JP2006193473A - Aryl polyadamantane derivative having carboxyl group or acid anhydride group and process for producing the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a new carboxy or acid anhydride group-containing aryl polyadamantane derivative or a salt thereof or an equivalent thereto useful as a raw material for functional materials excellent in electrical properties, thermal properties, etc. <P>SOLUTION: The carboxy or acid anhydride group-containing aryl polyadamantane derivative is represented by formula(1)(wherein, R<SP>1</SP>to R<SP>6</SP>are each H, an aromatic cyclic group of formula(2) or (3) or another substituent, wherein at least one of them is the group of formula(2) or (3); and k is an integer of 1-3; in formula(2) or (3), ring Z<SP>1</SP>and ring Z<SP>2</SP>are each an aromatic ring; ring Z<SP>3</SP>is a ring constituting a cyclic acid anhydride; m and n are each an integer of ≥1; and each of the aromatic rings may contain substituent(s) other than the groups shown in formula(2) or (3)). <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention includes flexible wiring board (base material, cover material) material, CCL (copper-clad laminate) material, interlayer insulating film material for semiconductor devices and multilayer wiring boards, adhesive material, liquid crystal alignment film material, paint material, optical material Arylpolyadamantane derivatives or salts or equivalents thereof having a novel carboxyl group or acid anhydride group, useful as raw materials such as materials, additives, aerospace materials and vehicle materials, or raw materials thereof, and the arylpolyadamantanes The present invention relates to a method for producing a derivative, a novel aryl polyadamantane derivative used as a raw material for the synthesis, and a method for producing the same.

  Since an adamantane derivative has a stable carbon skeleton structure, it has electrical properties such as heat resistance, water resistance, optical properties, light transmission, low dielectric constant, water absorption, adhesion, thermal properties, mechanical properties and It is used as a raw material for functional materials such as various highly functional polymers having excellent physical properties. On the other hand, aromatic polyesters, aromatic polyimides (aramids), polybenzoxazoles, polybenzs obtained by reacting aromatic carboxylic acids or aromatic carboxylic acid anhydrides with biphenols, aromatic diamines, aminophenols, etc. Imidazole and the like have excellent properties in terms of heat resistance, chemical resistance, electrical insulation, mechanical strength, and the like, and thus are widely used as engineering plastics in automobiles, electrical electronics, precision machinery industries, and the like. In recent years, in the fields of electrical and electronic parts, precision machine parts, automobile machine parts, etc., further miniaturization and refinement have been advanced, and higher performance has been demanded with respect to characteristics such as heat resistance of materials.

  US Pat. No. 4,142,036 discloses carboxyphenyladamantane derivatives such as 1,3-bis (4-carboxyphenyl) adamantane and 1,3-bis (3,4-dicarboxyphenyl) adamantane. However, polymers obtained using these compounds as monomers are not sufficient in terms of heat resistance and the like when used as functional materials, and polymer raw materials having higher heat resistance and other characteristics are required. .

U.S. Pat. No. 4,142,036

An object of the present invention is to provide an arylpolyadamantane derivative or a salt thereof having a novel carboxyl group or acid anhydride group, which is useful as a raw material for a functional material having excellent electrical properties, thermal properties, mechanical properties, optical properties, physical properties, and the like. Alternatively, an equivalent and an efficient method for producing the aryl polyadamantane derivative are provided.
Another object of the present invention is to provide a novel aryl polyadamantane derivative useful for synthesizing the aryl polyadamantane derivative having the carboxyl group or the acid anhydride group and an efficient production method thereof.

  As a result of diligent studies to achieve the above object, the present inventors have found an aryl polyadamantane derivative having a novel carboxyl group or acid anhydride group derived from a polyadamantane compound in which 2 to 4 adamantane rings are bonded. The present invention has been completed.

［式中、Ｒ¹、Ｒ²、Ｒ³、Ｒ⁴、Ｒ⁵、Ｒ⁶は、同一又は異なって、水素原子、下記式（２）又は（３）

（式中、環Ｚ¹、環Ｚ²は芳香環を示し、環Ｚ³は環状酸無水物を構成する環を示す。ｍ、ｎはそれぞれ１以上の整数を示す。各芳香環は式中に示される基以外の置換基を有していてもよい）
で表される芳香族環式基、又はその他の置換基を示す。但し、Ｒ¹、Ｒ²、Ｒ³、Ｒ⁴、Ｒ⁵、Ｒ⁶のうち少なくとも１つは式（２）又は（３）で表される基である。ｋは１〜３の整数を示す。ｋが２又は３の場合、複数個のＲ⁴、Ｒ⁶はそれぞれ同一であっても異なっていてもよい。アダマンタン環は橋頭位以外の部位に置換基を有していてもよい］
で表されるカルボキシル基又は酸無水物基を有するアリールポリアダマンタン誘導体又はその塩若しくは等価体を提供する。 That is, the present invention provides the following formula (1):

[Wherein R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ are the same or different and represent a hydrogen atom, the following formula (2) or (3)

(In the formula, ring Z ¹ and ring Z ² represent an aromatic ring, ring Z ³ represents a ring constituting a cyclic acid anhydride, and m and n each represents an integer of 1 or more. And may have a substituent other than the group shown in FIG.
The aromatic cyclic group represented by these, or another substituent is shown. However, at least one of R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ is a group represented by the formula (2) or (3). k represents an integer of 1 to 3. When k is 2 or 3, the plurality of R ⁴ and R ⁶ may be the same or different. The adamantane ring may have a substituent at a site other than the bridgehead position]
An aryl polyadamantane derivative having a carboxyl group or an acid anhydride group, or a salt or equivalent thereof is provided.

［式中、Ｒ^1a、Ｒ^2a、Ｒ^3a、Ｒ^4a、Ｒ^5a、Ｒ^6aは、同一又は異なって、水素原子、下記式（５）

（式中、環Ｚ¹は芳香環を示す。Ｘ¹は酸化又は加水分解によりカルボキシル基に変換可能な基を示す。ｍは１以上の整数を示す。ｍが２以上の場合、複数個のＸ¹は同一であっても異なっていてもよく、また、複数個のＸ¹が互いに結合して、環Ｚ¹を構成する１又は２以上の原子とともに環を形成していてもよい。芳香環は式中に示される基以外の置換基を有していてもよい。前記Ｘ¹はこれらの置換基と結合して環Ｚ¹を構成する１又は２以上の原子とともに環を形成していてもよい）
で表される芳香族環式基、又はその他の置換基を示す。但し、Ｒ^1a、Ｒ^2a、Ｒ^3a、Ｒ^4a、Ｒ^5a、Ｒ^6aのうち少なくとも１つは式（５）で表される基である。ｋは１〜３の整数を示す。ｋが２又は３の場合、複数個のＲ^4a、Ｒ^6aはそれぞれ同一であっても異なっていてもよい。アダマンタン環は橋頭位以外の部位に置換基を有していてもよい］
で表されるアリールポリアダマンタン誘導体を酸化又は加水分解に付して、下記式（６）

［式中、Ｒ^1b、Ｒ^2b、Ｒ^3b、Ｒ^4b、Ｒ^5b、Ｒ^6bは、同一又は異なって、水素原子、下記式（２）

（式中、環Ｚ¹は芳香環を示す。ｍは１以上の整数を示す。芳香環は式中に示される基以外の置換基を有していてもよい）
で表される芳香族環式基、又はその他の置換基を示す。但し、Ｒ^1b、Ｒ^2b、Ｒ^3b、Ｒ^4b、Ｒ^5b、Ｒ^6bのうち少なくとも１つは式（２）で表される基である。ｋは１〜３の整数を示す。ｋが２又は３の場合、複数個のＲ^4b、Ｒ^6bはそれぞれ同一であっても異なっていてもよい。アダマンタン環は橋頭位以外の部位に置換基を有していてもよい］
で表される化合物を得ることを特徴とするカルボキシル基を有するアリールポリアダマンタン誘導体の製造法を提供する。 The present invention also provides the following formula (4):

[Wherein, R ^1a , R ^2a , R ^3a , R ^4a , R ^5a , R ^6a are the same or different and represent a hydrogen atom, the following formula (5)

(In the formula, ring Z ¹ represents an aromatic ring. X ¹ represents a group that can be converted into a carboxyl group by oxidation or hydrolysis. M represents an integer of 1 or more. X ¹ may be the same or different, and a plurality of X ¹ may be bonded to each other to form a ring with one or more atoms constituting the ring Z ¹ . The ring may have a substituent other than the group shown in the formula, and X ¹ is bonded to these substituents to form a ring together with one or more atoms constituting the ring Z ^1. May be)
The aromatic cyclic group represented by these, or another substituent is shown. However, at least one of R ^1a , R ^2a , R ^3a , R ^4a , R ^5a and R ^6a is a group represented by the formula (5). k represents an integer of 1 to 3. When k is 2 or 3, the plurality of R ^4a and R ^6a may be the same or different. The adamantane ring may have a substituent at a site other than the bridgehead position]
An aryl polyadamantane derivative represented by the following formula (6) is subjected to oxidation or hydrolysis:

[Wherein, R ^1b , R ^2b , R ^3b , R ^4b , R ^5b , R ^6b are the same or different and represent a hydrogen atom, the following formula (2)

(In the formula, ring Z ¹ represents an aromatic ring. M represents an integer of 1 or more. The aromatic ring may have a substituent other than the group shown in the formula).
The aromatic cyclic group represented by these, or another substituent is shown. However, at least one of R ^1b , R ^2b , R ^3b , R ^4b , R ^5b and R ^6b is a group represented by the formula (2). k represents an integer of 1 to 3. When k is 2 or 3, the plurality of R ^4b and R ^6b may be the same or different. The adamantane ring may have a substituent at a site other than the bridgehead position]
A process for producing an arylpolyadamantane derivative having a carboxyl group, characterized in that a compound represented by the formula:

［式中、Ｒ^1a、Ｒ^2a、Ｒ^3a、Ｒ^4a、Ｒ^5a、Ｒ^6aは、同一又は異なって、水素原子、下記式（８）

（式中、環Ｚ²は芳香環を示す。Ｘ²、Ｘ³は酸化により環Ｚ²を構成する１又は２以上の原子とともに環状の酸無水物基を形成可能な基を示す。Ｘ²、Ｘ³は互いに結合して環Ｚ²を構成する１又は２以上の原子とともに環を形成していてもよい。ｎは１以上の整数を示す。ｎが２以上の場合、複数個のＸ²、Ｘ³はそれぞれ同一であっても異なっていてもよい。芳香環は式中に示される基以外の置換基を有していてもよい）
で表される芳香族環式基、又はその他の置換基を示す。但し、Ｒ^1a、Ｒ^2a、Ｒ^3a、Ｒ^4a、Ｒ^5a、Ｒ^6aのうち少なくとも１つは式（８）で表される基である。ｋは１〜３の整数を示す。ｋが２又は３の場合、複数個のＲ^4a、Ｒ^6aはそれぞれ同一であっても異なっていてもよい。アダマンタン環は橋頭位以外の部位に置換基を有していてもよい］
で表されるアリールポリアダマンタン誘導体を酸化して、下記式（９）

［式中、Ｒ^1b、Ｒ^2b、Ｒ^3b、Ｒ^4b、Ｒ^5b、Ｒ^6bは、同一又は異なって、水素原子、下記式（３）

（式中、環Ｚ²は芳香環を示し、環Ｚ³は環状酸無水物を構成する環を示す。ｎは１以上の整数を示す。芳香環は式中に示される基以外の置換基を有していてもよい）
で表される芳香族環式基、又はその他の置換基を示す。但し、Ｒ^1b、Ｒ^2b、Ｒ^3b、Ｒ^4b、Ｒ^5b、Ｒ^6bのうち少なくとも１つは式（３）で表される基である。ｋは１〜３の整数を示す。ｋが２又は３の場合、複数個のＲ^4b、Ｒ^6bはそれぞれ同一であっても異なっていてもよい。アダマンタン環は橋頭位以外の部位に置換基を有していてもよい］
で表される化合物を得ることを特徴とする酸無水物基を有するアリールポリアダマンタン誘導体の製造法を提供する。 The present invention further provides the following formula (7):

[Wherein R ^1a , R ^2a , R ^3a , R ^4a , R ^5a , R ^6a are the same or different and represent a hydrogen atom, the following formula (8)

(In the formula, ring Z ² represents an aromatic ring. X ² and X ³ represent groups capable of forming a cyclic acid anhydride group together with one or more atoms constituting ring Z ² by oxidation. X ² X ³ may be bonded to each other to form a ring together with one or more atoms constituting the ring Z ^2. n represents an integer of 1 or more, and when n is 2 or more, a plurality of X ² and X ³ may be the same or different, and the aromatic ring may have a substituent other than the group shown in the formula)
The aromatic cyclic group represented by these, or another substituent is shown. However, at least one of R ^1a , R ^2a , R ^3a , R ^4a , R ^5a , R ^6a is a group represented by the formula (8). k represents an integer of 1 to 3. When k is 2 or 3, the plurality of R ^4a and R ^6a may be the same or different. The adamantane ring may have a substituent at a site other than the bridgehead position]
An aryl polyadamantane derivative represented by the following formula (9) is oxidized:

[Wherein, R ^1b , R ^2b , R ^3b , R ^4b , R ^5b , R ^6b are the same or different and represent a hydrogen atom, the following formula (3)

(In the formula, ring Z ² represents an aromatic ring, ring Z ³ represents a ring constituting a cyclic acid anhydride, and n represents an integer of 1 or more. The aromatic ring is a substituent other than the group shown in the formula. You may have)
The aromatic cyclic group represented by these, or another substituent is shown. However, at least one of R ^1b , R ^2b , R ^3b , R ^4b , R ^5b and R ^6b is a group represented by the formula (3). k represents an integer of 1 to 3. When k is 2 or 3, the plurality of R ^4b and R ^6b may be the same or different. The adamantane ring may have a substituent at a site other than the bridgehead position]
A method for producing an arylpolyadamantane derivative having an acid anhydride group, which is characterized in that a compound represented by the formula:

［式中、Ｒ^1c、Ｒ^2c、Ｒ^3c、Ｒ^4c、Ｒ^5c、Ｒ^6cは、同一又は異なって、水素原子、下記式（１１）

（式中、環Ｚ²は芳香環を示す。ｎは１以上の整数を示す。芳香環は式中に示される基以外の置換基を有していてもよい）
で表される芳香族環式基、又はその他の置換基を示す。但し、Ｒ^1c、Ｒ^2c、Ｒ^3c、Ｒ^4c、Ｒ^5c、Ｒ^6cのうち少なくとも１つは式（１１）で表される基である。ｋは１〜３の整数を示す。ｋが２又は３の場合、複数個のＲ^4c、Ｒ^6cはそれぞれ同一であっても異なっていてもよい。アダマンタン環は橋頭位以外の部位に置換基を有していてもよい］
で表される化合物を脱水反応に付して、下記式（１２）

［式中、Ｒ^1d、Ｒ^2d、Ｒ^3d、Ｒ^4d、Ｒ^5d、Ｒ^6dは、同一又は異なって、水素原子、下記式（３）

（式中、環Ｚ²は芳香環を示し、環Ｚ³は環状酸無水物を構成する環を示す。ｎは１以上の整数を示す。芳香環は式中に示される基以外の置換基を有していてもよい）
で表される芳香族環式基、又はその他の置換基を示す。但し、Ｒ^1d、Ｒ^2d、Ｒ^3d、Ｒ^4d、Ｒ^5d、Ｒ^6dのうち少なくとも１つは式（３）で表される基である。ｋは１〜３の整数を示す。ｋが２又は３の場合、複数個のＲ^4d、Ｒ^6dはそれぞれ同一であっても異なっていてもよい。アダマンタン環は橋頭位以外の部位に置換基を有していてもよい］
で表される化合物を得ることを特徴とする酸無水物基を有するアリールポリアダマンタン誘導体の製造法を提供する。 The present invention further provides the following formula (10):

[Wherein R ^1c , R ^2c , R ^3c , R ^4c , R ^5c , R ^6c are the same or different and represent a hydrogen atom, the following formula (11)

(In the formula, ring Z ² represents an aromatic ring. N represents an integer of 1 or more. The aromatic ring may have a substituent other than the group shown in the formula.)
The aromatic cyclic group represented by these, or another substituent is shown. However, at least one of R ^1c , R ^2c , R ^3c , R ^4c , R ^5c and R ^6c is a group represented by the formula (11). k represents an integer of 1 to 3. When k is 2 or 3, the plurality of R ^4c and R ^6c may be the same or different. The adamantane ring may have a substituent at a site other than the bridgehead position]
Is subjected to a dehydration reaction to give the following formula (12):

[Wherein R ^1d , R ^2d , R ^3d , R ^4d , R ^5d , R ^6d are the same or different and represent a hydrogen atom, the following formula (3)

(In the formula, ring Z ² represents an aromatic ring, ring Z ³ represents a ring constituting a cyclic acid anhydride, and n represents an integer of 1 or more. The aromatic ring is a substituent other than the group shown in the formula. You may have)
The aromatic cyclic group represented by these, or another substituent is shown. However, at least one of R ^1d , R ^2d , R ^3d , R ^4d , R ^5d and R ^6d is a group represented by the formula (3). k represents an integer of 1 to 3. When k is 2 or 3, the plurality of R ^4d and R ^6d may be the same or different. The adamantane ring may have a substituent at a site other than the bridgehead position]
A method for producing an arylpolyadamantane derivative having an acid anhydride group, which is characterized in that a compound represented by the formula:

［式中、Ｒ^1d、Ｒ^2d、Ｒ^3d、Ｒ^4d、Ｒ^5d、Ｒ^6dは、同一又は異なって、水素原子、下記式（３）

（式中、環Ｚ²は芳香環を示し、環Ｚ³は環状酸無水物を構成する環を示す。ｎは１以上の整数を示す。芳香環は式中に示される基以外の置換基を有していてもよい）
で表される芳香族環式基、又はその他の置換基を示す。但し、Ｒ^1d、Ｒ^2d、Ｒ^3d、Ｒ^4d、Ｒ^5d、Ｒ^6dのうち少なくとも１つは式（３）で表される基である。ｋは１〜３の整数を示す。ｋが２又は３の場合、複数個のＲ^4d、Ｒ^6dはそれぞれ同一であっても異なっていてもよい。アダマンタン環は橋頭位以外の部位に置換基を有していてもよい］
で表される化合物を加水分解に付して、下記式（１０）

［式中、Ｒ^1c、Ｒ^2c、Ｒ^3c、Ｒ^4c、Ｒ^5c、Ｒ^6cは、同一又は異なって、水素原子、下記式（１１）

（式中、環Ｚ²は芳香環を示す。ｎは１以上の整数を示す。芳香環は式中に示される基以外の置換基を有していてもよい）
で表される芳香族環式基、又はその他の置換基を示す。但し、Ｒ^1c、Ｒ^2c、Ｒ^3c、Ｒ^4c、Ｒ^5c、Ｒ^6cのうち少なくとも１つは式（１１）で表される基である。ｋは１〜３の整数を示す。ｋが２又は３の場合、複数個のＲ^4c、Ｒ^6cはそれぞれ同一であっても異なっていてもよい。アダマンタン環は橋頭位以外の部位に置換基を有していてもよい］
で表される化合物を得ることを特徴とするカルボキシル基を有するアリールポリアダマンタン誘導体の製造法を提供する。 The present invention also provides the following formula (12):

[Wherein R ^1d , R ^2d , R ^3d , R ^4d , R ^5d , R ^6d are the same or different and represent a hydrogen atom, the following formula (3)

(In the formula, ring Z ² represents an aromatic ring, ring Z ³ represents a ring constituting a cyclic acid anhydride, and n represents an integer of 1 or more. The aromatic ring is a substituent other than the group shown in the formula. You may have)
The aromatic cyclic group represented by these, or another substituent is shown. However, at least one of R ^1d , R ^2d , R ^3d , R ^4d , R ^5d and R ^6d is a group represented by the formula (3). k represents an integer of 1 to 3. When k is 2 or 3, the plurality of R ^4d and R ^6d may be the same or different. The adamantane ring may have a substituent at a site other than the bridgehead position]
The compound represented by the following formula (10)

[Wherein R ^1c , R ^2c , R ^3c , R ^4c , R ^5c , R ^6c are the same or different and represent a hydrogen atom, the following formula (11)

(In the formula, ring Z ² represents an aromatic ring. N represents an integer of 1 or more. The aromatic ring may have a substituent other than the group shown in the formula.)
The aromatic cyclic group represented by these, or another substituent is shown. However, at least one of R ^1c , R ^2c , R ^3c , R ^4c , R ^5c and R ^6c is a group represented by the formula (11). k represents an integer of 1 to 3. When k is 2 or 3, the plurality of R ^4c and R ^6c may be the same or different. The adamantane ring may have a substituent at a site other than the bridgehead position]
A process for producing an arylpolyadamantane derivative having a carboxyl group, characterized in that a compound represented by the formula:

［式中、Ｒ^1a、Ｒ^2a、Ｒ^3a、Ｒ^4a、Ｒ^5a、Ｒ^6aは、同一又は異なって、水素原子、下記式（５）又は（８）

（式中、環Ｚ¹、環Ｚ²は芳香環を示す。Ｘ¹は酸化又は加水分解によりカルボキシル基に変換可能な基を示す。ｍは１以上の整数を示す。ｍが２以上の場合、複数個のＸ¹は同一であっても異なっていてもよく、また、複数個のＸ¹が互いに結合して、環Ｚ¹を構成する１又は２以上の原子とともに環を形成していてもよい。Ｘ²、Ｘ³は酸化により環Ｚ²を構成する１又は２以上の原子とともに環状の酸無水物基を形成可能な基を示す。Ｘ²、Ｘ³は互いに結合して環Ｚ²を構成する１又は２以上の原子とともに環を形成していてもよい。ｎは１以上の整数を示す。ｎが２以上の場合、複数個のＸ²、Ｘ³はそれぞれ同一であっても異なっていてもよい。各芳香環は式中に示される基以外の置換基を有していてもよい。前記Ｘ¹はこれらの置換基と結合して環Ｚ¹を構成する１又は２以上の原子とともに環を形成していてもよい）
で表される芳香族環式基、又はその他の置換基を示す。但し、Ｒ^1a、Ｒ^2a、Ｒ^3a、Ｒ^4a、Ｒ^5a、Ｒ^6aのうち少なくとも１つは式（５）又は（８）で表される基である。ｋは１〜３の整数を示す。ｋが２又は３の場合、複数個のＲ^4a、Ｒ^6aはそれぞれ同一であっても異なっていてもよい。アダマンタン環は橋頭位以外の部位に置換基を有していてもよい］
で表されるアリールポリアダマンタン誘導体を提供する。 The present invention further provides the following formula (13):

[Wherein, R ^1a , R ^2a , R ^3a , R ^4a , R ^5a , R ^6a are the same or different and represent a hydrogen atom, the following formula (5) or (8)

(In the formula, ring Z ¹ and ring Z ² represent an aromatic ring. X ¹ represents a group that can be converted to a carboxyl group by oxidation or hydrolysis. M represents an integer of 1 or more. When m is 2 or more. The plurality of X ¹ may be the same or different, and the plurality of X ¹ are bonded to each other to form a ring with one or more atoms constituting the ring Z ^1. which may .X ^2, X ³ is attached is .X ^2, X ³ indicating the one or more atoms with capable of forming a cyclic acid anhydride group group constituting the ring Z ² by oxidation with each other ring Z ^A ring may be formed together with 1 or 2 or more atoms constituting 2. n represents an integer of 1 or more, and when n is 2 or more, a plurality of X ² and X ³ are the same, Each aromatic ring may have a substituent other than the group shown in the formula, and X ¹ represents these substituents. And may form a ring together with one or more atoms constituting ring Z ¹ )
The aromatic cyclic group represented by these, or another substituent is shown. However, at least one of R ^1a , R ^2a , R ^3a , R ^4a , R ^5a and R ^6a is a group represented by the formula (5) or (8). k represents an integer of 1 to 3. When k is 2 or 3, the plurality of R ^4a and R ^6a may be the same or different. The adamantane ring may have a substituent at a site other than the bridgehead position]
An arylpolyadamantane derivative represented by the formula:

［式中、Ｒ^1e、Ｒ^2e、Ｒ^3e、Ｒ^4e、Ｒ^5e、Ｒ^6eは、同一又は異なって、水素原子、脱離してアダマンタン骨格にカルボカチオンを生成可能な置換基、又はその他の置換基を示す。但し、Ｒ^1e、Ｒ^2e、Ｒ^3e、Ｒ^4e、Ｒ^5e、Ｒ^6eのうち少なくとも１つは脱離してアダマンタン骨格にカルボカチオンを生成可能な置換基である。ｋは１〜３の整数を示す。ｋが２又は３の場合、複数個のＲ^4e、Ｒ^6eはそれぞれ同一であっても異なっていてもよい。アダマンタン環は橋頭位以外の部位に置換基を有していてもよい］
で表される化合物と、下記式（１５）又は（１６）

（式中、環Ｚ¹、環Ｚ²は芳香環を示す。Ｘ¹は酸化又は加水分解によりカルボキシル基に変換可能な基を示す。ｍは１以上の整数を示す。ｍが２以上の場合、複数個のＸ¹は同一であっても異なっていてもよく、また、複数個のＸ¹が互いに結合して、環Ｚ¹を構成する１又は２以上の原子とともに環を形成していてもよい。Ｘ²、Ｘ³は酸化により環Ｚ²を構成する１又は２以上の原子とともに環状の酸無水物基を形成可能な基を示す。Ｘ²、Ｘ³は互いに結合して環Ｚ²を構成する１又は２以上の原子とともに環を形成していてもよい。ｎは１以上の整数を示す。ｎが２以上の場合、複数個のＸ²、Ｘ³はそれぞれ同一であっても異なっていてもよい。各芳香環は式中に示される基以外の置換基を有していてもよい。前記Ｘ¹はこれらの置換基と結合して環Ｚ¹を構成する１又は２以上の原子とともに環を形成していてもよい）
で表される化合物とを反応させて、下記式（１３）

［式中、Ｒ^1a、Ｒ^2a、Ｒ^3a、Ｒ^4a、Ｒ^5a、Ｒ^6aは、同一又は異なって、水素原子、下記式（５）又は（８）

（式中、環Ｚ¹、環Ｚ²、Ｘ¹、Ｘ²、Ｘ³、ｍ、ｎは前記に同じ。各芳香環は式中に示される基以外の置換基を有していてもよい）
で表される芳香族環式基、又はその他の置換基を示す。但し、Ｒ^1a、Ｒ^2a、Ｒ^3a、Ｒ^4a、Ｒ^5a、Ｒ^6aのうち少なくとも１つは式（５）又は（８）で表される基である。ｋは１〜３の整数を示す。ｋが２又は３の場合、複数個のＲ^4a、Ｒ^6aはそれぞれ同一であっても異なっていてもよい。アダマンタン環は橋頭位以外の部位に置換基を有していてもよい］
で表される化合物を得ることを特徴とするアリールポリアダマンタン誘導体の製造法を提供する。 The present invention further provides the following formula (14):

[Wherein, R ^1e , R ^2e , R ^3e , R ^4e , R ^5e , R ^6e are the same or different, a hydrogen atom, a substituent capable of leaving to form a carbocation in the adamantane skeleton, or other substitution Indicates a group. However, at least one of R ^1e , R ^2e , R ^3e , R ^4e , R ^5e and R ^6e is a substituent capable of leaving and generating a carbocation in the adamantane skeleton. k represents an integer of 1 to 3. When k is 2 or 3, the plurality of R ^4e and R ^6e may be the same or different. The adamantane ring may have a substituent at a site other than the bridgehead position]
And a compound represented by the following formula (15) or (16):

(In the formula, ring Z ¹ and ring Z ² represent an aromatic ring. X ¹ represents a group that can be converted to a carboxyl group by oxidation or hydrolysis. M represents an integer of 1 or more. When m is 2 or more. The plurality of X ¹ may be the same or different, and the plurality of X ¹ are bonded to each other to form a ring with one or more atoms constituting the ring Z ^1. which may .X ^2, X ³ is attached is .X ^2, X ³ indicating the one or more atoms with capable of forming a cyclic acid anhydride group group constituting the ring Z ² by oxidation with each other ring Z ^A ring may be formed together with 1 or 2 or more atoms constituting 2. n represents an integer of 1 or more, and when n is 2 or more, a plurality of X ² and X ³ are the same, Each aromatic ring may have a substituent other than the group shown in the formula, and X ¹ represents these substituents. And may form a ring together with one or more atoms constituting ring Z ¹ )
Is reacted with a compound represented by the following formula (13):

[Wherein, R ^1a , R ^2a , R ^3a , R ^4a , R ^5a , R ^6a are the same or different and represent a hydrogen atom, the following formula (5) or (8)

(In the formula, ring Z ¹ , ring Z ² , X ¹ , X ² , X ³ , m and n are the same as above. Each aromatic ring may have a substituent other than the group shown in the formula. )
The aromatic cyclic group represented by these, or another substituent is shown. However, at least one of R ^1a , R ^2a , R ^3a , R ^4a , R ^5a and R ^6a is a group represented by the formula (5) or (8). k represents an integer of 1 to 3. When k is 2 or 3, the plurality of R ^4a and R ^6a may be the same or different. The adamantane ring may have a substituent at a site other than the bridgehead position]
A process for producing an arylpolyadamantane derivative characterized in that a compound represented by the formula:

  In the present specification, k, m, n, and p each represent the number of groups in parentheses.

According to the present invention, a novel aryl polyadamantane derivative having a carboxyl group or an acid anhydride group useful as a raw material for a functional material excellent in electrical characteristics, thermal characteristics, mechanical characteristics, optical characteristics, physical characteristics, and the like, and its efficiency A typical manufacturing method is provided.
In addition, according to the present invention, a novel aryl polyadamantane derivative useful for synthesizing an arylpolyadamantane derivative having the above carboxyl group or acid anhydride group and an efficient production method thereof are provided.

The aryl polyadamantane derivative having a carboxyl group or an acid anhydride group of the present invention is represented by the formula (1). In the formula (1), R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ are the same or different and are a hydrogen atom, an aromatic cyclic represented by the formula (2) or (3). Represents a group or other substituent. However, at least one of R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ is a group represented by the formula (2) or (3). k represents an integer of 1 to 3. When k is 2 or 3, the plurality of R ⁴ and R ⁶ may be the same or different. The adamantane ring may have a substituent at a site other than the bridge head position. In formulas (2) and (3), ring Z ¹ and ring Z ² represent aromatic rings, and ring Z ³ represents a ring constituting a cyclic acid anhydride. m and n each represent an integer of 1 or more. m is preferably an integer of 1 to 4. n is preferably 1 or 2. Each aromatic ring may have a substituent other than the group shown in the formula. The compound represented by Formula (1) may have both the group represented by Formula (2) and the group represented by Formula (3).

  The compound represented by the formula (1) is functional by polymerization or reaction utilizing a carboxyl group or acid anhydride group or by polymerization of a polymerizable monomer having a polymerizable group introduced into the carboxyl group or acid anhydride group. It can be derived into a polymer. For example, a compound having one aromatic cyclic group represented by the formula (2) or (3) has a polyadamantane ring in the side chain by introducing a polymerizable group into a carboxyl group or an acid anhydride group. It can be used as a monomer raw material for a polymer (pendant type). Moreover, according to the compound which has one aromatic cyclic group represented by Formula (2) or (3), by making it react with the polymer which has a group which can react with a carboxyl group or an acid anhydride group, aryl A polyadamantane skeleton to which groups are bonded can be introduced as a side chain of the polymer. On the other hand, a compound having two aromatic cyclic groups represented by the formula (2) or (3) (particularly a compound having one aromatic cyclic group on each end of the adamantane ring) is a carboxyl group or It can be used as a monomer raw material for a polymer (main chain type) synthesized by a condensation reaction using an acid anhydride group. Further, a compound having three or more aromatic cyclic groups represented by the formula (2) or (3) (in particular, a compound having at least one aromatic cyclic group at each end of the adamantane ring) is 3 It can be used as a raw material for a higher-order polymer having a dimensional network structure.

Examples of the aromatic ring in ring Z ¹ and ring Z ² include aromatic carbocycles such as benzene ring, naphthalene ring, anthracene ring, phenanthrene ring, triphenylene ring; pyridine ring, pyrazine ring, pyrimidine ring, pyridazine ring, quinoline ring An aromatic heterocyclic ring such as an acridine ring, a naphthyridine ring, a quinoxaline ring, a furan ring, a benzofuran ring, and a thiophene ring. The aromatic ring may be condensed with a non-aromatic ring (an alicyclic ring such as a cyclohexane ring; a non-aromatic heterocyclic ring such as a piperidine ring, an oxolane ring, or an oxane ring).

The aromatic ring (ring Z ¹ , ring Z ² ) may have a substituent other than the group shown in the formula in order to impart or improve solvent solubility, heat resistance, and other functions. Good. Examples of such a substituent include a halogen atom, an alkyl group which may have a halogen atom, an alkoxy group which may have a halogen atom, a hydroxyl group which may be protected with a protecting group, and a protecting group. And a hydroxy (halo) alkyl group which may be protected with an amino group, an amino group which may be protected with a protecting group, an acyl group which may be protected with a protecting group, a cyano group, and an aryl group. The number of the substituents is about 0 to 4.

Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Examples of the alkyl group which may have a halogen atom include alkyl groups having about 1 to 15 carbon atoms such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, s-butyl, t-butyl, pentyl and hexyl. (Preferably a C _1-10 alkyl group, more preferably a C _1-6 alkyl group); a haloalkyl group having about 1 to 15 carbon atoms such as trifluoromethyl, pentafluoroethyl group (preferably a C _1-10 haloalkyl group, More preferred examples include C _1-6 haloalkyl groups. As the alkyl group which may have a halogen atom, an alkyl group having 1 to 6 carbon atoms or a haloalkyl group having 1 to 6 carbon atoms is particularly preferable. Examples of the alkoxy group which may have a halogen atom include 1 to 1 carbon atoms such as methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutyloxy, s-butyloxy, t-butyloxy, pentyloxy and hexyloxy groups. About 15 alkoxy groups (preferably C _1-10 alkoxy groups, more preferably C _1-6 alkoxy groups); about 1-15 haloalkoxy groups such as trifluoromethoxy groups (preferably C _1-10 halos) An alkoxy group, and more preferably a C _1-6 haloalkoxy group). Examples of the hydroxy (halo) alkyl group include hydroxymethyl, hydroxyethyl, hydroxypropyl, 1-hydroxy-1-methylethyl group, 2,2,2-trifluoro-1-trifluoromethyl-1-hydroxyethyl group (Preferably, a hydroxy-C _1-4 alkyl group, a hydroxy-C _1-4 haloalkyl group, etc.).

Examples of the hydroxyl protecting group in the hydroxyl group or hydroxy (halo) alkyl group include protecting groups commonly used in the field of organic synthesis, for example, alkyl groups (for example, C _1-4 alkyl such as methyl and t-butyl groups). Group), an alkenyl group (eg, allyl group), a cycloalkyl group (eg, cyclohexyl group), an aryl group (eg, 2,4-dinitrophenyl group), an aralkyl group (eg, benzyl group); Substituted methyl group (eg, methoxymethyl, methylthiomethyl, benzyloxymethyl, t-butoxymethyl, 2-methoxyethoxymethyl group, etc.), substituted ethyl group (eg, 1-ethoxyethyl group, etc.), tetrahydropyranyl group, tetrahydrofuran Nyl group, 1-hydroxyalkyl group (for example, 1-hydroxyethyl group) A group capable of forming an acetal or hemiacetal group with a hydroxyl group; an acyl group (for example, a C _1-6 aliphatic acyl group such as formyl, acetyl, propionyl, butyryl, isobutyryl, pivaloyl group); an acetoacetyl group An aromatic acyl group such as a benzoyl group), an alkoxycarbonyl group (eg, a C _1-4 alkoxy-carbonyl group such as a methoxycarbonyl group), an aralkyloxycarbonyl group, a substituted or unsubstituted carbamoyl group, a substituted silyl group ( For example, when there are two or more hydroxyl groups (including hydroxymethyl groups) in the molecule, a divalent hydrocarbon group (for example, methylene, ethylidene) which may have a substituent. Isopropylidene, cyclopentylidene, cyclohexylidene, Njiriden group, etc.), and others.

Examples of the protecting group for the amino group include an alkyl group, an aralkyl group, an acyl group, and an alkoxycarbonyl group exemplified as the protecting group for the hydroxyl group. Examples of the acyl group include C _1-6 aliphatic acyl groups such as formyl, acetyl, propionyl, butyryl, isobutyryl, and pivaloyl groups; aromatic acyl groups such as acetoacetyl groups and benzoyl groups. As the protecting group for the acyl group, a protecting group conventionally used in the field of organic synthesis can be used. Examples of the protected form of the acyl group include acetal (including hemiacetal). Examples of the aryl group include a phenyl group and a naphthyl group.

  Among the substituents that the aromatic ring may have, a halogen atom, an alkyl group that may have a halogen atom, a hydroxyl group that may be protected with a protecting group, or a protective group that is protected with Particularly preferred are amino groups and aryl groups.

The ring constituting the cyclic acid anhydride in the ring Z ³ is preferably a 5-membered ring or a 6-membered ring (when Z ² is polycyclic). In Formula (2) and Formula (3), the substitution position of the carboxyl group or acid anhydride group is not particularly limited, and can be appropriately selected according to the application and polymer design. For example, when the aromatic ring is a benzene ring, the carboxyl group or acid anhydride group may be any of the ortho position, meta position, para position, 2,3 position, 3,4 position, etc. The para position is easy to synthesize due to the orientation, and the para position or the 3, 4 position is particularly useful as a monomer for polymerization. When the aromatic ring is polycyclic, the substitution position of the carboxyl group or the acid anhydride group can be selected according to the case of the benzene ring.

  The adamantane ring represented by formula (1) has a substituent other than the group represented by formula (2) or (3) in order to impart or improve solvent solubility, heat resistance, and other functions. May be. The substituent may be bonded to either the bridge head position or the non-bridge position of the adamantane ring.

  Examples of the substituent that the adamantane ring may have include, for example, a halogen atom, an alkyl group that may have a halogen atom, an alkoxy group that may have a halogen atom, and a protective group. Good hydroxyl group, hydroxy (halo) alkyl group optionally protected with a protecting group, amino group optionally protected with a protecting group, carboxyl group optionally protected with a protecting group, protected with a protecting group A sulfo group that may be protected, an acyl group that may be protected with a protecting group, a cyano group, a nitro group, an oxo group (═O), and the like.

Halogen atom, alkyl group optionally having halogen atom, alkoxy group optionally having halogen atom, hydroxy (halo) alkyl group, acyl group, hydroxyl group and hydroxyl group in hydroxy (halo) alkyl group The protecting group, the protecting group for the amino group, and the protecting group for the acyl group are the same as in the case of the substituents of the rings Z ¹ and Z ² . Examples of the carboxyl group protected with a protecting group include an alkoxycarbonyl group (for example, a C _1-6 alkoxycarbonyl group such as methoxycarbonyl, ethoxycarbonyl, and butoxycarbonyl groups), a cycloalkyloxycarbonyl group, and an aryloxycarbonyl group. Aralkyloxycarbonyl group, trialkylsilyloxycarbonyl group, substituted or unsubstituted carbamoyl group and the like. Examples of the sulfo group protected by a protecting group include alkoxysulfonyl groups (for example, C _1-6 alkoxysulfonyl groups such as methoxysulfonyl, ethoxysulfonyl, and butoxysulfonyl groups), cycloalkyloxysulfonyl groups, aryloxysulfonyl groups, and aralkyls. Examples thereof include an oxysulfonyl group, a trialkylsilyloxysulfonyl group, a substituted or unsubstituted sulfamoyl group.

  Among the substituents that the adamantane ring may have, it has a function of remarkably increasing the solvent solubility, so that it is protected with an alkyl group, a halogen atom, or a protecting group that may have a halogen atom. The hydroxyl group which may be sufficient is preferable, and especially a C1-C6 alkyl group or a C1-C6 haloalkyl group is preferable. Moreover, in order to improve functionality, the substituent which the adamantane ring may have is preferably a hydroxyl group which may be protected with a protecting group, an amino group which may be protected with a protecting group, or the like.

  When the substituent (for example, an alkyl group which may have a halogen atom) is bonded to the bridge head position of the adamantane ring, it may be bonded to one of the bridge head positions of the adamantane ring. It is particularly preferred that it is bonded to two bridgehead positions. Moreover, it is also preferable to have this substituent at all two bridgehead positions of each of a plurality of adamantane rings.

  The compound represented by the formula (1) can form a salt when it has an acidic group or a basic group in the molecule. Such salts are also included in the present invention. Examples of the salt having an acidic group such as a carboxyl group or a sulfo group (sulfonic acid group) in the molecule include alkali metal salts such as sodium salts, alkaline earth metal salts such as magnesium salts, and ammonium salts. Is done. Examples of the salt having a basic group such as an amino group in the molecule include inorganic acid salts such as hydrochloride, sulfate, nitrate and phosphate; organic acids such as p-toluenesulfonate and acetate Salt. The salt can be produced by a conventional salt forming reaction.

The compound represented by the formula (1) can be derived into an equivalent of carboxylic acid by a conventional method. The present invention also includes such carboxylic acid equivalents. Examples of carboxylic acid equivalents include esters, carboxylic anhydrides, amides, hydrazides, and the like. Examples of the ester include alkyl esters such as methyl ester, ethyl ester, isopropyl ester and t-butyl ester (particularly C _1-6 alkyl ester); aryl esters such as phenyl ester (particularly C _6-15 aryl ester); Aralkyl esters such as benzyl esters (especially C _6-16 aralkyl esters, etc.); Hemiacetal esters such as methoxymethyl esters, tetrahydropyranyl esters, tetrahydrofuranyl esters, methoxyethoxymethyl esters; Silyl esters such as trimethylsilyl esters; N-hydroxysuccinimide And active esters such as yl esters. Examples of carboxylic acid anhydrides include mixed acid anhydrides with acetic acid. Examples of the amide include N, N-dimethylamide and pyrrolidinylamide. Examples of the hydrazide include hydrazide and N-phenylhydrazide. Induction of the carboxylic acid equivalent can be performed by utilizing a reaction generally used.

