JPWO2019151263A1 - Method for Producing 1,1-Di-substituted Hydrazine Compound and Method for Producing Polymerizable Compound - Google Patents

Abstract

Provided is a production method capable of efficiently producing the 1,1-di-substituted hydrazine compound which is the target product. In an organic solvent containing at least one aprotic polar solvent, the hydradino compound represented by the following formula (I) is used in the presence of a phosphoric acid-based compound having an aqueous solution pH of 8 or more and 14 or less. A method for producing a 1,1-di-substituted hydrazine compound represented by the following formula (II), which is reacted with a compound represented by R-Hal. [Chemical 1]

Description

The present invention relates to a method for producing a 1,1-disubstituted hydrazine compound capable of efficiently producing a 1,1-di-substituted hydrazine compound which is a target product.
Further, the present invention is a method for producing a polymerizable compound using a 1,1-di-substituted hydrazine compound efficiently produced by the method for producing a 1,1-di-substituted hydrazine compound of the present invention. It is about.

1,1-Di-substituted hydrazine compounds such as 1,1-di-substituted hydrazinobenzothiazole are useful as production intermediates for various industrial raw materials, pharmaceuticals, pesticides and the like.
As a conventional method for producing a 1,1-di-substituted hydrazine compound, for example, (i) "a method for obtaining 2- (1-methylhydrazino) benzothiazole by a reaction between 2-chlorobenzothiazole and methylhydrazine". (See, for example, Patent Document 1), (ii) "2- (N-methylamino) benzothiazole and the like are converted into nitroso compounds with nitrite and then reduced with a reducing agent to 2- (1). -Method for obtaining methylhydrazino) benzothiazole "(see, for example, Patent Document 1), (iii)" Hydradinobenzothiazole was used as a raw material, and potassium carbonate, cesium carbonate, or hexamethyldisilazane was used as a base. , A method for synthesizing various 1,1-di-substituted hydradinobenzothiazoles (1,1-di-substituted products) ”(see, for example, Patent Document 2).

However, in the conventional method for producing 1,1-di-substituted hydradinobenzothiazole, the reaction is carried out using a large amount of an expensive reagent, and then the by-product 1,2-di-substituted product is removed by column purification. It involves a process of performing, and has a big problem in terms of cost for industrial implementation.

Therefore, in order to solve the above problems, a specific amount of alkali metal hydroxide, alkaline earth metal hydroxide, and alkali metal alkoxide are used in a mixed solvent composed of an aprotonic polar solvent and an aromatic hydrocarbon solvent. By reacting a predetermined hydrazino compound with a predetermined halogen compound in the presence of at least one base selected from the above group, the desired 1,1-di-substituted hydrazine compound has been obtained ( For example, see Patent Document 3).

Japanese Unexamined Patent Publication No. 61-151181 International Publication No. 12/147904 JP-A-2016-190818

In recent years, it has been required to obtain a 1,1-di-substituted hydrazine compound in a high yield. However, the conventional method for producing a 1,1-disubstituted hydrazine compound as described in Patent Documents 1 to 3 has room for improvement in obtaining a 1,1-di-substituted hydrazine compound in a high yield. there were.

The present invention has been made in view of the above circumstances, and is a method for producing a 1,1-disubstituted hydrazine compound capable of efficiently producing a 1,1-di-substituted hydrazine compound which is a target product. The purpose is to provide.
Further, the present invention is a method for producing a polymerizable compound using a 1,1-disubstituted hydrazine compound efficiently produced by the method for producing a 1,1-di-substituted hydrazine compound of the present invention. The purpose is to provide.

As a result of diligent research to solve the above problems, the present inventors have carried out R-Hal of a predetermined hydrazine compound in an organic solvent containing at least one aprotic polar solvent in the presence of a predetermined phosphoric acid compound. It has been found that a 1,1-di-substituted hydrazine compound, which is a target product, can be efficiently produced by reacting with a compound represented by (1), and the present invention has been completed.
Thus, according to the present invention, a method for producing a 1,1-di-substituted hydrazine compound and a method for producing a polymerizable compound shown below are provided.

（式中、Ｘは、酸素原子、硫黄原子、−ＣＨ_２−、−ＣＨＲ^１１−、−ＣＲ^１１Ｒ^１２−、または、−ＮＲ^１１−を表す。ここで、Ｒ^１１、Ｒ^１２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のアルキル基を表す。
Ｒ^１〜Ｒ^４は、それぞれ独立して、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、モノ置換アミノ基、ジ置換アミノ基、−ＯＣＦ_３、−Ｃ（＝Ｏ）−Ｏ−Ｒ^１３、または、−Ｏ−Ｃ（＝Ｏ）−Ｒ^１３を表す。ここで、Ｒ^１３は、水素原子、または、置換基を有していてもよい炭素数１〜１０のアルキル基を表す。Ｒ^１〜Ｒ^４は、すべて同一であっても、相異なっていてもよく、環を構成する少なくとも１つのＣ−Ｒ^１〜Ｃ−Ｒ^４は窒素原子に置き換えられていてもよい。）
で表されるヒドラジノ化合物を、
水溶液のｐＨが８以上１４以下となるリン酸系化合物の存在下、
式（ＩＩＩ）：Ｒ−Ｈａｌ（Ｈａｌは、塩素原子、臭素原子、または、ヨウ素原子を表し、Ｒは、置換基を有していてもよい炭素数１〜６０の有機基を表す。）で表される化合物と反応させる、下記式（ＩＩ）で表される１，１−ジ置換ヒドラジン化合物の製造方法。

（式中、Ｘ、Ｒ、Ｒ^１〜Ｒ^４は、前記と同じ意味を表す。）[1] In an organic solvent containing at least one aprotic polar solvent, the following formula (I)

(Wherein, X represents an oxygen atom, a sulfur ^{_{atom, -CH 2 -, - CHR 11}} -, - CR 11 R 12 -, or, ^{-NR 11} -. Represents ^here, R ^{11, R 12} are each Independently, it represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms which may have a substituent.
R ^{1 to} R ⁴ are independently hydrogen atom, halogen atom, alkyl group having 1 to 6 carbon atoms, cyano group, nitro group, and carbon atoms 1 to 6 in which at least one hydrogen atom is substituted with a halogen atom. Alkyl group, alkoxy group with 1 to 6 carbon atoms, alkylthio group with 1 to 6 carbon atoms, mono-substituted amino group, di-substituted amino group, -OCF ₃ , -C (= O) -OR ¹³ , or Represents −OC (= O) −R ¹³ . Here, R ¹³ represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms which may have a substituent. R ^{1 to} R ⁴ may all be the same or different from each other, and at least one C-R ^{1 to} C-R ⁴ constituting the ring may be replaced with a nitrogen atom. )
The hydrazino compound represented by
In the presence of a phosphoric acid compound that makes the pH of the aqueous solution 8 or more and 14 or less
Formula (III): R-Hal (Hal represents a chlorine atom, a bromine atom, or an iodine atom, and R represents an organic group having 1 to 60 carbon atoms which may have a substituent). A method for producing a 1,1-di-substituted hydrazine compound represented by the following formula (II), which is reacted with the represented compound.

(In the formula, X, R, R ^{1 to} R ⁴ have the same meanings as described above.)

[2] The production method according to the above [1], wherein the phosphoric acid compound is at least one base selected from the group consisting of an alkali metal phosphate and an alkali metal phosphoric acid monohydrogen salt.

[3] The production method according to the above [2], wherein the phosphoric acid compound is an alkali metal phosphate.

[4] The production method according to the above [3], wherein the alkali metal phosphate is tripotassium phosphate or trisodium phosphate.

[5] The production method according to any one of [1] to [4] above, wherein the phosphoric acid compound is used in an amount of 1.0 equivalent or more and 3.0 equivalent or less with respect to the hydradino compound.

[6] After completion of the reaction, there is a step of adding an acidic protonal solvent to the reaction solution to bring the pH of the mixed solution of the reaction solution and the acidic protonic solvent to 8 or less. The production method according to any one of [5].

[7] The production method according to [6] above, wherein the acidic protonic solvent is an acidic aqueous solution.

[8] The production method according to [7] above, wherein the pH of the acidic aqueous solution is 1.5 or more and less than 7.

[9] The production method according to any one of [1] to [8] above, wherein all of R ^{1 to} R ⁴ are hydrogen atoms.

[10] The production method according to any one of [1] to [9] above, wherein X is a sulfur atom.

[11] The aprotic polar solvent comprises N, N-dimethylformamide, N, N-dimethylacetamide, N-methylpyrrolidone, acetonitrile, 1,3-dimethyl-2-imidazolidinone, and dimethyl sulfoxide. The production method according to any one of the above [1] to [10], which is at least one selected from the group.

（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−ＣＲｂＲｃ−、−ＣＲｃＲｂ−Ｏ−、−Ｏ−ＣＨ_２−ＣＨ_２−、−ＣＨ_２−ＣＨ_２−Ｏ−、−Ｃ（＝Ｏ）−Ｏ−、−Ｏ−Ｃ（＝Ｏ）−、−Ｃ（＝Ｏ）−Ｓ−、−Ｓ−Ｃ（＝Ｏ）−、−ＮＲ^１４−Ｃ（＝Ｏ）−、−Ｃ（＝Ｏ）−ＮＲ^１４−、−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−ＣＲｂＲｃ−、−ＣＲｃＲｂ−Ｏ−Ｃ（＝Ｏ）−、−Ｏ−Ｃ（＝Ｏ）−ＣＲｂＲｃ−、−ＣＲｃＲｂ−Ｃ（＝Ｏ）−Ｏ−、−Ｏ−Ｃ（＝Ｏ）−ＮＲ^１４−、−ＮＲ^１４−Ｃ（＝Ｏ）−Ｏ−、−Ｏ−Ｃ（＝Ｏ）−ＣＨ_２−Ｓ−、−Ｓ−ＣＨ_２−Ｃ（＝Ｏ）−Ｏ−、または、−Ｏ−Ｃ（＝Ｏ）−Ｏ−を表す。ここで、Ｒ^１４は、水素原子、または、炭素数１〜６のアルキル基を表し、Ｒｃ、Ｒｂは、それぞれ独立して、水素原子、炭素数６〜１２の置換基を有していてもよい芳香族炭化水素環基、または、炭素数３〜１２の置換基を有していてもよい芳香族複素環基を表す。
Ｇａ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^１５−Ｃ（＝Ｏ）−、−Ｃ（＝Ｏ）−ＮＲ^１５−、−ＮＲ^１５−、または、−Ｃ（＝Ｏ）−に置換された基、のいずれかの有機基である。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。ここで、Ｒ^１５は、水素原子、または、炭素数１〜６のアルキル基を表す。
Ｈａｌは、塩素原子、臭素原子、または、ヨウ素原子を表す。）[12] The production method according to any one of the above [1] to [11], wherein the compound represented by the formula (III) is the following formula (IV-1).

(In the formula, Ra represents a cyclic group having at least one of an aromatic hydrocarbon ring and an aromatic heterocycle.
Y is a chemical single bond, -O -, - S -, - C (= O) -, - O-CRbRc -, - CRcRb-O -, - O-CH 2 -CH 2 -, - CH 2 -CH ₂ -O-, -C (= O) -O-, -OC (= O)-, -C (= O) -S-, -SC (= O)-, -NR ^{14 -C (= O) -, -} C (= O) -NR 14 -, - 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-CRbRc -, - CRcRb-O-C (= O) -, - O-C (= O) -CRbRc -, - CRcRb- ^{C (= O) -O -,} - O-C (= O) -NR 14 -, - NR 14 -C (= O) -O -, - O-C (= O) -CH 2 -S-, It represents −S—CH ₂₋ C (= O) −O− or −OC (= O) −O−. Here, R ¹⁴ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and Rc and Rb may independently have a hydrogen atom and a substituent having 6 to 12 carbon atoms, respectively. It represents a good aromatic hydrocarbon ring group or an aromatic heterocyclic group which may have a substituent having 3 to 12 carbon atoms.
Ga is, -CH ₂ contained (i) a divalent aliphatic hydrocarbon group having 1 to 20 carbon atoms, and, in the divalent aliphatic hydrocarbon group (ii) 3 to 20 carbon atoms - at least one One is -O-, -S-, -OC (= O)-, -C (= O) -O-, -OC (= O) -O-, -NR ¹⁵ -C (= O) ^{) -, - C (= O} ) -NR 15 -, - NR 15 -, or, -C (= O) - is a substituted group, the one of the organic groups. However, this excludes cases where two or more -O- or -S- are adjacent to each other. Here, R ¹⁵ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.
Hal represents a chlorine atom, a bromine atom, or an iodine atom. )

（式中、Ｇｂは、（ｉ）置換基を有していてもよい炭素数１〜２０の脂肪族炭化水素基、および、（ｉｉ）置換基を有していてもよい炭素数３〜２０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^１５−Ｃ（＝Ｏ）−、−Ｃ（＝Ｏ）−ＮＲ^１５−、−ＮＲ^１５−、または、−Ｃ（＝Ｏ）−に置換された基、のいずれかの有機基である。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。
ここで、Ｒ^１５は、水素原子、または、炭素数１〜６のアルキル基を表す。
Ｈａｌは、塩素原子、臭素原子、または、ヨウ素原子を表す。）[13] The production method according to any one of [1] to [11] above, wherein the compound represented by the formula (III) is the following formula (IV-2).

(In the formula, Gb has (i) an aliphatic hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, and (ii) an aliphatic hydrocarbon group having 3 to 20 carbon atoms which may have a substituent. At least one of -CH _2- contained in the aliphatic hydrocarbon group of is -O-, -S-, -OC (= O)-, -C (= O) -O-, -O-C. ^{(= O) -O -, -} NR 15 -C (= O) -, - C (= O) -NR 15 -, - NR 15 -, or, -C (= O) - substituted radicals, However, this does not apply to the case where two or more -O- or -S- are adjacent to each other.
Here, R ¹⁵ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.
Hal represents a chlorine atom, a bromine atom, or an iodine atom. )

（式中、Ｑは、水素原子、または、置換基を有していてもよい炭素数１〜６のアルキル基を表す。
Ａｒは、置換基を有していてもよい芳香族炭化水素環基、または、置換基を有していてもよい芳香族複素環基を表し、
Ｙ^１〜Ｙ^８は、それぞれ独立して、化学的な単結合、−Ｏ−、−Ｏ−ＣＨ_２−、−ＣＨ_２−Ｏ−、−Ｏ−ＣＨ_２−ＣＨ_２−、−ＣＨ_２−ＣＨ_２−Ｏ−、−Ｃ（＝Ｏ）−Ｏ−、−Ｏ−Ｃ（＝Ｏ）−、−Ｏ−Ｃ（＝Ｏ）−Ｏ−、−Ｃ（＝Ｏ）−Ｓ−、−Ｓ−Ｃ（＝Ｏ）−、−ＮＲ^１６−Ｃ（＝Ｏ）−、−Ｃ（＝Ｏ）−ＮＲ^１６−、−ＣＦ_２−Ｏ−、−Ｏ−ＣＦ_２−、−ＣＨ_２−ＣＨ_２−、−ＣＦ_２−ＣＦ_２−、−Ｏ−ＣＨ_２−ＣＨ_２−Ｏ−、−ＣＨ＝ＣＨ−Ｃ（＝Ｏ）−Ｏ−、−Ｏ−Ｃ（＝Ｏ）−ＣＨ＝ＣＨ−、−ＣＨ_２−Ｃ（＝Ｏ）−Ｏ−、−Ｏ−Ｃ（＝Ｏ）−ＣＨ_２−、−ＣＨ_２−Ｏ−Ｃ（＝Ｏ）−、−Ｃ（＝Ｏ）−Ｏ−ＣＨ_２−、−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−、−ＣＨ＝ＣＨ−、−Ｎ＝ＣＨ−、−ＣＨ＝Ｎ−、−Ｎ＝Ｃ（ＣＨ_３）−、−Ｃ（ＣＨ_３）＝Ｎ−、−Ｎ＝Ｎ−、または、−Ｃ≡Ｃ−を表す。ここで、Ｒ^１６は、水素原子、または、炭素数１〜６のアルキル基を表す。
Ａ^１、Ａ^２、Ｂ^１およびＢ^２は、それぞれ独立して、置換基を有していてもよい環状脂肪族基、または、置換基を有していてもよい芳香族基を表す。
Ｇ^１およびＧ^２は、それぞれ独立して、（ｉ）炭素数１〜３０の２価の脂肪族炭化水素基、および、（ｉｉ）炭素数３〜３０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^１７−Ｃ（＝Ｏ）−、−Ｃ（＝Ｏ）−ＮＲ^１７−、−ＮＲ^１７−、または、−Ｃ（＝Ｏ）−に置換された基、のいずれかの有機基である。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。ここで、Ｒ^１７は、水素原子、または、炭素数１〜６のアルキル基を表し、Ｇ^１およびＧ^２の前記有機基に含まれる水素原子は、炭素数１〜５のアルキル基、炭素数１〜５のアルコキシ基、シアノ基、または、ハロゲン原子に置換されていてもよい。
Ｐ^１およびＰ^２は、それぞれ独立して、ハロゲン原子、または、メチル基で置換されていてもよい炭素数２〜１０のアルケニル基を表す。
ｎおよびｍは、それぞれ独立して、０または１を表す。〕

（式中、Ｒ^１〜Ｒ^４、Ｒ、Ａｒ、Ｑ、Ｘ、Ｙ^１〜Ｙ^８、Ａ^１、Ａ^２、Ｂ^１、Ｂ^２、Ｇ^１、Ｇ^２、Ｐ^１、Ｐ^２、ｎおよびｍは、それぞれ前記と同じ意味を表す。）[14] A step of reacting a 1,1-di-substituted hydrazine compound produced by the production method according to any one of [1] to [13] above with a compound represented by the following formula (V) is included. A method for producing a polymerizable compound represented by the following formula (VI).

(In the formula, Q represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms which may have a substituent.
Ar represents an aromatic hydrocarbon ring group which may have a substituent or an aromatic heterocyclic group which may have a substituent.
Y ¹ to Y ⁸ are each independently a chemical single _{bond, -O -, - O-CH} 2 -, - CH 2 -O -, - O-CH 2 -CH 2 -, - CH 2 - CH ₂ -O-, -C (= O) -O-, -O-C (= O)-, -O-C (= O) -O-, -C (= O) -S-, -S ^{-C (= O) -, -} NR 16 -C (= O) -, - C (= O) -NR 16 -, - CF 2 -O -, - O-CF 2 -, - CH 2 -CH 2 _{-, - CF 2 -CF 2 -} , - O-CH 2 -CH 2 -O -, - CH = CH-C (= O) -O -, - O-C (= O) -CH = CH-, -CH ₂ -C (= O) -O-, -O-C (= O) -CH _2- , -CH ₂ -O-C (= O)-, -C (= O) -O-CH _{2 -, - 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 -, - CH = CH -, - N = CH -, - CH = N -, - N = C (CH 3) -, - C (CH 3) = N-, -N = N-, or -C≡C-. Here, R ¹⁶ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.
A ¹ , A ² , B ¹ and B ² each independently represent a cyclic aliphatic group which may have a substituent or an aromatic group which may have a substituent.
G ¹ and G ² are independently composed of (i) a divalent aliphatic hydrocarbon group having 1 to 30 carbon atoms and (ii) a divalent aliphatic hydrocarbon group having 3 to 30 carbon atoms. At least one of the included −CH ₂₋ is −O−, −S−, −OC (= O) −, −C (= O) −O−, −OC (= O) −O− ^{, -NR 17 -C (= O)} -, - C (= O) -NR 17 -, - NR 17 -, or, -C (= O) - substituted radicals, or organic groups in the is there. However, this excludes cases where two or more -O- or -S- are adjacent to each other. Here, R ¹⁷ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and the hydrogen atom contained in the organic group of G ¹ and G ² is an alkyl group having 1 to 5 carbon atoms and a carbon number of carbon atoms. It may be substituted with 1 to 5 alkoxy groups, cyano groups, or halogen atoms.
P ¹ and P ² each independently represent a halogen atom or an alkenyl group having 2 to 10 carbon atoms which may be substituted with a methyl group.
n and m independently represent 0 or 1, respectively. ]

(In the formula, R ^{1 to} R ⁴ , R, Ar, Q, X, Y ^{1 to} Y ⁸ , A ¹ , A ² , B ¹ , B ² , G ¹ , G ² , P ¹ , P ² , n and Each of m has the same meaning as described above.)

（式中、Ｒ^１〜Ｒ^４、Ｒ、Ａｒ、Ｑ、Ｘ、Ｙ^１〜Ｙ^８、Ａ^１、Ａ^２、Ｂ^１、Ｂ^２、Ｇ^１、Ｇ^２、Ｐ^１、Ｐ^２、ｎおよびｍは、それぞれ前記と同じ意味を表す。）[15] A method for producing a polymerizable compound represented by the following formula (VI), which is derived from the 1,1-di-substituted hydrazine compound produced by the production method according to any one of [1] to [13] above. ..

(In the formula, R ^{1 to} R ⁴ , R, Ar, Q, X, Y ^{1 to} Y ⁸ , A ¹ , A ² , B ¹ , B ² , G ¹ , G ² , P ¹ , P ² , n and Each of m has the same meaning as described above.)

（式中、Ｒ^１〜Ｒ^４、Ａｒ、Ｑ、Ｘ、Ｙ^１〜Ｙ^８、Ａ^１、Ａ^２、Ｂ^１、Ｂ^２、Ｇ^１、Ｇ^２、Ｐ^１、Ｐ^２、ｎおよびｍは、それぞれ前記と同じ意味を表す。
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−ＣＲｂＲｃ−、−ＣＲｃＲｂ−Ｏ−、−Ｏ−ＣＨ_２−ＣＨ_２−、−ＣＨ_２−ＣＨ_２−Ｏ−、−Ｃ（＝Ｏ）−Ｏ−、−Ｏ−Ｃ（＝Ｏ）−、−Ｃ（＝Ｏ）−Ｓ−、−Ｓ−Ｃ（＝Ｏ）−、−ＮＲ^１４−Ｃ（＝Ｏ）−、−Ｃ（＝Ｏ）−ＮＲ^１４−、−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−ＣＲｂＲｃ−、−ＣＲｃＲｂ−Ｏ−Ｃ（＝Ｏ）−、−Ｏ−Ｃ（＝Ｏ）−ＣＲｂＲｃ−、−ＣＲｃＲｂ−Ｃ（＝Ｏ）−Ｏ−、−Ｏ−Ｃ（＝Ｏ）−ＮＲ^１４−、−ＮＲ^１４−Ｃ（＝Ｏ）−Ｏ−、−Ｏ−Ｃ（＝Ｏ）−ＣＨ_２−Ｓ−、−Ｓ−ＣＨ_２−Ｃ（＝Ｏ）−Ｏ−、または、−Ｏ−Ｃ（＝Ｏ）−Ｏ−を表す。ここで、Ｒ^１４は、水素原子、または、炭素数１〜６のアルキル基を表し、Ｒｃ、Ｒｂは、それぞれ独立して、水素原子、炭素数６〜１２の置換基を有していてもよい芳香族炭化水素環基、または、炭素数３〜１２の置換基を有していてもよい芳香族複素環基を表す。
Ｇａ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^１５−Ｃ（＝Ｏ）−、−Ｃ（＝Ｏ）−ＮＲ^１５−、−ＮＲ^１５−、または、−Ｃ（＝Ｏ）−に置換された基、のいずれかの有機基である。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。ここで、Ｒ^１５は、水素原子、または、炭素数１〜６のアルキル基を表す。[16] Production of the polymerizable compound according to the above [14] or [15], wherein the polymerizable compound represented by the formula (VI) is a polymerizable compound represented by the following formula (VII-1). Method.

