JP2007008859A - Method for producing silicon compound - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for producing a high-purity silicon compound having starting ability of living radical polymerization in a short time. <P>SOLUTION: The method for producing a silicon compound represented by formula (1) (A is a polymerization initiation group; R<SP>1</SP>is a 1-4C alkyl; R<SP>2</SP>is a 1-20C alkyl, a 6-20C aryl or a 7-20C arylalkyl; n is an integer of 1-3) comprises a process for reacting a compound represented by formula (2) (X<SP>1</SP>is a halogen) with a compound represented by formula (3). <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a method for producing a silicon compound characterized by having a polymerization initiating ability for an addition polymerizable monomer.

  Graft polymerization onto a solid surface is a polymerization method that can impart various surface characteristics by changing the type of addition polymerizable monomer to be polymerized. Therefore, this polymerization method has been widely adopted as one of surface modification methods. However, for graft polymerization onto inorganic solid surfaces, the surface graft density is controlled for the purpose of uniform surface modification, and the primary structure of the graft chain (molecular weight, molecular weight distribution, monomer arrangement pattern, etc.) is strictly controlled. There is a problem that it is difficult.

  As advanced science and technology develops, in the field of graft polymerization to solid surfaces, it is becoming increasingly important to produce polymer materials based on precise design and create new functional polymer surfaces. ing. In order to arbitrarily control the surface characteristics, it is extremely important to graft a polymer having a clear structure. Otherwise, it is difficult to precisely analyze the properties of the molecular structure and surface characteristics of the surface graft polymer, and it is impossible to achieve surface modification tailored to the purpose.

  From such a background, a silicon compound having a living radical polymerization initiating group (hereinafter sometimes referred to as LRP-SCA) is used to treat the inorganic solid surface with a silane coupling agent, and then the polymerization initiating group. Attempts have been made to solve the above problems by the so-called surface-initiated graft polymerization method, in which a living radical polymerization of an addition-polymerizable monomer is performed starting from the above (Non-Patent Documents 1 to 3). In view of the versatility of addition polymerizable monomers in living radical polymerization, by changing the type of addition polymerizable monomers used in this graft polymerization method, new properties on various inorganic solid surfaces can be added. It is also possible to do.

When such an excellent method is applied at an industrial level, a method for producing a high-purity LRP-SCA in a short time and in a high yield must be established. In previous studies, LRP- was introduced by introducing an alkoxysilane into a compound having a living radical polymerization initiating group on one side of the molecular chain and a double bond on the other side using a hydrosilylation reaction. SCA has been manufactured. For example, in Non-Patent Document 1 described above, LRP-SCA is synthesized according to Scheme 1 shown below.
<Scheme 1>

However, this synthesis method has a reaction yield as low as 62%, and the trimethoxysilane used may generate explosive silane gas due to disproportionation, which is not necessarily an industrially suitable method. In Non-Patent Document 3, the same method is carried out using triethoxysilane, but there are problems such as extremely long reaction completion time. Moreover, since the catalyst components (Pt etc.) used for hydrosilylation reaction remain, it is difficult to manufacture high purity LRP-SCA. Therefore, a method for producing high-purity LRP-SCA in a short time and in a high yield has never been known.
Chem. Commun., 2000, (21), p.2083-2084 Polymer Preprints, 2003, 44 (1), p.532-533 Polymer Preprints, 2002, 43 (2), p.271-272

  An object of the present invention is to provide a method for producing a silicon compound having a living radical polymerization initiating ability in a short time with high purity.

In the case of a silicon compound having a living radical polymerization initiating ability, the present inventors have a higher hydrosilylation reaction with a double bond in the Si—H functional group of chlorosilane than in the Si—H functional group of alkoxysilane. I knew that it would proceed in yield. Then, as an efficient method for producing a silicon compound having a living radical polymerization initiating group and an alkoxysilyl group as a functional group, first, a living radical polymerization initiating group, a compound having a double bond, and hydrosilylation with chlorosilane are performed. A method for producing chlorosilane having a polymerization initiating ability and then alkoxylating the chlorosilane was developed.
That is, the present invention has the following configuration.

ここに、Ａは重合開始基であり；Ｒ^１は炭素数１〜４のアルキルであり；Ｒ^２は炭素数１〜２０のアルキル、炭素数６〜２０のアリール、または炭素数７〜２０のアリールアルキルであり；Ｘ^１はハロゲンであり；そして、ｎは１〜３の整数である。 [1] A method for producing a silicon compound represented by formula (1), comprising a step of reacting a compound represented by formula (2) with a compound represented by formula (3):

Here, A is a polymerization initiating group; R ¹ is alkyl having 1 to 4 carbon atoms; R ² is alkyl having 1 to 20 carbon atoms, aryl having 6 to 20 carbon atoms, or 7 to 20 carbon atoms. X ¹ is a halogen; and n is an integer from 1 to 3.

ここに、Ａは重合開始基であり；Ｒ^１は炭素数１〜４のアルキルであり；Ｒ^２は炭素数１〜２０のアルキル、炭素数６〜２０のアリールまたは炭素数７〜２０のアリールアルキルであり；Ｘ^１はハロゲンであり；そしてｎは１〜３の整数である。 [2] A step of subjecting a compound represented by formula (4) to a hydrosilylation reaction of a compound represented by formula (5) to obtain a compound represented by formula (2), and the compound represented by formula (2) And a step of reacting the compound represented by (3) with the method for producing a silicon compound represented by the formula (1):

Here, A is a polymerization initiating group; R ¹ is alkyl having 1 to 4 carbon atoms; R ² is alkyl having 1 to 20 carbon atoms, aryl having 6 to 20 carbon atoms, or aryl having 7 to 20 carbon atoms X ¹ is halogen; and n is an integer from 1 to 3.

[3] The production method according to the item [1] or [2], wherein A is a living radical polymerization initiating group.

式（６−１）において、Ｒ^３は水素、炭素数１〜２０のアルキル、炭素数６〜２０のアリール、または炭素数７〜２０のアリールアルキルであり；Ｒ^４は炭素数１〜２０のアルキル、炭素数６〜２０のアリール、または炭素数７〜２０のアリールアルキルであり；そして、Ｘ^２はハロゲンである：

式（６−２）において、Ｒ^５は炭素数１〜３のアルキルであり；ａは０〜２の整数であり；Ｘ^３はハロゲンであり；そして、−ＳＯ_２Ｘ^３の結合位置は不対電子を有する炭素に対してオルト位、メタ位またはパラ位であって、Ｒ^５の結合位置は−ＳＯ_２Ｘ^３の結合位置を除く任意の位置である：

式（６−３）において、Ｚ^１は炭素数１〜３であって任意の−ＣＨ_２−が−Ｏ−で置き換えられてもよいアルキレンであり；Ｒ^６は炭素数１〜３のアルキルであり；ａは０〜２の整数であり；Ｘ^４はハロゲンであり；そして、Ｚ^１の結合位置は不対電子を有する炭素に対してメタ位またはパラ位であって、Ｒ^６の置換位置はＺ^１の結合位置を除く任意の位置である：

式（６−４）において、Ｒ^８およびＲ^９は独立して水素、炭素数１〜１２のアルキル、炭素数６〜１０のシクロアルキルまたは炭素数６〜１０のアリールであり、そしてＲ^８およびＲ^９は互いに結合してＮとともに環を形成してもよく；Ｒ^７は炭素数１〜３のアルキルであり；Ｚ^２は炭素数１〜３であって任意の−ＣＨ_２−が−Ｏ−で置き換えられてもよいアルキレンであり；ａは０〜２の整数であり；そして、Ｚ^２の結合位置は不対電子を有する炭素に対してメタ位またはパラ位であり、Ｒ^７の結合位置はＺ^２の結合位置を除く任意の位置である。 [4] A is a living radical polymerization initiating group having a group represented by any one of formula (6-1), formula (6-2), formula (6-3) and formula (6-4). , [1] or [2]

In Formula (6-1), R ³ is hydrogen, alkyl having 1 to 20 carbons, aryl having 6 to 20 carbons, or arylalkyl having 7 to 20 carbons; R ⁴ is 1 to 20 carbons Alkyl, aryl having 6 to 20 carbon atoms, or arylalkyl having 7 to 20 carbon atoms; and X ² is halogen:

In Formula (6-2), R ⁵ is alkyl having 1 to 3 carbon atoms; a is an integer of 0 to 2; X ³ is halogen; and —SO ₂ X ³ is not bonded to the bonding position. In the ortho, meta, or para position relative to the carbon having the counter electron, the bonding position of R ⁵ is any position except the bonding position of —SO ₂ X ³ :

In Formula (6-3), Z ¹ is alkylene having 1 to 3 carbon atoms, and arbitrary —CH ₂ — may be replaced by —O—; R ⁶ is alkyl having 1 to 3 carbon atoms; Yes; a is an integer of 0 to 2; X ⁴ is halogen; and the bonding position of Z ¹ is the meta position or para position to the carbon having an unpaired electron, and the substitution position of R ⁶ Is any position except the bonding position of Z ¹ :

In formula (6-4), R ⁸ and R ⁹ are independently hydrogen, alkyl having 1 to 12 carbons, cycloalkyl having 6 to 10 carbons or aryl having 6 to 10 carbons, and R ⁸ and R ⁹ may be bonded to each other to form a ring together with N; R ⁷ is alkyl having 1 to 3 carbons; Z ² is 1 to 3 carbons and any —CH ₂ — is —O - be alkylene which may be replaced by; a is an integer from 0 to 2; and the bonding position of Z ² is meta or para to the carbon having the unpaired electron, the binding of R ⁷ position is an arbitrary position excluding the bonding positions of Z ^2.

式（７−１）において、Ｒ^３は水素、炭素数１〜２０のアルキル、炭素数６〜２０のアリール、または炭素数７〜２０のアリールアルキルであり；Ｒ^４は炭素数１〜２０のアルキル、炭素数６〜２０のアリール、または炭素数７〜２０のアリールアルキルであり；Ｘ^２はハロゲンであり；Ｚ^３は炭素数１〜１０のアルキレンであり；そして、このアルキレンにおいて、炭素数が３であるとき１つの−ＣＨ_２−は−Ｏ−で置き換えられてもよく、炭素数が３を超えるとき１つの−ＣＨ_２−または隣り合わない複数の−ＣＨ_２−は−Ｏ−で置き換えられてもよい：

式（７−２）において、Ｒ^５は炭素数１〜３のアルキルであり；ａは０〜２の整数であり；Ｘ^３はハロゲンであり；Ｚ^３は単結合または炭素数１〜１０のアルキレンであり、そしてこのアルキレンにおいて、炭素数が２以上であるとき任意の−ＣＨ_２−は−Ｏ−で置き換えられてもよく；そして、−ＳＯ_２Ｘ^３の結合位置はＺ^３の結合位置に対してオルト位、メタ位またはパラ位であって、Ｒ^５の結合位置は−ＳＯ_２Ｘ^３の結合位置を除く任意の位置である：

式（７−３）において、Ｚ^１は炭素数１〜３であって任意の−ＣＨ_２−は−Ｏ−で置き換えられてもよいアルキレンであり；Ｒ^６は炭素数１〜３のアルキルであり；ａは０〜２の整数であり；Ｘ^４はハロゲンであり；Ｚ^３は単結合または炭素数１〜１０のアルキレンであり、そしてこのアルキレンにおいて、炭素数が２以上であるとき任意の−ＣＨ_２−は−Ｏ−で置き換えられてもよく；そして、Ｚ^１の結合位置はＺ^３の結合位置に対してメタ位またはパラ位であって、Ｒ^６の置換位置はＺ^１の結合位置を除く任意の位置である：

式（７−４）において、Ｒ^８およびＲ^９は独立して水素、炭素数１〜１２のアルキル、炭素数６〜１０のシクロアルキル、または炭素数６〜１０のアリールであり、そしてＲ^８およびＲ^９は互いに結合してＮとともに環を形成してもよく；Ｒ^７は炭素数１〜３のアルキルであり；Ｚ^２は炭素数１〜３であって任意の−ＣＨ_２−は−Ｏ−で置き換えられてもよいアルキレンであり；ａは０〜２の整数であり；Ｚ^３は単結合または炭素数１〜１０のアルキレンであり、そしてこのアルキレンにおいて、炭素数が２以上であるとき任意の−ＣＨ_２−は−Ｏ−で置き換えられてもよく；そして、Ｚ^２の結合位置はＺ^３の結合位置に対してメタ位またはパラ位であり、Ｒ^７の結合位置はＺ^２の結合位置を除く任意の位置である。 [5] The item [1] or [A], wherein A is a group represented by any one of formulas (7-1), (7-2), (7-3), and (7-4) The production method according to item 2]:

In Formula (7-1), R ³ is hydrogen, alkyl having 1 to 20 carbons, aryl having 6 to 20 carbons, or arylalkyl having 7 to 20 carbons; R ⁴ has 1 to 20 carbons Alkyl, aryl having 6 to 20 carbon atoms, or arylalkyl having 7 to 20 carbon atoms; X ² is halogen; Z ³ is alkylene having 1 to 10 carbon atoms; and When — is 3, one —CH ₂ — may be replaced by —O—, and when the number of carbons exceeds 3, one —CH ₂ — or a plurality of non-adjacent —CH ₂ — is —O—. May be replaced:

In Formula (7-2), R ⁵ is alkyl having 1 to 3 carbon atoms; a is an integer of 0 to 2; X ³ is halogen; Z ³ is a single bond or 1 to 10 carbon atoms. And in this alkylene, when the number of carbon atoms is 2 or more, any —CH ₂ — may be replaced by —O—; and —SO ₂ X ³ is bonded to Z ³ In the ortho, meta or para position, the bonding position of R ⁵ is any position except the bonding position of —SO ₂ X ³ :

In formula (7-3), Z ¹ is alkylene having 1 to 3 carbon atoms, and arbitrary —CH ₂ — may be replaced by —O—; R ⁶ is alkyl having 1 to 3 carbon atoms; Yes; a is an integer of 0 to 2; X ⁴ is a halogen; Z ³ is a single bond or alkylene having 1 to 10 carbon atoms, and in the alkylene, any number of carbon atoms is 2 or more. —CH ₂ — may be replaced by —O—; and the bonding position of Z ¹ is meta or para to the bonding position of Z ³ , and the substitution position of R ⁶ is the bonding of Z ¹ Any position except position:

In Formula (7-4), R ⁸ and R ⁹ are independently hydrogen, alkyl having 1 to 12 carbons, cycloalkyl having 6 to 10 carbons, or aryl having 6 to 10 carbons, and R ⁸ And R ⁹ may combine with each other to form a ring with N; R ⁷ is alkyl having 1 to 3 carbons; Z ² is 1 to 3 carbons, and any —CH ₂ — is — Alkylene which may be replaced by O-; a is an integer of 0 to 2; Z ³ is a single bond or alkylene having 1 to 10 carbons, and the alkylene has 2 or more carbons when arbitrary -CH ₂ - may be replaced by -O-; and the bonding position of ^{Z 2} is meta or para position with respect to the binding position of ^{Z 3,} the bonding position of ^{R 7} is ^{Z 2} It is an arbitrary position excluding the coupling position.

