JPWO2019230848A1 - Method for producing polymerizable compound - Google Patents

Abstract

In the method for producing a polymerizable compound of the present invention, a compound represented by the formula (I) and a compound represented by the formula (II) are reacted in an organic solvent in the presence of a base and / or a dehydration condensing agent. , A step (1) of obtaining a reaction solution containing the compound represented by the formula (III), a step (2) of hydrolyzing the compound represented by the formula (II) or the dehydration condensing agent contained in the reaction solution, and the formula ( It has a step (3) of adding the compound represented by IV) and reacting it with the compound represented by the formula (III). In the formula, Q represents a hydrogen atom or the like, Fg1 or Fg2 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 elimination group, and n represents an integer of 1 to 20. , Y1 and Y2 represent -C (= O) -O-, -OC (= O)-etc., X represents an oxygen atom, a sulfur atom, etc., R represents a hydrogen atom, an organic group, etc. RX represents a hydrogen atom, a halogen atom and the like. [Chemical 1]

Description

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

In recent years, as a technique capable of thinning a retardation plate, particularly a retardation plate having anti-wavelength dispersibility, a retardation plate is created by applying a polymerizable composition containing a low molecular weight polymerizable compound to a film substrate. Attention is being paid to how to do this.

（式中、Ａは、それぞれ独立して、水素原子、メチル基または塩素原子を表し、Ｒは、水素原子または置換基を有していてもよい炭素数１〜６０の有機基を表し、Ｘは、酸素原子、硫黄原子、−Ｃ（Ｒ^１）（Ｒ^２）−、または、−Ｎ−Ｒ^１−を表し、ここで、Ｒ^１およびＲ^２は、それぞれ独立して、水素原子または置換基を有していてもよい炭素数１〜１０のアルキル基を表し、Ｒ^Ｘは、水素原子、ハロゲン原子、炭素数１〜６のアルキル基、シアノ基、ニトロ基、少なくとも１つの水素原子がハロゲン原子で置換された炭素数１〜６のアルキル基、炭素数１〜６のアルコキシ基、炭素数１〜６のアルキルチオ基、一置換アミノ基、二置換アミノ基、−ＯＣＦ_３、−Ｃ（＝Ｏ）−Ｏ−Ｒ^３、または、−Ｏ−Ｃ（＝Ｏ）−Ｒ^３を表し、ここで、Ｒ^３は、前記Ｒ^１、Ｒ^２と同じ意味を表し、複数のＲ^Ｘ同士は、すべて同一であっても、相異なっていてもよく、環を構成する任意のＣ−Ｒ^Ｘは、窒素原子に置き換えられていてもよく、ｎは、１〜２０のいずれかの整数を表す。）And, for example, Patent Document 1 has a practically low melting point and high solubility in a general-purpose solvent, which can be suitably used for the preparation of a polymerizable composition, and further, uniform polarization conversion in a wide wavelength range is performed. As a polymerizable compound capable of forming a possible optical film, a polymerizable compound represented by the following formula (α) is disclosed.

(In the formula, A independently represents a hydrogen atom, a methyl group or a chlorine atom, R represents an organic group having 1 to 60 carbon atoms which may have a hydrogen atom or a substituent, and X. Represents an oxygen atom, a sulfur atom, -C (R ¹ ) (R ² )-, or -N-R ^1- , where R ¹ and R ² are independent hydrogen atoms or substitutions, respectively. represents an alkyl group having 1 to 10 carbon atoms which may have a group, R ^X is a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, a cyano group, a nitro group, at least one hydrogen atom Alkyl group having 1 to 6 carbon atoms substituted with halogen atom, alkoxy group having 1 to 6 carbon atoms, alkylthio group having 1 to 6 carbon atoms, monosubstituted amino group, disubstituted amino group, -OCF ₃ , -C ( = O) ^{-O-R 3,} or represents -O-C (= O) -R 3, wherein, ^{R 3,} said ^R 1, represents the same meaning as ^{R 2,} a plurality of ^{R X} each other all be the same or different phase, any C-R ^X constituting the ring may be replaced with a nitrogen atom, n represents represents an integer of from 1 to 20 .)

（式中、Ａおよびｎは、前記と同じ意味を表し、Ｌは脱離基を表す。）
で示される化合物と、２，５−ジヒドロキシベンズアルデヒドとを塩基存在下で反応（エステル化反応）させて、下記式（β）：

（式中、Ａおよびｎは、前記と同じ意味を表す。）
で表される化合物を含む反応液を得た後、得られた反応液に下記式（ＩＶ）：

（式中、Ｘ、ＲおよびＲ^Ｘは、前記と同じ意味を表す。）
で示される化合物と酸性水溶液とを添加して、エステル化反応で生成する塩類を酸性水溶液に溶解させながら式（α）で示される重合性化合物を合成する方法が提案されている。Further, in Patent Document 1, as a method for producing a polymerizable compound represented by the above formula (α) with high purity and high yield, the following formula (II):

(In the formula, A and n have the same meanings as described above, and L represents a leaving group.)
The compound represented by (1) and 2,5-dihydroxybenzaldehyde are reacted in the presence of a base (esterification reaction), and the following formula (β):

(In the formula, A and n have the same meanings as described above.)
After obtaining a reaction solution containing the compound represented by the following formula (IV):

(In the formula, X, R and ^RX have the same meanings as described above.)
A method has been proposed in which the compound represented by (1) and an acidic aqueous solution are added to dissolve the salts produced by the esterification reaction in the acidic aqueous solution to synthesize the polymerizable compound represented by the formula (α).

International Publication No. 2015/141784

However, there is room for improvement in the conventional method for producing a polymerizable compound in which the compound represented by the formula (IV) and the acidic aqueous solution are added at the same time in terms of further improving the yield of the polymerizable compound.

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

As a result of diligent research to solve the above problems, the present inventors have condensed the compound represented by the following formula (I) and the compound represented by the following formula (II) into a base and / or dehydration condensation in an organic solvent. After reacting in the presence of an agent to obtain a reaction solution containing the compound represented by the following formula (III), a predetermined component contained in the obtained reaction solution is hydrolyzed, and then the following By adding the compound represented by the formula (IV) and reacting the compound represented by the formula (IV) with the compound represented by the formula (III), the polymerizable compound represented by the following formula (A) is highly yielded. We have found that it can be obtained at a rate, and have completed the present invention.

（式中、Ｑは、水素原子または炭素数１〜６のアルキル基を表し、Ｆｇ^１およびＦｇ^２は、それぞれ独立して、水酸基、−ＣＨ_２ＯＨ、または、−ＣＨ_２ＣＨ_２ＯＨを表す。）
で示される化合物と、下記式（ＩＩ）

（式中、Ａは、水素原子、メチル基または塩素原子を表し、Ｌは、水酸基または脱離基を表し、ｎは、１〜２０のいずれかの整数を表す。）
で示される化合物とを、塩基および／または脱水縮合剤存在下にてエステル化させて、下記式（ＩＩＩ）

（式中、Ｙ^１およびＹ^２は、それぞれ独立して、−Ｃ（＝Ｏ）−Ｏ−、−Ｏ−Ｃ（＝Ｏ）−、−ＣＨ_２−Ｏ−Ｃ（＝Ｏ）−、−Ｃ（＝Ｏ）−Ｏ−ＣＨ_２−、−ＣＨ_２−ＣＨ_２−Ｏ−Ｃ（＝Ｏ）−、または、−Ｃ（＝Ｏ）−Ｏ−ＣＨ_２−ＣＨ_２−を表し、Ｑ、Ａおよびｎは、前記と同じ意味を表す。）
で示される化合物を含む反応液を得る工程（１）、
前記工程（１）で得られた反応液に含まれる前記式（ＩＩ）で示される化合物または、前記脱水縮合剤を加水分解する工程（２）、
並びに、
前記工程（２）の後、下記式（ＩＶ）

（式中、Ｘは、酸素原子、硫黄原子、−Ｃ（Ｒ^１）（Ｒ^２）−、または、−Ｎ−Ｒ^１−を表し、ここで、Ｒ^１およびＲ^２は、それぞれ独立して、水素原子または置換基を有していてもよい炭素数１〜１０のアルキル基を表し、Ｒは、水素原子または置換基を有していてもよい炭素数１〜６０の有機基を表し、Ｒ^Ｘは、水素原子、ハロゲン原子、炭素数１〜６のアルキル基、シアノ基、ニトロ基、少なくとも１つの水素原子がハロゲン原子で置換された炭素数１〜６のアルキル基、炭素数１〜６のアルコキシ基、炭素数１〜６のアルキルチオ基、一置換アミノ基、二置換アミノ基、−ＯＣＦ_３、−Ｃ（＝Ｏ）−Ｏ−Ｒ^３、または、−Ｏ−Ｃ（＝Ｏ）−Ｒ^３を表し、ここで、Ｒ^３は、前記Ｒ^１、Ｒ^２と同じ意味を表し、複数のＲ^Ｘ同士は、すべて同一であっても、相異なっていてもよく、環を構成する任意のＣ−Ｒ^Ｘは、窒素原子に置き換えられていてもよい。）
で示される化合物を加えて前記式（ＩＩＩ）で示される化合物と反応させる工程（３）を有する、下記式（Ａ）

（式中、Ｙ^１、Ｙ^２、Ａ、Ｒ、Ｒ^Ｘ、Ｘ、Ｑおよびｎは、前記と同じ意味を表す。）で示される重合性化合物の製造方法。
＜２＞前記工程（２）では、前記反応液に水または水溶液を添加して前記加水分解を行う、＜１＞に記載の重合性化合物の製造方法。
＜３＞前記工程（２）では、前記反応液に酸性水溶液を添加する、＜２＞に記載の重合性化合物の製造方法。
＜４＞前記酸性水溶液の酸成分が、無機酸および／または炭素数１〜２０の有機酸である、＜３＞に記載の重合性化合物の製造方法。
＜５＞前記酸性水溶液の酸成分が、塩酸、硫酸、リン酸、ホウ酸、スルホン酸類、スルフィン酸類、ギ酸、酢酸、シュウ酸、クエン酸、アスコルビン酸、酒石酸およびリンゴ酸からなる群から選ばれる少なくとも一種である、＜３＞または＜４＞に記載の重合性化合物の製造方法。
＜６＞前記Ｒが、置換基を有していてもよい炭素数１〜６０のアルキル基、置換基を有していてもよい炭素数２〜６０のアルケニル基、置換基を有していてもよい炭素数２〜６０のアルキニル基、置換基を有していてもよい炭素数６〜１８の芳香族炭化水素環基、置換基を有していてもよい炭素数２〜１８の芳香族複素環基、または、Ｒａ−Ｙ−Ｇ−（式中、Ｒａは、芳香族炭化水素環および芳香族複素環の少なくとも一方を有する環状基を表し、Ｙは、化学的な単結合、−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−、または、−Ｏ−Ｃ（＝Ｏ）−Ｏ−を表し、ここで、Ｒ^４は、水素原子または炭素数１〜６のアルキル基を表し、ＲｃおよびＲｂは、それぞれ独立して、水素原子、置換基を有していてもよい炭素数６〜１８の芳香族炭化水素環基、または、置換基を有していてもよい炭素数２〜１８の芳香族複素環基を表し、Ｇは、（ｉ）炭素数１〜２０の２価の脂肪族炭化水素基、および、（ｉｉ）炭素数３〜２０の２価の脂肪族炭化水素基に含まれる−ＣＨ_２−の少なくとも一つが、−Ｏ−、−Ｓ−、−Ｏ−Ｃ（＝Ｏ）−、−Ｃ（＝Ｏ）−Ｏ−、−Ｏ−Ｃ（＝Ｏ）−Ｏ−、−ＮＲ^５−Ｃ（＝Ｏ）−、−Ｃ（＝Ｏ）−ＮＲ^５−、−ＮＲ^５−、または、−Ｃ（＝Ｏ）−に置換された基、のいずれかの有機基（ただし、−Ｏ−または−Ｓ−がそれぞれ２以上隣接して介在する場合を除く。）であり、ここで、Ｒ^５は、水素原子、または、炭素数１〜６のアルキル基を表す。）である、＜１＞〜＜５＞の何れかに記載の重合性化合物の製造方法。
＜７＞前記Ｒ^Ｘが全て水素原子である、＜１＞〜＜６＞の何れかに記載の重合性化合物の製造方法。
＜８＞前記工程（３）において、更に酸性水溶液を加えて反応を行う、＜１＞〜＜７＞の何れかに記載の重合性化合物の製造方法。
＜９＞前記式（ＩＩ）で示される化合物が、下記式（ＩＩａ）

（式中、Ａ、Ｌおよびｎは、前記と同じ意味を表す。）
で示される化合物である、＜１＞〜＜８＞の何れかに記載の重合性化合物の製造方法。Thus, according to the present invention, the following methods for producing the polymerizable compounds <1> to <9> are provided.
<1> In an organic solvent, the following formula (I)

(In the formula, Q represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and Fg ¹ and Fg ² independently represent a hydroxyl group, -CH ₂ OH, or -CH ₂ CH ₂ OH, respectively. .)
The compound represented by and the following formula (II)

(In the formula, A represents a hydrogen atom, a methyl group or a chlorine atom, L represents a hydroxyl group or a leaving group, and n represents an integer of 1 to 20.)
The compound represented by (3) is esterified in the presence of a base and / or a dehydration condensing agent to formulate (III) below.

(In the equation, Y ¹ and Y ² are independently -C (= O) -O-, -OC (= O)-, -CH _2- OC (= O)-,-, respectively. _{C (= O) -O-CH} 2 -, - CH 2 -CH 2 -O-C (= O) -, _{or, -C (= O) -O-} CH 2 -CH 2 - represent, Q, A and n have the same meanings as described above.)
Step (1) of obtaining a reaction solution containing the compound represented by
The 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
After the step (2), the following formula (IV)

(In the formula, X represents an oxygen atom, a sulfur atom, -C (R ¹ ) (R ² )-, or -N-R ^1- , where R ¹ and R ² are independent of each other. , Represents an alkyl group having 1 to 10 carbon atoms which may have a hydrogen atom or a substituent, and R represents an organic group having 1 to 60 carbon atoms which may have a hydrogen atom or a substituent. ^RX is 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 one hydrogen atom is replaced with a halogen atom, and 1 to 6 carbon atoms. An alkoxy group of 6, an alkylthio group having 1 to 6 carbon atoms, a mono-substituted amino group, a di-substituted amino group, -OCF ₃ , -C (= O) -OR ³ , or -OC (= O). represents -R ^3, wherein, R ^3, said R ^1, represents the same meaning as R ^2, each other a plurality of R ^X, all be the same, or different phases constituting the ring any C-R ^X may be replaced by a nitrogen atom.)
The following formula (A), which comprises the step (3) of adding the compound represented by the above formula (III) and reacting with the compound represented by the formula (III).

(In the formula, Y ¹ , Y ² , A, R, ^RX , X, Q and n have the same meanings as described above.) A method for producing a polymerizable compound.
<2> The method for producing a polymerizable compound according to <1>, wherein in the step (2), water or an aqueous solution is added to the reaction solution to carry out the hydrolysis.
<3> The method for producing a polymerizable compound according to <2>, wherein in the step (2), an acidic aqueous solution is added to the reaction solution.
<4> The method for producing a polymerizable compound according to <3>, wherein the acid component of the acidic aqueous solution is an inorganic acid and / or an organic acid having 1 to 20 carbon atoms.
<5> The acid component of the acidic aqueous solution is selected from the group consisting of hydrochloric acid, sulfuric acid, phosphoric acid, boric acid, sulfonic acids, sulfin acids, formic acid, acetic acid, oxalic acid, citric acid, ascorbic acid, tartrate acid and malic acid. The method for producing a polymerizable compound according to <3> or <4>, which is at least one kind.
<6> The R has 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, and a substituent. Alkinyl group having 2 to 60 carbon atoms, aromatic hydrocarbon ring group having 6 to 18 carbon atoms which may have a substituent, and aromatic group having 2 to 18 carbon atoms which may have a substituent. A heterocyclic group or Ra-Y-G- (in the formula, Ra represents a cyclic group having at least one of an aromatic hydrocarbon ring and an aromatic heterocycle, where Y is a chemical 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-, -OC (= O)-, -C (= O) -S-, -SC (= 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) represents -O-, wherein, R ⁴ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, Rc and Rb are each independently a hydrogen atom, which may have a substituent carbon It represents an aromatic hydrocarbon ring group of number 6 to 18 or an aromatic heterocyclic group having 2 to 18 carbon atoms which may have a substituent, and G is (i) 2 having 1 to 20 carbon atoms. At least one of the valent aliphatic hydrocarbon group and (ii) -CH _2- contained in the divalent aliphatic hydrocarbon group having 3 to 20 carbon atoms is -O-, -S-, -O-. C (= O) -, - C (= O) -O -, - O-C (= O) -O -, - NR 5 -C (= O) -, - C (= O) -NR 5 - , -NR ^5- , or a group substituted with -C (= O)-, except when two or more organic groups (provided that -O- or -S- are adjacent to each other are interposed. ), Where R ⁵ is a hydrogen atom, or , Represents an alkyl group having 1 to 6 carbon atoms. ), The method for producing a polymerizable compound according to any one of <1> to <5>.
<7> wherein R ^X are all hydrogen atom, a manufacturing method of the polymerizable compound according to any one of <1> to <6>.
<8> The method for producing a polymerizable compound according to any one of <1> to <7>, wherein the reaction is carried out by further adding an acidic aqueous solution in the step (3).
<9> The compound represented by the above formula (II) is the following formula (IIa).

(In the formula, A, L and n have the same meanings as described above.)
The method for producing a polymerizable compound according to any one of <1> to <8>, which is a compound represented by.

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

Hereinafter, the present invention will be described in detail. In the present invention, "may have a substituent" means "unsubstituted or has a substituent". When an organic group such as an alkyl group or an aromatic hydrocarbon ring group contained in the general formula has a substituent, the carbon number of the organic group having the substituent does not include the carbon number of the substituent. And. For example, when an aromatic hydrocarbon ring group having 6 to 18 carbon atoms has a substituent, the carbon number of the aromatic hydrocarbon ring group having 6 to 18 carbon atoms does not include the carbon number of such a substituent. It shall be. On the other hand, it is assumed that the "number of π electrons contained in the ring structure in Ra" also includes the π electrons of the ring structure contained in the substituent. Further, in the present invention, the "alkyl group" means a chain (linear or branched) saturated hydrocarbon group, and the "alkyl group" is a cyclic saturated hydrocarbon group, "cyclo". "Alkyl groups" shall not be included.

The present invention relates to a compound represented by the following formula (I) (hereinafter, may be referred to as “compound (I)”) in the presence of a base and / or a dehydration condensing agent in an organic solvent, and the following formula (II). (Hereinafter, sometimes referred to as "Compound (II)") is esterified with the compound represented by the following formula (III) (hereinafter, sometimes referred to as "Compound (III)"). A step (1) of obtaining a reaction solution containing the above, for example, a step (2) of adding 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). After the step (2), there is a step (3) of adding a compound represented by the following formula (IV) (hereinafter, may be referred to as “compound (IV)”) and reacting with the compound (III). This is a method for producing a polymerizable compound represented by the following formula (A) (hereinafter, may be referred to as “polymerizable compound (A)”).

