CN112166108B - Method for producing polymerizable compound - Google Patents

Method for producing polymerizable compound Download PDF

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CN112166108B
CN112166108B CN201980033257.8A CN201980033257A CN112166108B CN 112166108 B CN112166108 B CN 112166108B CN 201980033257 A CN201980033257 A CN 201980033257A CN 112166108 B CN112166108 B CN 112166108B
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substituent
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reaction
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CN112166108A (en
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奥山久美
坂本圭
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Zeon Corp
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Zeon Corp
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D277/00—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings
    • C07D277/60—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings condensed with carbocyclic rings or ring systems
    • C07D277/62—Benzothiazoles
    • C07D277/68—Benzothiazoles with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached in position 2
    • C07D277/82—Nitrogen atoms
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F20/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
    • C08F20/02—Monocarboxylic acids having less than ten carbon atoms, Derivatives thereof
    • C08F20/10—Esters
    • C08F20/26—Esters containing oxygen in addition to the carboxy oxygen
    • C08F20/30—Esters containing oxygen in addition to the carboxy oxygen containing aromatic rings in the alcohol moiety

Abstract

The method for producing a polymerizable compound of the present invention comprises the following steps: a step (1) of reacting a compound represented by formula (I) with a compound represented by formula (II) in an organic solvent in the presence of a base and/or a dehydration condensing agent to obtain a reaction solution containing a compound represented by formula (III); a step (2) of hydrolyzing a compound represented by the formula (II) or a dehydration condensing agent contained in the reaction solution; and (3) adding the compound represented by the formula (IV) to react with the compound represented by the formula (III). Wherein Q represents a hydrogen atom or the like, fg 1 、Fg 2 Represents 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 1 、Y 2 represents-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, R X Represents 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 a high yield.
Background
In recent years, as a technique capable of thinning a phase difference plate, particularly a phase difference plate having inverse wavelength dispersion, a method of producing a phase difference 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 practically low melting point and high solubility in a general-purpose solvent and which 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 is each independently a hydrogen atom, a methyl group or a chlorine atom, R is a hydrogen atom or an organic group having 1 to 60 carbon atoms which may have a substituent, X is an oxygen atom, a sulfur atom or a-C (R) 1 )(R 2 ) -or-N-R 1 Where R is 1 And R is 2 Each independently represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms which may have a substituent, R X Represents 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 with a halogen atom, an alkoxy group having 1 to 6 carbon atoms, an alkylthio group having 1 to 6 carbon atoms, a monosubstituted amino group, a disubstituted amino group, -OCF 3 、-C(＝O)-O-R 3 or-O-C (=o) -R 3 Here, R is 3 Representing R as described above 1 、R 2 Identical meaning, a plurality of R X All of which may be the same or different from each other, and any of C-R constituting a ring X Can be substituted by nitrogen atoms, n represents any integer from 1 to 20. )
In patent document 1, as a method for producing a polymerizable compound represented by the above formula (α) in high purity and good yield, the following method has been proposed: in an organic solvent, the following formula (II):
[ chemical formula 2]
(wherein A and n have the same meanings as defined above, and L represents a leaving group.)
The represented compound is reacted with 2, 5-dihydroxybenzaldehyde in the presence of a base (esterification reaction) to give 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) below was added to the obtained reaction solution:
[ chemical formula 4]
(wherein, X, R and R X The same meaning as described above is indicated. )
The compound represented by the formula (a) and an acidic aqueous solution are prepared by dissolving an ester produced by an esterification reaction in the acidic aqueous solution, and synthesizing a polymerizable compound represented by the formula (a).
Prior art literature
Patent literature
Patent document 1: international publication No. 2015/141784.
Disclosure of Invention
Problems to be solved by the invention
However, in the above conventional method for producing a polymerizable compound by adding a compound represented by the formula (IV) and an acidic aqueous solution at the same time, 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 that can be used for producing an optical film or the like in a high yield.
Solution for solving the problem
The present inventors have conducted intensive studies to solve the above problems, and as a result, have found that a polymerizable compound represented by the following formula (a) can be obtained in 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 condensing agent to obtain a reaction solution containing the compound represented by the following formula (III), hydrolyzing a predetermined component 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).
Thus, according to the present invention, the following <1> to <9> can be provided.
<1> a method for producing a polymerizable compound, comprising the steps of:
step (1) of esterifying 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 condensing 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 1 And Fg 2 Each independently represents hydroxy, -CH 2 OH or-CH 2 CH 2 OH。)
[ 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 any integer of 1 to 20.)
[ chemical formula 7]
(wherein Y is 1 And Y 2 Each independently represents-C (=O) -O-, -O-C (=O) -, -CH 2 -O-C(＝O)-、-C(＝O)-O-CH 2 -、-CH 2 -CH 2 -O-C (=o) -or-C (=o) -O-CH 2 -CH 2 -, Q, A and n represent the same meanings as described above. )
A step (2) of hydrolyzing the compound represented by the formula (II) or the dehydration condensing agent contained in the reaction solution obtained in the step (1); and
and (3) adding a compound represented by the following formula (IV) to react with the compound represented by the following formula (III) after the step (2).
[ chemical formula 8]
(wherein X represents an oxygen atom, a sulfur atom, -C (R) 1 )(R 2 ) -or-N-R 1 Where R is 1 And R is 2 Each 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 X Represents 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 with a halogen atom, an alkoxy group having 1 to 6 carbon atoms, an alkylthio group having 1 to 6 carbon atoms, a monosubstituted amino group, a disubstituted amino group, -OCF 3 、-C(＝O)-O-R 3 or-O-C (=o) -R 3 Here, R is 3 Representing R as described above 1 、R 2 Identical meaning, a plurality of R X All of which may be the same or different from each other, and any of C-R constituting a ring X Can be substituted with nitrogen atoms. )
The polymerizable compound is represented by the following formula (a).
[ chemical formula 9]
(wherein Y is 1 、Y 2 、A、R、R X X, 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 perform the hydrolysis.
<3> the method for producing a polymerizable compound according to <2>, wherein an acidic aqueous solution is added to the reaction solution in the step (2).
<4> the process 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 process for producing a polymerizable compound according to <3> or <4>, wherein the acid component of the acidic aqueous solution is at least one acid 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, wherein R is 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 bond, -O-, -S-, -C (=O) -, -O-C (Rb) (Rc) -, -C (Rb) (Rc) -O-, -O-CH) 2 -CH 2 -、-CH 2 -CH 2 -O-、-C(＝O)-O-、-O-C(＝O)-、-C(＝O)-S-、-S-C(＝O)-、-NR 4 -C(＝O)-、-C(＝O)-NR 4 -、-CH＝CH-C(＝O)-O-、-O-C(＝O)-CH＝CH-、-CH 2 -CH 2 -C(＝O)-O-、-O-C(＝O)-CH 2 -CH 2 -、-CH 2 -CH 2 -O-C(＝O)-、-C(＝O)-O-CH 2 -CH 2 -、-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)-NR 4 -、-NR 4 -C(＝O)-O-、-O-C(＝O)-CH 2 -S-、-S-CH 2 -C (=o) -O-or-O-C (=o) -O-, where R 4 And each of Rc and Rb independently represents at least one of a hydrogen atom, an aromatic hydrocarbon ring group having 6 to 18 carbon atoms which may have a substituent, or an aromatic heterocyclic group having 2 to 18 carbon atoms which may have a substituent, G is-CH which is at least one of (i) an aliphatic hydrocarbon group having 1 to 20 carbon atoms and (ii) an aliphatic hydrocarbon group having 3 to 20 carbon atoms and having 2 carbon atoms 2 -is surrounded by-O-, -S-, -O-C (=o) -, -C (=o) -O-, -O-C (=o) -O-, -NR 5 -C(＝O)-、-C(＝O)-NR 5 -、-NR 5 -or-C (=o) -substituted group (except in case of more than 2 adjacent-O-or-S-each), where R 5 Represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. ).
<7>According to<1>～<6>The method for producing a polymerizable compound according to any one of the above, wherein R is X All hydrogen atoms.
<8> the process 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 carry out a reaction.
<9> the process for producing a polymerizable compound according to any one of <1> to <8>, wherein the compound represented by the above 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 above formula (a) which can be used for producing an optical film or the like can be obtained in a high yield.
Detailed Description
The present invention is described in detail below. In the present invention, "optionally substituted" means "unsubstituted or substituted". In the case where 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 substituent is not included in 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 the aromatic hydrocarbon ring group having 6 to 18 carbon atoms does not include such a substituent. On the other hand, "pi electrons included in the ring structure in Ra" also includes pi electrons included in the ring structure included in the substituent. In the present invention, "alkyl" refers to a chain (straight or branched) saturated hydrocarbon group, and "alkyl" does not include "cycloalkyl" which is 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 the presence of a base and/or a dehydration condensing agent in an organic solvent 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, and hydrolyzing the compound (II) or the dehydration condensing 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)") to react with the compound (III) after the step (2).
[ chemical formula 11]
In the production method of the present invention, since compound (II) or the dehydration condensing agent is hydrolyzed in step (2) after compound (II) is reacted with compound (II) in step (1), compound (II) (when L of compound (II) is a leaving group (for example, halogen atom, organic sulfonyl group, or the like) remaining when compound (I) is reacted with compound (II) in step (1) or dehydration condensing agent (when L of compound (II) is a hydroxyl group) that can be used in step (1) can be hydrolyzed in 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 the dehydration condensing 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.
(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 the step (1) of the present invention is carried out in the presence of a base and/or a dehydration condensing 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 methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, neopentyl, n-hexyl, and isohexyl. Among them, Q is preferably a hydrogen atom.
In addition, in the compound (I), fg 1 And Fg 2 Each independently represents hydroxy, -CH 2 OH or-CH 2 CH 2 OH, preferably hydroxy or-CH 2 OH, more preferably hydroxy.
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.
In addition, 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; organic sulfonyloxy groups such as methanesulfonyloxy, p-toluenesulfonyloxy, trifluoromethanesulfonyloxy, camphorsulfonyloxy, benzenesulfonyloxy and the like. Among these, halogen atoms are preferable, and chlorine atoms are more preferable, from the viewpoint of obtaining the target product at low cost and with good yield.
In the compound (II), n represents an integer of 1 to 20. N is preferably an integer of 2 to 8, and more preferably 6.
In addition, from the viewpoint of improving the characteristics of an optical film or the like produced using the obtained polymerizable compound, the compound (II) is preferably a compound represented by the following formula (IIa).
[ 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) used 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, compound (III) having different groups on the left and right can be obtained. That is, 1 mol of the compound (I) is reacted with 1 mol of the compound (II-1) and then reacted with 1 mol of the compound (II-2), whereby the compound (III) having different groups on the left and right sides can be obtained.
Here, examples of the alkali that can be used in the step (1) include: organic bases such as triethylamine, diisopropylethylamine, pyridine, 4- (dimethylamino) pyridine (N, N-dimethyl-4-aminopyridine), and 2, 6-lutidine; inorganic bases such as sodium hydroxide, sodium carbonate, and sodium hydrogencarbonate.
The amount of the base to be used is usually 1 to 3 moles based on 1 mole of the compound (II).
In addition, when 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 performed in the presence of a base or may be performed in the absence of a base.
Examples of the dehydration condensing agent that can be used in the 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 in the step (1) is usually performed in the presence of a dehydration condensing agent.
The reaction is carried out in an organic solvent. The organic solvent to be used is not particularly limited as long as it is an organic solvent inactive to the reaction. Examples thereof include: a chlorine-based solvent such as chloroform or methylene chloride; amide solvents such as N-methylpyrrolidone, N-dimethylformamide, N-dimethylacetamide, and hexamethylphosphoric triamide; 1, 4-Di Ether solvents such as an alkane, cyclopentylmethyl ether, tetrahydrofuran, tetrahydropyran, and 1, 3-dioxolane; sulfur-containing solvents such as dimethylsulfoxide 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 yields.
The amount of the organic solvent to be used is not particularly limited, and may be appropriately determined in consideration of the kind of the compound to be used, the reaction scale, etc., and is usually 1 to 50g per 1g of the compound (II).
The reaction method includes: (a) A method of adding compound (II) or an organic solvent solution of compound (II) to an organic solvent solution containing compound (I) and a base and/or a dehydration condensing agent; (b) A method of adding the compound (I) or an organic solvent solution of the compound (I) to an organic solvent solution containing the compound (II) and a base and/or a dehydration condensing agent; (c) A method of adding a base and/or a dehydration condensing agent to an organic solvent solution of the compound (I) and the compound (II) is preferable 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, preferably-15℃to +30℃.
The reaction time also depends on the scale of the reaction, usually from a few minutes to a few hours.
The obtained reaction solution is maintained at the above temperature, and is directly supplied to the subsequent step (2) without washing, extraction operation, or the like.
In addition, 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 such or after purification as desired.
For example, a compound in which L is a halogen atom in the compound (II) 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 have the same meanings as those of the compounds (I) and (II).
In the compound (III), Y is 1 And Y 2 Each independently represents-C (=O) -O-, -O-C (=O) -, -CH 2 -O-C(＝O)-、-C(＝O)-O-CH 2 -、-CH 2 -CH 2 -O-C (=o) -, or-C (=o) -O-CH 2 -CH 2 -, 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) to obtain the compound represented by the following formula (IIIa) as the compound (III).
[ chemical formula 13]
(in the above-mentioned scheme, Q, A, Y 1 、Y 2 And n represents the same as above. )
(step (2))
In the step (2), a reaction is performed in which the compound (II) remaining when the compound (I) is reacted with the compound (II) in the step (1) or the dehydration condensing 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 condensing agent is hydrolyzed.
The hydrolysis in the step (2) is performed by adding water or an aqueous solution to the reaction solution obtained in the step (1), for example. The amount of water added in the step (2) is not particularly limited as long as it is an amount capable of hydrolyzing the residual compound (II) or the dehydration condensing agent, and is usually 1.05 to 500 mol times, more preferably 1.5 to 300 mol times, and still more preferably 1.5 to 200 mol times the reaction equivalent.
