerizable compound 2 as a pale yellow solid. The yield was 69% (based on 2, 5-dihydroxybenzaldehyde).

Comparative example 12 Synthesis of polymerizable Compound 2

Step 1: the same operation as in step 1 of example 1 was performed.

Step 2: synthesis of polymerizable Compound 2

18.39g of intermediate A synthesized in step 1 of example 1, 183.9g of chloroform and 6.4g of N, N-dimethylformamide were charged into a 3-port reactor equipped with a thermometer under a nitrogen flow, and cooled to 10 ℃ or lower. The reaction temperature was controlled to 10 ℃ or lower, and 6.0g (50.54mmol) of thionyl chloride was added dropwise thereto. After the completion of the dropwise addition, the reaction solution was returned to 25 ℃ and stirred for 1 hour. After the reaction was completed, 138g of chloroform was separated under reduced pressure using a rotary evaporator. Thereafter, 46g of fresh chloroform was added to obtain a chloroform solution (8). In a 3-port reactor equipped with a thermometer, 2.76g (20.0mmol) of 2, 5-dihydroxybenzaldehyde and 12.84g (119.8mmol) of 2, 6-lutidine were dissolved in 92g of chloroform in a nitrogen stream, and the mixture was cooled to 10 ℃ or lower. The chloroform solution (8) was slowly added dropwise to the reactor while keeping the reactor internal temperature at 10 ℃ or lower. After completion of the dropwise addition, the reaction solution was kept at 10 ℃ or lower for 1 hour to conduct the reaction (step (1)).

After the reaction was completed, the temperature was maintained at 10 ℃ or lower, 725g of a 1.0 equivalent hydrochloric acid aqueous solution, 10.38g (23.9mmol) of the intermediate E synthesized in step 2 of example 8 and 0.33g of 2, 6-di-t-butyl-p-cresol were added to the reaction mixture, and the reaction mixture was heated to 40 ℃ to conduct the reaction for 4 hours (step (3)).

After completion of the reaction, the aqueous layer was separated at 40 ℃ and subjected to a liquid separation operation. To the obtained organic layer was added 0.92g of Rokahelp #479 (manufactured by Mitsui Metal mining Co., Ltd.), and after stirring at 25 ℃ for 30 minutes, it was filtered off with a filter equipped with 0.6g of Rokahelp # 479. The filter was washed with 9.2g of chloroform and combined with the filtrate obtained previously. The chloroform solution was slowly added dropwise to 367.8g of methanol at 25 ℃ to precipitate a solid. After aging for 30 minutes while keeping the current temperature under slow stirring, the precipitated solid was collected by filtration. The obtained solid was dissolved in 147g of chloroform, and 0.92g of Rokahelp #479 (manufactured by Mitsui Metal mining Co., Ltd.) was added thereto, and after stirring at 25 ℃ for 30 minutes, the mixture was filtered off through a filter equipped with 0.6g of Rokahelp # 479. The filter was washed with 36.8g of chloroform and combined with the filtrate obtained previously. The chloroform solution was slowly added dropwise to 184g of methanol at 25 ℃ to precipitate a solid. After aging for 30 minutes while keeping the current temperature under slow stirring, the precipitated solid was collected by filtration. The filtrate was washed with methanol and then dried under vacuum to obtain 21.13g of polymerizable compound 2 as a pale yellow solid. The yield was 78% (based on 2, 5-dihydroxybenzaldehyde).

Comparative example 13 Synthesis of polymerizable Compound 2

The same operation as in example 11 was carried out, except that 12.13g (119.8mmol) of triethylamine was changed to 12.84g (119.8mmol) of 2, 6-lutidine in step 3 of comparative example 11. As a result, 20.32g of the polymerizable compound 2 was obtained as a pale yellow solid. The yield was 75% (based on 2, 5-dihydroxybenzaldehyde).

The results of examples 8 to 10 and comparative examples 11 to 13 are summarized in Table 2.

[ Table 2]

Example 11 Synthesis of polymerizable Compound 1

Step 1: synthesis of intermediate F

[ chemical formula 33]

The synthesis was carried out by referring to International publication No. 2017/150622.

Step 2: synthesis of mixture 2

[ chemical formula 34]

The synthesis was carried out as follows by applying the method described in International publication No. 2016/159193.