(In the formula, R ^{1 to} R ⁴ , Ar, Q, X, Y ^{1 to} Y ⁸ , A ¹ , A ² , B ¹ , B ² , G ¹ , G ² , P ¹ , P ² , n and m are , Each have the same meaning as described above.
Ra represents a cyclic group having at least one of an aromatic hydrocarbon ring and an aromatic heterocycle.
Y is a chemical single bond, -O -, - S -, - C (= O) -, - O-CRbRc -, - CRcRb-O -, - O-CH 2 -CH 2 -, - CH 2 -CH ₂ -O-, -C (= O) -O-, -OC (= O)-, -C (= O) -S-, -SC (= O)-, -NR ^{14 -C (= O) -, -} C (= O) -NR 14 -, - 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-CRbRc -, - CRcRb-O-C (= O) -, - O-C (= O) -CRbRc -, - CRcRb- ^{C (= O) -O -,} - O-C (= O) -NR 14 -, - NR 14 -C (= O) -O -, - O-C (= O) -CH 2 -S-, It represents −S—CH ₂₋ C (= O) −O− or −OC (= O) −O−. Here, R ¹⁴ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and Rc and Rb may independently have a hydrogen atom and a substituent having 6 to 12 carbon atoms, respectively. It represents a good aromatic hydrocarbon ring group or an aromatic heterocyclic group which may have a substituent having 3 to 12 carbon atoms.
Ga is, -CH ₂ contained (i) a divalent aliphatic hydrocarbon group having 1 to 20 carbon atoms, and, in the divalent aliphatic hydrocarbon group (ii) 3 to 20 carbon atoms - at least one One is -O-, -S-, -OC (= O)-, -C (= O) -O-, -OC (= O) -O-, -NR ¹⁵ -C (= O) ^{) -, - C (= O} ) -NR 15 -, - NR 15 -, or, -C (= O) - is a substituted group, the one of the organic groups. However, this excludes cases where two or more -O- or -S- are adjacent to each other. Here, R ¹⁵ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.

（式中、Ｒ^１〜Ｒ^４、Ａｒ、Ｑ、Ｘ、Ｙ^１〜Ｙ^８、Ａ^１、Ａ^２、Ｂ^１、Ｂ^２、Ｇ^１、Ｇ^２、Ｐ^１、Ｐ^２、ｎおよびｍは、それぞれ前記と同じ意味を表す。
Ｇｂは、（ｉ）置換基を有していてもよい炭素数１〜２０の脂肪族炭化水素基、および、（ｉｉ）置換基を有していてもよい炭素数３〜２０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^１５−Ｃ（＝Ｏ）−、−Ｃ（＝Ｏ）−ＮＲ^１５−、−ＮＲ^１５−、または、−Ｃ（＝Ｏ）−に置換された基、のいずれかの有機基である。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。ここで、Ｒ^１５は、水素原子、または、炭素数１〜６のアルキル基を表す。[17] Production of the polymerizable compound according to the above [14] or [15], wherein the polymerizable compound represented by the formula (VI) is a polymerizable compound represented by the following formula (VII-2). Method.

(In the formula, R ^{1 to} R ⁴ , Ar, Q, X, Y ^{1 to} Y ⁸ , A ¹ , A ² , B ¹ , B ² , G ¹ , G ² , P ¹ , P ² , n and m are , Each have the same meaning as described above.
Gb has (i) an aliphatic hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, and (ii) an aliphatic hydrocarbon group having 3 to 20 carbon atoms which may have a substituent. At least one of -CH _2- contained in the hydrogen group is -O-, -S-, -OC (= O)-, -C (= O) -O-, -OC (= O). ^{-O -, - NR 15 -C (} = O) -, - C (= O) -NR 15 -, - NR 15 -, or, -C (= O) - substituted radicals, one of It is an organic group. However, this excludes cases where two or more -O- or -S- are adjacent to each other. Here, R ¹⁵ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.

According to the present invention, there is provided a method for producing a 1,1-disubstituted hydrazine compound capable of efficiently producing a 1,1-di-substituted hydrazine compound which is a target product.
Further, according to the present invention, a polymerizable compound for producing a polymerizable compound using the 1,1-di-substituted hydrazine compound efficiently produced by the method for producing a 1,1-di-substituted hydrazine compound of the present invention. A manufacturing method is provided.

Hereinafter, the present invention will be described in detail. In addition, in this invention, "may have a substituent" means "unsubstituted or having 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 20 carbon atoms has a substituent, the carbon number of the aromatic hydrocarbon ring group having 6 to 20 carbon atoms does not include the carbon number of such a substituent. It shall be. On the other hand, in "the number of π electrons contained in the ring structure in Ra", "the number of π electrons contained in the ring structure in Ra ¹ ", and "the number of π electrons contained in the ring structure in Ra ² " Also includes 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 group" shall not be included.

(Method for producing 1,1-di-substituted hydrazine compound represented by formula (II))
Hereinafter, a method for producing the 1,1-di-substituted hydrazine compound represented by the formula (II) of the present invention will be described in detail.
The method for producing a 1,1-di-substituted hydrazine compound represented by the formula (II) of the present invention may be referred to as a hydrazino compound represented by the following formula (I) (hereinafter, "hydrazino compound (I)"). ) Is a compound represented by the formula (III): R-Hal in an organic solvent containing at least one aprotonic polar solvent in the presence of a phosphoric acid-based compound having an aqueous solution pH of 8 or more and 14 or less. , May be referred to as "compound (III)").
Here, the 1,1-disubstituted hydrazine compound produced by the method for producing a 1,1-di-substituted hydrazine compound of the present invention can be used, for example, when preparing the polymerizable compound of the present invention.

<X>
In formulas (I) and (II), X is an oxygen atom, a sulfur ^{_{atom, -CH 2 -, - CHR 11}} -, - CR 11 R 12 -, or, ^{-NR 11} - represents a. Among these, an oxygen atom, a sulfur atom, and −CH ₂ − are preferable, an oxygen atom and a sulfur atom are more preferable, and a sulfur atom is particularly preferable, in that the effect of the present invention can be more easily obtained.
Here, R ¹¹ and R ¹² each independently represent a hydrogen atom or an alkyl group having 1 to 10 carbon atoms which may have a substituent. Among these, a hydrogen atom, a methyl group and an ethyl group are preferable.
Incidentally, X is ^-CR 11 ^{R 12} - if it ^{is, R 11} and ^{R 12} may be the same or different.

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 in R ¹¹ and R ¹² 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. Among these, a methyl group and an ethyl group are preferable.

The substituents of the alkyl groups having 1 to 10 carbon atoms of R ¹¹ and R ¹² include halogen atoms such as fluorine atom and chlorine atom; cyano group; substituted amino group such as methylamino group and dimethylamino 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; nitro group; phenyl group, 1-naphthyl group, 2-naphthyl group and the like. Examples thereof include an aryl group; a cycloalkyl group having 3 to 8 carbon atoms such as a cyclopropyl group and a cyclopentyl group; a hydroxyl group;
The alkyl groups of R ¹¹ and R ¹² having 1 to 10 carbon atoms may have a plurality of substituents. When the alkyl groups having 1 to 10 carbon atoms of R ¹¹ and R ¹² have a plurality of substituents, the respective substituents may be the same or different.

<R ^{1 to} R ⁴ >
In formulas (I) and (II), R ^{1 to} R ⁴ are independently hydrogen atoms; halogen atoms such as fluorine atom, chlorine atom and bromine atom; carbon such as methyl group, ethyl group and propyl group. Alkyl groups of numbers 1 to 6; cyano groups; nitro groups; trifluoromethyl groups, pentafluoroethyl groups, and other alkyl groups having 1 to 6 carbon atoms in which at least one hydrogen atom is substituted with halogen; methoxy groups, ethoxy groups, An alkoxy group having 1 to 6 carbon atoms such as an isopropoxy group and a butoxy group; an alkylthio group having 1 to 6 carbon atoms in which at least one hydrogen atom such as a methylthio group or an ethylthio group is replaced with a sulfur atom; a methylamino group, Mono-substituted amino groups such as ethylamino group and acetylamino group; Di-substituted amino groups such as dimethylamino group, diethylamino group and phenylmethylamino group; -OCF ₃ ; -C (= O) -OR ¹³ ; or -O-C (= O) -R ¹³ is represented. Here, R ¹³ 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. An alkyl group having 1 to 10 carbon atoms which may have a substituent of R ¹³ has the same meaning as an alkyl group having 1 to 10 carbon atoms which may have a substituent of R ¹¹ and R ^12. , The preferred example thereof is the same.
Among these, R ¹ to R ⁴ are each independently is preferably a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and more preferably all of R ¹ to R ⁴ is a hydrogen atom.

R ^{1 to} R ⁴ may all be the same or different from each other, and at least one C-R ^{1 to} C-R ⁴ constituting the ring may be replaced with a nitrogen atom. Specific examples of groups in which at least one of CR ^{1 to} CR ⁴ is replaced with a nitrogen atom are shown below. However, the group in which at least one of C-R ^{1 to} C-R ⁴ is replaced with a nitrogen atom is not limited to this.

〔各式中、Ｘは、前記と同じ意味を表し、その好適例も前記と同じであり、Ｒ^１〜Ｒ^４は、前記と同じ意味を表し、その好適例も前記と同じである。〕

[In the formulas, X is the same meanings as defined above, the preferred examples thereof are also the same as above, R ¹ to R ⁴ are as defined above, the preferred examples are also the same as above. ]

<Hal>
In formula (III), H represents a chlorine atom, a bromine atom, or an iodine atom. Among these, chlorine atom and bromine atom are preferable, and chlorine atom is more preferable, because the effect of the present invention can be more easily obtained.

<R>
In formulas (II) and (III), R represents an organic group having 1 to 60 carbon atoms which may have a substituent, and is represented by Ra-Y-Ga (Ga binds to Hal). (Ie, formula (III): R-Hal is of formula (IV-1): Ra-Y-Ga-Hal), that is represented by Gb (ie, formula) (III): R-Hal is of formula (IV-2): Gb-Hal).

The organic group having 1 to 60 carbon atoms of the organic group having 1 to 60 carbon atoms which may have a substituent of R is not particularly limited. For example, (i) an alkyl group having 1 to 60 carbon atoms. (Ii) an alkenyl group having 2 to 60 carbon atoms; (iii) an alkynyl group having 2 to 60 carbon atoms; and the like.

<< (i) Alkyl group having 1 to 60 carbon atoms >>
Alkyl groups having 1 to 60 carbon atoms include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, t-butyl group, n-pentyl group and 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 n-hexyl is preferable because the effect of the present invention can be more easily obtained. Groups are particularly preferred.

<< (ii) Alkenyl group having 2 to 60 carbon atoms >>
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.

<< (iii) alkynyl group having 2 to 60 carbon atoms >>
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 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; methyl. Substituted amino groups such as an amino group, an ethylamino group, an acetylamino group and a dimethylamino group; and the like can be mentioned.

<< Ra >>
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.

-Aromatic hydrocarbon ring-
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.

− Aromatic heterocycle −
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 oxadiazol ring. , Oxazole ring, oxazolopyrazine ring, oxazolopyridine ring, oxazolopyrazine ring, oxazolopyrimidine ring, quinazoline ring, quinoxalin ring, quinoline ring, synnoline ring, thiazylazole ring, thiazole 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, benzimidazole ring, benzoxaziazole ring, benzoxazole ring, benzo Examples thereof include a thiasiazol ring, a benzothiazole ring, a benzothiophene ring, a benzotriazine ring, a benzotriazole ring, a benzopyrazole ring, a penzopyranone ring, and the like.
Among these, the aromatic heterocycles include monocyclic aromatic heterocycles such as furan ring, pyrane ring, thiophene ring, oxazole ring, oxaziazole ring, thiazole ring, and thiazazole ring; and benzothiazole ring and benzoxazole. 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, thia Aromatic heterocycles of fused rings such as zolopyrazine ring, benzoisoxazole ring, benzoxazole ring, and benzothiazazole ring; are preferable.

The aromatic hydrocarbon ring and the aromatic heterocycle contained in Ra may have a substituent. Examples of such substituents include halogen atoms such as fluorine atom and chlorine atom; cyano group; alkyl groups having 1 to 6 carbon atoms such as methyl group, ethyl group and propyl group; and 2 to 6 carbon atoms such as vinyl group and 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 20 carbon atoms such as phenyl group and naphthyl group; -OCF ₃ ; -C (= O) -R ^x ; -C (= O) -OR ^x ; -OC (= O) -R ^x ; and -SO ₂ R ^b ; and the like. Here, R ^x is "(i) an alkyl group having 1 to 20 carbon atoms which may have a substituent" and "(ii) an alkenyl group having 2 to 20 carbon atoms which may have a substituent". , "A cycloalkyl group having 3 to 12 carbon atoms which may have a (iii) substituent", or "Aromatic carbide having 5 to 12 carbon atoms which may have a (iv) substituent". Represents "hydrogen ring group". 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 20 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 contained in Ra, a halogen atom, a cyano group, an alkyl group having 1 to 6 carbon atoms, and an alkoxy group having 1 to 6 carbon atoms are preferable.
In addition, Ra may have a plurality of substituents selected from the above-mentioned substituents. When Ra has a plurality of substituents, the substituents may be the same or different.

−R ^x −
−− (I) Alkyl group having 1 to 20 carbon atoms which may have a substituent −−
The "alkyl group having 1 to 20 carbon atoms" of "(i) alkyl group having 1 to 20 carbon atoms which may have a substituent" of ^Rx includes a methyl group, an ethyl group and an n-propyl group. , 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 Examples thereof include a-hexadecyl group, an n-heptadecyl group, an n-octadecyl group, an n-nonadecil group and an n-icosyl group.
The carbon number of "(i) an alkyl group having 1 to 20 carbon atoms which may have a substituent" is preferably 1 to 12, and more preferably 1 to 10.

−− (Ii) An alkenyl group having 2 to 20 carbon atoms which may have a substituent −−
The "alkenyl group having 2 to 20 carbon atoms" of the "alkenyl group having 2 to 20 carbon atoms which may have a (ii) substituent" of ^Rx includes a vinyl group, a propenyl group, an isopropenyl group, and the like. Butenyl group, isobutenyl 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 , Icosenyl group and the like.
The carbon number of the "alkenyl group having 2 to 20 carbon atoms which may have a (ii) substituent" is preferably 2 to 12.

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

--A cycloalkyl group having 3 to 12 carbon atoms which may have a (iii) substituent ---
The "cycloalkyl group having 3 to 12 carbon atoms" of the "cycloalkyl group having 3 to 12 carbon atoms which may have a (iii) substituent" of ^Rx includes a cyclopropyl group, a cyclobutyl group and a cyclopentyl group. Examples include a group, a cyclohexyl group, a cyclooctyl group and the like. Among these, a cyclopentyl group and a cyclohexyl group are preferable.
As the substituent of "cycloalkyl group having 3 to 12 carbon atoms" of "cycloalkyl group having 3 to 12 carbon atoms which may have (iii) substituent" of ^Rx , a fluorine atom and a chlorine atom Halogen atoms such as; cyano 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 and ethoxy Examples thereof include an alkoxy group having 1 to 6 carbon atoms such as a group and an isopropoxy group; a nitro group; an aromatic hydrocarbon ring group having 6 to 20 carbon atoms such as a phenyl group and a naphthyl group; Among these, fluorine is used as a substituent of "cycloalkyl group having 3 to 12 carbon atoms" of "cycloalkyl group having 3 to 12 carbon atoms which may have (iii) substituent" of ^Rx. Halogen atoms such as atoms and chlorine atoms; cyano group; alkyl groups having 1 to 6 carbon atoms such as methyl group, ethyl group and propyl group; alkoxy groups having 1 to 6 carbon atoms such as methoxy group, ethoxy group and isopropoxy group A nitro group; an aromatic hydrocarbon ring group having 6 to 20 carbon atoms such as a phenyl group and a naphthyl group; is preferable.
The "cycloalkyl group having 3 to 12 carbon atoms" of "cycloalkyl group having 3 to 12 carbon atoms which may have a (iii) substituent" of ^Rx has a plurality of substituents. May be.
When the "cycloalkyl group having 3 to 12 carbon atoms" of "cycloalkyl group having 3 to 12 carbon atoms which may have a (iii) substituent" of ^Rx has a plurality of substituents, a plurality of The substituents may be the same or different from each other.

−− (Iv) Aromatic hydrocarbon ring group having 5 to 18 carbon atoms which may have a substituent −−
The "aromatic hydrocarbon ring group having 5 to 18 carbon atoms" of the "aromatic hydrocarbon ring group having 5 to 18 carbon atoms which may have a (iv) substituent" of ^Rx is a phenyl group. , 1-naphthyl group, 2-naphthyl group and the like. 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.
As the substituent of R ^x "aromatic hydrocarbon ring group having 5 to 18 carbon atoms which may have a (iv) substituent", a halogen atom such as a fluorine atom or a chlorine atom; a cyano group; a dimethylamino N, N-dialkylamino groups having 2 to 12 carbon atoms such as groups; alkoxy groups having 1 to 20 carbon atoms such as methoxy groups, ethoxy groups, isopropoxy groups and butoxy groups; methoxymethoxy groups, methoxyethoxy groups and the like. An alkoxy group having 1 to 12 carbon atoms substituted with an alkoxy group having 1 to 12 carbon atoms; a nitro group; an aromatic hydrocarbon ring group having 6 to 20 carbon atoms such as a phenyl group and a naphthyl group; a triazolyl group, a pyrrolyl group, Aromatic heterocyclic group having 2 to 20 carbon atoms such as furanyl group and thiophenyl group; cycloalkyl group having 3 to 8 carbon atoms such as cyclopropyl group, cyclopentyl group and cyclohexyl group; cyclopentyloxy group and cyclohexyloxy group Cycloalkyloxy group having 3 to 8 carbon atoms; cyclic ether group having 2 to 12 carbon atoms such as tetrahydrofuranyl group, tetrahydropyranyl group, dioxolanyl group and dioxanyl group; phenoxy group, naphthoxy group and the like having 6 to 14 carbon atoms. Aryloxy group; fluoroalkyl group having 1 to 12 carbon atoms in which at least one hydrogen atom is substituted with a fluorine atom, such as trifluoromethyl group, pentafluoroethyl group, -CH ₂ CF _3, etc .; -OCF ₃ ; benzofuryl Groups; benzopyranyl groups; benzodioxolyl groups; benzodioxanyl groups; and the like. Among these, as the substituent of R ^x "aromatic hydrocarbon ring group having 5 to 12 carbon atoms which may have a (iv) substituent", a halogen atom such as a fluorine atom or a chlorine atom; cyano Group; alkoxy group having 1 to 20 carbon atoms such as methoxy group, ethoxy group, isopropoxy group and butoxy group; nitro group; aromatic hydrocarbon ring group having 6 to 20 carbon atoms such as phenyl group and naphthyl group; triazolyl group , Aromatic heterocyclic groups having 2 to 20 carbon atoms such as pyrrolyl group, furanyl group and thiophenyl group; cycloalkyl groups having 3 to 8 carbon atoms such as cyclopropyl group, cyclopentyl group and cyclohexyl group; trifluoromethyl group, At least one substituent selected from a fluoroalkyl group having 1 to 12 carbon atoms in which at least one hydrogen atom is substituted with a fluorine atom, such as a pentafluoroethyl group and -CH ₂ CF ₃ , -OCF ₃ ; is preferable. ..
It should be noted that there are a plurality of "aromatic hydrocarbon ring groups having 5 to 18 carbon atoms" of "aromatic hydrocarbon ring groups having 5 to 18 carbon atoms which may have (iv) substituents" of ^Rx. It may have a substituent of. The "aromatic hydrocarbon ring group having 5 to 18 carbon atoms" of the "aromatic hydrocarbon ring group having 5 to 18 carbon atoms which may have a (iv) substituent" of ^Rx is a plurality of substituents. If, 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".

A preferred specific example of Ra, "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" is 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 which may have a substituent and has 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 −, oxygen atom or 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. ] (Where 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.)

In addition, "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" of Ra 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 of Ra, which is a cyclic group having at least one of an aromatic hydrocarbon ring having 6 to 30 carbon atoms and an aromatic heterocyclic ring having 2 to 30 carbon atoms, include a fluorine atom and a chlorine atom. Halogen atom; cyano 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 and pentafluoroethyl group 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 dimethylamino group; methoxy group, ethoxy group, isopropoxy group, etc. An alkoxy group having 1 to 6 carbon atoms; a nitro group; an aromatic hydrocarbon ring group having 6 to 20 carbon atoms such as a phenyl group and a naphthyl group; -OCF ₃ ; -C (= O) -R ^x ; -C ( = O) -OR ^x ; -OC (= O) -R ^x ; -SO ₂ R ^b ; and the like. Here, R ^x 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.