Then, in the production method of the present invention, compound (I) and compound (II) are reacted in step (1) to obtain compound (III), and then compound (II) or a dehydration condensing agent is used in step (2). Is hydrolyzed, so that the L of the compound (II) (compound (II)) remaining when the compound (I) and the compound (II) are reacted in the step (1) is a desorbing group (for example, halogen). In the case of atoms, organic sulfonyloxy groups, etc.), or the dehydration condensing agent that can be used in step (1) (when L of compound (II) is a hydroxyl group) can be hydrolyzed in step (2). Therefore, according to the production method of the present invention, when the compound (III) and the compound (IV) are reacted in the step (3), the compound (II) remaining in the step (1) or the dehydration condensing agent and the compound ( The polymerizable compound represented by the formula (A) can be obtained in a high yield by preventing the reaction with IV).

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

Here, in the compound (I) represented by the formula (I), Q represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. Examples of the alkyl group having 1 to 6 carbon atoms include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, a t-butyl group, an n-pentyl group and an isopentyl group. Examples thereof include a neopentyl group, an n-hexyl group, and an isohexyl group. Above all, Q is preferably a hydrogen atom.
Further, in compound (I), Fg ¹ and Fg ² independently represent a hydroxyl group, −CH ₂ OH, or −CH ₂ CH ₂ OH, and preferably a hydroxyl group or −CH _{2 OH.} It is more preferably a hydroxyl group.

（式中、Ａ、Ｌおよびｎは、前記と同じ意味を表す。）In the compound (II) represented by the formula (II), A represents a hydrogen atom, a methyl group or a chlorine atom, and is preferably a hydrogen atom.
Further, in compound (II), L represents a hydroxyl group or a leaving group. Leaving groups include halogen atoms such as chlorine atom, bromine atom and iodine atom; organic substances such as methanesulfonyloxy group, p-toluenesulfonyloxy group, trifluoromethylsulfonyloxy group, camphorsulfonyloxy group and benzenesulfonyloxy group. Sulfonyl group; etc. Among these, a halogen atom is preferable, and a chlorine atom is more preferable, from the viewpoint of obtaining the desired product at low cost and in high yield.
Further, in compound (II), n represents any integer from 1 to 20. As n, an integer of 2 to 8 is preferable, and 6 is more preferable.
From the viewpoint of enhancing the characteristics of the optical film or the like prepared by using the obtained polymerizable compound, the compound (II) is preferably a compound represented by the following formula (IIa).

(In the formula, A, L and n have 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: 1, in terms of the molar ratio of compound (I): compound (II). It is 3, more preferably 1: 2 to 1: 2.5, and even more preferably 1: 2.01 to 1: 2.5.
In step (1), two different compounds (compound (II-1) and compound (II-2)) are used as compound (II), and if the reaction is carried out stepwise, they have different groups on the left and right. Compound (III) can be obtained. That is, a compound (III) having different groups on the left and right is reacted by reacting 1 mol of compound (I) with 1 mol of compound (II-1) and then reacting with 1 mol of compound (II-2). ) Can be obtained.

Here, examples of the base that can be used in step (I) include organics such as triethylamine, diisopropylethylamine, pyridine, 4- (dimethylamino) pyridine (N, N-dimethyl-4-aminopyridine), and 2,6-lutidine. Bases; inorganic bases such as sodium hydroxide, sodium carbonate, sodium hydrogen carbonate;
The amount of the base used is usually 1 to 3 mol per 1 mol of compound (II).
When L of the compound (II) represented by the formula (II) is a leaving group (for example, a halogen atom, an organic sulfonyloxy group, etc.), the reaction of the step (1) usually involves the presence of a base. Do below. When L of the compound (II) represented by the formula (II) is a hydroxyl group, the reaction of step (1) may be carried out in the presence of a base or in the absence of a base. May be good.

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, N, N-diisopropylcarbodiimide and the like. ..
When L of the compound (II) represented by the formula (II) is a hydroxyl group, the reaction of the step (1) is usually carried out in the presence of a dehydration condensing agent.

The reaction is carried out in an organic solvent. The organic solvent used is not particularly limited as long as it is inert to the reaction. For example, chlorine-based solvents such as chloroform and methylene chloride; amide-based solvents such as N-methylpyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide and hexamethylphosphate triamide; 1,4-dioxane and cyclopentylmethyl. Ether-based solvents such as ether, tetrahydrofuran, tetrahydropyran, 1,3-dioxolane; sulfur-containing solvents such as dimethylsulfoxide and sulfolane; nitrile-based solvents such as acetonitrile; ester-based solvents such as ethyl acetate and propyl acetate; benzene and toluene , Aromatic hydrocarbon solvents such as xylene; aliphatic hydrocarbon solvents such as n-pentane, n-hexane, n-octane; alicyclic hydrocarbon solvents such as cyclopentane, cyclohexane; and these solvents. A mixed solvent composed of two or more of the above; and the like.
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 desired product in good yield.

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

As a reaction method, (a) a method of adding an organic solvent solution of compound (II) or compound (II) to an organic solvent solution containing compound (I) and a base and / or a dehydration condensing agent, (b). A method of adding compound (I) or an organic solvent solution of compound (I) to an organic solvent solution containing compound (II) and a base and / or a dehydration condensing agent, (c) compound (I) and compound (II). ), The method of adding the base and / or the dehydration condensing agent to the organic solvent solution; and the like; the method (a) is preferable because the desired product can be obtained in good yield.

The reaction temperature is in the temperature range from −20 ° C. to the boiling point of the solvent used, preferably −15 ° C. to + 30 ° C.
The reaction time is usually several minutes to several hours, depending on the scale of the reaction.
The obtained reaction solution is directly subjected to the next step (2) while maintaining the above temperature without performing a washing / extraction operation or the like.

Most of the compound (I) and the compound (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). As the compound (I), a commercially available compound (I) can be used as it is or after being purified if desired.
For example, among compound (II), the compound in which L is a halogen atom can be produced by the method described in International Publication No. 2015/141784.

（式中、Ｑ、Ａ、Ｙ^１、Ｙ^２およびｎは、前記と同じ意味を表す。）Then, 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).
Further, in compound (III), Y ¹ and Y ² are independently -C (= O) -O-, -OC (= O)-, and -CH _2- OC (= O), respectively. _{) -, - C (= O} ) -O-CH 2 -, - CH 2 -CH 2 -O-C (= O) -, _{or, -C (= O) -O-} CH 2 -CH 2 - and It is preferably −C (= O) −O− and −OC (= O) −.
In the step (1), it is preferable to use the compound represented by the above formula (IIa) as the compound (II) and obtain the compound represented by the following formula (IIIa) as the compound (III).

(In the formula, Q, A, Y ¹ , Y ² and n have the same meanings as described above.)

(Step (2))
In the step (2), the compound (II) remaining when the compound (I) and the compound (II) are reacted in the step (1), or the dehydration condensing agent used in the step (1) is hydrolyzed. Make a reaction. 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, etc.), the remaining compound (for example, a halogen atom, an organic sulfonyloxy group, etc.) 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 carried out, for example, by adding water or an aqueous solution to the reaction solution obtained in the step (1). The amount of water added in the step (2) is not a problem as long as it can hydrolyze the remaining compound (II) or the dehydration condensing agent, and may be equal to or more than the reaction equivalent, but is usually 1.05-. It is preferably 500 mol times, more preferably 1.5 to 300 mol times, still more preferably 1.5 to 200 mol times.
Further, in the step (2), it is preferable to add an aqueous solution. Here, examples of the aqueous solution include a basic aqueous solution and an acidic aqueous solution, and an acidic aqueous solution is preferable.

Here, the acidic aqueous solution is not particularly limited, but an acidic aqueous solution having a pH of 6 or less is preferable, and an acidic aqueous solution having a pH of 2 or less is more preferable.
The acid components of the acidic aqueous solution include inorganic acids such as hydrochloric acid, sulfuric acid, phosphoric acid, carbonic acid, boric acid, perchloric acid and nitrate; carboxylic acids such as formic acid, acetic acid, butyric acid and trifluoroacetic acid; oxalic acid and citrus. Hydroxy acids such as acids, ascorbic acid, tartaric acid, malic acid, lactic acid; sulfonic acids such as p-toluene sulfonic acid, methane sulfonic acid, trifluoromethane sulfonic acid, 10-campar sulfonic acid; Organic acids can be mentioned. These can be used alone or in combination of two or more.
Among these, inorganic acids and / or organic acids having 1 to 20 carbon atoms are preferable from the viewpoint of satisfactorily hydrolyzing compound (II), and hydrochloric acid, sulfuric acid, phosphoric acid, boric acid, sulfonic acids, sulfinic acids and formic acids. , Acetic acid, oxalic acid, citric acid, ascorbic acid, tartrate acid and malic acid, at least one selected from the group is more preferable, and hydrochloric acid and sulfonic acids are even more preferable.
The concentration of the acidic aqueous solution is preferably 0.1 mol / L to 2 mol / L, more preferably 0.5 mol / L to 1.5 mol / L. When the concentration of the acidic aqueous solution is at least the above lower limit value, the compound (II) or the dehydration condensing agent can be satisfactorily hydrolyzed. Further, when the concentration of the acidic aqueous solution is not more than the above upper limit value, side reactions such as decomposition of the compound (III) produced in the step (1) can be suppressed.

The amount of the acidic aqueous solution used is preferably such that the remaining compound (II) or the dehydration condensing agent can be hydrolyzed and the reaction can be catalyzed in the step (3) described later. For example, in the case of a 1.0 specified acidic aqueous solution, it is 1 to 50 parts by mass, preferably 5 to 50 parts by mass with respect to 10 parts by mass of compound (II). When the amount of the acidic aqueous solution used is not less than the above lower limit, the compound (II) or the dehydration condensing agent can be hydrolyzed satisfactorily and the reaction can be catalyzed in the step (3). Further, when the amount of the acidic aqueous solution used is not more than the above upper limit value, side reactions such as decomposition of the compound (III) produced in the step (1) can be suppressed.
The acidic aqueous solution required to catalyze the reaction in the step (3) described later may be further added after hydrolyzing the compound (II) or the dehydration condensing agent.

Here, the hydrolysis reaction in the step (2) can be optionally carried out under stirring. The reaction time in the step (2) is not particularly limited as long as the compound (II) or the dehydration condensing agent is sufficiently hydrolyzed, but can be, for example, 1 minute or more and 5 hours or less, and 15 minutes or more and 1 It is preferably less than an hour. When the reaction time is at least the above lower limit value, the compound (II) or the dehydration condensing agent can be satisfactorily hydrolyzed. Further, if the reaction time is not more than the above upper limit value, 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 is sufficiently hydrolyzed, but can be, for example, −5 ° C. or higher and 50 ° C. or lower, and 0 ° C. or higher. The temperature is preferably 50 ° C. or lower. When the reaction temperature is at least the above lower limit value, the compound (II) or the dehydration condensing agent can be satisfactorily hydrolyzed. Further, when the reaction temperature is not more than the above upper limit value, side reactions such as decomposition of the compound (III) produced in the step (1) can be suppressed.

Then, in the step (2), when L is a leaving group (for example, a halogen atom, an organic sulfonyloxy group, etc.), the remaining compound (II) is hydrolyzed and L is a hydroxyl group (for example). It becomes the compound shown in II). Alternatively, in step (2), when L is a hydroxyl group, for example, the carbodiimide compound used as a dehydration condensing agent is converted into a urea compound.
The reaction solution after the step (2) can be directly applied to the next step (3) without performing post-treatment operations such as washing and extraction.

(Step (3))
The step (3) is a step of adding the compound (IV) after the step (2) to react the compound (III) with the compound (IV).
Then, in the production method of the present invention, since the step (3) is carried out after the step (2) is carried out, the compound (II) remaining in the step (1) or the dehydration condensing agent reacts with the compound (IV). The polymerizable compound represented by the formula (A) can be obtained in a high yield even if the amount of the compound (IV) used is small.

Here, in the compound (IV) represented by the formula (IV), X represents an oxygen atom, a sulfur atom, -C (R ¹ ) (R ² )-, or -N-R ^1- . Here, R ¹ and R ² each independently represent an alkyl group having 1 to 10 carbon atoms which may have a hydrogen atom or a substituent.

Examples of the alkyl group having 1 to 10 carbon atoms of the alkyl group having 1 to 10 carbon atoms which may have a substituent of R ¹ and R ^{2 include a methyl group, an ethyl group, an n-propyl group and an isopropyl group.} n-butyl group, sec-butyl group, t-butyl group, n-pentyl group, isopentyl group, neopentyl group, n-hexyl group, isohexyl group, 3-heptyl group, n-octyl group, n-nonyl group, Examples thereof include an n-decyl group.
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; substituted amino group such as dimethylamino group; and 1 to 6 carbon atoms such as methoxy group and ethoxy group. Alkoxy group; nitro group; aryl group such as phenyl group; cycloalkyl group having 3 to 8 carbon atoms such as cyclopropyl group and cyclopentyl group; hydroxyl group; and the like.

Among these, X is preferably an oxygen atom, a sulfur atom, or −CH _2- , more preferably an oxygen atom or a sulfur atom, and sulfur, because the effect of the present invention can be more easily obtained. Atoms are particularly preferred.

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

Here, 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, and an aromatic group having 6 to 18 carbon atoms. Examples thereof include a group hydrocarbon ring group and an aromatic heterocyclic group having 2 to 18 carbon atoms.

The alkyl group having 1 to 60 carbon atoms includes a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, a t-butyl group, an n-pentyl group, and an n-hexyl group. , N-Heptyl group, n-Undecyl group, n-Dodecyl group, 1-methylpentyl group, 1-ethylpentyl group and the like. Among these, an alkyl group having 1 to 12 carbon atoms is preferable, an n-butyl group, an n-hexyl group, and an n-octyl group are more preferable, and an n-hexyl group is more preferable because the effect of the present invention can be more easily obtained. Groups are particularly preferred.

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

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

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

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

Examples of the substituent of the organic group having 1 to 60 carbon atoms in R include a cyano group; a nitro group; a hydroxyl group; a halogen atom such as a fluorine atom, a chlorine atom and a bromine atom; and a methyl group and an ethyl group having 1 to 6 carbon atoms. Alkyl group; methoxy group, ethoxy group, n-propoxy group, isopropoxy group, n-butoxy group, t-butoxy group and other alkoxy groups having 1 to 6 carbon atoms; methoxymethoxy group, methoxyethoxy group, ethoxyethoxy group 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 such as a cyclopropyl group, a cyclopentyl group, a cyclohexyl group, and a cycloheptyl group; a methylamino Substituted amino groups such as groups, ethylamino groups, acetylamino groups and dimethylamino groups; and the like.

Further, examples of the organic group having 1 to 60 carbon atoms include a group represented by the formula: Ra-Y-G-.

Here, Ra represents a cyclic group having at least one of an aromatic hydrocarbon ring and an aromatic heterocycle.
Among these, aromatic hydrocarbon ring groups having 6 to 30 carbon atoms are more preferable because the effects of the present invention can be more easily obtained.

Examples of the aromatic hydrocarbon ring include a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, a pyrene ring, a fluorene ring and the like. Among these, a benzene ring, a naphthalene ring, an anthracene ring, and a fluorene ring are preferable, and a benzene ring and a naphthalene ring are more preferable, in that the effect of the present invention can be more easily obtained.

Examples of the aromatic heterocycle include 1H-isoindole-1,3 (2H) -dione ring, 1-benzofuran ring, 2-benzofuran ring, acrydin ring, isoquinoline ring, imidazole ring, indole ring, and oxadiazole ring. , Oxazol ring, Oxazolopyrazine ring, Oxazolopyridine ring, Oxazolopyridadyl ring, Oxazolopyrimidine ring, Kinazoline ring, Kinoxalin ring, Kinolin ring, Sinnoline ring, Thiasiazol ring, Thiazol ring, Thiazolopyrazine ring, Chia Zolopyridine ring, thiazolopyridazine ring, thiazolopyrimidine ring, thiophene ring, triazine ring, triazole ring, naphthylidine ring, pyrazine ring, pyrazole ring, pyranone ring, pyran ring, pyridine ring, pyridazine ring, pyrimidine ring, pyrrol ring, Phenantridin ring, phthalazine ring, furan ring, benzo [b] thiophene ring, benzo [c] thiophene ring, benzoisoxazole ring, benzoisothiazole ring, benzoimidazole ring, benzoxaziazole ring, benzoxazole ring, benzo Examples thereof include a thiadiazol ring, a benzothiazole ring, a benzothiophene ring, a benzotriazine ring, a benzotriazole ring, a benzopyrazole ring, a penzopyranone ring, and a xanthene ring.
Among these, the aromatic heterocycles include monocyclic aromatic heterocycles such as furan ring, pyran ring, thiophene ring, oxazole ring, oxaziazole ring, thiazole ring, and thiazazole ring; and benzothiazole ring and benzo. Oxazole ring, quinoline ring, 1-benzofuran ring, 2-benzofuran ring, benzo [b] thiophene ring, 1H-isoindole-1,3 (2H) -dione ring, benzo [c] thiophene ring, thiazolopyridine ring, Aromatic heterocycles of fused rings such as thiazolopyrazine ring, benzoisoxazole ring, benzoxazole ring, benzothiazazole ring, and xanthene ring; are preferable.

The aromatic hydrocarbon ring and the aromatic heterocycle contained in Ra may have a substituent. Examples of such a substituent include a halogen atom such as a fluorine atom and a chlorine atom; a cyano group; an alkyl group having 1 to 6 carbon atoms such as a methyl group, an ethyl group and a propyl group; and 2 to 6 carbon atoms such as a vinyl group and an allyl group. Alkenyl group of 1 to 6 alkyl groups in which at least one hydrogen atom such as a trifluoromethyl group or pentafluoroethyl group is substituted with halogen; N, N-dialkyl having 2 to 12 carbon atoms such as a dimethylamino group. Amino group; alkoxy group having 1 to 6 carbon atoms such as methoxy group, ethoxy group and isopropoxy group; nitro group; aromatic hydrocarbon ring group having 6 to 18 carbon atoms such as phenyl group and naphthyl group; -OCF ₃ ; ^{-C (= O) -R Y;} -C (= O) -O-R Y; -O-C (= O) -R Y; and _-SO 2 ^{R b;} and the like. Here, ^RY is (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, (i). iii) Represents a cycloalkyl group having 3 to 12 carbon atoms which may have a substituent, or an aromatic hydrocarbon ring group having 6 to 18 carbon atoms which may have an (iv) substituent. Further, R ^b is an alkyl group having 1 to 6 carbon atoms such as a methyl group and an ethyl group; or an alkyl group having 1 to 6 carbon atoms such as a phenyl group, a 4-methylphenyl group and a 4-methoxyphenyl group. It represents an aromatic hydrocarbon ring group having 6 to 18 carbon atoms, which may have an alkoxy group having 1 to 6 carbon atoms as a substituent.
Among these, as the substituent of the aromatic hydrocarbon ring and the aromatic heterocycle of Ra, a halogen atom, a cyano group, an alkyl group having 1 to 6 carbon atoms, and an alkoxy group having 1 to 6 carbon atoms are preferable.
Ra may have a plurality of substituents selected from the above-mentioned substituents. When Ra has a plurality of substituents, the substituents may be the same or different.