83.05g (0.397mol) of trans-1, 4-cyclohexanedicarboxylic acid dichloride, 600g of cyclopentylmethyl ether and 230g of tetrahydrofuran are introduced into a 3-port reactor with a thermometer in a nitrogen stream. 100.0g (0.378mol) of intermediate F synthesized in the above step 1 was added thereto, and the reactor was immersed in an ice bath to adjust the internal temperature of the reaction solution to 0 ℃. Then, 40.20g (0.397mol) of triethylamine was slowly added dropwise over 30 minutes while keeping the internal temperature of the reaction solution at 10 ℃ or lower. After completion of the dropwise addition, the entire contents were further stirred at 10 ℃ or lower for 1 hour. To the obtained reaction solution was added 250g of distilled water, and after washing at 50 ℃ for 2 hours, the aqueous layer was separated. 250g of fresh distilled water was added and washing was further carried out at 50 ℃ for 2 hours. This operation was performed 3 times in total. After washing at 40 ℃ for 30 minutes with a further 416g of a 1mol/l buffer solution (pH: 5.5) composed of acetic acid and sodium acetate, the buffer solution was separated. After washing at 40 ℃ for 30 minutes using 416g of a new 1mol/l buffer solution (pH: 5.5) of acetic acid and sodium acetate, the buffer solution was separated. This operation was performed 5 times in total. Further, 250g of distilled water was added to the obtained organic layer, and after washing at 40 ℃ for 30 minutes, the aqueous layer was separated. 1300g of n-hexane was added dropwise to the obtained organic layer over 1 hour at 40 ℃. Thereafter, the mixture was cooled to 0 ℃ and stirred for further 1 hour to precipitate a solid, and the precipitated solid was collected by filtration. The filtrate was washed with n-hexane and then dried under vacuum to obtain 142.0g of a white solid. The crystals obtained were analyzed by HPLC, and the amount of intermediate a was determined from a calibration curve, which revealed that the intermediate a contained 68.5 mass%. In addition, use¹³C-NMR

Alkane-d 8) the crystals obtained were analyzed to calculate the content of cyclohexanedicarboxylic acid, and the crystals were crystallizedThe fruit is below the detection limit.

And step 3: synthesis of polymerizable Compound 1

43.8g (30 g (71.7mmol) of the intermediate A) of the mixture 2 composed mainly of the intermediate A synthesized in the above step 2, 300g of chloroform and 10.5g (143.4mmol) of N, N-dimethylformamide were charged into a 3-port reactor equipped with a thermometer under a nitrogen flow, and cooled to 10 ℃ or lower. 9.81g (82.44mmol) of thionyl chloride was added dropwise thereto while keeping the reaction temperature at 10 ℃ or lower. After the completion of the dropwise addition, the reaction solution was returned to 25 ℃ and stirred for 1 hour. After completion of the reaction, 225g of chloroform was separated by a rotary evaporator and concentrated. Thereafter, 75g of fresh chloroform was added to obtain a chloroform solution of the acid chloride of intermediate A. In a 3-port reactor separately provided with a thermometer, 4.5g (32.58mmol) of 2, 5-dihydroxybenzaldehyde and 19.78g (195.5mmol) of triethylamine were dissolved in 150g of chloroform under a nitrogen flow, and the resulting solution was cooled to 10 ℃ or lower. The entire amount of the chloroform solution of the acid chloride of the previously synthesized intermediate a was slowly added dropwise to the solution while keeping the reaction temperature at 10 ℃ or lower. After completion of the dropwise addition, the entire contents were further stirred at 5 to 10 ℃ for 1 hour (step (1)).

After the reaction, 120g of a 1.0N aqueous hydrochloric acid solution was added to the reaction mixture while keeping the temperature at 10 ℃ or lower. Thereafter, the reaction mixture was stirred at 10 ℃ or lower for 30 minutes to effect a reaction (step (2)).

Thereafter, 10.58g (42.4mmol) of the intermediate B synthesized in step 2 of the above example 1 and 0.3g of 2, 6-di-t-butyl-p-cresol were added. Thereafter, the reaction solution was heated to 40 ℃ to carry out a reaction for 4 hours (step (3)).

