JP2011038093A - Polyvinyl ether resin - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a resin for producing a polymer carrier having a nearly spherical shape and including an amino group-containing polyvinyl ether resin. <P>SOLUTION: The polyvinyl ether resin includes a structural unit represented by formula (1). <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to a polyvinyl ether resin and the like.

Polymer carriers containing polyvinyl ether resins having amino groups (amino group-containing polyvinyl ether resins) are known as carriers for the production of separation materials for liquid chromatography or immobilized enzyme catalyst materials that use enzyme molecular recognition as the separation mode. Yes. For example, Patent Document 1 discloses that a film-acting polyvinyl ether polyamine terpolymer obtained by polymerizing _2- vinyloxyethylphthalimide and alkyl vinyl ether in acetone using BF ₃ EtOEt as a catalyst and deprotecting with hydrazine, ie, An amino group-containing polyvinyl ether resin as a polymer carrier (membrane carrier) having a membrane shape is described.
By the way, when the polymer carrier is used after being packed in a packed column with a separation material for liquid chromatography or an immobilized enzyme catalyst material, a polymer carrier having a substantially spherical particle shape (substantially spherical particle shape) is required. A polymer carrier having a substantially spherical particle shape and containing an amino group-containing polyvinyl ether resin has not been known so far.

JP-T 2010-521133 Publication [0135]

  Under such circumstances, there is a need for a resin that is substantially spherical and can produce a polymer carrier containing an amino group-containing polyvinyl ether resin.

（式中、ｍは０以上の整数を表わし、ｎは２以上の整数を表わす。Ｒ^１、Ｒ^２およびＲ^３はそれぞれ独立に、水素原子、置換基を有していてもよいアルキル基または置換基を有していてもよいアリール基を表わし、Ｒ^１とＲ^２とが結合して環を形成していてもよく、Ｒ^２とＲ^３とが結合して環を形成していてもよい。
Ｒ^４およびＲ⁵はそれぞれ独立に、水素原子、置換基を有していてもよいアルキル基、置換基を有していてもよいアリール基、置換基を有していてもよいアルコキシカルボニル基、置換基を有していてもよいアリールオキシカルボニル基、置換基を有していてもよいアシル基、置換基を有していてもよいアルキルスルホニル基または置換基を有していてもよいアリールスルホニル基を表わし、Ｒ^４およびＲ⁵のうちの少なくとも一つは、置換基を有していてもよいアルコキシカルボニル基、置換基を有していてもよいアリールオキシカルボニル基、置換基を有していてもよいアシル基、置換基を有していてもよいアルキルスルホニル基または置換基を有していてもよいアリールスルホニル基である。また、Ｒ^４とＲ⁵とが結合して、これらが結合している窒素原子と一緒になって環を形成していてもよい。）
で示される構造単位を含むポリビニルエーテル樹脂。 As a result of intensive studies to solve the above problems, the present inventor has reached the following present invention.
[1] Formula (1)

(In the formula, m represents an integer of 0 or more, and n represents an integer of 2 or more. R ¹ , R ² and R ³ each independently represents a hydrogen atom, an alkyl group which may have a substituent, or Represents an aryl group which may have a substituent, R ¹ and R ² may be bonded to form a ring, or R ² and R ³ may be bonded to form a ring; Good.
R ⁴ and R ⁵ are each independently a hydrogen atom, an alkyl group which may have a substituent, an aryl group which may have a substituent, an alkoxycarbonyl group which may have a substituent, Aryloxycarbonyl group which may have a substituent, acyl group which may have a substituent, alkylsulfonyl group which may have a substituent or arylsulfonyl which may have a substituent And at least one of R ⁴ and R ⁵ has an alkoxycarbonyl group which may have a substituent, an aryloxycarbonyl group which may have a substituent, or a substituent. An acyl group which may be substituted, an alkylsulfonyl group which may have a substituent, or an arylsulfonyl group which may have a substituent. R ⁴ and R ⁵ may be bonded together to form a ring together with the nitrogen atom to which they are bonded. )
A polyvinyl ether resin containing a structural unit represented by:

（式中、ｐは０以上の整数を表わす。ｑおよびrはそれぞれ独立に、２以上の整数を表わす。Ｒ⁶、Ｒ⁷およびＲ⁸はそれぞれ独立に、水素原子、置換基を有していてもよいアルキル基または置換基を有していてもよいアリール基を表わし、Ｒ⁶とＲ⁷とが結合して、これらが結合している炭素原子と一緒になって環を形成していてもよく、Ｒ⁷とＲ⁸とが結合して、これらが結合している炭素原子と一緒になって環を形成していてもよい。）
で示される化合物である［２］記載のポリビニルエーテル樹脂。 [2] The polyvinyl ether resin according to [1], including a structural unit derived from a monomer having two or more carbon-carbon unsaturated bonds in the molecule in addition to the structural unit represented by the formula (1).
[3] A monomer having two or more carbon-carbon unsaturated bonds in the molecule is represented by the formula (2m):

(In the formula, p represents an integer of 0 or more. Q and r each independently represents an integer of 2 or more. R ⁶ , R ⁷ and R ⁸ each independently have a hydrogen atom or a substituent. Represents an optionally substituted alkyl group or an optionally substituted aryl group, and R ⁶ and R ⁷ are bonded together to form a ring together with the carbon atoms to which they are bonded. Alternatively, R ⁷ and R ⁸ may be bonded together to form a ring together with the carbon atom to which they are bonded.)
The polyvinyl ether resin according to [2], which is a compound represented by the formula:

（式中、ｓは０以上の整数を表わし、ｔは０以上の整数を表わす。Ｒ^９、Ｒ^１0およびＲ^１１はそれぞれ独立に、水素原子、置換基を有していてもよいアルキル基または置換基を有していてもよいアリール基を表し、Ｒ^９とＲ^１0とが結合して環を形成していてもよく、Ｒ^１0とＲ^１１とが結合して環を形成していてもよい。Ｒ^１２は、水素原子、水酸基、置換基を有していてもよいアルキル基、置換基を有していてもよいアリール基、置換基を有していてもよいアルキルオキシ基または置換基を有していてもよいアリールオキシ基を表わす。）
で示される構造単位をさらに含む［１］〜［３］のいずれか記載のポリビニルエーテル樹脂。
［５］ 式（１）において、Ｒ^４およびＲ^５のうち少なくとも一方が、置換基を有していてもよいアルキルオキシカルボニル基または置換基を有していてもよいアリールオキシカルボニル基である［１］〜［４］のいずれか記載のポリビニルエーテル樹脂。 [4] Formula (3):

(In the formula, s represents an integer of 0 or more, and t represents an integer of 0 or more. R ⁹ , R ¹⁰ and R ¹¹ are each independently a hydrogen atom, an alkyl group which may have a substituent, or An aryl group which may have a substituent, R ⁹ and R ¹⁰ may be bonded to form a ring, or R ¹⁰ and R ¹¹ may be bonded to form a ring; R ¹² is a hydrogen atom, a hydroxyl group, an alkyl group which may have a substituent, an aryl group which may have a substituent, an alkyloxy group which may have a substituent or a substituent. Represents an aryloxy group which may have
The polyvinyl ether resin according to any one of [1] to [3], further comprising a structural unit represented by:
[5] In Formula (1), at least one of R ⁴ and R ⁵ is an alkyloxycarbonyl group which may have a substituent or an aryloxycarbonyl group which may have a substituent [ The polyvinyl ether resin according to any one of [1] to [4].

（式中、ｍは０以上の整数を表わし、ｎは２以上の整数を表わす。Ｒ^１、Ｒ^２およびＲ^３はそれぞれ独立に、水素原子、置換基を有していてもよいアルキル基または置換基を有していてもよいアリール基を表わし、Ｒ^１とＲ^２とが結合して環を形成していてもよく、Ｒ^２とＲ^３とが結合して環を形成していてもよい。Ｒは、水素原子、置換基を有していてもよいアルキル基または置換基を有していてもよいアリール基を表わす。）
で示される構造単位に変換されたポリビニルエーテル樹脂。 [6] In the polyvinyl ether resin according to [2] or [3], the structural unit represented by the formula (1) is represented by the formula (10):

(In the formula, m represents an integer of 0 or more, and n represents an integer of 2 or more. R ¹ , R ² and R ³ each independently represents a hydrogen atom, an alkyl group which may have a substituent, or Represents an aryl group which may have a substituent, R ¹ and R ² may be bonded to form a ring, or R ² and R ³ may be bonded to form a ring; R represents a hydrogen atom, an alkyl group which may have a substituent, or an aryl group which may have a substituent.
A polyvinyl ether resin converted into a structural unit represented by

（式中、ｍは０以上の整数を表わし、ｎは２以上の整数を表わす。Ｒ^１、Ｒ^２およびＲ^３はそれぞれ独立に、水素原子、置換基を有していてもよいアルキル基または置換基を有していてもよいアリール基を表わし、Ｒ^１とＲ^２とが結合して環を形成していてもよく、Ｒ^２とＲ^３とが結合して環を形成していてもよい。Ｒは、水素原子、置換基を有していてもよいアルキル基または置換基を有していてもよいアリール基を表わす。）
で示される構造単位と２個以上の炭素−炭素不飽和結合を分子内に有するモノマーから導かれる構造単位とを含むポリビニルエーテル樹脂。 [7] Formula (10):

(In the formula, m represents an integer of 0 or more, and n represents an integer of 2 or more. R ¹ , R ² and R ³ each independently represents a hydrogen atom, an alkyl group which may have a substituent, or Represents an aryl group which may have a substituent, R ¹ and R ² may be bonded to form a ring, or R ² and R ³ may be bonded to form a ring; R represents a hydrogen atom, an alkyl group which may have a substituent, or an aryl group which may have a substituent.
And a structural unit derived from a monomer having two or more carbon-carbon unsaturated bonds in the molecule.

（式中、ｐは０以上の整数を表わす。ｑおよびrはそれぞれ独立に、２以上の整数を表わす。Ｒ⁶、Ｒ⁷およびＲ⁸はそれぞれ独立に、水素原子、置換基を有していてもよいアルキル基または置換基を有していてもよいアリール基を表わし、Ｒ⁶とＲ⁷とが結合して、これらが結合している炭素原子と一緒になって環を形成していてもよく、Ｒ⁷とＲ⁸とが結合して、これらが結合している炭素原子と一緒になって環を形成していてもよい。）
で示される化合物である［７］記載のポリビニルエーテル樹脂。 [8] A monomer having two or more carbon-carbon unsaturated bonds in the molecule is represented by the formula (2m):

(In the formula, p represents an integer of 0 or more. Q and r each independently represents an integer of 2 or more. R ⁶ , R ⁷ and R ⁸ each independently have a hydrogen atom or a substituent. Represents an optionally substituted alkyl group or an optionally substituted aryl group, and R ⁶ and R ⁷ are bonded together to form a ring together with the carbon atoms to which they are bonded. Alternatively, R ⁷ and R ⁸ may be bonded together to form a ring together with the carbon atom to which they are bonded.)
The polyvinyl ether resin according to [7], which is a compound represented by:

（式中、ｓは０以上の整数を表わし、ｔは０以上の整数を表わす。Ｒ^９、Ｒ^１0およびＲ^１１はそれぞれ独立に、水素原子、置換基を有していてもよいアルキル基または置換基を有していてもよいアリール基を表し、Ｒ^９とＲ^１0とが結合して環を形成していてもよく、Ｒ^１0とＲ^１１とが結合して環を形成していてもよい。Ｒ^１２は、水素原子、水酸基、置換基を有していてもよいアルキル基、置換基を有していてもよいアリール基、置換基を有していてもよいアルコキシ基または置換基を有していてもよいアリールオキシ基を表わす。）
で示される構造単位をさらに含む［６］〜［８］のいずれか記載のポリビニルエーテル樹脂。 [9] Formula (3):

(In the formula, s represents an integer of 0 or more, and t represents an integer of 0 or more. R ⁹ , R ¹⁰ and R ¹¹ are each independently a hydrogen atom, an alkyl group which may have a substituent, or An aryl group which may have a substituent, R ⁹ and R ¹⁰ may be bonded to form a ring, or R ¹⁰ and R ¹¹ may be bonded to form a ring; R ¹² represents a hydrogen atom, a hydroxyl group, an alkyl group which may have a substituent, an aryl group which may have a substituent, an alkoxy group which may have a substituent or a substituent. Represents an aryloxy group which may be present.)
The polyvinyl ether resin according to any one of [6] to [8], further comprising a structural unit represented by:

（式中、ｍは０以上の整数を表わし、ｎは２以上の整数を表わす。Ｒ^１、Ｒ^２およびＲ^３はそれぞれ独立に、水素原子、置換基を有していてもよいアルキル基または置換基を有していてもよいアリール基を表わし、Ｒ^１とＲ^２とが結合して環を形成していてもよく、Ｒ^２とＲ^３とが結合して環を形成していてもよい。
Ｒ^４およびＲ⁵はそれぞれ独立に、水素原子、置換基を有していてもよいアルキル基、置換基を有していてもよいアリール基、置換基を有していてもよいアルコキシカルボニル基、置換基を有していてもよいアリールオキシカルボニル基、置換基を有していてもよいアシル基、置換基を有していてもよいアルキルスルホニル基または置換基を有していてもよいアリールスルホニル基であり、Ｒ^４およびＲ⁵のうち少なくとも一つは、置換基を有していてもよいアルコキシカルボニル基、置換基を有していてもよいアリールオキシカルボニル基、置換基を有していてもよいアシル基、置換基を有していてもよいアルキルスルホニル基または置換基を有していてもよいアリールスルホニル基である。また、Ｒ^４とＲ⁵とが結合して、これらが結合している窒素原子と一緒になって環を形成していてもよい。）
で示される化合物の付加重合反応を行う工程を含む式（１）：

（式中、ｍ、ｎ、Ｒ^１、Ｒ^２、Ｒ^３、Ｒ^４およびＲ⁵は上記と同一の意味を表わす。）
で示される構造単位を含むポリビニルエーテル樹脂の製造方法。 [10] Formula (1 m):

(In the formula, m represents an integer of 0 or more, and n represents an integer of 2 or more. R ¹ , R ² and R ³ each independently represents a hydrogen atom, an alkyl group which may have a substituent, or Represents an aryl group which may have a substituent, R ¹ and R ² may be bonded to form a ring, or R ² and R ³ may be bonded to form a ring; Good.
R ⁴ and R ⁵ are each independently a hydrogen atom, an alkyl group which may have a substituent, an aryl group which may have a substituent, an alkoxycarbonyl group which may have a substituent, Aryloxycarbonyl group which may have a substituent, acyl group which may have a substituent, alkylsulfonyl group which may have a substituent or arylsulfonyl which may have a substituent And at least one of R ⁴ and R ⁵ has an alkoxycarbonyl group which may have a substituent, an aryloxycarbonyl group which may have a substituent, or a substituent. Or an acylsulfonyl group which may have a substituent, or an arylsulfonyl group which may have a substituent. R ⁴ and R ⁵ may be bonded together to form a ring together with the nitrogen atom to which they are bonded. )
Formula (1) including the process of performing addition polymerization reaction of the compound shown by:

(In the formula, m, n, R ¹ , R ² , R ³ , R ⁴ and R ⁵ have the same meaning as described above.)
The manufacturing method of the polyvinyl ether resin containing the structural unit shown by these.

（式中、ｍは０以上の整数を表わし、ｎは２以上の整数を表わす。Ｒ^１、Ｒ^２およびＲ^３はそれぞれ独立に、水素原子、置換基を有していてもよいアルキル基または置換基を有していてもよいアリール基を表わし、Ｒ^１とＲ^２とが結合して環を形成していてもよく、Ｒ^２とＲ^３とが結合して環を形成していてもよい。Ｒは、水素原子、置換基を有していてもよいアルキル基または置換基を有していてもよいアリール基を表わす。）
で示される構造単位に変換する工程を有するポリビニルエーテル樹脂の製造方法。 [11] The production method according to [10], comprising a step of suspension polymerization of the compound represented by the formula (1m) in water.
[12] The structural unit represented by the formula (1) contained in the polyvinyl ether resin obtained by the production method of [10] or [11] is represented by the formula (10):

(In the formula, m represents an integer of 0 or more, and n represents an integer of 2 or more. R ¹ , R ² and R ³ each independently represents a hydrogen atom, an alkyl group which may have a substituent, or Represents an aryl group which may have a substituent, R ¹ and R ² may be bonded to form a ring, or R ² and R ³ may be bonded to form a ring; R represents a hydrogen atom, an alkyl group which may have a substituent, or an aryl group which may have a substituent.
The manufacturing method of the polyvinyl ether resin which has the process converted into the structural unit shown by these.

  ADVANTAGE OF THE INVENTION According to this invention, resin which can manufacture the polymeric support | carrier which is substantially spherical particle shape and contains amino group containing polyvinyl ether resin can be provided.

2 is an optical micrograph showing the appearance of resin A obtained in Example 1. FIG. 3 is an optical micrograph showing the appearance of resin A ′ obtained in Example 2. 2 is an optical micrograph showing the appearance of resin B obtained in Example 3. 4 is an optical micrograph showing the appearance of resin B ′ obtained in Example 4. 6 is an optical micrograph showing the appearance of resin C obtained in Example 5. 6 is an optical micrograph showing the appearance of resin D obtained in Example 6.

（式中、ｍは０以上、好ましくは１以上、より好ましくは１〜１０の整数を表わし、ｎは２以上の整数を表わす。Ｒ^１、Ｒ^２およびＲ^３はそれぞれ独立に、水素原子、置換基を有していてもよいアルキル基または置換基を有していてもよいアリール基を表わし、Ｒ^１とＲ^２とが結合して環を形成していてもよく、Ｒ^２とＲ^３とが結合して環を形成していてもよい。
Ｒ^４およびＲ⁵はそれぞれ独立に、水素原子、置換基を有していてもよいアルキル基、置換基を有していてもよいアリール基、置換基を有していてもよいアルコキシカルボニル基、置換基を有していてもよいアリールオキシカルボニル基、置換基を有していてもよいアシル基、置換基を有していてもよいアルキルスルホニル基または置換基を有していてもよいアリールスルホニル基を表わす。ただし、Ｒ^４およびＲ⁵のうち少なくとも一つは、置換基を有していてもよいアルコキシカルボニル基、置換基を有していてもよいアリールオキシカルボニル基、置換基を有していてもよいアシル基、置換基を有していてもよいアルキルスルホニル基または置換基を有していてもよいアリールスルホニル基である。また、Ｒ^４とＲ⁵とが結合して、これらが結合している窒素原子と一緒になって環を形成していてもよい。）
で示される構造単位（以下、構造単位（１）と略記する。）を含むポリビニルエーテル樹脂（以下、樹脂（１）と略記する。）について、説明する。 First, formula (1):

(In the formula, m represents an integer of 0 or more, preferably 1 or more, more preferably 1 to 10, and n represents an integer of 2 or more. R ¹ , R ² and R ³ each independently represents a hydrogen atom, Represents an alkyl group which may have a substituent or an aryl group which may have a substituent, and R ¹ and R ² may combine to form a ring; R ² and R ³ May combine with each other to form a ring.
R ⁴ and R ⁵ are each independently a hydrogen atom, an alkyl group which may have a substituent, an aryl group which may have a substituent, an alkoxycarbonyl group which may have a substituent, Aryloxycarbonyl group which may have a substituent, acyl group which may have a substituent, alkylsulfonyl group which may have a substituent or arylsulfonyl which may have a substituent Represents a group. However, at least one of R ⁴ and R ⁵ may have an alkoxycarbonyl group which may have a substituent, an aryloxycarbonyl group which may have a substituent, or a substituent. They are an acyl group, an alkylsulfonyl group which may have a substituent, or an arylsulfonyl group which may have a substituent. R ⁴ and R ⁵ may be bonded together to form a ring together with the nitrogen atom to which they are bonded. )
A polyvinyl ether resin (hereinafter abbreviated as “resin (1)”) containing the structural unit (hereinafter abbreviated as “structural unit (1)”) will be described.