Examples of the alkyl group having 1 to 20 carbon atoms of the alkyl group having 1 to 20 carbon atoms which may have a substituent (i) of ^{RY include a methyl group, an ethyl group, an n-propyl group and an isopropyl group.} n-butyl group, isobutyl group, 1-methylpentyl group, 1-ethylpentyl group, sec-butyl group, t-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, Examples thereof include n-heptadecyl group, n-octadecyl group, n-nonadecil group, n-icosyl group and the like.
(I) The number of carbon atoms of the alkyl group having 1 to 20 carbon atoms which may have a substituent is preferably 1 to 12, and more preferably 1 to 10.

Examples of the alkenyl group having 2 to 20 carbon atoms of the alkenyl group having 2 to 20 carbon atoms which may have the (ii) substituent of ^{RY include a vinyl group, a propenyl group, an isopropenyl group, a butenyl group and an isobutenyl group.} Group, pentenyl group, hexenyl group, heptenyl group, octenyl group, nonenyl group, decenyl group, undecenyl group, dodecenyl group, tridecenyl group, tetradecenyl group, pentadecenyl group, hexadecenyl group, heptadecenyl group, octadecenyl group, nonadesenyl group, icodecenyl group, etc. Can be mentioned.
The alkenyl group having 2 to 20 carbon atoms which may have the (ii) substituent is preferably 2 to 12 carbon atoms.

^RY , an alkyl group having 1 to 20 carbon atoms which may have a (i) substituent and an alkyl group having 1 to 20 carbon atoms and (ii) which may have a substituent (ii) having 2 to 20 carbon atoms. Examples of the substituent of the alkenyl group having 2 to 20 carbon atoms of the alkenyl group of 20 include a halogen atom such as a fluorine atom and a chlorine atom; a cyano group; and an N, N-dialkylamino group having 2 to 12 carbon atoms such as a dimethylamino group. An alkoxy group having 1 to 20 carbon atoms such as a methoxy group, an ethoxy group, an isopropoxy group and a butoxy group; 1 to 12 carbon atoms substituted with an alkoxy group having 1 to 12 carbon atoms such as a methoxymethoxy group and a methoxyethoxy group. 12 alkoxy groups; nitro group; aromatic hydrocarbon ring group having 6 to 18 carbon atoms such as phenyl group and naphthyl group; triazolyl group, pyrrolyl group, furanyl group, thiophenyl group, benzothiazole-2-ylthio group and the like. Aromatic heterocyclic group having 2 to 18 carbon atoms; cycloalkyl group having 3 to 8 carbon atoms such as cyclopropyl group, cyclopentyl group and cyclohexyl group; cycloalkyl group having 3 to 8 carbon atoms such as cyclopentyloxy group and cyclohexyloxy group. Oxy group; cyclic ether group having 2 to 12 carbon atoms such as tetrahydrofuranyl group, tetrahydropyranyl group, dioxolanyl group and dioxanyl group; aryloxy group having 6 to 14 carbon atoms such as phenoxy group and naphthoxy group; trifluoromethyl group , Pentafluoroethyl group, -CH ₂ CF _3, etc., fluoroalkyl group having 1 to 12 carbon atoms in which at least one hydrogen atom is substituted with a fluorine atom; benzofuryl group; benzopyranyl group; benzodioxolyl group; benzo Dioxanyl group; and the like. Among these, ^RY may have (i) an alkyl group having 1 to 20 carbon atoms which may have a substituent and (ii) an alkyl group having 1 to 20 carbon atoms. Examples of the substituent of the alkenyl group having 2 to 20 carbon atoms include halogen atoms such as fluorine atom and chlorine atom; cyano group; methoxy group, ethoxy group, isopropoxy group, butoxy group and the like. An alkoxy group having 1 to 20 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; a furanyl group, a thiophenyl group, a benzothiazole-2-ylthio group and the like. 2 to 18 aromatic heterocyclic groups; cycloalkyl groups having 3 to 8 carbon atoms such as cyclopropyl group, cyclopentyl group and cyclohexyl group; at least such as _{trifluoromethyl group, pentafluoroethyl group, -CH 2} CF _{3 etc.} A fluoroalkyl group having 1 to 12 carbon atoms in which one hydrogen atom is substituted with a fluorine atom; is preferable.
It should be noted that, in ^RY , an alkyl group having 1 to 20 carbon atoms which may have a (i) substituent and an alkyl group having 1 to 20 carbon atoms and (ii) which may have a substituent may have a carbon number of carbon atoms. The alkenyl group having 2 to 20 carbon atoms of the 2 to 20 alkenyl groups may have a plurality of substituents selected from the above-mentioned substituents. ^RY 's (i) alkyl group having 1 to 20 carbon atoms which may have a substituent may have an alkyl group having 1 to 20 carbon atoms and (ii) an alkyl group having 2 to 20 carbon atoms which may have a substituent. When the alkenyl group having 2 to 20 carbon atoms of the 20 alkenyl group has a plurality of substituents, the plurality of substituents may be the same or different from each other.

The cycloalkyl group having 3 to 12 carbon atoms of the cycloalkyl group having 3 to 12 carbon atoms which may have the (iii) substituent of ^{RY includes a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, and a cyclohexyl group.} , Cyclooctyl group and the like. Among these, a cyclopentyl group and a cyclohexyl group are preferable.
The substituent of the cycloalkyl group having 3 to 12 carbon atoms of the cycloalkyl group having 3 to 12 carbon atoms which may have the (iii) substituent of ^{RY is a halogen atom such as a fluorine atom or a chlorine atom.} Cyan group; N, N-dialkylamino group having 2 to 12 carbon atoms such as dimethylamino group; alkyl group having 1 to 6 carbon atoms such as methyl group, ethyl group and propyl group; methoxy group, ethoxy group and isopropoxy Examples thereof include an alkoxy group having 1 to 6 carbon atoms such as a group; 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, as the substituent of the cycloalkyl group having 3 to 12 carbon atoms of the cycloalkyl group having 3 to 12 carbon atoms which may have the (iii) substituent of ^{RY, a fluorine atom and a chlorine atom} Halogen atoms such as; cyano group; alkyl group having 1 to 6 carbon atoms such as methyl group, ethyl group and propyl group; alkoxy group having 1 to 6 carbon atoms such as methoxy group, ethoxy group and isopropoxy group; nitro group; An aromatic hydrocarbon ring group having 6 to 18 carbon atoms such as a phenyl group and a naphthyl group; is preferable.
In addition, the cycloalkyl group having 3 to 12 carbon atoms of the cycloalkyl group having 3 to 12 carbon atoms which may have the (iii) substituent of ^{RY may have a plurality of substituents.} .. When the cycloalkyl group having 3 to 12 carbon atoms of the cycloalkyl group having 3 to 12 carbon atoms which may have the (iii) substituent of ^{RY has a plurality of substituents, the plurality of substituents have each other.} It may be the same or different.

^{The aromatic hydrocarbon ring group having 6 to 18 carbon atoms which may have the (iv) substituent of RY} includes a phenyl group and 1-naphthyl as the aromatic hydrocarbon ring group having 6 to 18 carbon atoms. Groups, 2-naphthyl groups and the like can be mentioned. Among these, a phenyl group and a naphthyl group are preferable, and a phenyl group, a 1-naphthyl group and a 2-naphthyl group are more preferable.
Examples of the substituent of the aromatic hydrocarbon ring group having 6 to 18 carbon atoms which may have the (iv) substituent of ^{RY include a halogen atom such as a fluorine atom and a chlorine atom; a cyano group; a dimethylamino group and the like.} N, N-dialkylamino group having 2 to 12 carbon atoms; alkoxy group having 1 to 20 carbon atoms such as methoxy group, ethoxy group, isopropoxy group and butoxy group; An alkoxy group having 1 to 12 carbon atoms substituted with an alkoxy group of 1 to 12; a nitro group; an aromatic heterocyclic group having 2 to 18 carbon atoms such as a triazolyl group, a pyrrolyl group, a furanyl group and a thiophenyl group; cyclopropyl Cycloalkyl group having 3 to 8 carbon atoms such as group, cyclopentyl group and cyclohexyl group; cycloalkyloxy group having 3 to 8 carbon atoms such as cyclopentyloxy group and cyclohexyloxy group; tetrahydrofuranyl group, tetrahydropyranyl group and dioxolanyl group , Cyclic ether group having 2 to 12 carbon atoms such as dioxanyl group; aryloxy group having 6 to 14 carbon atoms such as phenoxy group and naphthoxy group; trifluoromethyl group, pentafluoroethyl group, -CH ₂ CF _3, etc. Fluoroalkyl groups having 1 to 12 carbon atoms in which at least one hydrogen atom is substituted with a fluorine atom; −OCF ₃ ; benzofuryl group; benzopyranyl group; benzodioxolyl group; benzodioxanyl group; and the like can be mentioned. Among these, as the substituent of the aromatic hydrocarbon ring group having 6 to 18 carbon atoms which may have the (iv) substituent of ^{RY, a halogen atom such as a fluorine atom and a chlorine atom; a cyano group;} An alkoxy group having 1 to 20 carbon atoms such as a methoxy group, an ethoxy group, an isopropoxy group and a butoxy group; a nitro group; an aromatic heterocycle having 2 to 18 carbon atoms such as a triazolyl group, a pyrrolyl group, a furanyl group and a thiophenyl group. Group: Cycloalkyl group having 3 to 8 carbon atoms such as cyclopropyl group, cyclopentyl group and cyclohexyl group; at least one hydrogen atom such as _{trifluoromethyl group, pentafluoroethyl group and -CH 2} CF _{3 is a fluorine atom.} At least one substituent selected from a fluoroalkyl group having 1 to 12 carbon atoms substituted with −OCF _{3; is preferable.}
In addition, 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 the (iv) substituent of ^{RY has a plurality of substituents.} You may have. When 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 the (iv) substituent of ^{RY has a plurality of substituents,} The substituents may be the same or different.

Here, the "carbon number" of the cyclic group having at least one of the aromatic hydrocarbon ring and the aromatic heterocycle of Ra is at least one of the aromatic hydrocarbon ring and the aromatic heterocycle containing no carbon atom of the substituent. It means the number of carbon atoms of the organic group itself having.
When Ra has a plurality of aromatic hydrocarbon rings and / or a plurality of aromatic heterocycles, each may be the same or different.

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

Preferred specific examples of Ra's cyclic group having at least one of an aromatic hydrocarbon ring having 6 to 30 carbon atoms and an aromatic heterocycle having 2 to 30 carbon atoms are shown below. However, the present invention is not limited to those shown below. In the following equation, "-" extends from an arbitrary position on the ring and represents a bond with Y.

1) Specific examples of the hydrocarbon ring group having at least one aromatic hydrocarbon ring having 6 to 30 carbon atoms and which may have a substituent include the following formulas (1-1) to (1-21). ), And a hydrocarbon ring group having 6 to 18 carbon atoms represented by the formulas (1-8) to (1-21) and the like is preferable. The groups represented by the following formulas (1-1) to (1-21) may have a substituent.

（各式中、Ａは、−ＣＨ_２−、−ＮＲ^ｃ−、酸素原子、硫黄原子、−ＳＯ−または−ＳＯ_２−を表し、
ＢおよびＤは、それぞれ独立して、−ＮＲ^ｃ−、酸素原子、硫黄原子、−ＳＯ−または−ＳＯ_２−を表し、
Ｅは、−ＮＲ^ｃ−、酸素原子または硫黄原子を表す。
ここで、Ｒ^ｃは、水素原子、または、メチル基、エチル基、プロピル基等の炭素数１〜６のアルキル基を表す。（但し、各式中において酸素原子、硫黄原子、−ＳＯ−、−ＳＯ_２−は、それぞれ隣接しないものとする。））2) A heterocyclic group having a substituent and having at least one aromatic ring selected from the group consisting of an aromatic hydrocarbon ring having 6 to 30 carbon atoms and an aromatic heterocyclic ring having 2 to 30 carbon atoms. Specific examples of the above include structures represented by the following formulas (2-1) to (2-51), and the number of carbon atoms 2 to represented by the formulas (2-11) to (2-51) and the like. 16 heterocyclic groups are preferred. The groups represented by the following formulas (2-1) to (2-51) may have a substituent.

(In each equation, A represents −CH ₂ −, −NR ^c −, oxygen atom, sulfur atom, −SO − _{or −SO 2−.}
B and D independently ^{represent −NR c} −, oxygen atom, sulfur atom, −SO _{− or −SO 2−} , respectively.
E represents −NR ^c −, an oxygen atom or a sulfur atom.
Here, R ^c represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms such as a methyl group, an ethyl group and a propyl group. ) (Provided that the oxygen atom in the in each formula, a sulfur atom, -SO -, - - SO ₂ shall not adjacent, respectively.)

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

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

（式（ｉ−４）中、Ｊは、−ＣＨ_２−、−ＮＲ^ｄ−、酸素原子、硫黄原子、−ＳＯ−または−ＳＯ_２−を表し、Ｒ^ｄは水素原子または炭素数１〜６のアルキル基を表す。）Further, it is preferable that Ra is any of the following (i-1) to (i-6). The groups represented by the following formulas (i-1) to (i-6) may have a substituent.

(In formula (i-4), J represents −CH ₂ −, −NR ^d −, oxygen atom, sulfur atom, −SO _{− or −SO 2−} , and R ^d is a hydrogen atom or 1 to 6 carbon atoms. Represents the alkyl group of.)

The cyclic group of Ra having at least one of an aromatic hydrocarbon ring having 6 to 30 carbon atoms and an aromatic heterocycle having 2 to 30 carbon atoms may have one or more substituents. When having a plurality of substituents, the plurality of substituents may be the same or different from each other.

Examples of the substituent contained in the 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 in Ra include a halogen atom such as a fluorine atom and a chlorine atom. Cyan group; Alkyl group having 1 to 6 carbon atoms such as methyl group, ethyl group and propyl group; Alkenyl group having 2 to 6 carbon atoms such as vinyl group and allyl group; Trifluoromethyl group, pentafluoroethyl group and the like 1 to 6 alkyl groups having 1 to 6 carbon atoms in which at least one hydrogen atom is substituted with halogen; N, N-dialkylamino groups having 2 to 12 carbon atoms such as a dimethylamino group; carbons such as a methoxy group, an ethoxy group and an isopropoxy group number 1-6 alkoxy group; a nitro group; a phenyl group, an aromatic having 6 to 18 carbon atoms such as naphthyl hydrocarbon ring ^{_{group; -OCF 3; -C (= O}} ) -R Y; -C (= O ^{) -O-R Y; -O-} C (= O) -R Y; -SO 2 R b; and the like. Here, ^RY and R ^b have the same meanings as described above, and preferred examples thereof are also the same as described above. When having a plurality of substituents, the plurality of substituents may be the same or different from each other.
Among these, at least one substituent selected from 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.

Further, Y is a chemical single bond, −O−, −S−, −C (= O) −, −OC (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 ) -OC (= O)-, -OC (= 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) - Represents O- or -OC (= O) -O-. Here, R ⁴ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and Rc and Rb are independently aromatics having 6 to 18 carbon atoms which may have a hydrogen atom and a substituent. Group Hydrocarbon Represents an aromatic heterocyclic group having 2 to 18 carbon atoms which may have a ring group or a substituent.

Among these, Y is a chemical single bond, −O−, −OC (Rb) (Rc) −, −C (Rb) (Rc) in that the effect of the present invention can be more easily obtained. _{-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) -OC (Rb) (Rc)-, -C (Rb) (Rc) -OC (= O)-, -OC (= 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-, -OC (= O) -O- are preferable. , chemical single bond, -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) -, - 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) -OC (= O)-, -OC (= 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 -, -OC (= O) -CH ₂ -S- is more preferable, and chemical single bonds, -O-, -OC (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) -OC (Rb) (Rc)-, -C (Rb) ( Rc) -OC (= O)-, -OC (= 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- is especially good Good.
Here, R ⁴ represents (i) a hydrogen atom or (ii) an alkyl group having 1 to 6 carbon atoms such as a methyl group and an ethyl group, and among these, R ⁴ is preferably a hydrogen atom.
Rc and Rb independently have a hydrogen atom and an aromatic hydrocarbon ring group having 6 to 18 carbon atoms which may have a substituent, or 2 to 2 carbon atoms which may have a substituent. Represents 18 aromatic heterocyclic groups. Rc and Rb may be the same as each other or may be different from each other.
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, of Rb and Rc. Specific examples of the above-mentioned Ra include those having a specified number of carbon atoms among those similar to Ra. Examples of the substituents of Rb and Rc include those similar to those of the substituents of Ra, and the preferred ones thereof are also the same. Further, when having a plurality of substituents, they may be the same or different from each other.
Rc and Rb are preferably an aromatic hydrocarbon ring group having 6 to 18 carbon atoms, which may independently have a hydrogen atom and a substituent, and further independently, a hydrogen atom, a phenyl group or a hydrogen atom or a phenyl group. A naphthyl group is preferable, and a combination in which both Rc and Rb are hydrogen atoms at the same time, a combination in which a hydrogen atom and a phenyl group are present, or a combination in which a hydrogen atom and a naphthyl group are present is particularly preferable.
A preferred combination of Ra-Y- is
Ra is selected from the general formulas (i-1) to (i-6), and Y is a chemical single bond, -OZ, -OC (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) -OC ( Rb) (Rc) -Z, -C (Rb) (Rc) -OC (= O) -Z, -OC (= O) -C (Rb) (Rc) -Z, -C (Rb) ) (Rc) -C (= O) -O-Z, -NR ^4- C (= O) -O-Z, -S-CH _2- C (= O) -O-Z Preferably
Ra is selected from the general formulas (i-1) to (i-6), and Y is a chemical single bond, -OZ, -C (Rb) (Rc) -OZ, -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) -OC (= O) -Z, -C (Rb) (Rc) -C (= O) -O-Z, -NR ^4- C (= O) -O-Z, A combination selected from −S—CH _2- C (= O) −OZ is more preferred.
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). preferable. Rb and Rc have the same meanings as described above, and Z indicates the direction of binding to G. Further, "●" in the groups represented by the following formulas (ii-1) to (ii-45) and the groups represented by (iii-1) to (iii-46) is a bond with G. Indicates the site.
The groups represented by the following formulas (ii-1) to (ii-45) and the groups represented by (iii-1) to (iii-46) may have a substituent.
In the following formulas (ii-26) to (ii-32) and the following formulas (iii-26) to (iii-32), J is −CH _2- , −NR ^d −, oxygen atom, sulfur atom, It represents −SO − or −SO ₂₋ , and R ^d represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.