After the reaction was completed, the aqueous layer was separated. Further, 105g of distilled water was put into the organic layer, and the mixture was stirred at 40 ℃ for 30 minutes to clean the organic layer. After separating the aqueous layer, the organic layer was cooled to 25 ℃ and 1.5g of Rokahelp #479 was added and stirred for 30 minutes. Thereafter, Rokahelp #479 was removed by filtration using a Tung mountain funnel paved with 1g of Rokahelp # 479. From the obtained organic layer, 180g of chloroform was separated by a rotary evaporator and concentrated. To the obtained organic layer was added 210g of hexane over 1 hour to precipitate a solid, which was then filtered to obtain a pale yellow solid. The resulting pale yellow solid was dissolved in 120g of tetrahydrofuran at 25 ℃ and 1.5g of Rokahelp #479 was added thereto and stirred for 30 minutes. Thereafter, Rokahelp #479 was removed by filtration using a Tung mountain funnel paved with 1g of Rokahelp # 479. To the obtained organic layer, 165g of methanol was slowly dropped at 15 ℃ to precipitate a solid, which was then filtered to obtain a solid. The obtained solid was dried by a vacuum dryer to obtain 35.1g of polymerizable compound 1 as a pale yellow solid. The yield was 92.0% (based on 2, 5-dihydroxybenzaldehyde).

Example 12 Synthesis of polymerizable Compound 1

Step 1: synthesis of intermediate G

The synthesis was carried out as follows using the method described in International publication No. 16/159193.

83.05g (0.397mol) of trans-1, 4-cyclohexanedicarboxylic acid dichloride, 600g of cyclopentylmethyl ether and 230g of tetrahydrofuran are introduced into a 3-port reactor with a thermometer in a nitrogen stream. 100.0g (0.378mol) of intermediate F synthesized in step 1 of example 11 above was added thereto, and the reactor was immersed in an ice bath to adjust the internal temperature of the reaction solution to 0 ℃. Then, 40.20g (0.397mol) of triethylamine was slowly added dropwise over 30 minutes while keeping the internal temperature of the reaction solution at 10 ℃ or lower. After completion of the dropwise addition, the entire contents were further stirred at 10 ℃ or lower for 1 hour. To the resulting reaction solution was added 250g of distilled water, and the mixture was washed at 50 ℃ for 2 hours, followed by separation of the aqueous layer. 250g of fresh distilled water was added and further washed at 50 ℃ for 2 hours. This operation was performed 3 times in total. After the organic layer was further washed at 40 ℃ for 30 minutes using 416g of a 1 mol/liter buffer solution (pH: 5.5) composed of acetic acid and sodium acetate, the buffer solution was separated. The organic layer was washed at 40 ℃ for 30 minutes using 416g of a new 1 mol/liter buffer solution (pH: 5.5) composed of acetic acid and sodium acetate, and the buffer solution was separated. This operation was performed 5 times in total. Further, 250g of distilled water was added to the obtained organic layer, and the mixture was washed at 40 ℃ for 30 minutes. The organic layer obtained by separating the aqueous layer was slowly cooled to 0 ℃ while stirring, and stirred at 0 ℃ for 1 hourAfter that, the precipitated solid was filtered off. 1400g of n-hexane was added dropwise to the filtrate over 1 hour. Thereafter, the mixture was stirred at 0 ℃ for 1 hour to precipitate a solid, and the precipitated solid was collected by filtration. After the filtrate was washed with n-hexane, it was vacuum-dried to obtain 105.7g of a white solid. The crystals obtained were analyzed by HPLC, and the amount of intermediate G was determined from the calibration curve, which revealed that the intermediate a contained 91.3 mass%. In addition, use¹³C-NMR

Alkane-d 8) the obtained crystals were analyzed to calculate the content of cyclohexanedicarboxylic acid, and the results were below the detection limit.

Step 2: synthesis of polymerizable Compound 1

The same operation as in example 11 was carried out except that 43.8G (30G (71.7mmol) of the mixture 2 mainly composed of the intermediate a synthesized in step 2 of example 11 was changed to 32.9G (30G (71.7mmol) of the intermediate a) of the intermediate G synthesized in step 1 in step 3 of example 11. As a result, 35.0g of polymerizable compound 1 was obtained as a pale yellow solid. The yield was 91.8% (based on 2, 5-dihydroxybenzaldehyde).