<< Y >>
Y is a chemical single bond, -O -, - S -, - C (= O) -, - O-CRbRc -, - CRbRc-O -, - O-CH 2 -CH 2 -, - CH 2 -CH ₂ -O-, -C (= O) -O-, -OC (= O)-, -C (= O) -S-, -SC (= O)-, -NR ^{14 -C (= O) -, -} C (= O) -NR 14 -, - 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-CRbRc -, - CRcRb-O-C (= O) -, - O-C (= O) -CRbRc -, - CRcRb- ^{C (= O) -O -,} - O-C (= O) -NR 14 -, - NR 14 -C (= O) -O -, - O-C (= O) -CH 2 -S-, It represents −S—CH ₂₋ C (= O) −O− or −OC (= O) −O−. Here, R ¹⁴ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and Rc and Rb may independently have a hydrogen atom and a substituent having 6 to 12 carbon atoms, respectively. It represents a good aromatic hydrocarbon ring group or an aromatic heterocyclic group which may have a substituent having 3 to 12 carbon atoms.
The Y, among these, in terms of effect is more easily obtained in the present invention, a chemical single bond, -O -, - O-CRbRc -, - CRbRc-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-CRbRc-, -CRcRb-OC (= O)-, -O-C (= O) -CRbRc-, -CRcRb-C (= O) -O-, -OC (= ^{O) -NR 14 -, - NR} 14 -C (= O) -O -, - O-C (= O) -CH 2 -S -, - S-CH 2 -C (= O) -O-, -O-C (= O) -O- , preferably, a chemical single bond, -O -, - O-CRbRc -, - CRcRb-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- CRbRc-, -CRcRb-OC (= O)-, -O-C (= O) -CRbRc-, -CRcRb-C (= O) -O-, -OC (= O) -NR ¹⁴ -, -NR ^14- C (= O) -O-, -S-CH _2- C (= O) -O-, -OC (= O) -CH ₂ -S- are more preferable and chemically. single bond, -O, such _{-, - O-CRbRc -,} - CRcRb-O -, - O-CH 2 -CH 2 -, - CH 2 -CH 2 -O -, - C (= O) -O-, -O-C (= O)-, -CH _2- CH _2- C (= O) -O-, -O-C (= O) -CH _2- CH _2- , -C (= O) -O -CRbRc-, -CRcRb-OC (= O)-, -O-C (= O) -CRbRc-, -CRcRb-C (= O) -O-, -O-C (= O) -NR _{^{14 -, - NR 14 -C (}} = O) -O -, - S-CH 2 -C (= O) -O -, - O-C (= O) -CH 2 -S- are particularly preferred.
Here, R ¹⁴ 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 ¹⁴ is preferably a hydrogen atom.
Rc and Rb each independently have a hydrogen atom, an aromatic hydrocarbon ring group which may have a substituent having 6 to 12 carbon atoms, or a substituent having 3 to 12 carbon atoms. Represents a good aromatic heterocyclic group. Rc and Rb may be the same as each other or may be different from each other.
An aromatic hydrocarbon ring group of Rb and Rc which may have a substituent having 6 to 12 carbon atoms, or an aromatic heterocyclic ring group which may have a substituent having 3 to 12 carbon atoms. Specific examples of the above-mentioned Ra include those having a specified carbon number 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 which may independently have a hydrogen atom and a substituent having 6 to 12 carbon atoms, and further, each independently has a hydrogen atom, a phenyl group or a hydrogen atom. A naphthyl group is preferable, and a combination in which both Rc and Rb are hydrogen atoms at the same time, a hydrogen atom and a phenyl group, or a hydrogen atom and a naphthyl group are 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, -O-CRbRc-Z, -CRbRc-O-Z,- _{O-CH 2 -CH 2 -Z,} -CH 2 -CH 2 -O-Z, -C (= O) -O-Z, -O-C (= O) -Z, -CH 2 -CH 2 - C (= O) -O-Z, -O-C (= O) -CH _2- CH _2- Z, -C (= O) -O-CRbRc-Z, -CRbRc-OC (= O) -Z, -OC (= O) -CRbRc-Z, -CRbRc-C (= O) -O-Z, -NR ^14- C (= O) -O-Z, -S-CH _2- C A combination selected from (= O) -O-Z is preferred.
Ra is selected from the general formulas (i-1) to (i-6), and Y is a chemical single bond, -O-Z, -CRbRc-O-Z, -CH _2- CH _2- O. -Z, -C (= O) -O-Z, -O-C (= O) -Z, -CH _2- CH _2- C (= O) -O-Z, -CRbRc-OC (= Selected from O) -Z, -CRbRc-C (= O) -O-Z, -NR ^14- C (= O) -O-Z, -S-CH _2- C (= O) -O-Z Combination is more preferable
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 Ga. In addition, the groups represented by the following formulas (ii-1) to (ii-45) and the ● in the groups represented by (iii-1) to (iii-46) indicate the binding site with Ga. Shown.
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.

<< Ga >>
Ga 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.
Ga is more preferably contained in (i) a divalent aliphatic hydrocarbon group having 1 to 20 carbon atoms and (ii) a divalent aliphatic hydrocarbon group having 3 to 20 carbon atoms -CH _2. - at least one of the, -O -, - S -, - O-C (= O) -, - C (= O) -O -, - O-C (= O) -O -, - NR 15 - C (= O) -, - C (= O) -NR 15 -, - NR 15 -, or, -C (= O) - is a substituted group, the one of the organic groups. However, this excludes cases where two or more -O- or -S- are adjacent to each other.
Here, R ¹⁵ 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 Ga 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;
Examples of the substituent of Ga include alkyl groups having 1 to 5 carbon atoms such as hydroxyl groups, methyl groups, ethyl groups and propyl groups; alkoxy groups having 1 to 5 carbon atoms such as methoxy groups, ethoxy groups and isopropoxy groups; cyano Group: Examples include a halogen atom such as a fluorine atom and a chlorine atom.
Here, with respect to Ga, the "divalent aliphatic hydrocarbon group" is preferably a divalent chain aliphatic hydrocarbon group, more preferably an alkylene group. Further, the carbon number of the "divalent aliphatic hydrocarbon group" is preferably 3 to 20, 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 2 to 18 carbon atoms.

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

As the structure of Ga, 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 number of carbon atoms in Ga is 3 or more, it is preferable that both ends of Ga are −CH ₂ − (both ends of Ga 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 15 -C (= O) -, - C (= O) -NR 15 -, - NR 15 -, or , -C (= O)-Substituted groups ", -O- and -S- do not replace the contiguous -CH _2- in the aliphatic hydrocarbon groups (ie, -O-O- and-. It is preferable that it does not form a structure of —S—S— (that is, it is preferable except when two or more −O− or −S− are adjacent to each other).
It is preferred that −C (= O) − does not replace the contiguous −CH ₂₋ in the aliphatic hydrocarbon group (ie, does not form a −C (= O) −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 15 -C (= O) -, - C (= O) -NR 15 -, - NR 15 -, or, -C (= O )-It is most preferable to be substituted with -O-, and the so-called ethyleneoxy, which is substituted with -O- for every 2 carbon atoms, is used as a repeating unit, and both ends of Ga are -CH _2-. Is preferable.

Examples of Ga include (i) "divalent chain aliphatic hydrocarbon groups having 1 to 18 carbon atoms, preferably 3 to 18 carbon atoms, and divalent chain aliphatic hydrocarbon groups having 3 to 18 carbon atoms. At least one of -CH _2- contained in the hydrocarbon group is -O-, -S-, -OC (= O)-, -C (= O) -O-, or -C (= O). ) It is an organic group of any of the groups substituted with −, and it is preferable to exclude the case where two or more of −O− or −S− are adjacent to each other ”, and (ii)“ 3 to 18 carbon atoms. It is more preferably a divalent chain aliphatic hydrocarbon group of the above, (iii) "alkylene group having 3 to 18 carbon atoms" is further preferable, and (iv) "unsubstituted unsubstituted having 4 to 16 carbon atoms". "Alkylene group" is even more preferable, (v) "unsubstituted alkylene group having 5 to 14 carbon atoms" is even more preferable, and (vi) "unsubstituted alkylene group having 6 to 12 carbon atoms" is even more preferable. (Vii) "Unsubstituted alkylene group having 6 to 10 carbon atoms" is particularly preferable, and "n-hexylene group, n-octylene group" is most preferable.

<< Gb >>
Gb is an organic group having 1 to 20 carbon atoms which may have a substituent, and is preferably an organic group having 3 to 20 carbon atoms which may have a substituent.
Gb is more preferably (i) an aliphatic hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, and (ii) 3 to 20 carbon atoms which may have a substituent. At least one of -CH _2- contained in the aliphatic hydrocarbon group of is -O-, -S-, -OC (= O)-, -C (= O) -O-, -O-C. ^{(= O) -O -, -} NR 15 -C (= O) -, - C (= O) -NR 15 -, - NR 15 -, or, -C (= O) - substituted radicals, It is one of the organic groups of. However, this excludes cases where two or more -O- or -S- are adjacent to each other.
Here, R ¹⁵ 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 Gb includes a hydroxyl group; an alkyl group having 1 to 5 carbon atoms such as a methyl group, an ethyl group and a propyl group; and 1 to 5 carbon atoms such as a methoxy group, an ethoxy group and a propoxy group. An alkoxy group; a cyano group; a halogen atom such as a fluorine atom and a chlorine atom;
Here, with respect to Gb, the "aliphatic hydrocarbon group" is preferably a chain aliphatic hydrocarbon group, more preferably an alkyl group, an alkynyl group, or an alkenyl group. Further, the carbon number of the "aliphatic hydrocarbon group" is preferably 3 to 20, more preferably 3 to 18. The "aliphatic hydrocarbon group" is preferably an aliphatic hydrocarbon group having 2 to 20 carbon atoms, preferably a chain aliphatic hydrocarbon group having 2 to 18 carbon atoms, and carbon. More preferably, it is an alkyl group (eg, n-hexyl group), an alkynyl group (eg, 2-butynyl group), or an alkenyl group (eg, 1-butenyl group) of number 2-18.

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

As the structure of Gb, an unsubstituted alkyl group, alkynyl group, or alkenyl group having 4 to 16 carbon atoms is preferable, and an unsubstituted alkyl group, alkynyl group, or alkenyl group having 4 to 14 carbon atoms is more preferable. , A unsubstituted alkyl group, alkynyl group, or alkenyl group having 4 to 12 carbon atoms is more preferable, and an unsubstituted alkyl group, alkynyl group, or alkenyl group having 4 to 10 carbon atoms is particularly preferable. An unsubstituted alkyl group of 10 to 10 is even more preferable, and an n-hexyl group is most preferable.

When the number of carbon atoms of Gb is 3 or more, it is preferable that one end of Gb (bonding side with Hal) is −CH ₂ − (one end of Gb is not replaced). In addition, "(ii) at least one of -CH _2- contained in an aliphatic hydrocarbon group having 3 to 20 carbon atoms is -O-, -S-, -OC (= O)-, -C ( ^{= O) -O -, - O} -C (= O) -O -, - NR 15 -C (= O) -, - C (= O) -NR 15 -, - NR 15 -, or, -C In "groups substituted with (= O)-", -O- and -S- do not replace the contiguous -CH _2- in the aliphatic hydrocarbon group (ie, -O-O- and -S-". It is preferable that it does not form the structure of S- (that is, it is preferable except when two or more -O- or -S- are adjacent to each other), and -C (= O)-is an aliphatic hydrocarbon. It is preferable not to replace the continuous −CH ₂₋ in the hydrogen group (that is, not to form the −C (= O) −C (= O) − structure).
At least one of -CH _2- contained in an aliphatic hydrocarbon group having 3 to 20 carbon atoms is -O-, -S-, -OC (= O)-, -C (= O) -O-. ^{, -O-C (= O)} -O -, - NR 15 -C (= O) -, - C (= O) -NR 15 -, - NR 15 -, or, -C (= O) - in When it is substituted, it is most preferably substituted with −O−, and the so-called ethyleneoxy, which is substituted with −O− every 2 carbon atoms, is used as a repeating unit, and one end of Gb (bonding side with Hal) is It is preferably −CH ₂₋ .

As Gb, (i) "a chain aliphatic hydrocarbon group having 1 to 18 carbon atoms which may have a substituent, preferably 3 to 18 carbon atoms, and a substituent may be used. At least one of -CH _2- contained in a good chain aliphatic hydrocarbon group having 3 to 18 carbon atoms is -O-, -S-, -OC (= O)-, -C (= O). ) It is an organic group of either -O- or a group substituted with -C (= O)-, except when -O- or -S- is interposed adjacent to each other. " It is more preferable that (iii) "a chain aliphatic hydrocarbon group having 3 to 18 carbon atoms which may have a substituent" is more preferable, and (iii) "even if it has a substituent". A good alkyl group, alkynyl group, or alkenyl group having 3 to 18 carbon atoms is even more preferable, and (iv) "unsubstituted alkyl group, alkynyl group, or alkenyl group having 4 to 16 carbon atoms" is even more preferable. , (V) "Unsubstituted alkyl group, alkynyl group, or alkenyl group having 4 to 14 carbon atoms" is even more preferable, and (vi) "Unsubstituted alkyl group, alkynyl group having 4 to 12 carbon atoms," Or an alkenyl group is even more preferred, (vii) an "unsubstituted alkyl group having 4 to 10 carbon atoms, an alkynyl group, or an alkenyl group" is particularly preferable, and an unsubstituted alkyl group having 4 to 10 carbon atoms is further preferred. It is particularly preferable, and the "n-hexyl group" is most preferable.

<Reaction between hydrazino compound (I) and compound (III)>
The reaction between the hydrazino compound (I) and the compound (III) is carried out in an organic solvent containing at least one aprotic polar solvent (hereinafter, may be simply referred to as “organic solvent”).
The amount of the organic solvent used is not particularly limited, but is preferably 0.1 mL or more, more preferably 0.5 mL or more, and more preferably 1 mL or more per 1 g of the compound (I). It is particularly preferable, and it is preferably 50 mL or less, more preferably 20 mL or less, and particularly preferably 15 mL or less.

The reaction temperature is usually −10 ° C. or higher, which is lower than the boiling point of the solvent used, preferably 40 ° C. or higher, more preferably 60 ° C. or higher, particularly preferably 80 ° C. or higher, and particularly preferably 150 ° C. or lower. It is preferably 120 ° C. or lower, and more preferably 120 ° C. or lower. The reaction time is usually several minutes to several hours, depending on the scale of the reaction.
The reaction is preferably carried out in an inert atmosphere such as in a nitrogen stream.

<Aprotic polar solvent>
The aprotonic polar solvent is a polar solvent having no proton donating property, and is, for example, a ketone solvent such as acetone, methyl ethyl ketone, 2-pentanone, 2-hexanone, methyl isobutyl ketone, diisobutyl ketone; methyl acetate, ethyl acetate. , Ester solvents such as propyl acetate, isopropyl acetate, butyl acetate, methyl propionate, ethyl propionate; sulfone solvents such as diethyl sulfone and diphenyl sulfone; sulfoxide solvents such as dimethyl sulfoxide and diethyl sulfoxide; N, N, N Amin-based solvents such as', N'-tetramethylethylenediamine, N, N-dimethylaniline; amide-based solvents such as N, N-dimethylformamide, N, N-dimethylacetamide, N-methylpyrrolidone; 1,3-dimethyl -2-Urea solvents such as imidazolidinone; nitrile solvents such as acetonitrile, propionitrile and benzonitrile; nitro compounds such as nitromethane and nitrobenzene; and the like. Each of these solvents can be used alone or in combination of two or more.

Among these, as the aprotonic polar solvent, a sulfoxide solvent, an amide solvent, a nitrile solvent, and a urea solvent are preferably used, and N, N-dimethylformamide, N, N-dimethylacetamide, and N-methyl It is more preferable to use pyrrolidone, acetonitrile, 1,3-dimethyl-2-imidazolidinone and dimethyl sulfoxide, and it is preferable to use N, N-dimethylformamide, N, N-dimethylacetamide and N-methyl-2-pyrrolidone. Especially preferable.

The ratio of the hydrazino compound (I) to the compound (III) used is preferably 1: 1 to 1: 2, more preferably 1: 1 to 1: 1.5 in terms of molar ratio. : 1 to 1: 1.3 is more preferable, and 1: 1 to 1: 1.25 is more preferable. By carrying out the reaction at such a usage ratio, the desired product can be obtained in good yield.

The reaction between the hydrazino compound (I) and the compound (III) is carried out in the organic solvent in the presence of a phosphoric acid-based compound.
Specifically, a method in which (α) hydrazino compound (I) is dissolved in the organic solvent, a phosphoric acid-based compound and compound (III) are added thereto, and the whole content is stirred, (β) compound (III). Was dissolved in the organic solvent, hydrazino compound (I) and phosphoric acid-based compound were added thereto, and the whole mixture was stirred. (Γ) Hydradino compound (I) and compound (III) were added to the organic solvent. Examples thereof include a method in which the compound is dissolved, a phosphoric acid-based compound is added thereto, and the whole content is stirred, and the method (α) or (β) is preferable.

In the method (α), the compound (III) and the phosphoric acid-based compound may be added simultaneously to the organic solvent solution of the hydrazino compound (I), or the compound (III) may be added to the organic solvent solution of the hydrazino compound (I). Although the phosphoric acid-based compound may be added after the addition of III), it is preferable to add the phosphoric acid-based compound to the organic solvent solution of the hydrazino compound (I) and then the compound (III).
Further, the compound (III) may be added as it is, or a compound (III) dissolved in an organic solvent may be added.
Further, as the phosphoric acid compound, a solid state compound may be added, or a phosphoric acid compound dissolved (suspended) in an organic solvent may be added.
In the method (β), the hydrazino compound (I) and the phosphoric acid-based compound may be added simultaneously to the organic solvent solution of the compound (III), or the hydradino compound (Hydrazino compound (III)) may be added to the organic solvent solution of the compound (III). Although the phosphoric acid-based compound may be added after the addition of I), it is preferable to add the phosphoric acid-based compound after adding the hydrazino compound (I) to the organic solvent solution of the compound (III).
Further, the hydradino compound (I) may be added as it is, or a hydradino compound (I) dissolved in an organic solvent may be added.
Further, as the phosphoric acid compound, a solid state compound may be added, or a phosphoric acid compound dissolved (suspended) in an organic solvent may be added.
Further, in any of the methods, the hydrazino compound (I) or the compound (III) may be added dropwise as needed.

<Phosphoric acid compound>
The phosphoric acid-based compound is not particularly limited as long as the pH of the aqueous solution is 8 or more and 14 or less, and examples thereof include alkali metal phosphate and alkali metal phosphoric acid monohydrogen salt.
Among these, alkali metal phosphate is preferable, tripotassium phosphate and trisodium phosphate are more preferable, and tripotassium phosphate is particularly preferable in terms of reaction rate and yield.
The pH of the aqueous solution of the phosphoric acid compound is not particularly limited as long as it is 8 or more and 14 or less, but it is preferably 8.5 or more and preferably 10 or more in terms of reaction rate and yield. It is preferable, and in terms of reaction rate and yield, it is preferably 13.5 or less, and more preferably 13 or less.

The amount of the phosphoric acid-based compound used is not particularly limited, but is 1.0 equivalent to the hydradino compound represented by the above formula (I) in that the desired product can be obtained in a high yield. The above is preferable, 1.1 equivalents or more is more preferable, 1.2 equivalents or more is particularly preferable, 2.0 equivalents or less is preferable, and 1.8 equivalents or less. It is more preferably present, and particularly preferably 1.5 equivalents or less.

<Post-processing operation>
After completion of the reaction, the desired product can be isolated by performing a normal post-treatment operation in synthetic organic chemistry. In the present invention, it is preferable to have a step of adding a protonic solvent to the reaction solution, and the pH of the mixed solution of the reaction solution and the acidic protonal solvent is added by adding the acidic protonal solvent to the reaction solution. It is more preferable to have a step of reducing the amount to 8 or less. Thereby, a high-purity target product can be easily obtained in high yield.
In addition, in this invention, especially when the compound (Ra-Y-Ga-Hal) represented by the formula (IV-1) is used as the compound (R-Hal) represented by the formula (III), it is described above. It is preferable to carry out the process.

The protic solvent to be used is not particularly limited as long as it is a protic solvent which is a poor solvent for the target 1,1-di-substituted hydrazine compound. For example, water; monohydric alcohols such as ethanol, propanol, butanol, hexanol, cyclopentanol, cyclohexanol, benzyl alcohol; polyhydric alcohols such as ethylene glycol, propylene glycol and glycerin; oxy such as methyl cellosolve and dimethoxypropanol. Alcohol compounds; and mixed solvents composed of two or more of these; and the like. Of these, it is particularly preferable to use water.
When an acidic aqueous solution is used as the acidic protonic solvent, it is preferably an acidic aqueous solution having a pH of 1.5 or more and less than 7, and more preferably an acidic aqueous solution having a pH of 1.7 or more and less than 7. An acidic aqueous solution having a pH of 1.8 or more and less than 7 is particularly preferable.
The acidic aqueous solution is not particularly limited. For example, citric acid aqueous solution; acetic acid aqueous solution; acetic acid and sodium acetate, potassium hydrogen phthalate and sodium hydroxide, potassium dihydrogen phosphate and sodium hydroxide, sodium citrate and hydroxide. A mixed buffer solution of sodium, potassium dihydrogen phosphate, citric acid, etc.; Among these, an aqueous citric acid solution is preferable because of its low cost.

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

According to the method for producing a 1,1-di-substituted hydrazine compound of the present invention, the easily available hydrazine compound (I) is used as a raw material, and an inexpensive reagent is used to ensure high reaction selectivity, high yield, and safety. , The desired 1,1-di-substituted hydrazine compound can be produced.

(Method for producing a polymerizable compound represented by the formula (VI))
Hereinafter, a method for producing a polymerizable compound represented by the formula (VI) of the present invention will be described in detail.
The method for producing the polymerizable compound represented by the formula (VI) of the present invention includes the 1,1-di-substituted hydrazine compound produced by the above-mentioned method for producing the 1,1-di-substituted hydrazine compound of the present invention and the following formula. It is characterized by including a step of reacting with a compound represented by (V) (hereinafter, may be referred to as “compound (V)”).
The method for producing the polymerizable compound represented by the formula (VI) of the present invention is derived from the 1,1-di-substituted hydrazine compound produced by the above-mentioned method for producing the 1,1-di-substituted hydrazine compound of the present invention. It is characterized by being done.

<Compound represented by formula (V), polymerizable compound represented by formula (VI)>
<< Q >>
In formulas (V) and (VI), Q represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms which may have a substituent. Examples of the alkyl group having 1 to 6 carbon atoms of the alkyl group having 1 to 6 carbon atoms which may have a substituent include a methyl group, an ethyl group, a propyl group, an isopropyl group and the like. Examples thereof include aromatic hydrocarbon groups having 6 to 12 carbon atoms such as a phenyl group and a naphthalene group.
Among these, Q is preferably a hydrogen atom.

<< Ar >>
In formulas (V) and (VI), Ar represents an aromatic hydrocarbon ring group which may have a substituent or an aromatic heterocyclic group which may have a substituent.
Among these, Ar is preferably an aromatic hydrocarbon ring group.

-Aromatic hydrocarbon ring group-
The aromatic hydrocarbon ring group has the same meaning as the "aromatic hydrocarbon ring" of the "cyclic group having at least one of an aromatic hydrocarbon ring and an aromatic heterocycle" of Ra, and a preferred example thereof is also the Ra. It is the same as the preferred example of the "aromatic hydrocarbon ring" of the "cyclic group having at least one of the aromatic hydrocarbon ring and the aromatic heterocycle" of the above, and the substituent is also the "aromatic hydrocarbon ring and the aromatic hydrocarbon ring of Ra". It is the same as the substituent of the "aromatic hydrocarbon ring" of the "cyclic group having at least one of the aromatic heterocycles".

− Aromatic heterocyclic group −
The aromatic heterocyclic group has the same meaning as the "aromatic heterocycle" of the "cyclic group having at least one of an aromatic hydrocarbon ring and an aromatic heterocycle" of Ra, and a preferred example thereof is also the "aromatic heterocycle" of Ra. It is the same as a preferable example of the "aromatic heterocyclic group" of the "cyclic group having at least one of the aromatic hydrocarbon ring and the aromatic heterocycle", and the substituent thereof is also the "aromatic hydrocarbon ring and the aromatic" of Ra. It is the same as the substituent of the "aromatic heterocycle" of the "cyclic group having at least one of the heterocycles".

<< Y ^{1 to} Y ⁸ >>
In formula (V) and formula ^(VI), Y 1 ~Y ⁸ are each independently a chemical single _{bond, -O -, - O-CH} 2 -, - CH 2 -O -, - O- _{CH 2 -CH 2 -, - CH} 2 -CH 2 -O -, - C (= O) -O -, - O-C (= O) -, - O-C (= O) -O -, - C (= O) -S-, -SC (= O)-, -NR ^16- C (= O)-, -C (= O) -NR ^16- , -CF _2- O-, -O _{-CF 2 -, - CH 2 -CH} 2 -, - CF 2 -CF 2 -, - O-CH 2 -CH 2 -O -, - CH = CH-C (= O) -O -, - O- _{C (= O) -CH = CH} -, - CH 2 -C (= O) -O -, - O-C (= O) -CH 2 -, - CH 2 -O-C (= O) -, _{-C (= O) -O-CH} 2 -, - 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 -, - CH = CH -, - N = CH -, - CH = N -, - N = C ( It represents CH ₃ )-, -C (CH ₃ ) = N-, -N = N-, or -C≡C-. Here, R ¹⁶ 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.
Among these, Y ^{1 to} Y ⁸ are independently chemically single bonds, -O-, -OC (= O)-, -C (= O) -O-, or -O. -C (= O) -O- is preferable.