式（７−１）において、Ｒ^３は水素、炭素数１〜２０のアルキル、炭素数６〜２０のアリール、または炭素数７〜２０のアリールアルキルであり；Ｒ^４は炭素数１〜２０のアルキル、炭素数６〜２０のアリール、または炭素数７〜２０のアリールアルキルであり；Ｘ^２はハロゲンであり；そして、Ｚ^３は炭素数１〜１０のアルキレンであり；このアルキレンにおいて、炭素数が３であるとき１つの−ＣＨ_２−は−Ｏ−で置き換えられてもよく、炭素数が３を超えるとき１つの−ＣＨ_２−または隣り合わない複数の−ＣＨ_２−は−Ｏ−で置き換えられてもよい：

式（７−２）において、Ｒ^５は炭素数１〜３のアルキルであり；ａは０〜２の整数であり；Ｘ^３はハロゲンであり；Ｚ^３は単結合または炭素数１〜１０のアルキレンであり、そしてこのアルキレンにおいて、炭素数が２以上であるとき任意の−ＣＨ_２−は−Ｏ−で置き換えられてもよく；そして、−ＳＯ_２Ｘ^３の結合位置はＺ^３の結合位置に対してオルト位、メタ位またはパラ位であって、Ｒ^５の結合位置は−ＳＯ_２Ｘ^３の結合位置を除く任意の位置である：

式（７−３）において、Ｚ^１は炭素数１〜３であって任意の−ＣＨ_２−は−Ｏ−で置き換えられてもよいアルキレンであり；Ｒ^６は炭素数１〜３のアルキルであり；ａは０〜２の整数であり；Ｘ^４はハロゲンであり；Ｚ^３は単結合または炭素数１〜１０のアルキレンであり、そしてこのアルキレンにおいて、炭素数が２以上であるとき任意の−ＣＨ_２−は−Ｏ−で置き換えられてもよく；そして、Ｚ^１の結合位置はＺ^３の結合位置に対してメタ位またはパラ位であって、Ｒ^６の置換位置はＺ^１の結合位置を除く任意の位置である：

式（７−４）において、Ｒ^８およびＲ^９は独立して水素、炭素数１〜１２のアルキル、炭素数６〜１０のシクロアルキル、または炭素数６〜１０のアリールであり、そしてＲ^８およびＲ^９は互いに結合してＮとともに環を形成してもよく；Ｒ^７は炭素数１〜３のアルキルであり；Ｚ^２は炭素数１〜３であって任意の−ＣＨ_２−は−Ｏ−で置き換えられてもよいアルキレンであり；ａは０〜２の整数であり；Ｚ^３は単結合または炭素数１〜１０のアルキレンであり、そしてこのアルキレンにおいて、炭素数が２以上であるとき任意の−ＣＨ_２−は−Ｏ−で置き換えられてもよく；そして、Ｚ^２の結合位置はＺ^３の結合位置に対してメタ位またはパラ位であり、Ｒ^７の結合位置はＺ^２の結合位置を除く任意の位置である。 [6] R ¹ is methyl, ethyl, propyl, 1-methylethyl, butyl, or 1,1-dimethylethyl; n is 2 or 3, and A is a formula (7-1) or a formula (7 -2), the production method according to item [1] or [2], which is a group represented by any one of formulas (7-3) and (7-4):

In Formula (7-1), R ³ is hydrogen, alkyl having 1 to 20 carbons, aryl having 6 to 20 carbons, or arylalkyl having 7 to 20 carbons; R ⁴ has 1 to 20 carbons Alkyl, aryl having 6 to 20 carbon atoms, or arylalkyl having 7 to 20 carbon atoms; X ² is halogen; and Z ³ is alkylene having 1 to 10 carbon atoms; When — is 3, one —CH ₂ — may be replaced by —O—, and when the number of carbons exceeds 3, one —CH ₂ — or a plurality of non-adjacent —CH ₂ — is —O—. May be replaced:

In Formula (7-2), R ⁵ is alkyl having 1 to 3 carbon atoms; a is an integer of 0 to 2; X ³ is halogen; Z ³ is a single bond or 1 to 10 carbon atoms. And in this alkylene, when the number of carbon atoms is 2 or more, any —CH ₂ — may be replaced by —O—; and —SO ₂ X ³ is bonded to Z ³ In the ortho, meta or para position, the bonding position of R ⁵ is any position except the bonding position of —SO ₂ X ³ :

In formula (7-3), Z ¹ is alkylene having 1 to 3 carbon atoms, and arbitrary —CH ₂ — may be replaced by —O—; R ⁶ is alkyl having 1 to 3 carbon atoms; Yes; a is an integer of 0 to 2; X ⁴ is a halogen; Z ³ is a single bond or alkylene having 1 to 10 carbon atoms, and in the alkylene, any number of carbon atoms is 2 or more. —CH ₂ — may be replaced by —O—; and the bonding position of Z ¹ is meta or para to the bonding position of Z ³ , and the substitution position of R ⁶ is the bonding of Z ¹ Any position except position:

In Formula (7-4), R ⁸ and R ⁹ are independently hydrogen, alkyl having 1 to 12 carbons, cycloalkyl having 6 to 10 carbons, or aryl having 6 to 10 carbons, and R ⁸ And R ⁹ may combine with each other to form a ring with N; R ⁷ is alkyl having 1 to 3 carbons; Z ² is 1 to 3 carbons, and any —CH ₂ — is — Alkylene which may be replaced by O-; a is an integer of 0 to 2; Z ³ is a single bond or alkylene having 1 to 10 carbons, and the alkylene has 2 or more carbons when arbitrary -CH ₂ - may be replaced by -O-; and the bonding position of ^{Z 2} is meta or para position with respect to the binding position of ^{Z 3,} the bonding position of ^{R 7} is ^{Z 2} It is an arbitrary position excluding the coupling position.

[7] The production method according to item [5], wherein A is a group represented by formula (7-1), formula (7-2), or formula (7-3).

[8] The production method according to item [6], wherein A is a group represented by formula (7-1), formula (7-2), or formula (7-3).

[9] The production method according to item [5], wherein A is a group represented by formula (7-1):

[10] The production method according to item [6], wherein A is a group represented by formula (7-1).

[11] The item [6], wherein A is represented by the formula (7-1); R ³ is hydrogen, methyl or ethyl; R ⁴ is methyl or ethyl; and X ² is chlorine or bromine. The manufacturing method as described in.

[12] R ¹ is methyl or ethyl; n is 3, A is represented by formula (7-1); in formula (7-1), X ² is bromine, R ³ and R ⁴ Are both methyl, and Z ³ is —C ₃ H ₆ —, —C ₄ H ₈ — or —C ₂ H ₄ —O—C ₃ H ₆ —.

[13] Item [1] or [2], wherein the compound represented by formula (2) is reacted with the compound represented by formula (3) in a molar ratio of 1 to 10 times with respect to this compound. The production method according to item.

  The method for producing a silicon compound having living radical polymerization initiating ability provided by the present invention is a simpler and more efficient method than conventional production methods, and produces a high-purity silicon compound at an industrial level safely and at low cost. it can.

In the present invention, both alkyl and alkylene may be linear groups or branched groups. “Arbitrary” used in the present invention indicates that not only the position but also the number can be arbitrarily selected. For example, alkyl in which any —CH ₂ — may be replaced by —O— includes groups such as alkyl, alkoxyalkyl, alkoxyalkoxyalkyl. However, in the present invention, the case where —CH ₂ — bonded to the ester group is replaced by —O— and the case where a plurality of consecutive —CH ₂ — are replaced by —O— are not included. In the following description, the compound represented by formula (1) may be referred to as compound (1). The compounds represented by other formulas may be represented by the same simplified method.

ここに、Ａは重合開始基であり、Ｒ^１は炭素数１〜４のアルキルであり、Ｒ^２は炭素数１〜２０のアルキル、炭素数６〜２０のアリール、または炭素数７〜２０のアリールアルキルであり、Ｘ^１はハロゲンであり、そしてｎは１〜３の整数である。本発明において、「重合開始基」は重合開始部位を有する基を意味する。 The production method of the present invention is a method for producing the compound (1), and includes a step of reacting the compound represented by the formula (2) with the compound represented by the formula (3).

Here, A is a polymerization initiating group, R ¹ is alkyl having 1 to 4 carbon atoms, R ² is alkyl having 1 to 20 carbon atoms, aryl having 6 to 20 carbon atoms, or 7 to 20 carbon atoms. Arylalkyl, X ¹ is halogen, and n is an integer from 1 to 3. In the present invention, the “polymerization initiating group” means a group having a polymerization initiating site.

これらの式における記号の意味は前記の通りである。 A more specific example of the production method of the present invention is a step of obtaining a compound represented by the above formula (2) by hydrosilylating a compound represented by the formula (5) with a compound represented by the formula (4). And a step of reacting the compound represented by the formula (2) with the compound represented by the formula (3).

The meanings of the symbols in these formulas are as described above.

  A preferred example of A is a group having a living radical polymerization initiation site. Examples of such A have a group having an α-haloester bond, a group having a halogenated sulfonyl group, a group having a haloalkylphenyl group, a group having an MgBr group, a group having a dithiocarbamate group, and a nitroxyl group. It is a group. A group having a haloalkylphenyl group generates a radical in the presence of a copper chloride / amine complex, and becomes an initiator of cationic polymerization in the presence of silver chlorate. Examples of haloalkylphenyl are chloromethylphenyl, bromomethylphenyl, iodomethylphenyl, and the like. More preferred examples of A are a group having an α-haloester bond, a group having a halogenated sulfonyl group, a group having a haloalkylphenyl group, and a group having a dithiocarbamate group. The most preferred example of A is a group having an α-haloester bond. In the following description, a group having an α-haloester bond may be referred to as an α-haloester group.

  The group having an α-haloester bond means a group having α-halocarbonyloxy as a terminal group. As a polymerization method using this α-halocarbonyloxy as a radical polymerization initiation group, an atom transfer radical polymerization method is known. The polymerization catalyst used in this method is a metal complex having a group 8 element, group 9, group 10 or group 11 element in the periodic table as a central metal atom. In this atom transfer radical polymerization, it is known that a group having α-halocarbonyloxy has an excellent polymerization initiating ability. It is also well known that this polymerization is a living polymerization. That is, the compound produced by the present invention has excellent polymerization initiating ability in the presence of a transition metal complex, and can continue to maintain living polymerizability. The silicon compound produced according to the present invention can initiate polymerization for any radically polymerizable monomer, and in particular, can exhibit excellent living polymerizability for styrene derivatives. is there.

  The silicon compound having an α-haloester group produced according to the present invention can be led to a large number of derivatives by applying various organic reactions. For example, it can be derived into silsesquioxane having an organometallic functional group by reacting lithium, magnesium, zinc or the like with the silicon compound produced according to the present invention. Specifically, zinc is reacted with the silicon compound produced according to the present invention to induce silsesquioxane having an organozinc functional group, and then converted to alcohol by adding an aldehyde or ketone. Can do. That is, silsesquioxane having an organozinc functional group is useful as an intermediate raw material used in so-called reformate key reaction.

  Since the α-haloester group has a strong electrophilicity, it can be converted into an amino group, a mercapto group or the like using various nucleophilic reagents. Further, a silicon compound having an α-haloester group can be converted to a ketone by treating with an enamine to form an imine salt and hydrolyzing the imine salt. That is, the silicon compound produced by the present invention is also useful as an intermediate material used for the Stoke-enamine reaction. It is also possible to obtain silsesquioxane derivatives having various organic functional groups and polymerizable functional groups by reacting the silicon compound produced according to the present invention with an aliphatic or aromatic Grignard reagent. Therefore, the silicon compound having an α-haloester group can be used not only as a polymerization initiator but also as an intermediate useful for various organic syntheses.