Example 13 Synthesis of polymerizable Compound 1

Step 1: synthesis of intermediate H

83.05g (0.397mol) of trans-1, 4-cyclohexanedicarboxylic acid dichloride and 830g of cyclopentylmethyl ether (CPME) are introduced into a 3-port reactor with a thermometer in a nitrogen stream. 100g (0.378mol) of intermediate F synthesized in step 1 of example 11 and 1.67g of 2, 6-di-t-butyl-p-cresol were added thereto, and the reactor was immersed in an ice bath to adjust the internal temperature of the reaction solution to 0 ℃. Then, 40.2g (0.397mol) of triethylamine was slowly added dropwise over 20 minutes while keeping the internal temperature of the reaction solution at 10 ℃ or lower. After the completion of the dropwise addition, the mixture was stirred at 10 ℃ or lower for 1 hour. 250g of distilled water was added to the obtained reaction solution at 10 ℃ or lower, and the mixture was heated to 50 ℃. Thereafter, the plate was washed at 50 ℃ for 2 hours. Separating the aqueous layer, adding 250g of fresh distilled water at 50 deg.CAnd cleaning for 2 hours. This operation was performed 3 times in total. The obtained organic layer was cooled to 40 ℃, then 200g of methanol was added, slowly cooled to 0 ℃, and slowly stirred for 1 hour, thereby precipitating a solid. The precipitated solid was removed by filtration to obtain a filtrate. The filtrate in the filter was washed with 100g of methanol prepared separately and cooled to 0 ℃, and the washing liquid obtained by the washing was combined with the previous filtrate. The filtrate combined with the washing solution was further stirred at 40 ℃ for 30 minutes using 416g of a 1 mol/liter buffer solution (pH5.5) composed of acetic acid and sodium acetate to wash. After washing, the mixture was separated into liquid and aqueous layer, 416g of a 1mol/L buffer solution (pH5.5) composed of acetic acid and sodium acetate was added again, and the mixture was stirred at 40 ℃ for 30 minutes. This operation was performed 5 times in total, liquid separation was performed, an aqueous layer was separated, 250g of distilled water was added to the obtained organic layer (oil layer), and washing was performed at 40 ℃ for 30 minutes. This operation was performed 2 times in total, liquid separation was performed, 1200g of n-hexane was added to the obtained organic layer, and the mixture was slowly cooled to 0 ℃ to precipitate a solid, and the precipitated solid was collected by filtration. After the filtrate was washed with n-hexane, it was dried under vacuum to obtain 98.55g of a white solid as intermediate H. The obtained white solid was quantitatively analyzed by high performance liquid chromatography, and as a result, the content of intermediate a in the white solid was 92.6% by mass. In addition, use¹³C-NMR

Alkane-d 8) the obtained crystals were analyzed to calculate the content of cyclohexanedicarboxylic acid, and the results were below the detection limit.

Step 2: synthesis of polymerizable Compound 1

The same operation as in example 11 was carried out except that 43.8g (30 g (71.7mmol) of the mixture 2 composed mainly of the intermediate a synthesized in step 2 of example 11 was changed to 32.4g (30 g (71.7mmol) of the intermediate a) of the intermediate H synthesized in step 1 in step 3 of example 11. As a result, 35.7g of polymerizable compound 1 was obtained as a pale yellow solid. The yield was 93.6% (based on 2, 5-dihydroxybenzaldehyde).

Example 14 Synthesis of polymerizable Compound 1

The same operation as in example 11 was carried out except that 17.46g (163.0mmol) of 2, 6-lutidine and 43.8mg (0.36mmol) of N, N-dimethyl-4-aminopyridine (DMAP) were used in combination instead of 19.78g (195.5mmol) of triethylamine in step 3 of example 11. As a result, 34.9g of the polymerizable compound 1 was obtained as a pale yellow solid. The yield was 91.5% (based on 2, 5-dihydroxybenzaldehyde).