<< A ¹ , A ² , B ¹ and B ² >>
In formula (V) and formula (VI), A ¹ , A ² , B ¹ and B ² each independently have a cyclic aliphatic group or a substituent which may have a substituent. Represents an aromatic group that may be present.
Among these, A ¹ , A ² , B ¹ and B ² each independently have a cyclic aliphatic group having 5 to 20 carbon atoms or a substituent which may have a substituent. An aromatic group having 2 to 20 carbon atoms may be preferable.

Specific examples of the cyclic aliphatic group include cyclopentane-1,3-diyl, cyclohexane-1,4-diyl, 1,4-cycloheptane-1,4-diyl, cyclooctane-1,5-diyl and the like. Cycloalkanediyl groups having 5 to 20 carbon atoms; bicycloalkandyl groups having 5 to 20 carbon atoms such as decahydronaphthalene-1,5-diyl and decahydronaphthalene-2,6-diyl; and the like can be mentioned. Among them, as the cyclic aliphatic group, a cycloalkandyl group having 5 to 20 carbon atoms which may be substituted is preferable, a cyclohexanediyl group is more preferable, and a 1,4-cyclohexylene group is particularly preferable, and trans-1 , 4-Cyclohexylene group is more preferred.

Specific examples of the aromatic group include 1,2-phenylene group, 1,3-phenylene group, 1,4-phenylene group, 1,4-naphthylene group, 1,5-naphthylene group and 2,6-naphthylene group. , 4,4'-Aromatic hydrocarbon ring group having 6 to 20 carbon atoms such as biphenylene group; furan-2,5-diyl, thiophene-2,5-diyl, pyridine-2,5-diyl, pyrazine- Aromatic heterocyclic groups having 2 to 20 carbon atoms such as 2,5-diyl; and the like. Among them, as the aromatic group, an aromatic hydrocarbon ring group having 6 to 20 carbon atoms is preferable, a phenylene group is more preferable, and a 1,4-phenylene group is particularly preferable.

Examples of the substituent of the cyclic aliphatic group and the aromatic group include halogen atoms such as fluorine atom, chlorine atom and bromine atom; alkyl groups having 1 to 6 carbon atoms such as methyl group and ethyl group; methoxy group and isopropoxy. Examples thereof include an alkoxy group having 1 to 5 carbon atoms such as a group; a nitro group; a cyano group; and the like. The cyclic aliphatic group, the cyclic aliphatic group having 5 to 20 carbon atoms, the aromatic group, and the aromatic group having 2 to 20 carbon atoms may have at least one substituent selected from the above-mentioned substituents. Good. When a plurality of substituents are provided, each substituent may be the same or different from each other.

It is preferable that A ¹ and A ² are cyclic aliphatic groups which may have a substituent, and B ¹ and B ² are aromatic groups which may have a substituent.
A ¹ and A ² are trans-1,4-cyclohexylene groups which may independently have a substituent represented by the formula (a), and B ¹ and B ² are formulas (B ¹ and B ² ). A combination of 1,4-phenylene groups, which may have a substituent represented by b), A ¹ and A ² each independently have a substituent represented by the formula (b). A combination of 1,4-phenylene groups, in which n and m are independently 0, is more preferable.

前述した式（ａ）および（ｂ）中、Ｒ^０は、ハロゲン原子、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；シアノ基；ニトロ基；トリフルオロメチル基、ペンタフルオロエチル基等の少なくとも１つの水素原子がハロゲンで置換された炭素数１〜６アルキル基；メトキシ基、エトキシ基、プロポキシ基等の炭素数１〜６のアルコキシ基；−ＯＣＦ_３；−Ｃ（＝Ｏ）−Ｏ−Ｒ^ｘ；または−Ｏ−Ｃ（＝Ｏ）−Ｒ^ｘを表し、Ｒ^ｘは、前記と同じ意味を表し、その好適例も前記と同じである。
Ｒ^０としては、溶解性向上の観点から、フッ素原子、塩素原子等のハロゲン原子；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；シアノ基；ニトロ基；トリフルオロメチル基、ペンタフルオロエチル基等の少なくとも１つの水素原子がハロゲンで置換された炭素数１〜６アルキル基；メトキシ基、エトキシ基、プロポキシ基等の炭素数１〜６のアルコキシ基；が好ましい。なお、Ｒ^０が複数の場合は、複数のＲ^０は互いに同一でも異なっていてもよい。さらに、ｐ１は、０〜４の整数を表し、０であることが好ましい。

In the above formulas (a) and (b), ^R0 is an alkyl group having 1 to 6 carbon atoms such as a halogen atom, a methyl group, an ethyl group, and a propyl group; a cyano group; a nitro group; a trifluoromethyl group, a penta. Alkyl group having 1 to 6 carbon atoms in which at least one hydrogen atom such as fluoroethyl group is substituted with halogen; alkoxy group having 1 to 6 carbon atoms such as methoxy group, ethoxy group, propoxy group; -OCF ₃ ; -C ( = O) -OR ^x ; or -OC (= O) -R ^x , where R ^x has the same meaning as described above, and preferred examples thereof are also the same as described above.
From the viewpoint of improving solubility, R ⁰ includes halogen atoms such as fluorine atom and chlorine atom; alkyl groups having 1 to 6 carbon atoms such as methyl group, ethyl group and propyl group; cyano group; nitro group; trifluoromethyl. Alkyl groups having 1 to 6 carbon atoms in which at least one hydrogen atom such as a group or pentafluoroethyl group is substituted with halogen; an alkoxy group having 1 to 6 carbon atoms such as a methoxy group, an ethoxy group or a propoxy group; are preferable. In the case R ⁰ is plural, a plurality of R ⁰ is may be the same or different from each other. Further, p1 represents an integer of 0 to 4, and is preferably 0.

<< G ¹ and G ² >>
In formulas (V) and (VI), G ¹ and G ² are independently divalent aliphatic hydrocarbon groups having 1 to 30 carbon atoms and divalent fats having 3 to 30 carbon atoms, respectively. At least one of -CH _2- contained in the group hydrocarbon group is -O-, -S-, -OC (= O)-, -C (= O) -O-, -OC (= ^{O) -O -, - NR 17} -C (= O) -, - C (= O) -NR 17 -, - NR 17 -, or, -C (= O) - or substituted groups Except when two or more -O- or -S- are adjacent to each other. Here, R ¹⁷ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and a hydrogen atom or a methyl group is preferable. The hydrogen atom contained in the organic group of G ¹ and G ² is an alkyl group having 1 to 5 carbon atoms such as a methyl group, an ethyl group and a propyl group; and 1 to 5 carbon atoms such as a methoxy group, an ethoxy group and a propoxy group. Alkoxy group; cyano group; or may be substituted with a halogen atom such as a fluorine atom or a chlorine atom.

In addition, G ¹ and G ² are independent of each other, and when the number of carbon atoms is 3 or more, both ends of G ¹ and G ² are −CH ₂ − (both ends of G ¹ and G ² are replaced). Not) is preferable. In addition, "at least one of -CH _2- contained in a divalent aliphatic hydrocarbon group having 3 to 30 carbon atoms is -O-, -S-, -OC (= O)-, -C ( ^{= O) -O -, - O} -C (= O) -O -, - NR 17 -C (= O) -, - C (= O) -NR 17 -, - NR 17 -, or, -C In "groups substituted with (= O)-", -O- and -S- do not replace the contiguous -CH _2- in the aliphatic hydrocarbon group (ie, -O-O- and -S-". It is preferable that it does not form the structure of S- (that is, it is preferable except when two or more -O- or -S- are adjacent to each other), and -C (= O)-is an aliphatic hydrocarbon. It is preferable not to replace the continuous −CH ₂₋ in the hydrogen group (that is, not to form the −C (= O) −C (= O) − structure). R ¹⁷ is the same as described above, and a preferred example thereof is also the same as described above.

G ¹ and G ² are independently contained in (i) "divalent aliphatic hydrocarbon group having 1 to 18 carbon atoms and divalent aliphatic hydrocarbon group having 3 to 18 carbon atoms". At least one of -CH _2- is -O-, -S-, -OC (= O)-, -C (= O) -O-, -O-C (= O) -O-, ^{-NR 17 -C (= O) -} , - C (= O) -NR 17 -, - NR 17 -, or, -C (= O) - (preferably, -O -, - S -, - O It is preferably an organic group of any one of −C (= O) −, −C (= O) −O−, or a group substituted with −C (= O) −) ”, (ii). More preferably, it is an alkylene group having 1 to 18 carbon atoms which may have a substituent. R ¹⁷ is the same as described above, and a preferred example thereof is also the same as described above.
The hydrogen atom contained in the organic group of G ¹ and G ² is an alkyl group having 1 to 5 carbon atoms such as a methyl group, an ethyl group and a propyl group; and 1 to 5 carbon atoms such as a methoxy group, an ethoxy group and a propoxy group. Alkoxy group; cyano group; or; may be substituted with a halogen atom such as a fluorine atom or a chlorine atom.
Examples of the substituent of the alkylene group having 1 to 18 carbon atoms include 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. Group; cyano group; or; halogen atom such as fluorine atom, chlorine atom;

<< P ¹ and P ² >>
In formulas (V) and (VI), P ¹ and P ² each independently represent an alkenyl group having 2 to 10 carbon atoms which may be substituted with a halogen atom or a methyl group.
Examples of the alkenyl group having 2 to 10 carbon atoms of the alkenyl group having 2 to 10 carbon atoms which may have a substituent include a vinyl group, a propenyl group, an isopropenyl group, a butenyl group, an isobutenyl group, a pentenyl group and a hexenyl group. , Heptenyl group, octenyl group, nonenyl group, decenyl group and the like. P ¹ and ^{P 2} are each _{independently,} CH 2 = CH- (vinyl _{group), CH 2 = C (CH} 3) -, _{or, CH 2 = C (Cl)} - it is preferably, CH ₂ = CH- (vinyl group) is more preferable.

<< n and m >>
In formula (V) and formula (VI), n and m are independently 0 or 1, respectively, and 1 is more preferable independently.
When both n and m are 1, B ¹ and B ² in the above-mentioned formulas (V) and (VI) are cyclic aliphatic groups which may independently have a substituent. It is preferably a cyclic aliphatic group having 5 to 20 carbon atoms which may have a substituent.

<< Polymerizable compound represented by formula (VI) >>
The main chain portion of the polymerizable compound represented by the formula (VI) is not particularly limited, but has a target structure centered on Ar (that is, Y ¹ and Y ² , A ¹ and A). ² , Y ³ and Y ⁴ , B ¹ and B ² , n and m, Y ⁵ and Y ⁶ , G ¹ and G ² , Y ⁷ and Y ⁸ , P ¹ and P ² are the same (Ar It is the target as the center))) is preferable.

（式中、Ｒ^１〜Ｒ^４、Ａｒ、Ｑ、Ｘ、Ｙ^１〜Ｙ^８、Ａ^１、Ａ^２、Ｂ^１、Ｂ^２、Ｇ^１、Ｇ^２、Ｐ^１、Ｐ^２、ｎ、ｍ、Ｒａ、Ｙ、および、Ｇａは、それぞれ前記と同じ意味を表し、その好適例も前記と同じである。

（式中、Ｒ^１〜Ｒ^４、Ａｒ、Ｑ、Ｘ、Ｙ^１〜Ｙ^８、Ａ^１、Ａ^２、Ｂ^１、Ｂ^２、Ｇ^１、Ｇ^２、Ｐ^１、Ｐ^２、ｎ、ｍ、および、Ｇｂは、それぞれ前記と同じ意味を表し、その好適例も前記と同じである。）

（式（ＩＩＩ−１）および（ＩＩＩ−２）中、Ｙ^１〜Ｙ^８、Ａ^１、Ａ^２、Ｂ^１、Ｂ^２、Ｇ^１、Ｇ^２、Ｐ^１、Ｐ^２、Ｙ、Ｒ^１〜Ｒ^４、Ｑ、Ｒ^０、ｎ、ｍ、およびｐ１は前記と同じ意味を表し、その好適例も前記と同じである。ｐおよびｐ２は、ｐ１と同じ意味を表し、その好適例もｐ１の好適例と同じである。The polymerizable compound represented by the formula (VI) is preferably a polymerizable compound represented by any of the following formulas (VII-1) and (VII-2), and the following formula (III-1), It is more preferably a polymerizable compound represented by any one of (III-2), (III-3) and (III-4), and particularly preferably the following formula (III-1).

(In the formula, R ^{1 to} R ⁴ , Ar, Q, X, Y ^{1 to} Y ⁸ , A ¹ , A ² , B ¹ , B ² , G ¹ , G ² , P ¹ , P ² , n, m, Ra, Y, and Ga have the same meanings as described above, and preferred examples thereof are also the same as described above.

(In the formula, R ^{1 to} R ⁴ , Ar, Q, X, Y ^{1 to} Y ⁸ , A ¹ , A ² , B ¹ , B ² , G ¹ , G ² , P ¹ , P ² , n, m, And Gb have the same meanings as described above, and preferred examples thereof are also the same as described above.)

(Formula (III-1) and (III-2) ^{in, Y 1 ~Y 8, A 1} , A 2, B 1, B 2, G 1, G 2, P 1, P 2, Y, R 1 ~ ^{R 4, Q, R 0,} n, m, and p1 are as defined above, the preferred embodiment .p and p2 is also the same as above, the same meanings as p1, its preferred examples are also the p1 It is the same as a preferable example.

In formulas (III-1) and (III-2), Ga has 1 to 18 carbon atoms which may have a substituent, preferably an alkylene group having 3 to 18 carbon atoms, and 3 to 18 carbon atoms. At least one of -CH _2- contained in the alkylene group of is -O-, -S-, -OC (= O)-, -C (= O) -O-, or -C (= O). ) Represents an organic group of any of the groups substituted with −, except when two or more −O− or −S− are adjacent to each other. Here, as the substituent having the organic group of Ga, an alkyl group having 1 to 5 carbon atoms such as a methyl group, an ethyl group and a propyl group; and an alkyl group having 1 to 5 carbon atoms such as a methoxy group, an ethoxy group and a propoxy group. Examples thereof include an alkoxy group; a cyano group; a halogen atom such as a fluorine atom and a chlorine atom.
Incidentally, formula (III-1) and in (III-2), when the number of carbon atoms of the Ga is 3 or more, both ends of Ga is -CH ₂ - (the both ends of the Ga are not substituted) be It is preferable that −C (= O) − does not replace the continuous −CH ₂₋ in Ga (that is, it does not form the structure of −C (= O) −C (= O) −). preferable.
Further, in the formulas (III-1) and (III-2), Ga is preferably an unsubstituted alkylene group having 4 to 16 carbon atoms, more preferably an unsubstituted alkylene group having 5 to 14 carbon atoms, and has a carbon number of 5 to 14. An unsubstituted alkylene group of 6 to 12 is particularly preferable, and an unsubstituted alkylene group having 6 to 10 carbon atoms is most preferable.
In formulas (III-1) and (III-2), Ra ¹ and Ra ² are cyclic groups having 2 to 30 carbon atoms, each independently having one of an aromatic hydrocarbon ring and an aromatic heterocycle. Yes,
In formulas (III-1) and (III-2), the number of π electrons contained in the ring structure in Ra ¹ is preferably 8 or more, and the number of π electrons contained in the ring structure in Ra ² is It is preferably 4 or more, more preferably the number of π electrons contained in the ring structure in Ra ¹ is 8 or more, and the number of π electrons contained in the ring structure in Ra ² is 6 or more. Is more preferable.
In formulas (III-1) and (III-2), the preferred examples of Ra ¹ and Ra ² are the same as the preferred examples of Ra.

As a combination of Ga, Y, and Ra ^{1 in} the formula (III-1),
(I) At least one of -CH _2- contained in the alkylene group having 1 to 18 carbon atoms (preferably 3 to 18 carbon atoms) and the alkylene group having 3 to 18 carbon atoms in Ga is -O-, Groups substituted with -S-, -OC (= O)-, -C (= O) -O-, or -C (= O)-(where -O- or -S- are respectively. (Except when two or more are adjacent to each other), any of the organic groups
Y is a chemical single bond, -O-Z, -O-CRbRc -Z, -CRbRc-O-Z, -O-CH 2 -CH 2 -Z, -CH 2 -CH 2 -O-Z, -C (= O) -O-Z, -O-C (= O) -Z, -CH _2- CH ₂ -C (= O) -O-Z, -O-C (= O) -CH ₂ -CH _2- Z, -C (= O) -O-CRbRc-Z, -CRbRc-OC (= O) -Z, -OC (= O) -CRbRc-Z, -CRbRc-C ( = O) -O-Z, -NR ^14- C (= O) -O-Z, or -S-CH _2- C (= O) -O-Z (however, R ¹⁴ , Rb, Rc has the same meaning as above, and Z indicates the direction of binding to Ga.)
Ra ¹ is a cyclic group having 8 or more π electrons contained in the ring structure, preferably in combination.
(II) At least one of -CH _2- contained in an alkylene group having 1 to 18 carbon atoms (preferably 3 to 18 carbon atoms) and an alkylene group having 3 to 18 carbon atoms in Ga is -O-, It is an organic group of either -C (= O)-or a group substituted with -S- (except when two or more -O- or -S- are adjacent to each other).
Y is a chemical single bond, -O-Z, -CRbRc-O-Z, -CH _2- CH _2- O-Z, -C (= O) -O-Z, -OC (= O) ) -Z, -CH _2- CH _2- C (= O) -O-Z, -CRbRc-OC (= O) -Z, -CRbRc-C (= O) -O-Z, -NR ¹⁴ -C (= O) -O-Z or _a -S-CH 2 -C (= O ) -O-Z, ( provided ^that, R 14, Rb, Rc are as defined above, Z is It shows the direction of binding with Ga.)
A combination in which Ra ¹ is a cyclic group having 8 or more π electrons contained in the ring structure is more preferable.
(III) Ga is an alkylene group having 1 to 18 carbon atoms (preferably 3 to 18 carbon atoms).
As Ra ^1- Y-, the combination of the above formulas (ii-1) to (ii-35) is more preferable (however, J in the group is -CH _2- , -NR ^d- , oxygen atom, sulfur. It represents an atom, -SO- or -SO _2- (R ^d represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms), and ● in the group indicates a bond site with Ga.)
(IV) Ga is an alkylene group having 1 to 18 carbon atoms (preferably 3 to 18 carbon atoms), and as Ra ¹ −Y−, the above formulas (iii-1) to (iii−33), (iii− 44) to (iii-46) are particularly preferred. (However, J in the group represents -CH _2- , -NR ^d- , oxygen atom, sulfur atom, -SO- or -SO _2- (R ^d is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. ), ● in the base indicates the binding site with Ga.)

As a combination of Ga, Y, and Ra ^{2 in} the formula (III-2),
(I) At least one of -CH _2- contained in the alkylene group having 1 to 18 carbon atoms (preferably 3 to 18 carbon atoms) and the alkylene group having 3 to 18 carbon atoms in Ga is -O-, Groups substituted with -S-, -OC (= O)-, -C (= O) -O-, or -C (= O)-(where -O- or -S- are respectively. (Except when two or more are adjacent to each other), any of the organic groups
Y is a chemical single bond, -O-Z, -O-CRbRc -Z, -CRbRc-O-Z, -O-CH 2 -CH 2 -Z, -CH 2 -CH 2 -O-Z, -C (= O) -O-Z, -O-C (= O) -Z, -CH _2- CH ₂ -C (= O) -O-Z, -O-C (= O) -CH ₂ -CH _2- Z, -C (= O) -O-CRbRc-Z, -CRbRc-OC (= O) -Z, -OC (= O) -CRbRc-Z, -CRbRc-C ( = O) -O-Z, -NR ^14- C (= O) -O-Z, or -S-CH _2- C (= O) -O-Z (however, R ¹⁴ , Rb, Rc has the same meaning as above, and Z indicates the direction of binding to Ga.)
Ra ² is a cyclic group having 6 or more π electrons contained in the ring structure, preferably in combination.
(II) At least one of -CH _2- contained in an alkylene group having 1 to 18 carbon atoms (preferably 3 to 18 carbon atoms) and an alkylene group having 3 to 18 carbon atoms in Ga is -O-, It is an organic group of either -C (= O)-or a group substituted with -S- (except when two or more -O- or -S- are adjacent to each other).
Y is a chemical single bond, -O-Z, -CRbRc-O-Z, -CH _2- CH _2- O-Z, -C (= O) -O-Z, -OC (= O) ) -Z, -CH _2- CH _2- C (= O) -O-Z, -CRbRc-OC (= O) -Z, -CRbRc-C (= O) -O-Z, -NR ¹⁴ -C (= O) -O-Z or _a -S-CH 2 -C (= O ) -O-Z, ( provided ^that, R 14, Rb, Rc are as defined above, Z is It shows the direction of binding with Ga.)
Ra ² is a cyclic group having 6 or more π electrons contained in the ring structure, more preferably in combination.
(III) Ga is an alkylene group having 1 to 18 carbon atoms (preferably 3 to 18 carbon atoms).
Ra ^2- Y- is more preferably given by the above formulas (ii-1) to (ii-45) (however, J in the group is -CH _2- , -NR ^d- , oxygen atom, sulfur. It represents an atom, -SO- or -SO _2- (R ^d represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms), and ● in the group indicates a bond site with Ga).
(IV) Ga is an alkylene group having 1 to 18 carbon atoms (preferably 3 to 18 carbon atoms), and Ra ^2- Y− may be of the above formulas (iii-1) to (iii-46). Especially preferable. (However, J in the group represents -CH _2- , -NR ^d- , oxygen atom, sulfur atom, -SO- or -SO _2- (R ^d is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. ), ● in the base indicates the binding site with Ga.)

（式（ｉｉｉ−１）中、Ｙ^１〜Ｙ^８、Ａ^１、Ａ^２、Ｂ^１、Ｂ^２、Ｇ^１、Ｇ^２、Ｐ^１、Ｐ^２、Ｒ^１〜Ｒ^４、Ｑ、Ｇａ、Ｙ、Ｒａ^１、Ｒ^０、ｍ、ｎおよびｐは前記と同じ意味を表し、その好適例も前記と同じである。）

（式（ｉｉｉ−２）中、Ｒ^１〜Ｒ^４、Ｑ、Ｇａ、Ｙ、およびＲａ^１は前記と同じ意味を表し、その好適例も前記と同じである。ｋおよびｌは、それぞれ独立して、１〜１８の整数を表す。）

Here, the polymerizable compound represented by the above formula (III-1) is preferably a polymerizable compound represented by the following formula (iii-1), and is represented by the following formula (iii-2). It is more preferable that it is a polymerizable compound, and it is particularly preferable that it is any of the following formulas (1) to (21).

(In the formula (iii-1), Y ^{1 to} Y ⁸ , A ¹ , A ² , B ¹ , B ² , G ¹ , G ² , P ¹ , P ² , R ^{1 to} R ⁴ , Q, Ga, Y. , Ra ¹ , R ⁰ , m, n and p have the same meanings as described above, and preferred examples thereof are also the same as described above.)

(In the formula (iii-2), R ^{1 to} R ⁴ , Q, Ga, Y, and Ra ¹ have the same meanings as described above, and the preferred examples thereof are also the same as described above. K and l are independent of each other. Represents an integer from 1 to 18.