（上記式中、Ｒ^A、Ｒ^B、Ｒ^C、Ｒ^Dは、同一又は異なって、水素原子、又は炭素数１〜６のハロゲン原子を有していてもよいアルキル基を示す。ベンゼン環又はナフタレン環は式中に示される基以外の置換基を有していてもよく、有していなくてもよい。ｋは１〜３の整数を示す。ｋが２又は３の場合、複数個のＲ^C、Ｒ^Dはそれぞれ同一であっても異なっていてもよい。ｐは０又は１を示す。アダマンタン環は橋頭位以外の部位に置換基を有していてもよく、有していなくてもよい） Among the compounds represented by the formula (1), the following formulas (1a), (1b), (1c), (1d), (1e), (1f), (1g), (1h), (1i) , (1j), (1k) and (1l) are particularly preferred.

(In the above formula, R ^A , R ^B , R ^C and R ^D are the same or different and each represents a hydrogen atom or an alkyl group which may have a halogen atom having 1 to 6 carbon atoms. The naphthalene ring may or may not have a substituent other than the group shown in the formula, k represents an integer of 1 to 3. When k is 2 or 3, R ^C and R ^D may be the same or different, and p represents 0 or 1. The adamantane ring may or may not have a substituent at a site other than the bridgehead position. Also good)

The substituent that the benzene ring or naphthalene ring may have is the same as the substituent that Z ¹ and Z ² may have. The substituent that the adamantane ring may have is the same as the substituent that the adamantane ring in the formula (1) may have.

  As a typical example of the compound in which p = 0 among the compounds represented by the formula (1a), 3- (4-carboxyphenyl) -1,1′-biadamantane, 3′-bromo-3- (4 -Carboxyphenyl) -1,1'-biadamantane, 3- (4-carboxyphenyl) -3'-hydroxy-1,1'-biadamantane, 3- (4-carboxyphenyl) -5,7-dimethyl- 1,1'-biadamantane, 3- (4-carboxyphenyl) -5 ', 7'-dimethyl-1,1'-biadamantane, 3- (4-carboxyphenyl) -5,5', 7,7 '-Tetramethyl-1,1'-biadamantane, 3'-bromo-3- (4-carboxyphenyl) -5,5', 7,7'-tetramethyl-1,1'-biadamantane, 3- (4-Carboxyphenyl) -3 ' Hydroxy-5,5 ', 7,7'-tetramethyl-1,1'-biadamantane, 3- (4-carboxyphenyl) -5,5', 7,7'-tetrakis (trifluoromethyl) -1 4-carboxyphenylbiadamantane derivatives such as 1,1'-biadamantane; 3- (4-carboxyphenyl) -1,1 ': 3', 1 "-triadamantane, 3- (4-carboxyphenyl) -5, 5-carboxyphenyltriadamantane derivatives such as 5 ', 5 ", 7,7', 7" -hexamethyl-1,1 ': 3', 1 "-triadamantane; 3- (4-carboxyphenyl) -1 , 1 ': 3', 1 ": 3", 1 "'-tetraadamantane, 3- (4-carboxyphenyl) -5, 5', 5", 5 "', 7, 7', 7" , 7 ""-octamethyl-1 1 ': 3', 1 ": 3", 1 '' '- such as 4-carboxyphenyl tetra adamantane derivatives such as tetra-adamantane and the like.

  Representative examples of the compound represented by the formula (1a) where p = 1 are 3,3′-bis (4-carboxyphenyl) -1,1′-biadamantane, 3,3′- Bis (4-carboxyphenyl) -5,7-dimethyl-1,1′-biadamantane, 3,3′-bis (4-carboxyphenyl) -5,5 ′, 7,7′-tetramethyl-1, Bis (4-carboxy) such as 1'-biadamantane, 3,3'-bis (4-carboxyphenyl) -5,5 ', 7,7'-tetrakis (trifluoromethyl) -1,1'-biadamantane Phenyl) biadamantane derivatives; 3,3 ″ -bis (4-carboxyphenyl) -1,1 ′: 3 ′, 1 ″ -triadamantane, 3,3 ″ -bis (4-carboxyphenyl) -5,5 ′ , 5 ″, 7, 7 ′, 7 ″ Bis (4-carboxyphenyl) triadamantane derivatives such as methyl-1,1 ′: 3 ′, 1 ″ -triadamantane; 3,3 ′ ″-bis (4-carboxyphenyl) -1,1 ′: 3 ′ , 1 ″: 3 ″, 1 ″ ″-tetraadamantane, 3,3 ″ ″-bis (4-carboxyphenyl) -5,5 ′, 5 ″, 5 ″ ″, 7,7 ′, 7 ″ , 7 ′ ″-octamethyl-1,1 ′: 3 ′, 1 ″: 3 ″, bis (4-carboxyphenyl) tetraadamantane derivatives such as 1 ′ ″-tetraadamantane and the like.

  As a representative example of the compound represented by formula (1b) where p = 0, 3- (2-carboxyphenyl) -1,1′-biadamantane, 3′-bromo-3- (2 -Carboxyphenyl) -1,1'-biadamantane, 3- (2-carboxyphenyl) -3'-hydroxy-1,1'-biadamantane, 3- (2-carboxyphenyl) -5,7-dimethyl- 1,1'-biadamantane, 3- (2-carboxyphenyl) -5 ', 7'-dimethyl-1,1'-biadamantane, 3- (2-carboxyphenyl) -5,5', 7,7 '-Tetramethyl-1,1'-biadamantane, 3'-bromo-3- (2-carboxyphenyl) -5,5', 7,7'-tetramethyl-1,1'-biadamantane, 3- (2-carboxyphenyl) -3 ' Hydroxy-5,5 ', 7,7'-tetramethyl-1,1'-biadamantane, 3- (2-carboxyphenyl) -5,5', 7,7'-tetrakis (trifluoromethyl) -1 , 1′-biadamantane, 3- (2-carboxy-5-phenylphenyl) -1,1′-biadamantane, 3′-bromo-3- (2-carboxy-5-phenylphenyl) -1,1 ′ -Biadamantane, 3- (2-carboxy-5-phenylphenyl) -3'-hydroxy-1,1'-biadamantane, 3- (2-carboxy-5-phenylphenyl) -5,7-dimethyl-1 , 1'-biadamantane, 3- (2-carboxy-5-phenylphenyl) -5 ', 7'-dimethyl-1,1'-biadamantane, 3- (2-carboxy-5-phenylphenyl) -5 5 ', 7,7'-tetramethyl-1,1'-biadamantane, 3'-bromo-3- (2-carboxy-5-phenylphenyl) -5,5', 7,7'-tetramethyl- 1,1′-biadamantane, 3- (2-carboxy-5-phenylphenyl) -3′-hydroxy-5,5 ′, 7,7′-tetramethyl-1,1′-biadamantane, 3- ( 2-carboxyphenylbiadamantane derivatives such as 2-carboxy-5-phenylphenyl) -5,5 ′, 7,7′-tetrakis (trifluoromethyl) -1,1′-biadamantane; Phenyl) -1,1 ′: 3 ′, 1 ″ -triadamantane, 3- (2-carboxyphenyl) -5,5 ′, 5 ″, 7,7 ′, 7 ″ -hexamethyl-1,1 ′: 3 ', 1 "-triadamantane Any 2-carboxyphenyltriadamantane derivative; 3- (2-carboxyphenyl) -1,1 ′: 3 ′, 1 ″: 3 ″, 1 ′ ″-tetraadamantane, 3- (2-carboxyphenyl) -5 , 5 ′, 5 ″, 5 ′ ″, 7, 7 ′, 7 ″, 7 ′ ″-octamethyl-1, 1 ′: 3 ′, 1 ″: 3 ″, 1 ′ ″-tetraadamantane, etc. And 2-carboxyphenyltetraadamantane derivatives.

  Representative examples of the compound represented by formula (1b) where p = 1 are 3,3′-bis (2-carboxyphenyl) -1,1′-biadamantane, 3,3′- Bis (2-carboxyphenyl) -5,7-dimethyl-1,1′-biadamantane, 3,3′-bis (2-carboxyphenyl) -5,5 ′, 7,7′-tetramethyl-1, 1'-biadamantane, 3,3'-bis (2-carboxyphenyl) -5,5 ', 7,7'-tetrakis (trifluoromethyl) -1,1'-biadamantane, 3,3'-bis (2-carboxy-5-phenylphenyl) -1,1′-biadamantane, 3,3′-bis (2-carboxy-5-phenylphenyl) -5,7-dimethyl-1,1′-biadamantane, 3,3′-bis (2-carboxy-5- Enylphenyl) -5 ', 7'-dimethyl-1,1'-biadamantane, 3,3'-bis (2-carboxy-5-phenylphenyl) -5,5', 7,7'-tetramethyl- 1,1'-biadamantane, 3,3'-bis (2-carboxy-5-phenylphenyl) -5,5 ', 7,7'-tetrakis (trifluoromethyl) -1,1'-biadamantane, etc. Bis (2-carboxyphenyl) biadamantane derivative; 3,3 ″ -bis (2-carboxyphenyl) -1,1 ′: 3 ′, 1 ″ -triadamantane, 3,3 ″ -bis (2-carboxyphenyl) ) -5,5 ′, 5 ″, 7,7 ′, 7 ″ -hexamethyl-1,1 ′: 3 ′, 1 ″ -bis (2-carboxyphenyl) triadamantane derivatives such as triadamantane; 3,3 ′ ′ ′ -Bis ( -Carboxyphenyl) -1,1 ': 3', 1 ": 3", 1 ""-tetraadamantane, 3,3 ""-bis (2-carboxyphenyl) -5,5 ', 5 ", Bis (2-carboxyphenyl) such as 5 ′ ″, 7,7 ′, 7 ″, 7 ″ ″-octamethyl-1,1 ′: 3 ′, 1 ″: 3 ″, 1 ′ ″-tetraadamantane Examples thereof include tetraadamantane derivatives.

  Representative examples of the compound represented by formula (1c) where p = 0 are 3- (3,4-dicarboxyphenyl) -1,1′-biadamantane, 3- (3,4 -Dicarboxyphenyl) -5,7-dimethyl-1,1'-biadamantane, 3- (3,4-dicarboxyphenyl) -5 ', 7'-dimethyl-1,1'-biadamantane, 3- (3,4-dicarboxyphenyl) biadamantane derivatives such as (3,4-dicarboxyphenyl) -5,5 ′, 7,7′-tetramethyl-1,1′-biadamantane; 4-dicarboxyphenyl) -1,1 ': 3', 1 "-triadamantane, 3- (3,4-dicarboxyphenyl) -5,5 ', 5", 7,7', 7 "- Hexamethyl-1,1 ′: 3 ′, 1 ″ -triadamantane etc. 3,4-dicarboxyphenyl) triadamantane derivative; 3- (3,4-dicarboxyphenyl) -1,1 ′: 3 ′, 1 ″: 3 ″, 1 ′ ″-tetraadamantane, 3- (3 , 4-dicarboxyphenyl) -5,5 ′, 5 ″, 5 ′ ″, 7,7 ′, 7 ″, 7 ″ ″-octamethyl-1,1 ′: 3 ′, 1 ″: 3 ″, And (3,4-dicarboxyphenyl) tetraadamantane derivatives such as 1 ′ ″-tetraadamantane.

  As representative examples of the compound represented by formula (1c) where p = 1, 3,3′-bis (3,4-dicarboxyphenyl) -1,1′-biadamantane, 3, 3'-bis (3,4-dicarboxyphenyl) -5,7-dimethyl-1,1'-biadamantane, 3,3'-bis (3,4-dicarboxyphenyl) -5,5 ', 7 3,3′-bis (3,4-dicarboxyphenyl) biadamantane derivatives such as 3,7′-tetramethyl-1,1′-biadamantane; 3,3 ″ -bis (3,4-dicarboxyphenyl) -1,1 ': 3', 1 "-triadamantane, 3,3" -bis (3,4-dicarboxyphenyl) -5,5 ', 5 ", 7,7', 7" -hexamethyl- 1,1 ′: 3 ′, 1 ″ -Tridamantane and other bis (3,4-dicarbo Cyphenyl) triadamantane derivatives; 3,3 ′ ″-bis (3,4-dicarboxyphenyl) -1,1 ′: 3 ′, 1 ″: 3 ″, 1 ′ ″-tetraadamantane, 3,3 ′ ″ ′ -Bis (3,4-dicarboxyphenyl) -5,5 ′, 5 ″, 5 ″ ′, 7,7 ′, 7 ″, 7 ″ ″-octamethyl-1,1 ′: 3 ′, Examples thereof include bis (3,4-dicarboxyphenyl) tetraadamantane derivatives such as 1 ″: 3 ″, 1 ′ ″-tetraadamantane.

  Representative examples of the compound represented by formula (1d) where p = 0 are 3- (2,3-dicarboxyphenyl) -1,1′-biadamantane, 3- (2,3 -Dicarboxyphenyl) -5,7-dimethyl-1,1'-biadamantane, 3- (2,3-dicarboxyphenyl) -5 ', 7'-dimethyl-1,1'-biadamantane, 3- (2,3-dicarboxyphenyl) biadamantane derivatives such as (2,3-dicarboxyphenyl) -5,5 ′, 7,7′-tetramethyl-1,1′-biadamantane; 3- (2, 3-dicarboxyphenyl) -1,1 ′: 3 ′, 1 ″ -triadamantane, 3- (2,3-dicarboxyphenyl) -5,5 ′, 5 ″, 7,7 ′, 7 ″- Such as hexamethyl-1,1 ′: 3 ′, 1 ″ -triadamantane 2,3-dicarboxyphenyl) triadamantane derivatives; 3- (2,3-dicarboxyphenyl) -1,1 ′: 3 ′, 1 ″: 3 ″, 1 ′ ″-tetraadamantane, 3- (2 , 3-dicarboxyphenyl) -5,5 ′, 5 ″, 5 ′ ″, 7,7 ′, 7 ″, 7 ″ ″-octamethyl-1,1 ′: 3 ′, 1 ″: 3 ″, And (2,3-dicarboxyphenyl) tetraadamantane derivatives such as 1 ′ ″-tetraadamantane.

  As typical examples of the compound represented by formula (1d) where p = 1, 3,3′-bis (2,3-dicarboxyphenyl) -1,1′-biadamantane, 3, 3'-bis (2,3-dicarboxyphenyl) -5,7-dimethyl-1,1'-biadamantane, 3,3'-bis (2,3-dicarboxyphenyl) -5,5 ', 7 3,3′-bis (2,3-dicarboxyphenyl) biadamantane derivatives such as 3,7′-tetramethyl-1,1′-biadamantane; 3,3 ″ -bis (2,3-dicarboxyphenyl) -1,1 ': 3', 1 "-triadamantane, 3,3" -bis (2,3-dicarboxyphenyl) -5,5 ', 5 ", 7,7', 7" -hexamethyl- 1,1 ′: 3 ′, 1 ″ -bis (2,3-dicarbo Cyphenyl) triadamantane derivatives; 3,3 ′ ″-bis (2,3-dicarboxyphenyl) -1,1 ′: 3 ′, 1 ″: 3 ″, 1 ′ ″-tetraadamantane, 3,3 ′ ″ ″ -Bis (2,3-dicarboxyphenyl) -5,5 ′, 5 ″, 5 ″ ′, 7,7 ′, 7 ″, 7 ″ ″-octamethyl-1,1 ′: 3 ′, Examples thereof include bis (2,3-dicarboxyphenyl) tetraadamantane derivatives such as 1 ″: 3 ″, 1 ′ ″-tetraadamantane.

  Representative examples of the compound represented by formula (1e) where p = 0 include 3- (2,5-dicarboxyphenyl) -1,1′-biadamantane, 3- (2,5 -Dicarboxyphenyl) -5,7-dimethyl-1,1'-biadamantane, 3- (2,5-dicarboxyphenyl) -5 ', 7'-dimethyl-1,1'-biadamantane, 3- (2,5-dicarboxyphenyl) biadamantane derivatives such as (2,5-dicarboxyphenyl) -5,5 ′, 7,7′-tetramethyl-1,1′-biadamantane; 3- (2, 5-dicarboxyphenyl) -1,1 ′: 3 ′, 1 ″ -triadamantane, 3- (2,5-dicarboxyphenyl) -5,5 ′, 5 ″, 7,7 ′, 7 ″- Such as hexamethyl-1,1 ′: 3 ′, 1 ″ -triadamantane 2,5-dicarboxyphenyl) triadamantane derivatives; 3- (2,5-dicarboxyphenyl) -1,1 ′: 3 ′, 1 ″: 3 ″, 1 ″ ′-tetraadamantane, 3- (2 , 5-dicarboxyphenyl) -5,5 ′, 5 ″, 5 ′ ″, 7,7 ′, 7 ″, 7 ″ ″-octamethyl-1,1 ′: 3 ′, 1 ″: 3 ″, And (2,5-dicarboxyphenyl) tetraadamantane derivatives such as 1 ′ ″-tetraadamantane.

  As representative examples of the compound represented by formula (1e) where p = 1, 3,3′-bis (2,5-dicarboxyphenyl) -1,1′-biadamantane, 3, 3'-bis (2,5-dicarboxyphenyl) -5,7-dimethyl-1,1'-biadamantane, 3,3'-bis (2,5-dicarboxyphenyl) -5,5 ', 7 3,3′-bis (2,5-dicarboxyphenyl) biadamantane derivatives such as 1,7′-tetramethyl-1,1′-biadamantane; 3,3 ″ -bis (2,5-dicarboxyphenyl) -1,1 ': 3', 1 "-triadamantane, 3,3" -bis (2,5-dicarboxyphenyl) -5,5 ', 5 ", 7,7', 7" -hexamethyl- 1,1 ′: 3 ′, 1 ″ -Tridamantane and other bis (2,5-dicarbo Cyphenyl) triadamantane derivatives; 3,3 ′ ″-bis (2,5-dicarboxyphenyl) -1,1 ′: 3 ′, 1 ″: 3 ″, 1 ″ ″-tetraadamantane, 3,3 ′ ″ ″ -Bis (2,5-dicarboxyphenyl) -5,5 ′, 5 ″, 5 ″ ″, 7,7 ′, 7 ″, 7 ″ ″-octamethyl-1,1 ′: 3 ′, Examples thereof include bis (2,5-dicarboxyphenyl) tetraadamantane derivatives such as 1 ″: 3 ″, 1 ″ ′-tetraadamantane.

  Representative examples of the compound represented by the formula (1f) where p = 0 include 3- (2,3,5,6-tetracarboxyphenyl) -1,1′-biadamantane, 3- (2,3,5,6-tetracarboxyphenyl) -5,7-dimethyl-1,1'-biadamantane, 3- (2,3,5,6-tetracarboxyphenyl) -5 ', 7'- (2) such as dimethyl-1,1'-biadamantane, 3- (2,3,5,6-tetracarboxyphenyl) -5,5 ', 7,7'-tetramethyl-1,1'-biadamantane , 3,5,6-tetracarboxyphenyl) biadamantane derivative; 3- (2,3,5,6-tetracarboxyphenyl) -1,1 ′: 3 ′, 1 ″ -triadamantane, 3- (2, 3,5,6-tetracarboxyphenyl) -5,5 ' (2,3,5,6-tetracarboxyphenyl) triadamantane derivatives such as 5 ″, 7,7 ′, 7 ″ -hexamethyl-1,1 ′: 3 ′, 1 ″ -triadamantane; 3- (2 , 3,5,6-tetracarboxyphenyl) -1,1 ′: 3 ′, 1 ″: 3 ″, 1 ″ ″-tetraadamantane, 3- (2,3,5,6-tetracarboxyphenyl)- 5,5 ′, 5 ″, 5 ′ ″, 7,7 ′, 7 ″, 7 ″ ″-octamethyl-1,1 ′: 3 ′, 1 ″: 3 ″, 1 ″ ″-tetraadamantane, etc. (2,3,5,6-tetracarboxyphenyl) tetraadamantane derivatives and the like.

  As a representative example of the compound represented by formula (1f) where p = 1, 3,3′-bis (2,3,5,6-tetracarboxyphenyl) -1,1′-bi Adamantane, 3,3′-bis (2,3,5,6-tetracarboxyphenyl) -5,7-dimethyl-1,1′-biadamantane, 3,3′-bis (2,3,5,6) -Tetracarboxyphenyl) -5,5 ', 7,7'-tetramethyl-1,1'-biadamantane and other 3,3'-bis (2,3,5,6-tetracarboxyphenyl) biadamantane derivatives 3,3 ″ -bis (2,3,5,6-tetracarboxyphenyl) -1,1 ′: 3 ′, 1 ″ -triadamantane, 3,3 ″ -bis (2,3,5,6- Tetracarboxyphenyl) -5,5 ', 5 ", 7,7', 7" -hexame Bis (2,3,5,6-tetracarboxyphenyl) triadamantane derivatives such as 1,3 ′, 3 ′, 1 ″ -triadamantane; 3,3 ′ ″-bis (2,3,5, 6-tetracarboxyphenyl) -1,1 ′: 3 ′, 1 ″: 3 ″, 1 ″ ″-tetraadamantane, 3,3 ″ ″-bis (2,3,5,6-tetracarboxyphenyl) -5, 5 ', 5 ", 5"', 7, 7 ', 7 ", 7" "-octamethyl-1, 1': 3 ', 1": 3 ", 1" "-tetraadamantane And bis (2,3,5,6-tetracarboxyphenyl) tetraadamantane derivatives.