Example 15 Synthesis of polymerizable Compound 1

The same operations as in example 11 were carried out except that in step 3 of example 11, 32.9G (30G (71.7mmol) of intermediate A as the main component in intermediate A-containing mixture 2 synthesized in step 2 of example 11 was changed to 32.9G (30G (71.7mmol) of intermediate A) of intermediate G synthesized in step 1 of example 12, and that 17.46G (163.0mmol) of 2, 6-lutidine and 43.8mg (0.36mmol) of N, N-dimethyl-4-aminopyridine were used in combination with 19.78G (195.5mmol) of triethylamine. As a result, 35.2g of polymerizable compound 1 was obtained as a pale yellow solid. The yield was 92.3% (based on 2, 5-dihydroxybenzaldehyde).

Example 16 Synthesis of polymerizable Compound 1

The same operations as in example 11 were carried out except that in step 3 of example 11, 32.4g (30 g (71.7mmol) of intermediate A as the main component in intermediate A-containing mixture 2 synthesized in step 2 of example 11 was changed to 32.4g (30 g (71.7mmol) of intermediate A) of intermediate H synthesized in step 1 of example 13, and that 17.46g (163.0mmol) of 2, 6-lutidine and 43.8mg (0.36mmol) of N, N-dimethyl-4-aminopyridine were used in combination with 19.78g (195.5mmol) of triethylamine. As a result, 35.8g of the polymerizable compound 1 was obtained as a pale yellow solid. The yield was 93.9% (based on 2, 5-dihydroxybenzaldehyde).

Example 17 Synthesis of polymerizable Compound 1

The same operation as in example 11 was carried out except that 9.81g (82.44mmol) of thionyl chloride was changed to 8.79g (73.85mmol) of thionyl chloride and 19.78g (195.5mmol) of triethylamine was changed to a combination of 17.46g (163.0mmol) of 2, 6-lutidine and 43.8mg (0.36mmol) of N, N-dimethyl-4-aminopyridine in step 3 of example 11. As a result, 35.5g of polymerizable compound 1 was obtained as a pale yellow solid. The yield was 93.1% (based on 2, 5-dihydroxybenzaldehyde).

Example 18 Synthesis of polymerizable Compound 1

The same operations as in example 11 were carried out in step 3 of example 11 except that, in step 1 of example 12, 43.8G (30G (71.7mmol) of the mixture 2 composed mainly of the intermediate A synthesized in step 2 of example 11 was changed to 32.9G (30G (71.7mmol) of the intermediate A) of the intermediate G synthesized in step 1 of example 11, 9.81G (82.44mmol) of thionyl chloride was changed to 8.79G (73.85mmol) of thionyl chloride, and 19.78G (195.5mmol) of triethylamine was changed to 17.46G (163.0mmol) of 2, 6-lutidine and 43.8mg (0.36mmol) of N, N-dimethyl-4-aminopyridine. As a result, 35.6g of polymerizable compound 1 was obtained as a pale yellow solid. The yield was 93.4% (based on 2, 5-dihydroxybenzaldehyde).

Example 19 Synthesis of polymerizable Compound 1

The same operations as in example 11 were carried out in step 3 of example 11 except that 43.8g (30 g (71.7mmol) of the mixture 2 composed mainly of the intermediate A synthesized in step 2 of example 11 was changed to 32.4g (30 g (71.7mmol) of the intermediate A) of the intermediate H synthesized in step 1 of example 13, 9.81g (82.44mmol) of thionyl chloride was changed to 8.79g (73.85mmol) of thionyl chloride, and 19.78g (195.5mmol) of triethylamine was changed to 17.46g (163.0mmol) of 2, 6-lutidine and 43.8mg (0.36mmol) of N, N-dimethyl-4-aminopyridine. As a result, 36.0g of polymerizable compound 1 was obtained as a pale yellow solid. The yield was 94.4% (based on 2, 5-dihydroxybenzaldehyde).

Example 20 Synthesis of polymerizable Compound 1

Step 1: synthesis of intermediate I

In step 1 of example 13, 1200g of n-hexane was changed to 1200g of n-heptane, and the n-hexane of the filtrate was washedThe same operation as in example 13 was carried out except for changing the reaction solution to n-heptane, to obtain 97.40g of a white solid as intermediate I. The obtained white solid was quantified by high performance liquid chromatography, and the content of intermediate a in the white solid was 94.7% by mass. In addition, use¹³C-NMR

Alkane-d 8) the obtained crystals were analyzed to calculate the content of cyclohexanedicarboxylic acid, and the results were below the detection limit.