In the step (2), an aqueous solution is preferably added. The aqueous solution includes an alkaline aqueous solution and an acidic aqueous solution, and an acidic aqueous solution is preferable.
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.
The acid component of the acidic aqueous solution includes: 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; organic acids such as sulfinic acids, e.g., benzenesulfonic acid. These can be used singly or in combination of two or more.
Among these, from the viewpoint of satisfactory hydrolysis of the compound (II), an inorganic acid and/or an organic acid having 1 to 20 carbon atoms is preferable, at least one selected from 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 acid are further preferable.
The concentration of the acidic aqueous solution is preferably 0.1mol/L to 2mol/L, more preferably 0.5mol/L to 1.5mol/L. If the concentration of the acidic aqueous solution is not less than the above lower limit, the compound (II) or the dehydration condensing agent can be hydrolyzed well. If the concentration of the acidic aqueous solution 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 amount of the acidic aqueous solution to be used is preferably an amount capable of hydrolyzing the residual compound (II) or the dehydration condensing agent and catalyzing the reaction in the step (3) described below as much as possible. For example, in the case of an acidic aqueous solution having a concentration of 1.0 equivalent, the amount of the acidic aqueous solution to be used is 1 to 50 parts by mass, preferably 5 to 50 parts by mass, based on 10 parts by mass of the compound (II). If the amount of the acidic aqueous solution to be used is not less than the above lower limit, the compound (II) or the dehydration condensing agent can be hydrolyzed well and the reaction can be catalyzed in the step (3). If the amount of the acidic aqueous solution to be used is not more than the upper limit, side reactions such as decomposition of the compound (III) produced in the step (1) can be suppressed.
In the step (3) described later, the acidic aqueous solution necessary for the catalytic reaction may be further added after hydrolyzing the compound (II) or the dehydration condensing agent.
The hydrolysis reaction in the step (2) may be optionally performed with stirring. The reaction time in the step (2) is not particularly limited as long as the compound (II) or the dehydration condensing agent can be sufficiently hydrolyzed, and can be, for example, 1 minute or more and 5 hours or less, preferably 15 minutes or more and 1 hour or less. If the reaction time is not less than the above lower limit, the compound (II) or the dehydration condensing 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 condensing agent can be sufficiently hydrolyzed, and may be, for example, from-5 ℃ to 50 ℃, preferably from 0 ℃ to 50 ℃. If the reaction temperature is not less than the above lower limit, the compound (II) or the dehydration condensing agent can be hydrolyzed favorably. 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 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, the carbodiimide compound used as the dehydration condensing agent is converted into the urea compound.
The reaction solution after the step (2) is subjected to the step (3) may be directly supplied to the subsequent step without performing a 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 the dehydration condensing 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 even if the amount of the compound (IV) used is small.
In the compound (IV) represented by the formula (IV), X represents an oxygen atom, a sulfur atom or-C (R) 1 )(R 2 ) -or-N-R 1 -. Here, R is 1 And R is 2 Each independently represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms which may have a substituent.
As R 1 、R 2 The number of carbon atoms capable of having a substituent isExamples of the alkyl group having 1 to 10 carbon atoms in the alkyl group 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, n-decyl and the like.
Examples of the substituent of the alkyl group having 1 to 10 carbon atoms include: halogen atoms such as fluorine atom and chlorine atom; cyano group; a substituted amino group such as dimethylamino; 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 and cyclopentyl; hydroxyl, 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 invention 2 More preferably an oxygen atom or a sulfur atom, and particularly preferably a sulfur atom.
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 methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, n-pentyl, n-hexyl, n-heptyl, n-undecyl, n-dodecyl, 1-methylpentyl, and 1-ethylpentyl. Of these, alkyl groups having 1 to 12 carbon atoms are preferable, n-butyl groups, n-hexyl groups, and n-octyl groups are more preferable, and n-hexyl groups are 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 vinyl, allyl, isopropenyl, and butenyl groups, and alkenyl groups having 2 to 12 carbon atoms are preferable.
Examples of the alkynyl group having 2 to 60 carbon atoms include propynyl group, propargyl group, butynyl group, and the like, and alkynyl groups having 2 to 12 carbon atoms are preferable.
Examples of the aromatic hydrocarbon ring group having 6 to 18 carbon atoms include phenyl, 1-naphthyl and 2-naphthyl.
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 of the organic group having 1 to 60 carbon atoms for R include: 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; alkoxy groups having 1 to 6 carbon atoms such as methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy and tert-butoxy; alkoxy groups having 1 to 6 carbon atoms, such as methoxymethoxy, methoxyethoxy and ethoxyethoxy, which are substituted with alkoxy groups having 1 to 6 carbon atoms; cycloalkyl groups having 3 to 8 carbon atoms such as cyclopropyl, cyclopentyl, cyclohexyl and cycloheptyl groups; substituted amino groups such as methylamino, ethylamino, acetamido, dimethylamino, and the like.
Further, as the organic group having 1 to 60 carbon atoms, the formula: ra-Y-G-.
Here, ra represents a cyclic group having at least one of an aromatic hydrocarbon ring and an aromatic heterocyclic ring.
Among these, aromatic hydrocarbon ring groups having 6 to 30 carbon atoms are more preferable from the viewpoint of more easily obtaining the effects of the present invention.
Examples of the aromatic hydrocarbon ring include benzene ring, naphthalene ring, anthracene ring, phenanthrene ring, pyrene ring, fluorene ring, and the like. Among these, benzene rings, naphthalene rings, anthracene rings, and fluorene rings are preferable, and benzene rings and naphthalene rings are more preferable, since the effects of the present invention can be more easily obtained.
Examples of the aromatic heterocyclic ring include a 1H-isoindole-1, 3 (2H) -dione ring, a 1-benzofuran ring, a 2-benzofuran ring, an acridine ring, an isoquinoline ring, an imidazole ring, an indole ring, a,Diazole ring, < >>Azole ring, (-) ->Azolopyrazine ring, -/-, and>azolopyridine ring, ->Azolopyridazine ring, -/-, and>an azolopyrimidine ring, a quinazoline ring, a quinoxaline ring, a quinoline ring, a cinnoline ring, a thiadiazole ring, a thiazole ring, a thiazolopyrazine ring, a thiazolopyridine 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 ring, a pyrrole ring, a phenanthridine ring, a phthalazine ring, a furan ring, a benzo [ b ]]Thiophene ring, benzo [ c ]]Thiophene ring, benziso->An azole ring, a benzisothiazole ring, a benzimidazole ring, and benzo->Diazole ring, benzo->An azole ring, a benzothiadiazole ring, a benzothiazole ring, a benzothiophene ring, a benzotriazine ring, a benzotriazole ring, a benzopyrazole ring, a benzopyrone ring, a xanthene ring, and the like.
Among these, as the aromatic heterocycle, preferable is: furan ring, pyran ring, thiophene ring,Azole ring, (-) -> ring aromatic heterocycles such as an diazole ring, a thiazole ring and a thiadiazole ring; benzothiazole ring, benzo +.>Azole ring, quinoline ring, 1-benzofuran ring, 2-benzofuran ring, and benzo [ b ]]Thiophene ring, 1H-isoindole-1, 3 (2H) -dione ring, benzo [ c ]]Thiophene ring, thiazolopyridine ring, thiazolopyrazine ring, benzisotropic +.>Azole ring, benzo->Condensed ring aromatic heterocycles such as diazole ring, benzothiadiazole ring and xanthene ring.
The aromatic hydrocarbon ring and the aromatic heterocyclic ring of Ra may have a substituent. Examples of the substituent include: halogen atoms such as fluorine atom and chlorine atom; 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 and allyl; alkyl groups having 1 to 6 carbon atoms in which at least 1 hydrogen atom such as trifluoromethyl, pentafluoroethyl and the like is substituted with halogen; n, N-dialkylamino having 2 to 12 carbon atoms such as dimethylamino; 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; -OCF 3 ；-C(＝O)-R Y ；-C(＝O)-O-R Y ；-O-C(＝O)-R Y -SO 2 R b Etc. Here, R is Y Represents (i) an alkyl group having 1 to 20 carbon atoms which may have a substituent, (ii) an alkenyl group having 2 to 20 carbon atoms which may have a substituent, (iii) a cycloalkyl group having 3 to 12 carbon atoms which may have a substituent, or (iv) an aromatic hydrocarbon ring group having 6 to 18 carbon atoms which may have a substituent. In addition, R b Represents an alkyl group having 1 to 6 carbon atoms such as methyl or ethylThe method comprises the steps of carrying out a first treatment on the surface of the Or an aromatic hydrocarbon ring group having 6 to 18 carbon atoms which may have an alkyl group having 1 to 6 carbon atoms or an alkoxy group having 1 to 6 carbon atoms as a substituent, 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 which Ra has, preferred are 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.
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 Y Examples of the alkyl group having 1 to 20 carbon atoms which may have a substituent (i) which is an alkyl group having 1 to 20 carbon atoms include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, 1-methylpentyl group, 1-ethylpentyl group, sec-butyl group, tert-butyl group, n-pentyl group, isopentyl group, neopentyl group, n-hexyl group, isohexyl group, n-heptyl group, n-octyl group, n-nonyl group, n-decyl group, n-undecyl group, n-dodecyl group, n-tridecyl group, n-tetradecyl group, n-pentadecyl group, n-hexadecyl group, n-heptadecyl group, n-octadecyl group, n-nonadecyl group, and n-eicosyl group.
The number of carbon atoms of the alkyl group which may have a substituent (i) is preferably 1 to 12, more preferably 1 to 10.
As R Y The alkenyl group having 2 to 20 carbon atoms of the alkenyl group which may have a substituent (ii) may include vinyl, propenyl, isopropenyl, butenyl, isobutenyl, pentenyl, hexenyl, heptenyl, octenyl, nonenyl, decenyl, undecenyl, dodecenyl, tridecenyl, tetradecenyl, pentadecenyl, hexadecenyl, heptadecenyl, octadecenyl, nonadecenyl, eicosadienyl and the like.
The number of carbon atoms of the alkenyl group having 2 to 20 carbon atoms which may have a substituent (ii) is preferably 2 to 12.
As R Y (i) the number of carbon atoms which may have a substituentExamples of the substituent (ii) for the alkyl group having 1 to 20 carbon atoms which is an alkyl group having 1 to 20 carbon atoms and the alkenyl group having 2 to 20 carbon atoms which may have a substituent(s) are 2 to 20 carbon atoms: halogen atoms such as fluorine atom and chlorine atom; cyano group; n, N-dialkylamino having 2 to 12 carbon atoms such as dimethylamino; alkoxy groups having 1 to 20 carbon atoms such as methoxy, ethoxy, isopropoxy and butoxy groups; alkoxy groups having 1 to 12 carbon atoms, such as methoxymethoxy and methoxyethoxy, which are substituted with alkoxy groups 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-ylsulfanyl group and the like; cycloalkyl groups having 3 to 8 carbon atoms such as cyclopropyl, cyclopentyl, cyclohexyl and the like; a cyclic alkoxy group having 3 to 8 carbon atoms such as a cyclopentyloxy group and a cyclohexyloxy group; tetrahydrofuranyl, tetrahydropyranyl, dioxolanyl, and dioctanyl Cyclic ether groups having 2 to 12 carbon atoms such as alkyl groups; aryloxy groups having 6 to 14 carbon atoms such as phenoxy and naphthoxy; trifluoromethyl, pentafluoroethyl, -CH 2 CF 3 A fluoroalkyl group having 1 to 12 carbon atoms in which at least 1 hydrogen atom is replaced with a fluorine atom; benzofuranyl; benzopyranyl; benzodioxolyl; benzodi->Alkyl groups, and the like. Among these, R is Y (i) an alkyl group having 1 to 20 carbon atoms which may have a substituent(s) of an alkyl group having 1 to 20 carbon atoms and (ii) a substituent(s) of an alkenyl group having 2 to 20 carbon atoms which may have a substituent(s) of an alkenyl group having 2 to 20 carbon atoms, preferably: halogen atoms such as fluorine atom and chlorine atom; cyano group; alkoxy groups having 1 to 20 carbon atoms such as methoxy, ethoxy, isopropoxy and butoxy groups; 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-ylsulfanyl and the like; cyclopropyl, cyclopentyl,Cycloalkyl groups having 3 to 8 carbon atoms such as cyclohexyl groups; trifluoromethyl, pentafluoroethyl, -CH 2 CF 3 And fluoroalkyl groups having 1 to 12 carbon atoms in which at least 1 hydrogen atom is replaced with a fluorine atom.
In addition, R Y The (i) alkyl group having 1 to 20 carbon atoms which may have a substituent and the (ii) alkenyl group having 2 to 20 carbon atoms which may have a substituent may have a plurality of substituents selected from the above substituents. At R Y When (i) an alkyl group having 1 to 20 carbon atoms which may have an alkyl group having 1 to 20 carbon atoms as a substituent and (ii) an alkenyl group having 2 to 20 carbon atoms which may have an alkenyl group having 2 to 20 carbon atoms as a substituent have a plurality of substituents, the plurality of substituents may be the same or different from each other.
As R Y The cycloalkyl group having 3 to 12 carbon atoms which may have a cycloalkyl group having 3 to 12 carbon atoms as a substituent (iii) includes cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclooctyl and the like. Among these, cyclopentyl and cyclohexyl are preferable.