In formulas (III-3) and (III-4), Gb is an alkyl group, an alkynyl group, or an alkenyl group having 1 to 18 carbon atoms, preferably 3 to 18 carbon atoms, which may have a substituent. , And at least one of -CH _2- contained in an alkyl group, an alkynyl group, or an alkenyl group having 3 to 18 carbon atoms is -O-, -S-, -OC (= O)-,-. Represents an organic group of either C (= O) -O- or a group substituted with -C (= O) -, but with two or more adjacent -O- or -S-, respectively. Except when doing. Here, as the substituent contained in the organic group of Gb, a hydroxyl group; an alkyl group having 1 to 5 carbon atoms such as a methyl group, an ethyl group and a propyl group; and 1 to 1 carbon atoms such as a methoxy group, an ethoxy group and a propoxy group. An alkoxy group of 5; a cyano group ;; a halogen atom such as a fluorine atom and a chlorine atom can be mentioned.
In the formulas (III-3) and (III-4), when the number of carbon atoms of Gb is 3 or more, one end of Gb (bonding side with Hal) is −CH ₂ − (one end of Gb). but it has not been replaced) is preferred, and, -C (= O) - is, successive -CH ₂ in Gb - not replace (i.e., -C (= O) -C ( = O) - of It does not form a structure).
Further, in the formulas (III-3) and (III-4), Gb is preferably an unsubstituted alkyl group, an alkynyl group, or an alkenyl group having 4 to 16 carbon atoms, and is optionally unsubstituted having 5 to 14 carbon atoms. , Alkyl group, alkynyl group, or alkenyl group is more preferable, and an unsubstituted alkyl group having 6 to 12 carbon atoms, an alkynyl group, or an alkenyl group is particularly preferable, and an unsubstituted alkyl group having 6 to 10 carbon atoms, Alkynyl groups or alkenyl groups are most preferred.

（式（ｉｉｉ−３）中、Ｙ^１〜Ｙ^８、Ａ^１、Ａ^２、Ｂ^１、Ｂ^２、Ｇ^１、Ｇ^２、Ｐ^１、Ｐ^２、Ｒ^１〜Ｒ^４、Ｑ、Ｇｂ、Ｒ^０、ｍ、ｎおよびｐは前記と同じ意味を表し、その好適例も前記と同じである。）

（式（ｉｉｉ−４）中、Ｒ^１〜Ｒ^４、Ｑ、およびＧｂは前記と同じ意味を表し、その好適例も前記と同じである。ｋおよびｌは、それぞれ独立して、１〜１８の整数を表す。）

Here, the polymerizable compound represented by the above formula (III-3) is preferably a polymerizable compound represented by the following formula (iii-3), and is represented by the following formula (iii-4). It is more preferable that it is a polymerizable compound, and it is particularly preferable that it is any of the following formulas (22) to (29).

(In the formula ^{(iii-3), Y 1} ~Y 8, A 1, A 2, B 1, B 2, G 1, G 2, P 1, P 2, R 1 ~R 4, Q, Gb, R ⁰ , m, n and p have the same meanings as described above, and preferred examples thereof are also the same as described above.)

(In the formula ^{(iii-4), R 1} ~R 4, Q, and Gb are as defined above, the preferred examples are also the same as the .k and l are each independently 1 to 18 Represents an integer of.)

The polymerizable compound represented by the above formula (VI) can be synthesized by combining known synthetic reactions. That is, various documents (for example, International Publication No. 12/141245, International Publication No. 12/147904, International Publication No. 13/046781, International Publication No. 13/180217, International Publication No. 14/061709, International Publication No. 14/065176, International Publication 14/126113, International Publication No. 15/025793, International Publication No. 15/0646998, International Publication No. 15-140302, International Publication No. 15/129654, International Publication No. 15 It can be synthesized by referring to the method described in / 141784, International Publication No. 16/159193, International Publication No. 17-134139, International Publication No. 17/150622) and the like.

<Reaction between 1,1-di-substituted hydrazine compound and compound (V)>
The reaction between the 1,1-di-substituted hydrazine compound and compound (V) is, for example, a halogen-based solvent such as chloroform; a hydrocarbon-based solvent such as toluene; an alcohol-based solvent such as ethanol; ethers such as tetrahydrofuran and cyclopentylmethyl ether. It is carried out in an organic solvent generally used for organic synthesis such as a system solvent. Further, these two or more types may be mixed and used.
The amount of the organic solvent used is not particularly limited, but is preferably 0.1 mL or more, more preferably 0.5 mL or more, and 1 mL or more per 1 g of the 1,1-di-substituted hydrazine compound. It is particularly preferably 50 mL or less, more preferably 40 mL or less, even more preferably 20 mL or less, and particularly preferably 15 mL or less.

The reaction temperature is usually −10 ° C. or higher, which is lower than the boiling point of the solvent used, preferably 20 ° C. or higher, more preferably 40 ° C. or higher, particularly preferably 45 ° C. or higher, and 100 ° C. or lower. It is preferably 80 ° C. or lower, more preferably 60 ° C. or lower. The reaction time is usually several minutes to several hours, depending on the scale of the reaction.
The reaction is preferably carried out in an inert atmosphere such as in a nitrogen stream.

The ratio of the 1,1-di-substituted hydrazine compound to the compound (V) is preferably 1: 0.5 to 1: 2 in terms of molar ratio, preferably 1: 0.5 to 1: 1.5. It is more preferable that there is, and it is particularly preferable that it is 1: 0.5 to 1: 1. By carrying out the reaction at such a usage ratio, the desired product can be obtained in good yield.

The reaction rate of the 1,1-di-substituted hydrazine compound and compound (V) can be improved by the presence of an acid. For example, it is carried out in the organic solvent in the presence of an aqueous solution of a sulfonic acid compound such as (±) -10-camphorsulfonic acid or an inorganic acid such as an aqueous hydrochloric acid solution.
Specifically, the (α) 1,1-di-substituted hydrazine compound is dissolved in the organic solvent, the compound (V) and an aqueous solution of a sulfonic acid compound or an inorganic acid are added thereto, and the whole content is stirred. A method in which the (β) compound (V) is dissolved in the organic solvent, a 1,1-di-substituted hydrazine compound and an aqueous solution of a sulfonic acid compound or a mechanical acid are added thereto, and the whole content is stirred. , (Γ) 1,1-Disubstituted hydrazine compound and compound (V) are dissolved in the organic solvent, an aqueous solution of a sulfonic acid compound or an inorganic acid is added thereto, and the whole content is stirred, (δ). After carrying out the reaction for producing the compound (V), a method of adding the 1,1-di-substituted hydrazine compound and an aqueous solution of a sulfonic acid compound or an inorganic acid to the reaction solution as it is and stirring the whole content is mentioned. The methods (γ) and (δ) are preferable, and the method (δ) is more preferable.

In the method (γ), the 1,1-disubstituted hydrazine compound and the compound (V) may be added to the organic solvent at the same time, or the compound (V) may be added to the solution of the 1,1-di substituted hydrazine compound. Or 1,1-disubstituted hydrazine compound may be added to the organic solution of compound (V), but 1,1-di-substituted hydrazine compound and compound (V) may be used as an organic solvent. It is preferable to add them at the same time.
Further, the 1,1-di-substituted hydrazine compound may be added as it is, or a 1,1-di-substituted hydrazine compound dissolved in the organic solvent may be added.
Further, the compound (V) may be added as it is, or a compound (V) in which the compound (V) is dissolved in the organic solvent may be added.
In the method (δ), the 1,1-di-substituted hydrazine compound may be added to the reaction solution as a solid, or may be added after being dissolved in the organic solvent, but may be added as a solid. preferable.
Further, in any of the methods, the sulfonic acid-based compound may be added in a solid state, or a sulfonic acid-based compound dissolved (suspended) in a mixed solvent may be added.
Then, in any of the methods, an aqueous solution of the 1,1-di-substituted hydrazine compound and the compound (V) and the sulfonic acid-based compound or the inorganic acid may be added dropwise as needed.

After completion of the reaction, the desired product can be isolated by performing a normal post-treatment operation in synthetic organic chemistry. In the present invention, for example, the reaction solution is put into water, extracted with an organic solvent such as ethyl acetate, the organic layer is dried over anhydrous sodium sulfate or the like, sodium sulfate or the like is filtered off, and the organic solvent is separated from the filtrate. By purifying the solid obtained by distillation under reduced pressure by column chromatography, a high-purity target product can be easily obtained in high yield. Further, a method of precipitating the target substance by putting the reaction solution into water, extracting with an organic solvent such as ethyl acetate, cooling the organic layer, or adding a poor solvent is more convenient. In addition, a high-purity target product can be obtained in high yield.

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

According to the method for producing a polymerizable compound of the present invention, an easily available hydradino compound (I) is used as a starting material, and an inexpensive reagent is used to achieve high reaction selectivity, high yield, and safety. A polymerizable compound can be produced.

The polymerizable compound produced by the method for producing a polymerizable compound of the present invention can be advantageously used, for example, when preparing a polymer constituting an optical film or the like.

<Optical film>
The optical film includes a layer having an optical function. The optical function simply means transmission, reflection, refraction, birefringence, and the like. Here, the optical film can be used for an optical variant, an alignment film for a liquid crystal display element, a color filter, a low-pass filter, an optical polarizing prism, various optical filters, and the like.

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 compound 1)
<Step 1: Synthesis of Intermediate A>

To a three-port reactor equipped with a thermometer, 500.5 g (2.69 mol) of 1-naphthylacetic acid was added to 1049 g of toluene 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 to prepare a solution. The prepared solution was heated using a Dean-Stark apparatus, 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, 742 g of 5.8 mass% sodium bicarbonate water was added to the reaction solution cooled to 25 ° C., and the solution was separated and washed. After the liquid separation, the organic layer was further washed with 500 g of water. After washing, 7 g of a filtration aid (trade name: Rocahelp # 479, manufactured by Mitsui Mining & Smelting Co., Ltd.) was added to the organic layer, and the mixture was stirred at room temperature for 30 minutes and filtered to remove the filtration aid. The solvent was distilled off from the organic layer with a rotary evaporator to obtain 755 g of a light brown oil containing Intermediate A. Quantification by high performance liquid chromatography revealed that the light brown oil containing this intermediate A contained 93.0% by mass of the intermediate A. This light brown oil was not refined and was used as it was in the next reaction (step 2: synthesis of compound 1).

<Step 2: Synthesis of Compound 1>

In a three-port reactor equipped with a thermometer, 59.52 g of light brown oil containing Intermediate A synthesized in Step 1 (55.35 g (0.182 mol) as the net amount of Intermediate A) and 235 g of N-methyl-2-pyrrolidone was added to prepare a uniform solution. To the homogeneous solution was added 25.0 g (0.151 mol) of 2-hydrazinobenzothiazole. Then, 48.18 g (0.227 mol) of tripotassium phosphate was added, and the whole volume was stirred at 100 ° C. for 3 hours. Quantification by high performance liquid chromatography revealed that the following hydrazide compound A was contained in a small amount at this stage. 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 0.5 mol / L citric acid aqueous solution (pH: 1.9), stirred at an internal temperature of 60 ° C. for 30 minutes, and then the aqueous layer was extracted. The pH at that time was 6.8. 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, and 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 Compound 1 as a white solid. The yield was 56.4 mol%. Quantification by high performance liquid chromatography revealed that the following hydrazide compound A was not contained at this stage.

(Example 2: Synthesis of compound 1)
<Step 1: Synthesis of Intermediate A>

To a three-port reactor equipped with a thermometer, 500.5 g (2.69 mol) of 1-naphthylacetic acid was added to 1049 g of toluene 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 to prepare a solution. The prepared solution was heated using a Dean-Stark apparatus, 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, 742 g of 5.8 mass% sodium bicarbonate water was added to the reaction solution cooled to 25 ° C., and the solution was separated and washed. After the liquid separation, the organic layer was further washed with 500 g of water. After washing, 7 g of a filtration aid (trade name: Rocahelp # 479, manufactured by Mitsui Mining & Smelting Co., Ltd.) was added to the organic layer, and the mixture was stirred at room temperature for 30 minutes and filtered to remove the filtration aid. The solvent was distilled off from the organic layer using a rotary evaporator to obtain 755 g of a light brown oil containing Intermediate A. Quantification by high performance liquid chromatography revealed that the light brown oil containing this intermediate A contained 93.0% by mass of the intermediate A. This light brown oil was distilled under reduced pressure to obtain 508 g of Intermediate A as a light yellow oil. The yield was 65.1 mol%.

実施例１のステップ２において、中間体Ａを含む淡茶色オイル５９．５２ｇ（中間体Ａ正味の量として、５５．３５ｇ（０．１８２ｍｏｌ））を用いる代わりに、実施例２のステップ１で合成した淡黄色オイルとしての中間体Ａ５５．３５ｇ（０．１８２ｍｏｌ）を用いたこと以外は、実施例１のステップ２と同様の操作を行い、化合物１を白色固体として４２．０ｇ得た。収率は６４．２モル％であった。<< Step 2: Synthesis of Compound 1 >>

Synthesized in Step 1 of Example 2 instead of using 59.52 g of light brown oil containing Intermediate A (55.35 g (0.182 mol) as the net amount of Intermediate A). The same operation as in Step 2 of Example 1 was carried out except that 55.35 g (0.182 mol) of the intermediate A was used as the light yellow oil, and 42.0 g of Compound 1 was obtained as a white solid. The yield was 64.2 mol%.

(Comparative Example 1: Synthesis of Compound 1)

Instead of using 48.18 g (0.227 mol) of tripotassium phosphate in step 2 of Example 1, 15.45 g (0.227 mol) of sodium ethoxide was used, and in step 2 of Example 1, the reaction was carried out. The same operation as in Example 1 was carried out except that the temperature was changed from 100 ° C. to 60 ° C. to obtain 23.27 g of a pale yellow solid containing compound 1. When the obtained pale yellow solid was quantified by high performance liquid chromatography, it was found that 12.24 g of Compound 1 was contained. The yield of compound 1 was 18.7 mol%. Quantification by high performance liquid chromatography revealed that, in addition to compound 1, two impurities (the following hydroxyl group-containing compound A and hydrazide compound A) were mainly contained.

(Comparative Example 2: Synthesis of Compound 1)
Instead of using 48.18 g (0.227 mol) of tripotassium phosphate in step 2 of Example 1, 12.73 g (0.227 mol) of potassium hydroxide was used, and in step 2 of Example 1, the reaction was carried out. The same operation as in Example 1 was carried out except that the temperature was changed from 100 ° C. to 60 ° C. to obtain 35.31 g of a pale yellow solid containing compound 1. When the obtained pale yellow solid was quantified by high performance liquid chromatography, it was found that 16.96 g of Compound 1 was contained. The yield of compound 1 was 25.9 mol%. Quantification by high performance liquid chromatography revealed that, in addition to compound 1, two impurities (the following hydroxyl group-containing compound A and hydrazide compound A) were mainly contained.

(Example 3: Synthesis of polymerizable compound 1)

温度計を備えた３口反応器において、窒素気流中、トランス−１，４−シクロヘキサンジカルボン酸ジクロライド８３．０５ｇ（０．４０ｍｏｌ）をシクロペンチルメチルエーテル６００ｇに加えて、氷浴下にて５℃に冷却した。この溶液に、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（ＤＫＳＨ社製）１００ｇ（０．３８ｍｏｌ）、２，６−ジターシャーリーブチル−４−メチルフェノール１．６７ｇ、および、テトラヒドロフラン（ＴＨＦ）２３０ｇを加えた。そこへ、強撹拌下にて、トリエチルアミン４０．２ｇ（０．４０ｍｏｌ）をゆっくりと滴下した。滴下終了後、５℃にて、１時間反応を行った。反応終了後、水２５０ｇを加えた後、５０℃に昇温して４時間撹拌した。その後、水層を抜き出して得られた有機層に１ｍｏｌ／Ｌ濃度の酢酸／酢酸ナトリウム緩衝水溶液４１６ｇを加えて３０分撹拌した後、水層を抜き出した。更に、有機層を水２５０ｇで洗浄して得られた有機層を集め、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（容積比））により精製することで、中間体Ｂを白色固体として７５ｇ得た。収率は４７．４モル％であった。中間体Ｂの構造は^１Ｈ−ＮＭＲで同定した。^１Ｈ−ＮＭＲスペクトルデータを下記に示す。<Step 1: Synthesis of Intermediate B>

In a three-port reactor equipped with a thermometer, 83.05 g (0.40 mol) of trans-1,4-cyclohexanedicarboxylic acid dichloride was added to 600 g of cyclopentyl methyl ether in a nitrogen stream to 5 ° C. under an ice bath. Cooled. In this solution, 100 g (0.38 mol) of 4- (6-acryloyloxy-hex-1-yloxy) phenol (manufactured by DKSH), 1.67 g of 2,6-diter shirley butyl-4-methylphenol, and tetrahydrofuran. 230 g of (THF) was added. To there, 40.2 g (0.40 mol) of triethylamine was slowly added dropwise under strong stirring. After completion of the dropping, the reaction was carried out at 5 ° C. for 1 hour. After completion of the reaction, 250 g of water was added, the temperature was raised to 50 ° C., and the mixture was stirred for 4 hours. Then, 416 g of a 1 mol / L concentration acetic acid / sodium acetate buffered aqueous solution was added to the organic layer obtained by extracting the aqueous layer, and the mixture was stirred for 30 minutes, and then the aqueous layer was extracted. Further, the organic layer obtained by washing the organic layer with 250 g of water 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)) to obtain 75 g of intermediate B as a white solid. Obtained. The yield was 47.4 mol%. The structure of Intermediate B was identified by ^{1 1} H-NMR. ^{1 1} H-NMR spectrum data is shown below.

^{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).

温度計を備えた３口反応器において、窒素気流中、前記ステップ１で合成した中間体Ｂ：１０．００ｇ（２３．９０ｍｍｏｌ）、２，５−ジヒドロキシベンズアルデヒド１．３２ｇ（９．５６ｍｍｏｌ）、および４−（ジメチルアミノ）ピリジン２３４ｍｇ（１．９２ｍｍｏｌ）をクロロホルム８０ｍＬに加えた。室温下にて、Ｎ，Ｎ’−ジイソプロピルカルボジイミド３．２ｇ（２５．３６ｍｍｏｌ）をゆっくりと滴下した。滴下終了後、２３℃にて３時間撹拌した。反応終了後、反応液を直接シリカゲルカラムクロマトグラフィー（クロロホルムのみからクロロホルム：ＴＨＦ＝９：１（容積比）にグラジエント）により精製することで、中間体Ｃを白色固体として６．８０ｇ得た。収率は７５．７モル％であった。中間体Ｃの構造は^１Ｈ−ＮＭＲで同定した。^１Ｈ−ＮＭＲスペクトルデータを下記に示す。<Step 2: Synthesis of Intermediate C>

Intermediate B: 10.00 g (23.90 mmol), 2,5-dihydroxybenzaldehyde 1.32 g (9.56 mmol), and 2.5-dihydroxybenzaldehyde synthesized in step 1 in a nitrogen stream in a three-port reactor equipped with a thermometer. 234 mg (1.92 mmol) of 4- (dimethylamino) pyridine was added to 80 mL of chloroform. At room temperature, 3.2 g (25.36 mmol) of N, N'-diisopropylcarbodiimide was slowly added dropwise. After completion of the dropping, the mixture was stirred at 23 ° C. for 3 hours. After completion of the reaction, the reaction solution was directly purified by silica gel column chromatography (diient from chloroform only to chloroform: THF = 9: 1 (volume ratio)) to obtain 6.80 g of Intermediate C as a white solid. The yield was 75.7 mol%. The structure of Intermediate C was identified by ^{1 1} H-NMR. ^{1 1} H-NMR spectrum data is shown below.

¹ H-NMR (500 MHz, DMSO-d ₆ , TMS, δppm): 10.02 (s, 1H), 7.67 (d, 1H, J = 3.0Hz), 7.55 (dd, 1H, J) = 3.0Hz, 8.5Hz), 7.38 (d, 1H, J = 8.5Hz), 6.99-7.04 (m, 4H), 6.91-6.96 (m, 4H) , 6.32 (dd, 2H, J = 1.5Hz, 17.5Hz), 6.17 (dd, 2H, J = 10.0Hz, 17.5Hz), 5.93 (dd, 2H, J = 1) .5Hz, 10.0Hz), 4.11 (t, 4H, J = 6.5Hz), 3.95 (t, 4H, J = 6.5Hz), 2.56-2.81 (m, 4H) , 2.10-2.26 (m, 8H), 1.50-1.76 (m, 16H), 1.33-1.49 (m, 8H).

<Step 3: Synthesis of polymerizable compound 1>
In a three-port reactor equipped with a thermometer, compound 1: 3.6 g (8.31 mmol) synthesized in Example 1 and intermediate C: 6.00 g (synthesized in step 2) were synthesized in a nitrogen stream in a nitrogen stream. 6.39 mmol) was dissolved in 12.0 mL of ethanol and 120 mL of THF. To this solution was added 0.30 g (1.28 mmol) of (±) -10-camphorsulfonic acid, and the whole volume was stirred at 50 ° C. for 4 hours. After completion of the reaction, the reaction solution was put into 200 mL of distilled water and extracted twice with 200 mL of ethyl acetate. The ethyl acetate layer was dried over anhydrous sodium sulfate, and then sodium sulfate was filtered off. Ethyl acetate was distilled off from the filtrate under reduced pressure using a rotary evaporator to obtain a yellow solid. This yellow solid was purified by silica gel column chromatography (chloroform: THF = 95: 5) to obtain 7.8 g of polymerizable compound 1 as a yellow solid. The yield was 90.2 mol%. The structure of the target product (polymerizable compound 1) was identified by ^{1 1} H-NMR. ^{1 1} H-NMR spectrum data is shown below.

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).

In an organic solvent containing at least one aprotonic polar solvent, the hydradino compound represented by the formula (I) is combined with the compound represented by the formula (III): R-Hal in the presence of a predetermined phosphoric acid-based compound. The method for producing the 1,1-di-substituted hydrazine compounds (yield: 56.4 mol% to 64.2 mol%) of the reacted Examples 1 and 2 is a comparative example in which a predetermined phosphoric acid-based compound is not used. Compared with the methods for producing the 1,1-di-substituted hydrazine compounds 1 and 2 (yield: 18.7 mol% to 25.9 mol%), the 1,1-di-substituted hydrazine compound which is the target product was obtained. It turned out that it could be manufactured efficiently.