（式中、ｍ、ｎ、Ｒ^１、Ｒ^２、Ｒ^３、Ｒ^４およびＲ⁵は上記と同一の意味を表わす。）
で示される化合物（以下、化合物（１ｍ）と略記する。）から導かれる。 The structural unit (1) has the formula (1m):

(In the formula, m, n, R ¹ , R ² , R ³ , R ⁴ and R ⁵ have the same meaning as described above.)
(Hereinafter abbreviated as compound (1m)).

Examples of the alkyl group in R ¹ , R ² , R ³ , R ⁴ and R ⁵ include an alkyl group having 1 to 50 carbon atoms such as a methyl group, an ethyl group, a propyl group and a butyl group. Alkyl groups having 1 to 6 carbon atoms are more preferable. Such an alkyl group may be linear, branched, or cyclic. Such an alkyl group may have a substituent, and any substituent may be used as long as it does not affect the addition polymerization reaction of the compound (1m). Specifically, an alkoxy group having 1 to 10 carbon atoms such as a methoxy group, an ethoxy group, and a propoxy group, an aryl group having 6 to 15 carbon atoms such as a phenyl group, and an aryloxy group having 6 to 15 carbon atoms such as a phenoxy group , A fluorine atom, a chlorine atom, a bromine atom, an iodine atom, an acetyl group, an acyl group having 2 to 10 carbon atoms such as a benzoyl group, an acyloxy group having 2 to 10 carbon atoms such as an acetoxy group, and a carbon number such as a benzyl group 7 to 15 aralkyl groups may be mentioned.

Examples of the aryl group in R ¹ , R ² , R ³ , R ⁴ and R ⁵ include aryl groups having 6 to 15 carbon atoms such as a phenyl group, a 1-naphthyl group and a 2-naphthyl group. Such an aryl group may have a substituent as long as it does not affect the addition polymerization reaction of the compound (1m). Specific examples include the same substituents as the alkyl group.

で示される部分構造は、式（１ｐ−Ａ）で示される部分構造であり、Ｒ^１とＲ^２とが結合して、それらが結合している炭素原子とともにシクロヘキセン環を形成する場合、式（１ｍ）における式（１ｐ）で示される部分構造は、式（１ｐ−Ｂ）で示される部分構造である。

Examples of the ring formed by combining R ¹ and R ² together with the carbon atom to which they are bonded include a cyclopentene ring and a cyclohexene ring. When R ¹ and R ² are combined to form a cyclopentene ring with the carbon atom to which they are bonded, formula (1p) in formula (1m):

Is a partial structure represented by the formula (1p-A), and when R ¹ and R ² are combined to form a cyclohexene ring together with the carbon atom to which they are bonded, The partial structure represented by the formula (1p) in 1m) is a partial structure represented by the formula (1p-B).

Examples of the ring formed by combining R ² and R ³ together with the carbon atom to which they are bonded include a cyclopentane ring and a cyclohexane ring. When R ¹ and R ² are combined to form a cyclopentane ring together with the carbon atom to which they are bonded, the partial structure represented by formula (1p) in formula (1m) is represented by formula (1p-C) In the case where R ¹ and R ² are bonded to form a cyclohexane ring together with the carbon atoms to which they are bonded, the partial structure represented by the formula (1p) in the formula (1m) is , A partial structure represented by the formula (1p-D).

Examples of the alkoxycarbonyl group for R ⁴ and R ⁵ include the methoxycarbonyl group, ethoxycarbonyl group, propoxycarbonyl group, 2-propoxycarbonyl group, butoxycarbonyl group, 2-butoxycarbonyl group, and tert-butoxycarbonyl group. Examples thereof include groups composed of 1 to 10 alkoxy groups and a carbonyl group. Such an alkoxycarbonyl group may have a substituent, and examples of the substituent include an aryl group having 6 to 15 carbon atoms such as a phenyl group and a 9H-fluoren-9-yl group. Examples of the alkoxycarbonyl group having a substituent include a phenylmethoxycarbonyl group and a 9H-fluoren-9-ylmethoxycarbonyl group. Among these, a tert-butoxycarbonyl group and a 9H-fluoren-9-ylmethoxycarbonyl group are preferable.
Examples of the aryloxycarbonyl group in R ⁴ and R ⁵ include groups composed of the aryloxy group having 6 to 15 carbon atoms such as a phenoxycarbonyl group and a carbonyl group. The aryloxycarbonyl group may have a substituent, and examples of the substituent include an alkyl group having 1 to 10 carbon atoms such as a methyl group, an alkoxy group having 1 to 10 carbon atoms such as a methoxy group, and a nitro group. , Fluorine atom, chlorine atom, bromine atom and iodine atom. Examples of the aryloxycarbonyl group having a substituent include 4-methoxyphenoxycarbonyl group, 4-methylphenoxycarbonyl group, 4-nitrophenoxycarbonyl group, 4-chlorophenoxycarbonyl group, 4-bromophenoxycarbonyl group, 4-iodophenoxy. Carbonyl group, 2-methoxyphenoxycarbonyl group, 2-methylphenoxycarbonyl group, 2-nitrophenoxycarbonyl group, 2-chlorophenoxycarbonyl group, 2-bromophenoxycarbonyl group, 2-iodophenoxycarbonyl group, 3-methoxyphenoxycarbonyl group Group, 3-methylphenoxycarbonyl group, 3-nitrophenoxycarbonyl group, 3-chlorophenoxycarbonyl group, 3-bromophenoxycarbonyl group and 3-iodophenoxycarbonyl group And the like. Among these, a phenoxycarbonyl group and a 4-nitrophenoxycarbonyl group are preferable.

Examples of the acyl group in R ⁴ and R ⁵ include carbon numbers such as acetyl group, ethylcarbonyl group, propylcarbonyl group, 2-propylcarbonyl group, butylcarbonyl group, 2-butylcarbonyl group, tert-butylcarbonyl group, and benzoyl group. 2-10 aliphatic or aromatic acyl groups are mentioned. Such an acyl group may have a substituent. Examples of the substituent include a fluorine atom, a chlorine atom, a bromine atom, an alkyl group having 1 to 10 carbon atoms such as a methyl group, an aryl group having 6 to 15 carbon atoms such as a phenyl group, and a carbon number 1 to 1 such as a trifluoromethyl group. 6 fluoroalkyl groups and nitro groups. Examples of the acyl group having a substituent include chloroacetyl group, dichloroacetyl group, trichloroacetyl group, trifluoroacetyl group, phenylacetyl group, 4-methylbenzoyl group, 4-methylbenzoyl group, 4-nitrobenzoyl group, 4- Chlorobenzoyl group, 4-bromobenzoyl group, 4-iodobenzoyl group, 4-trifluoromethylbenzoyl group, 3-methylbenzoyl group, 3-methylbenzoyl group, 3-nitrobenzoyl group, 3-chlorobenzoyl group, 3- Bromobenzoyl group, 3-iodobenzoyl group, 3-trifluoromethylbenzoyl group, 2-methylbenzoyl group, 2-methylbenzoyl group, 2-nitrobenzoyl group, 2-chlorobenzoyl group, 2-bromobenzoyl group, 2- Iodobenzoyl group and 2-trifluoromethyl Such as Nzoiru group, and the like. Among these, an acetyl group, a trichloroacetyl group, and a benzoyl group are preferable.

Examples of the alkylsulfonyl group for R ⁴ and R ⁵ include the alkyl groups having 1 to 10 carbon atoms such as a methylsulfonyl group, an ethylsulfonyl group, a propylsulfonyl group, a 2-propylsulfonyl group, a tert-butylsulfonyl group, and a butylsulfonyl group. And a group composed of a sulfonyl group. Such an alkylsulfonyl group may have a substituent, and examples of the substituent include a fluorine atom. Examples of the alkylsulfonyl group having a substituent include a trifluoromethylsulfonyl group. Among these, a methylsulfonyl group is preferable.
Examples of the arylsulfonyl group in R ⁴ and R ⁵ include groups composed of the aryl group having 6 to 15 carbon atoms such as a benzenesulfonyl group and a sulfonyl group. Such an arylsulfonyl group may have a substituent, and examples of the substituent include the same substituents as the aryl group. As the arylsulfonyl group having a substituent, 4-methylbenzenesulfonyl group, 4-nitrobenzenesulfonyl group, 4-chlorobenzenesulfonyl group, 4-bromobenzenesulfonyl group, 4-iodobenzenesulfonyl group, 4-trifluoromethylbenzenesulfonyl Group, 3-methylbenzenesulfonyl group, 3-nitrobenzenesulfonyl group, 3-chlorobenzenesulfonyl group, 3-bromobenzenesulfonyl group, 3-iodobenzenesulfonyl group, 3-trifluoromethylbenzenesulfonyl group, 2-methylbenzenesulfonyl group 2-methylbenzenesulfonyl group, 2-nitrobenzenesulfonyl group, 4-nitrobenzenesulfonyl group, 2,4-dinitrobenzenesulfonyl group, 2-chlorobenzenesulfonyl group, 2-bromobenzene Sulfonyl group, 2-iodobenzene sulfonyl group and 2-trifluoromethyl benzenesulfonyl group. Among these, 4-methylbenzenesulfonyl group and 2-nitrobenzenesulfonyl group are preferable.

In the compound (1m), at least one of R ⁴ and R ⁵ has an alkoxycarbonyl group which may have a substituent, an aryloxycarbonyl group which may have a substituent, or a substituent. Or an optionally substituted acylsulfonyl group, an optionally substituted alkylsulfonyl group, or an optionally substituted arylsulfonyl group. At least one of R ⁴ and R ⁵ is preferably a compound (1m) which is an optionally substituted alkoxycarbonyl group or an optionally substituted aryloxycarbonyl group, and R ⁴ Is more preferably an alkoxycarbonyl group which may have a substituent or an aryloxycarbonyl group which may have a substituent, wherein R ⁵ is a hydrogen atom (1m).

で示される部分構造としては、下記のものが挙げられる。

When R ⁴ and R ⁵ are bonded to form a ring together with the nitrogen atom to which they are bonded, formula (1q) in formula (1m):

Examples of the partial structure represented by:

  If m is too large, the reactivity of the addition polymerization of the compound (1m) tends to decrease. Therefore, m is preferably an integer of 1000 or less, more preferably an integer of 100 or less. Particularly preferred are the following integers. Further, m is preferably 1 or more, and more preferably 2 or more. N is preferably an integer of 30 or less, more preferably an integer of 10 or less, and an integer of 6 or less in that it is easy to obtain a raw material for producing the compound (1m). Is particularly preferred.

As the compound (1m),
Compound (1m) wherein R ¹ is a hydrogen atom,
Compound (1m), wherein R ¹ is an alkyl group having 1 to 10 carbon atoms,
Compound (1m) wherein R ¹ is a methyl group,
A compound (1m) in which R ¹ , R ² and R ³ are hydrogen atoms,
A compound (1m) in which R ¹ is an alkyl group having 1 to 10 carbon atoms, and R ² and R ³ are hydrogen atoms;
A compound (1m) in which R ¹ is a methyl group, and R ² and R ³ are hydrogen atoms;

a compound (1m) in which m is an integer of 0 to 1000;
a compound (1m) in which m is an integer of 0 to 100,
a compound (1m) in which m is an integer of 0 to 10;
Compound (1m), wherein n is an integer of 2 to 30,
a compound (1m) in which n is an integer of 2 to 10,
a compound (1m) in which n is an integer of 2 to 6,
a compound (1m) in which m is an integer of 0 to 10 and n is an integer of 2 to 10;
a compound (1m) in which m is an integer of 0 to 10 and n is an integer of 2 to 6;

A compound (1m) in which R ¹ is a hydrogen atom, m is an integer of 0 to 10, and n is an integer of 2 to 10;
Compound (1m), wherein R ¹ is an alkyl group having 1 to 10 carbon atoms, m is an integer of 0 to 10, and n is an integer of 2 to 10,
A compound (1m) in which R ¹ is a methyl group, m is an integer of 0 to 10, and n is an integer of 2 to 10;
A compound (1m) in which R ¹ , R ² and R ³ are hydrogen atoms, m is an integer of 0 to 10 and n is an integer of 2 to 10;
Compound (1m), wherein R ¹ is an alkyl group having 1 to 10 carbon atoms, R ² and R ³ are hydrogen atoms, m is an integer of 0 to 10, and n is an integer of 2 to 10,
Compound (1m), wherein R ¹ is a methyl group, R ² and R ³ are hydrogen atoms, m is an integer of 0 to 10, and n is an integer of 2 to 10,

A compound (1m) in which R ⁴ is an optionally substituted alkyloxycarbonyl group or an optionally substituted aryloxycarbonyl group, and R ⁵ is a hydrogen atom;
A compound (1m) in which R ⁴ is an optionally substituted alkyloxycarbonyl group, and R ⁵ is a hydrogen atom;
A compound (1m) in which R ⁴ is an optionally substituted aryloxycarbonyl group, and R ⁵ is a hydrogen atom;
A compound (1m) wherein R ⁴ is a tert-butoxycarbonyl group and R ⁵ is a hydrogen atom;
A compound (1m) wherein R ⁴ is a 9H-fluoren-9-ylmethoxycarbonyl group and R ⁵ is a hydrogen atom;
A compound (1m) in which R ⁴ is a phenoxycarbonyl group and R ⁵ is a hydrogen atom;
A compound (1m) in which R ⁴ is a 4-nitrophenoxycarbonyl group and R ⁵ is a hydrogen atom;
A compound (1m) in which R ⁴ is an acetyl group and R ⁵ is a hydrogen atom;
A compound (1m) in which R ⁴ is a trichloroacetyl group and R ⁵ is a hydrogen atom;
A compound (1m) in which R ⁴ is a benzoyl group and R ⁵ is a hydrogen atom;
A compound (1m) in which R ⁴ is a methylsulfonyl group and R ⁵ is a hydrogen atom;
A compound (1m) in which R ⁴ is a 4-methylbenzenesulfonyl group and R ⁵ is a hydrogen atom;
A compound (1m) in which R ⁴ is a 2-nitrobenzenesulfonyl group and R ⁵ is a hydrogen atom;
Compound (1m) in which R ⁴ and R ⁵ are combined to form a phthaloyl group,

R ¹ is a hydrogen atom, m is an integer of 0 to 10, n is an integer of 2 to 10, and R ⁴ has an alkyloxycarbonyl group or a substituent which may have a substituent. A compound (1m), which may be an aryloxycarbonyl group, and R ⁵ is a hydrogen atom,
R ¹ is a hydrogen atom, m is an integer of 0 to 10, n is an integer of 2 to 10, R ⁴ is an alkyloxycarbonyl group which may have a substituent, and R ⁵ is A compound that is a hydrogen atom (1 m),
R ¹ is a hydrogen atom, m is an integer of 0 to 10, n is an integer of 2 to 10, R ⁴ is an aryloxycarbonyl group which may have a substituent, and R ⁵ is A compound that is a hydrogen atom (1 m),
Compound (1m) wherein R ¹ is a hydrogen atom, m is an integer of 0 to 10, n is an integer of 2 to 10, R ⁴ is a tert-butoxycarbonyl group, and R ⁵ is a hydrogen atom ,
R ¹ is a hydrogen atom, m is an integer of 0 to 10, n is an integer of 2 to 10, R ⁴ is a 9H-fluoren-9-ylmethoxycarbonyl group, and R ⁵ is a hydrogen atom. A compound (1 m),
Compound (1m), wherein R ¹ is a hydrogen atom, m is an integer of 0 to 10, n is an integer of 2 to 10, R ⁴ is a phenoxycarbonyl group, and R ⁵ is a hydrogen atom,
A compound in which R ¹ is a hydrogen atom, m is an integer of 0 to 10, n is an integer of 2 to 10, R ⁴ is a 4-nitrophenoxycarbonyl group, and R ⁵ is a hydrogen atom (1m ),
A compound (1m) in which R ¹ is a hydrogen atom, m is an integer of 0 to 10, n is an integer of 2 to 10, R ⁴ is an acetyl group, and R ⁵ is a hydrogen atom;
A compound (1m) in which R ¹ is a hydrogen atom, m is an integer of 0 to 10, n is an integer of 2 to 10, R ⁴ is a trichloroacetyl group, and R ⁵ is a hydrogen atom;
Compound (1m), wherein R ¹ is a hydrogen atom, m is an integer of 0 to 10, n is an integer of 2 to 10, R ⁴ is a benzoyl group, and R ⁵ is a hydrogen atom,
Compound (1m), wherein R ¹ is a hydrogen atom, m is an integer of 0 to 10, n is an integer of 2 to 10, R ⁴ is a methylsulfonyl group, and R ⁵ is a hydrogen atom,
Compound (1m) in which R ¹ is a hydrogen atom, m is an integer of 0 to 10, n is an integer of 2 to 10, R ⁴ is a 4-methylbenzenesulfonyl group, and R ⁵ is a hydrogen atom. ),
Compound (1m) wherein R ¹ is a hydrogen atom, m is an integer of 0 to 10, n is an integer of 2 to 10, R ⁴ is a 2-nitrobenzenesulfonyl group, and R ⁵ is a hydrogen atom ,
R ¹ is a hydrogen atom, m is an integer of 0 to 10, n is an integer of 2 to 10, and R ⁴ and R ⁵ are combined to form a phthaloyl group (1m),

R ¹ is an alkyl group having 1 to 10 carbon atoms, m is an integer of 0 to 10, n is an integer of 2 to 10, and R ⁴ may have a substituent. Or an aryloxycarbonyl group optionally having substituent (s), wherein R ⁵ is a hydrogen atom (1m),
R ¹ is an alkyl group having 1 to 10 carbon atoms, m is an integer of 0 to 10, n is an integer of 2 to 10, and R ⁴ may have a substituent. Wherein R ⁵ is a hydrogen atom (1m),
R ¹ is an alkyl group having 1 to 10 carbon atoms, m is an integer of 0 to 10, n is an integer of 2 to 10, and R ⁴ may be an aryloxycarbonyl group which may have a substituent. Wherein R ⁵ is a hydrogen atom (1m),
R ¹ is an alkyl group having 1 to 10 carbon atoms, m is an integer of 0 to 10, n is an integer of 2 to 10, R ⁴ is a tert-butoxycarbonyl group, and R ⁵ is a hydrogen atom. A compound (1m),
R ¹ is an alkyl group having 1 to 10 carbon atoms, m is an integer of 0 to 10, n is an integer of 2 to 10, R ⁴ is a 9H-fluoren-9-ylmethoxycarbonyl group, Compound (1m) wherein R ⁵ is a hydrogen atom,
R ¹ is an alkyl group having 1 to 10 carbon atoms, m is an integer of 0 to 10, n is an integer of 2 to 10, R ⁴ is a phenoxycarbonyl group, and R ⁵ is a hydrogen atom. Compound (1 m),
R ¹ is an alkyl group having 1 to 10 carbon atoms, m is an integer of 0 to 10, n is an integer of 2 to 10, R ⁴ is a 4-nitrophenoxycarbonyl group, and R ⁵ is hydrogen. Compound (1m) that is an atom,
A compound in which R ¹ is an alkyl group having 1 to 10 carbon atoms, m is an integer of 0 to 10, n is an integer of 2 to 10, R ⁴ is an acetyl group, and R ⁵ is a hydrogen atom. (1m),
R ¹ is an alkyl group having 1 to 10 carbon atoms, m is an integer of 0 to 10, n is an integer of 2 to 10, R ⁴ is a trichloroacetyl group, and R ⁵ is a hydrogen atom. Compound (1 m),
A compound in which R ¹ is an alkyl group having 1 to 10 carbon atoms, m is an integer of 0 to 10, n is an integer of 2 to 10, R ⁴ is a benzoyl group, and R ⁵ is a hydrogen atom. (1m),
R ¹ is an alkyl group having 1 to 10 carbon atoms, m is an integer of 0 to 10, n is an integer of 2 to 10, R ⁴ is a methylsulfonyl group, and R ⁵ is a hydrogen atom. Compound (1 m),
R ¹ is an alkyl group having 1 to 10 carbon atoms, m is an integer of 0 to 10, n is an integer of 2 to 10, R ⁴ is a 4-methylbenzenesulfonyl group, and R ⁵ is hydrogen. Compound (1m) that is an atom,
R ¹ is an alkyl group having 1 to 10 carbon atoms, m is an integer of 0 to 10, n is an integer of 2 to 10, R ⁴ is a 2-nitrobenzenesulfonyl group, and R ⁵ is a hydrogen atom. A compound (1m),
Compound in which R ¹ is an alkyl group having 1 to 10 carbon atoms, m is an integer of 0 to 10, n is an integer of 2 to 10, and R ⁴ and R ⁵ are bonded to form a phthaloyl group. (1m),