As R Y The substituent (iii) of a cycloalkyl group having 3 to 12 carbon atoms which may have a substituent(s) is a cycloalkyl group having 3 to 12 carbon atoms, and examples thereof include: halogen atoms such as fluorine atom and chlorine atom; cyano group; n, N-dialkylamino having 2 to 12 carbon atoms such as dimethylamino; 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. Among these, R is Y (iii) a substituent of a cycloalkyl group having 3 to 12 carbon atoms which may have a substituent, preferably a cycloalkyl group having 3 to 12 carbon atoms: halogen atoms such as fluorine atom and chlorine atom; 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 Can be (iii) provided withCycloalkyl groups having 3 to 12 carbon atoms which are substituted with cycloalkyl groups having 3 to 12 carbon atoms may have a plurality of substituents. At R Y In (iii) when a cycloalkyl group having 3 to 12 carbon atoms, which may have a cycloalkyl group having 3 to 12 carbon atoms, has a plurality of substituents, the plurality of substituents may be the same or different from each other.
As R Y The aromatic hydrocarbon ring group having 6 to 18 carbon atoms which may have a substituent (iv) is an aromatic hydrocarbon ring group having 6 to 18 carbon atoms, and examples thereof include phenyl, 1-naphthyl and 2-naphthyl. Among these, phenyl and naphthyl are preferable, and phenyl, 1-naphthyl and 2-naphthyl are more preferable.
As R Y The substituent (iv) of the aromatic hydrocarbon ring group having 6 to 18 carbon atoms which may have a substituent(s) includes: halogen atoms such as fluorine atom and chlorine atom; cyano group; n, N-dialkylamino having 2 to 12 carbon atoms such as dimethylamino; alkoxy groups having 1 to 20 carbon atoms such as methoxy, ethoxy, isopropoxy and butoxy groups; alkoxy groups having 1 to 12 carbon atoms, such as methoxymethoxy and methoxyethoxy, which are substituted with alkoxy groups having 1 to 12 carbon atoms; 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; a cyclic alkoxy group having 3 to 8 carbon atoms such as a cyclopentyloxy group and a cyclohexyloxy group; tetrahydrofuranyl, tetrahydropyranyl, dioxolanyl, and dioctanyl Cyclic ether groups having 2 to 12 carbon atoms such as alkyl groups; aryloxy groups having 6 to 14 carbon atoms such as phenoxy and naphthoxy; trifluoromethyl, pentafluoroethyl, -CH 2 CF 3 A fluoroalkyl group having 1 to 12 carbon atoms in which at least 1 hydrogen atom is replaced with a fluorine atom; -OCF 3 The method comprises the steps of carrying out a first treatment on the surface of the Benzofuranyl; benzopyranyl; benzodioxolyl; benzodi->Alkyl groups, and the like. Among these, R is Y To @ isiv) a substituent which may have a substituent and is an aromatic hydrocarbon ring group having 6 to 18 carbon atoms, is preferably selected from the group consisting of: halogen atoms such as fluorine atom and chlorine atom; cyano group; alkoxy groups having 1 to 20 carbon atoms such as methoxy, ethoxy, isopropoxy and butoxy groups; 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, -CH 2 CF 3 A fluoroalkyl group having 1 to 12 carbon atoms in which at least 1 hydrogen atom is replaced with a fluorine atom; -OCF 3 The method comprises the steps of carrying out a first treatment on the surface of the At least 1 substituent of (c).
In addition, R Y 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 (iv) may have a plurality of substituents. At R Y In (iv) the case where 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 meaning of "the number of carbon atoms" of the cyclic group having at least one of an aromatic hydrocarbon ring and an aromatic heterocycle of Ra is: the number of carbon atoms of the organic group itself having at least one of an aromatic hydrocarbon ring and an aromatic heterocyclic ring, which does not contain a carbon atom of a substituent.
In the case where 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 heterocyclic ring having 2 to 30 carbon atoms.
Preferred examples of the cyclic group of at least one of an aromatic hydrocarbon ring having 6 to 30 carbon atoms and an aromatic heterocyclic ring having 2 to 30 carbon atoms in Ra are shown below. However, the present invention is not limited to the specific examples shown below. In the following formula, "-" represents a bond position extending from an arbitrary position of the ring and bonded to Y.
1) Specific examples of the hydrocarbon ring group which may have a substituent(s) and has at least one aromatic hydrocarbon ring having 6 to 30 carbon atoms include structures represented by the following formulas (1-1) to (1-21), and hydrocarbon ring groups having 6 to 18 carbon atoms represented by the formulas (1-8) to (1-21) and the like are preferable. The groups represented by the following formulas (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(s) and is selected from at least one of an aromatic hydrocarbon ring having 6 to 30 carbon atoms and an aromatic heterocyclic ring having 2 to 30 carbon atoms include structures represented by the following formulas (2-1) to (2-51), and the heterocyclic group having 2 to 16 carbon atoms represented by the formulas (2-11) to (2-51) is preferable. The groups represented by the following formulas (2-1) to (2-51) may have a substituent.
[ chemical formula 16]
[ chemical formula 17]
[ chemical formula 18]
[ chemical formula 19]
(in each formula, A represents-CH 2 -、-NR c -, oxygen atom, sulfur atom, -SO-or-SO 2 -，
B and D each independently represent-NR c -, oxygen atom, sulfur atom, -SO-or-SO 2 -，
E represents-NR c -, an oxygen atom or a sulfur atom.
Here, R is c The representation is: a hydrogen atom; or an alkyl group having 1 to 6 carbon atoms such as a methyl group, an ethyl group, or a propyl group. (wherein, in the formulae, an oxygen atom, a sulfur atom, -SO-, -SO 2 -not adjacent respectively. ))
Among the above, ra is preferably any one of the groups represented by the above formulas (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 further preferably 18 or less.
Further, ra is preferably any one 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-CH 2 -、-NR d -, oxygen atom, sulfur atom, -SO-or-SO 2 -，R d Represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. )
In addition, the cyclic group of Ra having at least one of an aromatic hydrocarbon ring having 6 to 30 carbon atoms and an aromatic heterocyclic ring having 2 to 30 carbon atoms 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 at least one of an aromatic hydrocarbon ring having 6 to 30 carbon atoms and an aromatic heterocyclic ring having 2 to 30 carbon atoms in Ra include: halogen atoms such as fluorine atom and chlorine atom; 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 and allyl; alkyl groups having 1 to 6 carbon atoms in which at least 1 hydrogen atom such as trifluoromethyl, pentafluoroethyl and the like is substituted with halogen; n, N-dialkylamino having 2 to 12 carbon atoms such as dimethylamino; 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; -OCF 3 ；-C(＝O)-R Y ；-C(＝O)-O-R Y ；-O-C(＝O)-R Y ；-SO 2 R b Etc. Here, R is Y And R is b The same meaning as described above is indicated, and preferred examples thereof are also the same as described above. In the case of having a plurality of substituents, the plurality of substituents may be the same 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.
In addition, Y represents a single chemical bond, -O-, -S-, -C (=O) -, -O-C (Rb) (Rc) -, -C (Rb) (Rc) -O-, -O-CH 2 -CH 2 -、-CH 2 -CH 2 -O-、-C(＝O)-O-、-O-C(＝O)-、-C(＝O)-S-、-S-C(＝O)-、-NR 4 -C(＝O)-、-C(＝O)-NR 4 -、-CH＝CH-C(＝O)-O-、-O-C(＝O)-CH＝CH-、-CH 2 -CH 2 -C(＝O)-O-、-O-C(＝O)-CH 2 -CH 2 -、-CH 2 -CH 2 -O-C(＝O)-、-C(＝O)-O-CH 2 -CH 2 -、-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)-NR 4 -、-NR 4 -C(＝O)-O-、-O-C(＝O)-CH 2 -S-、-S-CH 2 -C (=o) -O-or-O-C (=o) -O-. Here, R is 4 And Rc and Rb each independently represent a hydrogen atom, an aromatic hydrocarbon ring group having 6 to 18 carbon atoms which may have a substituent, or an aromatic heterocyclic group having 2 to 18 carbon atoms which may have a substituent.
Among these, Y is preferably a single bond, -O-C (Rb) (Rc) -, -C (Rb) (Rc) -O-, -O-CH, from the viewpoint of more easily obtaining the effect of the present invention 2 -CH 2 -、-CH 2 -CH 2 -O-、-C(＝O)-O-、-O-C(＝O)-、-CH 2 -CH 2 -C(＝O)-O-、-O-C(＝O)-CH 2 -CH 2 -、-CH 2 -CH 2 -O-C(＝O)-、-C(＝O)-O-CH 2 -CH 2 -、-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)-NR 4 -、-NR 4 -C(＝O)-O-、-O-C(＝O)-CH 2 -S-、-S-CH 2 -C (=o) -O-, -O-C (=o) -O-, more preferably a single bond, -O-C (Rb) (Rc) -, -C (Rb) (Rc) -O-, -O-CH 2 -CH 2 -、-CH 2 -CH 2 -O-、-C(＝O)-O-、-O-C(＝O)-、-CH 2 -CH 2 -C(＝O)-O-、-O-C(＝O)-CH 2 -CH 2 -、-CH 2 -CH 2 -O-C(＝O)-、-C(＝O)-O-CH 2 -CH 2 -、-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)-NR 4 -、-NR 4 -C(＝O)-O-、-S-CH 2 -C(＝O)-O-、-O-C(＝O)-CH 2 S-, particularly preferably a single chemical bond, -O-C (Rb) (Rc) -, -C (Rb) (Rc) -O-, -O-CH 2 -CH 2 -、-CH 2 -CH 2 -O-、-C(＝O)-O-、-O-C(＝O)-、-CH 2 -CH 2 -C(＝O)-O-、-O-C(＝O)-CH 2 -CH 2 -、-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)-NR 4 -、-NR 4 -C(＝O)-O-、-S-CH 2 -C(＝O)-O-、-O-C(＝O)-CH 2 -S-。
Here, R is 4 Represents (i) a hydrogen atom or (ii) a methyl group, an ethyl group or the like having a carbon number of1 to 6 alkyl groups, among these, R 4 Hydrogen atoms are preferred.
Rc and Rb each independently represent a hydrogen atom, an aromatic hydrocarbon ring group having 6 to 18 carbon atoms which may have a substituent, or an aromatic heterocyclic group having 2 to 18 carbon atoms which may have a substituent. Rc and Rb may be the same or different from each other.
Specific examples of the aromatic hydrocarbon ring group having 6 to 18 carbon atoms which may have a substituent or the aromatic heterocyclic group having 2 to 18 carbon atoms which may have a substituent of Rb and Rc include groups having a predetermined carbon number among the same groups as Ra. Examples of the substituents of Rb and Rc include the same substituents as those of Ra described above, and preferred substituents thereof are the same. In addition, when a plurality of substituents are present, they may be the same or different.
Rc and Rb are each independently preferably a hydrogen atom or an aromatic hydrocarbon ring group having 6 to 18 carbon atoms which may have a substituent, further each independently preferably a hydrogen atom, a phenyl group or a naphthyl group, and particularly preferably Rc and Rb are both a combination of 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-,
ra is preferably selected from the general formulae (i-1) to (i-6), Y is preferably 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 -CH 2 -Z、-CH 2 -CH 2 -O-Z、-C(＝O)-O-Z、-O-C(＝O)-Z、-CH 2 -CH 2 -C(＝O)-O-Z、-O-C(＝O)-CH 2 -CH 2 -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、-NR 4 -C(＝O)-O-Z、-S-CH 2 -a combination of C (=o) -O-Z.
More preferably, ra is selected from the general formulae (i-1) to (i-6) and Y is selected from the group consisting of a single bond, -O-Z, -C (Rb) (Rc) -O-Z, -CH 2 -CH 2 -O-Z、-C(＝O)-O-Z、-O-C(＝O)-Z、-CH 2 -CH 2 -C(＝O)-O-Z、-C(Rb)(Rc)-O-C(＝O)-Z、-C(Rb)(Rc)-C(＝O)-O-Z、-NR 4 -C(＝O)-O-Z、-S-CH 2 -a combination of C (=o) -O-Z.
Further, ra-Y-is particularly preferably any one of the following formulas (ii-1) to (ii-45), and most preferably any one of (iii-1) to (iii-46). Rb and Rc have the same meaning as described above, and Z represents a direction of bonding to G. In addition, "+points" among the groups represented by the following formulas (ii-1) to (ii-45) and the groups represented by (iii-1) to (iii-46) represent bonding sites with G.
The groups represented by the following formulas (ii-1) to (ii-45) and the groups represented by (iii-1) to (iii-46) may have substituents.
In the following formulae (ii-26) to (ii-32) and (iii-26) to (iii-32), J represents-CH 2 -、-NR d -, oxygen atom, sulfur atom, -SO-or-SO 2 -，R d Represents 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 3 to 20 carbon atoms 2-valent organic group which may have a substituent.
G is more preferably (i) a C1-20 aliphatic hydrocarbon group having 2 valence and capable of having a substituent; and (ii) a-CH group contained in a 2-valent aliphatic hydrocarbon group having 3 to 20 carbon atoms which may have a substituent 2 At least one of them is-O- -S-, -O-C (=o) -, -C (=o) -O-, -O-C (=o) -O-, -NR 5 -C(＝O)-、-C(＝O)-NR 5 -、-NR 5 -or-C (=o) -substituted group; any of the organic groups. Wherein, it does not contain the case where-O-or-S-exists adjacently for each of more than 2 (i.e., structures of-O-O-and-S-S-are not formed).
Here, R is 5 Represents 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 and propoxy; cyano group; halogen atoms such as fluorine atom and chlorine atom.
Here, in the case of G, the "aliphatic hydrocarbon group having a valence of 2" 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 "2-valent aliphatic hydrocarbon group" is preferably 3 to 20, more preferably 3 to 18. The "aliphatic hydrocarbon group having 2 valence" is preferably an aliphatic hydrocarbon group having 2 to 20 carbon atoms, more preferably a chain aliphatic hydrocarbon group having 2 to 18 carbon atoms, and still more preferably an alkylene group having 3 to 18 carbon atoms.
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 n-hexylene or n-octylene.