温度計を備えた３口反応器に、窒素気流中、２−ヒドラジノベンゾチアゾール１００ｇ（０．６０５ｍｏｌ）をＮ，Ｎ−ジメチルホルムアミド７５０ｇに加えた。次いで、１−ブロモヘキサン１１９．９ｇ（０．７２６ｍｏｌ）を加えた。この溶液にリン酸三カリウム１９２．７２ｇ（０．９０８ｍｏｌ）を加え、全容を１００℃で３時間攪拌した。高速液体クロマトグラフによる定量により、この段階では、下記の１，２置換された化合物Ｂが少量含まれていることが分かった。反応終了後、６０℃に降温した反応液にトルエン７５０ｇ、水７５０ｇを加えた後、６０℃を維持して、１５分間撹拌した。反応液を静置すると、三層に分離した。下層の二層を抜き出した。得られたトルエン層に１０質量％の塩化ナトリウム水溶液４３０ｇを加えて６０℃を維持して、１５分間撹拌した。水層を分液した後、得られた有機層を減圧下にて濃縮を行い、トルエン５６０ｇを抜き出した。濃縮後の有機層を６０℃に昇温し、水５００ｇを加えて、強撹拌しながら徐々に冷却した。０℃に到達した後、そのままの温度で１時間強撹拌した。このスラリー溶液をろ過した。得られた湿固体を５℃以下に冷却した水／メタノール＝１／４（質量比）の混合溶媒５００ｇを用いてかけ洗いして洗浄した。得られた湿固体を真空乾燥機で減圧乾燥させることで、化合物２を白色固体として１３２．８ｇ得た。収率は８８モル％であった。高速液体クロマトグラフによる定量により、この段階では、下記の１，２置換された化合物Ｂが含まれていないことが分かった。高速液体クロマトグラフによる純度は、９９％以上であった。

(Example 4: Synthesis of compound 2)

To a three-port reactor equipped with a thermometer, 100 g (0.605 mol) of 2-hydrazinobenzothiazole was added to 750 g of N, N-dimethylformamide in a nitrogen stream. Then 119.9 g (0.726 mol) of 1-bromohexane was added. 192.72 g (0.908 mol) of tripotassium phosphate was added to this solution, and the whole volume was stirred at 100 ° C. for 3 hours. Quantification by high performance liquid chromatography revealed that the following 1,2-substituted compound B was contained in a small amount at this stage. After completion of the reaction, 750 g of toluene and 750 g of water were added to the reaction solution cooled to 60 ° C., and then the mixture was stirred at 60 ° C. for 15 minutes. When the reaction solution was allowed to stand, it was separated into three layers. The lower two layers were extracted. 430 g of a 10 mass% sodium chloride aqueous solution was added to the obtained toluene layer, and the mixture was stirred at 60 ° C. for 15 minutes. After separating the aqueous layer, the obtained organic layer was concentrated under reduced pressure to extract 560 g of toluene. The temperature of the concentrated organic layer was raised to 60 ° C., 500 g of water was added, and the mixture was gradually cooled with strong stirring. After reaching 0 ° C., the mixture was stirred at the same temperature for 1 hour. This slurry solution was filtered. The obtained wet solid was washed by sprinkling with 500 g of a mixed solvent of water / methanol = 1/4 (mass ratio) cooled to 5 ° C. or lower. The obtained wet solid was dried under reduced pressure in a vacuum dryer to obtain 132.8 g of Compound 2 as a white solid. The yield was 88 mol%. Quantification by high performance liquid chromatography revealed that the following 1,2-substituted compound B was not contained at this stage. The purity by high performance liquid chromatography was 99% or more.

前記実施例４において、１−ブロモヘキサン１１９．９ｇ（０．７２６ｍｏｌ）を５−ブロモバレロニトリル１１７．６ｇ（０．７２６ｍｏｌ）に変更した以外は、実施例４と同様にして、白色固体として化合物３を１２６．７ｇ得た。収率は８５モル％であった。
全容を１００℃で３時間攪拌した段階では、高速液体クロマトグラフによる定量により、下記の１，２置換された化合物Ｃが少量含まれていることが分かったが、最終的な白色固体を取得した段階では、下記の１，２置換された化合物Ｃが含まれていないことが分かった。高速液体クロマトグラフによる純度は、９９％以上であった。

(Example 5: Synthesis of compound 3)

The compound as a white solid in the same manner as in Example 4 except that 11.9 g (0.726 mol) of 1-bromohexane was changed to 117.6 g (0.726 mol) of 5-bromovaleronitrile in Example 4. 126.7 g of 3 was obtained. The yield was 85 mol%.
At the stage where the whole volume was stirred at 100 ° C. for 3 hours, it was found by quantification by high performance liquid chromatography that a small amount of the following 1,2-substituted compound C was contained, but a final white solid was obtained. At the stage, it was found that the following 1,2-substituted compound C was not contained. The purity by high performance liquid chromatography was 99% or more.

前記実施例４において、１−ブロモヘキサン１１９．９ｇ（０．７２６ｍｏｌ）をブチル２−クロロエチルエーテル９９．２ｇ（０．７２６ｍｏｌ）に変更した以外は、実施例４と同様にして、白色固体として化合物４を１３９．７ｇ得た。収率は８７モル％であった。
全容を１００℃で３時間攪拌した段階では、高速液体クロマトグラフによる定量により、下記の１，２置換された化合物Ｄが少量含まれていることが分かったが、最終的な白色固体を取得した段階では、下記の１，２置換された化合物Ｄが含まれていないことが分かった。高速液体クロマトグラフによる純度は、９９％以上であった。

(Example 6: Synthesis of compound 4)

As a white solid in the same manner as in Example 4 except that 119.9 g (0.726 mol) of 1-bromohexane was changed to 99.2 g (0.726 mol) of butyl 2-chloroethyl ether in Example 4. 139.7 g of Compound 4 was obtained. The yield was 87 mol%.
At the stage where the whole volume was stirred at 100 ° C. for 3 hours, it was found by quantification by high performance liquid chromatography that a small amount of the following 1,2-substituted compound D was contained, but a final white solid was obtained. At the stage, it was found that the following 1,2-substituted compound D was not contained. The purity by high performance liquid chromatography was 99% or more.

前記実施例４において、１−ブロモヘキサン１１９．９ｇ（０．７２６ｍｏｌ）を４−ブロモ−１−ブテン９８．０１ｇ（０．７２６ｍｏｌ）に変更した以外は、実施例４と同様にして、白色固体として化合物５を１１５．４ｇ得た。収率は８７モル％であった。
全容を１００℃で３時間攪拌した段階では、高速液体クロマトグラフによる定量により、下記の１，２置換された化合物Ｅが少量含まれていることが分かったが、最終的な白色固体を取得した段階では、下記の１，２置換された化合物Ｅが含まれていないことが分かった。高速液体クロマトグラフによる純度は、９９％以上であった。

(Example 7: Synthesis of compound 5)

A white solid in the same manner as in Example 4 except that 11.9 g (0.726 mol) of 1-bromohexane was changed to 98.01 g (0.726 mol) of 4-bromo-1-butene in Example 4. As a result, 115.4 g of compound 5 was obtained. The yield was 87 mol%.
When the whole volume was stirred at 100 ° C. for 3 hours, it was found by quantification by high performance liquid chromatography that a small amount of the following 1,2-substituted compound E was contained, but a final white solid was obtained. It was found that the steps did not include the following 1,2-substituted compound E. The purity by high performance liquid chromatography was 99% or more.

前記実施例４において、１−ブロモヘキサン１１９．９ｇ（０．７２６ｍｏｌ）を１−ブロモ−２−ブチン９６．５５ｇ（０．７２６ｍｏｌ）に変更した以外は、実施例４と同様にして、白色固体として化合物６を１０７．０ｇ得た。収率は８７モル％であった。
全容を１００℃で３時間攪拌した段階では、高速液体クロマトグラフによる定量により、下記の１，２置換された化合物Ｆが少量含まれていることが分かったが、最終的な白色固体を取得した段階では、下記の１，２置換された化合物Ｆが含まれていないことが分かった。高速液体クロマトグラフによる純度は、９９％以上であった。

(Example 8: Synthesis of compound 6)

A white solid in the same manner as in Example 4 except that 11.9 g (0.726 mol) of 1-bromohexane was changed to 96.55 g (0.726 mol) of 1-bromo-2-butyne in Example 4. As a result, 107.0 g of compound 6 was obtained. The yield was 87 mol%.
At the stage where the whole volume was stirred at 100 ° C. for 3 hours, it was found by quantification by high performance liquid chromatography that a small amount of the following 1,2-substituted compound F was contained, but a final white solid was obtained. At the stage, it was found that the following 1,2-substituted compound F was not contained. The purity by high performance liquid chromatography was 99% or more.

前記実施例４において、１−ブロモヘキサン１１９．９ｇ（０．７２６ｍｏｌ）を１−ブロモ−２−（２−メトキシエトキシ）エタン１３２．９ｇ（０．７２６ｍｏｌ）に変更した以外は、実施例４と同様にして、白色固体として化合物７を１３４．２ｇ得た。収率は８３モル％であった。全容を１００℃で３時間攪拌した段階では、高速液体クロマトグラフによる定量により、下記の１，２置換された化合物Ｇが少量含まれていることが分かったが、最終的な白色固体を取得した段階では、下記の１，２置換された化合物Ｇが含まれていないことが分かった。高速液体クロマトグラフによる純度は、９９％以上であった。

(Example 9: Synthesis of compound 7)

Example 4 and Example 4 except that 11.9 g (0.726 mol) of 1-bromohexane was changed to 132.9 g (0.726 mol) of 1-bromo-2- (2-methoxyethoxy) ethane. Similarly, 134.2 g of Compound 7 was obtained as a white solid. The yield was 83 mol%. When the whole volume was stirred at 100 ° C. for 3 hours, it was found by quantification by high performance liquid chromatography that a small amount of the following 1,2-substituted compound G was contained, but a final white solid was obtained. At the stage, it was found that the following 1,2-substituted compound G was not contained. The purity by high performance liquid chromatography was 99% or more.

前記実施例４において、１−ブロモヘキサン１１９．９ｇ（０．７２６ｍｏｌ）をエチレングリコールモノ−２−クロロエチルエーテル９０．４ｇ（０．７２６ｍｏｌ）に変更した以外は、実施例４と同様にして、白色固体として化合物８を１２７．２ｇ得た。収率は８３モル％であった。全容を１００℃で３時間攪拌した段階では、高速液体クロマトグラフによる定量により、下記の１，２置換された化合物Ｈが少量含まれていることが分かったが、最終的な白色固体を取得した段階では、下記の１，２置換された化合物Ｈが含まれていないことが分かった。高速液体クロマトグラフによる純度は、９９％以上であった。

(Example 10: Synthesis of compound 8)

In the same manner as in Example 4 except that 11.9 g (0.726 mol) of 1-bromohexane was changed to 90.4 g (0.726 mol) of ethylene glycol mono-2-chloroethyl ether in Example 4. 127.2 g of Compound 8 was obtained as a white solid. The yield was 83 mol%. When the whole volume was stirred at 100 ° C. for 3 hours, it was found by quantification by high performance liquid chromatography that a small amount of the following 1,2-substituted compound H was contained, but a final white solid was obtained. At the stage, it was found that the following 1,2-substituted compound H was not contained. The purity by high performance liquid chromatography was 99% or more.

前記実施例４において、１−ブロモヘキサン１１９．９ｇ（０．７２６ｍｏｌ）を６−クロロ−１−ヘキサノール９９．２ｇ（０．７２６ｍｏｌ）に変更した以外は、実施例４と同様にして、白色固体として化合物９を１３４．９ｇ得た。収率は８４モル％であった。全容を１００℃で３時間攪拌した段階では、高速液体クロマトグラフによる定量により、下記の１，２置換された化合物Ｉが少量含まれていることが分かったが、最終的な白色固体を取得した段階では、下記の１，２置換された化合物Ｉが含まれていないことが分かった。高速液体クロマトグラフによる純度は、９９％以上であった。

(Example 11: Synthesis of compound 9)

A white solid in the same manner as in Example 4 except that 11.9 g (0.726 mol) of 1-bromohexane was changed to 99.2 g (0.726 mol) of 6-chloro-1-hexanol in Example 4. As a result, 134.9 g of compound 9 was obtained. The yield was 84 mol%. At the stage where the whole volume was stirred at 100 ° C. for 3 hours, it was found by quantification by high performance liquid chromatography that a small amount of the following 1, or 2-substituted compound I was contained, but a final white solid was obtained. At the stage, it was found that the following 1,2-substituted compound I was not contained. The purity by high performance liquid chromatography was 99% or more.

前記実施例４において、リン酸三カリウム１９２．７２ｇ（０．９０８ｍｏｌ）をナトリウムエトキシド６１．７９ｇ（０．９０８ｍｏｌ）を用い、また、反応温度を１００℃から８０℃に変更したこと以外は、実施例４と同様の操作を行い、白色固体として化合物２を１２０．７ｇを得た。収率は８０モル％であった。全容を８０℃で３時間攪拌した段階では、高速液体クロマトグラフによる定量により、前記の１，２置換された化合物Ｂが少量含まれていることが分かったが、最終的な白色固体を取得した段階では、前記の１，２置換された化合物Ｂが含まれていないことが分かった。高速液体クロマトグラフによる純度は、９９％以上であった。(Comparative Example 3: Synthesis of Compound 2)

Except that in Example 4, 192.72 g (0.908 mol) of tripotassium phosphate was used and 61.79 g (0.908 mol) of sodium ethoxide was used, and the reaction temperature was changed from 100 ° C. to 80 ° C. The same operation as in Example 4 was carried out to obtain 120.7 g of Compound 2 as a white solid. The yield was 80 mol%. At the stage where the whole volume was stirred at 80 ° C. for 3 hours, it was found by quantification by high performance liquid chromatography that a small amount of the above-mentioned 1,2-substituted compound B was contained, but a final white solid was obtained. At the stage, it was found that the 1,2-substituted compound B was not contained. The purity by high performance liquid chromatography was 99% or more.

前記実施例５において、リン酸三カリウム１９２．７２ｇ（０．９０８ｍｏｌ）をナトリウムエトキシド６１．７９ｇ（０．９０８ｍｏｌ）を用い、また、反応温度を１００℃から８０℃に変更したこと以外は、実施例５と同様の操作を行い、白色固体として化合物３を１１９．２ｇを得た。収率は８０モル％であった。全容を８０℃で３時間攪拌した段階では、高速液体クロマトグラフによる定量により、前記の１，２置換された化合物Ｃが少量含まれていることが分かったが、最終的な白色固体を取得した段階では、前記の１，２置換された化合物Ｃが含まれていないことが分かった。高速液体クロマトグラフによる純度は、９９％以上であった。(Comparative Example 4: Synthesis of Compound 3)

Except that in Example 5, 192.72 g (0.908 mol) of tripotassium phosphate was used and 61.79 g (0.908 mol) of sodium ethoxide was used, and the reaction temperature was changed from 100 ° C. to 80 ° C. The same operation as in Example 5 was carried out to obtain 119.2 g of Compound 3 as a white solid. The yield was 80 mol%. At the stage where the whole volume was stirred at 80 ° C. for 3 hours, it was found by quantification by high performance liquid chromatography that a small amount of the above-mentioned 1,2-substituted compound C was contained, but a final white solid was obtained. At the step, it was found that the 1,2-substituted compound C was not contained. The purity by high performance liquid chromatography was 99% or more.

前記実施例６において、リン酸三カリウム１９２．７２ｇ（０．９０８ｍｏｌ）をナトリウムエトキシド６１．７９ｇ（０．９０８ｍｏｌ）を用い、また、反応温度を１００℃から８０℃に変更したこと以外は、実施例６と同様の操作を行い、白色固体として化合物４を１２６．８ｇを得た。収率は７９モル％であった。全容を８０℃で３時間攪拌した段階では、高速液体クロマトグラフによる定量により、前記の１，２置換された化合物Ｄが少量含まれていることが分かったが、最終的な白色固体を取得した段階では、前記の１，２置換された化合物Ｄが含まれていないことが分かった。高速液体クロマトグラフによる純度は、９９％以上であった。(Comparative Example 5: Synthesis of Compound 4)

Except that in Example 6, 192.72 g (0.908 mol) of tripotassium phosphate was used and 61.79 g (0.908 mol) of sodium ethoxide was used, and the reaction temperature was changed from 100 ° C. to 80 ° C. The same operation as in Example 6 was carried out to obtain 126.8 g of Compound 4 as a white solid. The yield was 79 mol%. At the stage where the whole volume was stirred at 80 ° C. for 3 hours, it was found by quantification by high performance liquid chromatography that a small amount of the above-mentioned 1,2-substituted compound D was contained, but a final white solid was obtained. At the step, it was found that the 1,2-substituted compound D was not contained. The purity by high performance liquid chromatography was 99% or more.

前記実施例７において、リン酸三カリウム１９２．７２ｇ（０．９０８ｍｏｌ）をナトリウムエトキシド６１．７９ｇ（０．９０８ｍｏｌ）を用い、また、反応温度を１００℃から８０℃に変更したこと以外は、実施例７と同様の操作を行い、白色固体として化合物５を１０７．５ｇを得た。収率は８１モル％であった。全容を８０℃で３時間攪拌した段階では、高速液体クロマトグラフによる定量により、前記の１，２置換された化合物Ｅが少量含まれていることが分かったが、最終的な白色固体を取得した段階では、前記の１，２置換された化合物Ｅが含まれていないことが分かった。高速液体クロマトグラフによる純度は、９９％以上であった。(Comparative Example 6: Synthesis of Compound 5)

Except that 192.72 g (0.908 mol) of tripotassium phosphate was used in 61.79 g (0.908 mol) of sodium ethoxide in Example 7, and the reaction temperature was changed from 100 ° C. to 80 ° C. The same operation as in Example 7 was carried out to obtain 107.5 g of Compound 5 as a white solid. The yield was 81 mol%. At the stage where the whole volume was stirred at 80 ° C. for 3 hours, it was found by quantification by high performance liquid chromatography that a small amount of the above-mentioned 1,2-substituted compound E was contained, but a final white solid was obtained. It was found that the step did not contain the 1,2-substituted compound E. The purity by high performance liquid chromatography was 99% or more.

前記実施例８において、リン酸三カリウム１９２．７２ｇ（０．９０８ｍｏｌ）をナトリウムエトキシド６１．７９ｇ（０．９０８ｍｏｌ）を用い、また、反応温度を１００℃から８０℃に変更したこと以外は、実施例８と同様の操作を行い、白色固体として化合物６を９９．６ｇを得た。収率は８１モル％であった。全容を８０℃で３時間攪拌した段階では、高速液体クロマトグラフによる定量により、前記の１，２置換された化合物Ｆが少量含まれていることが分かったが、最終的な白色固体を取得した段階では、前記の１，２置換された化合物Ｆが含まれていないことが分かった。高速液体クロマトグラフによる純度は、９９％以上であった。(Comparative Example 7: Synthesis of Compound 6)

Except that in Example 8, 192.72 g (0.908 mol) of tripotassium phosphate was used and 61.79 g (0.908 mol) of sodium ethoxide was used, and the reaction temperature was changed from 100 ° C. to 80 ° C. The same operation as in Example 8 was carried out to obtain 99.6 g of Compound 6 as a white solid. The yield was 81 mol%. At the stage where the whole volume was stirred at 80 ° C. for 3 hours, it was found by quantification by high performance liquid chromatography that a small amount of the above-mentioned 1,2-substituted compound F was contained, but a final white solid was obtained. It was found that the step did not contain the 1,2-substituted compound F. The purity by high performance liquid chromatography was 99% or more.

前記実施例９において、リン酸三カリウム１９２．７２ｇ（０．９０８ｍｏｌ）をナトリウムエトキシド６１．７９ｇ（０．９０８ｍｏｌ）を用い、また、反応温度を１００℃から８０℃に変更したこと以外は、実施例９と同様の操作を行い、白色固体として化合物７を１１０．０ｇを得た。収率は６８モル％であった。全容を８０℃で３時間攪拌した段階では、高速液体クロマトグラフによる定量により、前記の１，２置換された化合物Ｇが少量含まれていることが分かったが、最終的な白色固体を取得した段階では、前記の１，２置換された化合物Ｇが含まれていないことが分かった。高速液体クロマトグラフによる純度は、９９％以上であった。(Comparative Example 8: Synthesis of Compound 7)

Except that in Example 9, 192.72 g (0.908 mol) of tripotassium phosphate was used and 61.79 g (0.908 mol) of sodium ethoxide was used, and the reaction temperature was changed from 100 ° C. to 80 ° C. The same operation as in Example 9 was carried out to obtain 110.0 g of Compound 7 as a white solid. The yield was 68 mol%. At the stage where the whole volume was stirred at 80 ° C. for 3 hours, it was found by quantification by high performance liquid chromatography that a small amount of the above-mentioned 1,2-substituted compound G was contained, but a final white solid was obtained. At the step, it was found that the 1,2-substituted compound G was not contained. The purity by high performance liquid chromatography was 99% or more.

前記実施例１０において、リン酸三カリウム１９２．７２ｇ（０．９０８ｍｏｌ）をナトリウムエトキシド６１．７９ｇ（０．９０８ｍｏｌ）を用い、また、反応温度を１００℃から８０℃に変更したこと以外は、実施例１０と同様の操作を行い、白色固体として化合物８を１０１．２ｇを得た。収率は６６モル％であった。全容を８０℃で３時間攪拌した段階では、高速液体クロマトグラフによる定量により、前記の１，２置換された化合物Ｈが少量含まれていることが分かったが、最終的な白色固体を取得した段階では、前記の１，２置換された化合物Ｈが含まれていないことが分かった。高速液体クロマトグラフによる純度は、９９％以上であった。(Comparative Example 9: Synthesis of Compound 8)

Except that in Example 10, 192.72 g (0.908 mol) of tripotassium phosphate was used and 61.79 g (0.908 mol) of sodium ethoxide was used, and the reaction temperature was changed from 100 ° C. to 80 ° C. The same operation as in Example 10 was carried out to obtain 101.2 g of Compound 8 as a white solid. The yield was 66 mol%. At the stage where the whole volume was stirred at 80 ° C. for 3 hours, it was found by quantification by high performance liquid chromatography that a small amount of the above-mentioned 1,2-substituted compound H was contained, but a final white solid was obtained. It was found that the step did not contain the 1,2-substituted compound H. The purity by high performance liquid chromatography was 99% or more.

前記実施例１１において、リン酸三カリウム１９２．７２ｇ（０．９０８ｍｏｌ）をナトリウムエトキシド６１．７９ｇ（０．９０８ｍｏｌ）を用い、また、反応温度を１００℃から８０℃に変更したこと以外は、実施例１１と同様の操作を行い、白色固体として化合物９を９６．３ｇを得た。収率は６０モル％であった。全容を８０℃で３時間攪拌した段階では、高速液体クロマトグラフによる定量により、前記の１，２置換された化合物Ｉが少量含まれていることが分かったが、最終的な白色固体を取得した段階では、前記の１，２置換された化合物Ｉが含まれていないことが分かった。高速液体クロマトグラフによる純度は、９９％以上であった。(Comparative Example 10: Synthesis of Compound 9)

Except that in Example 11, 192.72 g (0.908 mol) of tripotassium phosphate was used and 61.79 g (0.908 mol) of sodium ethoxide was used, and the reaction temperature was changed from 100 ° C. to 80 ° C. The same operation as in Example 11 was carried out to obtain 96.3 g of Compound 9 as a white solid. The yield was 60 mol%. At the stage where the whole volume was stirred at 80 ° C. for 3 hours, it was found by quantification by high performance liquid chromatography that a small amount of the above-mentioned 1,2-substituted compound I was contained, but a final white solid was obtained. It was found that the step did not contain the 1,2-substituted compound I. The purity by high performance liquid chromatography was 99% or more.

＜ステップ１：中間体Ｄの合成＞

国際公開第１７／１５０６２２号に記載の方法で合成した。(Example 12: Synthesis of polymerizable compound 2)

<Step 1: Synthesis of Intermediate D>

It was synthesized by the method described in International Publication No. 17/150622.