R ¹ is a methyl group, m is an integer of 0 to 10, n is an integer of 2 to 10, and R ⁴ has an alkyloxycarbonyl group or a substituent which may have a substituent. A compound (1m), which may be an aryloxycarbonyl group, and R ⁵ is a hydrogen atom,
R ¹ is a methyl group, m is an integer of 0 to 10, n is an integer of 2 to 10, R ⁴ is an alkyloxycarbonyl group which may have a substituent, and R ⁵ is A compound that is a hydrogen atom (1 m),
R ¹ is a methyl group, m is an integer of 0 to 10, n is an integer of 2 to 10, R ⁴ is an aryloxycarbonyl group which may have a substituent, and R ⁵ is A compound that is a hydrogen atom (1 m),
Compound (1m) wherein R ¹ is a methyl group, m is an integer of 0 to 10, n is an integer of 2 to 10, R ⁴ is a tert-butoxycarbonyl group, and R ⁵ is a hydrogen atom ,
R ¹ is a methyl group, m is an integer of 0 to 10, n is an integer of 2 to 10, R ⁴ is a 9H-fluoren-9-ylmethoxycarbonyl group, and R ⁵ is a hydrogen atom. A compound (1 m),
Compound (1m), wherein R ¹ is a methyl group, m is an integer of 0 to 10, n is an integer of 2 to 10, R ⁴ is a phenoxycarbonyl group, and R ⁵ is a hydrogen atom,
A compound in which R ¹ is a methyl group, m is an integer of 0 to 10, n is an integer of 2 to 10, R ⁴ is a 4-nitrophenoxycarbonyl group, and R ⁵ is a hydrogen atom (1m ),

A compound (1m) in which R ¹ is a methyl group, m is an integer of 0 to 10, n is an integer of 2 to 10, R ⁴ is an acetyl group, and R ⁵ is a hydrogen atom;
A compound (1m) in which R ¹ is a methyl group, m is an integer of 0 to 10, n is an integer of 2 to 10, R ⁴ is a trichloroacetyl group, and R ⁵ is a hydrogen atom;
A compound (1m) in which R ¹ is a methyl group, m is an integer of 0 to 10, n is an integer of 2 to 10, R ⁴ is a benzoyl group, and R ⁵ is a hydrogen atom;
Compound (1m), wherein R ¹ is a methyl group, m is an integer of 0 to 10, n is an integer of 2 to 10, R ⁴ is a methylsulfonyl group, and R ⁵ is a hydrogen atom,
A compound wherein R ¹ is a methyl group, m is an integer of 0 to 10, n is an integer of 2 to 10, R ⁴ is a 4-methylbenzenesulfonyl group, and R ⁵ is a hydrogen atom (1m ),
Compound (1m) wherein R ¹ is a methyl group, m is an integer of 0 to 10, n is an integer of 2 to 10, R ⁴ is a 2-nitrobenzenesulfonyl group, and R ⁵ is a hydrogen atom ,
R ¹ is a methyl group, m is an integer of 0 to 10, n is an integer of 2 to 10, and R ⁴ and R ⁵ are combined to form a phthaloyl group (1m),

R ¹ , R ² and R ³ are hydrogen atoms, m is an integer of 0 to 10, n is an integer of 2 to 10, and R ⁴ may have a substituent alkyloxycarbonyl group Or an aryloxycarbonyl group optionally having substituent (s), wherein R ⁵ is a hydrogen atom (1m),
R ¹ , R ² and R ³ are hydrogen atoms, m is an integer of 0 to 10, n is an integer of 2 to 10, and R ⁴ may have a substituent alkyloxycarbonyl group Wherein R ⁵ is a hydrogen atom (1m),
R ¹ , R ² and R ³ are hydrogen atoms, m is an integer of 0 to 10, n is an integer of 2 to 10, and R ⁴ may have an optionally substituted aryloxycarbonyl group Wherein R ⁵ is a hydrogen atom (1m),
R ¹ , R ² and R ³ are hydrogen atoms, m is an integer of 0 to 10, n is an integer of 2 to 10, R ⁴ is a tert-butoxycarbonyl group, and R ⁵ is a hydrogen atom. A compound (1m),
R ¹ , R ² and R ³ are hydrogen atoms, m is an integer of 0 to 10, n is an integer of 2 to 10, R ⁴ is a 9H-fluoren-9-ylmethoxycarbonyl group, Compound (1m) wherein R ⁵ is a hydrogen atom,
R ¹ , R ² and R ³ are hydrogen atoms, m is an integer of 0 to 10, n is an integer of 2 to 10, R ⁴ is a phenoxycarbonyl group, and R ⁵ is a hydrogen atom. Compound (1 m),
R ¹ , R ² and R ³ are hydrogen atoms, m is an integer of 0 to 10, n is an integer of 2 to 10, R ⁴ is a 4-nitrophenoxycarbonyl group, and R ⁵ is hydrogen. Compound (1m) that is an atom,

A compound in which R ¹ , R ² and R ³ are hydrogen atoms, m is an integer of 0 to 10, n is an integer of 2 to 10, R ⁴ is an acetyl group, and R ⁵ is a hydrogen atom. (1m),
R ¹ , R ² and R ³ are hydrogen atoms, m is an integer of 0 to 10, n is an integer of 2 to 10, R ⁴ is a trichloroacetyl group, and R ⁵ is a hydrogen atom. Compound (1 m),
A compound in which R ¹ , R ² and R ³ are hydrogen atoms, m is an integer of 0 to 10, n is an integer of 2 to 10, R ⁴ is a benzoyl group, and R ⁵ is a hydrogen atom. (1m),
R ¹ , R ² and R ³ are hydrogen atoms, m is an integer of 0 to 10, n is an integer of 2 to 10, R ⁴ is a methylsulfonyl group, and R ⁵ is a hydrogen atom. Compound (1 m),
R ¹ , R ² and R ³ are hydrogen atoms, m is an integer of 0 to 10, n is an integer of 2 to 10, R ⁴ is a 4-methylbenzenesulfonyl group, and R ⁵ is hydrogen. Compound (1m) that is an atom,
R ¹ , R ² and R ³ are hydrogen atoms, m is an integer of 0 to 10, n is an integer of 2 to 10, R ⁴ is a 2-nitrobenzenesulfonyl group, and R ⁵ is a hydrogen atom. A compound (1m),
A compound in which R ¹ , R ² and R ³ are hydrogen atoms, m is an integer of 0 to 10, n is an integer of 2 to 10, and R ⁴ and R ⁵ are bonded to form a phthaloyl group. (1m),
R ¹ is an alkyl group having 1 to 10 carbon atoms, R ² and R ³ are hydrogen atoms, m is an integer of 0 to 10, n is an integer of 2 to 10, and R ⁴ is a substituent. A compound (1m) wherein R ⁵ is a hydrogen atom, which may be an alkyloxycarbonyl group optionally having substituents or an aryloxycarbonyl group optionally having substituents;

R ¹ is an alkyl group having 1 to 10 carbon atoms, R ² and R ³ are hydrogen atoms, m is an integer of 0 to 10, n is an integer of 2 to 10, and R ⁴ is a substituent. A compound (1m) in which R ⁵ is a hydrogen atom,
R ¹ is an alkyl group having 1 to 10 carbon atoms, R ² and R ³ are hydrogen atoms, m is an integer of 0 to 10, n is an integer of 2 to 10, and R ⁴ is a substituent. A compound (1m) which is an aryloxycarbonyl group optionally having R ⁵ and a hydrogen atom,
R ¹ is an alkyl group having 1 to 10 carbon atoms, R ² and R ³ are hydrogen atoms, m is an integer of 0 to 10, n is an integer of 2 to 10, and R ⁴ is tert- A compound (1m) which is a butoxycarbonyl group and R ⁵ is a hydrogen atom;
R ¹ is an alkyl group having 1 to 10 carbon atoms, R ² and R ³ are hydrogen atoms, m is an integer of 0 to 10, n is an integer of 2 to 10, and R ⁴ is 9H— A compound (1m) which is a fluoren-9-ylmethoxycarbonyl group and R ⁵ is a hydrogen atom;
R ¹ is an alkyl group having 1 to 10 carbon atoms, R ² and R ³ are hydrogen atoms, m is an integer of 0 to 10, n is an integer of 2 to 10, and R ⁴ is phenoxycarbonyl. A compound (1m), wherein R ⁵ is a hydrogen atom,
R ¹ is an alkyl group having 1 to 10 carbon atoms, R ² and R ³ are hydrogen atoms, m is an integer of 0 to 10, n is an integer of 2 to 10, and R ⁴ is 4- A compound (1m) which is a nitrophenoxycarbonyl group and R ⁵ is a hydrogen atom;

R ¹ is an alkyl group having 1 to 10 carbon atoms, R ² and R ³ are hydrogen atoms, m is an integer of 0 to 10, n is an integer of 2 to 10, and R ⁴ is an acetyl group. Wherein R ⁵ is a hydrogen atom (1m),
R ¹ is an alkyl group having 1 to 10 carbon atoms, R ² and R ³ are hydrogen atoms, m is an integer of 0 to 10, n is an integer of 2 to 10, and R ⁴ is trichloroacetyl. A compound (1m), wherein R ⁵ is a hydrogen atom,
R ¹ is an alkyl group having 1 to 10 carbon atoms, R ² and R ³ are hydrogen atoms, m is an integer of 0 to 10, n is an integer of 2 to 10, and R ⁴ is a benzoyl group. Wherein R ⁵ is a hydrogen atom (1m),
R ¹ is an alkyl group having 1 to 10 carbon atoms, R ² and R ³ are hydrogen atoms, m is an integer of 0 to 10, n is an integer of 2 to 10, and R ⁴ is methylsulfonyl. A compound (1m), wherein R ⁵ is a hydrogen atom,
R ¹ is an alkyl group having 1 to 10 carbon atoms, R ² and R ³ are hydrogen atoms, m is an integer of 0 to 10, n is an integer of 2 to 10, and R ⁴ is 4- A compound (1m) which is a methylbenzenesulfonyl group and R ⁵ is a hydrogen atom;
R ¹ is an alkyl group having 1 to 10 carbon atoms, R ² and R ³ are hydrogen atoms, m is an integer of 0 to 10, n is an integer of 2 to 10, and R ⁴ is 2- A compound (1m) which is a nitrobenzenesulfonyl group and R ⁵ is a hydrogen atom;
R ¹ is an alkyl group having 1 to 10 carbon atoms, R ² and R ³ are hydrogen atoms, m is an integer of 0 to 10, n is an integer of 2 to 10, R ⁴ and R ⁵ Are bonded to form a phthaloyl group (1m),

R ¹ is a methyl group, R ² and R ³ are hydrogen atoms, m is an integer of 0 to 10, n is an integer of 2 to 10, and R ⁴ has a substituent. A compound (1m) which is a good alkyloxycarbonyl group or an aryloxycarbonyl group which may have a substituent, and R ⁵ is a hydrogen atom,
R ¹ is a methyl group, R ² and R ³ are hydrogen atoms, m is an integer of 0 to 10, n is an integer of 2 to 10, and R ⁴ has a substituent. A compound (1m) which is a good alkyloxycarbonyl group and R ⁵ is a hydrogen atom;
R ¹ is a methyl group, R ² and R ³ are hydrogen atoms, m is an integer of 0 to 10, n is an integer of 2 to 10, and R ⁴ has a substituent. A compound (1m) which is a good aryloxycarbonyl group and R ⁵ is a hydrogen atom;
R ¹ is a methyl group, R ² and R ³ are hydrogen atoms, m is an integer of 0 to 10, n is an integer of 2 to 10, R ⁴ is a tert-butoxycarbonyl group, Compound (1m) wherein R ⁵ is a hydrogen atom,
R ¹ is a methyl group, R ² and R ³ are hydrogen atoms, m is an integer of 0 to 10, n is an integer of 2 to 10, and R ⁴ is 9H-fluoren-9-ylmethoxy. A compound (1m) which is a carbonyl group and R ⁵ is a hydrogen atom;
R ¹ is a methyl group, R ² and R ³ are hydrogen atoms, m is an integer of 0 to 10, n is an integer of 2 to 10, R ⁴ is a phenoxycarbonyl group, R ⁵ (1m) in which is a hydrogen atom,
R ¹ is a methyl group, R ² and R ³ are hydrogen atoms, m is an integer of 0 to 10, n is an integer of 2 to 10, and R ⁴ is a 4-nitrophenoxycarbonyl group. , Compound (1m) wherein R ⁵ is a hydrogen atom,

R ¹ is a methyl group, R ² and R ³ are hydrogen atoms, m is an integer of 0 to 10, n is an integer of 2 to 10, R ⁴ is an acetyl group, and R ⁵ is A compound that is a hydrogen atom (1 m),
R ¹ is a methyl group, R ² and R ³ are hydrogen atoms, m is an integer of 0 to 10, n is an integer of 2 to 10, R ⁴ is a trichloroacetyl group, R ⁵ (1m) in which is a hydrogen atom,
R ¹ is a methyl group, R ² and R ³ are hydrogen atoms, m is an integer of 0 to 10, n is an integer of 2 to 10, R ⁴ is a benzoyl group, and R ⁵ is A compound that is a hydrogen atom (1 m),
R ¹ is a methyl group, R ² and R ³ are hydrogen atoms, m is an integer of 0 to 10, n is an integer of 2 to 10, R ⁴ is a methylsulfonyl group, R ⁵ (1m) in which is a hydrogen atom,
R ¹ is a methyl group, R ² and R ³ are hydrogen atoms, m is an integer of 0 to 10, n is an integer of 2 to 10, and R ⁴ is a 4-methylbenzenesulfonyl group. , Compound (1m) wherein R ⁵ is a hydrogen atom,
R ¹ is a methyl group, R ² and R ³ are hydrogen atoms, m is an integer of 0 to 10, n is an integer of 2 to 10, R ⁴ is a 2-nitrobenzenesulfonyl group, The compound wherein R ⁵ is a hydrogen atom (1m), and
R ¹ is a methyl group, R ² and R ³ are hydrogen atoms, m is an integer of 0 to 10, n is an integer of 2 to 10, R ⁴ and R ⁵ are bonded, and phthaloyl The compound (1m) which forms group is mentioned.

In particular,
N-tert-butoxycarbonyl-2-vinyloxyethylamine,
N-tert-butoxycarbonyl-2- (2-vinyloxyethoxy) ethylamine,
N-tert-butoxycarbonyl-2- (2- (2-vinyloxyethoxy) ethoxy) ethylamine,
N-tert-butoxycarbonyl-2- (2- (2- (2-vinyloxyethoxy) ethoxy) ethoxy) ethylamine,
N-tert-butoxycarbonyl-2- (2- (2- (2- (2-vinyloxyethoxy) ethoxy) ethoxy) ethoxy) ethylamine,
N-tert-butoxycarbonyl-2- (2- (2- (2- (2- (2-vinyloxyethoxy) ethoxy) ethoxy) ethoxy) ethoxy) ethylamine),
N-tert-butoxycarbonyl-2- (2- (2- (2- (2- (2- (2- (2-vinyloxyethoxy) ethoxy) ethoxy) ethoxy) ethoxy) ethoxy) ethoxy) ethylamine),
N-tert-butoxycarbonyl-3-vinyloxypropylamine,
N-tert-butoxycarbonyl-2- (3-vinyloxypropoxy) ethylamine,
N-tert-butoxycarbonyl-4-vinyloxybutylamine,
N-tert-butoxycarbonyl-2- (4-vinyloxybutoxy) ethylamine,

N-acetyl-2-vinyloxyethylamine,
N-acetyl-2- (2-vinyloxyethoxy) ethylamine,
N-acetyl-2- (2- (2-vinyloxyethoxy) ethoxy) ethylamine,
N-acetyl-2- (2- (2- (2-vinyloxyethoxy) ethoxy) ethoxy) ethylamine,
N-acetyl-2- (2- (2- (2- (2-vinyloxyethoxy) ethoxy) ethoxy) ethoxy) ethylamine,
N-acetyl-2- (2- (2- (2- (2- (2-vinyloxyethoxy) ethoxy) ethoxy) ethoxy) ethoxy) ethylamine),
N-acetyl-2- (2- (2- (2- (2- (2- (2- (2-vinyloxyethoxy) ethoxy) ethoxy) -ethoxy) ethoxy) ethoxy) ethoxy) ethylamine),
N-acetyl-3-vinyloxypropylamine,
N-acetyl-2- (3-vinyloxypropoxy) ethylamine,
N-acetyl-4-vinyloxybutylamine,
N-acetyl-2- (4-vinyloxybutoxy) ethylamine,

N- (9H-fluoren-9-ylmethoxycarbonyl) -2-vinyloxyethylamine,
N- (9H-fluoren-9-ylmethoxycarbonyl) -2- (2-vinyloxyethoxy) ethylamine,
N- (9H-fluoren-9-ylmethoxycarbonyl) -2- (2- (2-vinyloxyethoxy) ethoxy) ethylamine,
N- (9H-fluoren-9-ylmethoxycarbonyl) -2- (2- (2- (2-vinyloxyethoxy) ethoxy) ethoxy) ethylamine,
N- (9H-fluoren-9-ylmethoxycarbonyl) -2- (2- (2- (2- (2-vinyloxyethoxy) ethoxy) ethoxy) ethoxy) ethylamine,
N- (9H-fluoren-9-ylmethoxycarbonyl) -2- (2- (2- (2- (2- (2-vinyloxyethoxy) ethoxy) ethoxy) ethoxy) ethoxy) ethylamine),
N- (9H-fluoren-9-ylmethoxycarbonyl) -2- (2- (2- (2- (2- (2- (2- (2-vinyloxyethoxy) ethoxy) ethoxy) -ethoxy) ethoxy)) Ethoxy) ethoxy) ethylamine,
N- (9H-fluoren-9-ylmethoxycarbonyl) -3-vinyloxypropylamine,
N- (9H-fluoren-9-ylmethoxycarbonyl) -2- (3-vinyloxypropoxy) ethylamine,
N-acetyl-4-vinyloxybutylamine,
N- (9H-fluoren-9-ylmethoxycarbonyl) -2- (4-vinyloxybutoxy) ethylamine,

N-tert-butoxycarbonyl-2- (1-methylvinyloxy) ethylamine,
N-tert-butoxycarbonyl-2- (2- (1-methylvinyloxy) ethoxy) ethylamine,
N-tert-butoxycarbonyl-2- (2- (2- (1-methylvinyloxy) ethoxy) ethoxy) ethylamine,
N-tert-butoxycarbonyl-2- (2- (2- (2- (1-methylvinyloxy) ethoxy) ethoxy) ethoxy) ethylamine,
N-tert-butoxycarbonyl-2- (2- (2- (2- (2- (1-methylvinyloxy) ethoxy) ethoxy) ethoxy) ethoxy) ethylamine)
N-tert-butoxycarbonyl-2- (2- (2- (2- (2- (2- (1-methylvinyloxy) ethoxy) ethoxy) ethoxy) ethoxy) ethoxy) ethylamine),
N-tert-butoxycarbonyl-2- (2- (2- (2- (2- (2- (2- (2- (1-methylvinyloxy) ethoxy) ethoxy) ethoxy) ethoxy) ethoxy) ethoxy) ethoxy) ethoxy ) Ethylamine,
N-tert-butoxycarbonyl-3- (1-methylvinyloxy) propylamine,
N-tert-butoxycarbonyl-2- (3- (1-methylvinyloxy) propoxy) ethylamine,
N-tert-butoxycarbonyl-4- (1-methylvinyloxy) butylamine,
N-tert-butoxycarbonyl-2- (4- (1-methylvinyloxy) butoxy) ethylamine,

N- (2-vinyloxyethyl) phthalimide,
N- (2- (2-vinyloxyethoxy) ethyl) phthalimide,
N- (2- (2- (2- (2-vinyloxyethoxy) ethoxy) ethyl) phthalimide,
N- (2- (2- (2- (2- (2-vinyloxyethoxy) ethoxy) ethoxy) ethyl) phthalimide)
N- (2- (2- (2- (2- (2-vinyloxyethoxy) ethoxy) ethoxy) ethoxy) ethyl) phthalimide,
N- (2- (2- (2- (2- (2- (2-vinyloxyethoxy) ethoxy) ethoxy) ethoxy) ethoxy) ethyl) phthalimide),
N- (2- (2- (2- (2- (2- (2- (2- (2-vinyloxyethoxy) ethoxy) ethoxy) ethoxy) ethoxy) ethoxy) ethoxy) ethyl) phthalimide),
N- (3-vinyloxypropanyl) phthalimide,
N- (2- (3-vinyloxypropoxy) ethyl) phthalimide,
N- (4-vinyloxybutyl) phthalimide, and
N- (2- (4-vinyloxybutoxy) ethyl) phthalimide is mentioned.