Step 2: synthesis of Compound 1

The same operation as in example 11 was carried out except that in step 3 of example 11, 43.8g (30 g (71.7mmol) of the mixture 2 composed mainly of the intermediate a synthesized in step 2 of example 11 was changed to 31.7g (30 g (71.7mmol) of the intermediate a) of the intermediate I synthesized in step 1, 9.81g (82.44mmol) of thionyl chloride was changed to 8.79g (73.85mmol) of thionyl chloride, and 19.78g (195.5mmol) of triethylamine was changed to 17.46g (163.0mmol) of 2, 6-lutidine and 43.8mg (0.36mmol) of N, N-dimethyl-4-aminopyridine. As a result, 36.1g of polymerizable compound 1 was obtained as a pale yellow solid. The yield was 94.7% (based on 2, 5-dihydroxybenzaldehyde).

Example 21 Synthesis of polymerizable Compound 1

The same operation as in example 11 was carried out except that in step 3 of example 11, 43.8g (30 g (71.7mmol) of the mixture 2 composed mainly of the intermediate a synthesized in step 2 of example 11) was changed to 31.7g (30 g (71.7mmol) of the intermediate a) of the intermediate I synthesized in step 1 of example 20, 9.81g (82.44mmol) of thionyl chloride was changed to 8.79g (73.85mmol) of thionyl chloride, 19.78g (195.5mmol) of triethylamine was changed to 17.46g (163.0mmol) of 2, 6-lutidine and 43.8mg (0.36mmol) of N, N-dimethyl-4-aminopyridine, and 210g of hexane used for precipitating a solid was changed to 210g of heptane. As a result, 36.0g of polymerizable compound 1 was obtained as a pale yellow solid. The yield was 94.4% (based on 2, 5-dihydroxybenzaldehyde).

The results of examples 11 to 21 are summarized in Table 3.

[ Table 3]

Industrial applicability

According to the production method of the present invention, the polymerizable compound represented by the formula (a) can be obtained in high yield, which is useful for producing optical films and the like.

Claims (9)

1. A method for producing a polymerizable compound, comprising the steps of:

a step (1) in which a compound represented by the following formula (I) and a compound represented by the following formula (II) are esterified in an organic solvent in the presence of a base and/or a dehydration condensation agent to obtain a reaction solution containing a compound represented by the following formula (III);

in the formula (I), Q represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, Fg¹And Fg²Each independently represents a hydroxyl group, -CH₂OH or-CH₂CH₂OH，

In the formula (II), A represents a hydrogen atom, a methyl group or a chlorine atom, L represents a hydroxyl group or a leaving group, n represents any integer of 1 to 20,

in the formula (III), Y¹And Y²Each independently of the otherAnd represents-C (═ O) -O-, -O-C (═ O) -, -CH₂-O-C(＝O)-、-C(＝O)-O-CH₂-、-CH₂-CH₂-O-C (═ O) -or-C (═ O) -O-CH₂-CH₂-, Q, A and n are as defined above,

a step (2) of hydrolyzing the compound represented by the formula (II) or the dehydration condensation agent contained in the reaction solution obtained in the step (1); and

a step (3) of adding a compound represented by the following formula (IV) after the step (2) and reacting the compound with a compound represented by the formula (III),

in the formula (IV), X represents an oxygen atom, a sulfur atom, -C (R)¹)(R²) -or-N-R¹-, where R¹And R²Each independently represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms which may have a substituent, R represents a hydrogen atom or an organic group having 1 to 60 carbon atoms which may have a substituent, R represents^XRepresents a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, a cyano group, a nitro group, an alkyl group having 1 to 6 carbon atoms in which at least 1 hydrogen atom is substituted by a halogen atom, an alkoxy group having 1 to 6 carbon atoms, an alkylthio group having 1 to 6 carbon atoms, a mono-substituted amino group, a di-substituted amino group, or a-OCF group₃、-C(＝O)-O-R³or-O-C (═ O) -R³Where R is³Is represented by the formula¹、R²Same meaning, a plurality of R^XMay or may not be identical to each other, and may form an arbitrary C-R ring^XCan be substituted by a nitrogen atom, and,

the polymerizable compound is represented by the following formula (A),

in the formula (A), Y¹、Y²、A、R、R^XX, Q and n are as defined above.