In addition, when the number of carbon atoms of G is 3 or more, it is preferable that both ends of G are-CH 2 - (G) the ends are not substituted). In addition, the group-CH contained in the aliphatic hydrocarbon group having 2 valences of 3 to 20 in "(ii) 2 At least one of them is-O- -S-, -O-C (=o) -, -C (=o) -O-, -O-C (=o) -O-, -NR 5 -C(＝O)-、-C(＝O)-NR 5 -、-NR 5 -or-C (=o) -substituted group ", preferably-C (=o) -unsubstituted aliphatic hydrocarbon group, is a continuous-CH 2 - (i.e. structures which do not form-C (=o) -).
-CH contained in aliphatic hydrocarbon group having 3 to 20 carbon atoms and having 2 valences 2 At least one of them is substituted by-O-, -S-, -O-C (=o) -, -C (=o) -O-、-O-C(＝O)-O-、-NR 5 -C(＝O)-、-C(＝O)-NR 5 -、-NR 5 In the case of-or-C (=o) -substitution, most preferably-O-substitution, preferably with so-called ethyleneoxy groups substituted with-O-every 2 carbon atoms as repeating units and with-CH at both ends of G 2 -。
As G, (i) "a C1-18, preferably C3-18, 2-valent chain aliphatic hydrocarbon group which may have a substituent, and-CH contained in the C3-18, 2-valent chain aliphatic hydrocarbon group which may have a substituent are preferable 2 At least one organic group selected from the group consisting of-O-, -S-, -O-C (=o) -, -C (=o) -O-and-C (=o) -is not included in the case where-O-and-S-are each present adjacently at 2 or more, 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, particularly preferably (vii) an unsubstituted alkylene group having 6 to 10 carbon atoms, most preferably "n-hexylene and n-octylene". 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; cyano group; halogen atoms such as fluorine atom and chlorine atom.
R X The representation is: 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; cyano group; a nitro group; alkyl groups having 1 to 6 carbon atoms in which at least 1 hydrogen atom such as trifluoromethyl, pentafluoroethyl and the like is substituted with halogen; alkoxy groups having 1 to 6 carbon atoms such as methoxy, ethoxy, isopropoxy and butoxy groups; alkylthio groups having 1 to 6 carbon atoms wherein at least 1 hydrogen atom of the alkylthio group, ethylthio group or the like is replaced with a sulfur atom; mono-substituted amino groups such as methylamino, ethylamino, acetamido, and the like; dimethylamino, diethylamino, phenylmethylDisubstituted amino groups such as a alkylamino group; -OCF 3 ；-C(＝O)-O-R 3 The method comprises the steps of carrying out a first treatment on the surface of the or-O-C (=o) -R 3 . Here, R is 3 Represents 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 R 3 The alkyl group having 1 to 10 carbon atoms which may have a substituent(s) may be mentioned as R 1 、R 2 The same alkyl groups as those having 1 to 10 carbon atoms which may have a substituent are also preferable.
Among these, R X Each independently is preferably a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, more preferably R X All hydrogen atoms.
R X Can be identical or different in all, at least 1C-R constituting a ring X Can be substituted with nitrogen atoms. C-R X Specific examples of the group in which at least 1 of them is substituted with a nitrogen atom are shown below. However, C-R X The group substituted by at least 1 nitrogen atom is not limited thereto.
[ chemical formula 23]
(wherein, R, X and R X The same meaning as described above is indicated. )
The amount of the compound (IV) used in the step (3) is preferably an amount 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 the hydrolysis is performed by adding water or an aqueous solution to the reaction solution in the step (2), the reaction in the step (3) is usually performed by adding the compound (IV) to a mixed solution obtained by adding water or an aqueous solution to the reaction solution in the step (2), and the reaction in the step (3) may be performed by separating the water or the aqueous solution added in the step (2) and then adding the compound (IV). In addition, in the step (3), the acidic aqueous solution for catalytic reaction may be newly added, and in particular, in the case of separating the water or the aqueous solution added in the step (2), the acidic aqueous solution for catalytic reaction is preferably newly added. The acidic aqueous solution to be newly added may be the same acidic aqueous solution as the acidic aqueous solution that can be used in the step (2).
Among the above, in the step (3), when the reaction solution obtained in the step (2) is used as it is (i.e., the compound (IV) is added to the mixed solution obtained in the step (2)) without performing post-treatment operations such as washing and extraction, the cost can be reduced, and this is preferable. In this case, in the step (2), an acidic aqueous solution is particularly preferably used. This is because the acidic aqueous solution added in the step (2) can be efficiently used as a catalyst for the reaction in the step (3).
The compound (IV) may be added after being dissolved in an appropriate organic solvent, as desired. The organic solvent used may be the same as the organic solvent exemplified in the step (1).
Further, the compound (IV) can be produced by a method described in, for example, japanese patent application laid-open No. 2015/141784, japanese patent application laid-open No. 2016-190818.
Here, in the present invention, 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 preferably 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) can be obtained in a higher yield and with a high purity.
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, more preferably 0.1g (organic solvent)/100 mL (water) or less.
As the water-immiscible organic solvent, there may be mentioned: esters such as ethyl acetate, isopropyl acetate, butyl acetate, dimethyl carbonate, and diethyl carbonate; halogenated hydrocarbons such as methylene chloride, 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 preferably from 0℃to 80℃from-20℃to the boiling point of the solvent used. The reaction time depends on the scale of the reaction, and is usually several minutes to 10 hours.
After the completion of the reaction, when the reaction solution was separated into 2 layers of an organic layer and an aqueous layer, water (saline solution) and a water-immiscible organic solvent were added as needed, and the organic layer was separated and removed.
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, and the solution is separated, and the organic layer is separated and removed.
In any case, the obtained organic layer may be subjected to a usual post-treatment operation in organic synthetic chemistry, and the desired polymerizable compound (a) may be isolated by performing a known separation and purification method such as a precipitation method, recrystallization method, distillation method, or chromatography column.
In the step (3), in order to reduce ionic impurities and remove insoluble components (high molecular weight substances), an adsorbent or a filter aid, or a combination of both may be used.
Examples of the adsorbent used herein include activated carbon and silica gel (main component SiO 2 ) Synthetic adsorbent (main component MgO, al) 2 O 3 、SiO 2 ) Activated clay, alumina, ion exchange resins, adsorption resins, and the like.
Examples of the filter aid include diatomaceous earth and silica gel (main component SiO 2 ) Synthetic zeolite, perlite, radio, and the like.
Among these, in the present invention, from the viewpoint of obtaining a target product of high purity in high yield by a simple operation, a method of concentrating the obtained organic layer to precipitate crystals of the target product from the concentrated solution is preferable; or any of a method of concentrating the obtained organic layer, adding a poor solvent to the concentrated solution, and precipitating crystals of the target product.
As the poor solvent used in the latter method, there may be mentioned: water; alcohols such as methanol and ethanol.
In addition, 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 (undissolved portions were formed), heated to complete dissolution, filtered while hot to remove insoluble materials, and then the filtrate was cooled to precipitate crystals.
Examples of the solvent used for recrystallization include poor solvents and ethers such as tetrahydrofuran, which are exemplified by the precipitation method.
In addition, from the viewpoint of obtaining a high-purity product, an antioxidant such as 2, 6-di-t-butyl-4-cresol is preferably added to the recrystallization solvent. The amount of the antioxidant to be added is 1 to 500mg relative to 100g of crystals of the target product.
The structure of the target product can be identified by measurement such as NMR spectrum, IR spectrum, mass spectrum, or the like, 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 polymerizable compound (A), Y 1 、Y 2 、A、R、R X X, Q and n are the same 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) to obtain the polymerizable compound represented by the following formula (Aa) as the polymerizable compound (a).
[ chemical formula 24]
(wherein Y is 1 、Y 2 、A、R、R X X, Q and n are the same as defined above. )
Examples
The present invention will be described in further detail with reference to examples. The present invention is not limited by 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 (0.52 mol) of trans-1, 4-cyclohexanedicarboxylic acid and 800ml of Tetrahydrofuran (THF) are introduced into a 3-port reactor with thermometer. To this, 33g (0.29 mol) of methanesulfonyl chloride was added, and the reactor was immersed in a water bath to bring the internal temperature of the reactor to 20 ℃. Next, 31.7g (0.31 mol) of triethylamine was added dropwise over 30 minutes while keeping the internal temperature of the reactor at 20 to 30 ℃. After the completion of the dropwise addition, the whole content was further stirred at 25℃for 2 hours. To the resultant reaction solution were added 3.2g (26.2 mmol) of 4- (dimethylamino) pyridine and 69g (0.26 mol) of 4- (6-acryloyloxy-hex-1-yloxy) phenol synthesized by Japanese patent application laid-open No. 2015-140302, and the reactor was immersed in a water bath again to bring the internal temperature of the reactor to 15 ℃. While maintaining the internal temperature of the reactor at 20 to 30 ℃, 31.7g (0.31 mol) of triethylamine was added dropwise thereto over 30 minutes, and after the completion of the addition, the entire content was stirred at 25℃for 2 hours. After completion of the reaction, 4000ml of distilled water and 500ml of saturated brine 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 removed from the filtrate by evaporation using 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 target product 1 H-NMR identification.
1 H-NMR(500MHz，DMSO-d 6 ，TMS，δppm)：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 by referring to Japanese patent application laid-open No. 2016-190818.
Structural use of target product 1 H-NMR identification.
1 H-NMR(500MHz，CDCl 3 ，TMS，δppm)：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)。
Step 3: synthesis of intermediate C
[ chemical formula 28]
In a nitrogen stream, 30g (71.7 mmol) of intermediate A synthesized in the above step 1, 300g of chloroform and 10.5g (143.4 mmol) of N, N-dimethylformamide were charged into a 3-port reactor having a thermometer, and cooled to 10℃or lower. While keeping the reaction temperature at 10℃or lower, 9.81g (82.44 mmol) of thionyl chloride was added dropwise thereto. After the completion of the dropwise addition, the reaction mixture was brought to 25℃and stirred for 1 hour. After the completion of the reaction, 225g of chloroform was separated by a rotary evaporator, and concentrated to prepare a chloroform solution.
Step 4: synthesis of polymerizable Compound 1
In a 3-port reactor with a thermometer, 4.5g (32.58 mmol) of 2, 5-dihydroxybenzaldehyde and 19.78g (195.5 mmol) of triethylamine were dissolved in 150g of chloroform in a nitrogen stream, and the resulting solution was cooled to 10℃or lower. While maintaining the reaction temperature at 10 ℃ or lower, the entire amount of the chloroform solution of intermediate C synthesized in step 3 was slowly added dropwise to the solution. After completion of the dropwise addition, the whole content was stirred at 5 to 10℃for 1 hour (step (1)).
After the completion of the reaction, 120g of a 1.0-normal hydrochloric acid aqueous solution was added to the reaction mixture while maintaining the temperature at 10℃or lower. Thereafter, the mixture was stirred at 10℃or lower for 30 minutes to effect a reaction (step (2)).
After the completion of the reaction, 10.58g (42.4 mmol) 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 mixture was heated to 40℃and reacted for 4 hours (step (3)).
After the completion of the reaction, the aqueous layer was separated. Further, 105g of distilled water was poured into the organic layer, and the organic layer was stirred at 40℃for 30 minutes, followed by washing. 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, filtration was performed with a tung mountain funnel covered with 1g of rokahelp#479 to remove rokahelp#479. 180g of chloroform was separated from the obtained organic layer by a rotary evaporator, and concentrated. 210g of hexane was added to the obtained organic layer over 1 hour to precipitate a solid, and a pale yellow solid was obtained by filtration. The resulting pale yellow solid was dissolved in 120g of tetrahydrofuran at 25℃and 1.5g of Rokahellp #479 was added thereto and stirred for 30 minutes. Thereafter, filtration was performed with a tung mountain funnel covered with 1g of rokahelp#479 to remove rokahelp#479. 165g of methanol was slowly added dropwise to the obtained organic layer 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 the polymerizable compound 1 as a pale yellow solid. The yield was 85% (based on 2, 5-dihydroxybenzaldehyde).
Structural use of target product 1 H-NMR identification.
1 H-NMR(400MHz，CDCl 3 ，TMS，δppm)：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 (71.7 mmol) of intermediate A synthesized in step 1 of example 1 above, 300g of toluene and 5.5g of N, N-dimethylformamide were charged in a 3-port reactor with a thermometer in a nitrogen stream, and cooled to 10℃or lower. While keeping the reaction temperature at 10℃or lower, 8.96g (75.3 mmol) of thionyl chloride was added dropwise thereto. After the completion of the dropwise addition, the reaction mixture was brought to 25℃and stirred for 1 hour. After the completion of the reaction, the reaction mixture was concentrated to half the amount of the reaction mixture by a rotary evaporator. Thereafter, toluene was added in the same amount as the amount separated, and the mixture was concentrated by a rotary evaporator until the amount of the reaction solution became half. This operation was repeated 3 times to conduct synthesis as a toluene solution.
Step 2: synthesis of polymerizable Compound 1
In a 3-port reactor with thermometer, 4.13g (29.9 mmol) of 2, 5-dihydroxybenzaldehyde and 7.62g (75.4 mmol) of triethylamine were dissolved in 150g of tetrahydrofuran in a nitrogen stream, and the resulting solution was cooled to 10℃or lower. 150g of the toluene solution of intermediate C synthesized in step 1 was slowly added dropwise to the reaction temperature of 10℃or lower. After completion of the dropwise addition, the whole content was stirred at 5 to 10℃for 1 hour (step (1)).
After the completion of the reaction, 30g of 1.0-normal hydrochloric acid aqueous solution was added to the reaction mixture while maintaining the temperature at 10℃or lower, and the mixture was stirred for 30 minutes at 10℃or lower (step (2)).
Thereafter, 9.7g (38.9 mmol) of intermediate B synthesized in step 2 of example 1 was added thereto, and the reaction was carried out at 40℃for 4 hours (step (3)).
After the completion of the reaction, the reaction mixture was cooled to 25℃and 300g of ethyl acetate and 300g of 10% by mass saline were added thereto to carry out a liquid separation operation. The obtained organic layer was further washed with 300g of 2 mass% saline solution 2 times.