In the present invention, a preferred embodiment of the method for producing a silicon compound having an α-haloester group is a method including a step of reacting a compound (3) with a halosilane compound represented by the formula (2-1). is there. At this time, a silicon compound represented by the formula (1-1) is obtained. Formula (2-1) is a formula when A in Formula (2) is a group represented by Formula (7-1). The compound (2-1) is obtained by a hydrosilylation reaction between the compound (4-1) and the compound (5) in which A in the formula (4) is a group represented by the formula (7-1).

The meanings of the symbols in these formulas are as follows. R ¹ is alkyl having 1 to 4 carbon atoms, R ² is alkyl having 1 to 20 carbon atoms, aryl having 6 to 20 carbon atoms, or arylalkyl having 7 to 20 carbon atoms, and X ¹ is halogen. , And n is an integer from 1 to 3. Preferred examples of R ¹ are methyl, ethyl, propyl, 1-methylethyl, butyl, and 1,1-dimethylethyl. And more preferred examples of R ¹ are methyl and ethyl.

R ² is alkyl having 1 to 20 carbons, aryl having 6 to 20 carbons, or arylalkyl having 7 to 20 carbons. A preferred example of this alkyl is alkyl having 1 to 4 carbon atoms. Preferred examples of aryl are phenyl and methylphenyl. Preferred examples of arylalkyl are benzyl and phenethyl. Preferred examples of R ² are methyl and ethyl. A particularly preferred example of R ² is methyl.

X ¹ is halogen, and preferred examples thereof are bromine and chlorine. And n is an integer of 1-3, 2 or 3 is preferable and 3 is more preferable.

In Formula (2-1), R ³ is hydrogen, alkyl having 1 to 20 carbons, aryl having 6 to 20 carbons, or arylalkyl having 7 to 20 carbons, and R ⁴ has 1 to 20 carbons. Alkyl, aryl having 6 to 20 carbons, or arylalkyl having 7 to 20 carbons. A preferred example of alkyl is alkyl having 1 to 4 carbon atoms. Preferred examples of aryl are phenyl and methylphenyl. Preferred examples of arylalkyl are benzyl and phenethyl. Preferred examples of R ³ or R ⁴ are methyl and ethyl. It is particularly preferred that R ³ and R ⁴ are both methyl.

X ² in the formula (2-1) is halogen, and preferred examples thereof are chlorine and bromine. A more preferred example of X ² is bromine.

Z ³ in Formula (2-1) is alkylene having 1 to 10 carbons. In this alkylene, one —CH ₂ — may be replaced with —O— when the carbon number is 3, and one or a plurality of non-adjacent —CH ₂ — is —O— when the carbon number exceeds 3. It may be replaced with-. Preferred examples of —O—Z ³ —CH ₂ CH ₂ — in formula (2-1) include —O—C ₃ H ₆ —, —O—C ₄ H ₈ —, —O—C ₅ H ₁₀ —, _{-O-C 6 H 12 -,} - O-C 2 H 4 O-C 3 H 6 -, - O-C 3 H 6 O-C 3 H 6 -, - O-C 3 H 6 O-C 2 _{H 4 O-C 3 H 6} -, and _{-O-C 2 H 4 O-} C 3 H 6 O-C 3 H 6 - it is. More preferred examples of —O—Z ³ —CH ₂ CH ₂ — include —O—C ₃ H ₆ —, —O—C ₄ H ₈ —, —O—C ₅ H ₁₀ —, —O—C ₆ H. ₁₂ -, and _{-O-C 2 H 4 O-} C 3 H 6 - is.

  As a polymerization method using a group having a halogenated sulfonyl as a polymerization initiation group, an atom transfer radical polymerization method is known. The polymerization catalyst used in this method is a metal complex having a group 8 element, group 9, group 10 or group 11 element in the periodic table as a central metal atom. In this atom transfer radical polymerization, it is known that a group having a halogenated sulfonyl has an excellent polymerization initiating ability. It is also well known that this polymerization is a living polymerization. That is, the compound produced by the present invention has excellent polymerization initiating ability in the presence of a transition metal complex, and can continue to maintain living polymerizability. The silicon compound produced according to the present invention can initiate polymerization for any radical polymerizable monomer, and in particular, exhibits excellent living polymerizability for (meth) acrylic acid derivatives. It is possible.

  Since the halogenated sulfonyl group has strong electrophilicity, the silicon compound having a halogenated sulfonyl group produced according to the present invention can synthesize various derivatives using various nucleophilic reagents. For example, conversion to sulfonic acid by acidic conditions, conversion to sulfonic acid by hydrolysis, conversion to sulfonic acid by hydrolysis, conversion to sulfonate by treatment with sodium hydroxide, treatment of various alcohols under basic conditions Thus, conversion to a sulfonic acid ester is possible, and conversion to a sulfonic acid amide is possible by treating with ammonia or an amine. That is, the silicon compound produced by the present invention can be used as a protecting group, and a part of the sulfonic acid amide derivative can also be used as a sulfa drug, for example, as an antibacterial drug. Further, it can be converted into a mercapto group using various reducing agents such as lithium aluminum hydride, and can be derived into an aromatic sulfone with various aromatic Grignard reagents. Therefore, the silicon compound produced by the present invention can be used not only as a polymerization initiator but also as an intermediate useful for various organic syntheses.

A preferred embodiment of a method for producing a silicon compound having a halogenated sulfonyl group is a method comprising a step of reacting a compound (3) with a halosilane compound represented by the formula (2-2). At this time, a silicon compound represented by the formula (1-2) is obtained. Formula (2-2) is a formula when A in Formula (2) is a group represented by Formula (7-2). And a compound (2-2) is obtained by hydrosilylation reaction of the compound (4-2) and A compound (5) whose A in Formula (4) is group shown by Formula (7-2).

In these formulas, R ¹ , R ² and n have the same meanings as those symbols in formula (1-1), and preferred ranges thereof are also the same. Meaning of X ¹ is the same as ^{X 1} in the formula (2-1), the same applies to its preferred range. R ⁵ is alkyl having 1 to 3 carbon atoms, a is an integer of 0 to 2, X ³ is halogen, and Z ³ is a single bond or alkylene having 1 to 10 carbon atoms. In this alkylene, when the number of carbon atoms is 2 or more, arbitrary —CH ₂ — may be replaced by —O—. The bonding position of —SO ₂ X ³ to the benzene ring is ortho, meta, or para with respect to the bonding position of Z ³ . The bonding position of R ^{5 is} an arbitrary position excluding the bonding positions of —SO ₂ X ³ and Z ³ .

Examples of R ⁵ are methyl, ethyl, propyl and 1-methylethyl. A representing the number of R ⁵ is 0, 1 or 2, and a more preferred example is 0. Preferred examples of X ³ are chlorine, bromine and iodine. More preferred examples of X ³ are chlorine and bromine.

Preferred examples of —Z ³ —CH ₂ CH ₂ — include alkylene having 2 to 5 carbon atoms, —OC ₃ H ₆ —, —OC ₄ H ₈ —, —CH ₂ OC ₃ H ₆ —, —CH ₂ OC _{4. H 8 -, - C 2 H} 4 OC 3 H 6 -, and _{-C 2 H 4 OC 4 H 8} - a.

  As a polymerization method using a haloalkylphenyl group as a radical polymerization initiation group, an atom transfer radical polymerization method is known. The polymerization catalyst used in this method is a metal complex having a group 8 element, group 9, group 10 or group 11 element in the periodic table as a central metal atom. In this atom transfer radical polymerization, it is known that a group having a haloalkylphenyl group has an excellent polymerization initiating ability. It is also well known that this polymerization is a living polymerization. That is, the compound produced by the present invention has excellent polymerization initiating ability in the presence of a transition metal complex, and can continue to maintain living polymerizability. The silicon compound produced according to the present invention can initiate polymerization for any radically polymerizable monomer, and in particular, can exhibit excellent living polymerizability for styrene derivatives. is there.

  Since the haloalkylphenyl group has strong electrophilicity, the silicon compound having a haloalkylphenyl group produced according to the present invention can introduce an amino group, a hydroxyl group, a mercapto group, etc. using various nucleophilic reagents. Therefore, the silicon compound produced by the present invention can be used not only as a polymerization initiator but also as an intermediate useful for various organic syntheses.

A preferred embodiment of the method for producing a silicon compound having a haloalkylphenyl group is a method comprising a step of reacting a compound (3) with a halosilane compound represented by the formula (2-3). At this time, a silicon compound represented by the formula (1-3) is obtained. Formula (2-3) is a formula when A is a group represented by Formula (7-3) in Formula (2). The compound (2-3) is obtained by a hydrosilylation reaction between the compound (4-3) and the compound (5) in which A is a group represented by the formula (7-3) in the formula (4).

In these formulas, R ¹ , R ² and n have the same meanings as those symbols in formula (1-1), and preferred ranges thereof are also the same. Meaning of X ¹ is the same as ^{X 1} in the formula (2-1), the same applies to its preferred range. R ⁶ is alkyl having 1 to 3 carbon atoms, a is an integer of 0 to 2, X ⁴ is halogen, Z ¹ is ¹ to 3 carbon atoms, and any —CH ₂ — is — Alkylene which may be replaced by O-, and Z ³ is a single bond or alkylene having 1 to 10 carbon atoms. In the alkylene having 1 to 10 carbon atoms, when the carbon number is 2 or more, arbitrary —CH ₂ — may be replaced by —O—. The bonding position of Z ¹ to the benzene ring is ortho, meta or para with respect to the bonding position of Z ³ . The bonding position of R ^{6 is} an arbitrary position excluding the bonding positions of Z ¹ and Z ³ .

Examples of R ⁶ are methyl, ethyl, propyl and 1-methylethyl. A representing the number of R ⁶ is 0, 1 or 2, but a more preferred example is 0. Preferred examples of X ⁴ are chlorine, bromine and iodine. More preferred examples of X ⁴ are chlorine and bromine.

Preferred examples of Z ¹ are —CH ₂ — and —CH ₂ CH ₂ —. Preferred examples of —Z ³ —CH ₂ CH ₂ — include alkylene having 2 to 5 carbon atoms, —OC ₃ H ₆ —, —OC ₄ H ₈ —, —CH ₂ OC ₃ H ₆ —, —CH ₂ OC _{4. H 8 -, - C 2 H} 4 OC 3 H 6 -, and _{-C 2 H 4 OC 4 H 8} - a.

  As a polymerization method using a dithiocarbamate group as a polymerization initiation group, a photo initiator-transfer agent-terminator polymerization method is known. In this photoiniferter polymerization, it is well known that a dithiocarbamate group undergoes radical dissociation by light and has excellent polymerization initiating ability and sensitizing ability. It is also well known that this photopolymerization is a living polymerization. Therefore, as long as the silicon compound produced according to the present invention having a dithiocarbamate group is irradiated with light, it is possible to continue to maintain the polymerization ability, and the ability to initiate photopolymerization with respect to any polymerizable monomer. Have. In particular, it is possible to develop excellent living polymerizability for (meth) acrylic derivatives. In addition, since the dithiocarbamate group has a polymerization initiating ability, and has pharmacological activity such as radiation resistance and herbicidal effect, complex forming ability, hydrophilicity and the like, these characteristics can also be utilized.

A preferred embodiment of the method for producing a silicon compound having a dithiocarbamate group is a method including a step of reacting a compound (3) with a halosilane compound represented by the formula (2-4). At this time, a silicon compound represented by the formula (1-4) is obtained. Formula (2-4) is a formula when A is a group represented by Formula (7-4) in Formula (2). The compound (2-4) is obtained by a hydrosilylation reaction between the compound (4-4) and the compound (5) in which A is a group represented by the formula (7-4) in the formula (4).

In these formulas, R ¹ , R ² and n have the same meanings as those symbols in formula (1-1), and preferred ranges thereof are also the same. Meaning of X ¹ is the same as ^{X 1} in the formula (2-1), the same applies to its preferred range. R ⁸ and R ⁹ are independently hydrogen, alkyl having 1 to 12 carbons, cycloalkyl having 6 to 10 carbons, or aryl having 6 to 10 carbons, and R ⁸ and R ⁹ are bonded to each other. A ring may be formed together with N. R ⁷ is alkyl having 1 to 3 carbon atoms, and a indicating the number is an integer of 0 to 2. Z ² is alkylene having 1 to 3 carbon atoms and any —CH ₂ — may be replaced by —O—, and Z ³ is a single bond or alkylene having 1 to 10 carbon atoms. In the alkylene having 1 to 10 carbon atoms, when the carbon number is 2 or more, arbitrary —CH ₂ — may be replaced by —O—. The bonding position of Z ² to the benzene ring is meta or para with respect to the bonding position of Z ³ . The bonding position of R ^{7 is} an arbitrary position excluding the bonding positions of Z ² and Z ³ .

Preferred examples of R ⁸ or R ⁹ are hydrogen, methyl, ethyl, propyl, 1-methylethyl, butyl, 2-methylpropyl, pentyl, 2-methylbutyl, hexyl, 2-methylpentyl, heptyl, octyl, decyl, phenyl , Cyclopentyl and cyclohexyl. R ⁸ and R ⁹ may both be one of these groups, one may be one of these groups and the other may be hydrogen.

R ⁸ and R ⁹ may combine with each other to form a ring with N. Examples of such dithiocarbamate groups are N-cyclotrimethylene dithiocarbamate group, N-cyclotetramethylene dithiocarbamate group, N-cyclopentamethylene dithiocarbamate group, N-cyclohexamethylene dithiocarbamate group, N-cyclohepta group. A methylenedithiocarbamate group and an N-cyclooctamethylenedithiocarbamate group. Examples of preferred dithiocarbamate groups are N, N-dimethyldithiocarbamate groups and N, N-diethyldithiocarbamate groups, with N, N-diethyldithiocarbamate groups being most preferred.

Examples of R ⁷ are methyl, ethyl, propyl and 1-methylethyl. A representing the number of R ⁷ is 0, 1 or 2, and a more preferred example is 0. Preferred examples of Z ² are —CH ₂ — and —CH ₂ CH ₂ —. Preferred examples of —Z ³ —CH ₂ CH ₂ — include alkylene having 2 to 5 carbon atoms, —OC ₃ H ₆ —, —OC ₄ H ₈ —, —CH ₂ OC ₃ H ₆ —, —CH ₂ OC _{4. H 8 -, - C 2 H} 4 OC 3 H 6 -, and _{-C 2 H 4 OC 4 H 8} - a.

A more preferable embodiment of the above preferable embodiments is that in which —O—Z ³ — is —O—CH ₂ —, —O—C ₂ H ₄ —, —O—C ₃ H ₆ —, or —O— (C _{2 H 4 O) h -CH 2} - in which the compound (4-1) as a starting material, a process for the preparation of a compound (1-1). h is an integer of 1-6.

これらの式における記号の意味は前記の通りである。 Next, the production method of the present invention will be described in more detail using a compound having an α-haloester group as an example. Compound (4-1) is obtained by reacting a compound having a hydroxyl group at the end and an addition polymerizable double bond at the other end with an acid halide in which a halogen is bonded to the α-position carbon. . And a compound (2-1) is obtained by making a hydrosilylation reaction of this compound and halogenated silane.

The meanings of the symbols in these formulas are as described above.

The production method of compound (2-1) will be described with specific examples. Compound (2-1-1) in which R ³ and R ⁴ are both methyl, X ¹ is Cl, X ² is Br, and n is 3 is prepared by the synthetic route shown in Scheme 3 can do. In Scheme 3, TEA, DCC and DMAP are triethylamine, 1,3-dicyclohexylcarbodiimide and 4-dimethylaminopyridine, respectively.
<Scheme 3>

式（２−１−４）において、ｈは１〜６である。 First, compound (4-1-1) (2-bromo-2-methyl-propionic acid allyl ester) is synthesized by reaction of 2-bromoisobutyryl bromide with allyl alcohol in the presence of triethylamine. Even if 2-bromo-2-methylpropionic acid and allyl alcohol are subjected to dehydration condensation in the presence of DCC-DMAP, they can be derived into 2-bromo-2-methyl-propionic acid allyl ester. Furthermore, by using this as a raw material and subjecting the compound (5-1) (Si—H functional trichlorosilane) to a hydrosilylation reaction in the presence of a Pt catalyst, the target compound (2-1-1) can be easily obtained. Obtainable. Examples of the compound (2-1) obtained by the same method as in Scheme 3 are shown below.

In Formula (2-1-4), h is 1-6.

  Next, a method for producing compound (1-1) by reacting compound (2-1) with compound (3) will be described. This reaction is usually carried out in an inert gas atmosphere such as argon gas or nitrogen gas, using a dry organic solvent inert to the raw material. The selection conditions of the solvent used for this reaction are that it does not react with the compound (1-1) and the compound (2-1), and is sufficiently dehydrated. Examples of solvents are tetrahydrofuran, toluene, and methylene chloride. A particularly preferred solvent is well-dehydrated methylene chloride. A solvent is not particularly required. It is necessary that the compound (3) is also sufficiently dehydrated. The usage-amount of a compound (3) is the range of 0.5-5.0 by the equivalent ratio with respect to the halogen which a compound (2-1) has. A preferable range of this equivalent ratio is 1.0 to 1.5. The reaction temperature is a temperature at which quantitative reactions can proceed without side reactions. Specifically, the reaction temperature is preferably between 0 ° C and 160 ° C, more preferably between 15 ° C and 80 ° C. Usually, when compound (3) is added to compound (2-1), a strong heat is generated. Therefore, it is most preferably carried out in a water bath. The reaction time is not particularly limited as long as it is a time sufficient for the quantitative reaction to proceed. Usually, the target silicon compound can be obtained when self-heating is subsided.

  The hydrogen halide produced as a by-product during the reaction induces a side reaction. To remove this, the reaction is carried out by discharging it out of the system by heating or coexisting an organic base. Examples of organic bases are pyridine, dimethylaniline, triethylamine and tetramethylurea. Other organic bases may be used as long as side reactions can be suppressed and the reaction can proceed rapidly. The most preferred example of the organic base is triethylamine.

  In order to separate the unreacted raw material compound and solvent from the compound (1-1), it is preferable to employ vacuum distillation. By this method, it is possible to prevent the decomposition of the compound (1-1) due to being kept under a high temperature condition for a long time. When the compound (1-1) has a high boiling point and it is difficult to distill, the unreacted raw material compound, by-product, solvent and the like may be simply distilled off under reduced pressure.

この際、副生するハロゲン化水素は、その他の低沸点成分とともに減圧下で溜去させてもよいし、有機塩基を共存させて反応を行い、生成した塩をろ別してから、濃縮してもよい。いずれにしても、高純度の化合物（１−１−１）を得ることができる。 A specific example shows a method for producing the compound (1-1) by reacting the compound (2-1) with the compound (3). The compound (1-1-1) in which R ¹ is methyl, X ² is Br, and n is 3 can be produced from the compound (2-1-1) by the synthetic route shown in Scheme 4. it can.
<Scheme 4>

At this time, the by-produced hydrogen halide may be distilled off under reduced pressure together with other low-boiling components, or the reaction may be performed in the presence of an organic base, and the produced salt may be filtered and concentrated. Good. In any case, a highly pure compound (1-1-1) can be obtained.

式（１−１−４）において、ｈは１〜６である。 Examples of the compound (1-1) that can be produced by the same method as in Scheme 4 are shown below.

In Formula (1-1-4), h is 1-6.

  As described above, a silicon compound having an α-haloester group can be produced, but compounds (1-2) to (1-4) can also be produced in the same manner.

  The silicon compound produced by the present invention has an alkoxy group on the silicon atom. This alkoxy group has high hydrolyzability and acts as a silane coupling agent that easily forms a good bond with an inorganic compound by hydrolysis or the like. Therefore, it is useful as a raw material for a composite material composed of an organic compound and an inorganic compound.

The silicon compound produced by the present invention is used as a silane coupling agent, inorganic fine particles such as SiO ₂ , Al ₂ O ₃ , MgO, metal silicon (silicon wafer, etc.), mica, stainless steel, aluminum, ceramics, cement, paper, glass It can be used for surface treatment of plastics, inorganic ceramic substrates, fabrics and the like. This surface treatment can be performed according to a normal method.

  The solid surface treated with the silicon compound produced according to the present invention can be an initiator of an addition polymerizable monomer. For example, by polymerizing an addition polymerizable monomer from inorganic fine particles treated with the silicon compound produced according to the present invention, inorganic fine particles in which a polymer with a clear structure is surface-grafted at high density can be obtained. . The inorganic fine particles having the polymer graft chain layer disposed on the surface can be arranged two-dimensionally or three-dimensionally through the polymer graft chain layer to form an ordered structure of the fine particles. Further, the distance between the fine particles can be controlled by changing the molecular weight of the polymer graft chain, and the arrangement of the inorganic fine particles in the ordered structure can be controlled. In addition, the inorganic fine particles obtained by this method have the advantage that the polymer graft chains are firmly fixed to the surface of the fine particles by siloxane bonds, so that the release of the polymer graft chains from the inorganic surface is remarkably suppressed. It also has. By treating the silicon compound of the present invention on a surface other than the inorganic fine particles, for example, a silicon wafer or glass, a silicon wafer or glass in which a polymer having a clear structure is surface grafted at a high density can be obtained. By this method, it is possible to impart surface characteristics completely different from those of a silicon wafer or glass, for example, characteristics such as refractive index, dielectric constant, and surface free energy. Further, the surface structure in which a polymer having a clear structure is patterned by transferring the silicon compound of the present invention to a silicon wafer or glass surface by a method such as micropattern printing and then polymerizing an addition polymerizable monomer. It is also possible to form. This method is a method of patterning a polymer by a process completely different from that of a conventional resist material, and active research is progressing in the semiconductor field, and application to this field is also possible.

  Since the silicon compound produced by the present invention has a living radical polymerization initiating group, it may be used as it is as an initiator. In this case, a polymer having a silane compound bonded to the terminal can be obtained, and this can also be used as a polymer coupling agent.

  The present invention will be described more specifically with reference to examples, but the present invention is not limited to the following examples.

Ａｒ雰囲気下、還流冷却器、温度計、滴下漏斗を取り付けた内容積５００ｍＬの４つ口フラスコに、２−プロペン−１−オール（１０．７ｇ）、メチレンクロライド（２４０ｇ）およびトリエチルアミン（２１．７ｇ）を仕込み、溶液をドライアイス−メタノール浴を用いて冷却し、液温を約−５５℃に保持した。次いで、この溶液に２−ブロモ−２−メチルプロピオニルブロマイド（４０．６ｇ、２−プロペン−１−オールに対して０．９６当量）を速やかに加え、−３７℃にて１時間撹拌した後、室温下で更に４時間撹拌した。反応終了後、トリエチルアミン−臭酸塩を濾過により除去した。得られた反応液にメチレンクロライド（２０ｍｌ）を加え、炭酸水素ナトリウム水溶液（３％、４００ｍｌ）による３回の洗浄、水（４００ｍｌ）による２回の洗浄を順次行ってから、無水硫酸マグネシウム（１５ｇ）にて乾燥した。その後、ロータリーエバポレータを用い、この溶液を濃縮した。得られた液体成分を減圧蒸留（７４℃、５２０Ｐａ）して、透明な液体を得た（２９．６ｇ、収率：８１％）。
<Production of 2-bromo-2-methyl-propionic acid-3-trimethoxysilanyl-propyl ester>
(Step 1) Synthesis of Compound (4-1-1)

Under an Ar atmosphere, a 500 mL four-necked flask equipped with a reflux condenser, a thermometer, and a dropping funnel was charged with 2-propen-1-ol (10.7 g), methylene chloride (240 g) and triethylamine (21.7 g). The solution was cooled using a dry ice-methanol bath, and the liquid temperature was kept at about -55 ° C. Next, 2-bromo-2-methylpropionyl bromide (40.6 g, 0.96 equivalent to 2-propen-1-ol) was quickly added to this solution, and the mixture was stirred at -37 ° C for 1 hour, The mixture was further stirred at room temperature for 4 hours. After completion of the reaction, triethylamine-bromide was removed by filtration. Methylene chloride (20 ml) was added to the resulting reaction solution, washed three times with an aqueous sodium hydrogen carbonate solution (3%, 400 ml) and twice with water (400 ml), and then anhydrous magnesium sulfate (15 g). ). The solution was then concentrated using a rotary evaporator. The obtained liquid component was distilled under reduced pressure (74 ° C., 520 Pa) to obtain a transparent liquid (29.6 g, yield: 81%).

As a result of gas chromatography analysis of the obtained liquid, a single peak was confirmed, and the presence of impurities and the like was hardly confirmed. From the results of IR, ¹ H-NMR and ¹³ C-NMR shown below, the obtained transparent liquid is compound (4-1-1) (2-bromo-2-methyl-propionic acid allyl ester). I understood.
GC purity: 99.7%
IR (KBr method): ν = 3010 (H ₂ C = C-), 2980 (-CH ₃ ), 2936 (-CH _2- ), 1738 (C = O), 1651 (C = C-), 1464 ( -CH _2- ), 1390 (-CH ₃ ), 1373 (-CH ₃ ), 1276 (COC), 1164 (COC), 640 (C-Br).
¹ H NMR (400 MHz, TMS standard: δ = 0.0 ppm): 5.94 (tt, 1H, CH ₂ = C H -CH _2- ), 5.39 (dd, 1H, C H ₂ = CH-CH _2- ), 5.33 _{(dd, 1H, C H 2} = CH-CH 2 -), 4.67 (d, 2H, CH 2 = CH-C H 2 -), 1.95 (s, 6H, -C (C H 3) 2).
¹³ C NMR (100MHz, TMS standard: δ = 0.0 ppm): 171.2 (C = O), 131.4 (C = C -CH 2 -), 118.5 (C = C-CH 2 -), 66.4 (C = C- C H _2- ), 55.7 ( -C (Br)), 30.8 (-C ( C H ₃ ) ₂ ).

Ｎ_２雰囲気下、還流冷却器、温度計、滴下漏斗を取り付けた内容積２００ｍＬの４つ口フラスコに、上記の化合物（４−１−１）（２７．０ｇ）およびトリクロロシラン（ＴＣＳ，３４ｍｌ、化合物（４−１−１）に対するモル比＝２．６）を仕込み、溶液を氷浴を用いて冷却した。これに、Ｐｔ触媒／キシレン溶液（１２３μｌ，Ｐｔ含有量：３ｗｔ.-%，Ｐｔ／Ｓｉ−Ｈモル比＝５．６×１０^−５）を添加し、氷浴温度で約３５分攪拌を行った後、室温まで温度を上昇させた。反応は発熱を伴って進行し、ガスクロマトグラフィーにおけるＴＣＳに対する生成物のピーク強度比が飽和に達したところで、反応終点とした（約２０時間）。その後、真空ポンプを用いて、反応液中に残留する未反応のＴＣＳおよび化合物（４−１−１）を減圧留去し、無色透明の液体（４２．２ｇ，収率：９８．１％）を得た。 (Step 2) Synthesis of Compound (2-1-1)

Under a N ₂ atmosphere, a 4-neck flask having an internal volume of 200 mL equipped with a reflux condenser, a thermometer, and a dropping funnel was charged with the above compound (4-1-1) (27.0 g) and trichlorosilane (TCS, 34 ml, The molar ratio with respect to the compound (4-1-1) = 2.6) was charged, and the solution was cooled using an ice bath. To this was added a Pt catalyst / xylene solution (123 μl, Pt content: 3 wt .-%, Pt / Si—H molar ratio = 5.6 × 10 ⁻⁵ ), and the mixture was stirred at an ice bath temperature for about 35 minutes. After that, the temperature was raised to room temperature. The reaction proceeded with an exotherm, and when the peak intensity ratio of the product to TCS in gas chromatography reached saturation, the reaction was terminated (about 20 hours). Then, using a vacuum pump, unreacted TCS and compound (4-1-1) remaining in the reaction solution were distilled off under reduced pressure to obtain a colorless transparent liquid (42.2 g, yield: 98.1%). Got.

As a result of gas chromatography analysis of the obtained transparent liquid, a single peak was confirmed, and the presence of impurities and the like was hardly confirmed. From the results of IR, ¹ H-NMR and ¹³ C-NMR shown below, the obtained transparent liquid was compound (2-1-1) (2-bromo-2-methyl-propionic acid-3-trichlorosilanyl). -Propyl ester).
GC purity: 98.1%
IR (KBr method): ν = 2980 (-CH ₃ ), 2936 (-CH _2- ), 2900 (-CH _2- ), 1738 (C = O), 1464 (-CH _2- ), 1392 (-CH _{3), 1373 (-CH 3)} , 1282 (Si-CH 2 -), 1164 (COC), 1110 (COC), 698 (C-Br), 590 (Si-Cl), 567 (Si-Cl).
¹ H NMR (400 MHz, TMS standard: δ = 0.0 ppm): 4.24 (t, 2H, -C H ₂ -O-), 2.00 (m, 2H, -CH ₂ -C H ₂ -CH _2- ), 1.95 (s, 6H, -C (Br) (C H ₃ ) ₂ ), 1.52 (t, 2H, -C H ₂ -Si).
¹³ C NMR (100 MHz, TMS standard: δ = 0.0 ppm): 171.7 ( C = O), 66.2 ( -C H ₂ -O-), 55.6 ( -C (Br)), 30.7 (( -C H ₃ ) ₂ ), 21.7 (Si-CH ₂ - C H _2- ), 20.7 (Si- C H _2- )

Ｎ_２雰囲気下、還流冷却器、温度計を取り付けた内容積５０ｍＬの３つ口フラスコに、上記の化合物（２−１−１）（５．８６ｇ）およびジクロロメタン（２０ｍＬ）を仕込んだ。ここに滴下ロートからメタノール（０．５８ｇ、化合物（２−１−１）に対して３．２当量）およびトリエチルアミン（５．１０ｇ、化合物（２−１−１）に対して２．９当量）を水浴を用いて系内温を保ちながら滴下し撹拌した。反応は発熱を伴って進行し、ガスクロマトグラフィーにおける化合物（２−１−１）に対する生成物のピーク強度比が飽和に達したところで終了とした（約１時間）。反応終了後、ロータリーエバポレータを用い、この溶液を濃縮した。得られた液体成分を減圧蒸留（１１３℃、１３０Ｐａ）して、透明な液体を得た（４．８２ｇ、収率：８６％）。 (Step 3) Synthesis of Compound (1-1-1)

Under a N ₂ atmosphere, the above compound (2-1-1) (5.86 g) and dichloromethane (20 mL) were charged into a 50 mL three-necked flask equipped with a reflux condenser and a thermometer. From this dropping funnel, methanol (0.58 g, 3.2 equivalents to compound (2-1-1)) and triethylamine (5.10 g, 2.9 equivalents to compound (2-1-1)) Was added dropwise using a water bath while stirring the system temperature and stirred. The reaction proceeded with exotherm, and was terminated when the peak intensity ratio of the product to the compound (2-1-1) in gas chromatography reached saturation (about 1 hour). After completion of the reaction, the solution was concentrated using a rotary evaporator. The obtained liquid component was distilled under reduced pressure (113 ° C., 130 Pa) to obtain a transparent liquid (4.82 g, yield: 86%).

As a result of gas chromatography analysis of the obtained liquid, a single peak was confirmed, and the presence of impurities and the like was hardly confirmed. From the results of IR, ¹ H-NMR and ¹³ C-NMR shown below, the obtained transparent liquid was compound (1-1-1) (2-bromo-2-methyl-propionic acid-3-trimethoxysila Nyl-propyl ester).
GC purity: 99.7%
IR (KBr method) ν = 2948 (-CH ₃ ), 2844 (Si-OCH ₃ ), 1738 (C = O), 1464 (-CH _2- ), 1392 (-CH ₃ ), 1373 (-CH ₃ ) , 1282 (COC), 1166 ( COC), 1089 (Si-OCH 3), 646 (C-Br)
¹ H-NMR (400MHz, TMS standard: δ = 0.0ppm): 4.15 ( t, 2H, -CH 2 -C H 2 -O -), 3.58 (s, 9H, Si- (OC H 3) 3), 1.93 (s, 6H, -C (C H ₃ ) ₂ ), 1.80 (q, 2H, -Si-CH ₂ -C H ₂ -CH _2- ), 0.71 (t, 2H, -Si-C H _2- CH ₂ -CH _2- )
¹³ C-NMR (100MHz, TMS standard: δ = 0.0ppm): 171.2 ( C = O), 68.5 (-Si-CH 2 -CH 2 - C H 2 -O -), 56.7 (- C (CH 3) ₂ ), 51.3 (Si- (O C H ₃ ) ₃ ), 31.6 (-C ( C H ₃ ) ₂ ), 22.6 (-Si-CH ₂ -C H ₂ -CH ₂ -O-), 5.96 (- Si- C H ₂ -CH ₂ -CH ₂ -O-)

Ａｒ雰囲気下、還流冷却器、温度計、滴下漏斗を取り付けた内容積５００ｍＬの４つ口フラスコに、３−ブテン−１−オール（１２．０ｇ）、メチレンクロライド（２４０ｍｌ）およびトリエチルアミン（１９．５ｇ）を仕込み、溶液をドライアイス−メタノール浴を用いて冷却し、液温を約−４５℃に保持した。次いで、この溶液に２−ブロモ−２−メチルプロピオニルブロマイド（３７．３ｇ、３−ブテン−１−オールに対して０．９８当量）を速やかに加え、−４０℃にて３０分間撹拌した後、室温下で更に６０分間撹拌した。反応終了後、トリエチルアミン−臭酸塩を濾過により除去した。得られた反応液にメチレンクロライド（２０ｍｌ）を加え、炭酸水素ナトリウム水溶液（３％、４００ｍｌ）による２回の洗浄、水（４００ｍｌ）による３回の洗浄を順次行ってから、無水硫酸マグネシウム（１５ｇ）にて乾燥した。その後、ロータリーエバポレーターを用い、この溶液を濃縮した。得られた液体成分を減圧蒸留（７９℃、１００Ｐａ）して、透明な液体を得た（３０．０ｇ、収率：８２％）。 <Production of 2-bromo-2-methyl-propionic acid-4-trimethoxysilanyl-butyl ester>
(Step 1) Synthesis of Compound (4-1-2)

Under an Ar atmosphere, a 500 mL four-necked flask equipped with a reflux condenser, a thermometer, and a dropping funnel was charged with 3-buten-1-ol (12.0 g), methylene chloride (240 ml) and triethylamine (19.5 g). The solution was cooled using a dry ice-methanol bath, and the liquid temperature was kept at about -45 ° C. Next, 2-bromo-2-methylpropionyl bromide (37.3 g, 0.98 equivalent to 3-buten-1-ol) was quickly added to this solution and stirred at −40 ° C. for 30 minutes. The mixture was further stirred at room temperature for 60 minutes. After completion of the reaction, triethylamine-bromide was removed by filtration. Methylene chloride (20 ml) was added to the resulting reaction solution, followed by two washings with an aqueous sodium hydrogen carbonate solution (3%, 400 ml) and three washings with water (400 ml), followed by anhydrous magnesium sulfate (15 g). ). Thereafter, this solution was concentrated using a rotary evaporator. The obtained liquid component was distilled under reduced pressure (79 ° C., 100 Pa) to obtain a transparent liquid (30.0 g, yield: 82%).

As a result of gas chromatography analysis of the obtained liquid, a single peak was confirmed, and the presence of impurities and the like was hardly confirmed. From the results of IR and ¹ H-NMR shown below, it was confirmed that the obtained transparent liquid was compound (4-1-2) (2-bromo-2-methyl-propionic acid-3-butenyl ester). all right.
IR (KBr method): ν = 3008 (H ₂ C = C-), 2982 (-CH ₃ ), 2934 (-CH _2- ), 1738 (C = O), 1644 (C = C-), 1464 ( -CH _2- ), 1392 (-CH ₃ ), 1373 (-CH ₃ ), 1280 (COC), 1168 (COC), 652 (C-Br).
¹ H NMR (400 MHz, TMS standard: δ = 0.0 ppm): 5.85-5.75 (m, 1H, CH ₂ = C H —CH ₂ —), 5.16-5.07 (m, 2H, C H ₂ = CH—CH ₂ -), 4.22 (t, 2H, CH ₂ = CH-CH ₂ -C H _2- ), 2.44 (q, 2H, CH ₂ = CH-C H _2- ), 1.92 (s, 6H, -C (C H ₃ ) ₂ ).

Ｎ_２雰囲気下、還流冷却器、温度計、滴下漏斗を取り付けた内容積１００ｍＬの４つ口フラスコに、化合物（４−１−２）（２７．２ｇ）およびトリクロロシラン（ＴＣＳ，１５．０ｍｌ、化合物（４−１−２）に対するモル比＝１．２）を仕込み、溶液を氷浴を用いて冷却した。これに、Ｐｔ触媒／キシレン溶液（２００μｌ，Ｐｔ含有量：３ｗｔ.-%，Ｐｔ／Ｓｉ−Ｈモル比＝２．１×１０^−４）を発熱を確認しながら３０分かけて氷浴温度で添加した後、室温まで温度を上昇させた。反応は発熱を伴って進行し、ガスクロマトグラフィーにおけるＴＣＳに対する生成物のピーク強度比が飽和に達したところで、反応終点とした（約２．５時間）。その後、真空ポンプを用いて、反応液中に残留する未反応のＴＣＳを減圧留去し、得られた液体成分を減圧蒸留（１２０℃、４００Ｐａ）して、透明な液体を得た（３７．７ｇ、収率：８６％）。 (Step 2) Synthesis of Compound (2-1-2)

In a N ₂ atmosphere, a 4-neck flask with an internal volume of 100 mL equipped with a reflux condenser, a thermometer, and a dropping funnel was added compound (4-1-2) (27.2 g) and trichlorosilane (TCS, 15.0 ml, The molar ratio with respect to the compound (4-1-2) = 1.2) was charged, and the solution was cooled using an ice bath. A Pt catalyst / xylene solution (200 μl, Pt content: 3 wt .-%, Pt / Si—H molar ratio = 2.1 × 10 ⁻⁴ ) was added to the ice bath temperature over 30 minutes while confirming the exotherm. After the addition, the temperature was raised to room temperature. The reaction proceeded with exotherm, and when the peak intensity ratio of the product to TCS in gas chromatography reached saturation, the reaction end point was determined (about 2.5 hours). Then, using a vacuum pump, unreacted TCS remaining in the reaction solution was distilled off under reduced pressure, and the obtained liquid component was distilled under reduced pressure (120 ° C., 400 Pa) to obtain a transparent liquid (37. 7 g, yield: 86%).

As a result of gas chromatography analysis of the obtained transparent liquid, the presence of impurities and the like was hardly confirmed. From the results of IR, ¹ H-NMR and ¹³ C-NMR shown below, the obtained transparent liquid was compound (2-1-2) (2-bromo-2-methyl-propionic acid-4-trichlorosilanyl). -Butyl ester).
IR (KBr method): ν = 2980 (-CH ₃ ), 2938 (-CH _2- ), 2874 (-CH _2- ), 1738 (C = O), 1464 (-CH _2- ), 1392 (-CH _{3), 1373 (-CH 3)} , 1280 (Si-CH 2 -), 1166 (COC), 1110 (COC), 694 (C-Br), 588 (Si-Cl), 565 (Si-Cl).
¹ H NMR (400 MHz, TMS standard: δ = 0.0 ppm): 4.22 (t, 2H, -C H ₂ -O-), 1.94 (s, 6H, -C (Br) (C H ₃ ) ₂ ), 1.83 (q, 2H, Si-CH ₂ -CH ₂ -C H ₂ -CH ₂ -O), 1.73 (q, 2H, Si-CH ₂ -C H ₂ -CH ₂ -CH ₂ -O), 1.47 (t , 2H, -C H ₂ -Si).
¹³ C NMR (100 MHz, TMS standard: δ = 0.0 ppm): 171.2 ( C = O), 64.7 ( -C H ₂ -O-), 55.6 ( -C (Br)), 30.6 (( -C H ₃ ) ₂ ), 30.2 (Si-CH ₂ -CH ₂ - C H ₂ -CH ₂ -O), 23.6 (Si-CH ₂ - C H ₂ -CH ₂ -CH ₂ -O), 18.7 (Si- C H ₂ -).

化合物（２−１−１）に替えて上記の化合物（２−１−２）を用いること以外は、実施例１の工程３と同様の操作を行うことにより、化合物（１−１−２）（２−ブロモ−２−メチル−プロピオン酸−４−トリメトキシシラニル−ブチルエステル）を得ることができる。 (Step 3) Synthesis of Compound (1-1-2) <Synthesis of 2-bromo-2-methyl-propionic acid-4-trimethoxysilanyl-butyl ester>

Compound (1-1-2) is obtained by performing the same operation as in Step 3 of Example 1, except that the above compound (2-1-2) is used in place of the compound (2-1-1). (2-bromo-2-methyl-propionic acid-4-trimethoxysilanyl-butyl ester) can be obtained.

２−プロペン−１−オールに替えて４−ペンテン−１−オールを用いる以外は、実施例１の工程１と同様の操作を行うことにより、化合物(４−１−３)（２−ブロモ−２−メチル−プロピオン酸−４−ペンテニルエステル）を得ることができる。 <Production of 2-bromo-2-methyl-propionic acid-5-trimethoxysilanyl-pentyl ester>
(Step 1) Synthesis of Compound (4-1-3)

Compound (4-1-3) (2-bromo-) was prepared in the same manner as in Step 1 of Example 1, except that 4-penten-1-ol was used instead of 2-propen-1-ol. 2-methyl-propionic acid-4-pentenyl ester).

化合物（４−１−１）に替えて上記の化合物（４−１−３）を用いること以外は、実施例１の工程２と同様の操作を行うことにより、目的の化合物(２−１−３)（２−ブロモ−２−メチル−プロピオン酸−５−トリクロロシラニルペンチルエステル）を得ることができる。 (Step 2) Synthesis of Compound (2-1-3)

The target compound (2-1-1) was obtained by carrying out the same operations as in Step 2 of Example 1, except that the above compound (4-1-3) was used in place of the compound (4-1-1). 3) (2-bromo-2-methyl-propionic acid-5-trichlorosilanylpentyl ester) can be obtained.

化合物（２−１−１）に替えて上記の化合物（２−１−３）を用いること以外は、実施例１の工程３と同様の操作を行うことにより、化合物(１−１−３)（２−ブロモ−２−メチル−プロピオン酸−５−トリメトキシシラニル−ペンチルエステル）を得ることができる。 (Step 3) Synthesis of Compound (1-1-3)

Compound (1-1-3) was prepared by performing the same operation as in Step 3 of Example 1, except that the above compound (2-1-3) was used in place of the compound (2-1-1). (2-bromo-2-methyl-propionic acid-5-trimethoxysilanyl-pentyl ester) can be obtained.

Ａｒ雰囲気下、還流冷却器、温度計、滴下漏斗を取り付けた内容積５００ｍＬの４つ口フラスコに、２−（アリルオキシ）エタノール（２１．０ｇ）、メチレンクロライド（２５０ｍｌ）およびトリエチルアミン（２２．５ｇ）を仕込み、溶液をドライアイス−メタノール浴を用いて冷却し、液温を約−３７℃に保持した。次いで、この溶液に２−ブロモ−２−メチルプロピオニルブロマイド（４１．５ｇ、２−（アリルオキシ）エタノールに対して０．８８当量）を速やかに加え、−１０℃にて１時間撹拌した後、室温下で更に１．５時間撹拌した。反応終了後、トリエチルアミン−臭酸塩を濾過により除去した。得られた反応液に炭酸水素ナトリウム水溶液（３％、３００ｍｌ）による３回の洗浄、水（３００ｍｌ）による３回の洗浄を順次行ってから、無水硫酸マグネシウム（１５ｇ）にて乾燥した。得られた液体成分を、シリカゲルカラムを用いて精製を行った後、その後、ロータリーエバポレータを用い、この溶液を濃縮し、透明な液体を得た（３６．７ｇ、収率：８５％）。 <Synthesis of 2-bromo-2-methylpropionic acid-2- (3-trimethoxysilanylpropyloxy) ethyl ester>
(Step 1) Synthesis of Compound (4-1-5)

Under an Ar atmosphere, a 500 mL four-necked flask equipped with a reflux condenser, thermometer, and dropping funnel was charged with 2- (allyloxy) ethanol (21.0 g), methylene chloride (250 ml) and triethylamine (22.5 g). The solution was cooled using a dry ice-methanol bath, and the liquid temperature was kept at about -37 ° C. Next, 2-bromo-2-methylpropionyl bromide (41.5 g, 0.88 equivalent to 2- (allyloxy) ethanol) was quickly added to this solution, and the mixture was stirred at −10 ° C. for 1 hour, and then room temperature. The mixture was further stirred for 1.5 hours. After completion of the reaction, triethylamine-bromide was removed by filtration. The resulting reaction solution was washed three times with an aqueous sodium hydrogen carbonate solution (3%, 300 ml) and three times with water (300 ml), and then dried over anhydrous magnesium sulfate (15 g). The obtained liquid component was purified using a silica gel column, and then the solution was concentrated using a rotary evaporator to obtain a transparent liquid (36.7 g, yield: 85%).

As a result of gas chromatography analysis of the obtained transparent liquid, a single peak was confirmed, and the presence of impurities and the like was hardly confirmed. From the results of IR and ¹ H-NMR shown below, the obtained transparent liquid is compound (4-1-5) (2-bromo-2-methylpropionic acid-2- (allyloxy) ethyl ester). I understood.
GC purity: 98.8%
IR (KBr method): ν = 3008 (H ₂ C = C-), 2980 (-CH ₃ ), 2936 (-CH _2- ), 2866 (-CH ₂ -O-), 1738 (C = O), 1649 (C = C -), 1464 (-CH 2 -), 1408 (-CH 3), 1390 (-CH 3), 1278 (COC), 1170 (COC), 1110 (COC), 646 (C-Br ).
¹ H NMR (400 MHz, TMS standard: δ = 0.0 ppm): 5.90 (tt, 1H, CH ₂ = C H -CH _2- ), 5.31 (dd, 1H, C H ₂ = CH-CH _2- ), 5.27 (Dd, 1H, C H ₂ = CH-CH _2- ), 4.33 (t, 2H, -O-CH ₂ -C H ₂ -OC = O), 4.04 (d, 2H, CH ₂ = CH-C H _2- ), 3.70 (t, 2H, -OC H ₂ -CH ₂ -OC = O), 1.95 (s, 6H, -C (C H ₃ ) ₂ ).

Ｎ_２雰囲気下、還流冷却器、温度計、滴下漏斗を取り付けた内容積１００ｍＬの４つ口フラスコに、上記の化合物（４−１−５）（２４．３ｇ）およびトリクロロシラン（ＴＣＳ；２０ｍｌ、化合物（４−１−５）に対するモル比＝１．９５）を仕込んだ。これに、Ｐｔ触媒／キシレン溶液（６３０μｌ，Ｐｔ含有量：３ｗｔ.-%，Ｐｔ／Ｓｉ−Ｈモル比＝４．９ｘ10^−４）を添加した。反応は発熱を伴って進行し、ガスクロマトグラフィーにおけるＴＣＳに対する生成物のピーク強度比が飽和に達したところで、反応終点とした（約４時間）。その後、真空ポンプを用いて、反応液中に残留する未反応のＴＣＳを減圧留去した後、ロータリーエバポレータを用いて、低沸点化合物を減圧留去し、粘ちょう性液体（３４．９ｇ，収率：９２％）を得た。 (Step 2) Synthesis of Compound (2-1-5) <Synthesis of 2-bromo-2-methylpropionic acid-2- (3-trichlorosilanylpropyloxy) ethyl ester>

Under a N ₂ atmosphere, a 100 mL four-necked flask equipped with a reflux condenser, a thermometer, and a dropping funnel was charged with the above compound (4-1-5) (24.3 g) and trichlorosilane (TCS; 20 ml, The molar ratio to the compound (4-1-5) = 1.95) was charged. A Pt catalyst / xylene solution (630 μl, Pt content: 3 wt .-%, Pt / Si—H molar ratio = 4.9 × 10 ⁻⁴ ) was added thereto. The reaction proceeded with exotherm, and when the peak intensity ratio of the product to TCS in gas chromatography reached saturation, the reaction end point was determined (about 4 hours). Thereafter, unreacted TCS remaining in the reaction solution was distilled off under reduced pressure using a vacuum pump, and then a low boiling point compound was distilled off under reduced pressure using a rotary evaporator to obtain a viscous liquid (34.9 g, collected). Rate: 92%).

As a result of conducting gas chromatography analysis of the obtained transparent liquid, purity was 94.0%. From the results of IR, ¹ H-NMR and ¹³ C-NMR shown below, the viscous liquid was compound (2-1-5) (2-bromo-2-methylpropionic acid-2- (3-trichlorosilanyl). Propyloxy) ethyl ester).
IR (KBr method): ν = 2938 (-CH ₃ ), 2878 (-CH _2- ), 1738 (C = O), 1464 (-CH _2- ), 1392 (-CH ₃ ), 1373 (-CH _{3 ), 1278 (Si-CH 2} -), 1168 (COC), 1110 (COC), 696 (C-Br), 646,588 (Si-Cl), 565 (Si-Cl).
¹ H NMR (400 MHz, TMS standard: δ = 0.0 ppm): 4.32 (t, 2H, -C H ₂ -OC = O-), 3.69 (t, 2H, -CH ₂ -OC H ₂ -CH ₂ -C = O-), 3.55 (t, 2H, -C H ₂ -O-CH ₂ -CH ₂ -C = O-), 1.95 (s, 6H, -C (Br) (CH ₃ ) ₂ ), 1.85 ( m, 2H, -CH ₂ -C H ₂ -CH _2- ), 1.52 (t, 2H, -C H ₂ -Si).
¹³ C NMR (100 MHz, TMS standard: δ = 0.0 ppm): 171.4 ( C = O), 71.4 ( -C H ₂ -O-CH ₂ -CH ₂ -C = O-), 68.2 ( -C H _2- OC = O-), 64.9 (-CH ₂ -O-CH ₂ - C H ₂ -C = O-), 55.5 ( -C (Br)), 30.7 (( -C H ₃ ) ₂ ), 22.6 (Si -CH ₂ - C H _2- ), 20.9 (Si- C H _2- ).

化合物（２−１−１）に替えて上記の化合物（２−１−５）を用いること以外は、実施例１の工程３と同様の操作を行うことにより、化合物（１−１−５）（２−ブロモ−２−メチルプロピオン酸−２−（３−トリメトキシシラニルプロピルオキシ）エチルエステル）を得ることができる。 (Step 3) Synthesis of Compound (1-1-5)

Compound (1-1-5) was prepared by performing the same operation as in Step 3 of Example 1, except that the above compound (2-1-5) was used in place of the compound (2-1-1). (2-bromo-2-methylpropionic acid-2- (3-trimethoxysilanylpropyloxy) ethyl ester) can be obtained.

２−（アリルオキシ）エタノールに替えて下記の式で示される化合物を用いること以外は、実施例４の工程１と同様の操作を行うことにより、重量平均分子量が３５０の化合物（４−１−６）（２−ブロモ−２−メチル−プロピオン酸−２−（アリルオキシ−ポリ（エチレンオキシ））エチルエステル）を得ることができる。

（この化合物は日本油脂株式会社製のユニオックスＰＫＡ−５００１であり、その重量平均分子量は２００である。すなわち、この式中のｐの計算による値は３．２である。） <Production of 2-bromo-2-methylpropionic acid-2-((3-trimethoxysilanylpropyloxy) -poly (ethyleneoxy)) ethyl ester>
(Step 1) Synthesis of Compound (4-1-6) <Synthesis of 2-bromo-2-methyl-propionic acid-2- (allyloxy-poly (ethyleneoxy)) ethyl ester>

A compound having a weight average molecular weight of 350 (4-1-6) is carried out in the same manner as in Step 1 of Example 4 except that a compound represented by the following formula is used instead of 2- (allyloxy) ethanol. ) (2-bromo-2-methyl-propionic acid-2- (allyloxy-poly (ethyleneoxy)) ethyl ester) can be obtained.

(This compound is UNIOX PKA-5001 manufactured by NOF Corporation and its weight average molecular weight is 200. That is, the value obtained by calculating p in this formula is 3.2.)

化合物（４−１−５）に替えて化合物（４−１−６）を用いること以外は、実施例４の工程２と同様の操作を行うことにより、重量平均分子量が４８６の化合物（２−１−６）（２−ブロモ−２−メチルプロピオン酸−２−（（３−トリクロロシラニルプロピルオキシ）−ポリ（エチレンオキシ））エチルエステル）を得ることができる。 (Step 2) Synthesis of Compound (2-1-6)

The compound (2-1) having a weight average molecular weight of 486 is obtained by conducting the same operation as in step 2 of Example 4 except that the compound (4-1-6) is used in place of the compound (4-1-5). 1-6) (2-bromo-2-methylpropionic acid-2-((3-trichlorosilanylpropyloxy) -poly (ethyleneoxy)) ethyl ester) can be obtained.

化合物（２−１−１）に替えて化合物（２−１−６）を用いること以外は、実施例１の工程３と同様の操作を行うことにより、化合物（１−１−６）（２−ブロモ−２−メチルプロピオン酸−２−（（３−トリメトキシシラニルプロピルオキシ）−ポリ（エチレンオキシ））エチルエステル）を得ることができる。 (Step 3) Synthesis of Compound (1-1-6)

Compound (1-1-6) (2) was prepared by conducting the same operation as in step 3 of Example 1, except that compound (2-1-6) was used in place of compound (2-1-1). -Bromo-2-methylpropionic acid-2-((3-trimethoxysilanylpropyloxy) -poly (ethyleneoxy)) ethyl ester) can be obtained.

メタノールに替えてエタノールを用いること以外は、実施例１の工程３と同様の操作を行うことにより、化合物（１−１−１ｂ）（２−ブロモ−２−メチル−プロピオン酸−３−トリエトキシシラニルプロピルエステル）を得ることができる。 <Production of 2-bromo-2-methyl-propionic acid-3-triethoxysilanylpropyl ester>

Compound (1-1-1b) (2-bromo-2-methyl-propionic acid-3-triethoxy) was prepared by performing the same operation as in Step 3 of Example 1 except that ethanol was used instead of methanol. Silanylpropyl ester) can be obtained.

Ｎ_２雰囲気下、還流冷却器、温度計を取り付けた内容積５０ｍＬの３つ口フラスコに、実施例２の工程２で得られた化合物（２−１−２）（４．７７ｇ）およびジクロロメタン（１９ｍＬ）を仕込んだ。ここに滴下ロートからエタノール（２．３８ｇ、化合物（２−１−２）に対して３．９当量）およびトリエチルアミン（４．６７ｇ、化合物（２−１−２）に対して３．５当量）を水浴を用いて系内温を保ちながら滴下し撹拌した。反応は発熱を伴って進行し、ガスクロマトグラフィーにおける化合物（２−１−２）に対する生成物のピーク強度比が飽和に達したところで終了とした（約１時間）。反応終了後、ろ過によりアミン塩を除去し、ロータリーエバポレータを用い、この溶液を濃縮した。得られた液体成分を減圧濃縮（８０℃、１３０Ｐａ）して、透明な液体を得た（５．０８ｇ、収率：９８％）。 <Production of 2-bromo-2-methyl-propionic acid-4-triethoxysilanyl-butyl ester>

In a N ₂ atmosphere, in a three-necked flask with an internal volume of 50 mL equipped with a reflux condenser and a thermometer, the compound (2-1-2) (4.77 g) obtained in Step 2 of Example 2 and dichloromethane ( 19 mL) was charged. From this dropping funnel, ethanol (2.38 g, 3.9 equivalents to compound (2-1-2)) and triethylamine (4.67 g, 3.5 equivalents to compound (2-1-2)) Was added dropwise using a water bath while stirring the system temperature and stirred. The reaction proceeded with exotherm, and was terminated when the peak intensity ratio of the product to the compound (2-1-2) in gas chromatography reached saturation (about 1 hour). After completion of the reaction, the amine salt was removed by filtration, and the solution was concentrated using a rotary evaporator. The obtained liquid component was concentrated under reduced pressure (80 ° C., 130 Pa) to obtain a transparent liquid (5.08 g, yield: 98%).

As a result of performing gas chromatography analysis of the obtained liquid, a single peak was confirmed, and the presence of impurities and the like was not confirmed. From the results of IR, ¹ H-NMR, ¹³ C-NMR and ²⁹ Si-NMR shown below, the obtained transparent liquid was compound (1-1-2b) (2-bromo-2-methyl-propionic acid- 4-triethoxysilanyl-butyl ester).
GC purity: 97.0%
IR (KBr method) ν = 2978 (-CH ₃ ), 2930 (-CH _2- ), 2888 (Si-OCH ₂ CH ₃ ), 1738 (C = O), 1464 (-CH _2- ), 1392 (- _{CH 3), 1373 (-CH 3} ), 1280 (COC), 1166 (COC), 1081 (Si-OCH 3), 650 (C-Br)
¹ H-NMR (400MHz, TMS standard: δ = 0.0ppm): 4.18 ( t, 2H, -CH 2 -C H 2 -O -), 3.82 (q, 6H, Si- (OC H 2 CH 3) 3 ), 1.93 (s, 6H, -C (C H ₃ ) ₂ ), 1.74 (q, 2H, -Si-CH ₂ -CH ₂ -C H ₂ -CH _2- ), 1.54 (q, 2H, -Si -CH ₂ -C H ₂ -CH ₂ -CH _2- ), 1.22 (t, 9H, Si- (OCH ₂ C H ₃ ) ₃ ), 0.67 (t, 2H, -Si-C H ₂ -CH _2- CH ₂ -CH _2- )
¹³ C-NMR (100MHz, TMS standard: δ = 0.0ppm): 171.3 ( C = O), 65.4 (-Si-CH 2 -CH 2 -CH 2 - C H 2 -O -), 58.2 (Si- ( O C H ₂ CH ₃ ) ₃ ), 55.8 ( -C (CH ₃ ) ₂ ), 31.4 (-Si-CH ₂ -CH ₂ - C H ₂ -CH ₂ -O-), 30.7 (-C ( C H _{3) 2), 19.2 (Si-} (OCH 2 C H 3) 3), 18.3 (-Si-CH 2 - C H 2 -CH 2 -CH 2 -O -), 9.95 (-Si- C H 2 - CH ₂ -CH ₂ -CH ₂ -O-)
²⁹ Si-NMR (79 MHz, TMS standard: δ = 0.0 ppm): −45.5

メタノールに替えてエタノールを用いること以外は、実施例３の工程３と同様の操作を行うことにより、化合物（１−１−３ｂ）（２−ブロモ−２−メチル−プロピオン酸−５−トリエトキシシラニルペンチルエステル）を得ることができる。 <Production of 2-bromo-2-methyl-propionic acid-5-triethoxysilanyl-pentyl ester>

Compound (1-1-3b) (2-bromo-2-methyl-propionic acid-5-triethoxy) was prepared in the same manner as in Step 3 of Example 3, except that ethanol was used instead of methanol. Silanylpentyl ester) can be obtained.

メタノールに替えてエタノールを用いること以外は、実施例４の工程３と同様の操作を行うことにより、化合物（１−１−５ｂ）（２−ブロモ−２−メチルプロピオン酸−２−（３−トリエトキシシラニルプロピルオキシ）エチルエステル）を得ることができる。 <Production of 2-bromo-2-methylpropionic acid-2- (3-triethoxysilanylpropyloxy) ethyl ester>

Compound (1-1-5b) (2-bromo-2-methylpropionic acid-2- (3-) was obtained by performing the same operation as in Step 3 of Example 4 except that ethanol was used instead of methanol. Triethoxysilanylpropyloxy) ethyl ester) can be obtained.

メタノールに替えてエタノールを用いること以外は、実施例５の工程３と同様の操作を行うことにより、化合物（１−１−６ｂ）（２−ブロモ−２−メチルプロピオン酸−２−（（３−トリエトキシシラニルプロピルオキシ）−ポリ（エチレンオキシ））エチルエステル）を得ることができる。 <Production of 2-bromo-2-methylpropionic acid-2-((3-triethoxysilanylpropyloxy) -poly (ethyleneoxy)) ethyl ester>

Compound (1-1-6b) (2-bromo-2-methylpropionic acid-2-((3) was obtained by performing the same operation as in Step 3 of Example 5 except that ethanol was used instead of methanol. -Triethoxysilanylpropyloxy) -poly (ethyleneoxy)) ethyl ester).

<Production of 2-bromo-2-methyl-propionic acid-3-dimethoxymethylsilanyl-propyl ester>
(Step 1) Synthesis of Compound (4-1-1) This step is the same as Step 1 in Example 1.

トリクロロシランに替えてメチルジクロロシランを用いること以外は、実施例１の工程２と同様の操作を行うことにより、化合物（２−１−１ｃ）（２−ブロモ−２−メチル−プロピオン酸−３−メチルジクロロシラニル−プロピルエステル）を得ることができる。 (Step 2) Synthesis of Compound (2-1-1c)

Compound (2-1-1c) (2-bromo-2-methyl-propionic acid-3 was obtained by performing the same operation as in Step 2 of Example 1, except that methyldichlorosilane was used instead of trichlorosilane. -Methyldichlorosilanyl-propyl ester).

化合物（２−１−１）に替えて化合物（２−１−１ｃ）を用いること以外は、実施例１の工程３と同様の操作を行うことにより、化合物（１−１−１ｃ）（２−ブロモ−２−メチル−プロピオン酸−３−ジメトキシメチルシラニル−プロピルエステル）を得ることができる。 (Step 3) Synthesis of Compound (1-1-1c)

Compound (1-1-1c) (2) is obtained by conducting the same operation as in step 3 of Example 1, except that compound (2-1-1c) is used in place of compound (2-1-1). -Bromo-2-methyl-propionic acid-3-dimethoxymethylsilanyl-propyl ester).

化合物（２−１−１）に替えて化合物（２−１−１ｃ）を用いることとメタノールに替えてエタノールを用いること以外は、実施例１の工程３と同様の操作を行うことにより、化合物（１−１−１ｄ）（２−ブロモ−２−メチル−プロピオン酸−３−ジエトキシメチルシラニル−プロピルエステル）を得ることができる。 <Production of 2-bromo-2-methyl-propionic acid-3-diethoxymethylsilanyl-propyl ester>

The compound was obtained by performing the same operation as in step 3 of Example 1 except that compound (2-1-1c) was used instead of compound (2-1-1) and ethanol was used instead of methanol. (1-1-1d) (2-bromo-2-methyl-propionic acid-3-diethoxymethylsilanyl-propyl ester) can be obtained.

<Production of 2-bromo-2-methyl-propionic acid-4-dimethoxymethylsilanyl-butyl ester>
(Step 1) Synthesis of Compound (4-1-2) This step is the same as Step 1 of Example 2.

トリクロロシランに替えてメチルジクロロシランを用いること以外は、実施例２の工程２と同様の操作を行うことにより、化合物（２−１−２ｃ）（２−ブロモ−２−メチル−プロピオン酸−３−メチルジクロロシラニル−ブチルエステル）を得ることができる。 (Step 2) Synthesis of Compound (2-1-2c) <Synthesis of 2-bromo-2-methyl-propionic acid-4-methyldichlorosilanyl-butyl ester>

Compound (2-1-2c) (2-bromo-2-methyl-propionic acid-3) was prepared in the same manner as in Step 2 of Example 2, except that methyldichlorosilane was used instead of trichlorosilane. -Methyldichlorosilanyl-butyl ester).

化合物（２−１−１）に替えて化合物（２−１−２ｃ）を用いること以外は、実施例１の工程３と同様の操作を行うことにより、化合物（１−１−２ｃ）（２−ブロモ−２−メチル−プロピオン酸−３−ジメトキシメチルシラニル−ブチルエステル）を得ることができる。 (Step 3) Synthesis of Compound (1-1-2c) <Synthesis of 2-bromo-2-methyl-propionic acid-4-dimethoxymethylsilanyl-butyl ester>

Compound (1-1-2c) (2) is obtained by conducting the same operation as in step 3 of Example 1, except that compound (2-1-2c) is used in place of compound (2-1-1). -Bromo-2-methyl-propionic acid-3-dimethoxymethylsilanyl-butyl ester).

化合物（２−１−１）に替えて化合物（２−１−２ｃ）を用いることとメタノールに替えてエタノールを用いること以外は、実施例１の工程３と同様の操作を行うことにより、化合物（１−１−２ｄ）（２−ブロモ−２−メチル−プロピオン酸−３−ジエトキシメチルシラニル−ブチルエステル）を得ることができる。 <Synthesis of 2-bromo-2-methyl-propionic acid-4-diethoxymethylsilanyl-butyl ester>

By performing the same operation as in Step 3 of Example 1, except that compound (2-1-2c) is used instead of compound (2-1-1) and ethanol is used instead of methanol, compound is obtained. (1-1-2d) (2-bromo-2-methyl-propionic acid-3-diethoxymethylsilanyl-butyl ester) can be obtained.

<Production of 2-bromo-2-methyl-propionic acid-5-dimethoxymethylsilanyl-pentyl ester>
(Step 1) Synthesis of Compound (4-1-3) This step is the same as Step 1 of Example 3.

化合物（４−１−１）に替えて化合物（４−１−３）を用いることとトリクロロシランに替えてメチルジクロロシランを用いること以外は、実施例１の工程２と同様の操作を行うことにより、化合物（２−１−３ｃ）（２−ブロモ−２−メチル−プロピオン酸−３−メチルジクロロシラニル−ペンチルエステル）を得ることができる。 (Step 2) Synthesis of Compound (2-1-3c)

Performing the same operations as in step 2 of Example 1 except that compound (4-1-3) is used instead of compound (4-1-1) and methyldichlorosilane is used instead of trichlorosilane. Thus, compound (2-1-3c) (2-bromo-2-methyl-propionic acid-3-methyldichlorosilanyl-pentyl ester) can be obtained.

化合物（２−１−１）に替えて化合物（２−１−３ｃ）を用いること以外は、実施例１の工程３と同様の操作を行うことにより、化合物（１−１−３ｃ）（２−ブロモ−２−メチル−プロピオン酸−３−ジメトキシメチルシラニル−ペンチルエステル）を得ることができる。 (Step 3) Synthesis of Compound (1-1-3c)

Compound (1-1-3c) (2) is obtained by conducting the same operation as in step 3 of Example 1, except that compound (2-1-3c) is used in place of compound (2-1-1). -Bromo-2-methyl-propionic acid-3-dimethoxymethylsilanyl-pentyl ester).

化合物（２−１−１）に替えて化合物（２−１−３ｃ）を用いることとメタノールに替えてエタノールを用いること以外は、実施例１の工程３と同様の操作を行うことにより、化合物（１−１−３ｄ）（２−ブロモ−２−メチル−プロピオン酸−３−ジエトキシメチルシラニル−ペンチルエステル）を得ることができる。 <Production of 2-bromo-2-methyl-propionic acid-5-diethoxymethylsilanyl-pentyl ester>

By performing the same operation as in step 3 of Example 1, except that compound (2-1-3c) is used instead of compound (2-1-1) and ethanol is used instead of methanol, compound is obtained. (1-1-3d) (2-bromo-2-methyl-propionic acid-3-diethoxymethylsilanyl-pentyl ester) can be obtained.

<Production of 2-bromo-2-methylpropionic acid-2- (3-dimethoxymethylsilanylpropyloxy) ethyl ester>
(Step 1) Synthesis of Compound (4-1-5) This step is the same as Step 1 of Example 4.

トリクロロシランに替えてメチルジクロロシランを用いること以外は、実施例４の工程２と同様の操作を行うことにより、化合物（２−１−５ｃ）（２−ブロモ−２−メチルプロピオン酸−２−（３−メチルジクロロシラニルプロピルオキシ）エチルエステル）を得ることができる。 (Step 2) Synthesis of Compound (2-1-5c) <Synthesis of 2-bromo-2-methylpropionic acid-2- (3-methyldichlorosilanylpropyloxy) ethyl ester>

Compound (2-1-5c) (2-bromo-2-methylpropionic acid-2-phenyl) was obtained by conducting the same operation as in Step 2 of Example 4, except that methyldichlorosilane was used instead of trichlorosilane. (3-methyldichlorosilanylpropyloxy) ethyl ester) can be obtained.

化合物（２−１−５）に替えて上記の化合物（２−１−５ｃ）を用いること以外は、実施例４の工程３と同様の操作を行うことにより、化合物（１−１−５ｃ）（２−ブロモ−２−メチルプロピオン酸−２−（３−ジメトキシメチルシラニルプロピルオキシ）エチルエステル）を得ることができる。 (Step 3) Synthesis of Compound (1-1-5c)

Compound (1-1-5c) was prepared in the same manner as in Step 3 of Example 4, except that the above compound (2-1-5c) was used in place of the compound (2-1-5). (2-bromo-2-methylpropionic acid-2- (3-dimethoxymethylsilanylpropyloxy) ethyl ester) can be obtained.

化合物（２−１−５）に替えて上記の化合物（２−１−５ｃ）を用いることとメタノールに替えてエタノールを用いること以外は、実施例４の工程３と同様の操作を行うことにより、化合物（１−１−５ｄ）（２−ブロモ−２−メチルプロピオン酸−２−（３−ジエトキシメチルシラニルプロピルオキシ）エチルエステル）を得ることができる。

<Production of 2-bromo-2-methylpropionic acid-2- (3-diethoxymethylsilanylpropyloxy) ethyl ester>

By performing the same operation as in Step 3 of Example 4 except that the above compound (2-1-5c) is used instead of the compound (2-1-5) and ethanol is used instead of methanol. Compound (1-1-5d) (2-bromo-2-methylpropionic acid-2- (3-diethoxymethylsilanylpropyloxy) ethyl ester) can be obtained.

Claims (13)

A method for producing a silicon compound represented by formula (1), comprising a step of reacting a compound represented by formula (2) with a compound represented by formula (3):

Here, A is a polymerization initiating group; R ¹ is alkyl having 1 to 4 carbon atoms; R ² is alkyl having 1 to 20 carbon atoms, aryl having 6 to 20 carbon atoms, or 7 to 20 carbon atoms. X ¹ is a halogen; and n is an integer from 1 to 3. A step of hydrosilylating the compound represented by the formula (5) with the compound represented by the formula (4) to obtain a compound represented by the formula (2), and the compound represented by the formula (2) by formula (3) A method for producing a silicon compound represented by the formula (1), comprising: reacting a compound represented by:

Here, A is a polymerization initiating group; R ¹ is alkyl having 1 to 4 carbon atoms; R ² is alkyl having 1 to 20 carbon atoms, aryl having 6 to 20 carbon atoms, or aryl having 7 to 20 carbon atoms X ¹ is halogen; and n is an integer from 1 to 3.   The production method according to claim 1 or 2, wherein A is a living radical polymerization initiating group. A is a living radical polymerization initiating group having a group represented by any one of formula (6-1), formula (6-2), formula (6-3) and formula (6-4). The production method according to 1 or 2:

In Formula (6-1), R ³ is hydrogen, alkyl having 1 to 20 carbons, aryl having 6 to 20 carbons, or arylalkyl having 7 to 20 carbons; R ⁴ is 1 to 20 carbons Alkyl, aryl having 6 to 20 carbon atoms, or arylalkyl having 7 to 20 carbon atoms; and X ² is halogen:

In Formula (6-2), R ⁵ is alkyl having 1 to 3 carbon atoms; a is an integer of 0 to 2; X ³ is halogen; and —SO ₂ X ³ is not bonded to the bonding position. In the ortho, meta, or para position relative to the carbon having the counter electron, the bonding position of R ⁵ is any position except the bonding position of —SO ₂ X ³ :

In Formula (6-3), Z ¹ is alkylene having 1 to 3 carbon atoms, and arbitrary —CH ₂ — may be replaced by —O—; R ⁶ is alkyl having 1 to 3 carbon atoms; Yes; a is an integer of 0 to 2; X ⁴ is halogen; and the bonding position of Z ¹ is the meta position or para position to the carbon having an unpaired electron, and the substitution position of R ⁶ Is any position except the bonding position of Z ¹ :

In formula (6-4), R ⁸ and R ⁹ are independently hydrogen, alkyl having 1 to 12 carbons, cycloalkyl having 6 to 10 carbons or aryl having 6 to 10 carbons, and R ⁸ and R ⁹ may be bonded to each other to form a ring together with N; R ⁷ is alkyl having 1 to 3 carbons; Z ² is 1 to 3 carbons and any —CH ₂ — is —O - be alkylene which may be replaced by; a is an integer from 0 to 2; and the bonding position of Z ² is meta or para to the carbon having the unpaired electron, the binding of R ⁷ position is an arbitrary position excluding the bonding positions of Z ^2. The production according to claim 1 or 2, wherein A is a group represented by any one of formula (7-1), formula (7-2), formula (7-3) and formula (7-4). Method:

In Formula (7-1), R ³ is hydrogen, alkyl having 1 to 20 carbons, aryl having 6 to 20 carbons, or arylalkyl having 7 to 20 carbons; R ⁴ has 1 to 20 carbons Alkyl, aryl having 6 to 20 carbon atoms, or arylalkyl having 7 to 20 carbon atoms; X ² is halogen; Z ³ is alkylene having 1 to 10 carbon atoms; and When — is 3, one —CH ₂ — may be replaced by —O—, and when the number of carbons exceeds 3, one —CH ₂ — or a plurality of non-adjacent —CH ₂ — is —O—. May be replaced:

In Formula (7-2), R ⁵ is alkyl having 1 to 3 carbon atoms; a is an integer of 0 to 2; X ³ is halogen; Z ³ is a single bond or 1 to 10 carbon atoms. And in this alkylene, when the number of carbon atoms is 2 or more, any —CH ₂ — may be replaced by —O—; and —SO ₂ X ³ is bonded to Z ³ In the ortho, meta or para position, the bonding position of R ⁵ is any position except the bonding position of —SO ₂ X ³ :

In formula (7-3), Z ¹ is alkylene having 1 to 3 carbon atoms, and arbitrary —CH ₂ — may be replaced by —O—; R ⁶ is alkyl having 1 to 3 carbon atoms; Yes; a is an integer of 0 to 2; X ⁴ is a halogen; Z ³ is a single bond or alkylene having 1 to 10 carbon atoms, and in the alkylene, any number of carbon atoms is 2 or more. —CH ₂ — may be replaced by —O—; and the bonding position of Z ¹ is meta or para to the bonding position of Z ³ , and the substitution position of R ⁶ is the bonding of Z ¹ Any position except position:

In Formula (7-4), R ⁸ and R ⁹ are independently hydrogen, alkyl having 1 to 12 carbons, cycloalkyl having 6 to 10 carbons, or aryl having 6 to 10 carbons, and R ⁸ And R ⁹ may combine with each other to form a ring with N; R ⁷ is alkyl having 1 to 3 carbons; Z ² is 1 to 3 carbons, and any —CH ₂ — is — Alkylene which may be replaced by O-; a is an integer of 0 to 2; Z ³ is a single bond or alkylene having 1 to 10 carbons, and the alkylene has 2 or more carbons when arbitrary -CH ₂ - may be replaced by -O-; and the bonding position of ^{Z 2} is meta or para position with respect to the binding position of ^{Z 3,} the bonding position of ^{R 7} is ^{Z 2} It is an arbitrary position excluding the coupling position. R ¹ is methyl, ethyl, propyl, 1-methylethyl, butyl, or 1,1-dimethylethyl; n is 2 or 3, and A is the formula (7-1), formula (7-2) The production method according to claim 1 or 2, which is a group represented by any one of formulas (7-3) and (7-4):

In Formula (7-1), R ³ is hydrogen, alkyl having 1 to 20 carbons, aryl having 6 to 20 carbons, or arylalkyl having 7 to 20 carbons; R ⁴ has 1 to 20 carbons Alkyl, aryl having 6 to 20 carbon atoms, or arylalkyl having 7 to 20 carbon atoms; X ² is halogen; and Z ³ is alkylene having 1 to 10 carbon atoms; When — is 3, one —CH ₂ — may be replaced by —O—, and when the number of carbons exceeds 3, one —CH ₂ — or a plurality of non-adjacent —CH ₂ — is —O—. May be replaced:

In Formula (7-2), R ⁵ is alkyl having 1 to 3 carbon atoms; a is an integer of 0 to 2; X ³ is halogen; Z ³ is a single bond or 1 to 10 carbon atoms. And in this alkylene, when the number of carbon atoms is 2 or more, any —CH ₂ — may be replaced by —O—; and —SO ₂ X ³ is bonded to Z ³ In the ortho, meta or para position, the bonding position of R ⁵ is any position except the bonding position of —SO ₂ X ³ :

In formula (7-3), Z ¹ is alkylene having 1 to 3 carbon atoms, and arbitrary —CH ₂ — may be replaced by —O—; R ⁶ is alkyl having 1 to 3 carbon atoms; Yes; a is an integer of 0 to 2; X ⁴ is a halogen; Z ³ is a single bond or alkylene having 1 to 10 carbon atoms, and in the alkylene, any number of carbon atoms is 2 or more. —CH ₂ — may be replaced by —O—; and the bonding position of Z ¹ is meta or para to the bonding position of Z ³ , and the substitution position of R ⁶ is the bonding of Z ¹ Any position except position:

In Formula (7-4), R ⁸ and R ⁹ are independently hydrogen, alkyl having 1 to 12 carbons, cycloalkyl having 6 to 10 carbons, or aryl having 6 to 10 carbons, and R ⁸ And R ⁹ may combine with each other to form a ring with N; R ⁷ is alkyl having 1 to 3 carbons; Z ² is 1 to 3 carbons, and any —CH ₂ — is — Alkylene which may be replaced by O-; a is an integer of 0 to 2; Z ³ is a single bond or alkylene having 1 to 10 carbons, and the alkylene has 2 or more carbons when arbitrary -CH ₂ - may be replaced by -O-; and the bonding position of ^{Z 2} is meta or para position with respect to the binding position of ^{Z 3,} the bonding position of ^{R 7} is ^{Z 2} It is an arbitrary position excluding the coupling position.   The manufacturing method of Claim 5 whose A is group shown by Formula (7-1), Formula (7-2), or Formula (7-3).   The manufacturing method of Claim 6 whose A is group shown by Formula (7-1), Formula (7-2), or Formula (7-3).   The production method according to claim 5, wherein A is a group represented by the formula (7-1):   The manufacturing method of Claim 6 whose A is group shown by Formula (7-1). The production according to claim 6, wherein A is represented by formula (7-1); R ³ is hydrogen, methyl or ethyl; R ⁴ is methyl or ethyl; and X ² is chlorine or bromine. Method. R ¹ is methyl or ethyl; n is 3, A is represented by formula (7-1); in formula (7-1), X ² is bromine, and R ³ and R ⁴ are both methyl And Z ³ is —C ₃ H ₆ —, —C ₄ H ₈ — or —C ₂ H ₄ —O—C ₃ H ₆ —. The production method according to claim 1 or 2, wherein the compound represented by the formula (2) is reacted with the compound represented by the formula (3) in an amount of 1 to 10 times in molar ratio to the compound.