2. The method for producing a polymerizable compound according to claim 1, wherein in the step (2), water or an aqueous solution is added to the reaction solution to carry out the hydrolysis.

3. The method for producing a polymerizable compound according to claim 2, wherein an acidic aqueous solution is added to the reaction solution in the step (2).

4. The method for producing a polymerizable compound according to claim 3, wherein an acid component of the acidic aqueous solution is an inorganic acid and/or an organic acid having 1 to 20 carbon atoms.

5. The method for producing a polymerizable compound according to claim 3 or 4, wherein the acid component of the acidic aqueous solution is at least one selected from the group consisting of hydrochloric acid, sulfuric acid, phosphoric acid, boric acid, sulfonic acids, sulfinic acids, formic acid, acetic acid, oxalic acid, citric acid, ascorbic acid, tartaric acid, and malic acid.

6. The method for producing a polymerizable compound according to any one of claims 1 to 5, wherein R represents an alkyl group having 1 to 60 carbon atoms which may have a substituent, an alkenyl group having 2 to 60 carbon atoms which may have a substituent, an alkynyl group having 2 to 60 carbon atoms which may have a substituent, an aromatic hydrocarbon ring group having 6 to 18 carbon atoms which may have a substituent, an aromatic heterocyclic group having 2 to 18 carbon atoms which may have a substituent, or Ra-Y-G-,

in the formula Ra-Y-G-, Ra represents a cyclic group having at least one of an aromatic hydrocarbon ring and an aromatic heterocyclic ring, and Y represents a single chemical bond, -O-, -S-, -C (═ O) -, -O-C (rb) (rc) -, -C (rb) (rc) -O-, -O-CH₂-CH₂-、-CH₂-CH₂-O-、-C(＝O)-O-、-O-C(＝O)-、-C(＝O)-S-、-S-C(＝O)-、-NR⁴-C(＝O)-、-C(＝O)-NR⁴-、-CH＝CH-C(＝O)-O-、-O-C(＝O)-CH＝CH-、-CH₂-CH₂-C(＝O)-O-、-O-C(＝O)-CH₂-CH₂-、-CH₂-CH₂-O-C(＝O)-、-C(＝O)-O-CH₂-CH₂-、-C(＝O)-O-C(Rb)(Rc)-、-C(Rb)(Rc)-O-C(＝O)-、-O-C(＝O)-C(Rb)(Rc)-、-C(Rb)(Rc)-C(＝O)-O-、-O-C(＝O)-NR⁴-、-NR⁴-C(＝O)-O-、-O-C(＝O)-CH₂-S-、-S-CH₂-C (═ O) -O-or-O-C (═ O) -O-, where R is⁴Represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, Rc and Rb each independently represents a hydrogen atom, an optionally substituted aromatic hydrocarbon ring group having 6 to 18 carbon atoms or an optionally substituted aromatic heterocyclic group having 2 to 18 carbon atoms, and G is at least one-CH group contained in (i) an aliphatic hydrocarbon group having 2 carbon atoms and (ii) an aliphatic hydrocarbon group having 2 carbon atoms and having 2 carbon atoms₂-by-O-, -S-, -O-C (═ O) -, -C (═ O) -O-, -O-C (═ O) -O-, -NR⁵-C(＝O)-、-C(＝O)-NR⁵-、-NR⁵Any one organic group of an-or-C (═ O) -substituted group, wherein each of-O-or-S-is present adjacent to 2 or more, except where R is present⁵Represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.

7. The method for producing a polymerizable compound according to any one of claims 1 to 6, wherein R is^XAll are hydrogen atoms.

8. The method for producing a polymerizable compound according to any one of claims 1 to 7, wherein an acidic aqueous solution is further added to the step (3) to perform a reaction.

9. The method for producing a polymerizable compound according to any one of claims 1 to 8, wherein the compound represented by the formula (II) is a compound represented by the following formula (IIa),

in the formula (IIa), A, L and n represent the same meanings as described above.