About 15% of the total mass was separated from the obtained organic layer by a rotary evaporator, and concentrated. After the solution was brought to 25 ℃, 300g of a mixed solvent of methanol and 60g of water was slowly added dropwise thereto. Thereafter, the mixture was cooled to 10℃to precipitate a solid, and the solid was obtained by filtration. To the obtained solid, 240g of tetrahydrofuran, 240g of methanol and 20mg of 2, 6-di-t-butyl-4-methylphenol were added, and the whole content was heated to 50℃to prepare a uniform solution. The solution was filtered hot at 50℃and the resulting filtrate was slowly cooled to 10℃and recrystallized. Crystals were obtained by filtration and dried with a vacuum dryer 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 (79.40 mmol) of trans-1, 4-cyclohexanedicarboxylic acid dichloride, 120g of cyclopentylmethyl ether (CPME) and 46g of tetrahydrofuran are introduced into a 3-port reactor with thermometer in a nitrogen flow. To this, 20g (75.67 mmol) 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 were added, and the reactor was immersed in an ice bath so that the internal temperature of the reactor became 0 ℃. Next, while keeping the internal temperature of the reactor at 10℃or lower, 8.0g (79.45 mmol) of triethylamine was slowly added dropwise over 30 minutes. After the completion of the dropwise addition, the whole content was further stirred for 1 hour while keeping the temperature at 10℃or lower.
To the resultant reaction solution was added 50g of distilled water. After the reaction solution was heated to 50 ℃, the reaction solution was washed for 2 hours (hydrolysis reaction), and then an aqueous layer was separated. The washing with water (hydrolysis reaction) was performed 3 times in total, and the washing was performed 6 hours in total. After the obtained organic layer was cooled to 40 ℃, 83.2g of a buffer solution (pH: 5.5) of acetic acid and sodium acetate at a concentration of 1mol/L was further added, and stirring was performed, whereby 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. After 240g of n-hexane was added to the obtained organic layer at 40 ℃, the organic layer was cooled to 0 ℃ to precipitate crystals. Thereafter, the precipitated crystals were collected by filtration. After washing the filtrate with n-hexane, it was dried in vacuo to give 26.91g of mixture 1 as a white solid.
The obtained crystals were analyzed by HPLC, and the monoester and the diester were quantified by a calibration curve, and as a result, it was found that the monoester was contained as the target product in an amount of 68.34 mass% (43.95 mmol). In addition, use 13 C-NMR (II)Alkyl-d 8 ) The obtained crystals were analyzed, and the content of cyclohexanedicarboxylic acid was calculated, so that the detection limit was not higher than 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 having a thermometer and cooled to 10℃or lower. The reaction temperature was controlled to 10℃or lower, and 6.0g (50.54 mmol) of thionyl chloride was added dropwise thereto. After the completion of the dropwise addition, the reaction mixture was brought to 25℃and stirred for 1 hour. After the completion of the reaction, 138g of chloroform was separated under reduced pressure by a rotary evaporator. Thereafter, 46g of new chloroform was added to obtain a chloroform solution (1). In addition, 2.76g (20.0 mmol) of 2, 5-dihydroxybenzaldehyde and 12.13g (119.8 mmol) of triethylamine were dissolved in 92g of chloroform in a 3-port reactor having a thermometer and cooled to 10℃or lower. While keeping the internal temperature of the reactor at 10℃or lower, the chloroform solution (1) was slowly added dropwise to the solution. After completion of the dropwise addition, the reaction mixture was further reacted for 1 hour while keeping the temperature of the reaction mixture at 10℃or lower (step (1)).
After the completion of the reaction, the temperature was maintained at 10℃or lower, 725g of a 1.0-normal 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 (26.0 mmol) of 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 solution was heated to 40℃for 4 hours to effect a reaction (step (3)).
After the reaction, the aqueous layer was separated at 40℃and subjected to a liquid separation operation. To the obtained organic layer, 0.92g of Rokahelp #479 (Sanyo Metal mining Co., ltd.) was added, and after stirring at 25℃for 30 minutes, it was filtered off with a filter coated with 0.6g of Rokahelp # 479. The filter was washed with 9.2g of chloroform and combined with the filtrate obtained previously. Next, 110g of chloroform was separated from the obtained organic layer under reduced pressure by a rotary evaporator, and concentrated. To this solution, 33g of tetrahydrofuran was added, and the mixture was cooled to 15℃with stirring. Next, 129g of 60% hexane (manufactured by Godo co., ltd.) was slowly dropped into the solution. Stirring was carried out 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-tert-butyl-p-cresol were added to the obtained solid, and after stirring at 25℃for 30 minutes, it was filtered off with a filter covered 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 obtained organic layer by a rotary evaporator. The resulting solution was brought to 15℃and 121g of methanol were slowly added dropwise. The current temperature was maintained for 30 minutes with stirring to precipitate a solid. Thereafter, the precipitated solid was collected by filtration. After the filtrate was washed with methanol, it was dried in vacuo to obtain 19.4g of polymerizable compound 1 as a pale yellow solid. The yield thereof was found to be 83% (based on 2, 5-dihydroxybenzaldehyde).
Example 4 Synthesis of polymerizable Compound 1
The same operations as in example 1 were carried out except that 19.78g (195.5 mmol) of triethylamine was changed to 20.97g (195.7 mmol) of 2, 6-lutidine in step 4 of example 1. As a result, 34.7g of a pale yellow solid of the polymerizable compound 1 was obtained. The yield thereof was found to be 91% (based on 2, 5-dihydroxybenzaldehyde).
Example 5 Synthesis of polymerizable Compound 1
The same operations as in example 3 were carried out except that 12.13g (119.8 mmol) of triethylamine was changed to 12.8g (120.0 mmol) of 2, 6-lutidine in step 2 of example 3. As a result, 21.1g of a pale yellow solid of the polymerizable compound 1 was obtained. The yield was 90% (based on 2, 5-dihydroxybenzaldehyde).
EXAMPLE 6 Synthesis of polymerizable Compound 1
The same operations as in example 3 were carried out except that 725g of the aqueous 1.0-equivalent-concentration hydrochloric acid solution was changed to 700g of the aqueous 1.0-equivalent-concentration methanesulfonic acid solution in step 2 of example 3. As a result, 19.9g of a pale yellow solid of the polymerizable compound 1 was obtained. The yield was 85% (based on 2, 5-dihydroxybenzaldehyde).
EXAMPLE 7 Synthesis of polymerizable Compound 1
The same operations as in example 3 were carried out except that 12.13g (119.8 mmol) of triethylamine was changed to 12.8g (120.0 mmol) of 2, 6-lutidine and 725g of 1.0 equivalent concentration aqueous hydrochloric acid solution was changed to 700g of 1.0 equivalent concentration aqueous methanesulfonic acid solution in step 2 of example 3. As a result, 20.6g of a pale yellow solid of the polymerizable compound 1 was obtained. The yield was 88% (based on 2, 5-dihydroxybenzaldehyde).
Comparative example 1 Synthesis of polymerizable Compound 1
Step 1-3: the same procedure as in steps 1 to 3 of example 1 was carried out.
Step 4: synthesis of polymerizable Compound 1
In a 3-port reactor with a thermometer, 4.5g (32.58 mmol) of 2, 5-dihydroxybenzaldehyde and 19.78g (195.5 mmol) of triethylamine were dissolved in 150g of chloroform in a nitrogen stream, and the resulting solution was cooled to 10℃or lower. While maintaining the reaction temperature at 10 ℃ or lower, the entire amount of the chloroform solution of intermediate C synthesized in step 3 was slowly added dropwise to the solution. After completion of the dropwise addition, the whole content was stirred at 5 to 10℃for 1 hour (step (1)).
After completion of the reaction, 120g of 1.0 equivalent concentration hydrochloric acid aqueous solution, 10.58g (42.4 mmol) of intermediate B synthesized in step 2 and 0.3g of 2, 6-di-t-butyl-p-cresol were added to the reaction solution while keeping the temperature below 10 ℃. Thereafter, the reaction mixture was heated to 40℃and reacted for 4 hours (step (3)).
After the completion of the reaction, the aqueous layer was separated. Further, 105g of distilled water was poured into the organic layer, and the organic layer was stirred at 40℃for 30 minutes, followed by washing. 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, filtration was performed with a tung mountain funnel covered with 1g of rokahelp#479 to remove rokahelp#479. 180g of chloroform was separated from the obtained organic layer by a rotary evaporator, and concentrated. 210g of hexane was added to the obtained organic layer over 1 hour to precipitate a solid, and a pale yellow solid was obtained by filtration. The resulting pale yellow solid was dissolved in 120g of tetrahydrofuran at 25℃and 1.5g of Rokahellp #479 was added thereto and stirred for 30 minutes. Thereafter, filtration was performed with a tung mountain funnel covered with 1g of rokahelp#479 to remove rokahelp#479. 165g of methanol was slowly added dropwise to the obtained organic layer 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 the 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 procedure as in step 1 of example 3 was performed.
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 with a thermometer and cooled to 10℃or lower. The reaction temperature was controlled to 10℃or lower, and 6.0g (50.54 mmol) of thionyl chloride was added dropwise thereto. After the completion of the dropwise addition, the reaction mixture was brought to 25℃and stirred for 1 hour. After the completion of the reaction, 138g of chloroform was separated under reduced pressure by a rotary evaporator. Thereafter, 46g of new chloroform was added to obtain a chloroform solution (2). In addition, 2.76g (20.0 mmol) of 2, 5-dihydroxybenzaldehyde and 12.13g (119.8 mmol) of triethylamine were dissolved in 92g of chloroform in a 3-port reactor having a thermometer and cooled to 10℃or lower. While keeping the internal temperature of the reactor at 10℃or lower, the chloroform solution (2) was slowly added dropwise to the solution. After completion of the dropwise addition, the reaction mixture was further reacted for 1 hour while keeping the temperature of the reaction mixture at 10℃or lower (step (1)).
After completion of the reaction, 725g of 1.0 equivalent concentration hydrochloric acid aqueous solution, 6.48g (26.0 mmol) 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 maintaining the temperature at 10℃or lower, and the reaction mixture was heated to 40℃for 4 hours to carry out the reaction (step (3)).
After the reaction, the aqueous layer was separated at 40℃and subjected to a liquid separation operation. To the obtained organic layer, 0.92g of Rokahelp #479 (Sanyo Metal mining Co., ltd.) was added, and after stirring at 25℃for 30 minutes, it was filtered off with a filter coated with 0.6g of Rokahelp # 479. The filter was washed with 9.2g of chloroform and combined with the filtrate obtained previously. Next, 110g of chloroform was separated from the obtained organic layer under reduced pressure by a rotary evaporator, and concentrated. To this solution, 33g of tetrahydrofuran was added, and the mixture was cooled to 15℃with stirring. Next, 129g of 60% hexane (manufactured by Godo co., ltd.) was slowly dropped into the solution. Stirring was carried out 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-tert-butyl-p-cresol were added to the obtained solid, and after stirring at 25℃for 30 minutes, it was filtered off with a filter covered 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 obtained organic layer by a rotary evaporator. The resulting solution was brought to 15℃and 121g of methanol were slowly added dropwise. Stirring was carried out at the current temperature for 30 minutes to precipitate a solid. Thereafter, the precipitated solid was collected by filtration. After the filtrate was washed with methanol, it was dried in vacuo 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 procedure as in steps 1 to 3 of example 1 was carried out.
Step 4: synthesis of polymerizable Compound 1
In a 3-port reactor having a thermometer, 4.5g (32.58 mmol) of 2, 5-dihydroxybenzaldehyde and 20.97g (195.7 mmol) of 2, 6-lutidine were dissolved in 150g of chloroform in a nitrogen stream, and the resulting solution was cooled to 10℃or lower. While maintaining the reaction temperature at 10 ℃ or lower, the entire amount of the chloroform solution of intermediate C synthesized in step 3 was slowly added dropwise to the solution. After completion of the dropwise addition, the whole content was stirred at 5 to 10℃for 1 hour (step (1)).
After completion of the reaction, 120g of 1.0 equivalent concentration hydrochloric acid aqueous solution, 10.58g (42.4 mmol) of intermediate B synthesized in step 2 and 0.3g of 2, 6-di-t-butyl-p-cresol were added to the reaction solution while keeping the temperature below 10 ℃. Thereafter, the reaction mixture was heated to 40℃and reacted for 4 hours (step (3)).
After the completion of the reaction, the aqueous layer was separated. Further, 105g of distilled water was poured into the organic layer, and the organic layer was stirred at 40℃for 30 minutes, followed by washing. 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, filtration was performed with a tung mountain funnel covered with 1g of rokahelp#479 to remove rokahelp#479. 180g of chloroform was separated from the obtained organic layer by a rotary evaporator, and concentrated. 210g of hexane was added to the obtained organic layer over 1 hour to precipitate a solid, and a pale yellow solid was obtained by filtration. The resulting pale yellow solid was dissolved in 120g of tetrahydrofuran at 25℃and 1.5g of Rokahellp #479 was added thereto and stirred for 30 minutes. Thereafter, filtration was performed with a tung mountain funnel covered with 1g of rokahelp#479 to remove rokahelp#479. 165g of methanol was slowly added dropwise to the obtained organic layer 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 the polymerizable compound 1 as a pale yellow solid. The yield thereof was found to be 77% (based on 2, 5-dihydroxybenzaldehyde).
Comparative example 4 Synthesis of polymerizable Compound 1
Step 1: the same procedure as in step 1 of example 3 was performed.