  In the resin (1), in addition to the structural unit (1), a structural unit derived from a monomer having two or more carbon-carbon unsaturated bonds in the molecule (hereinafter abbreviated as structural unit (2)). Can be included. As the carbon-carbon unsaturated bond, a carbon-carbon double bond is preferable. Since the resin (1) containing the structural unit (2) contains a cross-linked structure and is difficult to dissolve in a solvent, when the resin (1) is used as a filler for liquid chromatography, the mobile phase of the liquid chromatography As a result, the range of choice of the solvent to be used is expanded. When the resin (1) includes the structural unit (2), the content of the structural unit (1) in the resin (1) is usually 99 with respect to 100 mol in total of the structural unit (1) and the structural unit (2). The content of the structural unit (2) is usually 1 to 99 mol with respect to 100 mol in total of the structural unit (1) and the structural unit (2). By appropriately adjusting the content of the structural unit (2), the solubility of the resin (1) in the solvent can be controlled, and the content of the structural unit (2) leads to the structural unit (2) to be used. It can adjust suitably by adjusting the usage-amount of a monomer.

  A commercially available product can be used as the monomer for deriving the structural unit (2). Commercially available products include divinylbenzene, triaryl isocyanurate, ethylene glycol diacrylate, butylene glycol diacrylate, triethylene glycol diacrylate, trimethylolpropane triacrylate, pentaerythritol triacrylate, N, N′-methylenebisacrylamide, Ethylene glycol dimethacrylate, butylene glycol dimethacrylate, triethylene glycol dimethacrylate, trimethylolpropane trimethacrylate, pentaerythritol trimethacrylate, N, N'-methylenebismethacrylamide, ethylene glycol divinyl ether, butylene glycol divinyl ether , Triethylene glycol divinyl ether, trimethylolpropane trivinyl ether Include pentaerythritol ether and diaryl phthalate.

（式中、ｐは０以上の整数を表わす。ｑおよびrはそれぞれ独立に、２以上の整数を表わす。Ｒ⁶、Ｒ⁷およびＲ⁸はそれぞれ独立に、水素原子、置換基を有していてもよいアルキル基または置換基を有していてもよいアリール基を表わし、Ｒ⁶とＲ⁷とが結合して、これらが結合している炭素原子と一緒になって環を形成していてもよく、Ｒ⁷とＲ⁸とが結合して、これらが結合している炭素原子と一緒になって環を形成していてもよい。）
で示される化合物（以下、化合物（２ｍ）と略記する。）を用いることができる。
Ｒ⁶、Ｒ⁷およびＲ⁸の「置換基を有していてもよいアルキル基」および「置換基を有していてもよいアリール基」としては、それぞれ前記Ｒ^１、Ｒ^２およびＲ^３と同様のものが挙げられる。、Ｒ⁶とＲ⁷とが結合して、これらが結合している炭素原子と一緒になって形成する環としては、前記Ｒ^１とＲ^２とが結合して、それらが結合している炭素原子とともに形成する環と同様のものが挙げられる。Ｒ^７とＲ^８とが結合して、これらが結合している炭素原子と一緒になって形成する環としては、前記Ｒ^２とＲ^３とが結合して、それらが結合している炭素原子とともに形成する環と同様のものが挙げられる。
ｐが大きすぎると、化合物（２ｍ）の付加重合の反応性が低下し易くなる傾向があるため、ｐは１０００以下の整数であることが好ましく、１００以下の整数であることがより好ましく、１０以下の整数であることが特に好ましい。化合物（２ｍ）を製造するための原料の入手が容易であるという点で、ｑは３０以下の整数であることが好ましく、１０以下の整数であることがより好ましく、６以下の整数であることが特に好ましい。 As a monomer leading to the structural unit (2), the formula (2m):

(In the formula, p represents an integer of 0 or more. Q and r each independently represents an integer of 2 or more. R ⁶ , R ⁷ and R ⁸ each independently have a hydrogen atom or a substituent. Represents an optionally substituted alkyl group or an optionally substituted aryl group, and R ⁶ and R ⁷ are bonded together to form a ring together with the carbon atoms to which they are bonded. Alternatively, R ⁷ and R ⁸ may be bonded together to form a ring together with the carbon atom to which they are bonded.)
(Hereinafter, abbreviated as compound (2m)) can be used.
The “optionally substituted alkyl group” and the “optionally substituted aryl group” for R ⁶ , R ⁷ and R ⁸ are the above R ¹ , R ² and R ³ , respectively. The same thing is mentioned. , R ⁶ and R ⁷ are bonded to each other and the ring formed together with the carbon atom to which they are bonded is the carbon to which R ¹ and R ² are bonded to each other. The thing similar to the ring formed with an atom is mentioned. The ring formed by combining R ⁷ and R ⁸ together with the carbon atom to which they are bonded includes the carbon atom to which R ² and R ³ are bonded and to which they are bonded And the same ring as that formed together.
If p is too large, the reactivity of the addition polymerization of the compound (2m) tends to decrease. Therefore, p is preferably an integer of 1000 or less, more preferably an integer of 100 or less. Particularly preferred are the following integers. Q is preferably an integer of 30 or less, more preferably an integer of 10 or less, and an integer of 6 or less in that it is easy to obtain a raw material for producing the compound (2m). Is particularly preferred.

As the compound (2m),
3-vinyloxypropoxyethene, 4-vinyloxybutoxyethene, 5-vinyloxypentoxyethene, 6-vinyloxyhexoxyethene, 7-vinyloxyheptoxyethene, 8-vinyloxyoctoxyethene, 2-vinyloxy Ethoxyethene, 2- (2-vinyloxyethoxy) ethoxyethene, 2- (2- (2-vinyloxyethoxy) ethoxy) ethoxyethene, 2- (2- (2- (2-vinyloxyethoxy) ethoxy) ethoxy ) Ethoxyethene, 2- (2- (2- (2- (2-vinyloxyethoxy) ethoxy) ethoxy) ethoxy) ethoxyethene, 2- (2- (2- (2- (2- (2-vinyloxy) Ethoxy) ethoxy) ethoxy) ethoxy) ethoxy) ethoxyethene, 2- (2- (2- (2- (2- (2 (2- (2-vinyloxyethoxy) ethoxy) ethoxy) -ethoxy) ethoxy) ethoxy) ethoxy) ethoxyethene, 2- (2- (2- (2- (2- (2- (2- (2- (2- ( 2-vinyloxyethoxy) ethoxy) ethoxy) ethoxy) ethoxy) ethoxy) ethoxy) ethoxy) ethoxyethene, 2- (2- (2- (2- (2- (2- (2- (2- (2- ( 2-vinyloxyethoxy) ethoxy) ethoxy) ethoxy) ethoxy) ethoxy) ethoxy) ethoxy) ethoxy) ethoxy) ethene, 3- (2- (3-vinyloxypropoxy) ethoxy) propoxyethene, 4- (2- (4 -Vinyloxybutoxy) ethoxy) butoxyethene,

2- (1-methylvinyloxy) ethoxyethene-2- (2- (1-methylvinyloxy) ethoxy) ethoxyethene, 2- (2- (2- (1- (methylvinyloxy) ethoxy) ethoxy) ethoxyethene 2- (2- (2- (2- (2- (1-methylvinyloxy) ethoxy) ethoxy) ethoxy) ethoxyethene, 2- (2- (2- (2- (2- (1-methylvinyloxy) ethoxy) ) Ethoxy) ethoxy) ethoxy) ethoxyethene, 2- (2- (2- (2- (2- (2- (1-methylvinyloxy) ethoxy) ethoxy) ethoxy) ethoxy) ethoxy) ethoxyethene, 2- ( 2- (2- (2- (2- (2- (2- (2- (1-methylvinyloxy) ethoxy) ethoxy) ethoxy) ethoxy) ethoxy) ethoxy) ethoxy) ethoxy) , 2- (2- (2- (2- (2- (2- (2- (2- (2- (1-methylvinyloxy) ethoxy) ethoxy) ethoxy) ethoxy) ethoxy) ethoxy) ethoxy) ethoxy) ) Ethoxyethene, 2- (2- (2- (2- (2- (2- (2- (2- (2- (2- (1-methylvinyloxy) ethoxy) ethoxy) ethoxy) ethoxy) ethoxy)) Ethoxy) ethoxy) ethoxy) ethoxy) ethoxy) ethene, 3- (2- (3- (1-methylvinyloxy) propoxy) ethoxy) propoxyethene, 4- (2- (4- (1-methylvinyloxy) butoxy) ) Ethoxy) butoxyethene,

2- (2-methylvinyloxy) ethoxyethene, 2- (2- (2-methylvinyloxy) ethoxy) ethoxyethene, 2- (2- (2- (2-methylvinyloxy) ethoxy) ethoxy) ethoxyethene 2- (2- (2- (2- (2-methylvinyloxy) ethoxy) ethoxy) ethoxy) ethoxyethene, 2- (2- (2- (2- (2- (2-methylvinyloxy) ethoxy) ) Ethoxy) ethoxy) ethoxy) ethoxyethene, 2- (2- (2- (2- (2- (2- (2-methylvinyloxy) ethoxy) ethoxy) ethoxy) ethoxy) ethoxy) ethoxyethene, 2- ( 2- (2- (2- (2- (2- (2- (2- (2-methylvinyloxy) ethoxy) ethoxy) ethoxy) ethoxy) ethoxy) ethoxy) ethoxy) ethoxy) , 2- (2- (2- (2- (2- (2- (2- (2- (2- (2-methylvinyloxy) ethoxy) ethoxy) ethoxy) ethoxy) ethoxy) ethoxy) ethoxy) ethoxy) ) Ethoxyethene, 2- (2- (2- (2- (2- (2- (2- (2- (2- (2- (2-methylvinyloxy) ethoxy) ethoxy) ethoxy) ethoxy) ethoxy)) Ethoxy) ethoxy) ethoxy) ethoxy) ethoxy) ethene, 3- (2- (3- (2-methylvinyloxy) propoxy) ethoxy) propoxyethene, 4- (2- (4- (2-methylvinyloxy) butoxy) ) Ethoxy) butoxyethene,

2- (1-phenylvinyloxy) ethoxyethene, 2- (2- (1-phenylvinyloxy) ethoxy) ethoxyethene, 2- (2- (2- (1-phenylvinyloxy) ethoxy) ethoxy) ethoxyethene 2- (2- (2- (2- (1- (phenylvinyloxy) ethoxy) ethoxy) ethoxy) ethoxyethene, 2- (2- (2- (2- (2- (1-phenylvinyloxy) ethoxy) ) Ethoxy) ethoxy) ethoxy) ethoxyethene, 2- (2- (2- (2- (2- (2- (1-phenylvinyloxy) ethoxy) ethoxy) ethoxy) ethoxy) ethoxy) ethoxyethene, 2- ( 2- (2- (2- (2- (2- (2- (2- (1-phenylvinyloxy) ethoxy) ethoxy) ethoxy) ethoxy) ethoxy) ethoxy) eth) Ii) ethoxyethene, 2- (2- (2- (2- (2- (2- (2- (2- (2- (1-phenylvinyloxy) ethoxy) ethoxy) ethoxy) ethoxy) ethoxy) ethoxy)) Ethoxy) ethoxy) ethoxyethene, 2- (2- (2- (2- (2- (2- (2- (2- (2- (2- (1-phenylvinyloxy) ethoxy) ethoxy) ethoxy) ethoxy) ethoxy) ) Ethoxy) ethoxy) ethoxy) ethoxy) ethoxy) ethoxy) ethene, 3- (2- (3- (1-phenylvinyloxy) propoxy) ethoxy) propoxyethene, 4- (2- (4- (1-phenylvinyl) Oxy) butoxy) ethoxy) butoxyethene,

2- (2-phenylvinyloxy) ethoxyethene, 2- (2- (2-phenylvinyloxy) ethoxy) ethoxyethene, 2- (2- (2- (2-phenylvinyloxy) ethoxy) ethoxy) ethoxyethene 2- (2- (2- (2- (2-phenylvinyloxy) ethoxy) ethoxy) ethoxy) ethoxyethene, 2- (2- (2- (2- (2- (2-phenylvinyloxy) ethoxy) ) Ethoxy) ethoxy) ethoxy) ethoxyethene, 2- (2- (2- (2- (2- (2- (2-phenylvinyloxy) ethoxy) ethoxy) ethoxy) ethoxy) ethoxy) ethoxyethene, 2- ( 2- (2- (2- (2- (2- (2- (2- (2-phenylvinyloxy) ethoxy) ethoxy) ethoxy) ethoxy) ethoxy) ethoxy) eth) Ii) ethoxyethene, 2- (2- (2- (2- (2- (2- (2- (2- (2- (2-phenylvinyloxy) ethoxy) ethoxy) ethoxy) ethoxy) ethoxy) ethoxy)) Ethoxy) ethoxy) ethoxyethene, 2- (2- (2- (2- (2- (2- (2- (2- (2- (2- (2-phenylvinyloxy) ethoxy) ethoxy) ethoxy) ethoxy) ethoxy) ) Ethoxy) ethoxy) ethoxy) ethoxy) ethoxy) ethoxy) ethene, 3- (2- (3- (2-phenylvinyloxy) propoxy) ethoxy) propoxyethene, 4- (2- (4- (2-phenylvinyl) Oxy) butoxy) ethoxy) butoxyethene,

2- (cyclohexen-1-yloxy) ethoxyethene, 2- (2- (cyclohexen-1-yloxy) ethoxy) ethoxyethene, 2- (2- (2- (cyclohexen-1-yloxy) ethoxy) ethoxy) ethoxyethene , 2- (2- (2- (2- (cyclohexen-1-yloxy) ethoxy) ethoxy) ethoxy) ethoxyethene, 2- (2- (2- (2- (2- (cyclohexen-1-yloxy) ethoxy) ) Ethoxy) ethoxy) ethoxy) ethoxyethene, 2- (2- (2- (2- (2- (2- (cyclohexen-1-yloxy) ethoxy) ethoxy) ethoxy) ethoxy) ethoxy) ethoxyethene, 2- ( 2- (2- (2- (2- (2- (2- (2- (cyclohexen-1-yloxy) ethoxy) ethoxy) ethoxy) Xyl) ethoxy) ethoxy) ethoxy) ethoxy) ethoxyethene, 2- (2- (2- (2- (2- (2- (2- (2- (2- (cyclohexen-1-yloxy) ethoxy) ethoxy) ethoxy) Ethoxy) ethoxy) ethoxy) ethoxy) ethoxy) ethoxy) ethoxyethene, 2- (2- (2- (2- (2- (2- (2- (2- (2- (2- (cyclohexen-1-yloxy) ) Ethoxy) ethoxy) ethoxy) ethoxy) ethoxy) ethoxy) ethoxy) ethoxy) ethoxy) ethoxy) ethene, 3- (2- (3- (cyclohexen-1-yloxy) propoxy) ethoxy) propoxyethene and 4- (2- (4- (Cyclohexen-1-yloxy) butoxy) ethoxy) butoxyethene.

（式中、ｓは０以上の整数を表わし、ｔは０以上の整数を表わす。Ｒ^９、Ｒ^１0およびＲ^１１はそれぞれ独立に、水素原子、置換基を有していてもよいアルキル基または置換基を有していてもよいアリール基を表し、Ｒ^９とＲ^１0とが結合して環を形成していてもよく、Ｒ^１0とＲ^１１とが結合して環を形成していてもよい。Ｒ^１２は、水素原子、水酸基、置換基を有していてもよいアルキル基、置換基を有していてもよいアリール基、置換基を有していてもよいアルコキシ基または置換基を有していてもよいアリールオキシ基を表わす。）
で示される構造単位（以下、構造単位（３）と略記する。）を含むことができる。 Resin (1) contains, in addition to structural unit (1), formula (3):

(In the formula, s represents an integer of 0 or more, and t represents an integer of 0 or more. R ⁹ , R ¹⁰ and R ¹¹ are each independently a hydrogen atom, an alkyl group which may have a substituent, or An aryl group which may have a substituent, R ⁹ and R ¹⁰ may be bonded to form a ring, or R ¹⁰ and R ¹¹ may be bonded to form a ring; R ¹² represents a hydrogen atom, a hydroxyl group, an alkyl group which may have a substituent, an aryl group which may have a substituent, an alkoxy group which may have a substituent or a substituent. Represents an aryloxy group which may be present.)
(Hereinafter abbreviated as structural unit (3)).

（式中、ｓ、ｔ、Ｒ^９、Ｒ^１0、Ｒ^１１およびＲ^１２は上記と同一の意味を表わす。）
で示される化合物（以下、化合物（３ｍ）と略記する。）から導かれる。
Ｒ^９、Ｒ^１0、Ｒ^１１およびＲ^１２における置換基を有していてもよいアルキル基および置換基を有していてもよいアリール基は、それぞれ前記したものと同様のものが挙げられる。 The structural unit (3) has the formula (3m):

(In the formula, s, t, R ⁹ , R ¹⁰ , R ¹¹ and R ¹² have the same meaning as described above.)
(Hereinafter abbreviated as compound (3m)).
Examples of the alkyl group which may have a substituent and the aryl group which may have a substituent in R ⁹ , R ¹⁰ , R ¹¹ and R ¹² are the same as those described above.

The alkoxy group which may have a substituent in R ¹² is an unsubstituted carbon number such as a methoxy group, an ethoxy group, a propoxy group, a 2-propoxy group, a butoxy group, a 2-butoxy group, and a tert-butoxy group. An alkoxy group having 1 to 10 carbon atoms substituted with an aryl group having 6 to 15 carbon atoms such as a phenylmethoxy group, and 9H-fluorene-9 such as a 9H-fluoren-9-ylmethoxy group; -The C1-C10 alkoxy group substituted by the yl group is mentioned.
As the aryloxy group which may have a substituent in R ^12, an unsubstituted aryloxy group having 6 to 15 carbon atoms such as a phenoxy group, 1-naphthyloxy group, 2-naphthyloxy group, 2-methyl An aryloxy group having 6 to 15 carbon atoms substituted with an alkyl group having 1 to 10 carbon atoms such as a phenoxy group, a 3-methylphenoxy group and a 4-methylphenoxy group, a 2-methoxyphenoxy group, a 3-methoxyphenoxy group, Nitro groups such as aryloxy groups having 6 to 15 carbon atoms, 2-nitrophenoxy groups, 3-nitrophenoxy groups, 4-nitrophenoxy groups and the like substituted by alkoxy groups having 1 to 10 carbon atoms such as 4-methoxyphenoxy groups Aryloxy group having 6 to 15 carbon atoms, 4-chlorophenoxy group, 4-bromophenoxy group, 4-iodophenoxy group substituted with C6-C15 aryl substituted with halogen atoms such as 2-chlorophenoxy group, 2-bromophenoxy group, 2-iodophenoxy group, 3-chlorophenoxy group, 3-bromophenoxy group, 3-iodophenoxy group An oxy group is mentioned.