  As a representative example of the compound represented by formula (1g) where p = 0, a carboxylic acid corresponding to a representative example of the compound represented by formula (1c) wherein p = 0 Anhydrides are mentioned. As a typical example of the compound represented by formula (1g) where p = 1, the carboxylic acid corresponding to the typical example of the compound represented by formula (1c) wherein p = 1 And dianhydrides.

  As a representative example of the compound represented by formula (1h) where p = 0, the carboxylic acid corresponding to the representative example of the compound represented by formula (1f) wherein p = 0 And dianhydrides. As a representative example of the compound represented by formula (1h) where p = 1, a carboxylic acid corresponding to a representative example of the compound represented by formula (1f) wherein p = 1 Tetraanhydride is mentioned.

  As typical examples of the compound represented by formula (1i) where p = 0, 3- (4,5-dicarboxynaphthalen-1-yl) -1,1′-biadamantane, 3- (4,5-dicarboxynaphthalen-1-yl) -5,7-dimethyl-1,1'-biadamantane, 3- (4,5-dicarboxynaphthalen-1-yl) -5 ', 7'- (4) such as dimethyl-1,1'-biadamantane, 3- (4,5-dicarboxynaphthalen-1-yl) -5,5 ', 7,7'-tetramethyl-1,1'-biadamantane , 5-dicarboxynaphthalen-1-yl) biadamantane derivative; 3- (4,5-dicarboxynaphthalen-1-yl) -1,1 ′: 3 ′, 1 ″ -triadamantane, 3- (4 5-Dicarboxynaphthalen-1-yl) -5,5 ′ (4,5-dicarboxynaphthalen-1-yl) triadamantane derivatives such as 5 ″, 7,7 ′, 7 ″ -hexamethyl-1,1 ′: 3 ′, 1 ″ -triadamantane; 3- (4 , 5-Dicarboxynaphthalen-1-yl) -1,1 ′: 3 ′, 1 ″: 3 ″, 1 ′ ″-tetraadamantane, 3- (4,5-dicarboxynaphthalen-1-yl)- 5,5 ′, 5 ″, 5 ′ ″, 7,7 ′, 7 ″, 7 ″ ″-octamethyl-1,1 ′: 3 ′, 1 ″: 3 ″, 1 ″ ″-tetraadamantane, etc. (4,5-dicarboxynaphthalen-1-yl) tetraadamantane derivatives and the like.

  As a typical example of the compound represented by formula (1i) where p = 1, 3,3′-bis (4,5-dicarboxynaphthalen-1-yl) -1,1′-bi Adamantane, 3,3′-bis (4,5-dicarboxynaphthalen-1-yl) -5,7-dimethyl-1,1′-biadamantane, 3,3′-bis (4,5-dicarboxynaphthalene) −1-yl) -5,5 ′, 7,7′-tetramethyl-1,1′-biadamantane and other 3,3′-bis (4,5-dicarboxynaphthalen-1-yl) biadamantane derivatives 3,3 ″ -bis (4,5-dicarboxynaphthalen-1-yl) -1,1 ′: 3 ′, 1 ″ -triadamantane, 3,3 ″ -bis (4,5-dicarboxynaphthalene- 1-yl) -5,5 ', 5 ", 7,7', 7" -hexame Bis (4,5-dicarboxynaphthalen-1-yl) triadamantane derivatives such as ru-1,1 ′: 3 ′, 1 ″ -triadamantane; 3,3 ′ ″-bis (4,5-dicarboxyl Naphthalen-1-yl) -1,1 ′: 3 ′, 1 ″: 3 ″, 1 ″ ″-tetraadamantane, 3,3 ″ ″-bis (4,5-dicarboxynaphthalen-1-yl) -5, 5 ', 5 ", 5" ", 7, 7', 7", 7 ""-octamethyl-1, 1 ': 3', 1 ": 3", 1 ""-tetraadamantane And bis (4,5-dicarboxynaphthalen-1-yl) tetraadamantane derivatives.

  As typical examples of the compound represented by formula (1j) where p = 0, 3- (5,6-dicarboxynaphthalen-1-yl) -1,1′-biadamantane, 3- (5,6-dicarboxynaphthalen-1-yl) -5,7-dimethyl-1,1′-biadamantane, 3- (5,6-dicarboxynaphthalen-1-yl) -5 ′, 7′- (5) such as dimethyl-1,1'-biadamantane, 3- (5,6-dicarboxynaphthalen-1-yl) -5,5 ', 7,7'-tetramethyl-1,1'-biadamantane , 6-Dicarboxynaphthalen-1-yl) biadamantane derivative; 3- (5,6-dicarboxynaphthalen-1-yl) -1,1 ′: 3 ′, 1 ″ -triadamantane, 3- (5 6-Dicarboxynaphthalen-1-yl) -5,5 ′ (5,6-dicarboxynaphthalen-1-yl) triadamantane derivatives such as 5 ″, 7,7 ′, 7 ″ -hexamethyl-1,1 ′: 3 ′, 1 ″ -triadamantane; 3- (5 , 6-Dicarboxynaphthalen-1-yl) -1,1 ′: 3 ′, 1 ″: 3 ″, 1 ′ ″-tetraadamantane, 3- (5,6-dicarboxynaphthalen-1-yl)- 5,5 ′, 5 ″, 5 ′ ″, 7,7 ′, 7 ″, 7 ″ ″-octamethyl-1,1 ′: 3 ′, 1 ″: 3 ″, 1 ″ ″-tetraadamantane, etc. (5,6-dicarboxynaphthalen-1-yl) tetraadamantane derivatives and the like.

  As a typical example of the compound represented by formula (1j) where p = 1, 3,3′-bis (5,6-dicarboxynaphthalen-1-yl) -1,1′-bi Adamantane, 3,3′-bis (5,6-dicarboxynaphthalen-1-yl) -5,7-dimethyl-1,1′-biadamantane, 3,3′-bis (5,6-dicarboxynaphthalene) −1-yl) -5,5 ′, 7,7′-tetramethyl-1,1′-biadamantane and other 3,3′-bis (5,6-dicarboxynaphthalen-1-yl) biadamantane derivatives 3,3 ″ -bis (5,6-dicarboxynaphthalen-1-yl) -1,1 ′: 3 ′, 1 ″ -triadamantane, 3,3 ″ -bis (5,6-dicarboxynaphthalene-; 1-yl) -5,5 ', 5 ", 7,7', 7" -hexame Bis (5,6-dicarboxynaphthalen-1-yl) triadamantane derivatives such as ru-1,1 ′: 3 ′, 1 ″ -triadamantane; 3,3 ′ ″-bis (5,6-dicarboxyl) Naphthalen-1-yl) -1,1 ′: 3 ′, 1 ″: 3 ″, 1 ″ ″-tetraadamantane, 3,3 ″ ″-bis (5,6-dicarboxynaphthalen-1-yl) -5, 5 ', 5 ", 5" ", 7, 7', 7", 7 ""-octamethyl-1, 1 ': 3', 1 ": 3", 1 ""-tetraadamantane And bis (5,6-dicarboxynaphthalen-1-yl) tetraadamantane derivatives.

  As a representative example of the compound represented by formula (1k) where p = 0, the carboxylic acid corresponding to the representative example of the compound represented by formula (1i) wherein p = 0 Anhydrides are mentioned. As a representative example of the compound represented by formula (1k) where p = 1, the carboxylic acid corresponding to the representative example of the compound represented by formula (1i) wherein p = 1 And dianhydrides.

  As a representative example of the compound represented by formula (1l) where p = 0, a carboxylic acid corresponding to a representative example of the compound represented by formula (1j) wherein p = 0 Anhydrides are mentioned. As a typical example of the compound represented by formula (1l) where p = 1, a carboxylic acid corresponding to a typical example of the compound represented by formula (1j) wherein p = 1 And dianhydrides.

  The arylpolyadamantane derivative having a carboxyl group or an acid anhydride group of the present invention and a salt and an equivalent thereof have 2 to 4 adamantane skeletons, which are very stable and excellent in symmetry, and are reactive. It has a carboxyl group or an acid anhydride group that can be used as a functional group, or an equivalent group of a carboxyl group. Therefore, functions such as various high-functional polymers with excellent electrical properties such as heat resistance, water resistance, optical properties, light transmittance, low dielectric constant, water absorption, adhesion, thermal properties, mechanical properties and physical properties. Materials such as flexible wiring boards (base materials, cover materials) materials, CCL (copper-clad laminate) materials, interlayer insulation film materials for semiconductor devices and multilayer wiring boards, adhesive materials, liquid crystal alignment film materials, paint materials, It is useful as a raw material (monomer) such as an optical material, an additive, an aerospace material, a vehicle material, or a raw material thereof.

  Among the compounds represented by the formula (1) of the present invention, the compound in which the group represented by the formula (2) is bonded to the adamantane ring is, for example, an aryl polyadamantane derivative represented by the formula (4). Can be produced by oxidation or hydrolysis.

In the formula (4), R ^1a , R ^2a , R ^3a , R ^4a , R ^5a , R ^6a are the same or different and are a hydrogen atom, an aromatic cyclic group represented by the formula (5), or other The substituent of is shown. However, at least one of R ^1a , R ^2a , R ^3a , R ^4a , R ^5a and R ^6a is a group represented by the formula (5). k represents an integer of 1 to 3. When k is 2 or 3, the plurality of R ^4a and R ^6a may be the same or different. The adamantane ring may have a substituent at a site other than the bridge head position. In formula (5), ring Z ¹ represents an aromatic ring. X ¹ represents a group that can be converted to a carboxyl group by oxidation or hydrolysis. m represents an integer of 1 or more. When m is 2 or more, the plurality of X ¹ may be the same or different, and the plurality of X ¹ are bonded together to form one or more atoms constituting the ring Z ¹ A ring may be formed. The aromatic ring may have a substituent other than the group shown in the formula. X ¹ may be bonded to these substituents to form a ring together with one or more atoms constituting ring Z ¹ .

The aromatic ring (ring Z ¹ ) in formula (5) and the substituent that the aromatic ring may have are the same as those in formula (2). The other substituents in R ^1a , R ^2a , R ^3a , R ^4a , R ^5a , R ^6a and the substituents that may be present at sites other than the bridge head position of the adamantane ring are the same as in the case of formula (1). is there.

Among the groups that can be converted to a carboxyl group by oxidation or hydrolysis in X ¹ , examples of the group that can be converted to a carboxyl group by oxidation include, for example, an alkyl group, a low-order oxidation group of an alkyl group (carbon at the 1-position of the alkyl group) Organic groups having a carbon-hydrogen bond at the benzylic position of the aromatic ring such as a cycloalkyl group, and the like.

Examples of the alkyl group include primary or secondary such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, s-butyl, pentyl, isopentyl, hexyl, isohexyl, heptyl, octyl, 2-ethylhexyl, decyl group, and the like. And a secondary alkyl group. Among these, C _1-4 alkyl group, particularly a methyl group, an ethyl group, a C _1-3 alkyl group such as isopropyl group. Examples of the low-order oxidation group of the alkyl group include a hydroxyalkyl group, a formyl group, a formylalkyl group, and an alkyl group having an oxo group. Examples of the hydroxyalkyl group include hydroxymethyl, 1-hydroxyethyl, 1-hydroxypropyl, 1-hydroxy-1-methylethyl, 1-hydroxybutyl group (hydroxy-C _1-6 alkyl group and the like). . Examples of the formylalkyl group include formylmethyl, 1-formylethyl, 1-formylpropyl group and the like (formyl-C _1-6 alkyl group and the like). Examples of the alkyl group having an oxo group include aliphatic acyl groups such as acetyl, propionyl, butyryl, pentanoyl, and hexanoyl groups (C _1-6 aliphatic acyl group and the like). Among these, a low-order oxidation group corresponding to a C _1-4 alkyl group (particularly, a C _1-3 alkyl group) is preferable. Examples of the cycloalkyl group include a cyclopentyl group and a cyclohexyl group. The alkyl group, its lower oxidation group, and cycloalkyl group may have various substituents as long as they do not inhibit the reaction.

Of the groups that can be converted to a carboxyl group by oxidation or hydrolysis in X ^1, examples of the group that can be converted to a carboxyl group by hydrolysis include a cyano group, a carboxyl group protected by a protective group that can be removed by hydrolysis, and the like Is mentioned. Examples of the carboxyl group protected with a protecting group removable by hydrolysis include alkoxycarbonyl groups (particularly C _1-4 alkoxy-carbonyl groups) such as methoxycarbonyl and ethoxycarbonyl groups; phenyloxycarbonyl groups; benzyloxy Carbonyl group; methoxymethyloxycarbonyl group, tetrahydropyranyloxycarbonyl group, tetrahydrofuranyloxycarbonyl group, methoxyethoxymethyloxycarbonyl group; acyloxycarbonyl group such as acetyloxycarbonyl group, etc.).

Examples of the ring formed by combining a plurality of X ¹ together with one or more atoms constituting ring Z ¹ include, for example, a cycloalkene ring (particularly a 5-6 membered cycloalkene ring), a cyclic ether (Especially 5-6 membered cyclic ether; dihydrofuran ring, dihydropyran ring, etc.). Examples of the ring X ¹ is formed with one or more atoms constituting the ring Z ¹ bonded to other substituents on the aromatic ring include, for example, 5- to 6-membered lactone ring. These are also converted to carboxyl groups by oxidation and / or hydrolysis.

Representative examples of the aromatic cyclic group represented by the formula (5) include, for example, 4-methylphenyl, 2-methylphenyl, 2-methyl-5-phenylphenyl, 4-ethylphenyl, 4-isopropyl Phenyl, 4-cyclopentylphenyl, 4-cyclohexylphenyl, 4-hydroxymethylphenyl, 4-formylphenyl, 3,4-dimethylphenyl, 2,5-dimethylphenyl, 3-ethyl-4-methylphenyl, 2-ethyl- 5-methylphenyl, 4-ethyl-3-methylphenyl, 5-ethyl-2-methylphenyl, 3,4-diethylphenyl, 3,4-diisopropylphenyl, 3,4-bis (hydroxymethyl) phenyl, 3, 4-diformylphenyl, 2,3,5-trimethylphenyl, 2,3,6-trimethylphenyl, 2, , 5,6-tetramethyl such as methyl phenyl group, an alkyl group (especially C _1-4 alkyl group) and in total 1 to 4 is substituted with a substituent a phenyl group which is selected from the lower-order oxidized group of the alkyl group A phenyl group fused with a cycloalkane ring such as 5-indanyl, 5-tetralinyl, 6-tetralinyl group; a phenyl group fused with a ring constituting a cyclic ether such as 3-phthalanyl, 4-isochromanyl, 5-isochromanyl group; Phenyl group condensed with lactone ring such as 4-phthalidyl group, 3-phthalidyl group; 4-methylnaphthalen-1-yl, 5-methylnaphthalen-1-yl, 6-methylnaphthalen-1-yl, 5-methylnaphthalene -2-yl, 6-methylnaphthalen-2-yl, 4,5-dimethylnaphthalen-1-yl, 5,6-dimethylnaphthalene - yl, 5,6-dimethyl-2-yl group such as an alkyl group (especially C _1-4 alkyl group) and in total 1-4 substituents selected from lower-order oxidized group of the alkyl group Substituted naphthyl group; naphthyl group fused with cycloalkane ring; naphthyl group fused with ring constituting cyclic ether; 5-methylpyridin-2-yl, 4-methylpyridin-2-yl, 2-methylpyridine- 4-yl, 2-methylpyridin-5-yl, 4,5-dimethylpyridin-2-yl, 8-methylquinolin-5-yl, 2-methylquinolin-5-yl, 2-methylquinolin-6-yl A nitrogen-containing aromatic cyclic group substituted with a total of 1 to 4 substituents selected from an alkyl group (particularly a C _1-4 alkyl group) and a lower oxidation group of the alkyl group, such as a group, oxygen-containing Aromatic cyclic group or sulfur-containing Aromatic cyclic group; nitrogen-containing aromatic cyclic group, oxygen-containing aromatic cyclic group or sulfur-containing aromatic cyclic group condensed with a cycloalkane ring; nitrogen-containing aromatic ring condensed with a ring constituting a cyclic ether A formula group, an oxygen-containing aromatic cyclic group or a sulfur-containing aromatic cyclic group.

（式中、Ｙ¹、Ｙ²は、同一又は異なって、前記式（５）で表される基を示す。Ｒ^A、Ｒ^B、Ｒ^C、Ｒ^Dは、同一又は異なって、水素原子、又は炭素数１〜６のハロゲン原子を有していてもよいアルキル基を示す。ｋは１〜３の整数を示す。ｋが２又は３の場合、複数個のＲ^C、Ｒ^Dはそれぞれ同一であっても異なっていてもよい。ｐは０又は１を示す。アダマンタン環は橋頭位以外の部位に置換基を有していてもよく、有していなくてもよい） Among the compounds represented by the formula (4), a compound represented by the following formula (17) is particularly preferable.

(Wherein Y ¹ and Y ² are the same or different and represent the group represented by the formula (5). R ^A , R ^B , R ^C and R ^D are the same or different and represent a hydrogen atom, Or an alkyl group which may have a halogen atom having 1 to 6 carbon atoms, k represents an integer of 1 to 3. When k is 2 or 3, a plurality of R ^C and R ^D are the same. Or p may be 0 or 1. The adamantane ring may or may not have a substituent at a site other than the bridgehead position.

  In these compounds, as the group represented by the formula (5), the groups exemplified as the representative examples are preferable. The substituent that the adamantane ring may have is the same as the substituent that the adamantane ring in the formula (1) may have. Among these, an alkyl group which may have a halogen atom, a halogen atom, a hydroxyl group which may be protected with a protecting group, and the like are preferable, and in particular, an alkyl group having 1 to 6 carbon atoms or 1 to 6 carbon atoms. The haloalkyl group is preferred.

  As a typical example of a compound represented by formula (4) having k = 1 and having one aromatic cyclic group represented by formula (5), 3- (4-methylphenyl) -1 , 1'-biadamantane, 3- (2-methylphenyl) -1,1'-biadamantane, 3- (4-isopropylphenyl) -1,1'-biadamantane, 3- (2-isopropylphenyl)- 1,1'-biadamantane, 3- (2-methyl-5-phenylphenyl) -1,1'-biadamantane, 3- (3,4-dimethylphenyl) -1,1'-biadamantane, 3- (2,5-dimethylphenyl) -1,1'-biadamantane, 3- (3-ethyl-4-methylphenyl) -1,1'-biadamantane, 3- (2-ethyl-5-methylphenyl) -1,1'-biadamantane, 3- (4 Ethyl-3-methylphenyl) -1,1'-biadamantane, 3- (5-ethyl-2-methylphenyl) -1,1'-biadamantane, 3- (3,4-diethylphenyl) -1, 1'-biadamantane, 3- (2,5-diethylphenyl) -1,1'-biadamantane, 3- (3,4-diisopropylphenyl) -1,1'-biadamantane, 3- [3,4 -Bis (hydroxymethyl) phenyl] -1,1'-biadamantane, 3- (2,3,5,6-tetramethylphenyl) -1,1'-biadamantane, 3- (4-hydroxymethylphenyl) -1,1'-biadamantane, 3- (3-phthalanyl) -1,1'-biadamantane, 3- (4-isochromanyl) -1,1'-biadamantane, 3- (5-isochromanyl) -1 , 1'-bi Damantane, 3- (5-indanyl) -1,1'-biadamantane, 3- (5-tetralinyl) -1,1'-biadamantane, 3- (4-cyclopentylphenyl) -1,1'-biadamantane 3- (4-cyclohexylphenyl) -1,1'-biadamantane, 3'-bromo-3- (3,4-dimethylphenyl) -1,1'-biadamantane, 3'-bromo-3- ( 3-phthalanyl) -1,1'-biadamantane, 3'-hydroxy-3- (3,4-dimethylphenyl) -1,1'-biadamantane, 3- (4,5-dimethylnaphthalen-1-yl ) -1,1'-biadamantane, arylbiadamantane derivatives such as 3- (5,6-dimethylnaphthalen-1-yl) -1,1'-biadamantane; aryl corresponding to these compounds Examples include 5,7-dimethylbiadamantane derivatives, aryl-5 ′, 7′-dimethylbiadamantane derivatives, aryl-5,5 ′, 7,7′-tetramethylbiadamantane derivatives, and the like.