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 with a thermometer and cooled to 10℃or lower. The reaction temperature was controlled to 10℃or lower, and 6.0g (50.54 mmol) of thionyl chloride was added dropwise thereto. After the completion of the dropwise addition, the reaction mixture was brought to 25℃and stirred for 1 hour. After the completion of the reaction, 138g of chloroform was separated under reduced pressure by a rotary evaporator. Thereafter, 46g of new chloroform was added to obtain a chloroform solution (3). In addition, 2.76g (20.0 mmol) of 2, 5-dihydroxybenzaldehyde and 12.8g (120.0 mmol) of 2, 6-lutidine were dissolved in 92g of chloroform in a 3-port reactor having a thermometer and cooled to 10℃or lower. While keeping the internal temperature of the reactor at 10℃or lower, the chloroform solution (3) was slowly added dropwise to the solution. After completion of the dropwise addition, the reaction mixture was further reacted for 1 hour while keeping the temperature of the reaction mixture at 10℃or lower (step (1)).
After completion of the reaction, the reaction mixture was kept at 10℃or lower, 725g of 1.0-normal hydrochloric acid aqueous solution, 6.48g (26.0 mmol) of intermediate B synthesized in step 2 of example 1 and 0.33g of 2, 6-di-t-butyl-p-cresol were added thereto, and the reaction mixture was heated to 40℃for 4 hours to effect a reaction (step (3)).
After the reaction, the aqueous layer was separated at 40℃and subjected to a liquid separation operation. To the obtained organic layer, 0.92g of Rokahelp #479 (Sanyo Metal mining Co., ltd.) was added, and after stirring at 25℃for 30 minutes, it was filtered off with a filter coated with 0.6g of Rokahelp # 479. The filter was washed with 9.2g of chloroform and combined with the filtrate obtained previously. Next, 110g of chloroform was separated from the obtained organic layer under reduced pressure by a rotary evaporator, and concentrated. To this solution, 33g of tetrahydrofuran was added, and the mixture was cooled to 15℃with stirring. Next, 129g of 60% hexane (manufactured by Godo co., ltd.) was slowly dropped into the solution. The current temperature was maintained for 30 minutes with stirring 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-tert-butyl-p-cresol were added to the obtained solid, and after stirring at 25℃for 30 minutes, it was filtered off with a filter covered 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 obtained organic layer by a rotary evaporator. The resulting solution was brought to 15℃and 121g of methanol were slowly added dropwise. The current temperature was maintained for 30 minutes with stirring to precipitate a solid. Thereafter, the precipitated solid was collected by filtration. After the filtrate was washed with methanol, it was dried in vacuo to obtain 17.8g of polymerizable compound 1 as a pale yellow solid. The yield thereof was found to be 76% (based on 2, 5-dihydroxybenzaldehyde).
Comparative example 5 Synthesis of polymerizable Compound 1
Step 1: the same procedure as in step 1 of example 3 was performed.
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 with a thermometer and cooled to 10℃or lower. The reaction temperature was controlled to 10℃or lower, and 6.0g (50.54 mmol) of thionyl chloride was added dropwise thereto. After the completion of the dropwise addition, the reaction mixture was brought to 25℃and stirred for 1 hour. After the completion of the reaction, 138g of chloroform was separated under reduced pressure by a rotary evaporator. Thereafter, 46g of new chloroform was added to obtain a chloroform solution (4). In addition, 2.76g (20.0 mmol) of 2, 5-dihydroxybenzaldehyde and 12.8g (120.0 mmol) of 2, 6-lutidine were dissolved in 92g of chloroform in a 3-port reactor having a thermometer and cooled to 10℃or lower. While keeping the internal temperature of the reactor at 10℃or lower, the chloroform solution (4) was slowly added dropwise to the solution. After completion of the dropwise addition, the reaction mixture was further reacted for 1 hour while keeping the temperature of the reaction mixture at 10℃or lower (step (1)).
After completion of the reaction, the reaction mixture was kept at 10℃or lower, 700g of 1.0-normal aqueous methanesulfonic acid, 6.48g (26.0 mmol) of intermediate B synthesized in step 2 of example 1 and 0.33g of 2, 6-di-t-butyl-p-cresol were added thereto, and the reaction mixture was heated to 40℃to carry out the reaction for 4 hours (step (3)).
After the reaction, the aqueous layer was separated at 40℃and subjected to a liquid separation operation. To the obtained organic layer, 0.92g of Rokahelp #479 (Sanyo Metal mining Co., ltd.) was added, and after stirring at 25℃for 30 minutes, it was filtered off with a filter coated with 0.6g of Rokahelp # 479. The filter was washed with 9.2g of chloroform and combined with the filtrate obtained previously. Next, 110g of chloroform was separated from the obtained organic layer under reduced pressure by a rotary evaporator, and concentrated. To this solution, 33g of tetrahydrofuran was added, and the mixture was cooled to 15℃with stirring. Next, 129g of 60% hexane (manufactured by Godo co., ltd.) was slowly dropped into the solution. Stirring was carried out 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-tert-butyl-p-cresol were added to the obtained solid, and after stirring at 25℃for 30 minutes, it was filtered off with a filter covered 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 obtained organic layer by a rotary evaporator. The resulting solution was brought to 15℃and 121g of methanol were slowly added dropwise. The current temperature was maintained for 30 minutes with stirring to precipitate a solid. Thereafter, the precipitated solid was collected by filtration. After the filtrate was washed with methanol, it was dried in vacuo 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 procedure as in comparative example 1 was carried out except that the reaction time of step (3) in step 4 of comparative example 1 was changed from 4 hours to 8 hours. As a result, 28.6g of a pale yellow solid of the polymerizable compound 1 was obtained. The yield was 75% (based on 2, 5-dihydroxybenzaldehyde).
Comparative example 7 Synthesis of polymerizable Compound 1
The same procedure as in comparative example 2 was carried out except that the reaction time of step (3) in comparative example 2 was changed from 4 hours to 8 hours. As a result, 17.1g of a pale yellow solid of the polymerizable compound 1 was obtained. The yield thereof was found to be 73% (based on 2, 5-dihydroxybenzaldehyde).
Comparative example 8 Synthesis of polymerizable Compound 1
The same procedure as in comparative example 3 was carried out except that the reaction time of step (3) in step 4 of comparative example 3 was changed from 4 hours to 8 hours. As a result, 30.5g of a pale yellow solid of the polymerizable compound 1 was obtained. The yield was 80% (based on 2, 5-dihydroxybenzaldehyde).
Comparative example 9 Synthesis of polymerizable Compound 1
The same procedure as in comparative example 4 was carried out except that the reaction time of step (3) in step 2 of comparative example 4 was changed from 4 hours to 8 hours. As a result, 18.5g of a pale yellow solid of the polymerizable compound 1 was obtained. The yield thereof was found to be 79% (based on 2, 5-dihydroxybenzaldehyde).
Comparative example 10 Synthesis of polymerizable Compound 1
The same procedure as in comparative example 5 was carried out except that the reaction time of step (3) in step 2 of comparative example 5 was changed from 4 hours to 8 hours. As a result, 18.0g of a pale yellow solid of the polymerizable compound 1 was obtained. The yield thereof was found to be 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 (2.69 mol) of 1-naphthylacetic acid and 1049g of toluene were charged in a 3-port reactor having a thermometer in a nitrogen flow. Further, 349.5g (2.56 mol) of 6-chloro-1-hexanol and 48.6g (0.26 mol) of p-toluenesulfonic acid monohydrate were added. The solution was heated by using Dean-Stark, and azeotropic dehydration was performed for 2 hours (internal temperature: about 95 ℃ C.) while discharging the produced water out of the reaction system. After the completion of the reaction, the reaction mixture was cooled to 25℃and washed with 742g of a 5.8% by mass aqueous sodium hydrogencarbonate solution. After separation, the organic layer was further washed with 500g of water. Thereafter, 7g of rokahelp#479 was added to the organic layer, and after stirring at room temperature for 30 minutes, filtration was performed 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. As is known from quantitative analysis by high performance liquid chromatography, the pale brown oil containing intermediate D contains 93.0 mass% of intermediate D. The pale brown oil was used directly in the next reaction without purification.
Step 2: synthesis of intermediate E
[ chemical formula 32]
59.52g (net amount of intermediate D55.35 g (0.182 mol)) of pale brown oil containing intermediate D synthesized in the previous step 1 and 235g of N-methyl-2-pyrrolidone were charged in a 3-port reactor with a thermometer in a nitrogen flow to prepare a uniform solution. To this was added 25.0g (0.151 mol) of 2-hydrazinobenzothiazole. Next, 48.18g (0.227 mol) of tripotassium phosphate was added, and the whole was stirred at 100℃for 3 hours. After the completion of the reaction, 312.5g of ethyl acetate was added to the reaction mixture cooled to 60℃and the mixture was filtered while maintaining the temperature at 60 ℃. The organic layer as a filtrate was slowly added dropwise to 250g of a 0.5-normal aqueous citric acid solution, and the mixture was stirred at an internal temperature of 60℃for 30 minutes, followed by separation of the aqueous layer. 275g of a 9.1% by mass aqueous sodium chloride solution was further added to the organic layer, followed by stirring at an internal temperature of 60℃for 30 minutes, standing for 30 minutes, and separating the aqueous layer. Then, 262.5g of a 4.76 mass% aqueous sodium hydrogencarbonate solution was added to the organic layer, followed by stirring at an internal temperature of 60℃for 30 minutes, and then, the mixture was allowed to stand for 30 minutes, and the aqueous layer was separated. 250g of water was further added to the organic layer, followed by stirring at an internal temperature of 60℃for 30 minutes, and then standing for 30 minutes, to separate the aqueous layer. The resulting organic layer was slowly cooled to 0℃and stirred at 0℃for 30 minutes. The resulting solid was obtained by filtration. Thereafter, 150g of ethyl acetate was added to the obtained solid, and the mixture was heated to 60℃to prepare a homogeneous solution, and stirred for 30 minutes. Thereafter, the ethyl acetate solution was slowly cooled to 0℃and stirred at 0℃for 1 hour. The resultant solid was obtained 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 target product 1 H-NMR identification.
1 H-NMR(500MHz，CDCl 3 ，TMS，δppm)：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)。
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 in a 3-port reactor having a thermometer and cooled to 10℃or lower. The reaction temperature was controlled to 10℃or lower, and 6.0g (50.54 mmol) of thionyl chloride was added dropwise thereto. After the completion of the dropwise addition, the reaction mixture was brought to 25℃and stirred for 1 hour. After the completion of the reaction, 138g of chloroform was separated under reduced pressure by a rotary evaporator. Thereafter, 46g of new chloroform was added to obtain a chloroform solution (5). In addition, 2.76g (20.0 mmol) of 2, 5-dihydroxybenzaldehyde and 12.13g (119.8 mmol) of triethylamine were dissolved in 92g of chloroform in a 3-port reactor having a thermometer and cooled to 10℃or lower. While keeping the internal temperature of the reactor at 10℃or lower, the chloroform solution (5) was slowly added dropwise to the solution. After completion of the dropwise addition, the reaction mixture was further reacted for 1 hour while keeping the temperature of the reaction mixture at 10℃or lower (step (1)).
After completion of the reaction, the temperature was kept at 10℃or lower, 725g of a 1.0-normal 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 (23.9 mmol) of 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 the reaction, the aqueous layer was separated at 40℃and subjected to a liquid separation operation. To the obtained organic layer, 0.92g of Rokahelp #479 (Sanyo Metal mining Co., ltd.) was added, and after stirring at 25℃for 30 minutes, it was filtered off with a filter coated 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 and stirring slowly, the precipitated solid was collected by filtration. The obtained solid was dissolved in 147g of chloroform, 0.92g of Rokahelp #479 (Sanyo Metal mining Co., ltd.) was added, and after stirring at 25℃for 30 minutes, it was filtered off with a filter covered 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 and stirring slowly, the precipitated solid was collected by filtration. After the filtrate was washed with methanol, it was dried in vacuo to obtain 22.2g of polymerizable compound 2 as a pale yellow solid. The yield thereof was found to be 82% (based on 2, 5-dihydroxybenzaldehyde).
Structural use of target product 1 H-NMR identification.
1 H-NMR(500MHz，CDCl 3 ，TMS，δppm)：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 procedure 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 in a 3-port reactor having a thermometer and cooled to 10℃or lower. The reaction temperature was controlled to 10℃or lower, and 6.0g (50.54 mmol) of thionyl chloride was added dropwise thereto. After the completion of the dropwise addition, the reaction mixture was brought to 25℃and stirred for 1 hour. After the completion of the reaction, 138g of chloroform was separated under reduced pressure by a rotary evaporator. Thereafter, 46g of new chloroform was added to obtain a chloroform solution (6). In addition, 2.76g (20.0 mmol) of 2, 5-dihydroxybenzaldehyde and 12.84g (119.8 mmol) of 2, 6-lutidine were dissolved in 92g of chloroform in a 3-port reactor having a thermometer and cooled to 10℃or lower. While keeping the internal temperature of the reactor at 10℃or lower, the chloroform solution (6) was slowly added dropwise to the solution. After completion of the dropwise addition, the reaction mixture was further reacted for 1 hour while keeping the temperature of the reaction mixture at 10℃or lower (step (1)).
After the completion of the reaction, the temperature was maintained at 10℃or lower, 725g of a 1.0-normal 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 (23.9 mmol) of intermediate E synthesized in step 2 of example 8 above and 0.33g of 2, 6-di-t-butyl-p-cresol were added, and the reaction mixture was heated to 40℃for 4 hours to effect a reaction (step (3)).
After the reaction, the aqueous layer was separated at 40℃and subjected to a liquid separation operation. To the obtained organic layer, 0.92g of Rokahelp #479 (Sanyo Metal mining Co., ltd.) was added, and after stirring at 25℃for 30 minutes, it was filtered off with a filter coated 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 and stirring slowly, the precipitated solid was collected by filtration. The obtained solid was dissolved in 147g of chloroform, 0.92g of Rokahelp #479 (Sanyo Metal mining Co., ltd.) was added, and after stirring at 25℃for 30 minutes, it was filtered off with a filter covered 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 and stirring slowly, the precipitated solid was collected by filtration. After the filtrate was washed with methanol, it was dried in vacuo to obtain 24.9g of polymerizable compound 2 as a pale yellow solid. The yield thereof was found to be 92% (based on 2, 5-dihydroxybenzaldehyde).