国際公開第１６／１５９１９３号に記載の方法を適用して以下のようにして合成した。
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８３．０５ｇ（０．３９７ｍｏｌ）とシクロペンチルメチルエーテル６００ｇ、テトラヒドロフラン２３０ｇを加えた。そこへ、前記ステップ１で合成した中間体Ｄ１００．０ｇ（０．３７８ｍｏｌ）を加え、反応器を氷浴に浸して反応液内温を０℃とした。次いで、トリエチルアミン４０．２０ｇ（０．３９７ｍｏｌ）を、反応液内温を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℃以下にて１時間さらに攪拌した。得られた反応液に、蒸留水２５０ｇを加えて５０℃にて２時間洗浄を行った後、水層を抜き出した。新たな蒸留水２５０ｇを加えて５０℃にてさらに２時間洗浄を行った。この操作を合計で３回行った。有機層をさらに、濃度１ｍｏｌ／リットルの酢酸と酢酸ナトリウムからなる緩衝溶液（ｐＨ：５．５）４１６ｇを用いて４０℃にて３０分洗浄を行った後、緩衝溶液を抜き出した。新たな濃度１ｍｏｌ／リットルの酢酸と酢酸ナトリウムからなる緩衝溶液（ｐＨ：５．５）４１６ｇを用いて４０℃にて３０分洗浄を行った後、緩衝溶液を抜き出した。この操作を合計で５回行った。
さらに、得られた有機層に蒸留水２５０ｇを加えて４０℃で３０分洗浄した。水層を抜き出して得られた有機層を撹拌しながら徐々に０℃まで冷却し、０℃で１時間撹拌した後、析出した固体をろ別した。ろ液にノルマルヘキサン１４００ｇを１時間かけて滴下した。
その後、０℃で１時間撹拌して、固体を析出させ、析出した固体をろ取した。ろ過物をノルマルヘキサンで洗浄後、真空乾燥させて、白色固体を１０５．７ｇ得た。得られた結晶をＨＰＬＣにて分析を行い、検量線にて中間体Ｅの定量を行ったところ、目的物である中間体Ｅが、９１．３質量％で含まれていることが分かった。<Step 2: Synthesis of Intermediate E>

It was synthesized as follows by applying 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. 100.0 g (0.378 mol) of the intermediate D synthesized in step 1 was added thereto, and the reactor was immersed in an ice bath to set the internal temperature of 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 crystal was analyzed by HPLC and the intermediate E was quantified by a calibration curve. As a result, it was found that the target intermediate E was contained in an amount of 91.3% by mass.

<Step 3: Synthesis of polymerizable compound 2>
A mixture containing the intermediate E synthesized in step 2 as a main component in a nitrogen stream in a three-port reactor equipped with a thermometer: 32.86 g (30 g (71.7 mmol) as the net of the intermediate E) and 300 g of chloroform. , N, N-dimethylformamide (10.5 g (143.4 mmol)) was 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 with an evaporator and concentrated to synthesize an acid chloride of Intermediate E as a chloroform solution.
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 E previously synthesized was slowly added dropwise to this solution while keeping 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. 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. After completion of the reaction, 2: 10.58 g (42.4 mmol) of the compound synthesized in Example 4 and 0.3 g of 2,6-ditercious butyl-para-cresol were added. Then, the reaction solution was heated to 40 ° C. and reacted for 4 hours.
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 laid with 1 g of Rocahelp # 479 to remove Rocahelp # 479. 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 laid with 1 g of Rocahelp # 479 to remove Rocahelp # 479. 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 34.3 g of the polymerizable compound 2 as a pale yellow solid. The yield was 90 mol% (based on 2,5-dihydroxybenzaldehyde).

＜ステップ１：重合性化合物３の合成＞
前記実施例１２のステップ３において、前記実施例４で合成した化合物２：１０．５８ｇ（４２．４ｍｍｏｌ）を、前記実施例５で合成した化合物３：１０．４４ｇ（４２．４ｍｍｏｌ）に変更した以外は、実施例１２と同様にして、重合性化合物３を淡黄色固体として、３３．５ｇ得た。収率は８８モル％（２，５−ジヒドロキシベンズアルデヒド基準）であった。(Example 13: Synthesis of polymerizable compound 3)

<Step 1: Synthesis of polymerizable compound 3>
In step 3 of Example 12, the compound 2: 10.58 g (42.4 mmol) synthesized in Example 4 was changed to the compound 3: 10.44 g (42.4 mmol) synthesized in Example 5. Except for the above, 33.5 g of the polymerizable compound 3 was obtained as a pale yellow solid in the same manner as in Example 12. The yield was 88 mol% (based on 2,5-dihydroxybenzaldehyde).

＜ステップ１：重合性化合物４の合成＞
前記実施例１２のステップ３において、前記実施例４で合成した化合物２：１０．５８ｇ（４２．４ｍｍｏｌ）を、前記実施例６で合成した化合物４：１１．２５ｇ（４２．４ｍｍｏｌ）に変更した以外は、実施例１２と同様にして、重合性化合物４を淡黄色固体として、３４．４ｇ得た。収率は８９モル％（２，５−ジヒドロキシベンズアルデヒド基準）であった。(Example 14: Synthesis of polymerizable compound 4)

<Step 1: Synthesis of polymerizable compound 4>
In step 3 of Example 12, the compound 2: 10.58 g (42.4 mmol) synthesized in Example 4 was changed to the compound 4: 11.25 g (42.4 mmol) synthesized in Example 6. Except for the above, 34.4 g of the polymerizable compound 4 was obtained as a pale yellow solid in the same manner as in Example 12. The yield was 89 mol% (based on 2,5-dihydroxybenzaldehyde).

＜ステップ１：重合性化合物５の合成＞
前記実施例１２のステップ３において、前記実施例４で合成した化合物２：１０．５８ｇ（４２．４ｍｍｏｌ）を、前記実施例７で合成した化合物５：９．３０ｇ（４２．４ｍｍｏｌ）に変更した以外は、実施例１２と同様にして、重合性化合物５を淡黄色固体として、３１．６ｇ得た。収率は８５モル％（２，５−ジヒドロキシベンズアルデヒド基準）であった。(Example 15: Synthesis of polymerizable compound 5)

<Step 1: Synthesis of polymerizable compound 5>
In step 3 of Example 12, the compound 2: 10.58 g (42.4 mmol) synthesized in Example 4 was changed to the compound 5: 9.30 g (42.4 mmol) synthesized in Example 7. Except for the above, 31.6 g of the polymerizable compound 5 was obtained as a pale yellow solid in the same manner as in Example 12. The yield was 85 mol% (based on 2,5-dihydroxybenzaldehyde).

＜ステップ１：重合性化合物６の合成＞
前記実施例１２のステップ３において、前記実施例４で合成した化合物２：１０．５８ｇ（４２．４ｍｍｏｌ）を、前記実施例８で合成した化合物６：８．６２ｇ（４２．４ｍｍｏｌ）に変更した以外は、実施例１２と同様にして、重合性化合物６を淡黄色固体として、３０．４ｇ得た。収率は８３モル％（２，５−ジヒドロキシベンズアルデヒド基準）であった。(Example 16: Synthesis of polymerizable compound 6)

<Step 1: Synthesis of polymerizable compound 6>
In step 3 of Example 12, the compound 2: 10.58 g (42.4 mmol) synthesized in Example 4 was changed to the compound 6: 8.62 g (42.4 mmol) synthesized in Example 8. Except for the above, 30.4 g of the polymerizable compound 6 was obtained as a pale yellow solid in the same manner as in Example 12. The yield was 83 mol% (based on 2,5-dihydroxybenzaldehyde).

＜ステップ１：重合性化合物７の合成＞
前記実施例１２のステップ３において、前記実施例４で合成した化合物２：１０．５８ｇ（４２．４ｍｍｏｌ）を、前記実施例９で合成した化合物７：１１．３４ｇ（４２．４ｍｍｏｌ）に変更した以外は、実施例１２と同様にして、重合性化合物７を淡黄色固体として、３４．１ｇ得た。収率は８８モル％（２，５−ジヒドロキシベンズアルデヒド基準）であった。(Example 17: Synthesis of polymerizable compound 7)

<Step 1: Synthesis of polymerizable compound 7>
In step 3 of Example 12, the compound 2: 10.58 g (42.4 mmol) synthesized in Example 4 was changed to 7: 11.34 g (42.4 mmol) of the compound synthesized in Example 9. Except for the above, 34.1 g of the polymerizable compound 7 was obtained as a pale yellow solid in the same manner as in Example 12. The yield was 88 mol% (based on 2,5-dihydroxybenzaldehyde).

＜ステップ１：重合性化合物８の合成＞
前記実施例１２のステップ３において、前記実施例４で合成した化合物２：１０．５８ｇ（４２．４ｍｍｏｌ）を、前記実施例１０で合成した化合物８：１０．７４ｇ（４２．４ｍｍｏｌ）に変更した以外は、実施例１２と同様にして、重合性化合物８を淡黄色固体として、３３．３ｇ得た。収率は８７モル％（２，５−ジヒドロキシベンズアルデヒド基準）であった。(Example 18: Synthesis of polymerizable compound 8)

<Step 1: Synthesis of polymerizable compound 8>
In step 3 of Example 12, the compound 2: 10.58 g (42.4 mmol) synthesized in Example 4 was changed to the compound 8: 10.74 g (42.4 mmol) synthesized in Example 10. Except for the above, 33.3 g of the polymerizable compound 8 was obtained as a pale yellow solid in the same manner as in Example 12. The yield was 87 mol% (based on 2,5-dihydroxybenzaldehyde).

＜ステップ１：重合性化合物９の合成＞
前記実施例１２のステップ３において、前記実施例４で合成した化合物２：１０．５８ｇ（４２．４ｍｍｏｌ）を、前記実施例１１で合成した化合物９：１１．２５ｇ（４２．４ｍｍｏｌ）に変更した以外は、実施例１２と同様にして、重合性化合物９を淡黄色固体として、３４．０ｇ得た。収率は８８モル％（２，５−ジヒドロキシベンズアルデヒド基準）であった。(Example 19: Synthesis of polymerizable compound 9)

<Step 1: Synthesis of polymerizable compound 9>
In step 3 of Example 12, the compound 2: 10.58 g (42.4 mmol) synthesized in Example 4 was changed to the compound 9: 11.25 g (42.4 mmol) synthesized in Example 11. Except for the above, 34.0 g of the polymerizable compound 9 was obtained as a pale yellow solid in the same manner as in Example 12. The yield was 88 mol% (based on 2,5-dihydroxybenzaldehyde).

(Example 20: Synthesis of polymerizable compound 1)
A mixture containing intermediate E as a main component synthesized in step 2 of Example 12 in a nitrogen stream in a three-port reactor equipped with a thermometer: 10.95 g (10.00 g as net of intermediate E (23.). 90 mmol)), 100 g of chloroform, and 3.49 g of dimethylformamide (DMF) were added and cooled to 10 ° C. or lower. 3.27 g (27.48 mmol) of thionyl chloride was added dropwise thereto 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, the reaction solution was concentrated by an evaporator until the amount of the reaction solution was reduced to 1/4. Then, 25 g of chloroform was added to obtain a chloroform solution of acid chloride of Intermediate E. Separately, in a three-port reactor equipped with a thermometer, 1.50 g (10.86 mmol) of 2,5-dihydroxybenzaldehyde and 6.98 g (65.17 mmol) of 2,6-lutidine as a base were added in a nitrogen stream. , Dissolved in 50 g of chloroform and cooled to 10 ° C. or lower. A chloroform solution of the acid chloride of Intermediate E previously synthesized was slowly added dropwise to this solution while maintaining the internal temperature of the reaction solution 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. After that, 40 g of a 1.0 specified hydrochloric acid aqueous solution was further added, and the mixture was stirred at 10 ° C. or lower for 30 minutes to carry out the reaction.
After completion of the reaction, the compound 1: 6.12 g (14.12 mmol) synthesized in step 2 of Example 1 was further added to the obtained reaction solution at 10 ° C. or lower. Then, the reaction solution was heated to 40 ° C. and reacted for 4 hours. After completion of the reaction, the reaction solution was cooled to 25 ° C. and a liquid separation operation was performed. 0.50 g of Rocahelp # 479 (manufactured by Mitsui Mining & Smelting Co., Ltd.) was added to the obtained organic layer, and after stirring for 30 minutes, Rocahelp # 479 was filtered off. Then, about 80% of the total mass was extracted from the obtained reaction solution by an evaporator and concentrated. After adding 20 g of THF to this solution, the mixture was stirred for 1 hour. Next, 80 g of n-hexane was added dropwise to this solution, and the solution was cooled to 0 ° C. to precipitate crystals. Then, the precipitated crystals were collected by filtration. 108 g of THF, Locahelp # 479: 1.8 g, and 100 mg of 2,6-di-t-butyl-4-methylphenol were added to the obtained crystals, and the mixture was stirred for 30 minutes, and then Locahelp # 479 was filtered off. Then, 36 g of THF was distilled off from the obtained reaction solution by an evaporator.
After 117 g of methanol was added dropwise to the obtained solution, the mixture was cooled to 0 ° C. to precipitate crystals.
Then, the precipitated crystals were collected by filtration. The filtrate was washed with methanol and dried under vacuum to obtain 13.5 g of polymerizable compound 1. The isolated yield was 91.8 mol% (based on 2,5-dihydroxybenzaldehyde).

(Example 21: Synthesis of polymerizable compound 2)
In Example 20, the compound 1: 6.12 g (14.12 mmol) synthesized in step 2 of Example 1 was replaced with the compound 2: 3.52 g (14.12 mmol) synthesized in Example 4. Except for the above, the same procedure as in Example 20 was carried out to obtain 11.6 g of polymerizable compound 2. The isolated yield was 91.3 mol% (based on 2,5-dihydroxybenzaldehyde).

(Example 22: Synthesis of polymerizable compound 1)
<Step 1: Synthesis of mixture A>

It was synthesized as follows by applying 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. 100.0 g (0.378 mol) of the intermediate D synthesized in step 1 of Example 12 was added thereto, and the reactor was immersed in an ice bath to set 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 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 E was quantified by a calibration curve. As a result, it was found that the intermediate E was contained in an amount of 68.5% by mass.

<Step 2: Synthesis of polymerizable compound 1>
In Example 20, a mixture containing Intermediate E as a main component, which was synthesized in Step 2 of Example 12, 10.95 g (10.00 g (23.90 mmol) as the net of Intermediate E) was synthesized in Step 1. The same procedure as in Example 20 was carried out except that the mixture A: was replaced with 14.6 g (10.00 g (23.90 mmol) as the net of Intermediate E), and the polymerizable compound 1 was made into a pale yellow solid, 13 I got .35g. The isolated yield was 90.7 mol% (based on 2,5-dihydroxybenzaldehyde).

(Example 23: Synthesis of polymerizable compound 2)
In Example 20, a mixture containing Intermediate E as a main component, which was synthesized in Step 2 of Example 12, 10.95 g (10.00 g (23.90 mmol) as the net of Intermediate E) was added to Example 22. The compound A synthesized in step 1 was replaced with 14.6 g (intermediate E net 10.00 g (23.90 mmol)), and the compound synthesized in step 2 of Example 1 was 1: 6.12 g (14. 12 mmol) was replaced with the compound 2: 3.52 g (14.12 mmol) synthesized in Example 4, and the same procedure as in Example 20 was carried out to make the polymerizable compound 2 a pale yellow solid. 11.5 g was obtained. The yield was 90.5 mol% (based on 2,5-dihydroxybenzaldehyde).

(Example 24: Synthesis of polymerizable compound 2)
A mixture containing intermediate E as a main component synthesized in step 2 of Example 12 in a nitrogen stream in a three-port reactor equipped with a thermometer: 32.86 g (30 g (71.7 mmol) as net of intermediate E). ), 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 acid chloride of Intermediate E.
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 E previously synthesized was slowly added dropwise to this solution while keeping 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. 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. After completion of the reaction, 2: 10.58 g (42.4 mmol) of the compound synthesized in Example 4 and 0.3 g of 2,6-ditercious butyl-para-cresol were added. Then, the reaction solution was heated to 40 ° C. and reacted for 4 hours.
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 laid with 1 g of Rocahelp # 479 to remove Rocahelp # 479. 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 laid with 1 g of Rocahelp # 479 to remove Rocahelp # 479. 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 34.3 g of the polymerizable compound 2 as a pale yellow solid. The yield was 90 mol% (based on 2,5-dihydroxybenzaldehyde).

(Example 25: Synthesis of polymerizable compound 2)
In Example 24, 32.86 g (30 g (71.7 mmol) as the net of Intermediate E) of the mixture containing Intermediate E as the main component synthesized in Step 2 of Example 12 was added to the step of Example 22. The same procedure as in Example 24 was carried out to obtain the polymerizable compound 2 as a pale yellow solid, except that the mixture A synthesized in 1 was changed to 43.8 g (intermediate E net 30 g (71.7 mmol)). 34.5 g was obtained. The yield was 90.5 mol% (based on 2,5-dihydroxybenzaldehyde).

(Example 26: Synthesis of polymerizable compound 2)
<Step 1: Synthesis of Intermediate E>
To a three-port reactor equipped with a thermometer, 83.05 g (0.397 mol) of trans-1,4-cyclohexanedicarboxylic acid dichloride and 830 g of cyclopentyl methyl ether (CPME) were added in a nitrogen stream. To this, 100 g (0.378 mol) of the intermediate D synthesized in step 1 of Example 12 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. 250 g of distilled water was added to the obtained reaction solution, and the mixture was washed at 50 ° C. for 2 hours. After separating the liquids and extracting the aqueous layer, 250 g of distilled water was newly added and the mixture was washed at 50 ° C. for 2 hours. This operation was performed a total of three times. After cooling the obtained organic layer 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 (oil 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. did. The filtrate was washed with normal hexane and then vacuum dried to give 98.55 g of a white solid as an intermediate. When the obtained white solid was quantified by high performance liquid chromatography, the content of Intermediate E with respect to the white solid was 92.6% by mass. The yield of Intermediate E was 57.7 mol% based on Compound D.

<Step 2: Synthesis of polymerizable compound 2>
In Example 24, a mixture containing Intermediate E as a main component, which was synthesized in Step 2 of Example 12, 32.86 g (30 g (71.7 mmol) as the net of Intermediate E) was synthesized in Step 1. Mixture containing Intermediate E as a main component: In the same manner as in Example 24, the polymerizable compound 2 was used as a pale yellow solid, except that the mixture was changed to 32.40 g (30 g (71.7 mmol) as the net of Intermediate E). 34.6 g was obtained. The yield was 90.7 mol% (based on 2,5-dihydroxybenzaldehyde).

(Example 27: Synthesis of polymerizable compound 1)
A mixture containing intermediate E as a main component synthesized in step 2 of Example 12 in a nitrogen stream in a three-port reactor equipped with a thermometer: 10.95 g (10.00 g as net of intermediate E (23.). 90 mmol)), 100 g of chloroform, and 3.49 g of dimethylformamide (DMF) were added and cooled to 10 ° C. or lower. 3.27 g (27.48 mmol) of thionyl chloride was added dropwise thereto 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, 75 g of chloroform was extracted by an evaporator and concentrated. Then, 25 g of fresh chloroform was added to obtain a chloroform solution of the acid chloride of Intermediate E. Separately, in a three-port reactor equipped with a thermometer, 1.50 g (10.86 mmol) of 2,5-dihydroxybenzaldehyde and 6.98 g (65.17 mmol) of 2,6-lutidine as a base were added in a nitrogen stream. , Dissolved in 50 g of chloroform and cooled to 10 ° C. or lower. A chloroform solution of the acid chloride of Intermediate E previously synthesized was slowly added dropwise to this solution while maintaining the internal temperature of the reaction solution 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. After that, 40 g of a 1.0 specified hydrochloric acid aqueous solution was further added, and the mixture was stirred at 10 ° C. or lower for 30 minutes to carry out the reaction.
After completion of the reaction, the compound 1: 6.12 g (14.12 mmol) synthesized in step 2 of Example 1 was further added to the obtained reaction solution at 10 ° C. or lower. Then, the reaction solution was heated to 40 ° C. and reacted for 4 hours. After completion of the reaction, the reaction solution was cooled to 25 ° C. and a liquid separation operation was performed. 0.50 g of Rocahelp # 479 (manufactured by Mitsui Mining & Smelting Co., Ltd.) was added to the obtained organic layer, and after stirring for 30 minutes, Rocahelp # 479 was filtered off. Then, 60 g of chloroform was extracted from the obtained reaction solution by an evaporator and concentrated. After adding 20 g of THF to this solution, the mixture was stirred for 1 hour. Next, 80 g of n-hexane was added dropwise to this solution, and the solution was cooled to 0 ° C. to precipitate crystals. Then, the precipitated crystals were collected by filtration. 108 g of THF, Locahelp # 479: 1.8 g, and 100 mg of 2,6-di-t-butyl-4-methylphenol were added to the obtained crystals, and the mixture was stirred for 30 minutes, and then Locahelp # 479 was filtered off. Then, 36 g of THF was distilled off from the obtained reaction solution by an evaporator. After 117 g of methanol was added dropwise to the obtained solution, the mixture was cooled to 0 ° C. to precipitate crystals. Then, the precipitated crystals were collected by filtration. The filtrate was washed with methanol and dried under vacuum to obtain 13.5 g of polymerizable compound 1. The isolated yield was 91.8 mol% (based on 2,5-dihydroxybenzaldehyde).

(Example 28: Synthesis of polymerizable compound 2)
In Example 27, 10.95 g (10.00 g (23.90 mmol) as the net of Intermediate E) of the mixture containing Intermediate E as the main component synthesized in Step 2 of Example 12 was added to Example 26. Compound 1 synthesized in Step 2 of Example 1 above, in place of 10.80 g (10.00 g (23.90 mmol) as the net of Intermediate E) of the mixture containing Intermediate E as the main component synthesized in Step 1. The same procedure as in Example 27 was carried out in the same manner as in Example 27, except that 6.12 g (14.12 mmol) was replaced with the compound 2: 3.52 g (14.12 mmol) synthesized in Example 4 above. 2 was used as a pale yellow solid, and 11.47 g was obtained. The isolated yield was 90.2 mol% (based on 2,5-dihydroxybenzaldehyde).

(Example 29: Synthesis of polymerizable compound 2)
In Example 27, 10.95 g (10.00 g (23.90 mmol) as the net of Intermediate E) of the mixture containing Intermediate E as the main component synthesized in Step 2 of Example 12 was added to Example 22. The mixture A: 14.6 g (intermediate E net 10.00 g (23.90 mmol)) synthesized in step 1 was replaced, and the amount of thionyl chloride added was 3.27 g (27.48 mmol) to 2.93 g (). 24.63 mmol) and 6.98 g (65.17 mmol) of lutidine as a base, 6.98 g (65.17 mmol) of lutidine as a base and 14.6 mg (N, N-dimethyl-4-aminopyridine) Instead of the combined use of 0.12 mmol), the compound 1: 6.12 g (14.12 mmol) synthesized in step 2 of Example 1 was combined with the compound 2: 3.52 g (14.12 mmol) synthesized in Example 4. The same procedure as in Example 27 was carried out except that the mixture was replaced with 12 mmol) to obtain 11.57 g of the polymerizable compound 2 as a pale yellow solid. The isolated yield was 91.0 mol% (based on 2,5-dihydroxybenzaldehyde).