  As a typical example of a compound represented by formula (4) having k = 1 and having two aromatic cyclic groups represented by formula (5), 3,3′-bis (4-methyl Phenyl) -1,1′-biadamantane, 3,3′-bis (2-methylphenyl) -1,1′-biadamantane, 3,3′-bis (4-isopropylphenyl) -1,1′- Biadamantane, 3,3′-bis (2-isopropylphenyl) -1,1′-biadamantane, 3,3′-bis (2-methyl-5-phenylphenyl) -1,1′-biadamantane, 3, , 3'-bis (3,4-dimethylphenyl) -1,1'-biadamantane, 3,3'-bis (2,5-dimethylphenyl) -1,1'-biadamantane, 3,3'- Bis (3-ethyl-4-methylphenyl) -1,1'-biadamant 3,3'-bis (2-ethyl-5-methylphenyl) -1,1'-biadamantane, 3,3'-bis (4-ethyl-3-methylphenyl) -1,1'-bi Adamantane, 3,3′-bis (5-ethyl-2-methylphenyl) -1,1′-biadamantane, 3,3′-bis (3,4-diethylphenyl) -1,1′-biadamantane, 3,3'-bis (2,5-diethylphenyl) -1,1'-biadamantane, 3,3'-bis (3,4-diisopropylphenyl) -1,1'-biadamantane, 3,3 ' -Bis [3,4-bis (hydroxymethyl) phenyl] -1,1'-biadamantane, 3,3'-bis (2,3,5,6-tetramethylphenyl) -1,1'-biadamantane 3,3'-bis (4-hydroxymethylphenyl)- , 1'-biadamantane, 3,3'-bis (3-phthalanyl) -1,1'-biadamantane, 3,3'-bis (4-isochromanyl) -1,1'-biadamantane, 3,3 '-Bis (5-isochromanyl) -1,1'-biadamantane, 3,3'-bis (5-indanyl) -1,1'-biadamantane, 3,3'-bis (5-tetralinyl) -1 , 1'-biadamantane, 3,3'-bis (4-cyclopentylphenyl) -1,1'-biadamantane, 3,3'-bis (4-cyclohexylphenyl) -1,1'-biadamantane, 3, , 3'-bis (4,5-dimethylnaphthalen-1-yl) -1,1'-biadamantane, 3,3'-bis (5,6-dimethylnaphthalen-1-yl) -1,1'- Diaryl bia daman such as bia damantan Tan derivatives; diaryl-5,7-dimethylbiadamantane derivatives, diaryl-5,5 ′, 7,7′-tetramethylbiadamantane derivatives, and the like corresponding to these compounds.

  As a representative example of a compound represented by formula (4) having k = 2 and having one aromatic cyclic group represented by formula (5), 3- (4-methylphenyl) -1 , 1 ′: 3 ′, 1 ″ -triadamantane, 3- (2-methylphenyl) -1,1 ′: 3 ′, 1 ″ -triadamantane, 3- (3,4-dimethylphenyl) -1,1 ': 3', 1 "-triadamantane, 3- (2,5-dimethylphenyl) -1,1 ': 3', 1" -triadamantane, 3- [3,4-bis (hydroxymethyl) phenyl] -1,1 ': 3', 1 "-triadamantane, 3- (2,3,5,6-tetramethylphenyl) -1,1 ': 3', 1" -triadamantane, 3- (4 5-dimethylnaphthalen-1-yl) -1,1 ′: 3 ′, 1 ″ -triadamantane, 3- (5 -Aryltriadamantane derivatives such as dimethylnaphthalen-1-yl) -1,1 ': 3', 1 "-triadamantane; aryl-5,5 ', 5", 7,7' corresponding to these compounds , 7 ″ -hexamethyltriadamantane derivatives and the like.

  As a typical example of the compound represented by the formula (4) having k = 2 and having two aromatic cyclic groups represented by the formula (5), 3,3 ″ -bis (4-methyl Phenyl) -1,1 ′: 3 ′, 1 ″ -triadamantane, 3,3 ″ -bis (2-methylphenyl) -1,1 ′: 3 ′, 1 ″ -triadamantane, 3,3 ″ -bis (3,4-dimethylphenyl) -1,1 ': 3', 1 "-triadamantane, 3,3" -bis (2,5-dimethylphenyl) -1,1 ': 3', 1 "-tri Adamantane, 3,3 ″ -bis [3,4-bis (hydroxymethyl) phenyl] -1,1 ′: 3 ′, 1 ″ -triadamantane, 3,3 ″ -bis (2,3,5,6- Tetramethylphenyl) -1,1 ': 3', 1 "-triadamantane, 3,3" -bis (4,5-dimethylnaphth Len-1-yl) -1,1 ': 3', 1 "-triadamantane, 3,3" -bis (5,6-dimethylnaphthalen-1-yl) -1,1 ': 3', 1 " -Diaryl triadamantane derivatives such as triadamantane; and diaryl-5,5 ', 5 ", 7,7', 7" -hexamethyltriadamantane derivatives corresponding to these compounds.

  As a representative example of a compound represented by formula (4) having k = 3 and one aromatic cyclic group represented by formula (5), 3- (4-methylphenyl) -1 , 1 ': 3', 1 ": 3", 1 "'-tetraadamantane, 3- (2-methylphenyl) -1, 1': 3 ', 1": 3 ", 1" "-tetra Adamantane, 3- (3,4-dimethylphenyl) -1,1 ': 3', 1 ": 3", 1 "'-tetraadamantane, 3- (2,5-dimethylphenyl) -1,1' : 3 ', 1 ": 3", 1 ""-tetraadamantane, 3- [3,4-bis (hydroxymethyl) phenyl] -1, 1': 3 ', 1 ": 3", 1 " '-Tetraadamantane, 3- (2,3,5,6-tetramethylphenyl) -1,1': 3 ', 1 ": 3", 1 "'-tetraa Mantane, 3- (4,5-dimethylnaphthalen-1-yl) -1,1 ′: 3 ′, 1 ″: 3 ″, 1 ′ ″-tetraadamantane, 3- (5,6-dimethylnaphthalene-1 -Yl) -1,1 ': 3', 1 ": 3", aryltetraadamantane derivatives such as 1 ""-tetraadamantane; aryl-5,5 ', 5 ", 5' corresponding to these compounds ″ ″, 7, 7 ′, 7 ″, 7 ″ ″-octamethyltetraadamantane derivatives and the like.

  As a typical example of a compound represented by formula (4) having k = 3 and having two aromatic cyclic groups represented by formula (5), 3,3 ′ ″-bis (4 -Methylphenyl) -1,1 ': 3', 1 ": 3", 1 ""-tetraadamantane, 3,3 ""-bis (2-methylphenyl) -1,1 ': 3', 1 ″: 3 ″, 1 ″ ″-tetraadamantane, 3,3 ″ ″-bis (3,4-dimethylphenyl) -1,1 ′: 3 ′, 1 ″: 3 ″, 1 ″ ″ − Tetraadamantane, 3,3 ″ ″-bis (2,5-dimethylphenyl) -1,1 ′: 3 ′, 1 ″: 3 ″, 1 ″ ″-tetraadamantane, 3,3 ″ ″-bis [3,4-Bis (hydroxymethyl) phenyl] -1,1 ′: 3 ′, 1 ″: 3 ″, 1 ″ ″-tetraadamantane, 3,3 ″ ″-bis (2 3,5,6-tetramethylphenyl) -1,1 ′: 3 ′, 1 ″: 3 ″, 1 ″ ″-tetraadamantane, 3,3 ″ ″-bis (4,5-dimethylnaphthalene-1 -Yl) -1,1 ': 3', 1 ": 3", 1 ""-tetraadamantane, 3,3 ""-bis (5,6-dimethylnaphthalen-1-yl) -1,1 ': 3', 1 ": 3", diaryltetraadamantane derivatives such as 1 ""-tetraadamantane; diaryl-5,5 ', 5 ", 5" ", 7,7' corresponding to these compounds , 7 ″, 7 ′ ″-octamethyltetraadamantane derivatives and the like.

  The oxidation of the aryl polyadamantane derivative represented by the formula (4) may be carried out by any of an equivalent reaction method using an oxidant, a method using oxygen or an organic peracid as a oxygen source and a catalyst, and the like. Examples of the oxidizing agent include generally used oxidizing agents such as anhydrous nitrous acid, nitric acid, sulfuric acid, sodium hypochlorite, potassium persulfate, copper acetate, chromium oxide, manganese dioxide, potassium permanganate, potassium ferricyanide, Potassium chromate, nickel peroxide, ceric ammonium nitrate, ruthenium tetroxide, osmium tetroxide, palladium, organic peracids (m-chloroperbenzoic acid, perbenzoic acid, peracetic acid, t-butyl hydroperoxide, etc.), peroxidation Examples include hydrogen.

  As a catalyst used with oxygen or an organic peracid, a metal compound is mentioned, for example. Although it does not specifically limit as a metal element which comprises a metal compound, The periodic table 2-15 group metal element is used in many cases. In this specification, boron B is also included in the metal element. For example, as the metal element, a periodic table group 2 element (Mg, Ca, Sr, Ba, etc.), a group 3 element (Sc, lanthanoid element, actinoid element, etc.), a group 4 element (Ti, Zr, Hf, etc.), 5 Group elements (V, Nb, etc.), Group 6 elements (Cr, Mo, W, etc.), Group 7 elements (Mn, Tc, Re, etc.), Group 8 elements (Fe, Ru, etc.), Group 9 elements (Co, Rh, etc.) Group 10 elements (Ni, Pd, Pt, etc.), Group 11 elements (Cu, etc.), Group 12 elements (Zn, etc.), Group 13 elements (B, Al, In, etc.), Group 14 elements (Sn, Pb, etc.) Etc.), group 15 elements (Sb, Bi, etc.) and the like. Preferred metal elements include transition metal elements (periodic group 3-12 elements). Of these, silver, copper, vanadium, molybdenum, iron, nickel, cobalt, tungsten, manganese, rhenium, ruthenium, cerium, titanium, zirconium and the like are preferable. Boron, tellurium, bismuth, arsenic and tin are also preferable. The valence of the metal element is not particularly limited, and is about 0 to 6, for example.

Examples of the metal compound include simple substances, hydroxides, oxides (including composite oxides), halides (fluorides, chlorides, bromides, iodides), oxo acid salts (eg, nitrates, sulfates) of the above metal elements. , Phosphates, borates, carbonates, etc.), inorganic compounds such as isopolyacid salts, heteropolyacid salts; organic acid salts (eg acetate, propionate, cyanate, naphthenate, stearic acid) Salt) and organic compounds such as complexes. The ligands constituting the complex include OH (hydroxo), alkoxy (methoxy, ethoxy, propoxy, butoxy, etc.), acyl (acetyl, propionyl, etc.), alkoxycarbonyl (methoxycarbonyl, ethoxycarbonyl, etc.), acetylacetonato , Cyclopentadienyl group, halogen atom (chlorine, bromine, etc.), CO, CN, oxygen atom, H ₂ O (aquo), phosphine (triarylphosphine such as triphenylphosphine), phosphorus compound, NH ₃ (ammine) ), NO, NO ₂ (nitro), NO ₃ (nitrato), nitrogen-containing compounds such as ethylenediamine, diethylenetriamine, pyridine and phenanthroline.

  Specific examples of the metal compound include, for example, a cobalt compound, inorganic compounds such as cobalt hydroxide, cobalt oxide, cobalt chloride, cobalt bromide, cobalt nitrate, cobalt sulfate, and cobalt phosphate; cobalt acetate, naphthene Examples thereof include organic acid salts such as cobalt acid and cobalt stearate; divalent or trivalent cobalt compounds such as complexes such as cobalt acetylacetonate. Examples of vanadium compounds include inorganic compounds such as vanadium hydroxide, vanadium oxide, vanadium chloride, vanadyl chloride, vanadium sulfate, vanadyl sulfate, and sodium vanadate; complexes such as vanadium acetylacetonate and vanadylacetylacetonate Examples thereof include divalent to pentavalent vanadium compounds. Examples of other metal element compounds include compounds corresponding to the cobalt or vanadium compounds. A metal compound can be used individually or in combination of 2 or more types. In particular, when a cobalt compound and a manganese compound are combined, the reaction rate is often significantly improved. It is also preferable to use a combination of a plurality of metal compounds having different valences (for example, a divalent metal compound and a trivalent metal compound).

  Also, catalyst systems combining bromine compounds such as bromine and bromide salts with transition metal compounds, such as bromine compounds (hydrogen bromide, lithium bromide, sodium bromide, potassium bromide, cobalt bromide, manganese bromide, etc. ) And transition metal compounds [Group 3 elements (periodanoid elements, actinoid elements, etc.), Group 4 elements (Ti, Zr, etc.), Group 5 elements (V, Nb, etc.), Group 6 elements (Cr, Mo, W, etc.) Etc.), Group 7 elements (Mn, Tc, Re, etc.), Group 8 elements (Fe, Ru, etc.), Group 9 elements (Co, etc.), Group 10 elements (Ni, etc.), Group 11 elements (Cu, etc.)] And manganese compounds (manganese chloride, manganese acetate, manganese acetylacetonate, etc.), especially bromine compounds (especially bromide salts such as sodium bromide) / cobalt compounds / manganese compounds Ranaru catalyst system is preferred to indicate a high catalytic activity. When such a catalyst system is used, there is an advantage that it is possible to derive from a compound having a 3,4-dimethylphenyl group to a compound having a phenyl group having a ring constituting a cyclic acid anhydride in one pot.

  As the oxidation, a method using oxygen and a strong base can be employed. Examples of the strong base include alkali metal hydroxides such as sodium hydroxide, potassium hydroxide, and lithium hydroxide.

  Furthermore, in the oxidation reaction using oxygen, N-hydroxyphthalimide, N-acetoxyphthalimide, N-hydroxysuccinimide, N-hydroxy-1,8-naphthalenecarboxylic acid imide, N, N′-dihydroxy-1,8 are used as catalysts. A cyclic imide compound such as 4,5-naphthalenetetracarboxylic acid diimide may also be used. In this case, it is preferable to use the metal compound, particularly a cobalt compound and / or a manganese compound, as a promoter.

  Further, 2,2,6,6-tetramethylpiperazine-N-oxide-organic peracid reaction system, osmium tetroxide-N-methylmorpholine oxide reaction system, aldehyde (acetaldehyde, benzaldehyde, etc.) were used as the oxidation system. Catalytic oxidation reaction systems are also preferred.

  When a catalyst is used in the oxidation reaction, the amount of the catalyst used varies depending on the type of catalyst, the type of raw material compound, and the like, but the amount usually used in a general oxidation reaction can be employed. For example, when a catalyst in which the bromine compound, a transition metal compound (such as a cobalt compound) and a manganese compound are used as a catalyst, the amount of the bromine compound used is 1 mol of the compound represented by the formula (4). The amount of the transition metal compound used is usually a compound represented by the formula (4): 0.00001 to 5 mol, preferably 0.0001 to 1 mol, more preferably about 0.001 to 0.5 mol. It is usually 0.00001 to 5 mol, preferably 0.0001 to 1 mol, and more preferably about 0.001 to 0.5 mol with respect to 1 mol. It is 0.00001-5 mol normally with respect to 1 mol of compounds represented, Preferably it is 0.0001-1 mol, More preferably, it is about 0.001-0.5 mol.

  In the reaction system, a radical generator and a radical reaction accelerator may be present as necessary to promote the reaction. Examples of such components include halogen, peroxide, aldehyde, nitric acid and the like.

  The oxidation reaction is carried out in the presence or absence of a solvent inert to the reaction. The solvent varies depending on the type of oxidizing agent, the type of raw material compound, and the like. For example, halogenated hydrocarbons such as methylene chloride, 1,2-dichloroethane, chloroform, carbon tetrachloride; diethyl ether, dimethoxyethane, tetrahydrofuran Chain, cyclic ethers such as dioxane, nitriles such as acetonitrile and benzonitrile, esters such as ethyl acetate, carboxylic acids such as acetic acid, amides such as N, N-dimethylformamide, ketones such as acetone and methyl ethyl ketone, nitromethane and nitrobenzene Nitro compounds such as; mixtures thereof and the like. In particular, in a catalytic oxygen oxidation reaction, nitriles such as acetonitrile and benzonitrile; esters such as ethyl acetate; carboxylic acids such as acetic acid are preferable, and carboxylic acid solvents are particularly preferable.

  The reaction temperature in the oxidation reaction varies depending on the type of oxidizing agent, the type of raw material compound, and the like. For example, when an oxidizing agent other than oxygen (such as an oxidizing agent containing a metal) is used, for example, −50 ° C. to 300 ° C. ° C, preferably about -10 ° C to 150 ° C. In a reaction using an organic peracid or hydrogen peroxide as an oxidizing agent and a metal compound as a catalyst, the reaction temperature is, for example, -50 ° C to 200 ° C, preferably about -20 ° C to 100 ° C. In a reaction using oxygen as an oxidizing agent and a bromine compound / transition metal compound (cobalt compound, etc.) / Manganese compound catalyst system as a catalyst, for example, 0 to 250 ° C., preferably about 50 to 200 ° C., oxygen In the reaction using other than the above as the oxidizing agent, for example, 0 ° C. to 200 ° C., preferably about 20 ° C. to 150 ° C.

  When oxygen is used as the oxidizing agent, pure oxygen may be used, or oxygen or air diluted with an inert gas (for example, nitrogen, helium, argon, etc.) may be used. Oxygen may be generated in the system and used. The oxygen concentration in the supplied oxygen-containing gas is, for example, about 3 to 100 mol%. The reaction may be performed either in the presence of oxygen or in the circulation of oxygen. The reaction pressure may be any of normal pressure, reduced pressure, and increased pressure. The oxidation reaction may be carried out by any system such as batch system, semi-batch system, and continuous system.

  As the hydrolysis of the aryl polyadamantane derivative represented by the formula (4), any method such as acid hydrolysis and alkali hydrolysis can be employed. Examples of acids used in the acid hydrolysis include inorganic acids such as hydrochloric acid and sulfuric acid, sulfonic acids such as p-toluenesulfonic acid, benzenesulfonic acid, naphthalenesulfonic acid, methanesulfonic acid, and trifluoromethanesulfonic acid, and strong acidic cations. Exchange resin etc. are mentioned. Examples of the alkali used in the alkali hydrolysis include alkali metal-containing compounds such as alkali metal hydroxides such as sodium hydroxide and potassium hydroxide. The amount of alkali used and the amount of water used can be appropriately selected depending on the number of carboxyl groups to be generated. A catalytic amount of the acid may be used. The reaction is carried out in the presence of water, but an organic solvent may be added to the reaction system in order to increase the solubility of the reaction components. Examples of the organic solvent include water-soluble organic solvents such as alcohols such as methanol and ethanol and amides such as N, N-dimethylformamide. The reaction temperature is, for example, 20 to 300 ° C, preferably about 50 to 200 ° C. Hydrolysis may be carried out by any method such as batch method, semi-batch method, and continuous method. In the case of alkaline hydrolysis, after completion of the reaction, a compound having a free carboxyl group can be obtained by neutralization using an acid.

Oxidation or hydrolysis of the aryl polyadamantane derivative represented by the formula (4) produces the corresponding compound represented by the formula (6). In formula (6), R ^1b , R ^2b , R ^3b , R ^4b , R ^5b and R ^6b are the same or different and represent a hydrogen atom, an aromatic cyclic group represented by the formula (2), or others. The substituent of is shown. However, at least one of R ^1b , R ^2b , R ^3b , R ^4b , R ^5b and R ^6b is a group represented by the formula (2). k represents an integer of 1 to 3. When k is 2 or 3, the plurality of R ^4b and R ^6b may be the same or different. The adamantane ring may have a substituent at a site other than the bridge head position. Other substituents other than R ^1b , R ^2b , R ^3b , R ^4b , R ^5b , R ^6b and other substituents that may be present other than the bridge head of the adamantane ring include those represented by the formula (2) in the formula (1). ) Or the same as the substituent which the adamantane ring other than the group represented by (3) may have.

  The reaction product [compound represented by the formula (6)] is generally separated by liquid property adjustment, concentration, filtration, washing, extraction, crystallization, recrystallization, distillation, sublimation, salting out, column chromatography and the like. It can be separated and purified by a purification means. In particular, when the yield is high, the target product can be separated by liquid property adjustment, concentration, filtration, washing and the like. When there are many reaction by-products, the target product can be separated by crystallization, recrystallization, column chromatography or the like. In addition, crystallization is performed by, for example, treating the crude product with a crystallization solvent (ether such as tetrahydrofuran, aromatic hydrocarbon such as benzene, toluene and xylene, amide such as N, N-dimethylformamide; halogenated hydrocarbon such as chloroform. , A mixed solvent thereof, etc.) (including heating and dissolution), concentrating as necessary, and then cooling to precipitate crystals. Further, crystallization or recrystallization may be performed by combining a good solvent and a poor solvent (for example, methanol, acetone, water, etc.) of the target compound.

  Among the compounds represented by the formula (1) of the present invention, the compound in which the group represented by the formula (3) is bonded to the adamantane ring is, for example, an aryl polyadamantane derivative represented by the formula (7). It can manufacture by oxidizing.