Example 10 Synthesis of polymerizable Compound 2
The same operations as in example 8 were carried out except that 12.13g (119.8 mmol) of triethylamine was changed to 12.84g (119.8 mmol) of 2, 6-lutidine in step 3 of example 8. As a result, 24.9g of polymerizable compound 2 was obtained as a pale yellow solid. The yield thereof was found to be 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 performed.
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 in a 3-port reactor having a thermometer and cooled to 10℃or lower. The reaction temperature was controlled to 10℃or lower, and 6.0g (50.54 mmol) of thionyl chloride was added dropwise thereto. After the completion of the dropwise addition, the reaction mixture was brought to 25℃and stirred for 1 hour. After the completion of the reaction, 138g of chloroform was separated under reduced pressure by a rotary evaporator. Thereafter, 46g of new chloroform was added to obtain a chloroform solution (7). In addition, 2.76g (20.0 mmol) of 2, 5-dihydroxybenzaldehyde and 12.13g (119.8 mmol) of triethylamine were dissolved in 92g of chloroform in a 3-port reactor having a thermometer and cooled to 10℃or lower. While keeping the internal temperature of the reactor at 10℃or lower, the chloroform solution (7) was slowly added dropwise to the solution. After completion of the dropwise addition, the reaction mixture was further reacted for 1 hour while keeping the temperature of the reaction mixture at 10℃or lower (step (1)).
After completion of the reaction, the temperature was kept at 10℃or lower, 725g of 1.0-equivalent-concentration aqueous hydrochloric acid solution, 10.38g (23.9 mmol) of intermediate E synthesized in step 2 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 carry out the reaction for 4 hours (step (3)).
After the reaction, the aqueous layer was separated at 40℃and subjected to a liquid separation operation. To the obtained organic layer, 0.92g of Rokahelp #479 (Sanyo Metal mining Co., ltd.) was added, and after stirring at 25℃for 30 minutes, it was filtered off with a filter coated 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 and stirring slowly, the precipitated solid was collected by filtration. The obtained solid was dissolved in 147g of chloroform, 0.92g of Rokahelp #479 (Sanyo Metal mining Co., ltd.) was added, and after stirring at 25℃for 30 minutes, it was filtered off with a filter covered 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 and stirring slowly, the precipitated solid was collected by filtration. After the filtrate was washed with methanol, it was dried in vacuo 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 procedure 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 in a 3-port reactor having a thermometer and cooled to 10℃or lower. The reaction temperature was controlled to 10℃or lower, and 6.0g (50.54 mmol) of thionyl chloride was added dropwise thereto. After the completion of the dropwise addition, the reaction mixture was brought to 25℃and stirred for 1 hour. After the completion of the reaction, 138g of chloroform was separated under reduced pressure by a rotary evaporator. Thereafter, 46g of new chloroform was added to obtain a chloroform solution (8). In addition, 2.76g (20.0 mmol) of 2, 5-dihydroxybenzaldehyde and 12.84g (119.8 mmol) of 2, 6-lutidine were dissolved in 92g of chloroform in a 3-port reactor having a thermometer and cooled to 10℃or lower. While keeping the internal temperature of the reactor at 10℃or lower, the chloroform solution (8) was slowly added dropwise to the solution. After completion of the dropwise addition, the reaction mixture was further reacted for 1 hour while keeping the temperature of the reaction mixture at 10℃or lower (step (1)).
After completion of the reaction, the temperature was kept at 10℃or lower, 725g of 1.0-equivalent-concentration aqueous hydrochloric acid solution, 10.38g (23.9 mmol) of 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 carry out the reaction for 4 hours (step (3)).
After the reaction, the aqueous layer was separated at 40℃and subjected to a liquid separation operation. To the obtained organic layer, 0.92g of Rokahelp #479 (Sanyo Metal mining Co., ltd.) was added, and after stirring at 25℃for 30 minutes, it was filtered off with a filter coated 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 and stirring slowly, the precipitated solid was collected by filtration. The obtained solid was dissolved in 147g of chloroform, 0.92g of Rokahelp #479 (Sanyo Metal mining Co., ltd.) was added, and after stirring at 25℃for 30 minutes, it was filtered off with a filter covered 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 and stirring slowly, the precipitated solid was collected by filtration. After the filtrate was washed with methanol, it was dried in vacuo to obtain 21.13g of the polymerizable compound 2 as a pale yellow solid. The yield thereof was found to be 78% (based on 2, 5-dihydroxybenzaldehyde).
Comparative example 13 Synthesis of polymerizable Compound 2
The same operations as in example 11 were carried out except that 12.13g (119.8 mmol) of triethylamine was changed to 12.84g (119.8 mmol) of 2, 6-lutidine in step 3 of comparative example 11. As a result, 20.32g of 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 is performed with reference to International publication No. 2017/150622.
Step 2: synthesis of mixture 2
[ chemical formula 34]
The synthesis was performed as follows by using the method described in International publication No. 2016/159293.
83.05g (0.397 mol) of trans-1, 4-cyclohexanedicarboxylic acid dichloride, 600g of cyclopentylmethyl ether and 230g of tetrahydrofuran are introduced into a 3-port reactor with thermometer in a nitrogen stream. To this was added 100.0g (0.378 mol) of intermediate F synthesized in the above step 1, and the reactor was immersed in an ice bath to bring the internal temperature of the reaction solution to 0 ℃. Then, 40.20g (0.397 mol) of triethylamine was slowly added dropwise over 30 minutes while keeping the internal temperature of the reaction solution at 10℃or lower. After the completion of the dropwise addition, the whole content was further stirred at 10℃or lower for 1 hour. 250g of distilled water was added to the obtained reaction solution, followed by addition at 50 ℃ After 2 hours of washing, 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, 416g of a buffer solution (pH 5.5) of 1 mol/l concentration formed from acetic acid and sodium acetate was further used, and the buffer solution was separated. After washing at 40℃for 30 minutes using 416g of a new buffer solution (pH 5.5) of 1 mol/l concentration formed from 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 the organic layer was washed at 40℃for 30 minutes, followed by separating the aqueous layer. 1300g of n-hexane were added dropwise to the obtained organic layer at 40℃over 1 hour. Thereafter, the mixture was cooled to 0℃and stirred for 1 hour to precipitate a solid, and the precipitated solid was collected by filtration. After washing the filtrate with n-hexane, it was dried in vacuo to give 142.0g of a white solid. The obtained crystals were analyzed by HPLC, and the intermediate a was quantified by a calibration curve, and as a result, it was found that intermediate a was contained at 68.5 mass%. In addition, use 13 C-NMR (II)The alkyl-d 8) analysis of the crystals obtained gave a cyclohexane dicarboxylic acid content of less than the detection limit.
Step 3: synthesis of polymerizable Compound 1
In a nitrogen flow, 43.8g (30 g (71.7 mmol) of intermediate A) of the mixture 2 containing intermediate A as a main component synthesized in the above step 2, 300g of chloroform and 10.5g (143.4 mmol) of N, N-dimethylformamide were charged into a 3-port reactor having a thermometer, and cooled to 10℃or lower. While keeping the reaction temperature at 10℃or lower, 9.81g (82.44 mmol) of thionyl chloride was added dropwise thereto. After the completion of the dropwise addition, the reaction mixture was brought 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 new chloroform was added to obtain a chloroform solution of the acid chloride of intermediate A. In a nitrogen stream, 4.5g (32.58 mmol) of 2, 5-dihydroxybenzaldehyde and 19.78g (195.5 mmol) of triethylamine were dissolved in 150g of chloroform in a 3-port reactor with a thermometer additionally prepared, and the resulting solution was cooled to 10℃or lower. While maintaining the reaction temperature below 10 ℃, the entire amount of the chloroform solution of the acid chloride of intermediate a previously synthesized was slowly added dropwise to the solution. After completion of the dropwise addition, the whole content was stirred at 5 to 10℃for 1 hour (step (1)).
After the completion of the reaction, 120g of a 1.0-normal hydrochloric acid aqueous solution was added to the reaction mixture while maintaining the temperature at 10℃or lower. Thereafter, the mixture was stirred at 10℃or lower for 30 minutes to effect a reaction (step (2)).
Thereafter, 10.58g (42.4 mmol) of intermediate B synthesized in step 2 of the above-described example 1 and 0.3g of 2, 6-di-t-butyl-p-cresol were added. Thereafter, the reaction mixture was heated to 40℃and reacted for 4 hours (step (3)).
After the completion of the reaction, the aqueous layer was separated. Further, 105g of distilled water was poured 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, filtration was performed with a tung mountain funnel covered with 1g of rokahelp#479 to remove rokahelp#479. 180g of chloroform was separated from the obtained organic layer by a rotary evaporator, and concentrated. 210g of hexane was added to the obtained organic layer over 1 hour to precipitate a solid, and a pale yellow solid was obtained by filtration. The resulting pale yellow solid was dissolved in 120g of tetrahydrofuran at 25℃and 1.5g of Rokahellp #479 was added thereto and stirred for 30 minutes. Thereafter, filtration was performed with a tung mountain funnel covered with 1g of rokahelp#479 to remove rokahelp#479. 165g of methanol was slowly added dropwise to the obtained organic layer 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 the polymerizable compound 1 as a pale yellow solid. The yield thereof was found to be 92.0% (based on 2, 5-dihydroxybenzaldehyde).
EXAMPLE 12 Synthesis of polymerizable Compound 1
Step 1: synthesis of intermediate G
The synthesis was performed as follows using the method described in International publication No. 16/159293.
In a nitrogen stream, in a 3-port reactor with thermometer83.05g (0.397 mol) of trans-1, 4-cyclohexanedicarboxylic acid dichloride, 600g of cyclopentylmethyl ether and 230g of tetrahydrofuran were added. 100.0g (0.378 mol) of intermediate F synthesized in step 1 of example 11 above was added thereto, and the reactor was immersed in an ice bath to bring the internal temperature of the reaction solution to 0 ℃. Then, 40.20g (0.397 mol) of triethylamine was slowly added dropwise over 30 minutes while keeping the internal temperature of the reaction solution at 10℃or lower. After the completion of the dropwise addition, the whole content was further stirred at 10℃or lower for 1 hour. To the resulting reaction solution, 250g of distilled water was added, and after washing at 50℃for 2 hours, the aqueous layer was separated. 250g of fresh distilled water was added and the mixture was 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 buffer solution (pH: 5.5) formed of acetic acid and sodium acetate at a concentration of 1 mol/liter, the buffer solution was separated. After washing the organic layer with 416g of a new buffer solution (pH: 5.5) of 1 mol/l concentration formed from acetic acid and sodium acetate at 40℃for 30 minutes, 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 gradually cooled to 0℃while stirring, and after stirring at 0℃for 1 hour, the precipitated solid was filtered off. 1400g of n-hexane were 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 washing the filtrate with n-hexane, it was dried in vacuo to give 105.7g of a white solid. The obtained crystals were analyzed by HPLC, and intermediate G was quantitatively determined by a calibration curve, resulting in 91.3 mass% of intermediate a. In addition, use 13 C-NMR (II)The alkyl-d 8) analysis of the crystals obtained gave a cyclohexane dicarboxylic acid content of less than the detection limit.
Step 2: synthesis of polymerizable Compound 1
The same operations as in example 11 were carried out except that in step 3 of example 11, 43.8G (30G (71.7 mmol) of intermediate a) of the mixture 2 containing intermediate a as a main component synthesized in step 2 of example 11 was changed to 32.9G (30G (71.7 mmol) of intermediate a) of the intermediate G synthesized in step 1. As a result, 35.0g of polymerizable compound 1 was obtained as a pale yellow solid. The yield thereof was found to be 91.8% (based on 2, 5-dihydroxybenzaldehyde).
EXAMPLE 13 Synthesis of polymerizable Compound 1
Step 1: synthesis of intermediate H
83.05g (0.397 mol) 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 (0.378 mol) of intermediate F synthesized in step 1 of the above-described example 11, 1.67g of 2, 6-di-t-butyl-p-cresol were added thereto, and the reactor was immersed in an ice bath to bring the internal temperature of the reaction liquid to 0 ℃. Next, 40.2g (0.397 mol) 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 further 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 mixture was washed at 50℃for 2 hours. After separating the aqueous layer, 250g of fresh distilled water was added at 50℃and the mixture was washed at 50℃for 2 hours. This operation was performed 3 times in total. After the obtained organic layer was cooled to 40 ℃, 200g of methanol was added, the mixture was slowly cooled to 0 ℃, and the mixture was slowly stirred for 1 hour, whereby a solid was precipitated. The precipitated solid was removed by filtration to obtain a filtrate. The filtrate in the filter was washed with 100g of another prepared methanol cooled to 0 c, and the washing liquid obtained by the washing was combined with the previous filtrate. The filtrate combined with the washing liquid was further stirred at 40℃for 30 minutes using 416g of a buffer solution (pH 5.5) having a concentration of 1 mol/liter and formed of acetic acid and sodium acetate, and washed. After washing, the aqueous layer was separated, 416g of a buffer solution (pH 5.5) of 1 mol/liter strength 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, and the aqueous layer was separated, 250g of distilled water was added to the obtained organic layer (oil layer), and the mixture was washed at 40℃for 30 minutes. The operation was performed 2 times in total, and the solution was separated to obtain 1200g of n-hexane was added to the organic layer, and the mixture was cooled to 0℃slowly, whereby a solid was precipitated, and the precipitated solid was collected by filtration. After washing the filtrate with n-hexane, it was dried in vacuo to give 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 mass%. In addition, use 13 C-NMR (II)The alkyl-d 8) analysis of the crystals obtained gave a cyclohexane dicarboxylic acid content of less than the detection limit.