G is a divalent organic group having 1 to 20 carbon atoms which may have a substituent, and preferably a divalent organic group having 3 to 20 carbon atoms which may have a substituent. is there.
G is more preferably (i) a divalent aliphatic hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, and (ii) a carbon number which may have a substituent. _{At least one of -CH 2-} contained in 3 to 20 divalent aliphatic hydrocarbon groups is -O-, -S-, -OC (= O)-, -C (= O) -O. ^{-, - O-C (=} O) -O -, - NR 5 -C (= O) -, - C (= O) -NR 5 -, - NR 5 -, or, -C (= O) - An organic group of any of the groups substituted with. However, this does not apply to cases where two or more -O- or -S- are adjacent to each other (that is, the structures of -O-O- and -S-S- are not formed).
Here, R 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. The substituent of the organic group of G includes an alkyl group having 1 to 5 carbon atoms such as a methyl group, an ethyl group and a propyl group; and an alkoxy having 1 to 5 carbon atoms such as a methoxy group, an ethoxy group and a propoxy group. Groups; cyano groups; halogen atoms such as fluorine atoms and chlorine atoms;
Here, with respect to G, the "divalent aliphatic hydrocarbon group" is preferably a divalent chain aliphatic hydrocarbon group, more preferably an alkylene group. The carbon number of the "divalent aliphatic hydrocarbon group" is preferably 3 to 20, and more preferably 3 to 18. The "divalent aliphatic hydrocarbon group" is preferably a divalent aliphatic hydrocarbon group having 2 to 20 carbon atoms, and is a divalent chain aliphatic hydrocarbon having 2 to 18 carbon atoms. It is preferably a hydrogen group, more preferably an alkylene group having 3 to 18 carbon atoms.

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

As the structure of G, an unsubstituted alkylene group having 4 to 16 carbon atoms is preferable, an unsubstituted alkylene group having 5 to 14 carbon atoms is more preferable, and an unsubstituted alkylene group having 6 to 12 carbon atoms is further preferable. An unsubstituted alkylene group having 6 to 10 carbon atoms is particularly preferable, and an n-hexylene group and an n-octylene group are most preferable.

When the carbon number of G is 3 or more, it _{is preferable that both ends of G are −CH 2} − (both ends of G are not substituted). _{In addition, "(ii) at least one of -CH 2-} contained in a divalent aliphatic hydrocarbon group having 3 to 20 carbon atoms is -O-, -S-, -OC (= O)-,. -C (= O) -O -, - O-C (= O) -O -, - NR 5 -C (= O) -, - C (= O) -NR 5 -, - NR 5 -, or , -C (= O)-substituted group ", -C (= O)-does _{not replace the continuous -CH 2-} in the aliphatic hydrocarbon group (ie, -C (= O)). It does not form a −C (= O) − structure).
_{At least one of -CH 2-} contained in a divalent aliphatic hydrocarbon group having 3 to 20 carbon atoms is -O-, -S-, -OC (= O)-, -C (= O). ^{-O -, - O-C (} = O) -O -, - NR 5 -C (= O) -, - C (= O) -NR 5 -, - NR 5 -, or, -C (= O ) -When substituted with -O-, it is most preferable to be substituted with -O-, so-called ethyleneoxy, which is substituted with -O- for every 2 carbon atoms, is used as a repeating unit, and both ends of G are -CH _2- Is preferable.

G has (i) a divalent chain aliphatic hydrocarbon group having 1 to 18 carbon atoms, preferably 3 to 18 carbon atoms, which may have a substituent, and a substituent. at least one of the, -O - - -CH ₂ contained in the divalent chain aliphatic hydrocarbon group which may having carbon atoms of 3-18 optionally, - S -, - O- C (= O) - , -C (= O) -O-, or a group substituted with -C (= O)-, with two or more -O- or -S- intervening adjacent to each other. It is preferable that (iii) "it is a divalent chain aliphatic hydrocarbon group having 3 to 18 carbon atoms which may have a substituent", and (iii). "The alkylene group having 3 to 18 carbon atoms which may have a substituent" is further preferable, (iv) "an unsubstituted alkylene group having 4 to 16 carbon atoms" is even more preferable, and (v) "the number of carbon atoms". "5 to 14 unsubstituted alkylene groups" are even more preferable, (vi) "unsubstituted alkylene groups having 6 to 12 carbon atoms" are even more preferable, and (vi) "unsubstituted alkylene groups having 6 to 10 carbon atoms" are even more preferable. "Group" is particularly preferable, and "n-hexylene group, n-octylene group" is most preferable. Examples of the substituent of G include an alkyl group having 1 to 5 carbon atoms such as a methyl group, an ethyl group and a propyl group; an alkoxy group having 1 to 5 carbon atoms such as a methoxy group, an ethoxy group and an isopropoxy group; a cyano group; Examples thereof include halogen atoms such as fluorine atom and chlorine atom.

^RX is a hydrogen atom; a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom; an alkyl group having 1 to 6 carbon atoms such as a methyl group, an ethyl group, and a propyl group; a cyano group; a nitro group; a trifluoromethyl group, At least one hydrogen atom such as a pentafluoroethyl group is substituted with a halogen to form an alkyl group having 1 to 6 carbon atoms; an alkoxy group having 1 to 6 carbon atoms such as a methoxy group, an ethoxy group, an isopropoxy group, or a butoxy group; a methylthio group. , An alkylthio group having 1 to 6 carbon atoms in which at least one hydrogen atom such as an ethylthio group is substituted with a sulfur atom; a monosubstituted amino group such as a methylamino group, an ethylamino group or an acetylamino group; a dimethylamino group or a diethylamino group. It represents a disubstituted amino group such as a group or a phenylmethylamino group; -OCF ₃ ; -C (= O) -OR ³ ; or -OC (= O) -R ³ . Here, R ³ represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms which may have a substituent, and a methyl group or an ethyl group is preferable. The alkyl group having 1 to 10 carbon atoms which may have a substituent of R ³ is the same as the alkyl group having 1 to 10 carbon atoms which may have a substituent of ^{R 1} and R ^2. The same applies to the preferred examples thereof.
Among these, R ^X are each independently preferably a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and more preferably all R ^X is a hydrogen atom.

（式中、Ｒ、ＸおよびＲ^Ｘは、前記と同じ意味を表す。）R ^X, all be the same, or different phases, at least one C-R ^X constituting the ring may be replaced with a nitrogen atom. At least one of C-R ^X Specific examples of groups that are replaced by a nitrogen atom below. However, C-R at least one has been replaced by a nitrogen atom group of ^X is not limited thereto.

(In the formula, R, X and ^RX have the same meanings as described above.)

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

When water or an aqueous solution is added to the reaction solution in step (2) for hydrolysis, the reaction in step (3) is usually a mixed solution obtained by adding water or an aqueous solution to the reaction solution in step (2). The compound (IV) is added to the mixture, and the reaction of the step (3) may be carried out by adding the compound (IV) after extracting the water or the aqueous solution added in the step (2). Further, in the step (3), an acidic aqueous solution for catalyzing the reaction may be newly added, and in particular, when the water or the aqueous solution added in the step (2) is extracted, the acidity for catalyzing the reaction It is preferable to add a new aqueous solution. As the newly added acidic aqueous solution, the same ones listed as those that can be used in the step (2) can be used.
Among the above, in the step (3), the reaction solution obtained in the step (2) is used as it is without performing post-treatment operations such as washing and extraction (that is, the mixing obtained in the step (2)). Addition of compound (IV) to the liquid) is preferable because cost reduction can be achieved. In that case, it is particularly preferable to use an acidic aqueous solution in the step (2). 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).

Compound (IV) may be added after being dissolved in a suitable organic solvent, if desired. As the organic solvent to be used, the same one as exemplified in the above step (1) can be used.
Compound (IV) can be produced, for example, by the methods described in International Publication No. 2015/141784 and JP-A-2016-190818.

Here, in the present invention, the organic solvent used in the step (1) (first organic solvent) and the organic solvent used when the compound (IV) is added in the form of an organic solvent solution in the step (3) (3). It is preferable that at least one of the second organic solvent) is a water-immiscible organic solvent. By using a water-immiscible organic solvent as the first organic solvent and / or the second organic solvent, the high-purity polymerizable compound (A) can be obtained in a higher yield.

Here, the "water-immiscible organic solvent" has a solubility in water at 20 ° C. of 10 g (organic solvent) / 100 mL (water) or less, preferably 1 g (organic solvent) / 100 mL (water) or less, more preferably. It is an organic solvent of 0.1 g (organic solvent) / 100 mL (water) or less.
Examples of the water-immiscible organic solvent include esters such as ethyl acetate, isopropyl acetate, butyl acetate, dimethyl carbonate and diethyl carbonate; halogenated hydrocarbons such as methylene chloride, chloroform and 1,2-dichloroethane; benzene, toluene, etc. Aromatic hydrocarbons such as xylene; saturated hydrocarbons such as pentane, hexane and heptane; ethers such as diethyl ether and cyclopentylmethyl ether; alicyclic hydrocarbons such as cyclopentane and cyclohexane; and the like.

The reaction temperature in step (3) is from −20 ° C. to the boiling point of the solvent used, preferably 0 ° C. to 80 ° C. The reaction time is usually several minutes to 10 hours, depending on the scale of the reaction.

When the reaction solution is separated into two layers, an organic layer and an aqueous layer, after completion of the reaction, water (saline solution) and a water-immiscible organic solvent are added as necessary, and the liquids are separated to separate the organic layer. Sort.
If the reaction solution does not separate into two layers, water (saline solution) and a water-immiscible organic solvent are added as necessary, and the solution is separated to separate the organic layer.
In any case, the obtained organic layer is subjected to a usual post-treatment operation in synthetic organic chemistry, and if desired, a known separation / purification means such as a precipitation method, a recrystallization method, a distillation method, or column chromatography is performed. The target polymerizable compound (A) can be isolated.

In step (3), an adsorbent, a filtration aid, or a combination thereof can be used for reducing ionic impurities and removing insoluble matter (high molecular weight substance).
Examples of the adsorbent used here include activated carbon, silica gel (main component SiO ₂ ), synthetic adsorbent (main component MgO, Al ₂ O ₃ , SiO ₂ ), activated clay, alumina, ion exchange resin, adsorbent resin and the like. Be done.
Examples of the filtration aid include diatomaceous earth, silica gel (main component SiO ₂ ), synthetic zeolite, pearlite, radiolite and the like.

Above all, in the present invention, from the viewpoint that a high-purity target product can be obtained in good yield by a simple operation, a method of concentrating the obtained organic layer and precipitating crystals of the target product from the concentrated solution. Alternatively, any method of concentrating the obtained organic layer and adding a poor solvent to the concentrated solution to precipitate crystals of the target product is preferable.
Examples of the poor solvent used in the latter method include water; alcohols such as methanol and ethanol; and the like.

It is also preferable to purify the obtained crystals by a recrystallization method.
In the recrystallization method, the obtained (coarse) crystals are dissolved in a small amount of solvent (so that there is undissolved residue), and the crystals are heated to completely dissolve them, and then filtered by heat to remove insoluble matters. Then, the filtrate is cooled to precipitate crystals.
Examples of the solvent used for recrystallization include a poor solvent exemplified by the precipitation method and ethers such as tetrahydrofuran.
It is also preferable to add an antioxidant such as 2,6-di-t-butyl-4-methylphenol to the recrystallization solvent in order to obtain a high-purity product. The amount of the antioxidant added is 1 to 500 mg with respect to 100 g of the target crystal.

The structure of the target object can be identified by measurement of NMR spectrum, IR spectrum, mass spectrum, etc., elemental analysis, and the like.

（式中、Ｙ^１、Ｙ^２、Ａ、Ｒ、Ｒ^Ｘ、Ｘ、Ｑおよびｎは、前記と同じ意味を表す。）According to the present invention, the polymerizable compound (A) represented by the formula (A) can be obtained in a high yield in the step (3). In the polymerizable compound (A), Y ¹ , Y ² , A, R, ^RX , X, Q and n have the same meanings as described above.
Then, by using the polymerizable compound (A) obtained by the present invention, for example, a high-quality liquid crystal layer having no orientation defects can be formed.
In the present invention, it is preferable to use the compound represented by the above formula (IIa) as the compound (II) and obtain the polymerizable compound represented by the following formula (Aa) as the polymerizable compound (A).

(In the formula, Y ¹ , Y ² , A, R, ^RX , X, Q and n have the same meanings as described above.)

Hereinafter, the present invention will be described in more detail with reference to Examples. However, the present invention is not limited to the following examples.

(Example 1) Synthesis of polymerizable compound 1

温度計を備えた３口反応器に、窒素気流中、ｔｒａｎｓ−１，４−シクロヘキサンジカルボン酸９０ｇ（０．５２ｍｏｌ）とテトラヒドロフラン（ＴＨＦ）８００ｍｌを加えた。そこへ、メタンスルホニルクロライド３３ｇ（０．２９ｍｏｌ）を加え、反応器を水浴に浸して反応器内温を２０℃とした。次いで、トリエチルアミン３１．７ｇ（０．３１ｍｏｌ）を、反応器内温を２０〜３０℃に保持しながら、３０分間かけて滴下した。滴下終了後、全容を２５℃で２時間さらに攪拌した。得られた反応液に、４−（ジメチルアミノ）ピリジン３．２ｇ（２６．２ｍｍｏｌ）、及び、特開２０１５−１４０３０２号公報を参考に合成した４−（６−アクリロイルオキシ−ヘクス−１−イルオキシ）フェノール６９ｇ（０．２６ｍｏｌ）を加え、再度反応器を水浴に浸して反応器内温を１５℃とした。そこへ、トリエチルアミン３１．７ｇ（０．３１ｍｍｏｌ）を、反応器内温を２０〜３０℃に保持しながら、３０分間かけて滴下し、滴下終了後、全容を２５℃でさらに２時間攪拌した。反応終了後、反応液に蒸留水４０００ｍｌと飽和食塩水５００ｍｌを加え、酢酸エチル１０００ｍｌで２回抽出した。有機層を集め、無水硫酸ナトリウムで乾燥させ、硫酸ナトリウムをろ別した。ロータリーエバポレーターにてろ液から溶媒を蒸発除去した後、得られた残留物をシリカゲルカラムクロマトグラフィー（ＴＨＦ：トルエン＝１：９（体積比、以下にて同じ。））により精製することで、白色固体として中間体Ａを７０．６ｇ得た。収率６５％。Step 1: Synthesis of Intermediate A

To a three-port reactor equipped with a thermometer, 90 g (0.52 mol) of trans-1,4-cyclohexanedicarboxylic acid and 800 ml of tetrahydrofuran (THF) were added in a nitrogen stream. 33 g (0.29 mol) of methanesulfonyl chloride was added thereto, and the reactor was immersed in a water bath to bring the temperature inside the reactor to 20 ° C. Then, 31.7 g (0.31 mol) of triethylamine was added dropwise over 30 minutes while maintaining the temperature inside the reactor at 20 to 30 ° C. After completion of the dropping, the whole volume was further stirred at 25 ° C. for 2 hours. In the obtained reaction solution, 3.2 g (26.2 mmol) of 4- (dimethylamino) pyridine and 4- (6-acryloyloxy-hex-1-yloxy) synthesized with reference to JP-A-2015-140302 ) Phenol 69 g (0.26 mol) was added, and the reactor was immersed in a water bath again to bring the temperature inside the reactor to 15 ° C. 31.7 g (0.31 mmol) of triethylamine was added dropwise thereto over 30 minutes while maintaining the temperature inside the reactor at 20 to 30 ° C., and after completion of the addition, the whole volume was stirred at 25 ° C. for another 2 hours. After completion of the reaction, 4000 ml of distilled water and 500 ml of saturated brine were added to the reaction solution, and the mixture was extracted twice with 1000 ml of ethyl acetate. The organic layer was collected, dried over anhydrous sodium sulfate, and the sodium sulfate was filtered off. After evaporating and removing the solvent from the filtrate with a rotary evaporator, the obtained residue is purified by silica gel column chromatography (THF: toluene = 1: 9 (volume ratio, the same applies hereinafter)) to form a white solid. As a result, 70.6 g of intermediate A was obtained. Yield 65%.

The structure of the object ^{was identified by 1 1} H-NMR.
^{1 1} H-NMR (500 MHz, DMSO-d ₆ , TMS, δ ppm): 12.12 (s, 1H), 6.99 (d, 2H, J = 9.0 Hz), 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, 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).

特開２０１６−１９０８１８号公報を参考に中間体Ｂを合成した。Step 2: Synthesis of Intermediate B

Intermediate B was synthesized with reference to JP-A-2016-190818.

The structure of the object ^{was identified by 1 1} H-NMR.
^{1 1} H-NMR (500 MHz, CDCl ₃ , TMS, δ ppm): 7.60 (dd, 1H, J = 1.0 Hz, 8.0 Hz), 7.53 (dd, 1H, J = 1.0 Hz, 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).

温度計を備えた３口反応器に、窒素気流中、前記ステップ１で合成した中間体Ａ３０ｇ（７１．７ｍｍｏｌ）及びクロロホルム３００ｇ、Ｎ，Ｎ−ジメチルホルムアミド１０．５ｇ（１４３．４ｍｍｏｌ）を加えて、１０℃以下に冷却した。そこへ、塩化チオニル９．８１ｇ（８２．４４ｍｍｏｌ）を、反応温度を１０℃以下に保持しながら滴下した。滴下終了後、反応液を２５℃に戻して１時間撹拌した。反応終了後、エバポレーターにてクロロホルム２２５ｇを抜き出して濃縮して、クロロホルム溶液として合成した。Step 3: Synthesis of Intermediate C

To a three-port reactor equipped with a thermometer, 30 g (71.7 mmol) of the intermediate A synthesized in step 1 and 300 g of chloroform and 10.5 g (143.4 mmol) of N, N-dimethylformamide were added in a nitrogen stream. It was cooled to 10 ° C. or lower. 9.81 g (82.44 mmol) of thionyl chloride was added dropwise thereto while maintaining the reaction temperature at 10 ° C. or lower. After completion of the dropping, the reaction solution was returned to 25 ° C. and stirred for 1 hour. After completion of the reaction, 225 g of chloroform was extracted with an evaporator and concentrated to synthesize a chloroform solution.

Step 4: Synthesis of Polymerizable Compound 1 4.5 g (32.58 mmol) of 2,5-dihydroxybenzaldehyde and 19.78 g (195.5 mmol) of triethylamine in a nitrogen stream in a three-port reactor equipped with a thermometer. It was dissolved in 150 g of chloroform, and the obtained solution was cooled to 10 ° C. or lower. The entire amount of the chloroform solution of Intermediate C synthesized in step 3 was slowly added dropwise to this solution while maintaining the reaction temperature at 10 ° C. or lower. After completion of the dropping, the whole volume was further stirred at 5 to 10 ° C. for 1 hour (step (1)).
After completion of the reaction, 120 g of a 1.0 specified hydrochloric acid aqueous solution was added to the reaction solution while keeping the temperature below 10 ° C. Then, the reaction was carried out by stirring at 10 ° C. or lower for 30 minutes (step (2)).
After completion of the reaction, 10.58 g (42.4 mmol) of the intermediate B synthesized in step 2 and 0.3 g of 2,6-ditercious butyl-para-cresol were added. Then, the temperature of the reaction solution was raised to 40 ° C. and the reaction was carried out for 4 hours (step (3)).
After completion of the reaction, the aqueous layer was extracted. Further, 105 g of distilled water was added to the organic layer, and the organic layer was washed by stirring at 40 ° C. for 30 minutes. After extracting the aqueous layer, the organic layer was cooled to 25 ° C., 1.5 g of Rocahelp # 479 was added, and the mixture was stirred for 30 minutes. Then, filtration was performed with a Kiriyama funnel on which 1 g of Rocahelp # 479 was laid, and Rocahelp # 479 was removed. 180 g of chloroform was extracted from the obtained organic layer by a rotary evaporator and concentrated. 210 g 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 obtained pale yellow solid was dissolved in 120 g of tetrahydrofuran at 25 ° C., 1.5 g of Rocahelp # 479 was added, and the mixture was stirred for 30 minutes. Then, filtration was performed with a Kiriyama funnel on which 1 g of Rocahelp # 479 was laid, and Rocahelp # 479 was removed. 165 g of methanol was slowly added dropwise to the obtained organic layer at 15 ° C. to precipitate a solid, which was then filtered to obtain a solid. The obtained solid was dried in a vacuum dryer to obtain 32.4 g of the polymerizable compound 1 as a pale yellow solid. The yield was 85% (based on 2,5-dihydroxybenzaldehyde).

The structure of the object ^{was identified by 1 1} H-NMR.
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 30 g (71.) of intermediate A synthesized in step 1 of Example 1 in a nitrogen stream in a three-port reactor equipped with a thermometer. 7 mmol), 300 g of toluene, and 5.5 g of N, N-dimethylformamide were added, and the mixture was cooled to 10 ° C. or lower. 8.96 g (75.3 mmol) of thionyl chloride was added dropwise thereto while maintaining the reaction temperature at 10 ° C. or lower. After completion of the dropping, the reaction solution was returned to 25 ° C. and stirred for 1 hour. After completion of the reaction, the reaction solution was concentrated by an evaporator until the amount of the reaction solution was halved. Then, the same amount of toluene as the extracted amount was added, and the mixture was concentrated with an evaporator until the amount of the reaction solution was halved. This operation was repeated 3 times to synthesize a toluene solution.

Step 2: Synthesis of Polymerizable Compound 1 4.13 g (29.9 mmol) of 2,5-dihydroxybenzaldehyde and 7.62 g (75.4 mmol) of triethylamine in a nitrogen stream in a three-port reactor equipped with a thermometer. Was dissolved in 150 g of tetrahydrofuran, and the obtained solution was cooled to 10 ° C. or lower. To this solution, 150 g of the toluene solution of Intermediate C synthesized in step 1 was slowly added dropwise while maintaining the reaction temperature at 10 ° C. or lower. After completion of the dropping, the whole volume was further stirred at 5 to 10 ° C. for 1 hour (step (1)).
After completion of the reaction, 30 g of a 1.0 specified hydrochloric acid aqueous solution was added to the reaction solution while maintaining the temperature at 10 ° C. or lower, and the mixture was stirred at 10 ° C. or lower for 30 minutes (step (2)).
Then, 9.7 g (38.9 mmol) of the intermediate B synthesized in step 2 of Example 1 was added, the temperature was raised to 40 ° C., and the reaction was carried out for 4 hours (step (3)).
After completion of the reaction, the reaction solution was cooled to 25 ° C., 300 g of ethyl acetate and 300 g of 10% by mass saline solution were added to carry out a liquid separation operation. The obtained organic layer was further washed twice with 300 g of 2% by mass saline solution.
From the obtained organic layer, about 15% of the total mass was extracted by an evaporator and concentrated. After the solution was brought to 25 ° C., a mixed solvent of 300 g of methanol and 60 g of water was slowly added dropwise thereto. Then, the mixture was cooled to 10 ° C. to precipitate a solid, and the solid was obtained by filtration. 240 g of tetrahydrofuran, 240 g of methanol, and 20 mg of 2,6-di-t-butyl-4-methylphenol were added to the obtained solid, and the whole volume was heated to 50 ° C. to obtain a uniform solution. This solution was hot-filtered at 50 ° C., and the obtained filtrate was slowly cooled to 10 ° C. and recrystallized. Crystals were obtained by filtration and dried in a vacuum dryer to obtain 28.3 g of polymerizable compound 1 as a pale yellow solid. The yield was 81% (based on 2,5-dihydroxybenzaldehyde).

温度計を備えた３口反応器に、窒素気流中、ｔｒａｎｓ−１，４−シクロヘキサンジカルボン酸ジクロライド１６．６ｇ（７９．４０ｍｍｏｌ）と、シクロペンチルメチルエーテル（ＣＰＭＥ）１２０ｇと、テトラヒドロフラン４６ｇとを加えた。そこへ、特開２０１５−１４０３０２号公報を参考に合成した４−（６−アクリロイルオキシ−ヘクス−１−イルオキシ）フェノール２０ｇ（７５．６７ｍｍｏｌ）、２，６−ジターシャリーブチル−パラ−クレゾール０．３３ｇを加え、反応器を氷浴に浸して反応器内温を０℃とした。次いで、トリエチルアミン８．０ｇ（７９．４５ｍｍｏｌ）を、反応器内温を１０℃以下に保持しながら、３０分間かけてゆっくり滴下した。滴下終了後、全容を１０℃以下に保持しながら１時間さらに攪拌した。
得られた反応液に、蒸留水５０ｇを加えた。この反応液を５０℃に昇温した後、２時間洗浄（加水分解反応）した後、水層を抜き出した。この水による洗浄（加水分解反応）を合計３回、合計６時間実施した。得られた有機層を４０℃に冷却した後、さらに、濃度１ｍｏｌ／Ｌの酢酸と酢酸ナトリウムからなる緩衝溶液（ｐＨ：５．５）８３．２ｇを加えて、撹拌することで洗浄した。その後、緩衝溶液層（水層）を抜き出し、有機層を得た。この緩衝溶液による洗浄操作を合計５回行った。得られた有機層にさらに、蒸留水５０ｇで洗浄を行った後、水層を抜き出した。この蒸留水による洗浄を合計２回実施した。得られた有機層に、４０℃にてｎ−ヘキサン２４０ｇを加えた後、０℃まで冷却して結晶を析出させた。その後、析出した結晶をろ過によりろ取した。ろ過物をｎ−ヘキサンで洗浄後、真空乾燥させて、白色固体として混合物１を２６．９１ｇ得た。(Example 3) Synthesis of polymerizable compound 1 Step 1: Synthesis of mixture 1

To a three-port reactor equipped with a thermometer, 16.6 g (79.40 mmol) of trans-1,4-cyclohexanedicarboxylic acid dichloride, 120 g of cyclopentyl methyl ether (CPME), and 46 g of tetrahydrofuran were added in a nitrogen stream. .. There, 20 g (75.67 mmol) of 4- (6-acryloyloxy-hex-1-yloxy) phenol synthesized with reference to JP-A-2015-140302, 2,6-ditercious butyl-para-cresol 0. 33 g was added, and the reactor was immersed in an ice bath to bring the temperature inside the reactor to 0 ° C. Then, 8.0 g (79.45 mmol) of triethylamine was slowly added dropwise over 30 minutes while maintaining the temperature inside the reactor at 10 ° C. or lower. After completion of the dropping, the mixture was further stirred for 1 hour while keeping the whole volume at 10 ° C. or lower.
50 g of distilled water was added to the obtained reaction solution. The reaction solution was heated to 50 ° C., washed for 2 hours (hydrolysis reaction), and then the aqueous layer was extracted. This washing with water (hydrolysis reaction) was carried out a total of 3 times for a total of 6 hours. After cooling the obtained organic layer to 40 ° C., 83.2 g of a buffer solution (pH: 5.5) composed of acetic acid and sodium acetate having a concentration of 1 mol / L was further added, and the mixture was washed by stirring. Then, the buffer solution layer (aqueous layer) was extracted to obtain an organic layer. The washing operation with this buffer solution was performed a total of 5 times. The obtained organic layer was further washed with 50 g of distilled water, and then the aqueous layer was extracted. This washing with distilled water was carried out twice in total. 240 g of n-hexane was added to the obtained organic layer at 40 ° C., and then cooled to 0 ° C. to precipitate crystals. Then, the precipitated crystals were collected by filtration. The filtrate was washed with n-hexane and then vacuum dried to give 26.91 g of Mixture 1 as a white solid.

The obtained crystals were analyzed by HPLC, and the monoesters and diesters were quantified by a calibration curve. As a result, the target monoester was contained in an amount of 68.34% by mass (43.95 mmol). I understood. Moreover, when the obtained crystal was ^{analyzed by 13} C-NMR (dioxane-d ₈ ) and the content of cyclohexanedicarboxylic acid was calculated, it was below the detection limit.

Step 2: Synthesis of polymerizable compound 1: 26.91 g of the mixture synthesized in step 1, 183.9 g of chloroform, and N, N-dimethylformamide in a nitrogen stream in a three-port reactor equipped with a thermometer. 6.4 g was added and the mixture was cooled to 10 ° C. or lower. To this, 6.0 g (50.54 mmol) of thionyl chloride was added dropwise under control so that the reaction temperature was 10 ° C. or lower. After completion of the dropping, the reaction solution was returned to 25 ° C. and stirred for 1 hour. After completion of the reaction, 138 g of chloroform was extracted under reduced pressure with an evaporator. Then, 46 g of chloroform was newly added to obtain a chloroform solution (1). Separately, in a three-port reactor equipped with a thermometer, 2.76 g (20.0 mmol) of 2,5-dihydroxybenzaldehyde and 12.13 g (119.8 mmol) of triethylamine were dissolved in 92 g of chloroform in a nitrogen stream, and 10 It was cooled to below ° C. The chloroform solution (1) was slowly added dropwise to this solution while maintaining the temperature inside the reactor at 10 ° C. or lower. After completion of the dropping, the reaction was carried out for another 1 hour while keeping the reaction solution at 10 ° C. or lower (step (1)).
After completion of the reaction, 725 g of a 1.0 specified hydrochloric acid aqueous solution was added to the reaction solution at a temperature of 10 ° C. or lower, and the mixture was stirred at 10 ° C. or lower for 30 minutes (step (2)).
Then, 6.48 g (26.0 mmol) of the intermediate B synthesized in step 2 of Example 1 and 0.33 g of 2,6-ditercious butyl-para-cresol were added, and the temperature was raised to 40 ° C. for a 4-hour reaction. (Step (3)).
After completion of the reaction, the aqueous layer was extracted at 40 ° C. and a liquid separation operation was performed. 0.92 g of Rocahelp # 479 (manufactured by Mitsui Mining & Smelting Co., Ltd.) was added to the obtained organic layer, and the mixture was stirred at 25 ° C. for 30 minutes and then filtered through a filter covered with 0.6 g of Rocahelp # 479. The filter was washed with 9.2 g of chloroform and combined with the previously obtained filtrate. Then, 110 g of chloroform was extracted from the obtained organic layer under reduced pressure with an evaporator and concentrated. After adding 33 g of tetrahydrofuran to this solution, the solution was cooled to 15 ° C. with stirring. Then, 129 g of 60% hexane (manufactured by Gordo Co., Ltd.) was slowly added dropwise to this solution. The solid was precipitated by stirring at the same temperature for 30 minutes. Then, the precipitated solid was collected by filtration.
To the obtained solid, 88.3 g of tetrahydrofuran, Rocahelp # 479: 1.1 g, and 0.33 g of 2,6-ditercious butyl-para-cresol were added, and the mixture was stirred at 25 ° C. for 30 minutes, and then 0. It was filtered through a filter laid with 66 g of Rocahelp # 479. The filter was washed with 44 g of tetrahydrofuran and combined with the previously obtained filtrate. Then, 110 g of tetrahydrofuran was distilled off from the obtained organic layer by an evaporator. The obtained solution was brought to 15 ° C., and 121 g of methanol was slowly added dropwise. The solid was precipitated by stirring at the same temperature for 30 minutes. Then, the precipitated solid was collected by filtration. The filtrate was washed with methanol and dried under vacuum to obtain 19.4 g of polymerizable compound 1 as a pale yellow solid. The yield was 83% (based on 2,5-dihydroxybenzaldehyde).

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

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

(Example 6) Synthesis of polymerizable compound 1 In step 2 of Example 3, the same operation as in Example 3 except that 725 g of a 1.0 specified hydrochloric acid aqueous solution was changed to 700 g of a 1.0 specified methanesulfonic acid aqueous solution. Was done. As a result, 19.9 g of polymerizable compound 1 was obtained as a pale yellow solid. The yield was 85% (based on 2,5-dihydroxybenzaldehyde).

(Example 7) Synthesis of polymerizable compound 1 In step 2 of Example 3, 12.13 g (119.8 mmol) of triethylamine was changed to 12.8 g (120.0 mmol) of 2,6-lutidine, and 1.0 was specified. The same operation as in Example 3 was carried out except that 725 g of the hydrochloric acid aqueous solution was changed to 700 g of the 1.0 specified methanesulfonic acid aqueous solution. As a result, 20.6 g of polymerizable compound 1 was obtained as a pale yellow solid. The yield was 88% (based on 2,5-dihydroxybenzaldehyde).

(Comparative Example 1) Synthesis of Polymerizable Compound 1 Steps 1 to 3: The same operation as in Steps 1 to 3 of Example 1 was carried out.

Step 4: Synthesis of Polymerizable Compound 1 4.5 g (32.58 mmol) of 2,5-dihydroxybenzaldehyde and 19.78 g (195.5 mmol) of triethylamine in a nitrogen stream in a three-port reactor equipped with a thermometer. It was dissolved in 150 g of chloroform, and the obtained solution was cooled to 10 ° C. or lower. The entire amount of the chloroform solution of Intermediate C synthesized in step 3 was slowly added dropwise to this solution while maintaining the reaction temperature at 10 ° C. or lower. After completion of the dropping, the whole volume was further stirred at 5 to 10 ° C. for 1 hour (step (1)).
After completion of the reaction, while keeping the temperature at 10 ° C. or lower, 120 g of a 1.0 specified hydrochloric acid aqueous solution, 10.58 g (42.4 mmol) of the intermediate B synthesized in step 2, and 2,6-ditershaly butyl were added to the reaction solution. -Para-cresol 0.3 g was added. Then, the temperature of the reaction solution was raised to 40 ° C. and the reaction was carried out for 4 hours (step (3)).
After completion of the reaction, the aqueous layer was extracted. Further, 105 g of distilled water was added to the organic layer, and the organic layer was washed by stirring at 40 ° C. for 30 minutes. After extracting the aqueous layer, the organic layer was cooled to 25 ° C., 1.5 g of Rocahelp # 479 was added, and the mixture was stirred for 30 minutes. Then, filtration was performed with a Kiriyama funnel on which 1 g of Rocahelp # 479 was laid, and Rocahelp # 479 was removed. 180 g of chloroform was extracted from the obtained organic layer by a rotary evaporator and concentrated. 210 g 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 obtained pale yellow solid was dissolved in 120 g of tetrahydrofuran at 25 ° C., 1.5 g of Rocahelp # 479 was added, and the mixture was stirred for 30 minutes. Then, filtration was performed with a Kiriyama funnel on which 1 g of Rocahelp # 479 was laid, and Rocahelp # 479 was removed. 165 g of methanol was slowly added dropwise to the obtained organic layer at 15 ° C. to precipitate a solid, which was then filtered to obtain a solid. The obtained solid was dried in a vacuum dryer to obtain 27.5 g 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 operation as in Step 1 of Example 3 was carried out.

Step 2: In a three-port reactor equipped with a synthetic thermometer of polymerizable compound 1, 1: 26.91 g of the mixture synthesized in step 1, 183.9 g of chloroform, and N, N-dimethylformamide 6 in a nitrogen stream. .4 g was added and the mixture was cooled to 10 ° C. or lower. To this, 6.0 g (50.54 mmol) of thionyl chloride was added dropwise under control so that the reaction temperature was 10 ° C. or lower. After completion of the dropping, the reaction solution was returned to 25 ° C. and stirred for 1 hour. After completion of the reaction, 138 g of chloroform was extracted under reduced pressure with an evaporator. Then, 46 g of chloroform was newly added to obtain a chloroform solution (2). Separately, in a three-port reactor equipped with a thermometer, 2.76 g (20.0 mmol) of 2,5-dihydroxybenzaldehyde and 12.13 g (119.8 mmol) of triethylamine were dissolved in 92 g of chloroform in a nitrogen stream, and 10 It was cooled to below ° C. The chloroform solution (2) was slowly added dropwise to this solution while maintaining the temperature inside the reactor at 10 ° C. or lower. After completion of the dropping, the reaction was carried out for another 1 hour while keeping the reaction solution at 10 ° C. or lower (step (1)).
After completion of the reaction, 725 g of a 1.0 specified hydrochloric acid aqueous solution and 6.48 g (26.0 mmol) of the intermediate B synthesized in step 2 of Example 1 were added to the reaction solution at a temperature of 10 ° C. or lower, 2,6-. 0.33 g of jittery butyl-para-cresol was added, the temperature was raised to 40 ° C., and the reaction was carried out for 4 hours (step (3)).
After completion of the reaction, the aqueous layer was extracted at 40 ° C. and a liquid separation operation was performed. 0.92 g of Rocahelp # 479 (manufactured by Mitsui Mining & Smelting Co., Ltd.) was added to the obtained organic layer, and the mixture was stirred at 25 ° C. for 30 minutes and then filtered through a filter covered with 0.6 g of Rocahelp # 479. The filter was washed with 9.2 g of chloroform and combined with the previously obtained filtrate. Then, 110 g of chloroform was extracted from the obtained organic layer under reduced pressure with an evaporator and concentrated. After adding 33 g of tetrahydrofuran to this solution, the solution was cooled to 15 ° C. with stirring. Then, 129 g of 60% hexane (manufactured by Gordo Co., Ltd.) was slowly added dropwise to this solution. The solid was precipitated by stirring at the same temperature for 30 minutes. Then, the precipitated solid was collected by filtration.
To the obtained solid, 88.3 g of tetrahydrofuran, Rocahelp # 479: 1.1 g, and 0.33 g of 2,6-ditercious butyl-para-cresol were added, and the mixture was stirred at 25 ° C. for 30 minutes, and then 0. It was filtered through a filter laid with 66 g of Rocahelp # 479. The filter was washed with 44 g of tetrahydrofuran and combined with the previously obtained filtrate. Then, 110 g of tetrahydrofuran was distilled off from the obtained organic layer by an evaporator. The obtained solution was brought to 15 ° C., and 121 g of methanol was slowly added dropwise. The solid was precipitated by stirring at the same temperature for 30 minutes. Then, the precipitated solid was collected by filtration. The filtrate was washed with methanol and dried under vacuum to obtain 16.6 g 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 Steps 1 to 3: The same operation as in Steps 1 to 3 of Example 1 was carried out.

Step 4: Synthesis of Polymerizable Compound 1 4.5 g (32.58 mmol) of 2,5-dihydroxybenzaldehyde and 20.97 g (195) of 2,6-lutidine in a nitrogen stream in a three-port reactor equipped with a thermometer. .7 mmol) was dissolved in 150 g of chloroform and the resulting solution was cooled to 10 ° C. or lower. The entire amount of the chloroform solution of Intermediate C synthesized in step 3 was slowly added dropwise to this solution while maintaining the reaction temperature at 10 ° C. or lower. After completion of the dropping, the whole volume was further stirred at 5 to 10 ° C. for 1 hour (step (1)).
After completion of the reaction, while keeping the temperature at 10 ° C. or lower, 120 g of a 1.0 specified hydrochloric acid aqueous solution, 10.58 g (42.4 mmol) of the intermediate B synthesized in step 2, and 2,6-ditershaly butyl -Para-cresol 0.3 g was added. Then, the temperature of the reaction solution was raised to 40 ° C. and the reaction was carried out for 4 hours (step (3)).
After completion of the reaction, the aqueous layer was extracted. Further, 105 g of distilled water was added to the organic layer, and the organic layer was washed by stirring at 40 ° C. for 30 minutes. After extracting the aqueous layer, the organic layer was cooled to 25 ° C., 1.5 g of Rocahelp # 479 was added, and the mixture was stirred for 30 minutes. Then, filtration was performed with a Kiriyama funnel on which 1 g of Rocahelp # 479 was laid, and Rocahelp # 479 was removed. The obtained organic layer was concentrated by extracting 180 g of chloroform with a rotary evaporator. 210 g of hexane was added to the obtained organic layer in 1 hour to precipitate a solid, and a pale yellow solid was obtained by filtration. The obtained pale yellow solid was dissolved in 120 g of tetrahydrofuran at 25 ° C., 1.5 g of Rocahelp # 479 was added, and the mixture was stirred for 30 minutes. Then, filtration was performed with a Kiriyama funnel on which 1 g of Rocahelp # 479 was laid, and Rocahelp # 479 was removed. 165 g of methanol was slowly added dropwise to the obtained organic layer at 15 ° C. to precipitate a solid, which was then filtered to obtain a solid. The obtained solid was dried in a vacuum dryer to obtain 29.4 g of the polymerizable compound 1 as a pale yellow solid. The yield was 77% (based on 2,5-dihydroxybenzaldehyde).

(Comparative Example 4) Synthesis of Polymerizable Compound 1 Step 1: The same operation as in Step 1 of Example 3 was carried out.

Step 2: Synthesis of polymerizable compound 1: 26.91 g of the mixture synthesized in step 1, 183.9 g of chloroform, and N, N-dimethylformamide 6 in a nitrogen stream in a three-port reactor equipped with a thermometer. .4 g was added and the mixture was cooled to 10 ° C. or lower. To this, 6.0 g (50.54 mmol) of thionyl chloride was added dropwise under control so that the reaction temperature was 10 ° C. or lower. After completion of the dropping, the reaction solution was returned to 25 ° C. and stirred for 1 hour. After completion of the reaction, 138 g of chloroform was extracted under reduced pressure with an evaporator. Then, 46 g of chloroform was newly added to obtain a chloroform solution (3). Separately, in a three-port reactor equipped with a thermometer, 2.76 g (20.0 mmol) of 2,5-dihydroxybenzaldehyde and 12.8 g (120.0 mmol) of 2,6-lutidine were added to 92 g of chloroform in a nitrogen stream. It was melted and cooled to 10 ° C. or lower. The chloroform solution (3) was slowly added dropwise to this solution while maintaining the temperature inside the reactor at 10 ° C. or lower. After completion of the dropping, the reaction was carried out for another 1 hour while keeping the reaction solution at 10 ° C. or lower (step (1)).
After completion of the reaction, 725 g of a 1.0 specified hydrochloric acid aqueous solution, 6.48 g (26.0 mmol) of the intermediate B synthesized in step 2 of Example 1, and 2,6-diter were added to the reaction solution at 10 ° C. or lower. 0.33 g of Charlie Butyl-para-cresol was added, the temperature was raised to 40 ° C., and the reaction was carried out for 4 hours (step (3)).
After completion of the reaction, the aqueous layer was extracted at 40 ° C. and a liquid separation operation was performed. 0.92 g of Rocahelp # 479 (manufactured by Mitsui Mining & Smelting Co., Ltd.) was added to the obtained organic layer, and the mixture was stirred at 25 ° C. for 30 minutes and then filtered through a filter covered with 0.6 g of Rocahelp # 479. The filter was washed with 9.2 g of chloroform and combined with the previously obtained filtrate. Then, 110 g of chloroform was extracted from the obtained organic layer under reduced pressure with an evaporator and concentrated. After adding 33 g of tetrahydrofuran to this solution, the solution was cooled to 15 ° C. with stirring. Then, 129 g of 60% hexane (manufactured by Gordo Co., Ltd.) was slowly added dropwise to this solution. The solid was precipitated by stirring at the same temperature for 30 minutes. Then, the precipitated solid was collected by filtration. To the obtained solid, 88.3 g of tetrahydrofuran, Rocahelp # 479: 1.1 g, and 0.33 g of 2,6-ditercious butyl-para-cresol were added, and the mixture was stirred at 25 ° C. for 30 minutes, and then 0. It was filtered through a filter laid with 66 g of Rocahelp # 479. The filter was washed with 44 g of tetrahydrofuran and combined with the previously obtained filtrate. Then, 110 g of tetrahydrofuran was distilled off from the obtained organic layer by an evaporator. The obtained solution was brought to 15 ° C., and 121 g of methanol was slowly added dropwise. The solid was precipitated by stirring at the same temperature for 30 minutes. Then, the precipitated solid was collected by filtration. The filtrate was washed with methanol and dried under vacuum to obtain 17.8 g of polymerizable compound 1 as a pale yellow solid. The yield was 76% (based on 2,5-dihydroxybenzaldehyde).

(Comparative Example 5) Synthesis of Polymerizable Compound 1 Step 1: The same operation as in Step 1 of Example 3 was carried out.

Step 2: Synthesis of polymerizable compound 1: 26.91 g of the mixture synthesized in step 1, 183.9 g of chloroform, and N, N-dimethylformamide 6 in a nitrogen stream in a three-port reactor equipped with a thermometer. .4 g was added and the mixture was cooled to 10 ° C. or lower. To this, 6.0 g (50.54 mmol) of thionyl chloride was added dropwise under control so that the reaction temperature was 10 ° C. or lower. After completion of the dropping, the reaction solution was returned to 25 ° C. and stirred for 1 hour. After completion of the reaction, 138 g of chloroform was extracted under reduced pressure with an evaporator. Then, 46 g of chloroform was newly added to obtain a chloroform solution (4). Separately, in a three-port reactor equipped with a thermometer, 2.76 g (20.0 mmol) of 2,5-dihydroxybenzaldehyde and 12.8 g (120.0 mmol) of 2,6-lutidine were added to 92 g of chloroform in a nitrogen stream. It was melted and cooled to 10 ° C. or lower. The chloroform solution (4) was slowly added dropwise to this solution while maintaining the temperature inside the reactor at 10 ° C. or lower. After completion of the dropping, the reaction was carried out for another 1 hour while keeping the reaction solution at 10 ° C. or lower (step (1)).
After completion of the reaction, 700 g of a 1.0 specified aqueous solution of methanesulfonic acid, 6.48 g (26.0 mmol) of the intermediate B synthesized in step 2 of Example 1, and 2,6 were added to the reaction solution at 10 ° C. or lower. -Differential butyl-para-cresol 0.33 g was added, the temperature was raised to 40 ° C., and the reaction was carried out for 4 hours (step (3)).
After completion of the reaction, the aqueous layer was extracted at 40 ° C. and a liquid separation operation was performed. 0.92 g of Rocahelp # 479 (manufactured by Mitsui Mining & Smelting Co., Ltd.) was added to the obtained organic layer, and the mixture was stirred at 25 ° C. for 30 minutes and then filtered through a filter covered with 0.6 g of Rocahelp # 479. The filter was washed with 9.2 g of chloroform and combined with the previously obtained filtrate. Then, 110 g of chloroform was extracted from the obtained organic layer under reduced pressure with an evaporator and concentrated. After adding 33 g of tetrahydrofuran to this solution, the solution was cooled to 15 ° C. with stirring. Then, 129 g of 60% hexane (manufactured by Gordo Co., Ltd.) was slowly added dropwise to this solution. The solid was precipitated by stirring at the same temperature for 30 minutes. Then, the precipitated solid was collected by filtration. To the obtained solid, 88.3 g of tetrahydrofuran, Rocahelp # 479: 1.1 g, and 0.33 g of 2,6-ditercious butyl-para-cresol were added, and the mixture was stirred at 25 ° C. for 30 minutes, and then 0. It was filtered through a filter laid with 66 g of Rocahelp # 479. The filter was washed with 44 g of tetrahydrofuran and combined with the previously obtained filtrate. Then, 110 g of tetrahydrofuran was distilled off from the obtained organic layer by an evaporator. The obtained solution was brought to 15 ° C., and 121 g of methanol was slowly added dropwise. The solid was precipitated by stirring at the same temperature for 30 minutes. Then, the precipitated solid was collected by filtration. The filtrate was washed with methanol and dried under vacuum to obtain 17.6 g of polymerizable compound 1 as a pale yellow solid. The yield was 75% (based on 2,5-dihydroxybenzaldehyde).

(Comparative Example 6) Synthesis of Polymerizable Compound 1 The same operation as in Comparative Example 1 was 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, 28.6 g of polymerizable compound 1 was obtained as a pale yellow solid. The yield was 75% (based on 2,5-dihydroxybenzaldehyde).

(Comparative Example 7) Synthesis of Polymerizable Compound 1 The same operation as in Comparative Example 2 was carried out except that the reaction time of step (3) in Step 2 of Comparative Example 2 was changed from 4 hours to 8 hours. As a result, 17.1 g of polymerizable compound 1 was obtained as a pale yellow solid. The yield was 73% (based on 2,5-dihydroxybenzaldehyde).

(Comparative Example 8) Synthesis of Polymerizable Compound 1 The same operation as in Comparative Example 3 was 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, 30.5 g of polymerizable compound 1 was obtained as a pale yellow solid. The yield was 80% (based on 2,5-dihydroxybenzaldehyde).

(Comparative Example 9) Synthesis of Polymerizable Compound 1 The same operation as in Comparative Example 4 was 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, 18.5 g of polymerizable compound 1 was obtained as a pale yellow solid. The yield was 79% (based on 2,5-dihydroxybenzaldehyde).

(Comparative Example 10) Synthesis of Polymerizable Compound 1 The same operation as in Comparative Example 5 was 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, 18.0 g of polymerizable compound 1 was obtained as a pale yellow solid. The yield was 77% (based on 2,5-dihydroxybenzaldehyde).

The results of Examples 1 to 7 and Comparative Examples 1 to 10 are summarized in Table 1.

(Example 8) Synthesis of polymerizable compound 2

温度計を備えた３口反応器に、窒素気流中、１−ナフチル酢酸５００．５ｇ（２．６９ｍｏｌ）とトルエン１０４９ｇとを加えた。更に、６−クロロ−１−ヘキサノール３４９．５ｇ（２．５６ｍｏｌ）、パラトルエンスルホン酸１水和物４８．６ｇ（０．２６ｍｏｌ）を加えた。ディーンスタークを用いてこの溶液を加熱して、生成する水を反応系外に排出しながら共沸脱水（内温約９５℃）を２時間行った。反応終了後、反応液を２５℃まで冷却して、５．８質量％の重曹水７４２ｇで洗浄した。分液後、更に有機層を水５００ｇで洗浄した。その後、有機層にロカヘルプ＃４７９：７ｇを加えて室温下にて３０分撹拌した後、ろ過を行い、ロカヘルプ＃４７９を除去した。有機層からロータリーエバポレーターにて溶媒を留去して、中間体Ｄを含む淡茶色オイルを７５５ｇ得た。高速液体クロマトグラフによる定量により、この中間体Ｄを含む淡茶色オイルには中間体Ｄが９３．０質量％含まれていることが分かった。この茶色オイルの精製は行わず、そのまま次の反応に用いた。Step 1: Synthesis of intermediate D

To a three-port reactor equipped with a thermometer, 500.5 g (2.69 mol) of 1-naphthyl acetic acid and 1049 g of toluene were added in a nitrogen stream. Further, 349.5 g (2.56 mol) of 6-chloro-1-hexanol and 48.6 g (0.26 mol) of paratoluenesulfonic acid monohydrate were added. This solution was heated using Dean-Stark, and azeotropic dehydration (internal temperature of about 95 ° C.) was carried out for 2 hours while discharging the produced water to the outside of the reaction system. After completion of the reaction, the reaction solution was cooled to 25 ° C. and washed with 742 g of 5.8 mass% sodium bicarbonate water. After the liquid separation, the organic layer was further washed with 500 g of water. Then, Rocahelp # 479: 7 g was added to the organic layer, and the mixture was stirred at room temperature for 30 minutes and then filtered to remove Rocahelp # 479. The solvent was distilled off from the organic layer with a rotary evaporator to obtain 755 g of a light brown oil containing Intermediate D. Quantification by high performance liquid chromatography revealed that the light brown oil containing this intermediate D contained 93.0% by mass of the intermediate D. This brown oil was not refined and was used as it was in the next reaction.

温度計を備えた３口反応器に、窒素気流中、先のステップ１で合成した中間体Ｄを含む淡茶色オイル：５９．５２ｇ(中間体Ｄの正味量として、５５．３５ｇ（０．１８２ｍｏｌ）)およびＮ−メチル−２−ピロリドン：２３５ｇを投入し、均一な溶液とした。そこへ、２−ヒドラジノベンゾチアゾール：２５．０ｇ（０．１５１ｍｏｌ）を加えた。次いで、リン酸三カリウム：４８．１８ｇ（０．２２７ｍｏｌ）を加え、全容を１００℃で３時間攪拌した。反応終了後、６０℃に降温した反応液に酢酸エチル３１２．５ｇを加えた後、６０℃を維持して、ろ過を行った。ろ液である有機層を０．５規定のクエン酸水溶液２５０ｇにゆっくり滴下して、内温６０℃で３０分撹拌した後、水層を抜き出した。更に有機層に９．１質量％の塩化ナトリウム水溶液２７５ｇを加え、内温６０℃で３０分撹拌した後、３０分静置して水層を抜き出した。次いで有機層に４．７６質量％の炭酸水素ナトリウム水溶液２６２．５ｇを加え、内温６０℃で３０分撹拌した後、３０分静置して水層を抜き出した。更に有機層に水２５０ｇを加え、内温６０℃で３０分撹拌した後、３０分静置して水層を抜き出した。得られた有機層を徐々に０℃まで冷却して、０℃にて３０分撹拌した。生じた固体をろ過によって取得した。その後、取得した固体に酢酸エチル１５０ｇを加えて、６０℃まで昇温して均一溶液として、３０分撹拌した。その後、酢酸エチル溶液を徐々に０℃まで冷却して、０℃にて１時間撹拌した。生じた固体をろ過によって取得して、減圧乾燥させることで、中間体Ｅを白色固体として３６．９ｇ得た。収率は５６．４モル％であった。Step 2: Synthesis of intermediate E

Light brown oil containing intermediate D synthesized in step 1 above in a nitrogen stream in a three-port reactor equipped with a thermometer: 59.52 g (55.35 g (0.182 mol) as the net amount of intermediate D )) And N-methyl-2-pyrrolidone: 235 g were added to prepare a uniform solution. To that, 2-hydrazinobenzothiazole: 25.0 g (0.151 mol) was added. Then, tripotassium phosphate: 48.18 g (0.227 mol) was added, and the whole volume was stirred at 100 ° C. for 3 hours. After completion of the reaction, 312.5 g of ethyl acetate was added to the reaction solution cooled to 60 ° C., and then filtration was performed while maintaining 60 ° C. The organic layer as a filtrate was slowly added dropwise to 250 g of a 0.5N aqueous citric acid solution, stirred at an internal temperature of 60 ° C. for 30 minutes, and then the aqueous layer was extracted. Further, 275 g of a 9.1 mass% sodium chloride aqueous solution was added to the organic layer, the mixture was stirred at an internal temperature of 60 ° C. for 30 minutes, and then allowed to stand for 30 minutes to extract the aqueous layer. Next, 262.5 g of a 4.76 mass% sodium hydrogen carbonate aqueous solution was added to the organic layer, the mixture was stirred at an internal temperature of 60 ° C. for 30 minutes, and then allowed to stand for 30 minutes to extract the aqueous layer. Further, 250 g of water was added to the organic layer, the mixture was stirred at an internal temperature of 60 ° C. for 30 minutes, and then allowed to stand for 30 minutes to extract the aqueous layer. The obtained organic layer was gradually cooled to 0 ° C. and stirred at 0 ° C. for 30 minutes. The resulting solid was obtained by filtration. Then, 150 g of ethyl acetate was added to the obtained solid, the temperature was raised to 60 ° C. to prepare a uniform solution, and the mixture was stirred for 30 minutes. Then, the ethyl acetate solution was gradually cooled to 0 ° C., and the mixture was stirred at 0 ° C. for 1 hour. The resulting solid was obtained by filtration and dried under reduced pressure to obtain 36.9 g of Intermediate E as a white solid. The yield was 56.4 mol%.

The structure of the object ^{was identified by 1 1} H-NMR.
^{1 1} H-NMR (500 MHz, CDCl ₃ , TMS, δ ppm): 8.00 (d, 1H, J = 8.5 Hz), 7.85 (dd, 1H, J = 1.0 Hz, 8.0 Hz), 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 = 7.0 Hz), 1.63-1.54 (m, 4H), 1.32-1.22 (m, 4H).

Step 3: Synthesis of polymerizable compound 2: 26.91 g of the mixture synthesized in step 1 of Example 3 above, 183.9 g of chloroform, and N, in a nitrogen stream in a three-port reactor equipped with a thermometer. 6.4 g of N-dimethylformamide was added, and the mixture was cooled to 10 ° C. or lower. To this, 6.0 g (50.54 mmol) of thionyl chloride was added dropwise under control so that the reaction temperature was 10 ° C. or lower. After completion of the dropping, the reaction solution was returned to 25 ° C. and stirred for 1 hour. After completion of the reaction, 138 g of chloroform was extracted under reduced pressure with an evaporator. Then, 46 g of chloroform was newly added to obtain a chloroform solution (5). Separately, in a three-port reactor equipped with a thermometer, 2.76 g (20.0 mmol) of 2,5-dihydroxybenzaldehyde and 12.13 g (119.8 mmol) of triethylamine were dissolved in 92 g of chloroform in a nitrogen stream, and 10 It was cooled to below ° C. The chloroform solution (5) was slowly added dropwise to this solution while maintaining the temperature inside the reactor at 10 ° C. or lower. After completion of the dropping, the reaction was carried out for another 1 hour while keeping the reaction solution at 10 ° C. or lower (step (1)).
After completion of the reaction, 725 g of a 1.0 specified hydrochloric acid aqueous solution was added to the reaction solution at 10 ° C. or lower, and the mixture was stirred at 10 ° C. or lower for 30 minutes (step (2)).
Then, 10.38 g (23.9 mmol) of the intermediate E synthesized in step 2 and 0.33 g of 2,6-ditercious butyl-para-cresol were added, the temperature was raised to 40 ° C., and the reaction was carried out for 4 hours. (Step (3)).
After completion of the reaction, the aqueous layer was extracted at 40 ° C. and a liquid separation operation was performed. 0.92 g of Rocahelp # 479 (manufactured by Mitsui Mining & Smelting Co., Ltd.) was added to the obtained organic layer, and the mixture was stirred at 25 ° C. for 30 minutes and then filtered through a filter covered with 0.6 g of Rocahelp # 479. The filter was washed with 9.2 g of chloroform and combined with the previously obtained filtrate. This chloroform solution was slowly added dropwise to 367.8 g of methanol at 25 ° C. to precipitate a solid. After aging for 30 minutes with slow stirring at the same temperature, the precipitated solid was collected by filtration. The obtained solid was dissolved in 147 g of chloroform, 0.92 g of Rocahelp # 479 (manufactured by Mitsui Mining & Smelting Co., Ltd.) was added, and the mixture was stirred at 25 ° C. for 30 minutes, and then a filter covered with 0.6 g of Rocahelp # 479. I broke up. The filter was washed with 36.8 g of chloroform and combined with the previously obtained filtrate. This chloroform solution was slowly added dropwise to 184 g of methanol at 25 ° C. to precipitate a solid. After aging for 30 minutes with slow stirring at the same temperature, the precipitated solid was collected by filtration. The filtrate was washed with methanol and dried under vacuum to obtain 22.2 g of polymerizable compound 2 as a pale yellow solid. The yield was 82% (based on 2,5-dihydroxybenzaldehyde).

The structure of the object ^{was identified by 1 1} H-NMR.
^{1 1} H-NMR (500 MHz, CDCl ₃ , TMS, δ ppm): 7.97 (dd, 1H, J = 0.5 Hz, 8.5 Hz), 7.80 (ddd, 1H, J = 0.5 Hz, 0. 5Hz, 8.0Hz), 7.73-7.76 (m, 2H), 7.67-7.71 (m, 2H), 7.61 (s, 1H), 7.49 (ddd, 1H, J = 1.0Hz, 6.5Hz, 8.5Hz), 7.42 (ddd, 1H, J = 1.5Hz, 7.0Hz, 7.0Hz), 7.33-7.39 (m, 3H) , 7.18 (ddd, 1H, J = 1.0Hz, 7.5Hz, 8.0Hz), 7.10-7.14 (m, 2H), 6.95-7.01 (m, 4H), 6.85-6.90 (m, 4H), 6.405 (dd, 1H, J = 1.5Hz, 17.5Hz), 6.402 (dd, 1H, J = 1.5Hz, 17.5Hz) , 6.127 (dd, 1H, J = 10.5Hz, 17.5Hz), 6.124 (dd, 1H, J = 10.5Hz, 17.5Hz), 5.822 (dd, 1H, J = 1) .5Hz, 10.5Hz), 5.819 (dd, 1H, J = 1.5Hz, 10.5Hz), 4.16-4.22 (m, 6H), 4.08 (t, 2H, J =) 6.5Hz), 4.03 (s, 2H), 3.95 (t, 2H, J = 6.5Hz), 3.93 (t, 2H, J = 6.5Hz), 2.56-2. 67 (m, 4H), 2.28-2.36 (m, 8H), 1.59-1.83 (m, 20H), 1.42-1.56 (m, 8H), 1.24- 1.36 (m, 4H).

(Example 9) Synthesis of polymerizable compound 2 Step 1: The same operation as in Step 1 of Example 1 was carried out.

Step 2: Synthesis of polymerizable compound 2 Intermediate A: 18.39 g, chloroform 183.9 g, and N synthesized in step 1 of Example 1 in a nitrogen stream in a three-port reactor equipped with a thermometer. , 6.4 g of N-dimethylformamide was added, and the mixture was cooled to 10 ° C. or lower. To this, 6.0 g (50.54 mmol) of thionyl chloride was added dropwise under control so that the reaction temperature was 10 ° C. or lower. After completion of the dropping, the reaction solution was returned to 25 ° C. and stirred for 1 hour. After completion of the reaction, 138 g of chloroform was extracted under reduced pressure with an evaporator. Then, 46 g of chloroform was newly added to obtain a chloroform solution (6). Separately, in a three-port reactor equipped with a thermometer, 2.76 g (20.0 mmol) of 2,5-dihydroxybenzaldehyde and 12.84 g (119.8 mmol) of 2,6-lutidine were added to 92 g of chloroform in a nitrogen stream. It was melted and cooled to 10 ° C. or lower. The chloroform solution (6) was slowly added dropwise to this solution while maintaining the temperature inside the reactor at 10 ° C. or lower. After completion of the dropping, the reaction was carried out for another 1 hour while keeping the reaction solution at 10 ° C. or lower (step (1)).
After completion of the reaction, 725 g of a 1.0 specified hydrochloric acid aqueous solution was added to the reaction solution at a temperature of 10 ° C. or lower, and the mixture was stirred at 10 ° C. or lower for 30 minutes (step (2)).
Then, 10.38 g (23.9 mmol) of the intermediate E synthesized in step 2 of Example 8 and 0.33 g of 2,6-ditercious butyl-para-cresol were added, and the temperature was raised to 40 ° C. 4 A time reaction was carried out (step (3)).
After completion of the reaction, the aqueous layer was extracted at 40 ° C. and a liquid separation operation was performed. 0.92 g of Rocahelp # 479 (manufactured by Mitsui Mining & Smelting Co., Ltd.) was added to the obtained organic layer, and the mixture was stirred at 25 ° C. for 30 minutes and then filtered through a filter covered with 0.6 g of Rocahelp # 479. The filter was washed with 9.2 g of chloroform and combined with the previously obtained filtrate. This chloroform solution was slowly added dropwise to 367.8 g of methanol at 25 ° C. to precipitate a solid. After aging for 30 minutes with slow stirring at the same temperature, the precipitated solid was collected by filtration. The obtained solid was dissolved in 147 g of chloroform, 0.92 g of Rocahelp # 479 (manufactured by Mitsui Mining & Smelting Co., Ltd.) was added, and the mixture was stirred at 25 ° C. for 30 minutes, and then a filter covered with 0.6 g of Rocahelp # 479. I broke up. The filter was washed with 36.8 g of chloroform and combined with the previously obtained filtrate. This chloroform solution was slowly added dropwise to 184 g of methanol at 25 ° C. to precipitate a solid. After aging for 30 minutes with slow stirring at the same temperature, the precipitated solid was collected by filtration. The filtrate was washed with methanol and dried under vacuum to obtain 24.9 g of polymerizable compound 2 as a pale yellow solid. The yield was 92% (based on 2,5-dihydroxybenzaldehyde).

(Example 10) Synthesis of polymerizable compound 2 Example 8 except that in step 3 of Example 8, 12.13 g (119.8 mmol) of triethylamine was changed to 12.84 g (119.8 mmol) of 2,6-lutidine. The same operation as was performed. As a result, 24.9 g of polymerizable compound 2 was obtained as a pale yellow solid. The yield was 92% (based on 2,5-dihydroxybenzaldehyde).

(Comparative Example 11) Synthesis of Polymerizable Compound 2 Steps 1 to 3: The same operation as in Steps 1 to 3 of Example 8 was carried out.

Step 2: Synthesis of polymerizable compound 2: 26.91 g of the mixture synthesized in step 1 of Example 3 above, 183.9 g of chloroform, and N, in a nitrogen stream in a three-port reactor equipped with a thermometer. 6.4 g of N-dimethylformamide was added, and the mixture was cooled to 10 ° C. or lower. To this, 6.0 g (50.54 mmol) of thionyl chloride was added dropwise under control so that the reaction temperature was 10 ° C. or lower. After completion of the dropping, the reaction solution was returned to 25 ° C. and stirred for 1 hour. After completion of the reaction, 138 g of chloroform was extracted under reduced pressure with an evaporator. Then, 46 g of chloroform was newly added to obtain a chloroform solution (7). Separately, in a three-port reactor equipped with a thermometer, 2.76 g (20.0 mmol) of 2,5-dihydroxybenzaldehyde and 12.13 g (119.8 mmol) of triethylamine were dissolved in 92 g of chloroform in a nitrogen stream, and 10 It was cooled to below ° C. The chloroform solution (7) was slowly added dropwise to this solution while maintaining the temperature inside the reactor at 10 ° C. or lower. After completion of the dropping, the reaction was carried out for another 1 hour while keeping the reaction solution at 10 ° C. or lower (step (1)).
After completion of the reaction, 725 g of a 1.0 specified hydrochloric acid aqueous solution, 10.38 g (23.9 mmol) of the intermediate E synthesized in step 2, and 2,6-ditercious butyl-para were added to the reaction solution at 10 ° C. or lower. − Cresol 0.33 g was added, the temperature was raised to 40 ° C., and the reaction was carried out for 4 hours (step (3)).
After completion of the reaction, the aqueous layer was extracted at 40 ° C. and a liquid separation operation was performed. 0.92 g of Rocahelp # 479 (manufactured by Mitsui Mining & Smelting Co., Ltd.) was added to the obtained organic layer, and the mixture was stirred at 25 ° C. for 30 minutes and then filtered through a filter covered with 0.6 g of Rocahelp # 479. The filter was washed with 9.2 g of chloroform and combined with the previously obtained filtrate. This chloroform solution was slowly added dropwise to 367.8 g of methanol at 25 ° C. to precipitate a solid. After aging for 30 minutes with slow stirring at the same temperature, the precipitated solid was collected by filtration. The obtained solid was dissolved in 147 g of chloroform, 0.92 g of Rocahelp # 479 (manufactured by Mitsui Mining & Smelting Co., Ltd.) was added, and the mixture was stirred at 25 ° C. for 30 minutes, and then a filter covered with 0.6 g of Rocahelp # 479. I broke up. The filter was washed with 36.8 g of chloroform and combined with the previously obtained filtrate. This chloroform solution was slowly added dropwise to 184 g of methanol at 25 ° C. to precipitate a solid. After aging for 30 minutes with slow stirring at the same temperature, the precipitated solid was collected by filtration. The filtrate was washed with methanol and dried under vacuum to obtain 18.69 g of polymerizable compound 2 as a pale yellow solid. The yield was 69% (based on 2,5-dihydroxybenzaldehyde).

(Comparative Example 12) Synthesis of Polymerizable Compound 2 Step 1: The same operation as in Step 1 of Example 1 was carried out.

Step 2: Synthesis of polymerizable compound 2 Intermediate A: 18.39 g, chloroform 183.9 g, and N synthesized in step 1 of Example 1 in a nitrogen stream in a three-port reactor equipped with a thermometer. , 6.4 g of N-dimethylformamide was added, and the mixture was cooled to 10 ° C. or lower. To this, 6.0 g (50.54 mmol) of thionyl chloride was added dropwise under control so that the reaction temperature was 10 ° C. or lower. After completion of the dropping, the reaction solution was returned to 25 ° C. and stirred for 1 hour. After completion of the reaction, 138 g of chloroform was extracted under reduced pressure with an evaporator. Then, 46 g of chloroform was newly added to obtain a chloroform solution (8). Separately, in a three-port reactor equipped with a thermometer, 2.76 g (20.0 mmol) of 2,5-dihydroxybenzaldehyde and 12.84 g (119.8 mmol) of 2,6-lutidine were added to 92 g of chloroform in a nitrogen stream. It was melted and cooled to 10 ° C. or lower. The chloroform solution (8) was slowly added dropwise to this solution while maintaining the temperature inside the reactor at 10 ° C. or lower. After completion of the dropping, the reaction was carried out for another 1 hour while keeping the reaction solution at 10 ° C. or lower (step (1)).
After completion of the reaction, 725 g of a 1.0 specified hydrochloric acid aqueous solution, 10.38 g (23.9 mmol) of the intermediate E synthesized in step 2 of Example 8 and 2,6 were added to the reaction solution at a temperature of 10 ° C. or lower. -Differential butyl-para-cresol 0.33 g was added, the temperature was raised to 40 ° C., and the reaction was carried out for 4 hours (step (3)).
After completion of the reaction, the aqueous layer was extracted at 40 ° C. and a liquid separation operation was performed. 0.92 g of Rocahelp # 479 (manufactured by Mitsui Mining & Smelting Co., Ltd.) was added to the obtained organic layer, and the mixture was stirred at 25 ° C. for 30 minutes and then filtered through a filter covered with 0.6 g of Rocahelp # 479. The filter was washed with 9.2 g of chloroform and combined with the previously obtained filtrate. This chloroform solution was slowly added dropwise to 367.8 g of methanol at 25 ° C. to precipitate a solid. After aging for 30 minutes with slow stirring at the same temperature, the precipitated solid was collected by filtration. The obtained solid was dissolved in 147 g of chloroform, 0.92 g of Rocahelp # 479 (manufactured by Mitsui Mining & Smelting Co., Ltd.) was added, and the mixture was stirred at 25 ° C. for 30 minutes, and then a filter covered with 0.6 g of Rocahelp # 479. I broke up. The filter was washed with 36.8 g of chloroform and combined with the previously obtained filtrate. This chloroform solution was slowly added dropwise to 184 g of methanol at 25 ° C. to precipitate a solid. After aging for 30 minutes with slow stirring at the same temperature, the precipitated solid was collected by filtration. The filtrate was washed with methanol and dried under vacuum to obtain 21.13 g of polymerizable compound 2 as a pale yellow solid. The yield was 78% (based on 2,5-dihydroxybenzaldehyde).

(Comparative Example 13) Synthesis of Polymerizable Compound 2 Comparative Example 11 except that in step 3 of Comparative Example 11, 12.13 g (119.8 mmol) of triethylamine was changed to 12.84 g (119.8 mmol) of 2,6-lutidine. The same operation as was performed. As a result, 20.32 g 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.

国際公開第２０１７／１５０６２２号を参考にして合成した。(Example 11) Synthesis of polymerizable compound 1 Step 1: Synthesis of intermediate F

It was synthesized with reference to International Publication No. 2017/150622.

Step 2: Synthesis of mixture 2

The method described in International Publication No. 2016/159193 was applied and synthesized as follows.
To a three-port reactor equipped with a thermometer, 83.05 g (0.397 mol) of trans-1,4-cyclohexanedicarboxylic acid dichloride, 600 g of cyclopentyl methyl ether, and 230 g of tetrahydrofuran were added in a nitrogen stream. 100.0 g (0.378 mol) of the intermediate F synthesized in step 1 was added thereto, and the reactor was immersed in an ice bath to bring the temperature inside the reaction solution to 0 ° C. Then, 40.20 g (0.397 mol) of triethylamine was slowly added dropwise over 30 minutes while maintaining the internal temperature of the reaction solution at 10 ° C. or lower. After completion of the dropping, the whole volume was further stirred at 10 ° C. or lower for 1 hour. 250 g of distilled water was added to the obtained reaction solution, and the mixture was washed at 50 ° C. for 2 hours, and then the aqueous layer was extracted. 250 g of fresh distilled water was added, and the mixture was washed at 50 ° C. for another 2 hours. This operation was performed a total of three times. Further, the organic layer was washed with 416 g of a buffer solution (pH: 5.5) composed of acetic acid and sodium acetate having a concentration of 1 mol / liter at 40 ° C. for 30 minutes, and then the buffer solution was withdrawn. After washing at 40 ° C. for 30 minutes with 416 g of a new buffer solution (pH: 5.5) consisting of acetic acid and sodium acetate having a concentration of 1 mol / liter, the buffer solution was withdrawn. This operation was performed a total of 5 times. Further, 250 g of distilled water was added to the obtained organic layer, and the mixture was washed at 40 ° C. for 30 minutes, and then the aqueous layer was extracted. 1300 g of normal hexane was added dropwise to the obtained organic layer at 40 ° C. over 1 hour. Then, the mixture was cooled to 0 ° C. and stirred for another hour to precipitate a solid, and the precipitated solid was collected by filtration. The filtrate was washed with normal hexane and dried under vacuum to obtain 142.0 g of a white solid. The obtained crystals were analyzed by HPLC and the intermediate A was quantified by a calibration curve. As a result, it was found that the intermediate A was contained in an amount of 68.5% by mass. Moreover, when the obtained crystal was ^{analyzed by 13} C-NMR (dioxane-d8) and the content of cyclohexanedicarboxylic acid was calculated, it was below the detection limit.

Step 3: Synthesis of polymerizable compound 1 In a three-port reactor equipped with a thermometer, a mixture containing the intermediate A synthesized in step 2 as a main component in a nitrogen stream 2: 43.8 g (30 g as intermediate A). (71.7 mmol)), 300 g of chloroform, and 10.5 g (143.4 mmol) of N, N-dimethylformamide were added, and the mixture was cooled to 10 ° C. or lower. 9.81 g (82.44 mmol) of thionyl chloride was added dropwise thereto while maintaining the reaction temperature at 10 ° C. or lower. After completion of the dropping, the reaction solution was returned to 25 ° C. and stirred for 1 hour. After completion of the reaction, 225 g of chloroform was extracted by an evaporator and concentrated. Then, 75 g of fresh chloroform was added to obtain a chloroform solution of the acid chloride of Intermediate A. In a separately prepared three-port reactor equipped with a thermometer, 4.5 g (32.58 mmol) of 2,5-dihydroxybenzaldehyde and 19.78 g (195.5 mmol) of triethylamine were dissolved in 150 g of chloroform in a nitrogen stream. The obtained solution was cooled to 10 ° C. or lower. The entire amount of the chloroform solution of the acid chloride of Intermediate A previously synthesized was slowly added dropwise to this solution while maintaining the reaction temperature at 10 ° C. or lower. After completion of the dropping, the whole volume was further stirred at 5 to 10 ° C. for 1 hour (step (1)).
After completion of the reaction, 120 g of a 1.0 specified hydrochloric acid aqueous solution was added to the reaction solution while keeping the temperature below 10 ° C. Then, the reaction was carried out by stirring at 10 ° C. or lower for 30 minutes (step (2)).
Then, 10.58 g (42.4 mmol) of the intermediate B synthesized in step 2 of Example 1 and 0.3 g of 2,6-ditercious butyl-para-cresol were added. Then, the temperature of the reaction solution was raised to 40 ° C. and the reaction was carried out for 4 hours (step (3)).
After completion of the reaction, the aqueous layer was extracted. Further, 105 g of distilled water was added to the organic layer, and the mixture was washed by stirring at 40 ° C. for 30 minutes. After extracting the aqueous layer, the organic layer was cooled to 25 ° C., 1.5 g of Rocahelp # 479 was added, and the mixture was stirred for 30 minutes. Then, filtration was performed with a Kiriyama funnel on which 1 g of Rocahelp # 479 was laid, and Rocahelp # 479 was removed. 180 g of chloroform was extracted from the obtained organic layer by a rotary evaporator and concentrated. 210 g 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 obtained pale yellow solid was dissolved in 120 g of tetrahydrofuran at 25 ° C., 1.5 g of Rocahelp # 479 was added, and the mixture was stirred for 30 minutes. Then, filtration was performed with a Kiriyama funnel on which 1 g of Rocahelp # 479 was laid, and Rocahelp # 479 was removed. 165 g of methanol was slowly added dropwise to the obtained organic layer at 15 ° C. to precipitate a solid, and filtration was performed to obtain a solid. The obtained solid was dried in a vacuum dryer to obtain 35.1 g of the polymerizable compound 1 as a pale yellow solid. The yield was 92.0% (based on 2,5-dihydroxybenzaldehyde).