As the compound (3m), a commercially available product may be used, or a compound produced according to a known method may be used.
Specific examples of the compound (3m) include
3-vinyloxypropoxymethane, 4-vinyloxybutoxymethane, 5-vinyloxypentyloxymethane, 6-vinyloxyhexyloxymethane, 7-vinyloxyheptyloxymethane, 8-vinyloxyoctyloxymethane, 2-vinyloxy Ethoxymethane, 2- (2-vinyloxyethoxy) ethoxymethane, 2- (2- (2-vinyloxyethoxy) ethoxy) ethoxymethane, 2- (2- (2- (2-vinyloxyethoxy) ethoxy) ethoxy ) Ethoxymethane, 2- (2- (2- (2- (2-vinyloxyethoxy) ethoxy) ethoxy) ethoxy) ethoxymethane, 2- (2- (2- (2- (2- (2-vinyloxy) Ethoxy) ethoxy) ethoxy) ethoxy) ethoxy) ethoxymethane, 2- (2- (2- (2- (2- (2- (2- (2-vinyloxyethoxy) ethoxy) ethoxy) -ethoxy) ethoxy) ethoxy) ethoxy) ethoxymethane, 2- (2- (2- (2- (2- (2- ( 2- (2- (2- (2-vinyloxyethoxy) ethoxy) ethoxy) ethoxy) ethoxy) ethoxy) ethoxy) ethoxy) ethoxymethane, 3- (2- (3-methoxypropoxy) ethoxy) propoxyethene, 4- (2- (4-methoxybutoxy) ethoxy) butoxyethene,

3-vinyloxypropoxyethane, 4-vinyloxybutoxyethane, 5-vinyloxypentyloxyethane, 6-vinyloxyhexyloxyethane, 7-vinyloxyheptyloxyethane, 8-vinyloxyoctyloxyethane, 2-vinyloxy Ethoxyethane, 2- (2-vinyloxyethoxy) ethoxyethane, 2- (2- (2-vinyloxyethoxy) ethoxy) ethoxyethane, 2- (2- (2- (2-vinyloxyethoxy) ethoxy) ethoxy ) Ethoxyethane, 2- (2- (2- (2- (2-vinyloxyethoxy) ethoxy) ethoxy) ethoxy) ethoxyethane, 2- (2- (2- (2- (2- (2-vinyloxy) Ethoxy) ethoxy) ethoxy) ethoxy) ethoxy) ethoxyethane, 2- (2- (2- 2- (2- (2- (2- (2- (vinyloxyethoxy) ethoxy) ethoxy) -ethoxy) ethoxy) ethoxy) ethoxy) ethoxyethane, 2- (2- (2- (2- (2- (2 -(2- (2- (2-vinyloxyethoxy) ethoxy) ethoxy) ethoxy) ethoxy) ethoxy) ethoxy) ethoxy) ethoxyethane, 3- (2- (3-ethoxypropoxy) ethoxy) propoxyethene, 4- ( 2- (4-ethoxybutoxy) ethoxy) butoxyethene,

3-hydroxypropoxyethene, 4-hydroxybutoxyethene, 5-hydroxypentyloxyethene, 6-hydroxyhexyloxyethene, 7-hydroxyheptyloxyethene, 8-hydroxyoctyloxyethene, 2-hydroxyethoxyethene, 2- (2 -Hydroxyethoxy) ethoxyethene, 2- (2- (2-hydroxyethoxy) ethoxy) ethoxyethene, 2- (2- (2- (2-hydroxyethoxy) ethoxy) ethoxy) ethoxyethene, 2- (2- ( 2- (2- (2-hydroxyethoxy) ethoxy) ethoxy) ethoxy) ethoxyethene, 2- (2- (2- (2- (2- (2-hydroxyethoxy) ethoxy) ethoxy) ethoxy) ethoxy) ethoxyethene) , 2- (2- (2- (2- (2- (2- (2- 2-hydroxyethoxy) ethoxy) ethoxy) -ethoxy) ethoxy) ethoxy) ethoxy) ethoxyethene, 2- (2- (2- (2- (2- (2- (2- (2- (2-hydroxyethoxy)) Ethoxy) ethoxy) ethoxy) ethoxy) ethoxy) ethoxy) ethoxy) ethoxyethene,

3-vinyloxypropoxybenzene, 4-vinyloxybutoxybenzene, 5-vinyloxypentyloxybenzene, 6-vinyloxyhexyloxybenzene, 7-vinyloxyheptyloxybenzene, 8-vinyloxyoctyloxybenzene, 2-vinyloxy Ethoxybenzene, 2- (2-vinyloxyethoxy) ethoxybenzene, 2- (2- (2-vinyloxyethoxy) ethoxy) ethoxybenzene, 2- (2- (2- (2-vinyloxyethoxy) ethoxy) ethoxy ) Ethoxybenzene, 2- (2- (2- (2- (2-vinyloxyethoxy) ethoxy) ethoxy) ethoxy) ethoxybenzene, 2- (2- (2- (2- (2- (2-vinyloxy) Ethoxy) ethoxy) ethoxy) ethoxy) ethoxy) ethoxybe Zen, 2- (2- (2- (2- (2- (2- (2- (2-vinyloxyethoxy) ethoxy) ethoxy) ethoxy) ethoxy) ethoxy) ethoxy) ethoxybenzene, 2- (2- ( 2- (2- (2- (2- (2- (2- (2-vinyloxyethoxy) ethoxy) ethoxy) ethoxy) ethoxy) ethoxy) ethoxy) ethoxy) ethoxybenzene, 3- (2- (3-phenoxy Propoxy) ethoxy) propoxyethene, 4- (2- (4-phenoxybutoxy) ethoxy) butoxyethene,

Ethyl vinyl ether, propyl vinyl ether, 2-propyl vinyl ether, butyl vinyl ether, tert-butyl vinyl ether, pentyl vinyl ether, hexyl vinyl ether, heptyl vinyl ether, octyl vinyl ether, 2-ethylhexyl vinyl ether, nonyl vinyl ether, decyl vinyl ether, undecyl vinyl ether, dodecyl vinyl ether, tri Examples include decyl vinyl ether, tetradecyl vinyl ether, pentadecyl vinyl ether, hexadecyl vinyl ether, heptadecyl vinyl ether, and octadecyl vinyl ether.

  The content of the structural unit (1) in the resin (1) is usually 100 to 1 mol with respect to a total of 100 mol of the structural unit (1) and the structural unit (3), and the content of the structural unit (3). Is usually 0 to 99 mol with respect to 100 mol in total of the structural unit (1) and the structural unit (3). By appropriately adjusting the content of the structural unit (3), the content of the amino group in the resin (1) can be controlled, and the content of the structural unit (3) depends on the use of the compound (3m) to be used. It can adjust suitably by adjusting quantity. The content of amino groups in the resin (1) is one of the factors that determine the degree of hydrophilicity and the degree of hydrophobicity of the resin (1).

  The resin (1) preferably includes the structural unit (1), the structural unit (2), and the structural unit (3).

Then, the manufacturing method of resin (1) is demonstrated.
The resin (1) can be produced by polymerizing a monomer that gives the structural unit (1) such as the compound (1m). As long as the object of the present invention is achieved, as a monomer of the resin (1), a monomer that gives a structural unit (2) such as a compound (2m), and a structural unit (3) such as a compound (3m), if necessary. A monomer other than the monomer that provides the structural unit (1) such as a monomer that provides
The resin (1) containing the structural unit (1) and the structural unit (2) can be produced by polymerizing a monomer containing the compound (1m) and the compound (2m). The resin (1) containing the structural unit (1) and the structural unit (3) can be produced by polymerizing a monomer containing the compound (1m) and the compound (3m). The resin (1) containing the structural unit (1), the structural unit (2) and the structural unit (3) is produced by polymerizing a monomer containing the compound (1m), the compound (2m) and the compound (3m). can do.

  Examples of the method for producing the resin (1) include addition polymerization methods such as radical polymerization, cationic polymerization, and anionic polymerization. Radical polymerization is preferred from the viewpoint of obtaining a substantially spherical particle-shaped resin (1), and it is easy to obtain a substantially spherical particle-shaped resin (1) having a practical particle size as a filler for liquid chromatography. Suspension polymerization is more preferable.

Hereinafter, a method for producing the resin (1) by suspension polymerization will be described.
Suspension polymerization includes a step of subjecting compound (1m) or a monomer containing compound (1m) to suspension polymerization in water. The water can contain a water-soluble organic solvent that does not dissolve or hardly dissolve the compound (1m). Such suspension polymerization is described, for example, in J. Org. Sep. Sci. , 2005, 28, 1855-1875 and the like.
The suspension polymerization is preferably performed in the presence of a dispersion stabilizer. As the dispersion stabilizer, various commercially available ones can be used, and polymeric dispersion stabilizers such as polyvinyl alcohol, polyvinyl pyrrolidone, polyacrylic acid, hydroxyalkyl cellulose, and natural gum are preferable. The amount of the dispersion stabilizer used is, for example, in the range of 0.1 to 10% by weight with respect to the total weight of water and the dispersion stabilizer, and preferably in the range of 1 to 3% by weight.
Here, the suspension means that the compound (1m) or the monomer containing the compound (1m) is dispersed in water together with a dispersion stabilizer contained as necessary to form dispersed droplets.

  In addition to water, an organic solvent that is insoluble or hardly soluble in water and can dissolve the monomer to be used can also be used. Such an organic solvent is called porogen. By using porogen, a substantially spherical particle-shaped resin (1) having a porous surface can be obtained. Examples of porogen include toluene, toluene in which polystyrene is dissolved, cyclohexanol, dodecanol, tetradecanol and hexadecanol. The amount of porogen used is, for example, 0 to 300 parts by volume with respect to 100 parts by volume of the monomer.

By mixing water and the monomer and sufficiently stirring the resulting mixture, the monomer becomes dispersed droplets and is dispersed in water. The stirring can be performed using a normal stirring means such as a magnetic stirrer or a stirring motor. The faster the stirring speed, the better the dispersibility of the dispersed droplets. However, if the speed is too high, the energy cost tends to increase, and the faster the stirring speed, the smaller the spherical particle-shaped resin (1). It becomes easy to be done. Therefore, in order to obtain a substantially spherical particulate resin (1) having a desired particle size, the type and amount of the dispersion stabilizer, the type and amount of the monomer, the amount of water used, and the stirring speed are appropriately adjusted. When a magnetic stirrer is used as the stirring means, the stirring speed is usually adjusted to a range of 10 to 1500 rpm. Thus, a dispersion liquid in which dispersed droplets containing the monomer are dispersed in water is prepared.
Monomers are contained in the dispersed droplets. When porogen is used, porogen is usually contained in the dispersed droplets.

  The suspension polymerization is preferably performed in the presence of a polymerization initiator. As the polymerization initiator, it is more preferable to use a general radical polymerization initiator that generates radicals by heating or ultraviolet irradiation. Specific examples include peroxides such as benzoyl peroxide and ammonium persulfate, and azo compounds such as 2,2′-azobisisobutyronitrile and 2,2′-azobis (2,4-dimethylvaleronitrile). It is done. The amount of the polymerization initiator used is usually in the range of 0.1 to 10% by weight based on the total weight of the monomers, and is appropriately selected so that a resin (1) having a desired molecular weight can be obtained.

After the dispersion droplets are formed in water, the polymerization is started. Usually, the temperature of the obtained dispersion liquid is adjusted so that it may become suitable polymerization temperature according to the kind of polymerization initiator used. As for superposition | polymerization temperature, the range of 60-80 degreeC etc. are mentioned, for example.
The usage-amount of water can mention the range of 99-1 volume part with respect to a total of 100 volume parts of water, a monomer, and porogen, for example.

A polymerization initiator, a monomer and, if necessary, porogen are mixed to prepare an organic phase. The organic phase can contain additives such as thickeners and preservatives. An aqueous phase is prepared by mixing a dispersion stabilizer and water. By adding the prepared organic phase while stirring the prepared aqueous phase at a constant speed, the organic phase is dispersed in the aqueous phase to form dispersed droplets. Subsequently, the dispersion liquid in which the obtained dispersion droplets are formed is adjusted to a predetermined polymerization temperature. As described above, the polymerization initiator may be dissolved in advance in the organic phase, but a dispersion is prepared from the organic phase not containing the polymerization initiator and the aqueous phase, and the dispersion is prepared at a predetermined polymerization temperature. The polymerization initiator may be added to the dispersion during or after the adjustment to a predetermined polymerization temperature.
The polymerization time varies depending on the monomer used, the polymerization initiator, and the type and amount of porogen used, but is usually in the range of 3 minutes to 72 hours. By collecting a sample for analysis from the reaction mixture in the middle of the polymerization reaction and analyzing the sample by an appropriate analysis means, the degree of progress of the polymerization reaction can be confirmed and the end point of the polymerization reaction can also be determined. .

  After completion of the suspension polymerization, for example, by filtering the obtained reaction mixture, the substantially spherical particle-shaped resin (1) can be taken out. The taken out resin (1) can be washed with a solvent as necessary. Examples of the solvent used for the washing include alcohol solvents such as water and methanol.

（式中、ｍ、ｎ、Ｒ^１、Ｒ^２およびＲ^３は上記と同一の意味を表わし、Ｒは、水素原子、置換基を有していてもよいアルキル基または置換基を有していてもよいアリール基を表わす。）
で示される構造単位（以下、構造単位（１０）と略記する。）に変換されたポリビニルエーテル樹脂（以下、樹脂（１０）と略記する。）を得ることができる。すなわち、樹脂（１０）は、構造単位（１０）を含む樹脂である。
樹脂（１０）は、樹脂（１）の全ての構造単位（１）が構造単位（１０）に変換された樹脂であってもよいし、樹脂（１）の構造単位（１）の一部が構造単位（１０）に変換された樹脂であってもよいが、液体クロマトグラフィー用の高分子担体としての使用という観点から、樹脂（１）の全ての構造単位（１）が実質的に構造単位（１０）に変換された樹脂であることが好ましい。樹脂（１０）は、構造単位（２）を有することが好ましい。樹脂（１０）は、構造単位（１０）、構造単位（２）および構造単位（３）を含むことが好ましい。 The obtained resin (1) is a resin having the structural unit (1), and the structural unit (1) may have an alkoxycarbonyl group which may have a substituent or a substituent. An aryloxycarbonyl group, an acyl group optionally having substituent (s), an alkylsulfonyl group optionally having substituent (s), or an amino group protected by an arylsulfonyl group optionally having substituent (s) And abbreviated as an amino group protected with a protecting group. By removing the protecting group from the amino group protected by the protecting group of the resin (1), the structural unit (1) has the formula (10):

(In the formula, m, n, R ¹ , R ² and R ³ have the same meaning as described above, and R has a hydrogen atom, an alkyl group which may have a substituent, or a substituent. Represents a good aryl group.)
The polyvinyl ether resin (henceforth abbreviated as resin (10)) converted into the structural unit shown below (hereinafter abbreviated as structural unit (10)) can be obtained. That is, the resin (10) is a resin containing the structural unit (10).
The resin (10) may be a resin in which all the structural units (1) of the resin (1) are converted into the structural units (10), or a part of the structural units (1) of the resin (1) The resin converted into the structural unit (10) may be used, but from the viewpoint of use as a polymer carrier for liquid chromatography, all the structural units (1) of the resin (1) are substantially structural units. A resin converted into (10) is preferred. The resin (10) preferably has a structural unit (2). The resin (10) preferably includes the structural unit (10), the structural unit (2), and the structural unit (3).

Examples of the method for removing the protecting group from the amino group protected by the protecting group of the resin (1) include a method of reacting the resin (1) with a deprotecting agent. The deprotecting agent is appropriately selected depending on the type of protecting group, and examples thereof include the deprotecting agents described in Protective Groups in Orgnic Chemistry (Greene et al., John Wiley & Sons, Inc.) and the like. For example, in the case of the resin (1) having the structural unit (1) in which R ⁴ is a tert-butoxycarbonyl group and R ⁵ is a hydrogen atom, trifluoroacetic acid or hydrochloric acid / dioxane solution is used as a deprotecting agent. . For example, in the case of the resin (1) having the structural unit (1) in which R ⁴ is a 9H-fluoren-9-ylmethoxycarbonyl group and R ⁵ is a hydrogen atom, piperidine is used as a deprotecting agent.
By contacting the resin (1) with a deprotecting agent in an appropriate solvent, the deprotection reaction of the amino group protected by the protecting group can be carried out. The reaction time of the deprotection reaction varies depending on the types of R ⁴ and R ⁵ of the structural unit (1) in the resin (1), the type of the deprotecting agent, and the reaction temperature, but is usually in the range of 3 minutes to 15 hours. . What is necessary is just to adjust suitably the usage-amount of a deprotecting agent with content of the structural unit (1) in resin (1), for example, it is large excess with respect to the equivalent of the structural unit (1) in resin (1). By using an amount of the deprotecting agent, all of the structural units (1) in the resin (1) can be converted into the structural units (10).

  After completion of the deprotection reaction, the obtained reaction mixture is preferably washed with an organic solvent such as water, saturated aqueous sodium hydrogen carbonate or methanol to remove the remaining deprotecting agent. When an acid such as trifluoroacetic acid is used as a deprotecting agent, a salt of an amino group and an acid in the resin (10) may be formed. For example, by contacting the reaction mixture with an alkali. The amino group forming the salt can be a free amino group.

  The resin (10) thus obtained has an amino group capable of immobilizing an enzyme or the like and can be used as a carrier for preparing an immobilized enzyme. The resin (10) has substantially the same shape as that of the resin (1). For example, by using a substantially spherical particle-shaped resin (1), a substantially spherical particle-shaped resin (10) is obtained. Can do. The substantially spherical particle-shaped resin (10) is also suitable as a polymer carrier used for a separation material for liquid chromatography in addition to the carrier for immobilized enzyme. The polymer carrier containing the substantially spherical particle-shaped resin (10) can be converted into an immobilized enzyme catalyst by, for example, immobilizing the enzyme by an appropriate method. After the obtained immobilized enzyme catalyst is packed in a packed column, a substrate solution can be converted into a target product by the action of an enzyme by passing the solution of a predetermined substrate through the packed column. Since the immobilized enzyme catalyst has a substantially spherical particle shape, the packed tower packed with the immobilized enzyme catalyst has an advantage that the substrate solution is excellent in liquid permeability. In addition, even when the predetermined substrate is a gas, the packed tower packed with the immobilized enzyme catalyst has an advantage that the gas permeability of the substrate is excellent. Similarly, a separation material for liquid chromatography containing a polymer carrier containing resin (10) is also suitable for analysis means such as a separation column having excellent liquid permeability of the sample solution.

（式中、Ｒ^２１およびＲ^２２はそれぞれ独立に、メトキシ基、イソプロポキシ基、エトキシ基、ベンジルオキシ基、ジメチルアミノ基またはピペリジニル基を表わす。）
で示されるジアゾ化合物（以下、ジアゾ化合物（２３）と略記する。）の存在下に、式（２１）：

（式中、Ｒ^１、Ｒ^２、Ｒ^３、ｍおよびｎは上記と同一の意味を表わす。）
で示される化合物（以下、化合物（２１）と略記する。）と Compound (1m) can be produced, for example, by a method including the following steps (A) to (C).
Step (A): Phosphine Compound and Formula (23):

(In the formula, R ²¹ and R ²² each independently represents a methoxy group, an isopropoxy group, an ethoxy group, a benzyloxy group, a dimethylamino group, or a piperidinyl group.)
In the presence of a diazo compound represented by the formula (hereinafter abbreviated as diazo compound (23)):

(In the formula, R ¹ , R ² , R ³ , m and n have the same meaning as described above.)
(Hereinafter abbreviated as compound (21)) and

（式中、Ｒ^２0は、１，２−エチレン基、１，２−フェニレン基または１，３−プロピレン基を表わす。）
で示される化合物（以下、化合物（２２）と略記する。）とを反応させて、 Formula (22):

(In the formula, R ²⁰ represents a 1,2-ethylene group, a 1,2-phenylene group, or a 1,3-propylene group.)
And a compound represented by the following (hereinafter abbreviated as compound (22)),

（式中、Ｒ^１、Ｒ^２、Ｒ^３、Ｒ^２０、ｍおよびｎは上記と同一の意味を表わす。）
で示される化合物（以下、化合物（２４）と略記する。）を得る工程、 Formula (24):

(In the formula, R ¹ , R ² , R ³ , R ²⁰ , m and n have the same meaning as described above.)
A step of obtaining a compound represented by formula (hereinafter abbreviated as compound (24)),

（式中、Ｒ^１、Ｒ^２、Ｒ^３、ｍおよびｎは上記と同一の意味を表わす。）
で示される化合物（以下、化合物（２５）と略記する。）を得る工程、 Step (B): By converting the imide moiety of the obtained compound (24) into an amino group, the formula (25):

(In the formula, R ¹ , R ² , R ³ , m and n have the same meaning as described above.)
A step of obtaining a compound represented by formula (hereinafter abbreviated as compound (25)),

Step (C): A step of reacting the obtained compound (25) with an electrophile.

（式中、Ｒ^１、Ｒ^２、Ｒ^３およびｎは上記と同一の意味を表わし、ａは０以上の整数を表わす。）
で示される化合物と式（２７）：

（式中、ｂは１以上の整数を表わす。）
で示される化合物とを、塩基の存在下に反応させることにより製造することもできる。 As the compound (21), a commercially available product may be used. Compound (21) can also be produced, for example, according to the method described in J. Polym. Sci. Polym. Chem. Ed., 20, 2731-2734 (1982). In addition, the compound (21) in which m is an integer of 1 or more has the formula (26):

(Wherein R ¹ , R ² , R ³ and n represent the same meaning as described above, and a represents an integer of 0 or more.)
And a compound represented by formula (27):

(In the formula, b represents an integer of 1 or more.)
It can also manufacture by making the compound shown by react with presence of a base.

  As the compound (21), 2-vinyloxyethanol, 2- (2-vinyloxyethoxy) ethanol, 2- (2- (2-vinyloxyethoxy) ethoxy) ethanol, 2- (2- (2- (2 -Vinyloxyethoxy) ethoxy) ethoxy) ethanol, 2- (2- (2- (2- (2-vinyloxyethoxy) ethoxy) ethoxy) ethoxy) ethanol, 2- (2- (2- (2- (2 -(2-vinyloxyethoxy) ethoxy) ethoxy) ethoxy) ethoxy) ethanol, 2- (2- (2- (2- (2- (2- (2- (2-vinyloxyethoxy) ethoxy) ethoxy) ethoxy) ethoxy) ) Ethoxy) ethoxy) ethoxy) ethanol, 3-vinyloxypropanol, 2- (3-vinyloxypropoxy) ethanol, 4-vinyloxybut Bruno - Le, 2- (4-vinyloxy-butoxy) ethanol,

2- (1-methylvinyloxy) ethanol, 2- (2- (1-methylvinyloxy) ethoxy) ethanol, 2- (2- (2- (1-methylvinyloxy) ethoxy) ethoxy) ethanol, 2- (2- (2- (2- (1-methylvinyloxy) ethoxy) ethoxy) ethoxy) ethanol, 2- (2- (2- (2- (2- (2- (1-methylvinyloxy) ethoxy) ethoxy) ethoxy) ethoxy) ) Ethoxy) ethanol, 2- (2- (2- (2- (2- (2- (1-methylvinyloxy) ethoxy) ethoxy) ethoxy) ethoxy) ethoxy) ethanol, 2- (2- (2- ( 2- (2- (2- (2- (2- (1-methylvinyloxy) ethoxy) ethoxy) ethoxy) ethoxy) ethoxy) ethoxy) ethoxy) ethanol, 3- (1-methylvinyl Oxy) propanol, 2- (3- (1-methylvinyl) propoxy) ethanol, 4- (1-methylvinyl oxy) butanol, 2- (4- (1-methylvinyl oxy) butoxy) ethanol,

2- (2-methylvinyloxy) ethanol, 2- (2- (2-methylvinyloxy) ethoxy) ethanol, 2- (2- (2- (2-methylvinyloxy) ethoxy) ethoxy) ethanol, 2- (2- (2- (2- (2-methylvinyloxy) ethoxy) ethoxy) ethoxy) ethanol, 2- (2- (2- (2- (2- (2-methylvinyloxy) ethoxy) ethoxy) ethoxy) ) Ethoxy) ethanol, 2- (2- (2- (2- (2- (2- (2-methylvinyloxy) ethoxy) ethoxy) ethoxy) ethoxy) ethoxy) ethanol, 2- (2- (2- ( 2- (2- (2- (2- (2- (2-methylvinyloxy) ethoxy) ethoxy) ethoxy) ethoxy) ethoxy) ethoxy) ethoxy) ethanol, 3- (2-methylvinyl Oxy) propanol, 2- (3- (2-methylvinyl) propoxy) ethanol, 4- (2-methyl-vinyl oxy) butanol, 2- (4- (2-methyl-vinyl oxy) butoxy) ethanol,

2- (1-phenylvinyloxy) ethanol, 2- (2- (1-phenylvinyloxy) ethoxy) ethanol, 2- (2- (2- (1-phenylvinyloxy) ethoxy) ethoxy) ethanol, 2- (2- (2- (2- (1-phenylvinyloxy) ethoxy) ethoxy) ethoxy) ethanol, 2- (2- (2- (2- (2- (1-phenylvinyloxy) ethoxy) ethoxy) ethoxy) ) Ethoxy) ethanol, 2- (2- (2- (2- (2- (2- (1-phenylvinyloxy) ethoxy) ethoxy) ethoxy) ethoxy) ethoxy) ethanol, 2- (2- (2- ( 2- (2- (2- (2- (2- (2- (1-phenylvinyloxy) ethoxy) ethoxy) ethoxy) ethoxy) ethoxy) ethoxy) ethoxy) ethanol, 3- ( -Phenylvinyloxy) propanol-2- (3- (1-phenylvinyloxy) propoxy) ethanol, 4- (1-phenylvinyloxy) butanol-2- (4- (1-phenylvinyloxy) Butoxy) ethanol,

2- (2-phenylvinyloxy) ethanol, 2- (2- (2-phenylvinyloxy) ethoxy) ethanol, 2- (2- (2- (2-phenylvinyloxy) ethoxy) ethoxy) ethanol, 2- (2- (2- (2- (2-phenylvinyloxy) ethoxy) ethoxy) ethoxy) ethanol, 2- (2- (2- (2- (2- (2-phenylvinyloxy) ethoxy) ethoxy) ethoxy) ethoxy ) Ethoxy) ethanol, 2- (2- (2- (2- (2- (2- (2-phenylvinyloxy) ethoxy) ethoxy) ethoxy) ethoxy) ethoxy) ethanol, 2- (2- (2- ( 2- (2- (2- (2- (2- (2- (2-phenylvinyloxy) ethoxy) ethoxy) ethoxy) ethoxy) ethoxy) ethoxy) ethoxy) ethanol, 3- ( - phenyl vinyl oxy) propanol, 2- (3- (2-phenylvinyl) propoxy) ethanol, 4- (2-phenylvinyl oxy) butanol, 2- (4- (2-phenylvinyl oxy) butoxy) ethanol,

2- (cyclohexen-1-yloxy) ethanol, 2- (2- (cyclohexen-1-yloxy) ethoxy) ethanol, 2- (2- (2- (cyclohexen-1-yloxy) ethoxy) ethoxy) ethanol, 2- (2- (2- (2- (cyclohexen-1-yloxy) ethoxy) ethoxy) ethoxy) ethanol, 2- (2- (2- (2- (2- (cyclohexen-1-yloxy) ethoxy) ethoxy) ethoxy) ) Ethoxy) ethanol, 2- (2- (2- (2- (2- (2- (cyclohexen-1-yloxy) ethoxy) ethoxy) ethoxy) ethoxy) ethoxy) ethanol, 2- (2- (2- ( 2- (2- (2- (2- (2- (cyclohexen-1-yloxy) ethoxy) ethoxy) ethoxy) ethoxy) ethoxy) ) Ethoxy) ethoxy) ethanol, 3- (cyclohexen-1-yloxy) propanol, 2- (3- (cyclohexen-1-yloxy) propoxy) ethanol, 4- (cyclohexen-1-yloxy) butanol and 2- (4- (Cyclohexen-1-yloxy) butoxy) ethanol.

As the compound (22), a commercially available product is usually used. Specific examples include succinimide, phthalimide and glutarimide. The usage-amount of a compound (22) is 1 equivalent or more with respect to a compound (21), Preferably it is 1-5 equivalent.
A commercially available phosphine compound is also used. Specifically, triphenylphosphine, butylphosphine, tert-butylphosphine, diphenyl-2-pyridylphosphine, tricyclohexylphosphine, 4- (dimethylamino) phenyldiphenylphosphine, 4-diphenylphosphinopolystyrene and 4-diphenylphosphino Methyl polystyrene is mentioned. The usage-amount of a phosphine compound is 1 equivalent or more with respect to a compound (21), for example, Preferably it is 1-5 equivalent.
A commercially available diazo compound (23) is also used. Specifically, 1,1′-azobis (N, N-dimethylformamide), 1,1 ′-(azodicarbonyl) dipiperidine, dibenzyl azodicarboxylate, diethyl azodicarboxylate, diisopropyl azodicarboxylate and azodicarboxylic acid Dimethyl is mentioned. The usage-amount of a diazo compound (23) is 1 equivalent or more with respect to a compound (21), Preferably it is 1-5 equivalent.

The reaction between the compound (21) and the compound (22) in the step (A) is preferably performed in the presence of a solvent.
Solvents include aprotic polar solvents such as N, N-dimethylformamide, dimethyl sulfoxide, N, N-dimethylacetamide, acetonitrile, hexamethylphosphoric triamide, hydrocarbons such as hexane, cyclohexane, pentane, toluene, xylene Examples include solvents, ether solvents such as diethyl ether, tetrahydrofuran, 1,4-dioxane and anisole, and halogenated hydrocarbon solvents such as chloroform, dichloroethane and tetrachloroethane, and ether solvents are preferred. Two or more solvents can be mixed and used.
The usage-amount of a solvent can be suitably adjusted with the kind and usage-amount of a phosphine compound, a diazo compound (23), a compound (21), and a compound (22).
Examples of the reaction temperature include a range of −10 ° C. or more and a boiling point or less of the solvent to be used, and a range of 0 ° C. to 40 ° C. is preferable.
Although the reaction time varies depending on the type of reactant used and the amount of the reactant used, for example, a range of 3 minutes to 15 hours is mentioned.

  After completion of the reaction, the resulting reaction mixture is subjected to separation and purification operations such as extraction, recrystallization and various chromatography, whereby the compound (24) can be taken out. The extracted compound (24) may be used in the next step (B) as it is, or may be used in the next step (B) after purification. You may use the reaction mixture containing a compound (24) for the following process (B).

Specific examples of compound (24) include
N- (2-vinyloxyethyl) phthalimide, N- (2- (2-vinyloxyethoxy) ethyl) phthalimide, N- (2- (2- (2-vinyloxyethoxy) ethoxy) ethyl) phthalimide, N- (2- (2- (2- (2-vinyloxyethoxy) ethoxy) ethoxy) ethyl) phthalimide, N- (2- (2- (2- (2- (2-vinyloxyethoxy) ethoxy) ethoxy) ethoxy) ethoxy ) Ethyl) phthalimide, N- (2- (2- (2- (2- (2- (2-vinyloxyethoxy) ethoxy) ethoxy) ethoxy) ethoxy) ethoxy) ethyl) phthalimide, N- (2- (2- ( 2- (2- (2- (2- (2- (2- (vinyloxyethoxy) ethoxy) ethoxy) ethoxy) ethoxy) ethoxy) ethoxy) ethyl) phthalimide, N- ( - vinyloxypropyl) phthalimide, N- (2- (3- vinyloxy propoxy) ethyl) phthalimide, N-(4-vinyl oxy butyl) phthalimide, N- (2- (4- vinyloxy butoxy) ethyl) phthalimide,

N- (2-vinyloxyethyl) succinimide, N- (2- (2-vinyloxyethoxy) ethyl) succinimide, N- (2- (2- (2-vinyloxyethoxy) ethoxy) ethyl) succinimide, N- (2- (2- (2- (2-vinyloxyethoxy) ethoxy) ethoxy) ethyl) succinimide, N- (2- (2- (2- (2- (2-vinyloxyethoxy) ethoxy) ethoxy) ethoxy) ethoxy ) Ethyl) succinimide, N- (2- (2- (2- (2- (2- (2-vinyloxyethoxy) ethoxy) ethoxy) ethoxy) ethoxy) ethyl) succinimide, N- (2- (2- ( 2- (2- (2- (2- (2- (2-vinyloxyethoxy) ethoxy) ethoxy) ethoxy) ethoxy) ethoxy) ethoxy) ethyl) succin N- (3-vinyloxypropyl) succinimide, N- (2- (3-vinyloxypropoxy) ethyl) succinimide, N- (4-vinyloxybutyl) succinimide, N- (2- (4-vinyloxy) Butoxy) ethyl) succinimide,

N- (2-vinyloxyethyl) glutarimide, N- (2- (2-vinyloxyethoxy) ethyl) glutarimide, N- (2- (2- (2-vinyloxyethoxy) ethoxy) ethyl) glutarimide N- (2- (2- (2- (2-vinyloxyethoxy) ethoxy) ethoxy) ethyl) glutarimide, N- (2- (2- (2- (2- (2-vinyloxyethoxy) ethoxy) ) Ethoxy) ethoxy) ethyl) glutarimide, N- (2- (2- (2- (2- (2- (2-vinyloxyethoxy) ethoxy) ethoxy) ethoxy) ethoxy) ethyl) glutarimide, N- ( 2- (2- (2- (2- (2- (2- (2- (2-vinyloxyethoxy) ethoxy) ethoxy) ethoxy) ethoxy) ethoxy) ethoxy) ethyl) glutar) N- (3-vinyloxypropyl) glutarimide, N- (2- (3-vinyloxypropoxy) ethyl) glutarimide, N- (4-vinyloxybutyl) glutarimide, N- (2- (4 -Vinyloxybutoxy) ethyl) glutarimide,

N- (2- (1-methylvinyloxy) ethyl) phthalimide, N- (2- (2- (1-methylvinyloxy) ethoxy) ethyl) phthalimide, N- (2- (2- (2- (1 -Methylvinyloxy) ethoxy) ethoxy) ethyl) phthalimide, N- (2- (2- (2- (2- (1-methylvinyloxy) ethoxy) ethoxy) ethoxy) ethyl) phthalimide, N- (2- ( 2- (2- (2- (2- (2- (1-methylvinyloxy) ethoxy) ethoxy) ethoxy) ethoxy) ethyl) phthalimide, N- (2- (2- (2- (2- (2- (2- (2- (1-methylvinyloxy) ethoxy) ethoxy) ethoxy) ethoxy) ethoxy) ethyl) phthalimide, N- (2- (2- (2- (2- (2- (2- (2- (2- (1- Methyl vinyloxy) Toxi) ethoxy) ethoxy) ethoxy) ethoxy) ethoxy) ethoxy) ethyl) phthalimide, N- (3- (1-methylvinyloxy) propyl) phthalimide, N- (2- (3- (1-methylvinyloxy) propoxy ) Ethyl) phthalimide, N- (4- (1-methylvinyloxy) butyl) phthalimide, N- (2- (4- (1-methylvinyloxy) butoxy) ethyl) phthalimide, N- (2- (cyclohexene- 1-yloxy) ethyl) phthalimide, N- (2- (2- (cyclohexen-1-yloxy) ethoxy) ethyl) phthalimide, N- (2- (2- (2- (cyclohexen-1-yloxy) ethoxy) ethoxy ) Ethyl) phthalimide, N- (2- (2- (2- (2- (cyclohexen-1-yloxy) Ethoxy) ethoxy) ethoxy) ethyl) phthalimide, N- (2- (2- (2- (2- (2- (cyclohexen-1-yloxy) ethoxy) ethoxy) ethoxy) ethyl) phthalimide, N- (2- ( 2- (2- (2- (2- (2- (cyclohexen-1-yloxy) ethoxy) ethoxy) ethoxy) ethoxy) ethoxy) ethyl) phthalimide, N- (2- (2- (2- (2- (2- ( 2- (2- (2- (2- (2- (cyclohexen-1-yloxy) ethoxy) ethoxy) ethoxy) ethoxy) ethoxy) ethoxy) ethoxy) ethyl) phthalimide, N- (3- (cyclohexen-1-yloxy) propanyl) Phthalimide, N- (2- (3- (cyclohexen-1-yloxy) propoxy) ethyl) phthalimide, N- (4- (cycl Rohexen-1-yloxy) butyl) phthalimide and N- (2- (4- (cyclohexen-1-yloxy) butoxy) ethyl) phthalimide.

In the step (B), the conversion of the imide moiety of the compound (24) into an amino group is performed according to a known method described in Protective Groups in Orgnic Chemistry (Greene et al., John Wiley & Sons, inc.). be able to.
Among them, compound (24) and formula (26):
R ³⁰ —NH ₂ (26)
(Wherein R ³⁰ represents a hydrogen atom, an amino group, an alkyl group, an alkylamino group, an arylamino group or an aryl group.)
A method of reacting a compound represented by formula (hereinafter abbreviated as compound (26)) is preferred.

  Examples of the compound (26) include hydrazine, methylamine, ethylamine, propylamine, isopropylamine, aniline and naphthylamine. Usually, a commercially available compound (26) is used. The amount of compound (26) to be used is, for example, 1 equivalent or more, preferably 1 to 50 equivalents, relative to compound (24).

The reaction of compound (24) and compound (26) is preferably carried out in the presence of a solvent. Solvents include alcohol solvents such as methanol, ethanol, propanol, isopropanol, butanol and tert-butanol, aprotic polar solvents such as acetonitrile, hydrocarbon solvents such as hexane, cyclohexane, pentane, toluene and xylene, diethyl ether, tetrahydrofuran , Ether solvents such as 1,4-dioxane and anisole, and halogenated hydrocarbon solvents such as chloroform. Two or more solvents can be mixed and used. An alcohol solvent, an ether solvent, and a mixed solvent thereof are preferable, and a mixed solvent of an alcohol solvent and an ether solvent is more preferable. The usage-amount of a solvent is not restrict | limited, What is necessary is just to adjust suitably with the kind and usage-amount of a compound (24) and a compound (26).
The reaction temperature can mention the range of -10 degreeC or more and the boiling point of the solvent to be used, for example, The range of 25-80 degreeC is preferable. Although reaction time changes with kinds and reaction temperature of a compound (24) and a compound (26), the range of 3 minutes-15 hours can be mentioned, for example.

After completion of the reaction, for example, the compound (25) can be taken out by performing the following steps (a) to (c).
Step (a): After completion of the reaction, the obtained reaction mixture is concentrated, and the concentrated residue is charged onto a normal phase silica gel column using a weak elution solvent to adsorb compound (25) onto silica gel and weak elution. Step (b) of eluting and removing low-polar impurities with a solvent: Step (c) of eluting the compound (25) adsorbed on silica gel with a strong eluting solvent: Step of concentrating the solution containing the obtained compound (25) .

  The “weakly eluting solvent” means a developing solvent in which Rf value of the compound (25) is 0.1 or less as a result of analyzing a part of the obtained reaction mixture by normal phase thin layer silica gel chromatography. Examples of the weak elution solvent include ester solvents such as ethyl acetate and butyl acetate, chlorinated hydrocarbon solvents such as chloroform and dichloromethane, and hydrocarbon solvents such as hexane, cyclohexane, toluene, and xylene. Such weak elution solvents include ether solvents such as diethyl ether, diisopropyl ether, 1,4-dioxane, tetrahydrofuran, methyl tert-butyl ether, alcohol solvents such as methanol, ethanol, propanol, 2-propanol, butanol, tert-butanol, Alternatively, an aprotic polar solvent such as acetonitrile, acetone, or methyl tert-butyl ketone may be mixed.

  “Strong elution solvent” means a developing solvent in which Rf value of compound (25) is 0.3 or more as a result of analyzing a part of the obtained reaction mixture by normal phase thin layer silica gel chromatography. Examples of the strong elution solvent include alcohol solvents such as methanol, ethanol, propanol, 2-propanol, butanol and tert-butanol, and aprotic polar solvents such as acetonitrile, acetone and methyl tert-butyl ketone. Such strong elution solvents include ester solvents such as ethyl acetate and butyl acetate, chlorinated hydrocarbon solvents such as chloroform and dichloromethane, hydrocarbon solvents such as hexane, cyclohexane, toluene and xylene, or diethyl ether, diisopropyl ether, 1 Ether solvents such as 1,4-dioxane, tetrahydrofuran and methyl tert-butyl ether may be mixed.

  Specific examples of the compound (25) include 2-vinyloxyethylamine, 2- (2-vinyloxyethoxy) ethylamine, 2- (2- (2-vinyloxyethoxy) ethoxy) ethylamine, 2- (2- (2 -(2-vinyloxyethoxy) ethoxy) ethoxy) ethylamine, 2- (2- (2- (2- (2-vinyloxyethoxy) ethoxy) ethoxy) ethoxy) ethylamine, 2- (2- (2- (2 -(2- (2-vinyloxyethoxy) ethoxy) ethoxy) ethoxy) ethoxy) ethylamine, 2- (2- (2- (2- (2- (2- (2- (2-vinyloxyethoxy) ethoxy) ethoxy)) Ethoxy) ethoxy) ethoxy) ethoxy) ethoxy) ethylamine, 3-vinyloxypropylamine, 2- (3-vinyloxypropoxy) ethyl Min, 4-vinyl oxy butyl amine, 2- (4-vinyloxy-butoxy) ethylamine,

2- (1-methylvinyloxy) ethylamine, 2- (2- (1-methylvinyloxy) ethoxy) ethylamine, 2- (2- (2- (1-methylvinyloxy) ethoxy) ethoxy) ethylamine, 2- (2- (2- (2- (1-methylvinyloxy) ethoxy) ethoxy) ethoxy) ethylamine, 2- (2- (2- (2- (2- (1-methylvinyloxy) ethoxy) ethoxy) ethoxy) ethoxy ) Ethoxy) ethylamine, 2- (2- (2- (2- (2- (2- (1-methylvinyloxy) ethoxy) ethoxy) ethoxy) ethoxy) ethoxy) ethylamine, 2- (2- (2- ( 2- (2- (2- (2- (2- (2- (1-methylvinyloxy) ethoxy) ethoxy) ethoxy) ethoxy) ethoxy) ethoxy) ethoxy) ethylamine, 3- ( -Methylvinyloxy) propylamine, 2- (3- (1-methylvinyloxy) propoxy) ethylamine, 4- (1-methylvinyloxy) butylamine, 2- (4- (1-methylvinyloxy) butoxy) ethylamine ,

2- (2-methylvinyloxy) ethylamine, 2- (2- (2-methylvinyloxy) ethoxy) ethylamine, 2- (2- (2- (2-methylvinyloxy) ethoxy) ethoxy) ethylamine, 2- (2- (2- (2- (2-methylvinyloxy) ethoxy) ethoxy) ethoxy) ethylamine, 2- (2- (2- (2- (2- (2-methylvinyloxy) ethoxy) ethoxy) ethoxy) ethoxy ) Ethoxy) ethylamine, 2- (2- (2- (2- (2- (2- (2-methylvinyloxy) ethoxy) ethoxy) ethoxy) ethoxy) ethoxy) ethylamine, 2- (2- (2- ( 2- (2- (2- (2- (2- (2-methylvinyloxy) ethoxy) ethoxy) ethoxy) ethoxy) ethoxy) ethoxy) ethoxy) ethylamine, 3- ( -Methylvinyloxy) propylamine, 2- (3- (2-methylvinyloxy) propoxy) ethylamine, 4- (2-methylvinyloxy) butylamine, 2- (4- (2-methylvinyloxy) butoxy) ethylamine ,

2- (1-phenylvinyloxy) ethylamine, 2- (2- (1-phenylvinyloxy) ethoxy) ethylamine, 2- (2- (2- (1-phenylvinyloxy) ethoxy) ethoxy) ethylamine, 2- (2- (2- (2- (1-phenylvinyloxy) ethoxy) ethoxy) ethoxy) ethylamine, 2- (2- (2- (2- (2- (1-phenylvinyloxy) ethoxy) ethoxy) ethoxy) ethoxy ) Ethoxy) ethylamine, 2- (2- (2- (2- (2- (2- (1-phenylvinyloxy) ethoxy) ethoxy) ethoxy) ethoxy) ethoxy) ethylamine, 2- (2- (2- ( 2- (2- (2- (2- (2- (1- (Phenylvinyloxy) ethoxy) ethoxy) ethoxy) ethoxy) ethoxy) ethoxy) ethoxy) ethyl Min, 3- (1-phenylvinyloxy) propylamine, 2- (3- (1-phenylvinyloxy) propoxy) ethylamine, 4- (1-phenylvinyloxy) butylamine, 2- (4- (1-phenyl) Vinyloxy) butoxy) ethylamine,

2- (2-phenylvinyloxy) ethylamine, 2- (2- (2-phenylvinyloxy) ethoxy) ethylamine, 2- (2- (2- (2-phenylvinyloxy) ethoxy) ethoxy) ethylamine, 2- (2- (2- (2- (2-phenylvinyloxy) ethoxy) ethoxy) ethoxy) ethylamine, 2- (2- (2- (2- (2- (2-phenylvinyloxy) ethoxy) ethoxy) ethoxy) ethoxy ) Ethoxy) ethylamine, 2- (2- (2- (2- (2- (2- (2-phenylvinyloxy) ethoxy) ethoxy) ethoxy) ethoxy) ethoxy) ethylamine, 2- (2- (2- ( 2- (2- (2- (2- (2- (2-phenylvinyloxy) ethoxy) ethoxy) ethoxy) ethoxy) ethoxy) ethoxy) ethoxy) ethyl Min, 3- (2-phenylvinyloxy) propylamine, 2- (3- (2-phenylvinyloxy) propoxy) ethylamine, 4- (2-phenylvinyloxy) butylamine, 2- (4- (2-phenyl) Vinyloxy) butoxy) ethylamine,

2- (cyclohexen-1-yloxy) ethylamine, 2- (2- (cyclohexen-1-yloxy) ethoxy) ethylamine, 2- (2- (2- (cyclohexen-1-yloxy) ethoxy) ethoxy) ethylamine, 2- (2- (2- (2- (cyclohexen-1-yloxy) ethoxy) ethoxy) ethoxy) ethylamine, 2- (2- (2- (2- (2- (cyclohexen-1-yloxy) ethoxy) ethoxy) ethoxy) ethoxy ) Ethoxy) ethylamine, 2- (2- (2- (2- (2- (2- (cyclohexen-1-yloxy) ethoxy) ethoxy) ethoxy) ethoxy) ethoxy) ethylamine, 2- (2- (2- ( 2- (2- (2- (2- (2- (cyclohexen-1-yloxy) ethoxy) ethoxy) ethoxy) -e Xyl) ethoxy) ethoxy) ethoxy) ethylamine, 3- (cyclohexen-1-yloxy) propylamine, 2- (3- (cyclohexen-1-yloxy) propoxy) ethylamine, 4- (cyclohexen-1-yloxy) butylamine, and 2- (4- (cyclohexen-1-yloxy) butoxy) ethylamine.

  Examples of the electrophile used in the step (C) include tert-butyl chlorocarbonate, methyl chlorocarbonate, ethyl chlorocarbonate, di-tert-butyl dicarbonate, dimethyl dicarbonate, diethyl dicarbonate, 9H-fluorene-9 chlorocarbonate. -Ilmethyl, succinyloxycarbonic acid 9H-fluoren-9-ylmethyl, benzyl chloride, benzoyl chloride, 4-methylbenzoyl chloride, phthalic anhydride, phthaloyl dichloride, acetic chloride, acetic anhydride, trifluoroacetic anhydride and the like. The usage-amount of an electrophile is 1 equivalent or more with respect to a compound (25), Preferably it is 1.5-3 equivalent.

  The reaction between the compound (25) and the electrophile is preferably performed in the presence of a solvent. Solvents include N, N-dimethylformamide, dimethylsulfoxide, N, N-dimethylacetamide, acetonitrile, hexamethylphosphoric triamide and other aprotic polar solvents, hexane, cyclohexane, pentane, toluene, xylene and other hydrocarbons Examples of the solvent include ether solvents such as diethyl ether, tetrahydrofuran, 1,4-dioxane, and anisole, and halogenated hydrocarbon solvents such as chloroform. Two or more solvents can be mixed and used. Preferably, an ether solvent is used.

The reaction between compound (25) and the electrophile is carried out in the presence of a base. Examples of the base include organic bases such as triethylamine, diisopropylethylamine, N-methylimidazole, and pyridine, and inorganic bases such as sodium carbonate, potassium carbonate, cesium carbonate, sodium hydroxide, and potassium hydroxide. The usage-amount of a base is 1 equivalent or more with respect to a compound (25), Preferably it is 1.5-3 equivalent.
The reaction temperature is, for example, −10 ° C. or higher and lower than the boiling point of the solvent used, and preferably 0 to 80 ° C. Although reaction time changes with kinds and reaction temperature of a compound (25) and an electrophile, the range of 3 minutes-15 hours etc. are mentioned, for example.
After completion of the reaction, the compound (1m) can be taken out by subjecting the obtained reaction mixture to normal separation and purification operations such as extraction, recrystallization and various chromatography.

（式中、Ｒ^６、Ｒ^７、Ｒ^８およびｒは前記と同一の意味を表わし、ｘは０以上の整数を表わす。）
で示される化合物と式（３３）：

（式中、ｙは１以上の整数であり、ｘとｙの和がｐである。）
で示される化合物とを反応させることにより、製造することができる。 As the compound (2m), a commercially available compound may be used, for example, the compound represented by the formula (31):

(Wherein R ⁶ , R ⁷ , R ⁸ and r represent the same meaning as described above, and x represents an integer of 0 or more.)
And a compound represented by formula (33):

(In the formula, y is an integer of 1 or more, and the sum of x and y is p.)
It can manufacture by making the compound shown by react.

As the compound (3m), a commercially available product may be used, or in the method for producing the compound (2m), a compound having the terminal hydroxyl group of R ¹² instead of the compound represented by the formula (33) ( It can manufacture by implementing similarly except using the compound shown by 33).

Hereinafter, the present invention will be described in more detail with reference to examples.
Example 1
0.46 g of N-tert-butoxycarbonyl-2- (2-vinyloxyethoxy) ethylamine, 1.16 g of 2- (2-methoxyethoxy) ethoxyethene, 2.00 g of triethylene glycol divinyl ether and 2,2′- 200 mg of azobisisobutyronitrile was mixed to prepare a uniform solution (organic phase). The prepared organic phase was added while stirring an aqueous solution (aqueous phase) of polyvinyl alcohol (n = 2000, saponification degree about 80%) having a concentration of 2% by weight with a magnetic stirrer at a stirring speed of 200 rpm. The resulting mixture was stirred at room temperature (about 23 ° C.) for an additional 30 minutes to obtain a dispersion in which dispersed droplets of the organic phase were dispersed in the aqueous phase. The internal temperature of the dispersion was gradually raised to 70 ° C., and the dispersion was stirred at 70 ° C. for 20 hours. Then, after lowering the internal temperature of the obtained reaction mixture to room temperature, stirring was stopped and the obtained suspension was filtered. The obtained solid was washed with 200 mL of warm water and 200 mL of methanol, and then dried under reduced pressure to obtain a structural unit derived from N-tert-butoxycarbonyl-2- (2-vinyloxyethoxy) ethylamine, and 2- ( 2.0 g of a polyvinyl ether resin containing a structural unit derived from 2-methoxyethoxy) ethoxyethene and a structural unit derived from triethylene glycol divinyl ether was obtained. The obtained polyvinyl ether resin is referred to as Resin A. As a result of observing the resin A with an optical microscope (observation magnification: 240 times), it was found that the shape of the resin A was substantially spherical. An optical micrograph of Resin A is shown in FIG.

(Example 2)
An aqueous solution containing 0.5 mL of trifluoroacetic acid (trifluoroacetic acid / water (weight ratio) = 80/20) was added to 30 mg of the resin A obtained in Example 1, and the resulting mixture was stirred at room temperature for 15 minutes. . The obtained reaction mixture was filtered, and the obtained solid was washed with 5 mL methanol, and further washed with 10 mL saturated aqueous sodium hydrogen carbonate. Furthermore, after washing with 10 mL water and 10 mL methanol, it was dried under reduced pressure to obtain 25 mg of resin. The resulting resin is referred to as Resin A ′. As a result of observing the resin A ′ with an optical microscope (observation magnification: 240 times), it was found that the shape of the resin A ′ was substantially spherical. An optical micrograph of the resin A ′ is shown in FIG.
Resin A ′ 10 mg, ninhydrin 10 mg, and methanol 0.1 mL were mixed in a 1.5 mL microtube. When the microtube was heated at 80 ° C. for 15 minutes to conduct a color development test, the color of the contents changed to blue. From this result, it was found that the resin A ′ has an amino group. When the color development test was conducted in the same manner using the resin A obtained in Example 1 instead of the resin A ′, the color of the contents did not change to blue. Based on these results, the structural unit derived from N-tert-butoxycarbonyl-2- (2-vinyloxyethoxy) ethylamine in the resin A is converted to a structural unit derived from 2- (2-vinyloxyethoxy) ethylamine. Resin A ′ is a structural unit derived from 2- (2-vinyloxyethoxy) ethylamine, a structural unit derived from 2- (2-methoxyethoxy) ethoxyethene, and triethylene glycol divinyl ether. It was found to be a polyvinyl ether resin containing a derived structural unit.

(Example 3)
N-tert-butoxycarbonyl-2- (2- (2- (2- (2- (2-vinyloxyethoxy) ethoxy) ethoxy) ethoxy) ethoxy) ethylamine 1.0 g, butyl vinyl ether 0.74 g and triethylene glycol Divinyl ether (3.0 g) was mixed to prepare a uniform solution (organic phase). The prepared organic phase was added while stirring an aqueous solution (aqueous phase) of polyvinyl alcohol (n = 2000, saponification degree about 80%) having a concentration of 2% by weight with a magnetic stirrer at a stirring speed of 200 rpm. The obtained mixture was stirred at room temperature (about 23 ° C.) for 30 minutes to obtain a dispersion in which dispersed droplets of the organic phase were dispersed in the aqueous phase. The dispersion was stirred for an additional 15 minutes before adding 30 mg of 2,2′-azobisisobutyronitrile. The resulting dispersion was stirred at about room temperature for 15 minutes, then the internal temperature was gradually raised to 60 ° C., and the dispersion was stirred at 60 ° C. for 12 hours. Then, after lowering the internal temperature of the obtained reaction mixture to about room temperature, stirring was stopped and the obtained suspension was filtered. The obtained solid was washed with 200 mL of warm water and 200 mL of methanol, and then dried under reduced pressure to give N-tert-butoxycarbonyl-2- (2- (2- (2- (2- (2-vinyloxyethoxy)). 2.1 g of a polyvinyl ether resin containing structural units derived from ethoxy) ethoxy) ethoxy) ethoxy) ethylamine, structural units derived from butyl vinyl ether, and structural units derived from triethylene glycol divinyl ether was obtained. The obtained polyvinyl ether resin is referred to as Resin B. As a result of observing the resin B with an optical microscope (observation magnification: 240 times), the shape of the resin B was found to be substantially spherical particles. An optical micrograph of the resin B is shown in FIG.

Example 4
An aqueous solution containing 3 mL of trifluoroacetic acid (trifluoroacetic acid / water (weight ratio) = 80/20) was added to 100 mg of the resin B obtained in Example 3, and the resulting mixture was stirred for 1 hour at room temperature. The obtained reaction mixture was filtered, and the obtained solid was washed with 10 mL of water and 10 mL of methanol, and then dried under reduced pressure to obtain 70 mg of resin. The resulting resin is referred to as Resin B ′. As a result of observing the resin B ′ with an optical microscope (observation magnification: 240 times), it was found that the shape of the resin B ′ was substantially spherical particles. An optical microscope photograph of the resin B ′ is shown in FIG.
Resin B ′ 10 mg, ninhydrin 10 mg, and methanol 0.1 mL were mixed in a 1.5 mL microtube. When the microtube was heated at 80 ° C. for 15 minutes to conduct a color development test, the color of the contents changed to blue. From this result, it was found that the resin B ′ has an amino group. When a color development test was conducted in the same manner using the resin B obtained in Example 3 instead of the resin B ′, the color of the contents did not change to blue. From these results, the structure derived from N-tert-butoxycarbonyl-2- (2- (2- (2- (2- (2-vinyloxyethoxy) ethoxy) ethoxy) ethoxy) ethoxy) ethylamine in resin B) The unit is converted to a structural unit derived from 2- (2- (2- (2- (2- (2-vinyloxyethoxy) ethoxy) ethoxy) ethoxy) ethoxy) ethylamine, and resin B ′ is 2 A structural unit derived from-(2- (2- (2- (2- (2-vinyloxyethoxy) ethoxy) ethoxy) ethoxy) ethoxy) ethylamine, a structural unit derived from butyl vinyl ether, and triethylene glycol divinyl ether It turned out that it is a polyvinyl ether resin containing the structural unit derived from.

(Example 5)
Mixing 0.15 g of N-tert-butoxycarbonyl-2- (2-vinyloxyethoxy) ethylamine, 0.26 g of butyl vinyl ether, 0.67 g of triethylene glycol divinyl ether and 67 mg of 2,2′-azobisisobutyronitrile A homogeneous solution (organic phase) was prepared. The prepared organic phase was added while stirring an aqueous solution (aqueous phase) of polyvinyl alcohol (n = 2000, saponification degree about 80%) having a concentration of 2% by weight with a magnetic stirrer at a stirring speed of 200 rpm. The obtained mixture was stirred at room temperature (about 23 ° C.) for 30 minutes to obtain a dispersion in which dispersed droplets of the organic phase were dispersed in the aqueous phase. The internal temperature of the obtained dispersion was gradually raised to 70 ° C., and the dispersion was stirred at 70 ° C. for 20 hours. Then, after lowering the internal temperature of the obtained reaction mixture to about room temperature, stirring was stopped and the obtained suspension was filtered. The obtained solid was washed with 200 mL of warm water and 200 mL of methanol, and then dried under reduced pressure. A structural unit derived from N-tert-butoxycarbonyl-2- (2-vinyloxyethoxy) ethylamine and derived from butyl vinyl ether 2.5 g of a polyvinyl ether resin containing a structural unit and a structural unit derived from triethylene glycol divinyl ether was obtained. The obtained polyvinyl ether resin is referred to as Resin C. As a result of observing the resin C with an optical microscope (observation magnification: 240 times), it was found that the shape of the resin C was substantially spherical. An optical micrograph of the resin C is shown in FIG.

  In the same manner as described in Example 4, the obtained resin C is mixed with an aqueous solution of trifluoroacetic acid to thereby obtain a structural unit derived from 2- (2-vinyloxyethoxy) ethylamine and derived from butyl vinyl ether. And a structural unit derived from triethylene glycol divinyl ether can be obtained.

(Example 6)
N-tert-butoxycarbonyl-2- (2- (2- (2- (2- (2-vinyloxyethoxy) ethoxy) ethoxy) ethoxy) ethoxy) ethylamine 0.27 g, 2- (2-methoxyethoxy) ethoxy 0.39 g of ethene, 0.67 g of triethylene glycol divinyl ether and 67 mg of 2,2′-azobisisobutyronitrile were mixed to prepare a uniform solution (organic phase). The prepared organic phase was added while stirring an aqueous solution (aqueous phase) of polyvinyl alcohol (n = 2000, saponification degree about 80%) having a concentration of 2% by weight with a magnetic stirrer at a stirring speed of 200 rpm. The obtained mixture was stirred at room temperature (about 23 ° C.) for 30 minutes to obtain a dispersion in which dispersed droplets of the organic phase were dispersed in the aqueous phase. The internal temperature of the obtained dispersion was gradually raised to 65 ° C., and the dispersion was stirred at 65 ° C. for 20 hours. Then, after lowering the internal temperature of the obtained reaction mixture to about room temperature, stirring was stopped and the obtained suspension was filtered. The obtained solid was washed with 200 mL of warm water and 200 mL of methanol, and then dried under reduced pressure to give N-tert-butoxycarbonyl-2- (2- (2- (2- (2- (2-vinyloxyethoxy)). Polyvinyl ether resin 1 comprising a structural unit derived from ethoxy) ethoxy) ethoxy) ethoxy) ethylamine, a structural unit derived from 2- (2-methoxyethoxy) ethoxyethene, and a structural unit derived from triethylene glycol divinyl ether .9 g was obtained. The obtained polyvinyl ether resin is referred to as Resin D. As a result of observing the resin D with an optical microscope (observation magnification: 240 times), it was found that the shape of the resin D was substantially spherical. An optical micrograph of resin D is shown in FIG.

  In the same manner as described in Example 4, the obtained resin D was mixed with an aqueous solution of trifluoroacetic acid to give 2- (2- (2- (2- (2- (2-vinyloxyethoxy)). A polyvinyl ether resin comprising a structural unit derived from ethoxy) ethoxy) ethoxy) ethoxy) ethylamine, a structural unit derived from 2- (2-methoxyethoxy) ethoxyethene, and a structural unit derived from triethylene glycol divinyl ether Obtainable.

(Reference Example 1)
To 30 mL of a tetrahydrofuran solution containing 2.5 g of 2- (2-vinyloxyethoxy) ethanol, 3.1 g of phthalimide and 5.5 g of triphenylphosphine, 10.8 mL of a 40% diisopropyl azodicarboxylate toluene solution was added dropwise at room temperature. The resulting mixture was stirred for 2 hours at room temperature to obtain a mixture. A part of the mixture was subjected to preparative thin-layer chromatography, and the structure of the product was confirmed by NMR. The product was found to be N- (2- (2-vinyloxyethoxy) ethyl) phthalimide. .
¹ H-NMR (CDCl ₃ , 270 MHz): 7.85 (dd, J = 3.1, 5.6 Hz, 2H), 7.71 (dd, J = 3.3, 5.6 Hz, 2H), 6.39 (dd, J = 6.8, 14.3 Hz, 1H), 4.12 (dd, J = 2.1, 14.3Hz, 1H), 3.70-3.94 (m, 9H)

(Reference Example 2)
To a mixture containing N- (2- (2-vinyloxyethoxy) ethyl) phthalimide obtained in Reference Example 1, 3 mL of a 40% methylamine methanol solution was added dropwise at room temperature. The resulting mixture was stirred at 60 ° C. for 3 hours and then allowed to cool at room temperature. Precipitated N-methylphthalimide was removed by filtration, and then the filtrate was concentrated. The solution obtained by dissolving the concentrated residue in chloroform was charged onto a silica gel column, and after triphenylphosphine oxide in the mixture used in chloroform was eluted, the desired product was obtained with a chloroform / methanol (1/1) solution. Elute. The resulting solution was concentrated to obtain 1.5 g of 2- (2-vinyloxyethoxy) ethylamine. Yield: 60% (based on 2- (2-vinyloxyethoxy) ethanol)
ESI (+)-MS: 132 [M + H ⁺ calcd. For C ₆ H ₁₄ NO ₂ : 132.10]

(Reference Example 3)
To a 20 mL tetrahydrofuran solution of 1.5 g 2- (2-vinyloxyethoxy) ethylamine, 4.5 g di-tert-butyl dicarbonate was added at room temperature. The resulting mixture was stirred at room temperature for 3 hours. After concentrating the obtained reaction mixture, the concentrated residue was purified by silica gel column chromatography (developing solvent: hexane / ethyl acetate = 4/1), and N-tert-butoxycarbonyl-2- (2-vinyloxyethoxy) 2.64 g of ethylamine was obtained.
¹ H-NMR (CDCl ₃ , 270 MHz): 6.50 (dd, J = 6.9, 14.3 Hz, 1H), 4.96 (br. S, 1H), 4.21 (dd, J = 2.1, 14.3 Hz, 1H), 4.03 ( dd, J = 2.1, 6.8Hz, 1H), 3.84 (d, J = 6.4Hz, 1H), 3.83 (d, J = 4.8Hz, 1H), 3.71 (d, J = 4.8Hz, 1H), 3.69 ( d, J = 6.4Hz, 1H), 3.56 (t, J = 5.3Hz, 2H), 3.33 (q, J = 5.03, 2H), 1.45 (s, 9H)

(Reference Example 4)
To 20 mL of a tetrahydrofuran solution of 1.3 g of 2- (2-vinyloxyethoxy) ethanol and 1.4 g of N, N, N ′, N′-tetramethylpropane-1,3-diamine was added 1.9 g of toluenesulfonic acid chloride. Added at room temperature. The resulting mixture was stirred at room temperature for 3 hours. To the obtained reaction mixture, 20 mL of saturated aqueous sodium hydrogen carbonate was added, and the mixture was stirred for 5 minutes at room temperature. After adding 20 mL of ethyl acetate to the obtained mixture, liquid separation was carried out. The organic layer was washed twice with 20 mL of saturated aqueous sodium bicarbonate, twice with 20 mL of 1M aqueous potassium hydrogen sulfate solution, and further washed with 20 mL of saturated brine. The organic layer was dried over sodium sulfate and then filtered, and the obtained filtrate was concentrated to obtain 2.3 g of 2- (1-vinyloxyethoxy) ethyl toluenesulfonate. Yield: 80%
¹ H-NMR (CDCl ₃ , 270 MHz): 7.86 (dd, J = 2.0, 8.2 Hz, 2H), 7.34 (dd, J = 0.7, 8.6 Hz, 2H), 6.46 (dd, J = 6.8, 14.3 Hz, 1H), 4.14-4.20 (m, 3H), 4.01 (dd, J = 2.1, 6.8Hz, 1H), 3.65-3.78 (m, 6H), 2.45 (s, 3H)

(Reference Example 5)
To 20 mL of a tetrahydrofuran solution of 1.56 g of tetraethylene glycol, 1.35 g of potassium tert-butoxy was added at room temperature. The resulting mixture was stirred at room temperature for 15 minutes, and 10 mL of a tetrahydrofuran solution containing 2.3 g of 2- (1-vinyloxyethoxy) ethyl toluenesulfonate was added. The resulting mixture was stirred at 60 ° C. for 1 hour and then allowed to cool at room temperature. Insoluble matter was removed by filtration, and the obtained filtrate was concentrated. The concentrated residue was purified by silica gel column chromatography (developing solvent: ethyl acetate → ethyl acetate / acetone (20/1 → 10/1 → 5/1 → 3/1 → 2/1) and 2- (2- (2 There was obtained 0.76 g of-(2- (2- (2-vinyloxyethoxy) ethoxy) ethoxy) ethoxy) ethoxy) ethanol, yield: 31%
¹ H-NMR (CDCl ₃ , 270 MHz): 6.50 (dd, J = 6.9, 14.6 Hz, 1H), 4.19 (dd, J = 2.0, 14.2 Hz, 1H), 4.01 (dd, J = 2.1, 6.8 Hz, 1H), 3.85 (d, J = 6.4Hz, 1H), 3.84 (d, J = 5.3Hz, 1H), 3.59-3.79 (m, 22H), 2.78 (br.s, 1H)

(Reference Example 6)
20 mL of tetrahydrofuran solution containing 0.58 g of 2- (2- (2- (2- (2- (2-vinyloxyethoxy) ethoxy) ethoxy) ethoxy) ethoxy) ethanol, 0.33 g of phthalimide and 0.59 g of triphenylphosphine Then, 1.2 mL of a toluene solution of 40% diisopropyl azodicarboxylate was added dropwise at room temperature. The resulting mixture was stirred for 2 hours at room temperature. A part of the mixture was subjected to preparative thin layer chromatography, and the structure of the product was confirmed by NMR. The product was N- (2- (2- (2- (2- (2- (2-vinyl). It was found to be oxyethoxy) ethoxy) ethoxy) ethoxy) ethoxy) ethyl) phthalimide.
¹ H-NMR (CDCl ₃ , 270 MHz): 7.85 (dd, J = 3.1, 5.4 Hz, 2H), 7.71 (dd, J = 3.0, 5.4 Hz, 2H), 6.49 (dd, J = 6.6, 14.3 Hz, 1H), 4.18 (dd, J = 2.0, 14.3Hz, 1H), 4.00 (dd, J = 2.1, 6.8Hz, 1H), 3.58-3.92 (m, 24H)

(Reference Example 7)
40% methylamine was added to the mixture containing N- (2- (2- (2- (2- (2- (2-vinyloxyethoxy) ethoxy) ethoxy) ethoxy) ethoxy) ethyl) phthalimide obtained in Reference Example 6. / Methanol solution 3mL was dripped at room temperature. The resulting mixture was stirred at 60 ° C. for 3 hours and then allowed to cool at room temperature. Precipitated N-methylphthalimide was removed by filtration, and the obtained filtrate was concentrated. The concentrated residue was dissolved in chloroform, charged onto a silica gel column, triphenylphosphine oxide contained in the mixture used in chloroform was eluted, and then the target product was eluted with chloroform / methanol (1/1). The obtained solution was concentrated to obtain 0.25 g of 2- (2- (2- (2- (2- (2-vinyloxyethoxy) ethoxy) ethoxy) ethoxy) ethoxy) ethylamine). Yield: 43% (2- (2- (2- (2- (2- (2-vinyloxyethoxy) ethoxy) ethoxy) ethoxy) ethoxy) ethanol standard))
ESI (+)-MS: 308 [M + H ⁺ calcd. For C ₁₄ H ₃₀ NO ₆ : 308.21]

(Reference Example 8)
2- (2- (2- (2- (2- (2-vinyloxyethoxy) ethoxy) ethoxy) ethoxy) ethoxy) ethylamine) in 20 mL of tetrahydrofuran solution was added 0.47 g of di-tert-butyl dicarbonate. Added at room temperature. The resulting mixture was stirred at room temperature for 3 hours. After concentrating the obtained reaction mixture, the concentrated residue was purified by silica gel column chromatography (developing solvent: hexane / ethyl acetate (1/1) → ethyl acetate), and N-tert-butoxycarbonyl-2- (2- ( 0.33 g of 2- (2- (2- (2-vinyloxyethoxy) ethoxy) ethoxy) ethoxy) ethoxy) ethylamine was obtained.
¹ H-NMR (CDCl ₃ , 270 MHz): 6.49 (dd, J = 6.8, 14.3 Hz, 1H), 5.07 (br. S, 1H), 4.18 (dd, J = 2.0, 14.2 Hz, 1H), 4.01 ( dd, J = 2.0, 6.8Hz, 1H), 3.85 (d, J = 6.3Hz, 1H), 3.84 (d, J = 5.1Hz, 1H), 3.74 (d, J = 5.3Hz, 1H), 3.73 ( d, J = 6.6Hz, 1H), 3.62-3.67 (m, 16H), 3.54 (t, J = 5.1Hz, 2H), 3.31 (q, J = 5.3, 2H), 1.44 (s, 9H)

  A carrier for producing a separation material for liquid chromatography or an immobilized enzyme catalyst material, which comprises an amino group-containing polyvinyl ether resin provided by the present invention, and is a substantially spherical particle-shaped polymer carrier that uses molecular recognition by an enzyme as a separation mode. Useful for.

Claims (12)

Formula (1)

(In the formula, m represents an integer of 0 or more, and n represents an integer of 2 or more. R ¹ , R ² and R ³ each independently represents a hydrogen atom, an alkyl group which may have a substituent, or Represents an aryl group which may have a substituent, R ¹ and R ² may be bonded to form a ring, or R ² and R ³ may be bonded to form a ring; Good.
R ⁴ and R ⁵ are each independently a hydrogen atom, an alkyl group which may have a substituent, an aryl group which may have a substituent, an alkoxycarbonyl group which may have a substituent, Aryloxycarbonyl group which may have a substituent, acyl group which may have a substituent, alkylsulfonyl group which may have a substituent or arylsulfonyl which may have a substituent And at least one of R ⁴ and R ⁵ has an alkoxycarbonyl group which may have a substituent, an aryloxycarbonyl group which may have a substituent, or a substituent. An acyl group which may be substituted, an alkylsulfonyl group which may have a substituent, or an arylsulfonyl group which may have a substituent. R ⁴ and R ⁵ may be bonded together to form a ring together with the nitrogen atom to which they are bonded. )
A polyvinyl ether resin containing a structural unit represented by:   The polyvinyl ether resin according to claim 1, further comprising a structural unit derived from a monomer having two or more carbon-carbon unsaturated bonds in the molecule in addition to the structural unit represented by the formula (1). A monomer having two or more carbon-carbon unsaturated bonds in the molecule is represented by the formula (2m):

(In the formula, p represents an integer of 0 or more. Q and r each independently represents an integer of 2 or more. R ⁶ , R ⁷ and R ⁸ each independently have a hydrogen atom or a substituent. Represents an optionally substituted alkyl group or an optionally substituted aryl group, and R ⁶ and R ⁷ are bonded together to form a ring together with the carbon atoms to which they are bonded. Alternatively, R ⁷ and R ⁸ may be bonded together to form a ring together with the carbon atom to which they are bonded.)
The polyvinyl ether resin of Claim 2 which is a compound shown by these. Formula (3):

(In the formula, s represents an integer of 0 or more, and t represents an integer of 0 or more. R ⁹ , R ¹⁰ and R ¹¹ are each independently a hydrogen atom, an alkyl group which may have a substituent, or An aryl group which may have a substituent, R ⁹ and R ¹⁰ may be bonded to form a ring, or R ¹⁰ and R ¹¹ may be bonded to form a ring; R ¹² is a hydrogen atom, a hydroxyl group, an alkyl group which may have a substituent, an aryl group which may have a substituent, an alkyloxy group which may have a substituent or a substituent. Represents an aryloxy group which may have
The polyvinyl ether resin according to any one of claims 1 to 3, further comprising a structural unit represented by: In formula (1), at least one of R ⁴ and R ⁵ is an alkyloxycarbonyl group which may have a substituent or an aryloxycarbonyl group which may have a substituent. 5. The polyvinyl ether resin according to any one of 4. The polyvinyl ether resin of Claim 2 or 3 WHEREIN: A part or all of the structural unit shown by Formula (1) is Formula (10):

(In the formula, m represents an integer of 0 or more, and n represents an integer of 2 or more. R ¹ , R ² and R ³ each independently represents a hydrogen atom, an alkyl group which may have a substituent, or Represents an aryl group which may have a substituent, R ¹ and R ² may be bonded to form a ring, or R ² and R ³ may be bonded to form a ring; R represents a hydrogen atom, an alkyl group which may have a substituent, or an aryl group which may have a substituent.
A polyvinyl ether resin converted into a structural unit represented by Formula (10):

(In the formula, m represents an integer of 0 or more, and n represents an integer of 2 or more. R ¹ , R ² and R ³ each independently represents a hydrogen atom, an alkyl group which may have a substituent, or Represents an aryl group which may have a substituent, R ¹ and R ² may be bonded to form a ring, or R ² and R ³ may be bonded to form a ring; R represents a hydrogen atom, an alkyl group which may have a substituent, or an aryl group which may have a substituent.
And a structural unit derived from a monomer having two or more carbon-carbon unsaturated bonds in the molecule. A monomer having two or more carbon-carbon unsaturated bonds in the molecule is represented by the formula (2m):

(In the formula, p represents an integer of 0 or more. Q and r each independently represents an integer of 2 or more. R ⁶ , R ⁷ and R ⁸ each independently have a hydrogen atom or a substituent. Represents an optionally substituted alkyl group or an optionally substituted aryl group, and R ⁶ and R ⁷ are bonded together to form a ring together with the carbon atoms to which they are bonded. Alternatively, R ⁷ and R ⁸ may be bonded together to form a ring together with the carbon atom to which they are bonded.)
The polyvinyl ether resin of Claim 7 which is a compound shown by these. Formula (3):

(In the formula, s represents an integer of 0 or more, and t represents an integer of 0 or more. R ⁹ , R ¹⁰ and R ¹¹ are each independently a hydrogen atom, an alkyl group which may have a substituent, or An aryl group which may have a substituent, R ⁹ and R ¹⁰ may be bonded to form a ring, or R ¹⁰ and R ¹¹ may be bonded to form a ring; R ¹² represents a hydrogen atom, a hydroxyl group, an alkyl group which may have a substituent, an aryl group which may have a substituent, an alkoxy group which may have a substituent or a substituent. Represents an aryloxy group which may be present.)
The polyvinyl ether resin according to any one of claims 6 to 8, further comprising a structural unit represented by: Formula (1m):

(In the formula, m represents an integer of 0 or more, and n represents an integer of 2 or more. R ¹ , R ² and R ³ each independently represents a hydrogen atom, an alkyl group which may have a substituent, or Represents an aryl group which may have a substituent, R ¹ and R ² may be bonded to form a ring, or R ² and R ³ may be bonded to form a ring; Good.
R ⁴ and R ⁵ are each independently a hydrogen atom, an alkyl group which may have a substituent, an aryl group which may have a substituent, an alkoxycarbonyl group which may have a substituent, Aryloxycarbonyl group which may have a substituent, acyl group which may have a substituent, alkylsulfonyl group which may have a substituent or arylsulfonyl which may have a substituent And at least one of R ⁴ and R ⁵ has an alkoxycarbonyl group which may have a substituent, an aryloxycarbonyl group which may have a substituent, or a substituent. Or an acylsulfonyl group which may have a substituent, or an arylsulfonyl group which may have a substituent. R ⁴ and R ⁵ may be bonded together to form a ring together with the nitrogen atom to which they are bonded. )
Formula (1) including the process of performing addition polymerization reaction of the compound shown by:

(In the formula, m, n, R ¹ , R ² , R ³ , R ⁴ and R ⁵ have the same meaning as described above.)
The manufacturing method of the polyvinyl ether resin containing the structural unit shown by these.   The manufacturing method of Claim 10 including the process of carrying out suspension polymerization of the compound shown by a formula (1m) in water. The structural unit represented by the formula (1) contained in the polyvinyl ether resin obtained by the production method according to claim 10 or 11 is represented by the formula (10):

(In the formula, m represents an integer of 0 or more, and n represents an integer of 2 or more. R ¹ , R ² and R ³ each independently represents a hydrogen atom, an alkyl group which may have a substituent, or Represents an aryl group which may have a substituent, R ¹ and R ² may be bonded to form a ring, or R ² and R ³ may be bonded to form a ring; R represents a hydrogen atom, an alkyl group which may have a substituent, or an aryl group which may have a substituent.
The manufacturing method of the polyvinyl ether resin which has the process converted into the structural unit shown by these.

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