In formula (7), R ^1a , R ^2a , R ^3a , R ^4a , R ^5a , and R ^6a are the same or different and represent a hydrogen atom, an aromatic cyclic group represented by formula (8), or other Indicates a substituent. However, at least one of R ^1a , R ^2a , R ^3a , R ^4a , R ^5a , R ^6a is a group represented by the formula (8). k represents an integer of 1 to 3. When k is 2 or 3, the plurality of R ^4a and R ^6a may be the same or different. The adamantane ring may have a substituent at a site other than the bridge head position. In formula (8), ring Z ² represents an aromatic ring. X ² and X ³ each represents a group capable of forming a cyclic acid anhydride group together with one or more atoms constituting the ring Z ² by oxidation. X ² and X ³ may be bonded to each other to form a ring together with one or more atoms constituting the ring Z ² . n represents an integer of 1 or more. When n is 2 or more, the plurality of X ² and X ³ may be the same or different. The aromatic ring may have a substituent other than the group shown in the formula.

Ring Z ² is the same as described above. X ² and X ³ are the same as the group of X ¹ that can be converted to a carboxyl group by oxidation, but the positional relationship between X ² and X ³ is one or more atoms constituting the ring Z ² It is necessary to be in a position where a cyclic acid anhydride group can be formed. Usually, X ² and X ³ are in a positional relationship of 1, 2 or 1, 3 positions. Examples of the ring formed by combining X ² and X ³ together with one or more atoms constituting the ring Z ² include, for example, a cycloalkene ring (particularly a 5-6 membered cycloalkene ring), a cyclic ether (particularly, 5- to 6-membered cyclic ether; dihydrofuran ring, dihydropyran ring and the like) and a 5- to 6-membered lactone ring. R ^1a , R ^2a , R ^3a , R ^4a , R ^5a , R ^6a , and the substituents that may be present other than the bridge head position of the adamantane ring are the same as those in the above formula (4).

Typical examples of the aromatic cyclic group represented by the formula (8) include 3,4-dimethylphenyl, 3-ethyl-4-methylphenyl, 4-ethyl-3-methylphenyl, 3, 4-diethylphenyl, 3,4-diisopropylphenyl, 3,4-bis (hydroxymethyl) phenyl, 3,4-diformylphenyl, 2,3,5-trimethylphenyl, 2,3,6-trimethylphenyl, 2 Substituted with a total of 2 to 4 substituents selected from alkyl groups (especially C _1-4 alkyl groups) and lower oxidation groups of the alkyl groups, such as 1,3,5,6-tetramethylphenyl group Phenyl group; phenyl group fused with cycloalkane ring such as 5-indanyl, 5-tetralinyl, 6-tetralinyl group; 3-phthalanyl, 4-isochromanyl, 5-isochromanyl group, etc. A phenyl group in which a ring constituting a cyclic ether is condensed; a phenyl group in which a lactone ring such as a 4-phthalidoyl group or a 3-phthalidoyl group is condensed; 4,5-dimethylnaphthalen-1-yl, 5,6-dimethylnaphthalene-1 A total of 2 to 4 substituents selected from alkyl groups (especially C _1-4 alkyl groups) and lower oxidation groups of the alkyl groups, such as -yl and 5,6-dimethylnaphthalen-2-yl groups Substituted naphthyl group; naphthyl group fused with cycloalkane ring; naphthyl group fused with ring constituting cyclic ether; alkyl group such as 4,5-dimethylpyridin-2-yl group (especially C _1-4 alkyl) Group) and a nitrogen-containing aromatic cyclic group, an oxygen-containing aromatic cyclic group or a sulfur-containing aromatic cyclic group substituted with a total of 2 to 4 substituents selected from the lower oxidation groups of the alkyl group Cyclo Nitrogen-containing aromatic cyclic group, oxygen-containing aromatic cyclic group or sulfur-containing aromatic cyclic group fused with a lucan ring; nitrogen-containing aromatic cyclic group condensed with a ring constituting a cyclic ether, oxygen-containing aromatic Examples thereof include a cyclic group and a sulfur-containing aromatic cyclic group.

（式中、Ｙ³、Ｙ⁴は、同一又は異なって、前記式（８）で表される基を示す。Ｒ^A、Ｒ^B、Ｒ^C、Ｒ^Dは、同一又は異なって、水素原子、又は炭素数１〜６のハロゲン原子を有していてもよいアルキル基を示す。ｋは１〜３の整数を示す。ｋが２又は３の場合、複数個のＲ^C、Ｒ^Dはそれぞれ同一であっても異なっていてもよい。ｐは０又は１を示す。アダマンタン環は橋頭位以外の部位に置換基を有していてもよく、有していなくてもよい） Among the compounds represented by the formula (7), a compound represented by the following formula (18) is particularly preferable.

(Wherein Y ³ and Y ⁴ are the same or different and represent the group represented by the formula (8). R ^A , R ^B , R ^C and R ^D are the same or different and represent a hydrogen atom, Or an alkyl group which may have a halogen atom having 1 to 6 carbon atoms, k represents an integer of 1 to 3. When k is 2 or 3, a plurality of R ^C and R ^D are the same. Or p may be 0 or 1. The adamantane ring may or may not have a substituent at a site other than the bridgehead position.

  As the group represented by the formula (8), groups exemplified as the typical examples are preferable. The substituent that the adamantane ring may have is the same as the substituent that the adamantane ring in the formula (1) may have. Among these, an alkyl group which may have a halogen atom, a halogen atom, a hydroxyl group which may be protected with a protecting group, and the like are preferable, and in particular, an alkyl group having 1 to 6 carbon atoms or 1 to 6 carbon atoms. The haloalkyl group is preferred.

  As a typical example of the compound represented by the formula (7) having k = 1 and one aromatic cyclic group represented by the formula (8), 3- (3,4-dimethylphenyl) -1,1'-biadamantane, 3- (3-ethyl-4-methylphenyl) -1,1'-biadamantane, 3- (4-ethyl-3-methylphenyl) -1,1'-biadamantane 3- (3,4-diethylphenyl) -1,1'-biadamantane, 3- (3,4-diisopropylphenyl) -1,1'-biadamantane, 3- [3,4-bis (hydroxymethyl) ) Phenyl] -1,1'-biadamantane, 3- (2,3,5,6-tetramethylphenyl) -1,1'-biadamantane, 3- (3-phthalanyl) -1,1'-bi Adamantane, 3- (4-isochromanyl) -1,1'-bi Damantane, 3- (5-isochromanyl) -1,1′-biadamantane, 3- (5-indanyl) -1,1′-biadamantane, 3- (5-tetralinyl) -1,1′-biadamantane, 3'-bromo-3- (3,4-dimethylphenyl) -1,1'-biadamantane, 3'-bromo-3- (3-phthalanyl) -1,1'-biadamantane, 3'-hydroxy- 3- (3,4-dimethylphenyl) -1,1'-biadamantane, 3- (4,5-dimethylnaphthalen-1-yl) -1,1'-biadamantane, 3- (5,6-dimethyl) Arylbiadamantane derivatives such as naphthalen-1-yl) -1,1'-biadamantane; aryl-5,7-dimethylbiadamantane derivatives corresponding to these compounds, aryl-5 ', 7'-dimethyl Adamantane derivatives, aryl-5,5 ', 7,7'-tetramethyl biadamantane derivatives.

  As a typical example of the compound represented by the formula (7) having k = 1 and having two aromatic cyclic groups represented by the formula (8), 3,3′-bis (3,4 -Dimethylphenyl) -1,1'-biadamantane, 3,3'-bis (3-ethyl-4-methylphenyl) -1,1'-biadamantane, 3,3'-bis (4-ethyl-3) -Methylphenyl) -1,1'-biadamantane, 3,3'-bis (3,4-diethylphenyl) -1,1'-biadamantane, 3,3'-bis (3,4-diisopropylphenyl) -1,1'-biadamantane, 3,3'-bis [3,4-bis (hydroxymethyl) phenyl] -1,1'-biadamantane, 3,3'-bis (2,3,5,6 -Tetramethylphenyl) -1,1'-biadamantane, 3,3'-bis (3- Taranyl) -1,1'-biadamantane, 3,3'-bis (4-isochromanyl) -1,1'-biadamantane, 3,3'-bis (5-isochromanyl) -1,1'-biadamantane 3,3′-bis (5-indanyl) -1,1′-biadamantane, 3,3′-bis (5-tetralinyl) -1,1′-biadamantane, 3,3′-bis (4 Diarylbiadamantane derivatives such as 5-dimethylnaphthalen-1-yl) -1,1′-biadamantane and 3,3′-bis (5,6-dimethylnaphthalen-1-yl) -1,1′-biadamantane Diaryl-5,7-dimethylbiadamantane derivatives, diaryl-5 ', 7'-dimethylbiadamantane derivatives, diaryl-5,5', 7,7'-tetramethylbias corresponding to these compounds; Such as Kalimantan derivatives.

  As a typical example of a compound having k = 2 and one aromatic cyclic group represented by the formula (8) among the compounds represented by the formula (7), 3- (3,4-dimethylphenyl) -1,1 ': 3', 1 "-triadamantane, 3- [3,4-bis (hydroxymethyl) phenyl] -1,1 ': 3', 1" -triadamantane, 3- (2,3 , 5,6-tetramethylphenyl) -1,1 ′: 3 ′, 1 ″ -triadamantane, 3- (4,5-dimethylnaphthalen-1-yl) -1,1 ′: 3 ′, 1 ″- Aryl triadamantane derivatives such as triadamantane, 3- (5,6-dimethylnaphthalen-1-yl) -1,1 ′: 3 ′, 1 ″ -triadamantane; aryl-5,5 ′ corresponding to these compounds; , 5 ″, 7,7 ′, 7 ″ -hexamethyltriadamantan Body and the like.

  As a typical example of the compound represented by the formula (7) having k = 2 and having two aromatic cyclic groups represented by the formula (8), 3,3 ″ -bis (3,4 -Dimethylphenyl) -1,1 ': 3', 1 "-triadamantane, 3,3" -bis [3,4-bis (hydroxymethyl) phenyl] -1,1 ': 3', 1 "-tri Adamantane, 3,3 ″ -bis (2,3,5,6-tetramethylphenyl) -1,1 ′: 3 ′, 1 ″ -triadamantane, 3,3 ″ -bis (4,5-dimethylnaphthalene- 1-yl) -1,1 ′: 3 ′, 1 ″ -triadamantane, 3,3 ″ -bis (5,6-dimethylnaphthalen-1-yl) -1,1 ′: 3 ′, 1 ″ -tri Diaryltriadamantane derivatives such as adamantane; diaryl-5,5 ', corresponding to these compounds '', 7,7 ', 7 "- such as hexamethyltrisiloxane adamantane derivatives.

  As a typical example of a compound having k = 3 and one aromatic cyclic group represented by the formula (8) among the compounds represented by the formula (7), 3- (3,4-dimethylphenyl) -1,1 ': 3', 1 ": 3", 1 "'-tetraadamantane, 3- [3,4-bis (hydroxymethyl) phenyl] -1,1': 3 ', 1": 3 ", 1" '-tetraadamantane, 3- (2,3,5,6-tetramethylphenyl) -1,1': 3 ', 1 ": 3", 1 ""-tetraadamantane, 3- (4,5-dimethylnaphthalen-1-yl) -1,1 ′: 3 ′, 1 ″: 3 ″, 1 ′ ″-tetraadamantane, 3- (5,6-dimethylnaphthalen-1-yl)- 1,1 ′: 3 ′, 1 ″: 3 ″, 1 ′ ″-aryltetraadamantane derivatives such as tetraadamantane; Aryl-5,5 corresponding to the compound ', 5 ", 5' '', 7,7 ', 7", 7' '' - such as octamethyltetrasiloxane adamantane derivatives.

  As a typical example of a compound represented by the formula (7) having k = 3 and having two aromatic cyclic groups represented by the formula (8), 3,3 ′ ″-bis (3 , 4-Dimethylphenyl) -1,1 ′: 3 ′, 1 ″: 3 ″, 1 ″ ″-tetraadamantane, 3,3 ″ ″-bis [3,4-bis (hydroxymethyl) phenyl] − 1,1 ′: 3 ′, 1 ″: 3 ″, 1 ″ ″-tetraadamantane, 3,3 ″ ″-bis (2,3,5,6-tetramethylphenyl) -1,1 ′: 3 ′, 1 ″: 3 ″, 1 ″ ″-tetraadamantane, 3,3 ″ ″-bis (4,5-dimethylnaphthalen-1-yl) -1,1 ′: 3 ′, 1 ″: 3 ″ , 1 ″ ″-tetraadamantane, 3,3 ″ ″-bis (5,6-dimethylnaphthalen-1-yl) -1,1 ′: 3 ′, 1 ″: 3 ″, 1 ′ Diaryltetraadamantane derivatives such as '-tetraadamantane; diaryl-5,5', 5 ", 5" ', 7,7', 7 ", 7" "-octamethyltetraadamantane derivatives corresponding to these compounds Etc.

  The oxidation of the aryl polyadamantane derivative represented by the formula (7) can be carried out in the same manner as the oxidation of the aryl polyadamantane derivative represented by the above formula (4). In this case, it is preferable to carry out the reaction in the presence of a dehydrating agent (dehydrating agent) in the reaction system or by distilling off water using a dehydrating machine (dehydrating apparatus such as Dean Stark).

  Examples of the dehydrating agent include acetic anhydride, propionic anhydride, butanoic anhydride, trichloroacetic anhydride, monochloroacetic anhydride, carboxylic acid anhydrides such as trimellitic anhydride, and the like. Among these, acetic anhydride is particularly preferable. The usage-amount of an anhydrous agent is 0.1-1000 mol with respect to 1 mol of compounds represented by Formula (7), Preferably it is 1-100 mol, More preferably, it is about 2-20 mol. The reaction temperature in the case of using an anhydrous agent is, for example, about 20 to 200 ° C, preferably about 50 to 150 ° C.

  When the oxidation reaction is performed using a dehydrator, the reaction temperature is, for example, 20 ° C. or higher, preferably 50 ° C. or higher, more preferably 100 ° C. or higher (particularly 200 ° C. or higher). The upper limit of the reaction temperature is, for example, about 300 ° C., preferably about 270 ° C. In the case of using a dehydrator, an acid (for example, hydrochloric acid, sulfuric acid, p-toluenesulfonic acid, etc.) may be present in the reaction system in order to promote the reaction.

  In addition, as described above, a catalyst system in which a bromine compound such as bromine or bromide salt is combined with a transition metal compound, particularly a catalyst comprising a bromine compound (especially bromide salt such as sodium bromide) / cobalt compound / manganese compound. When a method of oxidizing with oxygen using a system is employed, a compound represented by formula (9) can be converted from a compound represented by formula (7) in one pot without using a dehydrating agent or a dehydrating machine. Moreover, it can be produced with a high yield.

By the reaction, an aryl polyadamantane derivative having a corresponding acid anhydride group represented by the formula (9) is generated. In formula (9), R ^1b , R ^2b , R ^3b , R ^4b , R ^5b and R ^6b are the same or different and represent a hydrogen atom, an aromatic cyclic group represented by formula (3), or other Indicates a substituent. However, at least one of R ^1b , R ^2b , R ^3b , R ^4b , R ^5b and R ^6b is a group represented by the formula (3). k represents an integer of 1 to 3. When k is 2 or 3, the plurality of R ^4b and R ^6b may be the same or different. The adamantane ring may have a substituent at a site other than the bridge head position. The other substituents in R ^1b , R ^2b , R ^3b , R ^4b , R ^5b , R ^6b and the substituents that may be present other than the bridge head position of the adamantane ring are the same as in the case of the above formula (6). . Separation and purification of the reaction product can be performed in the same manner as in the oxidation of the arylpolyadamantane derivative represented by the above formula (4).

  Of the compounds represented by the formula (1) of the present invention, the compound in which the group represented by the formula (3) is bonded to the adamantane ring is obtained by dehydrating the compound represented by the formula (10). It can also be manufactured by attaching to.

In the formula (10), R ^1c , R ^2c , R ^3c , R ^4c , R ^5c , R ^6c are the same or different and are a hydrogen atom, an aromatic cyclic group represented by the formula (11), or other The substituent of is shown. However, at least one of R ^1c , R ^2c , R ^3c , R ^4c , R ^5c and R ^6c is a group represented by the formula (11). k represents an integer of 1 to 3. When k is 2 or 3, the plurality of R ^4c and R ^6c may be the same or different. The adamantane ring may have a substituent at a site other than the bridge head position. In formula (11), ring Z ² represents an aromatic ring. n represents an integer of 1 or more. The aromatic ring may have a substituent other than the group shown in the formula.

Ring Z ² is the same as described above. As the positional relationship between the two carboxyl groups represented by the formula (11), it is necessary to be at a position where a cyclic acid anhydride group can be formed with one or more atoms constituting the ring Z ² . Usually, the two carboxyl groups are in the 1, 2, or 1, 3 position. Other substituents in R ^1c , R ^2c , R ^3c , R ^4c , R ^5c , and R ^6c and substituents that may be present other than the bridge head position of the adamantane ring are R ¹ , R in the formula (1) ² , R ³ , R ⁴ , R ⁵ , R ⁶ are the same as other substituents and substituents that may be present other than the bridge head position of the adamantane ring.

  Typical examples of the aromatic cyclic group represented by the formula (11) include 3,4-dicarboxyphenyl, 2,3,5-tricarboxyphenyl, and 2,3,6-tricarboxyphenyl. Phenyl groups substituted with 2 to 4 carboxyl groups such as 2,3,5,6-tetracarboxyphenyl group; 4,5-dicarboxynaphthalen-1-yl, 5,6-dicarboxynaphthalene-1- Naphthyl group substituted by 2 to 4 carboxyl groups such as yl, 5,6-dicarboxynaphthalen-2-yl group; 2 to 4 carboxyl groups such as 4,5-dicarboxypyridin-2-yl group Or a nitrogen-containing aromatic cyclic group, an oxygen-containing aromatic cyclic group, or a sulfur-containing aromatic cyclic group.

（式中、Ｙ⁵、Ｙ⁶は、同一又は異なって、前記式（１１）で表される基を示す。Ｒ^A、Ｒ^B、Ｒ^C、Ｒ^Dは、同一又は異なって、水素原子、又は炭素数１〜６のハロゲン原子を有していてもよいアルキル基を示す。ｋは１〜３の整数を示す。ｋが２又は３の場合、複数個のＲ^C、Ｒ^Dはそれぞれ同一であっても異なっていてもよい。ｐは０又は１を示す。アダマンタン環は橋頭位以外の部位に置換基を有していてもよく、有していなくてもよい） Among the compounds represented by the formula (10), a compound represented by the following formula (19) is particularly preferable.

(Wherein Y ⁵ and Y ⁶ are the same or different and represent the group represented by the formula (11). R ^A , R ^B , R ^C and R ^D are the same or different and represent a hydrogen atom, Or an alkyl group which may have a halogen atom having 1 to 6 carbon atoms, k represents an integer of 1 to 3. When k is 2 or 3, a plurality of R ^C and R ^D are the same. Or p may be 0 or 1. The adamantane ring may or may not have a substituent at a site other than the bridgehead position.

  As the group represented by the formula (11), groups exemplified as the typical examples are preferable. The substituent that the adamantane ring may have is the same as the substituent that the adamantane ring in the formula (1) may have. Among these, an alkyl group which may have a halogen atom, a halogen atom, a hydroxyl group which may be protected with a protecting group, and the like are preferable, and in particular, an alkyl group having 1 to 6 carbon atoms or 1 to 6 carbon atoms. The haloalkyl group is preferred.

  As a typical example of the compound represented by the formula (10) having k = 1 and one aromatic cyclic group represented by the formula (11), 3- (3,4-dicarboxyphenyl) ) -1,1'-biadamantane, 3- (2,3,5,6-tetracarboxyphenyl) -1,1'-biadamantane, 3'-bromo-3- (3,4-dicarboxyphenyl) -1,1'-biadamantane, 3'-hydroxy-3- (3,4-dicarboxyphenyl) -1,1'-biadamantane, 3- (4,5-dicarboxynaphthalen-1-yl)- Dicarboxyarylbiadamantane derivatives such as 1,1′-biadamantane, 3- (5,6-dicarboxynaphthalen-1-yl) -1,1′-biadamantane; dicarboxyaryl-corresponding to these compounds 5,7- Methyl biadamantane derivatives, dicarboxylate aryl -5 ', 7'-dimethyl biadamantane derivatives, dicarboxylate aryl-5,5', 7,7'-tetramethyl biadamantane derivatives.

  As a typical example of the compound represented by the formula (10) having k = 1 and having two aromatic cyclic groups represented by the formula (11), 3,3′-bis (3,4 -Dicarboxyphenyl) -1,1'-biadamantane, 3,3'-bis (2,3,5,6-tetracarboxyphenyl) -1,1'-biadamantane, 3,3'-bis (4 , 5-dicarboxynaphthalen-1-yl) -1,1′-biadamantane, 3,3′-bis (5,6-dicarboxynaphthalen-1-yl) -1,1′-biadamantane (Dicarboxyaryl) biadamantane derivatives; bis (dicarboxyaryl) -5,7-dimethylbiadamantane derivatives, bis (dicarboxyaryl) -5 ′, 7′-dimethylbiadamantane derivatives corresponding to these compounds, (Dicarboxyphenyl aryl) -5,5 ', like 7,7'-tetramethyl-biadamantane derivatives.