(Example 12) Synthesis of polymerizable compound 1 Step 1: Synthesis of intermediate G The compound was synthesized as follows using the method described in International Publication No. 16/159193.
To a three-port reactor equipped with a thermometer, 83.05 g (0.397 mol) of trans-1,4-cyclohexanedicarboxylic acid dichloride, 600 g of cyclopentyl methyl ether, and 230 g of tetrahydrofuran were added in a nitrogen stream. To this, 100.0 g (0.378 mol) of the intermediate F synthesized in step 1 of Example 11 was added, and the reactor was immersed in an ice bath to bring the temperature inside the reaction solution to 0 ° C. Then, 40.20 g (0.397 mol) of triethylamine was slowly added dropwise over 30 minutes while maintaining the internal temperature of the reaction solution at 10 ° C. or lower. After completion of the dropping, the whole volume was further stirred at 10 ° C. or lower for 1 hour. 250 g of distilled water was added to the obtained reaction solution, and the mixture was washed at 50 ° C. for 2 hours, and then the aqueous layer was extracted. 250 g of fresh distilled water was added, and the mixture was washed at 50 ° C. for another 2 hours. This operation was performed a total of three times. The organic layer was further washed with 416 g of a buffer solution (pH: 5.5) consisting of acetic acid and sodium acetate having a concentration of 1 mol / liter at 40 ° C. for 30 minutes, and then the buffer solution was withdrawn. After washing at 40 ° C. for 30 minutes with 416 g of a new buffer solution (pH: 5.5) consisting of acetic acid and sodium acetate having a concentration of 1 mol / liter, the buffer solution was withdrawn. This operation was performed a total of 5 times. Further, 250 g of distilled water was added to the obtained organic layer, and the mixture was washed at 40 ° C. for 30 minutes. The organic layer obtained by extracting the aqueous layer was gradually cooled to 0 ° C. with stirring, stirred at 0 ° C. for 1 hour, and then the precipitated solid was filtered off. 1400 g of normal hexane was added dropwise to the filtrate over 1 hour. Then, the mixture was stirred at 0 ° C. for 1 hour to precipitate a solid, and the precipitated solid was collected by filtration. The filtrate was washed with normal hexane and dried under vacuum to obtain 105.7 g of a white solid. The obtained crystals were analyzed by HPLC and the intermediate G was quantified by a calibration curve. As a result, it was found that the intermediate A was contained in an amount of 91.3% by mass. Moreover, when the obtained crystal was ^{analyzed by 13} C-NMR (dioxane-d8) and the content of cyclohexanedicarboxylic acid was calculated, it was below the detection limit.

Step 2: Synthesis of polymerizable compound 1 In step 3 of Example 11, a mixture containing the intermediate A synthesized in step 2 of Example 11 as a main component is 2: 43.8 g (30 g (71.7 mmol) as the intermediate A). )) Was changed to 32.9 g of the intermediate G synthesized in step 1 (30 g (71.7 mmol) as the intermediate A), and the same operation as in Example 11 was carried out. As a result, 35.0 g of the polymerizable compound 1 was obtained as a pale yellow solid. The yield was 91.8% (based on 2,5-dihydroxybenzaldehyde).

(Example 13) Synthesis of polymerizable compound 1 Step 1: Synthesis of intermediate H 83.05 g of trans-1,4-cyclohexanedicarboxylic acid dichloride in a nitrogen stream in a three-port reactor equipped with a thermometer (0. 397 mol) and 830 g of cyclopentyl methyl ether (CPME) were added. To this, 100 g (0.378 mol) of the intermediate F synthesized in step 1 of Example 11 and 1.67 g of 2,6-ditercious butyl-para-cresol were added, and the reactor was immersed in an ice bath for reaction. The temperature inside the liquid was set to 0 ° C. Then, 40.2 g (0.397 mol) of triethylamine was slowly added dropwise over 20 minutes while maintaining the internal temperature of the reaction solution at 10 ° C. or lower. After completion of the dropping, the mixture was further stirred at 10 ° C. or lower for 1 hour. To the obtained reaction solution, 250 g of distilled water was added at 10 ° C. or lower, and the temperature was raised to 50 ° C. Then, it was washed at 50 degreeC for 2 hours. After separating the liquids and extracting the aqueous layer, 250 g of fresh distilled water was newly added at 50 ° C., and the mixture was washed at 50 ° C. for 2 hours. This operation was performed a total of three times. The obtained organic layer was cooled to 40 ° C., 200 g of methanol was added, the mixture was gradually cooled, and the mixture was slowly stirred at 0 ° C. for 1 hour to precipitate a solid. The precipitated solid was removed by filtration to obtain a filtrate. The filter medium in the filter was washed with 100 g of methanol cooled to 0 ° C. prepared separately, and the washing liquid obtained by this washing and the previous filtrate were combined. The filtrate combined with this washing solution was further washed with 416 g of a buffer solution (pH 5.5) consisting of acetic acid and sodium acetate having a concentration of 1 mol / liter at 40 ° C. for 30 minutes. After washing, the solution was separated to extract the aqueous layer, and then 416 g of a buffer solution (pH 5.5) consisting of acetic acid and sodium acetate having a concentration of 1 mol / liter was newly added, and the mixture was stirred at 40 ° C. for 30 minutes. This operation was carried out 5 times in total, and 250 g of distilled water was added to the organic layer (oil layer) obtained by separating the liquid and extracting the aqueous layer, and washing was performed at 40 ° C. for 30 minutes. This operation was carried out twice in total, and 1200 g of normal hexane was added to the organic layer obtained by liquid separation, and the mixture was gradually cooled to 0 ° C. to precipitate a solid, and the precipitated solid was collected by filtration. The filtrate was washed with normal hexane and then vacuum dried to give 98.55 g of a white solid as Intermediate H. When the obtained white solid was quantified by high performance liquid chromatography, the content of Intermediate A with respect to the white solid was 92.6% by mass. Moreover, when the obtained crystal was ^{analyzed by 13} C-NMR (dioxane-d8) and the content of cyclohexanedicarboxylic acid was calculated, it was below the detection limit.

Step 2: Synthesis of polymerizable compound 1 In step 3 of Example 11, a mixture containing the intermediate A synthesized in step 2 of Example 11 as a main component is 2: 43.8 g (30 g (71.7 mmol) as the intermediate A). )) Was changed to 32.4 g of the intermediate H synthesized in step 1 (30 g (71.7 mmol) as the intermediate A), and the same operation as in Example 11 was carried out. As a result, 35.7 g of the polymerizable compound 1 was obtained as a pale yellow solid. The yield was 93.6% (based on 2,5-dihydroxybenzaldehyde).

(Example 14) Synthesis of polymerizable compound 1 In step 3 of Example 11, 19.78 g (195.5 mmol) of triethylamine was added to 17.46 g (163.0 mmol) of 2,6-lutidine and N, N-dimethyl-4. The same operation as in Example 11 was carried out except that the combination was changed to 43.8 mg (0.36 mmol) of -aminopyridine (DMAP). As a result, 34.9 g of the polymerizable compound 1 was obtained as a pale yellow solid. The yield was 91.5% (based on 2,5-dihydroxybenzaldehyde).

(Example 15) Synthesis of polymerizable compound 1 In step 3 of Example 11, a mixture containing the intermediate A synthesized in step 2 of Example 11 as a main component is 2: 43.8 g (30 g (71) as the intermediate A). .7 mmol)) was changed to 32.9 g of the intermediate G synthesized in step 1 of Example 12 (30 g (71.7 mmol) as the intermediate A), and 19.78 g (195.5 mmol) of triethylamine was changed to 2. , 6-Lutidine (17.46 g (163.0 mmol)) and N, N-dimethyl-4-aminopyridine (43.8 mg (0.36 mmol)) were used in combination, but the same procedure as in Example 11 was carried out. As a result, 35.2 g of the polymerizable compound 1 was obtained as a pale yellow solid. The yield was 92.3% (based on 2,5-dihydroxybenzaldehyde).

(Example 16) Synthesis of polymerizable compound 1 In step 3 of Example 11, a mixture containing the intermediate A synthesized in step 2 of Example 11 as a main component is 2: 43.8 g (30 g (71) as the intermediate A). .7 mmol)) was changed to 32.4 g of intermediate H: 32.4 g (30 g (71.7 mmol) as intermediate A) synthesized in step 1 of Example 13, and 19.7 g (195.5 mmol) of triethylamine was changed to 2 , 6-Lutidine (17.46 g (163.0 mmol)) and N, N-dimethyl-4-aminopyridine (43.8 mg (0.36 mmol)) were used in combination, but the same procedure as in Example 11 was carried out. As a result, 35.8 g of the polymerizable compound 1 was obtained as a pale yellow solid. The yield was 93.9% (based on 2,5-dihydroxybenzaldehyde).

(Example 17) Synthesis of polymerizable compound 1 In step 3 of Example 11, 9.81 g (82.44 mmol) of thionyl chloride was changed to 8.79 g (73.85 mmol) of thionyl chloride, and 19.78 g of triethylamine. Same as in Example 11 except that (195.5 mmol) was changed to a combination of 17.46 g (163.0 mmol) of 2,6-lutidine and 43.8 mg (0.36 mmol) of N, N-dimethyl-4-aminopyridine. Was performed. As a result, 35.5 g of the polymerizable compound 1 was obtained as a pale yellow solid. The yield was 93.1% (based on 2,5-dihydroxybenzaldehyde).

(Example 18) Synthesis of polymerizable compound 1 In step 3 of Example 11, a mixture containing the intermediate A synthesized in step 2 of Example 11 as a main component is 2: 43.8 g (30 g (71) as the intermediate A). .7 mmol)) was changed to 32.9 g of intermediate G: 32.9 g (30 g (71.7 mmol) as intermediate A) synthesized in step 1 of Example 12, and 9.81 g (82.44 mmol) of thionyl chloride was changed to thionyl chloride. Changed to 8.79 g (73.85 mmol) and added 19.78 g (195.5 mmol) of triethylamine to 17.46 g (163.0 mmol) of 2,6-lutidine and N, N-dimethyl-4-aminopyridine 43. The same operation as in Example 11 was carried out except that the combination was changed to 8 mg (0.36 mmol). As a result, 35.6 g of the polymerizable compound 1 was obtained as a pale yellow solid. The yield was 93.4% (based on 2,5-dihydroxybenzaldehyde).

(Example 19) Synthesis of polymerizable compound 1 In step 3 of Example 11, a mixture containing the intermediate A synthesized in step 2 of Example 11 as a main component is 2: 43.8 g (30 g (71) as the intermediate A). .7 mmol)) was changed to 32.4 g of intermediate H: 32.4 g (30 g (71.7 mmol) as intermediate A) synthesized in step 1 of Example 13, and 9.81 g (82.44 mmol) of thionyl chloride was changed to thionyl chloride. Changed to 8.79 g (73.85 mmol) and added 19.78 g (195.5 mmol) of triethylamine to 17.46 g (163.0 mmol) of 2,6-lutidine and N, N-dimethyl-4-aminopyridine 43. The same operation as in Example 11 was carried out except that the combination was changed to 8 mg (0.36 mmol). As a result, 36.0 g of the polymerizable compound 1 was obtained as a pale yellow solid. The yield was 94.4% (based on 2,5-dihydroxybenzaldehyde).

(Example 20) Synthesis of polymerizable compound 1 Step 1: Synthesis of intermediate I In step 1 of Example 13, 1200 g of normal hexane was changed to 1200 g of normal heptan, and normal hexane for washing the filtrate was changed to normal heptane. The same operation as in Example 13 was carried out except for the change to, and 97.40 g of a white solid as Intermediate I was obtained. When the obtained white solid was quantified by high performance liquid chromatography, the content of Intermediate A with respect to the white solid was 94.7% by mass. Moreover, when the obtained crystal was ^{analyzed by 13} C-NMR (dioxane-d8) and the content of cyclohexanedicarboxylic acid was calculated, it was below the detection limit.

Step 2: Synthesis of Compound 1 In Step 3 of Example 11, a mixture containing the intermediate A synthesized in Step 2 of Example 11 as a main component 2: 43.8 g (30 g (71.7 mmol) as Intermediate A). Was changed to Intermediate I: 31.7 g (30 g (71.7 mmol) as Intermediate A) synthesized in Step 1, and 9.81 g (82.44 mmol) of thionyl chloride was changed to 8.79 g (73.85 mmol) of thionyl chloride. ), And 19.78 g (195.5 mmol) of triethylamine was added to 17.46 g (163.0 mmol) of 2,6-lutidine and 43.8 mg (0.36 mmol) of N, N-dimethyl-4-aminopyridine. The same operation as in Example 11 was performed except that the combination was changed. As a result, 36.1 g of the polymerizable compound 1 was obtained as a pale yellow solid. The yield was 94.7% (based on 2,5-dihydroxybenzaldehyde).

(Example 21) Synthesis of polymerizable compound 1 In step 3 of Example 11, a mixture containing the intermediate A synthesized in step 2 of Example 11 as a main component is 2: 43.8 g (30 g (71) as the intermediate A). .7 mmol)) was changed to Intermediate I: 31.7 g (30 g (71.7 mmol) as Intermediate A) synthesized in Step 1 of Example 20, and 9.81 g (82.44 mmol) of thionyl chloride was changed to thionyl chloride. Change to 8.79 g (73.85 mmol) and add 19.78 g (195.5 mmol) of triethylamine to 17.46 g (163.0 mmol) of 2,6-rutidine and 43.8 mg (43.8 mg) of N, N-dimethyl-4-aminopyridine. The same operation as in Example 11 was carried out except that the combination was changed to 0.36 mmol) and 210 g of hexane used for precipitating the solid was changed to 210 g of heptane. As a result, 36.0 g of the polymerizable compound 1 was obtained as a pale yellow solid. The yield was 94.4% (based on 2,5-dihydroxybenzaldehyde).

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

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

Claims (9)

In an organic solvent, the following formula (I)

(In the formula, Q represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and Fg ¹ and Fg ² independently represent a hydroxyl group, -CH ₂ OH, or -CH ₂ CH ₂ OH, respectively. .)
The compound represented by and the following formula (II)

(In the formula, A represents a hydrogen atom, a methyl group or a chlorine atom, L represents a hydroxyl group or a leaving group, and n represents an integer of 1 to 20.)
The compound represented by (3) is esterified in the presence of a base and / or a dehydration condensing agent to formulate (III) below.

(In the equation, Y ¹ and Y ² are independently -C (= O) -O-, -OC (= O)-, -CH _2- OC (= O)-,-, respectively. _{C (= O) -O-CH} 2 -, - CH 2 -CH 2 -O-C (= O) -, _{or, -C (= O) -O-} CH 2 -CH 2 - represent, Q, A and n have the same meanings as described above.)
Step (1) of obtaining a reaction solution containing the compound represented by
The 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
After the step (2), the following formula (IV)

(In the formula, X represents an oxygen atom, a sulfur atom, -C (R ¹ ) (R ² )-, or -N-R ^1- , where R ¹ and R ² are independent of each other. , Represents an alkyl group having 1 to 10 carbon atoms which may have a hydrogen atom or a substituent, and R represents an organic group having 1 to 60 carbon atoms which may have a hydrogen atom or a substituent. ^RX is 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 one hydrogen atom is replaced with a halogen atom, and 1 to 6 carbon atoms. An alkoxy group of 6, an alkylthio group having 1 to 6 carbon atoms, a mono-substituted amino group, a di-substituted amino group, -OCF ₃ , -C (= O) -OR ³ , or -OC (= O). represents -R ^3, wherein, R ^3, said R ^1, represents the same meaning as R ^2, each other a plurality of R ^X, all be the same, or different phases constituting the ring any C-R ^X may be replaced by a nitrogen atom.)
The following formula (A), which comprises the step (3) of adding the compound represented by the above formula (III) and reacting with the compound represented by the formula (III).

(In the formula, Y ¹ , Y ² , A, R, ^RX , X, Q and n have the same meanings as described above.) A method for producing a polymerizable compound. The method for producing a polymerizable compound according to claim 1, wherein in the step (2), water or an aqueous solution is added to the reaction solution to carry out the hydrolysis. The method for producing a polymerizable compound according to claim 2, wherein in the step (2), an acidic aqueous solution is added to the reaction solution. The method for producing a polymerizable compound according to claim 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. The acid component of the acidic aqueous solution is at least one selected from the group consisting of hydrochloric acid, sulfuric acid, phosphoric acid, boric acid, sulfonic acids, sulfic acids, formic acid, acetic acid, oxalic acid, citric acid, ascorbic acid, tartaric acid and malic acid. The method for producing a polymerizable compound according to claim 3 or 4. The R may have 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, and a carbon which may have a substituent. An alkynyl group having a number of 2 to 60, an aromatic hydrocarbon ring group having 6 to 18 carbon atoms which may have a substituent, and an aromatic heterocyclic group having 2 to 18 carbon atoms which may have a substituent. , Or Ra-Y-G- (in the formula, Ra represents a cyclic group having at least one of an aromatic hydrocarbon ring and an aromatic heterocycle, and Y is a chemical 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-, -SC (= 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-, -OC (= O) -CH ₂ -S-, -S-CH _2- C (= O) -O-, or -O-C (= O) -O- Here, R ⁴ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and Rc and Rb each independently have a hydrogen atom and a substituent having 6 to 6 carbon atoms. It represents an aromatic hydrocarbon ring group of 18 or an aromatic heterocyclic group having 2 to 18 carbon atoms which may have a substituent, and G is (i) a divalent fat having 1 to 20 carbon atoms. _{At least one of the group hydrocarbon group and -CH 2-} contained in the (ii) divalent aliphatic hydrocarbon group having 3 to 20 carbon atoms is -O-, -S-, -OC (=). O)-, -C (= O) -O-, -O-C (= O) -O-, -NR ^5- C (= O)-, -C (= O) -NR ^5- , -NR ^{It is either an organic group of 5} − or a group substituted with −C (= O) − (except when two or more −O− or −S− are adjacent to each other). , Where R ⁵ is a hydrogen atom or carbon Represents an alkyl group of numbers 1-6. ), The method for producing a polymerizable compound according to any one of claims 1 to 5. Wherein R ^X are all hydrogen atom, a manufacturing method of the polymerizable compound according to any one of claims 1 to 6. The method for producing a polymerizable compound according to any one of claims 1 to 7, wherein the reaction is carried out by further adding an acidic aqueous solution in the step (3). The compound represented by the formula (II) is the following formula (IIa).

(In the formula, A, L and n have the same meanings as described above.)
The method for producing a polymerizable compound according to any one of claims 1 to 8, which is a compound represented by.