Step 2: synthesis of polymerizable Compound 1
The same operations as in example 11 were carried out except that in step 3 of example 11, 43.8g (30 g (71.7 mmol) of intermediate A) of the mixture 2 containing intermediate A as a main component synthesized in step 2 of example 11 was changed to 32.4g (30 g (71.7 mmol) of intermediate A) of the intermediate H synthesized in step 1. As a result, 35.7g of a pale yellow solid of the polymerizable compound 1 was obtained. The yield thereof was found to be 93.6% (based on 2, 5-dihydroxybenzaldehyde).
EXAMPLE 14 Synthesis of polymerizable Compound 1
The same operations as in example 11 were performed except that in step 3 of example 11, 19.78g (195.5 mmol) of triethylamine was changed to 17.46g (163.0 mmol) of 2, 6-lutidine and 43.8mg (0.36 mmol) of N, N-dimethyl-4-aminopyridine (DMAP) were used in combination. As a result, 34.9g of a pale yellow solid of the polymerizable compound 1 was obtained. The yield thereof was found to be 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, 43.8G (30G (71.7 mmol) of intermediate A) of the mixture 2 containing intermediate A as a main component synthesized in step 2 of example 11 was changed to 32.9G (30G (71.7 mmol) of intermediate A) of the intermediate G synthesized in step 1 of example 12, and 19.78G (195.5 mmol) of triethylamine was changed to 17.46G (163.0 mmol) of 2, 6-lutidine and 43.8mg (0.36 mmol) of N, N-dimethyl-4-aminopyridine were used in combination. As a result, 35.2g of polymerizable compound 1 was obtained as a pale yellow solid. The yield thereof was found to be 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, 43.8g (30 g (71.7 mmol) of intermediate A) of the mixture 2 containing intermediate A as a main component synthesized in step 2 of example 11 was changed to 32.4g (30 g (71.7 mmol) of intermediate A) of the intermediate H synthesized in step 1 of example 13, and 19.78g (195.5 mmol) of triethylamine was changed to 17.46g (163.0 mmol) of 2, 6-lutidine and 43.8mg (0.36 mmol) of N, N-dimethyl-4-aminopyridine were used in combination. As a result, 35.8g of a pale yellow solid of the polymerizable compound 1 was obtained. The yield thereof was found to be 93.9% (based on 2, 5-dihydroxybenzaldehyde).
EXAMPLE 17 Synthesis of polymerizable Compound 1
The same operations as in example 11 were conducted except that 9.81g (82.44 mmol) of thionyl chloride was changed to 8.79g (73.85 mmol) of thionyl chloride and 19.78g (195.5 mmol) of triethylamine was changed to 17.46g (163.0 mmol) of 2, 6-lutidine and 43.8mg (0.36 mmol) of N, N-dimethyl-4-aminopyridine were used in combination in step 3 of example 11. As a result, 35.5g of a pale yellow solid of the polymerizable compound 1 was obtained. 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 except that in step 3 of example 11, 43.8G (30G (71.7 mmol) of intermediate A) of the mixture 2 containing intermediate A as a main component synthesized in step 2 of example 11 was changed to 32.9G (30G (71.7 mmol) of intermediate A) of the intermediate G synthesized in step 1 of example 12, 9.81G (82.44 mmol) of thionyl chloride was changed to 8.79G (73.85 mmol) of thionyl chloride, and 19.78G (195.5 mmol) of triethylamine was changed to 17.46G (163.0 mmol) of 2, 6-lutidine and 43.8mg (0.36 mmol) of N, N-dimethyl-4-aminopyridine were used together. As a result, 35.6g of a pale yellow solid of the polymerizable compound 1 was obtained. 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 except that in step 3 of example 11, 43.8g (30 g (71.7 mmol) of intermediate A) of the mixture 2 containing intermediate A as a main component synthesized in step 2 of example 11 was changed to 32.4g (30 g (71.7 mmol) of intermediate A) of the intermediate H synthesized in step 1 of example 13, 9.81g (82.44 mmol) of thionyl chloride was changed to 8.79g (73.85 mmol) of thionyl chloride, and 19.78g (195.5 mmol) of triethylamine was changed to 17.46g (163.0 mmol) of 2, 6-lutidine and 43.8mg (0.36 mmol) of N, N-dimethyl-4-aminopyridine were used together. As a result, 36.0g of a pale yellow solid of the polymerizable compound 1 was obtained. The yield was 94.4% (based on 2, 5-dihydroxybenzaldehyde).
EXAMPLE 20 Synthesis of polymerizable Compound 1
Step 1: synthesis of intermediate I
The same operations as in example 13 were performed except that in step 1 of example 13, 1200g of n-hexane was changed to 1200g of n-heptane and the n-hexane for washing the filtrate was changed to n-heptane, to obtain 97.40g of a white solid as intermediate I. The obtained white solid was quantitatively determined by high performance liquid chromatography, and as a result, the content of intermediate a in the white solid was 94.7 mass%. In addition, use 13 C-NMR (II)The alkyl-d 8) analysis of the crystals obtained gave a cyclohexane dicarboxylic acid content of less than the detection limit.
Step 2: synthesis of Compound 1
The same operations as in example 11 were carried out, except that in step 3 of example 11, 43.8g (30 g (71.7 mmol) of intermediate A) of the mixture 2 containing intermediate A as a main component synthesized in step 2 of example 11 was changed to 31.7g (30 g (71.7 mmol) of intermediate A) of the intermediate I synthesized in step 1 above, 9.81g (82.44 mmol) of thionyl chloride was changed to 8.79g (73.85 mmol) of thionyl chloride, and 19.78g (195.5 mmol) of triethylamine was changed to 17.46g (163.0 mmol) of 2, 6-lutidine and 43.8mg (0.36 mmol) of N, N-dimethyl-4-aminopyridine were used together. As a result, 36.1g of a pale yellow solid of the polymerizable compound 1 was obtained. The yield was 94.7% (based on 2, 5-dihydroxybenzaldehyde).
EXAMPLE 21 Synthesis of polymerizable Compound 1
The same operations as in example 11 were carried out, except that in step 3 of example 11, 43.8g (30 g (71.7 mmol) of intermediate A) of the mixture 2 containing intermediate A as a main component synthesized in step 2 of example 11 was changed to 31.7g (30 g (71.7 mmol) of intermediate A) of the intermediate I synthesized in step 1 of example 20, 9.81g (82.44 mmol) of thionyl chloride was changed to 8.79g (73.85 mmol) of thionyl chloride, 19.78g (195.5 mmol) of triethylamine was changed to 17.46g (163.0 mmol) of 2, 6-lutidine and 43.8mg (0.36 mmol) of N, N-dimethyl-4-aminopyridine were used in combination, and 210g of hexane for precipitating a solid was changed to 210g of heptane. As a result, 36.0g of a pale yellow solid of the polymerizable compound 1 was obtained. 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 above formula (a) which can be used for producing an optical film or the like can be obtained in a high yield.

Claims (6)

1. A method for producing a polymerizable compound, comprising the steps of:
a step (1) of esterifying 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 condensing agent, thereby obtaining a reaction solution containing a compound represented by the following formula (III), wherein the dehydration condensing agent is a carbodiimide compound;
in the formula (I), Q represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, fg 1 And Fg 2 Each independently represents hydroxy, -CH 2 OH or-CH 2 CH 2 OH，
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), Y 1 And Y 2 Each independently represents-C (=O) -O-, -O-C (=O) -, -CH 2 -O-C(＝O)-、-C(＝O)-O-CH 2 -、-CH 2 -CH 2 -O-C (=o) -or-C (=o) -O-CH 2 -CH 2 -, Q, A and n are as defined above,
a step (2) of adding an acidic aqueous solution to the reaction solution obtained in the step (1), and hydrolyzing the compound represented by the formula (II) or the dehydration condensing agent contained in the reaction solution, wherein the acidic aqueous solution has an acid component of an inorganic acid and/or an organic acid having 1 to 20 carbon atoms; and
A step (3) of adding a compound represented by the following formula (IV) to react with a compound represented by the following formula (III) after the step (2),
in the formula (IV), X represents an oxygen atom, a sulfur atom or a-C (R) 1 )(R 2 ) -or-N (R) 1 ) Where R is 1 And R is 2 Each 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 X Represents 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 with a halogen atom, an alkoxy group having 1 to 6 carbon atoms, an alkylthio group having 1 to 6 carbon atoms, a monosubstituted amino group, a disubstituted amino group, -OCF 3 、-C(＝O)-O-R 3 or-O-C (=o) -R 3 Here, R is 3 Representing and said R 1 、R 2 Identical meaning, a plurality of R X All of which may be the same or different from each other, and any of C-R constituting a ring X Can be substituted by a nitrogen atom which is substituted by a nitrogen atom,
the R is 1 And R is 2 The substituent which can be provided is a halogen atom, a cyano group, a substituted amino group, an alkoxy group having 1 to 6 carbon atoms, a nitro group, an aryl group, a cycloalkyl group having 3 to 8 carbon atoms or a hydroxyl group,
wherein R may have a substituent such as a cyano group, a nitro group, a hydroxyl group, a halogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms substituted with an alkoxy group having 1 to 6 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms or a substituted amino group,
The polymerizable compound is represented by the following formula (A),
in the formula (A), Y 1 、Y 2 、A、R、R X X, Q and n are the same as defined above.
2. The method for producing a polymerizable compound according to claim 1, wherein the acid component of the acidic aqueous solution is at least one member 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.
3. The method for producing a polymerizable compound according to claim 1, wherein R is a substituent-capable alkyl group having 1 to 60 carbon atoms, a substituent-capable alkenyl group having 2 to 60 carbon atoms, a substituent-capable alkynyl group having 2 to 60 carbon atoms, a substituent-capable aromatic hydrocarbon ring group having 6 to 18 carbon atoms, a substituent-capable aromatic heterocyclic group having 2 to 18 carbon atoms 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, Y represents a single bond, -O-, -S-, -C (=O) -, -O-C (Rb) (Rc) -, -C (Rb) (Rc) -O-, -O-CH 2 -CH 2 -、-CH 2 -CH 2 -O-、-C(＝O)-O-、-O-C(＝O)-、-C(＝O)-S-、-S-C(＝O)-、-NR 4 -C(＝O)-、-C(＝O)-NR 4 -、-CH＝CH-C(＝O)-O-、-O-C(＝O)-CH＝CH-、-CH 2 -CH 2 -C(＝O)-O-、-O-C(＝O)-CH 2 -CH 2 -、-CH 2 -CH 2 -O-C(＝O)-、-C(＝O)-O-CH 2 -CH 2 -、-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)-NR 4 -、-NR 4 -C(＝O)-O-、-O-C(＝O)-CH 2 -S-、-S-CH 2 -C (=o) -O-or-O-C (=o) -O-, where R 4 Each of Rc and Rb independently represents a hydrogen atom, an aromatic hydrocarbon ring group having 6 to 18 carbon atoms which may have a substituent, or an aromatic heterocyclic group having 2 to 18 carbon atoms which may have a substituent, and G is at least one-CH contained in (i) an aliphatic hydrocarbon group having 1 to 20 carbon atoms and (2) an aliphatic hydrocarbon group having 3 to 20 carbon atoms 2 -is interrupted by-O-, -S-,-O-C(＝O)-、-C(＝O)-O-、-O-C(＝O)-O-、-NR 5 -C(＝O)-、-C(＝O)-NR 5 -、-NR 5 -or-C (=o) -substituted, wherein-O-or-S-are each present in more than 2 adjacent positions, where R 5 Represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms,
the substituent which Rc and Rb can have is halogen atom, cyano group, alkyl group with 1 to 6 carbon atoms, alkenyl group with 2 to 6 carbon atoms, alkyl group with 1 to 6 carbon atoms, N-dialkyl amino group with 2 to 12 carbon atoms, alkoxy group with 1 to 6 carbon atoms, nitro group, aromatic hydrocarbon ring group with 6 to 18 carbon atoms, wherein at least 1 hydrogen atom is replaced by halogen 3 、-C(＝O)-R Y 、-C(＝O)-O-R Y 、-O-C(＝O)-R Y or-SO 2 R b Here, R is Y Represents (i) an alkyl group having 1 to 20 carbon atoms which may have a substituent, (ii) an alkenyl group having 2 to 20 carbon atoms which may have a substituent, (iii) a cycloalkyl group having 3 to 12 carbon atoms which may have a substituent, or (iv) an aromatic hydrocarbon ring group having 6 to 18 carbon atoms which may have a substituent, and R b An aromatic hydrocarbon ring group having 6 to 18 carbon atoms which may have an alkyl group having 1 to 6 carbon atoms or an alkoxy group having 1 to 6 carbon atoms as a substituent,
the R is Y When the groups described in (i) and (ii) are represented, the substituents which can be provided are a halogen atom, a cyano group, an alkoxy group having 1 to 20 carbon atoms, a nitro group, an aromatic hydrocarbon ring group having 6 to 18 carbon atoms, an aromatic heterocyclic group having 2 to 18 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms or a fluoroalkyl group having 1 to 12 carbon atoms in which at least 1 hydrogen atom is substituted with a fluorine atom,
the R is Y When the group (iii) is represented, the substituent which it can have is a halogen atom, a cyano group, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a nitro group or an aromatic hydrocarbon ring group having 6 to 18 carbon atoms,
the R is Y When the group of (iv) is represented, it may have a substituentIs halogen atom, cyano group, alkoxy group having 1 to 20 carbon atoms, nitro group, aromatic heterocyclic group having 2 to 18 carbon atoms, cycloalkyl group having 3 to 8 carbon atoms, fluoroalkyl group having 1 to 12 carbon atoms in which at least 1 hydrogen atom is replaced by fluorine atom, or-OCF 3 。
4. The method for producing a polymerizable compound according to claim 1, wherein R is X All hydrogen atoms.
5. The method for producing a polymerizable compound according to claim 1, wherein in the step (3), an acidic aqueous solution is further added to perform a reaction.
6. The method for producing a polymerizable compound according to any one of claims 1 to 5, 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 have the same meanings as described above.
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