(Example 30: Synthesis of polymerizable compound 2)
In Example 27, the amount of thionyl chloride added was changed from 3.27 g (27.48 mmol) to 2.93 g (24.63 mmol), and 6.98 g (65.17 mmol) of lutidine as a base was used as a base. In place of the combined use of 6.98 g (65.17 mmol) of lutidine and 14.6 mg (0.12 mmol) of N, N-dimethyl-4-aminopyridine, and compound 1: 6 synthesized in step 2 of Example 1 above. The same procedure as in Example 27 was carried out to obtain the polymerizable compound 2 except that .12 g (14.12 mmol) was replaced with the compound 2: 3.52 g (14.12 mmol) synthesized in Example 4. 11.63 g was obtained as a pale yellow solid. The isolated yield was 91.5 mol% (based on 2,5-dihydroxybenzaldehyde).

(Example 31: Synthesis of polymerizable compound 2)
In Example 27, 10.95 g (10.00 g (23.90 mmol) as the net of Intermediate E) of the mixture containing Intermediate E as the main component synthesized in Step 2 of Example 12 was added to Example 26. The mixture containing Intermediate E as the main component synthesized in Step 1 was replaced with 10.80 g (10.00 g (23.90 mmol) as the net of Intermediate E), and the amount of thionyl chloride added was 3.27 g (27. Change from 48 mmol) to 2.93 g (24.63 mmol) and change 6.98 g (65.17 mmol) of lutidine as a base to 6.98 g (65.17 mmol) of lutidine as a base and N, N-dimethyl-4. Compound 2 synthesized in Example 4 by substituting 14.6 mg (0.12 mmol) of −aminopyridine with compound 1: 6.12 g (14.12 mmol) synthesized in step 2 of Example 1 above. The same procedure as in Example 27 was carried out except that the mixture was replaced with 3.52 g (14.12 mmol) to obtain 11.69 g of the polymerizable compound 2 as a pale yellow solid. The isolated yield was 92.0 mol% (based on 2,5-dihydroxybenzaldehyde).

(Example 32: Synthesis of polymerizable compound 1)
A mixture A containing the intermediate E synthesized in step 1 of Example 22 as a main component in a nitrogen stream in a three-port reactor equipped with a thermometer: 14.60 g (10.00 g (23) as the net of the intermediate E). .90 mmol)), 100 g of chloroform, and 3.49 g of dimethylformamide (DMF) were added and cooled to 10 ° C. or lower. 3.27 g (27.48 mmol) of thionyl chloride was added dropwise thereto 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, 75 g of chloroform was extracted by an evaporator and concentrated. Then, 25 g of chloroform was added to obtain a chloroform solution of acid chloride of Intermediate E. Separately, in a three-port reactor equipped with a thermometer, 1.50 g (10.86 mmol) of 2,5-dihydroxybenzaldehyde and 6.59 g (65.17 mmol) of triethylamine as a base as a base were added in a nitrogen stream. It was dissolved in 50 g of chloroform and cooled to 10 ° C. or lower. A chloroform solution of the acid chloride of Intermediate E previously synthesized was slowly added dropwise to this solution while maintaining the internal temperature of the reaction solution 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. After that, 40 g of a 1.0 specified hydrochloric acid aqueous solution was further added, and the mixture was stirred at 10 ° C. or lower for 30 minutes to carry out the reaction.
After completion of the reaction, the compound 1: 6.12 g (14.12 mmol) synthesized in step 2 of Example 1 was further added to the obtained reaction solution at 10 ° C. or lower. Then, the reaction solution was heated to 40 ° C. and reacted for 5 hours. After completion of the reaction, the reaction solution was cooled to 25 ° C. and a liquid separation operation was performed. 0.50 g of Rocahelp # 479 (manufactured by Mitsui Mining & Smelting Co., Ltd.) was added to the obtained organic layer, and after stirring for 30 minutes, Rocahelp # 479 was filtered off. The filtered Rocahelp # 479 was washed with 5 g of chloroform and combined with the previously obtained filtrate to obtain an organic layer.
Separately, 200 g of methanol was added at 25 ° C. in a nitrogen stream to a three-port reactor equipped with a thermometer. The previously obtained organic layer was slowly added dropwise to this methanol at 25 ° C. over 30 minutes. After completion of the dropping, the mixture was stirred as it was for 30 minutes. Then, the precipitated solid was filtered to obtain a solid. The obtained solid was dried in a vacuum dryer to obtain 13.49 g of the polymerizable compound 1 as a pale yellow solid. The yield was 91.7 mol% (based on 2,5-dihydroxybenzaldehyde).

(Example 33: Synthesis of polymerizable compound 1)
In Example 32, 14.60 g (10.00 g (23.90 mmol) as the net of Intermediate E) of the mixture A containing the intermediate E as the main component synthesized in Step 1 of Example 22 was added to Example 12. The same operation as in Example 32 was performed except that the mixture containing Intermediate E as the main component synthesized in Step 2 of the above was replaced with 10.95 g (10.00 g (23.90 mmol) as the net of Intermediate E). As a result, 13.53 g of the polymerizable compound 1 was obtained as a pale yellow solid. The isolated yield was 92.0 mol% (based on 2,5-dihydroxybenzaldehyde).

(Example 34: Synthesis of polymerizable compound 1)
In Example 32, 14.60 g (10.00 g (23.90 mmol) as the net of Intermediate E) of the mixture A containing the intermediate E as the main component synthesized in Step 1 of Example 22 was added to the Example. The same operation as in Example 32 was performed except that the mixture containing Intermediate E as the main component synthesized in Step 1 of 26 was replaced with 10.80 g (10.00 g (23.90 mmol) as the net of Intermediate E). This was carried out to obtain 13.55 g of the polymerizable compound 1 as a pale yellow solid. The isolated yield was 92.1 mol% (based on 2,5-dihydroxybenzaldehyde).

(Example 35: Synthesis of polymerizable compound 1)
In Example 32, 14.60 g (10.00 g (23.90 mmol) as the net of Intermediate E) of the mixture A containing the intermediate E as the main component synthesized in Step 1 of Example 22 was added to the Example. The mixture containing Intermediate E as the main component synthesized in Step 1 of 26 was replaced with 10.80 g (10.00 g (23.90 mmol) as the net of Intermediate E) and 6.59 g of triethylamine as the base (65. 17 mmol) was replaced with 6.98 g (65.17 mmol) of 2,6-lutidine as a base, and the same procedure as in Example 32 was carried out to make the polymerizable compound 1 a pale yellow solid. I got 65g. The isolated yield was 92.8 mol% (based on 2,5-dihydroxybenzaldehyde).

(Example 36: Synthesis of polymerizable compound 1)
In Example 32, the amount of thionyl chloride added was changed from 3.27 g (27.48 mmol) to 2.93 g (24.63 mmol), and 6.59 g (65.17 mmol) of triethylamine as a base was used as a base. The same operation as in Example 32 was carried out except that the combination of 6.98 g (65.17 mmol) of 2,6-lutidine and 14.6 mg (0.12 mmol) of N, N-dimethyl-4-aminopyridine was used. As a result, 13.58 g of the polymerizable compound 1 was obtained as a pale yellow solid. The isolated yield was 92.3 mol% (based on 2,5-dihydroxybenzaldehyde).

(Example 37: Synthesis of polymerizable compound 1)
In Example 32, 14.60 g (10.00 g (23.90 mmol) as the net of Intermediate E) of the mixture A containing the intermediate E as the main component synthesized in step 1 of Example 22 was added to Example 12. The mixture containing Intermediate E as the main component synthesized in Step 2 of the above was replaced with 10.95 g (10.00 g (23.90 mmol) as the net of Intermediate E), and the amount of thionyl chloride added was 3.27 g (27). Change from .48 mmol) to 2.93 g (24.63 mmol) and change 6.59 g (65.17 mmol) of triethylamine as a base to 6.98 g (65.17 mmol) of 2,6-lutidine as a base and N, The same procedure as in Example 32 was carried out except that the combination was replaced with 14.6 mg (0.12 mmol) of N-dimethyl-4-aminopyridine to obtain 13.64 g of the polymerizable compound 1 as a pale yellow solid. It was. The isolated yield was 92.7 mol% (based on 2,5-dihydroxybenzaldehyde).

(Example 38: Synthesis of polymerizable compound 1)
In Example 32, 14.60 g (10.00 g (23.90 mmol) as the net of Intermediate E) of the mixture A containing the intermediate E as the main component synthesized in Step 1 of Example 22 was added to the Example. Instead of the mixture containing Intermediate E as the main component synthesized in Step 1 of 26 (10.00 g (23.90 mmol) as the net of Intermediate E), the amount of thionyl chloride added was 3.27 g (27. Change from 48 mmol) to 2.93 g (24.63 mmol), and change 6.59 g (65.17 mmol) of triethylamine as a base to 6.98 g (65.17 mmol) of 2,6-lutidine as a base and N, N. The same procedure as in Example 32 was carried out except that the combination was replaced with 14.6 mg (0.12 mmol) of −dimethyl-4-aminopyridine to obtain 13.75 g of the polymerizable compound 1 as a pale yellow solid. .. The isolated yield was 93.5 mol% (based on 2,5-dihydroxybenzaldehyde).

(Example 39: Synthesis of polymerizable compound 1)
<Step 1: Synthesis of Intermediate E>
Except that in step 1 of Example 26, 1200 g of normal hexane was replaced with 1200 g of normal heptane, and washing of the filtrate with normal hexane was replaced with washing of the filtrate with normal heptane. The same operation as in step 1 was carried out to obtain 97.95 g of a white solid as an intermediate. When the obtained white solid was quantified by high performance liquid chromatography, the content of Intermediate E with respect to the white solid was 92.9% by mass. The yield of Intermediate E was 57.5 mol% based on Compound D.
<Step 2: Synthesis of polymerizable compound 1>
In Example 32, 14.60 g (10.00 g (23.90 mmol) as the net of Intermediate E) of the mixture A containing the intermediate E as the main component synthesized in Step 1 of Example 22 was added to the above step. The mixture containing Intermediate E as the main component synthesized in 1 was replaced with 10.76 g (10.00 g (23.90 mmol) as the net of Intermediate E), and the amount of thionyl chloride added was 3.27 g (27.48 mmol). ) To 2.93 g (24.63 mmol), and 6.59 g (65.17 mmol) of triethylamine as a base was replaced with 6.98 g (65.17 mmol) of 2,6-lutidine as a base and N, N-. The same procedure as in Example 30 was carried out except that the combination was replaced with 14.6 mg (0.12 mmol) of dimethyl-4-aminopyridine to obtain 13.80 g of the polymerizable compound 1 as a pale yellow solid. The isolated yield was 93.8 mol% (based on 2,5-dihydroxybenzaldehyde).

(Example 40: Synthesis of polymerizable compound 2)
In Example 27, 10.95 g (10.00 g (23.90 mmol) as the net of Intermediate E) of the mixture containing Intermediate E as the main component synthesized in Step 2 of Example 12 was added to Example 39. The mixture containing Intermediate E as the main component synthesized in Step 1 was replaced with 10.76 g (10.00 g (23.90 mmol) as the net of Intermediate E), and the amount of thionyl chloride added was 3.27 g (27. Change from 48 mmol) to 2.93 g (24.63 mmol) and change 6.98 g (65.17 mmol) of lutidine as a base to 6.98 g (65.17 mmol) of lutidine as a base and N, N-dimethyl-4. Compound 2 synthesized in Example 4 by substituting 14.6 mg (0.12 mmol) of −aminopyridine with compound 1: 6.12 g (14.12 mmol) synthesized in step 2 of Example 1 above. The same procedure as in Example 27 was carried out except that the mixture was replaced with 3.52 g (14.12 mmol) to obtain 11.72 g of the polymerizable compound 2 as a pale yellow solid. The isolated yield was 92.2 mol% (based on 2,5-dihydroxybenzaldehyde).

Claims (17)

In an organic solvent containing at least one aprotic polar solvent, the following formula (I)

(Wherein, X represents an oxygen atom, a sulfur ^{_{atom, -CH 2 -, - CHR 11}} -, - CR 11 R 12 -, or, ^{-NR 11} -. Represents ^here, R ^{11, R 12} are each Independently, it represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms which may have a substituent.
R ^{1 to} R ⁴ are independently hydrogen atom, halogen atom, alkyl group having 1 to 6 carbon atoms, cyano group, nitro group, and carbon atoms 1 to 6 in which at least one hydrogen atom is substituted with a halogen atom. Alkyl group, alkoxy group with 1 to 6 carbon atoms, alkylthio group with 1 to 6 carbon atoms, mono-substituted amino group, di-substituted amino group, -OCF ₃ , -C (= O) -OR ¹³ , or Represents −OC (= O) −R ¹³ . Here, R ¹³ represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms which may have a substituent. R ^{1 to} R ⁴ may all be the same or different from each other, and at least one C-R ^{1 to} C-R ⁴ constituting the ring may be replaced with a nitrogen atom. )
The hydrazino compound represented by
In the presence of a phosphoric acid compound that makes the pH of the aqueous solution 8 or more and 14 or less
Formula (III): R-Hal (Hal represents a chlorine atom, a bromine atom, or an iodine atom, and R represents an organic group having 1 to 60 carbon atoms which may have a substituent). A method for producing a 1,1-di-substituted hydrazine compound represented by the following formula (II), which is reacted with the represented compound.

(In the formula, X, R, R ^{1 to} R ⁴ have the same meanings as described above.) The production method according to claim 1, wherein the phosphoric acid-based compound is at least one base selected from the group consisting of an alkali metal phosphate and an alkali metal phosphoric acid monohydrogen salt. The production method according to claim 2, wherein the phosphoric acid compound is an alkali metal phosphate. The production method according to claim 3, wherein the alkali metal phosphate is tripotassium phosphate or trisodium phosphate. The production method according to any one of claims 1 to 4, wherein the phosphoric acid-based compound is used in an amount of 1.0 equivalent or more and 3.0 equivalent or less with respect to the hydradino compound. Any of claims 1 to 5, which comprises a step of adding an acidic protonal solvent to the reaction solution to bring the pH of the mixed solution of the reaction solution and the acidic protonic solvent to 8 or less after completion of the reaction. The manufacturing method described in. The production method according to claim 6, wherein the acidic protonic solvent is an acidic aqueous solution. The production method according to claim 7, wherein the pH of the acidic aqueous solution is 1.5 or more and less than 7. The production method according to any one of claims 1 to 8, wherein all of R ^{1 to} R ⁴ are hydrogen atoms. The production method according to any one of claims 1 to 9, wherein X is a sulfur atom. The aprotic polar solvent is selected from the group consisting of N, N-dimethylformamide, N, N-dimethylacetamide, N-methylpyrrolidone, acetonitrile, 1,3-dimethyl-2-imidazolidinone, and dimethyl sulfoxide. The production method according to any one of claims 1 to 10, which is at least one of the above-mentioned methods. The production method according to any one of claims 1 to 11, wherein the compound represented by the formula (III) is the following formula (IV-1).

(In the formula, Ra represents a cyclic group having at least one of an aromatic hydrocarbon ring and an aromatic heterocycle.
Y is a chemical single bond, -O -, - S -, - C (= O) -, - O-CRbRc -, - CRcRb-O -, - O-CH 2 -CH 2 -, - CH 2 -CH ₂ -O-, -C (= O) -O-, -OC (= O)-, -C (= O) -S-, -SC (= O)-, -NR ^{14 -C (= O) -, -} C (= O) -NR 14 -, - 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-CRbRc -, - CRcRb-O-C (= O) -, - O-C (= O) -CRbRc -, - CRcRb- ^{C (= O) -O -,} - O-C (= O) -NR 14 -, - NR 14 -C (= O) -O -, - O-C (= O) -CH 2 -S-, It represents −S—CH ₂₋ C (= O) −O− or −OC (= O) −O−. Here, R ¹⁴ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and Rc and Rb may independently have a hydrogen atom and a substituent having 6 to 12 carbon atoms, respectively. It represents a good aromatic hydrocarbon ring group or an aromatic heterocyclic group which may have a substituent having 3 to 12 carbon atoms.
Ga is, -CH ₂ contained (i) a divalent aliphatic hydrocarbon group having 1 to 20 carbon atoms, and, in the divalent aliphatic hydrocarbon group (ii) 3 to 20 carbon atoms - at least one One is -O-, -S-, -OC (= O)-, -C (= O) -O-, -OC (= O) -O-, -NR ¹⁵ -C (= O) ^{) -, - C (= O} ) -NR 15 -, - NR 15 -, or, -C (= O) - is a substituted group, the one of the organic groups. However, this excludes cases where two or more -O- or -S- are adjacent to each other. Here, R ¹⁵ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.
Hal represents a chlorine atom, a bromine atom, or an iodine atom. ) The production method according to any one of claims 1 to 11, wherein the compound represented by the formula (III) is the following formula (IV-2).

(In the formula, Gb has (i) an aliphatic hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, and (ii) an aliphatic hydrocarbon group having 3 to 20 carbon atoms which may have a substituent. At least one of -CH _2- contained in the aliphatic hydrocarbon group of is -O-, -S-, -OC (= O)-, -C (= O) -O-, -O-C. ^{(= O) -O -, -} NR 15 -C (= O) -, - C (= O) -NR 15 -, - NR 15 -, or, -C (= O) - substituted radicals, However, this does not apply to the case where two or more -O- or -S- are adjacent to each other.
Here, R ¹⁵ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.
Hal represents a chlorine atom, a bromine atom, or an iodine atom. ) The following formula (VI) includes a step of reacting the 1,1-di-substituted hydrazine compound produced by the production method according to any one of claims 1 to 13 with a compound represented by the following formula (V). A method for producing the represented polymerizable compound.

(In the formula, Q represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms which may have a substituent.
Ar represents an aromatic hydrocarbon ring group which may have a substituent or an aromatic heterocyclic group which may have a substituent.
Y ¹ to Y ⁸ are each independently a chemical single _{bond, -O -, - O-CH} 2 -, - CH 2 -O -, - O-CH 2 -CH 2 -, - CH 2 - CH ₂ -O-, -C (= O) -O-, -O-C (= O)-, -O-C (= O) -O-, -C (= O) -S-, -S ^{-C (= O) -, -} NR 16 -C (= O) -, - C (= O) -NR 16 -, - CF 2 -O -, - O-CF 2 -, - CH 2 -CH 2 _{-, - CF 2 -CF 2 -} , - O-CH 2 -CH 2 -O -, - CH = CH-C (= O) -O -, - O-C (= O) -CH = CH-, -CH ₂ -C (= O) -O-, -O-C (= O) -CH _2- , -CH ₂ -O-C (= O)-, -C (= O) -O-CH _{2 -, - 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 -, - CH = CH -, - N = CH -, - CH = N -, - N = C (CH 3) -, - C (CH 3) = N-, -N = N-, or -C≡C-. Here, R ¹⁶ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.
A ¹ , A ² , B ¹ and B ² each independently represent a cyclic aliphatic group which may have a substituent or an aromatic group which may have a substituent.
G ¹ and G ² are independently composed of (i) a divalent aliphatic hydrocarbon group having 1 to 30 carbon atoms and (ii) a divalent aliphatic hydrocarbon group having 3 to 30 carbon atoms. At least one of the included −CH ₂₋ is −O−, −S−, −OC (= O) −, −C (= O) −O−, −OC (= O) −O− ^{, -NR 17 -C (= O)} -, - C (= O) -NR 17 -, - NR 17 -, or, -C (= O) - substituted radicals, or organic groups in the is there. However, this excludes cases where two or more -O- or -S- are adjacent to each other. Here, R ¹⁷ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and the hydrogen atom contained in the organic group of G ¹ and G ² is an alkyl group having 1 to 5 carbon atoms and a carbon number of carbon atoms. It may be substituted with 1 to 5 alkoxy groups, cyano groups, or halogen atoms.
P ¹ and P ² each independently represent a halogen atom or an alkenyl group having 2 to 10 carbon atoms which may be substituted with a methyl group.
n and m independently represent 0 or 1, respectively. ]

(In the formula, R ^{1 to} R ⁴ , R, Ar, Q, X, Y ^{1 to} Y ⁸ , A ¹ , A ² , B ¹ , B ² , G ¹ , G ² , P ¹ , P ² , n and Each of m has the same meaning as described above.) A method for producing a polymerizable compound represented by the following formula (VI), which is derived from the 1,1-di-substituted hydrazine compound produced by the production method according to any one of claims 1 to 13.

(In the formula, R ^{1 to} R ⁴ , R, Ar, Q, X, Y ^{1 to} Y ⁸ , A ¹ , A ² , B ¹ , B ² , G ¹ , G ² , P ¹ , P ² , n and Each of m has the same meaning as described above.) The method for producing a polymerizable compound according to claim 14 or 15, wherein the polymerizable compound represented by the formula (VI) is a polymerizable compound represented by the following formula (VII-1).

(In the formula, R ^{1 to} R ⁴ , Ar, Q, X, Y ^{1 to} Y ⁸ , A ¹ , A ² , B ¹ , B ² , G ¹ , G ² , P ¹ , P ² , n and m are , Each have the same meaning as described above.
Ra represents a cyclic group having at least one of an aromatic hydrocarbon ring and an aromatic heterocycle.
Y is a chemical single bond, -O -, - S -, - C (= O) -, - O-CRbRc -, - CRcRb-O -, - O-CH 2 -CH 2 -, - CH 2 -CH ₂ -O-, -C (= O) -O-, -OC (= O)-, -C (= O) -S-, -SC (= O)-, -NR ^{14 -C (= O) -, -} C (= O) -NR 14 -, - 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-CRbRc -, - CRcRb-O-C (= O) -, - O-C (= O) -CRbRc -, - CRcRb- ^{C (= O) -O -,} - O-C (= O) -NR 14 -, - NR 14 -C (= O) -O -, - O-C (= O) -CH 2 -S-, It represents −S—CH ₂₋ C (= O) −O− or −OC (= O) −O−. Here, R ¹⁴ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and Rc and Rb may independently have a hydrogen atom and a substituent having 6 to 12 carbon atoms, respectively. It represents a good aromatic hydrocarbon ring group or an aromatic heterocyclic group which may have a substituent having 3 to 12 carbon atoms.
Ga is, -CH ₂ contained (i) a divalent aliphatic hydrocarbon group having 1 to 20 carbon atoms, and, in the divalent aliphatic hydrocarbon group (ii) 3 to 20 carbon atoms - at least one One is -O-, -S-, -OC (= O)-, -C (= O) -O-, -OC (= O) -O-, -NR ¹⁵ -C (= O) ^{) -, - C (= O} ) -NR 15 -, - NR 15 -, or, -C (= O) - is a substituted group, the one of the organic groups. However, this excludes cases where two or more -O- or -S- are adjacent to each other. Here, R ¹⁵ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. The method for producing a polymerizable compound according to claim 14 or 15, wherein the polymerizable compound represented by the formula (VI) is a polymerizable compound represented by the following formula (VII-2).

(In the formula, R ^{1 to} R ⁴ , Ar, Q, X, Y ^{1 to} Y ⁸ , A ¹ , A ² , B ¹ , B ² , G ¹ , G ² , P ¹ , P ² , n and m are , Each have the same meaning as described above.
Gb has (i) an aliphatic hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, and (ii) an aliphatic hydrocarbon group having 3 to 20 carbon atoms which may have a substituent. At least one of -CH _2- contained in the hydrogen group is -O-, -S-, -OC (= O)-, -C (= O) -O-, -OC (= O). ^{-O -, - NR 15 -C (} = O) -, - C (= O) -NR 15 -, - NR 15 -, or, -C (= O) - substituted radicals, one of It is an organic group. However, this excludes cases where two or more -O- or -S- are adjacent to each other. Here, R ¹⁵ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.