  As a typical example of the compound represented by the formula (10) having k = 2 and having one aromatic cyclic group represented by the formula (11), 3- (3,4-dicarboxyphenyl) ) -1,1 ′: 3 ′, 1 ″ -triadamantane, 3- (2,3,5,6-tetracarboxyphenyl) -1,1 ′: 3 ′, 1 ″ -triadamantane, 3- (4 , 5-dicarboxynaphthalen-1-yl) -1,1 ′: 3 ′, 1 ″ -triadamantane, 3- (5,6-dicarboxynaphthalen-1-yl) -1,1 ′: 3 ′, Dicarboxyaryl triadamantane derivatives such as 1 ″ -triadamantane; dicarboxyaryl-5,5 ′, 5 ″, 7,7 ′, 7 ″ -hexamethyltriadamantane derivatives corresponding to these compounds .

  As a typical example of the compound represented by the formula (10) having k = 2 and having two aromatic cyclic groups represented by the formula (11), 3,3 ″ -bis (3,4 -Dicarboxyphenyl) -1,1 ': 3', 1 "-triadamantane, 3,3" -bis (2,3,5,6-tetracarboxyphenyl) -1,1 ': 3', 1 " Triadamantane, 3,3 ″ -bis (4,5-dicarboxynaphthalen-1-yl) -1,1 ′: 3 ′, 1 ″ -Triadamantane, 3,3 ″ -bis (5,6-di Bis (dicarboxyaryl) triadamantane derivatives such as carboxynaphthalen-1-yl) -1,1 ′: 3 ′, 1 ″ -triadamantane; bis (dicarboxyaryl) -5,5 ′ corresponding to these compounds , 5 ″, 7,7 ′, 7 ″ -hexamethyltriada Such as lanthanum derivatives.

  As a typical example of a compound having k = 3 and one aromatic cyclic group represented by the formula (11) among the compounds represented by the formula (10), 3- (3,4-dicarboxyphenyl) ) -1,1 ′: 3 ′, 1 ″: 3 ″, 1 ′ ″-tetraadamantane, 3- (2,3,5,6-tetracarboxyphenyl) -1,1 ′: 3 ′, 1 ″ : 3 ″, 1 ′ ″-tetraadamantane, 3- (4,5-dicarboxynaphthalen-1-yl) -1,1 ′: 3 ′, 1 ″: 3 ″, 1 ′ ″-tetraadamantane, Dicarboxyaryltetraadamantane derivatives such as 3- (5,6-dicarboxynaphthalen-1-yl) -1,1 ′: 3 ′, 1 ″: 3 ″, 1 ′ ″-tetraadamantane; Corresponding dicarboxyaryl-5,5 ', 5 ", 5" ", 7,7', "7 '' '- such as octamethyltetrasiloxane adamantane derivatives.

  As a typical example of a compound represented by the formula (10) having k = 3 and having two aromatic cyclic groups represented by the formula (11), 3,3 ′ ″-bis (3 , 4-dicarboxyphenyl) -1,1 ′: 3 ′, 1 ″: 3 ″, 1 ″ ″-tetraadamantane, 3,3 ″ ″-bis (2,3,5,6-tetracarboxyphenyl) ) -1,1 ′: 3 ′, 1 ″: 3 ″, 1 ″ ″-tetraadamantane, 3,3 ″ ″-bis (4,5-dicarboxynaphthalen-1-yl) -1,1 ′ : 3 ', 1 ": 3", 1 "'-tetraadamantane, 3,3" '-bis (5,6-dicarboxynaphthalen-1-yl) -1, 1': 3 ', 1 " Bis (dicarboxyaryl) tetraadamantane derivatives such as 3 ″, 1 ′ ″-tetraadamantane; Bis (di-carboxy aryl) -5,5 ', 5 ", 5' '', 7,7 ', 7", 7' '' - such as octamethyltetrasiloxane adamantane derivatives.

  The dehydration of the polycarboxyaryl polyadamantane derivative represented by the formula (10) can be performed, for example, by adding a dehydrating agent (dehydrating agent) to the reaction system or by using a dehydrating machine (dehydrating apparatus such as Dean Stark). The reaction can be carried out while distilling off. The type of dehydrating agent, dehydration reaction conditions, and the like are the same as in the case of obtaining the compound represented by formula (9) from the compound represented by formula (7).

By the reaction, an aryl polyadamantane derivative having a corresponding acid anhydride group represented by the formula (12) is generated. In formula (12), R ^1d , R ^2d , R ^3d , R ^4d , R ^5d and R ^6d are the same or different and represent a hydrogen atom, an aromatic cyclic group represented by formula (3), or other Indicates a substituent. However, at least one of R ^1d , R ^2d , R ^3d , R ^4d , R ^5d and R ^6d is a group represented by the formula (3). k represents an integer of 1 to 3. When k is 2 or 3, the plurality of R ^4d and R ^6d may be the same or different. The adamantane ring may have a substituent at a site other than the bridge head position. Other substituents in R ^1d , R ^2d , R ^3d , R ^4d , R ^5d , R ^6d, and other substituents that may be present in addition to the bridge head position of the adamantane ring are R ¹ , R in the formula (1). ² , R ³ , R ⁴ , R ⁵ , R ⁶ are the same as other substituents and substituents that may be present other than the bridge head position of the adamantane ring. Separation and purification of the compound represented by formula (12), which is a reaction product, can be performed in the same manner as in the case of obtaining the compound represented by formula (9) from the compound represented by formula (7). .

  Moreover, it can also convert into the compound represented by the said Formula (10) by attaching | subjecting the compound represented by the said Formula (12) to hydrolysis. This is the reverse reaction of the dehydration reaction of the compound represented by the above formula (10).

  The method of hydrolysis can be carried out in the same manner as in the case of producing the compound represented by formula (6) by hydrolyzing the compound represented by formula (4). In this case, it is preferable to use a mixed solvent of water and a water-soluble organic solvent (for example, acetic acid, etc.) as the solvent. The ratio of water to the water-soluble solvent is, for example, the former / the latter (weight ratio) = 5/95 to 95/5, preferably about 10/90 to 50/50. Moreover, reaction temperature becomes like this. Preferably it is 50-150 degreeC, More preferably, it is about 80-130 degreeC.

  A polycarboxyphenyl polyadamantane derivative represented by the formula (10) is generated by the hydrolysis reaction. Separation and purification of the reaction product can be performed in the same manner as in the case of producing the compound represented by the formula (6) by hydrolyzing the compound represented by the formula (4).

  The compound represented by the formula (4) and the formula (7) used as a raw material when producing an arylpolyadamantane derivative having a carboxyl group or an acid anhydride group represented by the formula (1) of the present invention The compound can be produced by the following method. Equation (13) is a combination of Equation (4) and Equation (7).

The compound represented by the formula (13) can be obtained by reacting the compound represented by the formula (14) with the formula (15) or (16). In formula (14), R ^1e , R ^2e , R ^3e , R ^4e , R ^5e , and R ^6e are the same or different and are a hydrogen atom, a substituent capable of leaving to form a carbocation in the adamantane skeleton, or other The substituent of is shown. However, at least one of R ^1e , R ^2e , R ^3e , R ^4e , R ^5e and R ^6e is a substituent capable of leaving and generating a carbocation in the adamantane skeleton. k represents an integer of 1 to 3. When k is 2 or 3, the plurality of R ^4e and R ^6e may be the same or different. The adamantane ring may have a substituent at a site other than the bridge head position.

Examples of the group that can be eliminated to generate a carbocation in the adamantane skeleton include a hydroxyl group, a halogen atom, —ONO ₂ , and hydride (H). In particular, a hydroxyl group, a halogen atom, -ONO ₂ are preferred.

The other substituents in R ^1e , R ^2e , R ^3e , R ^4e , R ^5e , R ^6e and the substituents that may be present at sites other than the bridge head position of the adamantane ring are the R ¹ in the formula (1). , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ are the same as other substituents and substituents that may be present other than the bridge head position of the adamantane ring. In the preferred compound represented by the formula (14), at least one of R ^1e , R ^2e , R ^3e , R ^4e , R ^5e , R ^6e (more preferably 2 or more) has a halogen atom. Compounds that are good alkyl groups (particularly alkyl groups having 1 to 6 carbon atoms or haloalkyl groups having 1 to 6 carbon atoms) are included. Further, it has at least one alkyl group (particularly an alkyl group having 1 to 6 carbon atoms or a haloalkyl group having 1 to 6 carbon atoms) which may have a halogen atom at a site other than the bridge head position of the adamantane ring. Also preferred are compounds.

  Representative examples of the compound represented by the formula (14) include, for example, 3-bromo-1,1′-biadamantane, 3-bromo-5,5 ′, 7,7′-tetramethyl-1,1. '-Biadamantane, 3-bromo-5,5', 7,7'-tetraethyl-1,1'-biadamantane, 3-bromo-5,5 ', 7,7'-tetrabutyl-1,1'- Bromobiadamantane derivatives such as biadamantane, 3-bromo-5,5 ′, 7,7′-tetrakis (trifluoromethyl) -1,1′-biadamantane; 3,3′-dibromo-1,1′- Biadamantane, 3,3′-dibromo-5,5 ′, 7,7′-tetramethyl-1,1′-biadamantane, 3,3′-dibromo-5,5 ′, 7,7′-tetraethyl- 1,1'-biadamantane, 3,3'-dibromo-5,5 ' Dibromobi, such as 7,7'-tetrabutyl-1,1'-biadamantane, 3,3'-dibromo-5,5 ', 7,7'-tetrakis (trifluoromethyl) -1,1'-biadamantane Adamantane derivatives; 3-bromo-1,1 ′: 3 ′, 1 ″ -triadamantane, 5,5 ′, 5 ″, 7,7 ′, 7 ″ -hexamethyl-3-phenyl-1,1 ′: 3 ', 1 "-triadamantane, 3-bromo-5,5', 5", 7,7 ', 7 "-hexaethyl-1,1': 3 ', 1" -triadamantane, 3-bromo-5 5 ', 5 ", 7,7', 7" -hexabutyl-1,1 ': 3', 1 "-triadamantane, 3-bromo-5,5 ', 5", 7,7', 7 "- Bromoto such as hexakis (trifluoromethyl) -1,1 ′: 3 ′, 1 ″ -triadamantane Adamantane derivatives; 3,3 "-dibromo-1,1 ': 3', 1" -triadamantane, 3,3 "-dibromo-5,5 ', 5", 7,7', 7 "-hexamethyl-1 , 1 ': 3', 1 "-triadamantane, 3,3" -dibromo-5,5 ', 5 ", 7,7', 7" -hexaethyl-1,1 ': 3', 1 "-tri Adamantane, 3,3 "-dibromo-5,5 ', 5", 7,7', 7 "-hexabutyl-1,1 ': 3', 1" -triadamantane, 3,3 "-dibromo-5 Dibromotriadamantane derivatives such as 5 ', 5 ", 7,7', 7" -hexakis (trifluoromethyl) -1,1 ': 3', 1 "-triadamantane; 3-bromo-1,1 ': 3 ', 1 ": 3", 1 ""-tetraadamantane, 3-bromo-5,5 ", 5", 5 "" , 7, 7 ', 7 ", 7" "-octamethyl-1, 1': 3 ', 1": 3 ", 1" "-tetraadamantane, 3-bromo-5, 5', 5", 5 ′ ″, 7,7 ′, 7 ″, 7 ″ ″-octaethyl-1,1 ′: 3 ′, 1 ″: 3 ″, 1 ″ ″-tetraadamantane, 3-bromo-5,5 ′ , 5 ", 5" ', 7, 7', 7 ", 7" "-octabutyl-1, 1 ': 3', 1": 3 ", 1" "-tetraadamantane, 3-bromo- 5, 5 ′, 5 ″, 5 ′ ″, 7, 7 ′, 7 ″, 7 ′ ″-octakis (trifluoromethyl) -1, 1 ′: 3 ′, 1 ″: 3 ″, 1 ″ Bromotetraadamantane derivatives such as '-tetraadamantane; 3,3 "'-dibromo-1,1 ': 3', 1": 3 ", 1" "-tetraadamantane, 3,3" "-dibro -5, 5 ', 5 ", 5"', 7, 7 ', 7 ", 7" "-octamethyl-1, 1': 3 ', 1": 3 ", 1" "-tetraadamantane 3,3 ′ ″-dibromo-5,5 ′, 5 ″, 5 ″ ″, 7,7 ′, 7 ″, 7 ″ ″-octaethyl-1,1 ′: 3 ′, 1 ″: 3 ″, 1 ″ ″-tetraadamantane, 3,3 ″ ″-dibromo-5,5 ′, 5 ″, 5 ″ ″, 7,7 ′, 7 ″, 7 ″ ″-octabutyl-1,1 ′: 3 ′, 1 ″: 3 ″, 1 ″ ″-tetraadamantane, 3,3 ″ ″-dibromo-5,5 ′, 5 ″, 5 ″ ″, 7,7 ′, 7 ″, 7 Dibromotetraadamantane derivatives such as ″ ′ -octakis (trifluoromethyl) -1,1 ′: 3 ′, 1 ″: 3 ″, 1 ″ ″-tetraadamantane; and 3-hydroxy-1,1′-biada Pentane, 3-nitrooxy-1,1'-bi-hydroxy adamantane derivative wherein corresponding to each bromo adamantane derivative adamantane, and the like nitrooxymethyl adamantane derivative.

  The compound represented by the formula (14) includes an adamantane ring coupling reaction, a halogenation reaction (introduction of a halogen atom into the adamantane ring), an oxidation reaction (introduction of a hydroxyl group into the adamantane ring), and an esterification reaction. It can be produced by appropriately combining known reactions such as (introduction of a nitrooxy group into an adamantane ring).

In the formulas (15) and (16), the ring Z ¹ and the ring Z ² represent an aromatic ring. X ¹ represents a group that can be converted to a carboxyl group by oxidation or hydrolysis. m represents an integer of 1 or more. When m is 2 or more, the plurality of X ¹ may be the same or different, and the plurality of X ¹ are bonded together to form one or more atoms constituting the ring Z ¹ A ring may be formed. X ² and X ³ each represents a group capable of forming a cyclic acid anhydride group together with one or more atoms constituting the ring Z ² by oxidation. X ² and X ³ may be bonded to each other to form a ring together with one or more atoms constituting the ring Z ² . n represents an integer of 1 or more. When n is 2 or more, the plurality of X ² and X ³ may be the same or different. Each aromatic ring may have a substituent other than the group shown in the formula. X ¹ may be bonded to these substituents to form a ring together with one or more atoms constituting ring Z ¹ . Ring Z ¹ , ring Z ² , X ¹ , X ² , X ³ , substituents on the aromatic ring, and the like are the same as those in the above formulas (5) and (8).

  Typical examples of the compound represented by the formula (15) include compounds corresponding to those shown as typical examples of the aromatic cyclic group represented by the formula (5). Typical examples of the compound represented by the formula (16) include compounds corresponding to those shown as typical examples of the aromatic cyclic group represented by the formula (8).

  The reaction of the polyadamantane derivative represented by the formula (14) and the aromatic compound represented by the formula (15) or (16) is performed in the presence or absence of a solvent inert to the reaction. Examples of the solvent include hydrocarbons such as hexane, cyclohexane, and toluene; halogenated hydrocarbons such as methylene chloride, 1,2-dichloroethane, chloroform, carbon tetrachloride, and chlorobenzene; diethyl ether, dimethoxyethane, tetrahydrofuran, dioxane, and the like. Chain or cyclic ethers; Nitriles such as acetonitrile and benzonitrile; Esters such as ethyl acetate; Carboxylic acids such as acetic acid; Amides such as N, N-dimethylformamide; Ketones such as acetone and methyl ethyl ketone; Nitro compounds such as nitromethane and nitrobenzene A mixture thereof and the like.

  Generally the usage-amount of the aromatic compound represented by Formula (15) or (16) is 2-1000 mol with respect to 1 mol of polyadamantane derivatives represented by Formula (14), Preferably it is 10-300 mol. More preferably, it is about 50 to 200 mol. A large excess of the aromatic compound represented by the formula (15) or (16) may be used.

In this method, in order to promote the reaction, it is preferable to add a protonic acid, a Lewis acid, or a base into the system. For example, when a compound in which a group capable of generating a carbocation in the adamantane skeleton is a hydroxyl group or a -ONO ₂ group is used as the polyadamantane derivative represented by the formula (14), the reaction rate is increased. Therefore, the reaction is preferably performed in the presence of an acid (particularly a protonic acid). Examples of the acid include inorganic acids such as sulfuric acid, hydrogen chloride, hydrogen bromide, nitric acid and phosphoric acid; sulfonic acids such as methanesulfonic acid, trifluoromethanesulfonic acid, benzenesulfonic acid and p-toluenesulfonic acid; acetic acid and propion Carboxylic acids such as acids; heteropolyacids; cation exchange resins and the like. Among these, strong acids, for example, inorganic acids such as hydrogen chloride and sulfuric acid, sulfonic acids such as p-toluenesulfonic acid, heteropolyacids, strong acidic cation exchange resins and the like are preferable. The usage-amount of an acid is 0.01-10 mol with respect to 1 mol of polyadamantane derivatives represented by Formula (14), for example, Preferably it is about 0.1-5 mol.

When a compound (polyadamantane halide derivative) in which the group capable of generating a carbocation in the adamantane skeleton is a halogen atom (polyadamantane halide derivative) is used as the polyadamantane derivative represented by the formula (14), usually under heating. Perform the reaction. At this time, the reaction may be performed in the presence of a suitable base in order to capture the by-produced hydrogen halide. When a compound in which a group capable of generating a carbocation in the adamantane skeleton is a halogen atom is used, a Lewis acid (FeBr ₃ , FeCl ₃ , AlBr ₃ , AlCl ₃ , BF ₃ , ZrCl ₂ , ZrCl _{4) is used.} Etc.) may be carried out in the presence of (Friedelcraft reaction). The reaction temperature can be lowered by using a Lewis acid. As the Lewis acid, FeCl ₃ is particularly preferable. The usage-amount of a Lewis acid is 0.001-10 mol with respect to 1 mol of polyadamantane derivatives represented by Formula (14), for example, Preferably it is about 0.05-5 mol.

  The reaction temperature in the reaction of the polyadamantane derivative represented by the formula (14) and the aromatic compound represented by the formula (15) or (16) can be appropriately selected according to the type of the reaction component. For example, when a compound (polyadamantanol derivative) in which a group capable of generating a carbocation in the adamantane skeleton is a hydroxyl group (polyadamantanol derivative) or the like is used as the polyadamantane derivative represented by the formula (14), the reaction temperature is For example, it is 10-200 degreeC, Preferably it is 40-150 degreeC, More preferably, it is about 60-130 degreeC. When a compound or the like in which the group capable of generating a carbocation in the adamantane skeleton is a halogen atom as the polyadamantane derivative represented by the formula (14) is used, the reaction temperature is, for example, 100 to 250 ° C. Preferably, it is about 130-220 degreeC. In the case of using a compound in which a group capable of generating a carbocation in the adamantane skeleton by a halogen atom is used, when using a Lewis acid, the reaction temperature is, for example, −50 ° C. to 200 ° C., preferably −20 ° C. It is about -150 degreeC, More preferably, it is about -10 degreeC-100 degreeC.

  In addition, the amount of the aromatic compound represented by the formula (15) or (16) [equivalent ratio with the polyadamantane derivative represented by the formula (14)] or other reaction conditions is adjusted to adjust the formula ( 14) leaving a part of the halogen atom or hydroxyl group as a group capable of generating a carbocation in the adamantane skeleton by elimination in the polyadamantane derivative represented by 14), leaving an alkyl group or the like in the molecule. The compound represented by Formula (13) which has a halogen atom, a hydroxy group, etc. with the aromatic ring which it has can be manufactured. The reaction may be carried out by any system such as batch system, semi-batch system, and continuous system. The above catalyst and reaction accelerator may be added all at the beginning of the reaction, or may be added sequentially as the reaction proceeds.

  By the above reaction (dehydrohalogenation reaction, dehydration condensation reaction, etc.), the compound represented by the formula (14) can be eliminated at the bonding site of the group capable of generating a carbocation in the adamantane skeleton. The corresponding arylpolyadamantane derivative represented by the formula (13) to which the group represented by 8) is bonded is produced.

In the formula (13), R ^1a , R ^2a , R ^3a , R ^4a , R ^5a , and R ^6a are the same or different and are a hydrogen atom, an aromatic cyclic represented by the formula (5) or (8). Represents a group or other substituent. However, at least one of R ^1a , R ^2a , R ^3a , R ^4a , R ^5a and R ^6a is a group represented by the formula (5) or (8). k represents an integer of 1 to 3. When k is 2 or 3, the plurality of R ^4a and R ^6a may be the same or different. The adamantane ring may have a substituent at a site other than the bridge head position. In formulas (5) and (8), ring Z ¹ , ring Z ² , X ¹ , X ² , X ³ , m, and n are the same as described above. Each aromatic ring may have a substituent other than the group shown in the formula.

  After completion of the reaction, the reaction product can be separated and purified by general separation and purification means such as liquid adjustment, concentration, filtration, washing, extraction, crystallization, recrystallization, distillation, sublimation, column chromatography and the like. In particular, when the yield is high, the target product can be separated by liquid property adjustment, concentration, filtration, washing and the like. When there are many reaction by-products, the target product can be separated by crystallization, recrystallization, column chromatography or the like. In addition, crystallization is performed by, for example, treating the crude product with a crystallization solvent (ether such as tetrahydrofuran, aromatic hydrocarbon such as benzene, toluene and xylene, amide such as N, N-dimethylformamide; halogenated hydrocarbon such as chloroform. , A mixed solvent thereof, etc.) (including heating and dissolution), concentrating as necessary, and then cooling to precipitate crystals. Further, crystallization and recrystallization may be performed by combining a good solvent and a poor solvent (for example, methanol, water, etc.) of the target compound.

  In the arylpolyadamantane derivative having a carboxyl group or an acid anhydride group represented by the formula (1) of the present invention, each substituent on the adamantane ring, an aromatic represented by the formula (2) or (3) The introduction of each substituent on the aromatic ring of the cyclic group may be carried out at any stage of producing the aryl polyadamantane derivative having the carboxyl group or acid anhydride group. For example, the substituent may be introduced as a pre-process (or a process for producing the raw material) of each reaction process such as the oxidation reaction, hydrolysis reaction, dehydration reaction, dehydrohalogenation reaction and the like described above. The substituent may be introduced as a step or a final step. In the above oxidation reaction or hydrolysis reaction, the oxidizable group and a part of the hydrolyzed group may be left unreacted by appropriately adjusting the reaction conditions. In addition, the compound which has a cyano group in an aromatic ring can be obtained by making copper cyanide (CuCN) react with the compound which has a halogen atom in an aromatic ring.

  Hereinafter, the present invention will be described in more detail based on examples, but the present invention is not limited to these examples.

Example 1
Under a nitrogen atmosphere, the temperature of a mixed solution of 4.02 g of anhydrous ferric chloride (III) and 600 g of xylene was raised to 30 ° C., and then 20 g (46.7 mmol) of 3,3′-dibromo-1,1′-biadamantane. ) Was added slowly over 30 minutes. As 3,3′-dibromo-1,1′-biadamantane was added, the reaction solution changed from black to brown. The mixture was aged for 1 hour, 200 ml of water was added, liquid separation was performed, and the upper layer was concentrated. The concentrated precipitate is filtered off, repulped with 400 ml of acetone, and the crystals obtained by filtration are dried to give 3,3′-bis (3,4-dimethylphenyl) -1,1′-biphenyl. 20.1 g (42.0 mmol, yield 90%, GC measurement purity 98%) of adamantane was obtained.
¹ H-NMR (CDCl ₃ ) δ: 1.60-1.66 (m, 16H), 1.77-1.87 (q, 8H), 2.17 (s, 4H), 2.23 (s, 6H), 2.27 (s, 6H), 7.0 -7.2 (m, 6H)
FT-IR (cm ^-1 ): 2930-2850, 1506, 1448, 1344, 1026, 997, 808
GC-MS-spectrometry: 478 [EI method]

Example 2
Under a nitrogen atmosphere, a mixed solution of 3.3 g (3.3 mmol) of concentrated sulfuric acid, 600 g of xylene, and 20 g (66.1 mmol) of 3,3′-dihydroxy-1,1′-biadamantane was heated and stirred at 100 ° C. for 10 hours. . After completion of the reaction, the reaction mixture was cooled to room temperature, neutralized by adding 200 ml of a 10% by weight aqueous sodium carbonate solution, separated, and the upper layer was concentrated. The concentrated precipitate is filtered off, repulped with 400 ml of acetone, and the crystals obtained by filtration are dried to give 3,3′-bis (3,4-dimethylphenyl) -1,1′-biphenyl. 30 g (62.7 mmol, yield 95%, GC measurement purity 98%) of adamantane was obtained.

¹H-NMR[NaOH in CD₃OD（水酸化ナトリウムを重メタノールに対して１重量％溶解させた溶液中で測定）] δ：1.6-1.9(m, 24H), 2.17(br, 4H), 7.3-7.8(m, 6H)
FT-IR (cm^-1)：2931, 2885, 1838, 1774, 1259, 872, 735, 683
DI-MS-spectrometry ：563 [M+1] Example 3
3,3′-bis (3,4-dimethylphenyl) -1,1′-biadamantane 10 g (20.9 mmol), sodium bromide 0.52 g (5.1 mmol), cobalt acetate (II) 1.04 g ( 4.2 mmol), 0.10 g (0.4 mmol) of manganese acetate (II), and 200 g of acetic acid were reacted in the presence of oxygen (1 atm; 0.1 MPa) at 100 ° C. for 15 hours. After completion of the reaction, the reaction mixture was cooled to 15 ° C., and the precipitate was separated by filtration. This was repulped with 40 ml of acetic acid and 40 ml of acetonitrile, and the crystals obtained by filtration were dried to obtain a biadamantane derivative [3,3′- having two phthalic anhydride skeletons represented by the following formula (20). Bis (4-phthalic anhydride) -1,1′-biadamantane] was obtained in an amount of 5.0 g (42% yield).

¹ H-NMR [NaOH in CD ₃ OD (measured in a solution in which 1% by weight of sodium hydroxide is dissolved in heavy methanol)] δ: 1.6-1.9 (m, 24H), 2.17 (br, 4H), 7.3-7.8 (m, 6H)
FT-IR (cm ^-1 ): 2931, 2885, 1838, 1774, 1259, 872, 735, 683
DI-MS-spectrometry: 563 [M + 1]

Example 4
3,3′-bis (3,4-dimethylphenyl) -1,1′-biadamantane 10 g (20.9 mmol), sodium bromide 0.52 g (5.1 mmol), cobalt acetate (II) 1.04 g ( 4.2 mmol), 0.10 g (0.4 mmol) of manganese (II) acetate, and 200 g of acetic acid were reacted at 100 ° C. for 15 hours under pressure of 40 atm (= 4.04 MPa) of air. After completion of the reaction, the reaction mixture was cooled to 15 ° C., and the precipitate was separated by filtration. This is repulped with 40 ml of acetic acid and 40 ml of acetonitrile, and the crystals obtained by filtration are dried to obtain a biadamantane derivative [3,3′- having two phthalic anhydride skeletons represented by the above formula (20). Bis (4-phthalic anhydride) -1,1′-biadamantane] was obtained in an amount of 5.2 g (yield 45%).

Example 5
10 g (17.8 mmol) of a biadamantane derivative [3,3′-bis (4-phthalic anhydride) -1,1′-biadamantane] having two phthalic anhydride skeletons represented by the formula (20), A mixed solution of 100 g of acetic acid and 25 g of distilled water was reacted at 100 ° C. for 3 hours. After completion of the reaction, the reaction mixture was cooled to 15 ° C., and the precipitate was separated by filtration. This was repulped with 40 ml of acetonitrile, and the crystal obtained by filtration was dried to obtain 9.7 g (16 g) of 3,3′-bis (3,4-dicarboxyphenyl) -1,1′-biadamantane. 0.2 mmol, yield 92%).
FT-IR (cm ^-1 ): 2927, 2852, 1695, 1288, 885
DI-MS-spectrometry: 599 [M + 1]

Example 6
In a nitrogen atmosphere, a mixture of 80.0 g (0.26 mol) of 3,3′-dihydroxy-1,1′-biadamantane, 731.1 g (7.93 mol) of toluene, and 31.7 g (0.31 mol) of concentrated sulfuric acid Was heated and stirred at 100 ° C. for 6 hours. After completion of the reaction, the mixture was aged and stirred at room temperature for 1 hour, and the precipitate was separated by filtration and washed with toluene, methanol, and a saturated aqueous sodium carbonate solution. To the obtained crystals, 977 g of toluene was added, and the mixture was heated and stirred at 70 ° C. for 1 hour, filtered hot, and washed with methanol. By drying the obtained crystals, 91.8 g (0.2 mol, yield 71%, GC measurement purity 95%) of 3,3′-bis (4-methylphenyl) -1,1′-biadamantane was obtained. Obtained.
¹ H-NMR (CDCl ₃ , 500 MHz) δ: 1.5-1.6 (m, 16H), 1.7 (q, 8H), 2.1 (s, 4H), 2.2 (s, 6H), 7.0 (d, 4H), 7.1 (d, 4H)
GC-MS-spectrometry: 450 m / z [EI method]

Example 7
3,3′-bis (4-methylphenyl) -1,1′-biadamantane 70.1 g (155.5 mmol), cobalt acetate (II) 3.1 g (12.4 mmol), manganese acetate (II) 0. A mixed solution of 38 g (1.6 mmol) and 1400 g of acetic acid was heated and stirred at 110 ° C. for 18 hours in an oxygen atmosphere (1 atm = 0.1 MPa). After completion of the reaction, the reaction mixture was cooled to room temperature, and the precipitate was filtered off and washed with acetic acid. To the obtained precipitate, 1084 g of tetrahydrofuran was added, and the mixture was heated and stirred at 60 ° C. for 1 hour, and then cooled to room temperature. The precipitate was separated by filtration and washed with acetone. The obtained crystals were dried to obtain 67.9 g (133.0 mmol, yield 86%, HPLC purity 94%) of 3,3′-bis (4-carboxyphenyl) -1,1′-biadamantane. It was.
¹ H-NMR (DMSO-d6,500 MHz) δ: 1.61-1.65 (m, 16H), 1.8 (q, 8H), 2.1 (s, 4H), 7.5 (d, 4H), 7.8 (d, 4H), 12.7 (brs, 2H)
LC-MS-spectrometry: 509.4 m / z [M -]

Claims (7)

Following formula (1)

[Wherein R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ are the same or different and represent a hydrogen atom, the following formula (2) or (3)

(In the formula, ring Z ¹ and ring Z ² represent an aromatic ring, ring Z ³ represents a ring constituting a cyclic acid anhydride, and m and n each represents an integer of 1 or more. And may have a substituent other than the group shown in FIG.
The aromatic cyclic group represented by these, or another substituent is shown. However, at least one of R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ is a group represented by the formula (2) or (3). k represents an integer of 1 to 3. When k is 2 or 3, the plurality of R ⁴ and R ⁶ may be the same or different. The adamantane ring may have a substituent at a site other than the bridgehead position]
An arylpolyadamantane derivative having a carboxyl group or an acid anhydride group represented by the formula: Following formula (4)

[Wherein, R ^1a , R ^2a , R ^3a , R ^4a , R ^5a , R ^6a are the same or different and represent a hydrogen atom, the following formula (5)

(In the formula, ring Z ¹ represents an aromatic ring. X ¹ represents a group that can be converted into a carboxyl group by oxidation or hydrolysis. M represents an integer of 1 or more. X ¹ may be the same or different, and a plurality of X ¹ may be bonded to each other to form a ring with one or more atoms constituting the ring Z ¹ . The ring may have a substituent other than the group shown in the formula, and X ¹ is bonded to these substituents to form a ring together with one or more atoms constituting the ring Z ^1. May be)
The aromatic cyclic group represented by these, or another substituent is shown. However, at least one of R ^1a , R ^2a , R ^3a , R ^4a , R ^5a and R ^6a is a group represented by the formula (5). k represents an integer of 1 to 3. When k is 2 or 3, the plurality of R ^4a and R ^6a may be the same or different. The adamantane ring may have a substituent at a site other than the bridgehead position]
An aryl polyadamantane derivative represented by the following formula (6) is subjected to oxidation or hydrolysis:

[Wherein, R ^1b , R ^2b , R ^3b , R ^4b , R ^5b , R ^6b are the same or different and represent a hydrogen atom, the following formula (2)

(In the formula, ring Z ¹ represents an aromatic ring. M represents an integer of 1 or more. The aromatic ring may have a substituent other than the group shown in the formula).
The aromatic cyclic group represented by these, or another substituent is shown. However, at least one of R ^1b , R ^2b , R ^3b , R ^4b , R ^5b and R ^6b is a group represented by the formula (2). k represents an integer of 1 to 3. When k is 2 or 3, the plurality of R ^4b and R ^6b may be the same or different. The adamantane ring may have a substituent at a site other than the bridgehead position]
A process for producing an aryl polyadamantane derivative having a carboxyl group, characterized in that a compound represented by the formula: Following formula (7)

[Wherein R ^1a , R ^2a , R ^3a , R ^4a , R ^5a , R ^6a are the same or different and represent a hydrogen atom, the following formula (8)

(In the formula, ring Z ² represents an aromatic ring. X ² and X ³ represent groups capable of forming a cyclic acid anhydride group together with one or more atoms constituting ring Z ² by oxidation. X ² X ³ may be bonded to each other to form a ring together with one or more atoms constituting the ring Z ^2. n represents an integer of 1 or more, and when n is 2 or more, a plurality of X ² and X ³ may be the same or different, and the aromatic ring may have a substituent other than the group shown in the formula)
The aromatic cyclic group represented by these, or another substituent is shown. However, at least one of R ^1a , R ^2a , R ^3a , R ^4a , R ^5a , R ^6a is a group represented by the formula (8). k represents an integer of 1 to 3. When k is 2 or 3, the plurality of R ^4a and R ^6a may be the same or different. The adamantane ring may have a substituent at a site other than the bridgehead position]
An aryl polyadamantane derivative represented by the following formula (9) is oxidized:

[Wherein, R ^1b , R ^2b , R ^3b , R ^4b , R ^5b , R ^6b are the same or different and represent a hydrogen atom, the following formula (3)

(In the formula, ring Z ² represents an aromatic ring, ring Z ³ represents a ring constituting a cyclic acid anhydride, and n represents an integer of 1 or more. The aromatic ring is a substituent other than the group shown in the formula. You may have)
The aromatic cyclic group represented by these, or another substituent is shown. However, at least one of R ^1b , R ^2b , R ^3b , R ^4b , R ^5b and R ^6b is a group represented by the formula (3). k represents an integer of 1 to 3. When k is 2 or 3, the plurality of R ^4b and R ^6b may be the same or different. The adamantane ring may have a substituent at a site other than the bridgehead position]
A process for producing an aryl polyadamantane derivative having an acid anhydride group, characterized in that a compound represented by the formula: Following formula (10)

[Wherein R ^1c , R ^2c , R ^3c , R ^4c , R ^5c , R ^6c are the same or different and represent a hydrogen atom, the following formula (11)

(In the formula, ring Z ² represents an aromatic ring. N represents an integer of 1 or more. The aromatic ring may have a substituent other than the group shown in the formula.)
The aromatic cyclic group represented by these, or another substituent is shown. However, at least one of R ^1c , R ^2c , R ^3c , R ^4c , R ^5c and R ^6c is a group represented by the formula (11). k represents an integer of 1 to 3. When k is 2 or 3, the plurality of R ^4c and R ^6c may be the same or different. The adamantane ring may have a substituent at a site other than the bridgehead position]
Is subjected to a dehydration reaction to give the following formula (12):

[Wherein R ^1d , R ^2d , R ^3d , R ^4d , R ^5d , R ^6d are the same or different and represent a hydrogen atom, the following formula (3)

(In the formula, ring Z ² represents an aromatic ring, ring Z ³ represents a ring constituting a cyclic acid anhydride, and n represents an integer of 1 or more. The aromatic ring is a substituent other than the group shown in the formula. You may have)
The aromatic cyclic group represented by these, or another substituent is shown. However, at least one of R ^1d , R ^2d , R ^3d , R ^4d , R ^5d and R ^6d is a group represented by the formula (3). k represents an integer of 1 to 3. When k is 2 or 3, the plurality of R ^4d and R ^6d may be the same or different. The adamantane ring may have a substituent at a site other than the bridgehead position]
A process for producing an aryl polyadamantane derivative having an acid anhydride group, characterized in that a compound represented by the formula: Following formula (12)

[Wherein R ^1d , R ^2d , R ^3d , R ^4d , R ^5d , R ^6d are the same or different and represent a hydrogen atom, the following formula (3)

(In the formula, ring Z ² represents an aromatic ring, ring Z ³ represents a ring constituting a cyclic acid anhydride, and n represents an integer of 1 or more. The aromatic ring is a substituent other than the group shown in the formula. You may have)
The aromatic cyclic group represented by these, or another substituent is shown. However, at least one of R ^1d , R ^2d , R ^3d , R ^4d , R ^5d and R ^6d is a group represented by the formula (3). k represents an integer of 1 to 3. When k is 2 or 3, the plurality of R ^4d and R ^6d may be the same or different. The adamantane ring may have a substituent at a site other than the bridgehead position]
The compound represented by the following formula (10)

[Wherein R ^1c , R ^2c , R ^3c , R ^4c , R ^5c , R ^6c are the same or different and represent a hydrogen atom, the following formula (11)

(In the formula, ring Z ² represents an aromatic ring. N represents an integer of 1 or more. The aromatic ring may have a substituent other than the group shown in the formula.)
The aromatic cyclic group represented by these, or another substituent is shown. However, at least one of R ^1c , R ^2c , R ^3c , R ^4c , R ^5c and R ^6c is a group represented by the formula (11). k represents an integer of 1 to 3. When k is 2 or 3, the plurality of R ^4c and R ^6c may be the same or different. The adamantane ring may have a substituent at a site other than the bridgehead position]
A process for producing an aryl polyadamantane derivative having a carboxyl group, characterized in that a compound represented by the formula: Following formula (13)

[Wherein, R ^1a , R ^2a , R ^3a , R ^4a , R ^5a , R ^6a are the same or different and represent a hydrogen atom, the following formula (5) or (8)

(In the formula, ring Z ¹ and ring Z ² represent an aromatic ring. X ¹ represents a group that can be converted to a carboxyl group by oxidation or hydrolysis. M represents an integer of 1 or more. When m is 2 or more. The plurality of X ¹ may be the same or different, and the plurality of X ¹ are bonded to each other to form a ring with one or more atoms constituting the ring Z ^1. which may .X ^2, X ³ is attached is .X ^2, X ³ indicating the one or more atoms with capable of forming a cyclic acid anhydride group group constituting the ring Z ² by oxidation with each other ring Z ^A ring may be formed together with 1 or 2 or more atoms constituting 2. n represents an integer of 1 or more, and when n is 2 or more, a plurality of X ² and X ³ are the same, Each aromatic ring may have a substituent other than the group shown in the formula, and X ¹ represents these substituents. And may form a ring together with one or more atoms constituting ring Z ¹ )
The aromatic cyclic group represented by these, or another substituent is shown. However, at least one of R ^1a , R ^2a , R ^3a , R ^4a , R ^5a and R ^6a is a group represented by the formula (5) or (8). k represents an integer of 1 to 3. When k is 2 or 3, the plurality of R ^4a and R ^6a may be the same or different. The adamantane ring may have a substituent at a site other than the bridge head position]
An arylpolyadamantane derivative represented by: Following formula (14)

[Wherein, R ^1e , R ^2e , R ^3e , R ^4e , R ^5e , R ^6e are the same or different, a hydrogen atom, a substituent capable of leaving to form a carbocation in the adamantane skeleton, or other substitution Indicates a group. However, at least one of R ^1e , R ^2e , R ^3e , R ^4e , R ^5e and R ^6e is a substituent capable of leaving and generating a carbocation in the adamantane skeleton. k represents an integer of 1 to 3. When k is 2 or 3, the plurality of R ^4e and R ^6e may be the same or different. The adamantane ring may have a substituent at a site other than the bridgehead position]
And a compound represented by the following formula (15) or (16):

(In the formula, ring Z ¹ and ring Z ² represent an aromatic ring. X ¹ represents a group that can be converted to a carboxyl group by oxidation or hydrolysis. M represents an integer of 1 or more. When m is 2 or more. The plurality of X ¹ may be the same or different, and the plurality of X ¹ are bonded to each other to form a ring with one or more atoms constituting the ring Z ^1. which may .X ^2, X ³ is attached is .X ^2, X ³ indicating the one or more atoms with capable of forming a cyclic acid anhydride group group constituting the ring Z ² by oxidation with each other ring Z ^A ring may be formed together with 1 or 2 or more atoms constituting 2. n represents an integer of 1 or more, and when n is 2 or more, a plurality of X ² and X ³ are the same, Each aromatic ring may have a substituent other than the group shown in the formula, and X ¹ represents these substituents. And may form a ring together with one or more atoms constituting ring Z ¹ )
Is reacted with a compound represented by the following formula (13):

[Wherein, R ^1a , R ^2a , R ^3a , R ^4a , R ^5a , R ^6a are the same or different and represent a hydrogen atom, the following formula (5) or (8)

(In the formula, ring Z ¹ , ring Z ² , X ¹ , X ² , X ³ , m and n are the same as above. Each aromatic ring may have a substituent other than the group shown in the formula. )
The aromatic cyclic group represented by these, or another substituent is shown. However, at least one of R ^1a , R ^2a , R ^3a , R ^4a , R ^5a and R ^6a is a group represented by the formula (5) or (8). k represents an integer of 1 to 3. When k is 2 or 3, the plurality of R ^4a and R ^6a may be the same or different. The adamantane ring may have a substituent at a site other than the bridgehead position]
A process for producing an arylpolyadamantane derivative characterized in that a compound represented by the formula: