JP4931434B2 - Amino group-containing adamantane derivative and process for producing the same - Google Patents

Description

  The present invention relates to an amino group-containing adamantane derivative and a method for producing the same. The amino group-containing adamantane derivative of the present invention is useful as a raw material for an insulating film used for semiconductor production, particularly an insulating film having excellent heat resistance and mechanical strength and exhibiting a low relative dielectric constant.

  2. Description of the Related Art In recent years, in a semiconductor process in which circuit patterns are becoming finer, a lower dielectric constant of an interlayer insulating film is required. It is said that the construction of a hole structure is effective for lowering the dielectric constant of an interlayer insulating film. For silicon oxide-based interlayer insulating films, introduction of a hole structure using a foaming agent or the like has been proposed. . However, although this method can form vacancies, it is difficult to avoid linking of vacancies (continuation of vacancies), so there are difficulties in mechanical strength and thermal stability. The process had serious problems such as film breakage.

  The inventors of the present invention have found that an insulating film having pores at a molecular level formed by polymerization of a polyfunctional crosslinkable monomer can achieve both low dielectric constant and high mechanical strength ( For example, refer to Japanese Patent Application Laid-Open No. 2004-307804). However, in the current situation where higher integration of semiconductors has progressed, further reduction in dielectric constant has been demanded.

JP 2004-307804 A

  An object of the present invention is to provide an amino group-containing adamantane derivative capable of forming an insulating film and a polymer having a high heat resistance and an extremely low dielectric constant useful for the production of a semiconductor, and a method for producing the same.

  Another object of the present invention is to provide an amino group-containing adamantane derivative capable of forming a polymer having a high porosity and an insulating film, and a method for producing the same.

  As a result of intensive studies to achieve the above object, the inventors of the present invention perform the production of a polymer crosslinked body having a pore structure in two stages, that is, by previously forming a macromolecule that can constitute a desired pore size. Then, it has been found that an insulating film having a very low relative dielectric constant and a desired thickness can be efficiently obtained by advancing a polymerization reaction between the macromolecule and a specific monomer. More specifically, in a polymerization reaction in which a polymer is formed by reaction between functional groups at each of the 3 or 4 bridgehead positions of the adamantane skeleton, a macromolecule in which the polymerization reaction at each bridgehead position is stopped in one step is prepared in advance. After this and the monomer component are dissolved in an appropriate solvent and applied onto a substrate, for example, when heat treatment is performed, reactions such as chain extension, cyclization, and crosslinking proceed smoothly to have a desired size. It has been found that an insulating film made of a high molecular weight polymer having a pore structure in which pores are reliably formed, heat resistance and mechanical strength are high, and dielectric constant is extremely low can be obtained. The present invention has been completed based on these findings.

（式中、Ｘ ¹ 、Ｘ ² 、Ｘ ³ 、Ｘ ⁴ は、同一又は異なって、単結合、ベンゼン環、ビフェニル環、又はナフタレン環を示し、Ｒ ^a 、Ｒ ^b 、Ｒ ^c 、Ｒ ^d は、同一又は異なって、水素原子、炭素数１〜２０のアルキル基、炭素数２〜２０のアルケニル基、炭素数２〜２０のアルキニル基、３〜２０員のシクロアルキル基、３〜２０員のシクロアルケニル基、２〜４環の橋かけ環式炭素環、炭素数６〜２０の芳香族炭化水素基、Ｃ _3-20 シクロアルキル−Ｃ _1-4 アルキル基、Ｃ _7-18 アラルキル基、Ｃ _1-4 アルキル基が置換したフェニル基、Ｃ _1-4 アルキル基が置換したナフチル基、及びホルミル基から選択された基を示す。但し、Ｒ ^a 、Ｒ ^b 、Ｒ ^c 、Ｒ ^d のうち少なくとも３つは、ホルミル基を示す）
で表されるカルボニル基含有アダマンタン誘導体と、下記式（４’）

（式中、環Ｙはベンゼン環、ナフタレン環、アントラセン環、フェナントレン環、トリフェニレン環、ピレン環、ビフェニル環、ビフェニレン環、フルオレン環、スチルベン環から選択される環を示し、Ｒ ^e 、Ｒ ^f 、Ｒ ^g 、Ｒ ^h は環Ｙに結合している置換基であって、同一又は異なって、これらのうち２つはＣ _1-6 脂肪族アシル基、炭素数 _6〜20 芳香族アシル基、Ｃ _1-4 アルコキシ−カルボニル基、Ｃ _7-20 アラルキルオキシカルボニル基、脂肪族アルキリデン基、芳香族アルキリデン基から選択される保護基で保護されていてもよいアミノ基、残りの２つはＣ _1-6 アルキル基、３〜１５員のシクロアルキル基、Ｃ _7-20 アラルキル基、メトキシメチル基、ベンジルオキシメチル基、ｔ−ブトキシメチル基、２−メトキシエトキシメチル基、１−エトキシエチル基、１−メチル−１−メトキシエチル基、Ｃ _1-10 脂肪族アシル基、Ｃ _4-20 脂環式アシル基、Ｃ _7-20 芳香族アシル基、Ｃ _1-4 アルコキシ−カルボニル基、Ｃ _7-20 アラルキルオキシ−カルボニル基から選択される保護基で保護されていてもよいヒドロキシル基）
で表されるジヒドロキシジアミン誘導体との反応により、下記式（１’）

［式中、Ｘ ¹ 、Ｘ ² 、Ｘ ³ 、Ｘ ⁴ は、上記に同じ。Ｒ ¹ 、Ｒ ² 、Ｒ ³ 、Ｒ ⁴ は、アダマンタン環又は環Ｘ ¹ 、Ｘ ² 、Ｘ ³ 、Ｘ ⁴ に結合している置換基であって、同一又は異なって、水素原子、炭素数１〜２０のアルキル基、炭素数２〜２０のアルケニル基、炭素数２〜２０のアルキニル基、３〜２０員のシクロアルキル基、３〜２０員のシクロアルケニル基、２〜４環の橋かけ環式炭素環、炭素数６〜２０の芳香族炭化水素基、Ｃ _3-20 シクロアルキル−Ｃ _1-4 アルキル基、Ｃ _7-18 アラルキル基、Ｃ _1-4 アルキル基が置換したフェニル基、Ｃ _1-4 アルキル基が置換したナフチル基、ホルミル基、若しくは下記式（２Ａ’）、（２Ｂ’）又は（２Ｃ’）

（式（２Ａ’）、（２Ｂ’）、（２Ｃ’）中、環Ｙは前記に同じ。Ｒ ⁵ 及びＲ ⁶ は、同一又は異なって、Ｃ _1-6 アルキル基、３〜１５員のシクロアルキル基、Ｃ _7-20 アラルキル基、メトキシメチル基、ベンジルオキシメチル基、ｔ−ブトキシメチル基、２−メトキシエトキシメチル基、１−エトキシエチル基、１−メチル−１−メトキシエチル基、Ｃ _1-10 脂肪族アシル基、Ｃ _4-20 脂環式アシル基、Ｃ _7-20 芳香族アシル基、Ｃ _1-4 アルコキシ−カルボニル基、Ｃ _7-20 アラルキルオキシ−カルボニル基から選択される保護基で保護されていてもよいヒドロキシル基を示し、Ｒ ⁷ は、Ｃ _1-6 脂肪族アシル基、炭素数 _6〜20 芳香族アシル基、Ｃ _1-4 アルコキシ−カルボニル基、Ｃ _7-20 アラルキルオキシカルボニル基、脂肪族アルキリデン基、芳香族アルキリデン基から選択される保護基で保護されていてもよいアミノ基を示し、Ｒ′は水素原子を示す）
で表される基を示す。但し、Ｒ ¹ 、Ｒ ² 、Ｒ ³ 、Ｒ ⁴ のうち少なくとも３つは、同一又は異なって、式（２Ａ’）、（２Ｂ’）又は（２Ｃ’）で表される基を示す］
で表されるアミノ基含有アダマンタン誘導体を得るアミノ基含有アダマンタン誘導体の製造方法を提供する。 That is, the present invention provides the following formula (3 ′)

Wherein X ¹ , X ² , X ³ and X ⁴ are the same or different and each represents a single bond, a benzene ring, a biphenyl ring or a naphthalene ring, and R ^a , R ^b , R ^c and R ^d are The same or different, a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an alkynyl group having 2 to 20 carbon atoms, a 3 to 20 membered cycloalkyl group, and a 3 to 20 membered cyclo An alkenyl group, a bridged cyclic carbocycle having 2 to 4 rings, an aromatic hydrocarbon group having 6 to 20 carbon atoms, a C _3-20 cycloalkyl-C _1-4 alkyl group, a C _7-18 aralkyl group, C _{1 A} group selected from a phenyl group substituted with a _-4 alkyl group, a naphthyl group substituted with a C _1-4 alkyl group, and a formyl group, provided that at least 3 of R ^a , R ^b , R ^c and R ^d Represents a formyl group)
And a carbonyl group-containing adamantane derivative represented by the following formula (4 ′):

(In the formula, ring Y represents a ring selected from a benzene ring, naphthalene ring, anthracene ring, phenanthrene ring, triphenylene ring, pyrene ring, biphenyl ring, biphenylene ring, fluorene ring, and stilbene ring, and R ^e , R ^f , R ^g and R ^h are substituents bonded to the ring Y and are the same or different, and two of them are a C _1-6 aliphatic acyl group, a C _6-20 aromatic acyl group, a C _{1-4 an} alkoxy-carbonyl group, a C _7-20 aralkyloxycarbonyl group, an aliphatic alkylidene group, an amino group which may be protected with a protecting group selected from an aromatic alkylidene group, the remaining two are C _{1- 6} alkyl group, 3-15 membered cycloalkyl group, C _7-20 aralkyl groups, methoxymethyl group, benzyloxymethyl group, t-butoxymethyl group, 2-methoxyethoxymethyl group, 1-ethoxy Butyl group, 1-methyl-1-methoxyethyl group, C _1-10 aliphatic acyl group, C _4-20 cycloaliphatic acyl group, C _7-20 aromatic acyl group, C _1-4 alkoxy - carbonyl group, A hydroxyl group optionally protected with a protecting group selected from a C _7-20 aralkyloxy-carbonyl group)
By the reaction with a dihydroxydiamine derivative represented by the following formula (1 ′)

[Wherein, X ¹ , X ² , X ³ and X ⁴ are the same as above. R ¹ , R ² , R ³ , and R ⁴ are adamantane rings or substituents bonded to the rings X ¹ , X ² , X ³ , and X ⁴ , and they are the same or different and have a hydrogen atom, carbon number of 1 ˜20 alkyl group, C 2-20 alkenyl group, C 2-20 alkynyl group, 3-20 membered cycloalkyl group, 3-20 membered cycloalkenyl group, 2-4 bridged ring A carbocyclic ring, an aromatic hydrocarbon group having 6 to 20 carbon atoms, a C _3-20 cycloalkyl-C _1-4 alkyl group, a C _7-18 aralkyl group, a phenyl group substituted by a C _1-4 alkyl group, C _1-4 alkyl group substituted naphthyl group, formyl group, or the following formula (2A ′), (2B ′) or (2C ′)

(In formulas (2A ′), (2B ′) and (2C ′), ring Y is the same as defined above. R ⁵ and R ⁶ are the same or different and are each a C _1-6 alkyl group, a 3- to 15-membered cyclohexane. Alkyl group, C _7-20 aralkyl group, methoxymethyl group, benzyloxymethyl group, t-butoxymethyl group, 2-methoxyethoxymethyl group, 1-ethoxyethyl group, 1-methyl-1-methoxyethyl group, C _{1 -10} protecting group selected from aliphatic acyl group, C _4-20 alicyclic acyl group, C _7-20 aromatic acyl group, C _1-4 alkoxy-carbonyl group, C _7-20 aralkyloxy-carbonyl group R ⁷ is a C _1-6 aliphatic acyl group, a C _6-20 aromatic acyl group, a C _1-4 alkoxy-carbonyl group, a C _7-20 aralkyloxy group. Selected from carbonyl group, aliphatic alkylidene group, and aromatic alkylidene group An amino group which may be protected by a selected protecting group, and R ′ represents a hydrogen atom)
The group represented by these is shown. However, at least three of R ¹ , R ² , R ³ and R ⁴ are the same or different and represent a group represented by the formula (2A ′), (2B ′) or (2C ′)]
The manufacturing method of the amino group containing adamantane derivative which obtains the amino group containing adamantane derivative represented by these is provided.

［式中、Ｘ ¹ 、Ｘ ² 、Ｘ ³ 、Ｘ ⁴ は、同一又は異なって、単結合又は２価の芳香族性又は非芳香族性環式基を示し、Ｒ ¹ 、Ｒ ² 、Ｒ ³ 、Ｒ ⁴ は、アダマンタン環又は環Ｘ ¹ 、Ｘ ² 、Ｘ ³ 、Ｘ ⁴ に結合している置換基であって、同一又は異なって、水素原子、炭化水素基、保護基で保護されていてもよいカルボキシル基、アシル基、若しくは下記式（２Ａ）、（２Ｂ）又は（２Ｃ）

（式（２Ａ）、（２Ｂ）、（２Ｃ）中、環Ｙは、同一又は異なって、単環又は多環の芳香族性又は非芳香族性環を示し、Ｒ ⁵ 及びＲ ⁶ は、同一又は異なって、保護基で保護されていてもよいヒドロキシル基を示し、Ｒ ⁷ は、保護基で保護されていてもよいアミノ基を示し、Ｒ′はハロホルミル基以外のアシル基からカルボニル基を除した基を示す）
で表される基を示す。但し、Ｒ ¹ 、Ｒ ² 、Ｒ ³ 、Ｒ ⁴ のうち少なくとも３つは、同一又は異なって、式（２Ａ）、（２Ｂ）又は（２Ｃ）で表される基を示す］
で表されるアミノ基含有アダマンタン誘導体、下記式（３）

（式中、Ｘ ¹ 、Ｘ ² 、Ｘ ³ 、Ｘ ⁴ は、同一又は異なって、単結合又は２価の芳香族性又は非芳香族性環式基を示し、Ｒ ^a 、Ｒ ^b 、Ｒ ^c 、Ｒ ^d は、同一又は異なって、水素原子、炭化水素基、保護基で保護されていてもよいカルボキシル基又はアシル基を示す。但し、Ｒ ^a 、Ｒ ^b 、Ｒ ^c 、Ｒ ^d のうち少なくとも３つは、同一又は異なって、保護基で保護されていてもよいカルボキシル基又はアシル基を示す）
で表されるカルボニル基含有アダマンタン誘導体と、下記式（４）

（式中、環Ｙは単環又は多環の芳香族性又は非芳香族性環を示し、Ｒ ^e 、Ｒ ^f 、Ｒ ^g 、Ｒ ^h は環Ｙに結合している置換基であって、同一又は異なって、これらのうち２つは保護基で保護されていてもよいアミノ基、残りの２つは保護基で保護されていてもよいヒドロキシル基を示す）
で表されるジヒドロキシジアミン誘導体との反応により前記アミノ基含有アダマンタン誘導体を得るアミノ基含有アダマンタン誘導体の製造方法についても記載する。
Prior Symbol manufacturing method, a carbonyl group-containing adamantane derivative, sequentially or may be added to a solution of excess dihydroxy diamine derivative in excess of the stoichiometric amount. In this specification, in addition to the above invention, the following formula (1)

[Wherein, X ¹ , X ² , X ³ , X ⁴ are the same or different and each represents a single bond or a divalent aromatic or non-aromatic cyclic group, and R ¹ , R ² , R ³ , R ⁴ is an adamantane ring or a substituent bonded to the ring X ¹ , X ² , X ³ , X ⁴ and is the same or different and protected by a hydrogen atom, a hydrocarbon group, or a protecting group A good carboxyl group, acyl group, or the following formula (2A), (2B) or (2C)

(In the formulas (2A), (2B) and (2C), the rings Y are the same or different and represent a monocyclic or polycyclic aromatic or non-aromatic ring, and R ⁵ and R ⁶ are the same. Or, differently, it represents a hydroxyl group which may be protected by a protecting group , R ⁷ represents an amino group which may be protected by a protecting group, and R ′ represents a carbonyl group removed from an acyl group other than a haloformyl group. Group)
The group represented by these is shown. Provided that at least three of R ¹ , R ² , R ³ and R ⁴ are the same or different and represent a group represented by the formula (2A), (2B) or (2C)]
An amino group-containing adamantane derivative represented by the following formula (3):

Wherein X ¹ , X ² , X ³ and X ⁴ are the same or different and each represents a single bond or a divalent aromatic or non-aromatic cyclic group, and R ^a , R ^b , R ^c , R ^d are the same or different and each represents a hydrogen atom, a hydrocarbon group, a carboxyl group or an acyl group which may be protected by a protecting group, provided that at least one of R ^a , R ^b , R ^c and R ^d 3 are the same or different and each represents a carboxyl group or an acyl group which may be protected with a protecting group)
And a carbonyl group-containing adamantane derivative represented by the following formula (4):

(Wherein ring Y represents a monocyclic or polycyclic aromatic or non-aromatic ring, and R ^e , R ^f , R ^g , and R ^h are substituents bonded to ring Y, The same or different, two of these represent an amino group which may be protected with a protecting group, and the other two represent a hydroxyl group which may be protected with a protecting group)
It describes also about the manufacturing method of the amino group containing adamantane derivative which obtains the said amino group containing adamantane derivative by reaction with the dihydroxydiamine derivative represented by these.

  According to the amino group-containing adamantane derivative of the present invention, since it has a bulky steric structure, it prevents high density due to steric hindrance during the polymerization reaction, and high-quality pores having a large volume formed uniformly. A polymer can be produced. For this reason, an extremely low dielectric constant can be achieved, and an insulating film with high heat resistance and mechanical strength can be obtained. In addition, since an amino group-containing adamantane derivative is excellent in solubility in a solvent, an insulating film having a film thickness necessary for an interlayer insulating film can be easily formed. Since the insulating film thus obtained has a high porosity, it exhibits an extremely low relative dielectric constant. Moreover, it has high heat resistance and mechanical strength.

  The amino group-containing adamantane derivative of the present invention is a compound represented by the formula (1) and serves as a monomer component of a polymer having a pore structure.

In the formula (1), X ¹ , X ² , X ³ and X ⁴ are the same or different and each represents a single bond or a divalent aromatic or non-aromatic cyclic group. R ¹ , R ² , R ³ and R ⁴ are the same or different and are a hydrogen atom, a hydrocarbon group, a carboxyl group which may be protected with a protecting group, an acyl group, or the above formulas (2A) and (2B) Or the group represented by (2C) is shown. However, at least three of R ¹ , R ² , R ³ and R ⁴ are the same or different and represent a group represented by (2A), (2B) or (2C). The adamantane skeleton in the formula (1) may have a substituent as long as the properties of the reaction and the crosslinked polymer are not impaired.

The aromatic ring corresponding to the divalent aromatic cyclic group in X ¹ , X ² , X ³ , and X ⁴ includes a monocyclic or polycyclic aromatic carbocyclic ring and aromatic heterocyclic ring. In the present specification, the term “polycycle” refers to a condensed ring structure in which two adjacent rings share two or more atoms, and two or more rings are a single bond or a divalent hydrocarbon group. (Methylene group, vinylene group, etc.), used to mean including those having a structure bonded through one or more linking groups such as oxygen atom, nitrogen atom, silicon atom, sulfur atom and the like.

  Examples of the monocyclic aromatic hydrocarbon ring include a benzene ring. The polycyclic aromatic hydrocarbon ring has, for example, a condensed ring structure in which two or more aromatic rings such as naphthalene ring, anthracene ring, phenanthrene ring, triphenylene ring, pyrene ring each share two or more atoms. And those having a structure in which two or more aromatic rings such as a biphenyl ring, a biphenylene ring, a fluorene ring, and a stilbene ring are bonded via a linking group such as a single bond. Examples of the aromatic heterocycle include monocyclic or polycyclic aromatic heterocycles containing one or more heteroatoms such as oxygen atom, sulfur atom and nitrogen atom. Specific examples of the aromatic heterocyclic ring include a monocyclic ring such as a furan ring, a thiophene ring, a pyridine ring, and a picoline ring; a polycyclic ring such as a quinoline ring, an isoquinoline ring, an acridine ring, and a phenazine ring. These rings may have a substituent as long as the properties of the reaction and the crosslinked polymer are not impaired.

Non-aromatic rings corresponding to the divalent non-aromatic cyclic group in X ¹ , X ² , X ³ , X ⁴ include monocyclic or polycyclic alicyclic carbocycles and non-aromatic heterocycles. Includes a ring. As the alicyclic carbocycle, a cyclopropane ring, cyclobutane ring, cyclopentane ring, cyclohexane ring, cyclooctane ring and the like having about 3 to 20 members (preferably 3 to 15 members, more preferably 3 to 12 members) are used. Alkane ring; monocyclic alicyclic such as cycloalkene ring of about 3 to 20 members (preferably 3 to 15 members, more preferably 3 to 10 members) such as cyclopropene ring, cyclobutene ring, cyclopentene ring, cyclohexene ring Carbon ring; adamantane ring, perhydroindene ring, decalin ring, perhydrofluorene ring, perhydroanthracene ring, perhydrophenanthrene ring, tricyclodecane ring, tricycloundecane ring, tetracyclododecane ring, perhydroacenaphthene ring, Perhydrophenalene ring, norbornane ring, norbornene ring, etc. 2 Such as about 6 ring bridged cyclic carbon ring. Examples of the non-aromatic heterocycle include a 5- or 6-membered heterocycle having at least one heteroatom selected from an oxygen atom, a sulfur atom and a nitrogen atom, and a condensed ring containing these. The non-aromatic cyclic group may have a substituent as long as it does not impair the properties of the reaction or the crosslinked polymer.

Among these, X ¹ , X ² , X ³ , and X ⁴ are divalent aromatic or non-aromatic in that the volume of pores formed by polymerization is large and a low-density structure is easily obtained. An aromatic cyclic group is preferable, and a divalent aromatic ring is particularly preferably used in terms of heat resistance and mechanical strength. In terms of production efficiency and handleability, a benzene ring, a biphenyl ring, a naphthalene ring, or the like is often used as an aromatic ring corresponding to a divalent aromatic cyclic group.

The hydrocarbon group in R ¹ , R ² , R ³ , and R ⁴ includes an aliphatic hydrocarbon group, an alicyclic hydrocarbon group, an aromatic hydrocarbon group, a group in which these are bonded, and the like. Examples of the aliphatic hydrocarbon group include 1 to 20 carbon atoms (preferably 1 to 1) such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, s-butyl, t-butyl, pentyl, hexyl, decyl, and dodecyl groups. 10 or more preferably 1 to 6) linear or branched alkyl group; 2 to 20 carbon atoms (preferably 2 to 10) such as vinyl, allyl, 1-butenyl, 3-methyl-4-pentenyl group, etc. And more preferably about 2 to 5) linear or branched alkenyl group; ethynyl, propynyl, 1-butynyl, 2-butynyl group and the like having 2 to 20 carbon atoms (preferably 2 to 10, more preferably 2). -5) about a linear or branched alkynyl group.

  Examples of the alicyclic hydrocarbon group include a cycloalkyl group having about 3 to 20 members (preferably 3 to 15 members, more preferably 3 to 12 members) such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, and cyclooctyl groups. , Monocyclic alicyclic hydrocarbon groups such as cycloalkenyl groups of about 3 to 20 members (preferably 3 to 15 members, more preferably 3 to 10 members) such as cyclopropenyl, cyclobutenyl, cyclopentenyl and cyclohexenyl groups Adamantane ring, perhydroindene ring, decalin ring, perhydrofluorene ring, perhydroanthracene ring, perhydrophenanthrene ring, tricyclodecane ring, tricycloundecane ring, tetracyclododecane ring, perhydroacenaphthene ring, perhydro Phenalene ring, norbornane ring, norbol Such bridged cyclic hydrocarbon group having such bridged carbocyclic ring of about 2 to 4 rings such as down ring. Examples of the aromatic hydrocarbon group include aromatic hydrocarbon groups having about 6 to 20 carbon atoms (preferably 6 to 14) such as phenyl and naphthyl groups.

The hydrocarbon group in which an aliphatic hydrocarbon group and an alicyclic hydrocarbon group are bonded includes a cycloalkyl-alkyl group such as cyclopentylmethyl, cyclohexylmethyl, 2-cyclohexylethyl group (for example, C _3-20 cycloalkyl- C _1-4 alkyl group and the like). The hydrocarbon group in which an aliphatic hydrocarbon group and an aromatic hydrocarbon group are bonded to each other includes an aralkyl group (for example, a C _7-18 aralkyl group) and an alkyl-substituted aryl group (for example, about 1 to about 4). A phenyl group substituted with a C _1-4 alkyl group or a naphthyl group).

  The aliphatic hydrocarbon group, alicyclic hydrocarbon group, aromatic hydrocarbon group, and a group in which these groups are bonded may have a substituent. The substituent is not particularly limited as long as it does not impair the properties of the reaction and the crosslinked polymer.

Examples of the “protecting group” of the carboxyl group that may be protected with a protecting group in R ¹ , R ² , R ³ , and R ⁴ include an alkoxy group (methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, s - butoxy, t-butoxy, C _1-10 alkoxy groups such as hexyloxy; methoxymethyloxy, etc. (C _1-4 alkoxy) _1-2 C _1-4 alkoxy groups such as methoxyethoxymethyl group), a cycloalkyl Oxy groups (C _3-20 cycloalkyloxy groups such as cyclopentyloxy and cyclohexyloxy), tetrahydrofuranyloxy groups, tetrahydropyranyloxy groups, aryloxy groups (C _6-20 aryloxy groups such as phenoxy and methylphenoxy groups) ), Aralkyloxy group (benzyloxy, diphenylmethyloxy group) Which C _7-18 aralkyloxy group), trialkylsilyl group (trimethylsilyl oxy, tri C _1-4 alkylsilyl group such as triethylsilyl group), an optionally substituted amino group (an amino group; Mono- or di-substituted C _1-6 alkylamino groups such as methylamino, dimethylamino, ethylamino and diethylamino; cyclic amino groups such as pyrrolidino and piperidino groups), hydrazino groups which may have a substituent [hydrazino group, N - C ₇ such as a phenyl hydrazino group, (such as C _1-10 alkoxycarbonyl hydrazino group such as t- butoxycarbonyl hydrazino group) alkoxycarbonyl hydrazino group, an aralkyloxycarbonyl hydrazino group (benzyloxycarbonyl hydrazino group _-18 aralkyloxycarbonylhydrazino group)], Examples include acyloxy groups (C _1-10 acyloxy groups such as acetoxy and propionyloxy groups), acyl groups (C _1-10 acyl groups such as acetyl and propionyl groups), and the like. The protecting group for the carboxyl group is not limited to these, and other protecting groups used in the field of organic synthesis can also be used.

Preferred examples of the carboxyl group protected by a protecting group include C _1-6 alkoxy-carbonyl group, (C _1-4 alkoxy) _1-2 -C _1-4 alkoxy-carbonyl group, N-substituted carbamoyl group, tetrahydro A pyranyloxycarbonyl group, a tetrahydrofuranyloxycarbonyl group, an aryloxycarbonyl group, a trialkylsilyloxycarbonyl group, and a trialkoxymethyl group are included.

Examples of the acyl group in R ¹ , R ² , R ³ , and R ⁴ include aliphatic acyl groups (C _1-10 aliphatic acyl groups such as formyl, acetyl, propionyl, butyryl, isobutyryl, valeryl, and pivaloyl groups), fats Cyclic acyl groups (C _4-20 alicyclic acyl groups such as cyclohexylcarbonyl groups), aromatic acyl groups (C _7-20 aromatic acyl groups such as benzoyl and naphthoyl groups), haloformyl groups (halogenated carbonyl groups) [Chloroformyl group (carbonyl chloride group), bromoformyl group (carbonyl bromide group), fluoroformyl group (carbonyl fluoride group), iodoformyl group (carbonyl iodide group)], alkoxycarbonyl group (methoxycarbonyl, ethoxycarbonyl) , C _1-4 alkoxy, such as t- butoxycarbonyl - carbonyl group); aralkyloxy - Ca Boniru group (benzyloxycarbonyl group, C _7-20 aralkyloxycarbonyl group such as p- methoxybenzyloxycarbonyl group). Of these, a formyl group and the like are preferably used.

In formulas (2A), (2B), and (2C), ring Y represents a monocyclic or polycyclic aromatic or non-aromatic ring, and R ⁵ and R ⁶ are the same or different and are each a protecting group. And R ⁷ is the same or different and represents an amino group which may be protected with a protecting group. In the formula (1), groups represented by the formulas (2A), (2B), and (2C) may exist alone or in combination, and a plurality of formulas (2A), (2B), and (2C) The rings Y and R ⁵ etc. possessed by the group represented may be the same or different.

  The monocyclic or polycyclic aromatic ring in ring Y includes an aromatic carbocycle and an aromatic heterocycle. A benzene ring is mentioned as a monocyclic aromatic carbocyclic ring. Examples of polycyclic aromatic carbocycles include those having a condensed ring structure in which two or more aromatic rings such as naphthalene ring, anthracene ring, phenanthrene ring, triphenylene ring, pyrene ring each share two or more atoms Two or more aromatic rings such as a biphenyl ring, a biphenylene ring, a fluorene ring, and a stilbene ring are one or more linking groups [eg, single bond, divalent hydrocarbon group (methylene group, vinylene group, etc.), oxygen Atoms, nitrogen atoms, silicon atoms, sulfur atoms, etc.]. Examples of the aromatic heterocycle include monocyclic or polycyclic aromatic heterocycles containing one or more heteroatoms such as oxygen atom, sulfur atom and nitrogen atom. Specific examples of the aromatic heterocyclic ring include a monocyclic ring such as a furan ring, a thiophene ring, a pyridine ring, and a picoline ring; a polycyclic ring such as a quinoline ring, an isoquinoline ring, an acridine ring, and a phenazine ring.

  The monocyclic or polycyclic non-aromatic ring in ring Y includes an alicyclic hydrocarbon ring and a non-aromatic heterocyclic ring. Examples of the non-aromatic ring include a non-aromatic ring corresponding to the non-aromatic cyclic group in Y. The monocyclic or polycyclic aromatic or non-aromatic ring in ring Y may have a substituent as long as the properties of the reaction and the polymer crosslinked product are not impaired.

Examples of the “protecting group” of the hydroxyl group which may be protected with a protecting group in R ⁵ and R ⁶ include, for example, alkyl groups (methyl, ethyl, propyl, isopropyl, butyl, t-butyl, pentyl, hexyl groups, etc. C _1-6 alkyl group), cycloalkyl group (3- to 15-membered cycloalkyl group such as cyclopentyl group, cyclohexyl group), aralkyl group (C _7-20 aralkyl group such as benzyl group), substituted methyl group ( A substituted methyl group having a total carbon number of about 2 to 10 such as methoxymethyl, benzyloxymethyl, t-butoxymethyl, 2-methoxyethoxymethyl group), substituted ethyl group (1-ethoxyethyl, 1-methyl-1-methoxyethyl) Groups), acyl groups (formyl, acetyl, propionyl, butyryl, isobutyryl, valeryl, pivaloyl groups, etc.) C _1-10 aliphatic acyl group; C _4-20 alicyclic acyl group such as cyclohexylcarbonyl group; C _7-20 aromatic acyl group such as benzoyl, naphthoyl group, etc.), alkoxycarbonyl group (methoxycarbonyl, ethoxy C _1-4 alkoxy-carbonyl groups such as carbonyl and t-butoxycarbonyl), aralkyloxycarbonyl groups (C _7-20 aralkyloxy-carbonyl groups such as benzyloxycarbonyl group and p-methoxybenzyloxycarbonyl group) and the like. included. The hydroxyl-protecting group is not limited to these, and those commonly used in the field of organic synthesis can be used.

As "protecting groups" in the protected or unprotected amino group in R ⁷ is, for example, aliphatic acyl group (formyl, acetyl, propionyl, butyryl, isobutyryl, valeryl, C _1-6 aliphatic such as pivaloyl group group an acyl group), an aromatic acyl group (benzoyl, an aromatic acyl group having about 6 to 20 carbon atoms, such as naphthoyl group), alkoxycarbonyl groups (methoxycarbonyl, ethoxycarbonyl, such as t- butoxycarbonyl C _{1- 4} alkoxy-carbonyl groups, etc.), aralkyloxy-carbonyl groups (benzyloxycarbonyl groups, C _7-20 aralkyloxycarbonyl groups such as p-methoxybenzyloxycarbonyl groups), alkylidene groups (methylidene, ethylidene, propylidene, isopropylidene, Butylidene, isobutylidene, pe Chiriden, cyclopentylidene, Hekiriden, aliphatic alkylidene group such as cyclohexylidene group; benzylidene and aromatic alkylidene group such as methyl phenyl methylidene) and the like.

As an amino-protecting group other than the above, a protecting group (polyfunctional protecting group) capable of simultaneously protecting a plurality of amino groups can also be used. Such protecting groups include, for example, carbonyl group, oxalyl group, butane-2,3-diylidene group and the like. When such a protecting group is used, two groups out of R ⁵ , R ⁶ and R ⁷ are simultaneously protected by one polyfunctional protecting group to form a ring adjacent to ring Y. In addition, the amino group which may be protected with a protecting group in R ⁵ , R ⁶ and R ⁷ includes a mono-substituted amino group as long as the properties of the reaction and the final polymer crosslinked product are not impaired. Examples of mono-substituted amino groups include alkylamino groups such as methylamino group, ethylamino group, propylamino group, butylamino group and t-butylamino group; cycloalkylamino groups such as cyclohexylamino group; phenylamino group and the like An arylamino group such as benzylamino group, and the like. The amino-protecting group is not limited to these, and those commonly used in the field of organic synthesis can be used.

  Further, the amino group which may be protected with a protecting group includes a mono-substituted amino group as long as the properties of the reaction and the final polymer crosslinked product are not impaired. Examples of mono-substituted amino groups include alkylamino groups such as methylamino group, ethylamino group, propylamino group, butylamino group and t-butylamino group; cycloalkylamino groups such as cyclohexylamino group; phenylamino group and the like An arylamino group such as benzylamino group, and the like.

  R ′ in the formula (2A) represents a group obtained by removing a carbonyl group from an acyl group other than a haloformyl group. Specifically, for example, when the acyl group other than the haloformyl group is a formyl group, it means a hydrogen atom, and when the acyl group other than the haloformyl group is an acetyl group, it means a methyl group.

In formulas (2A), (2B), and (2C), a pair of groups (for example, N and R ⁵ , R ⁶ and R ⁷ ) among N, R ⁵ , R ⁶ , and R ⁷ bonded to ring Y is a ring From the viewpoint of ease of formation, it is preferably bonded to the position of the 1,2-position (α-position) or 1,3-position (β-position) of the constituent atoms of the ring Y. The pair of groups is preferably a combination of an amino group which may be protected with a protecting group and a hydroxyl group which may be protected with a protecting group. Of such a pair of groups, for example, R ⁵ and N can form a ring together with adjacent groups. That is, the group represented by the formula (2A) is bonded to the amide in the molecule and the ring Y by the cyclization reaction between the imine in the molecule and R ⁵ bonded to the ring Y. By the cyclization reaction with R ⁵ , a ring such as oxazole is formed, and the corresponding group represented by the formula (2C) can be generated. Of the pair of groups, for example, R ⁶ and R ⁷ can form a ring with a compound having one carbonyl group (for example, a carbonyl group-containing adamantane derivative represented by the formula (3)). .

As typical compounds of the amino group-containing adamantane derivative represented by the formula (1), R ¹ , R ² , R ³ and R ⁴ are all groups represented by the formula (2A), (2B) or (2C) The compound which is is illustrated below.

In the formula (1A), (1B), (1C), the ring Y ^a, Y ^b, Y ^c, Y ^d are the same or different and is similar to the ring Y in the formula (1), the ring Y ^a binding to ^{R 5a, R 6a, R 7a} , R 5b is bonded to the ring ^{Y b, R 6b, R 7b} , R 5c is attached to the ring ^{Y c, R 6c, R 7c} , R 5d of bonding to the ring Y ^d, R ^6d and R ^7d are the same or different and are the same as R ⁵ and the like in formula (2A) and the like. In the present specification, a compound containing 3 or more imines in a molecule represented by the above formula (1A) or the like is referred to as an “imine adamantane derivative”, and 3 or more amides in a molecule represented by the formula (1B). A compound containing a bond may be referred to as an “amide type adamantane derivative”, and a compound containing three or more rings such as oxazole in a molecule represented by the formula (1C) may be referred to as an “oxazole type adamantane derivative”.

In the amino group-containing adamantane derivative represented by the formula (1), the imine type adamantane derivative represented by the formula (1A) and the amide type adamantane derivative represented by the formula (1B) and the like are represented by the formula (1C). There is a relationship of an intermediate of an oxazole type adamantane derivative. Specifically, in the compound represented by the formula (1A) or the formula (1B), an imine or amide in the molecule forms a ring by bonding with R ⁵ bonded to the ring Y, and the compound represented by the formula (1C Oxazole-type adamantane derivatives represented by In addition, as an intermediate body of the compound represented by Formula (1C), it is not limited to the said Formula (1A) and (1B), For example, it is a compound which has both Formula (2A) and (2B) in a molecule | numerator. There may be.

Further, as representative compounds of the amino group-containing adamantane derivative represented by the formula (1), R ¹ , R ² and R ³ are all groups represented by the formula (2A), (2B) or (2C). A compound in which R ⁴ is a non-reactive group (hydrogen atom or hydrocarbon group) or a reactive functional group (carboxyl group or acyl group optionally protected by a protecting group) is exemplified below.

In the formulas (1A-Z), (1B-Z) and (1C-Z), Z represents a carboxyl group or an acyl group which may be protected with a protecting group, and the formulas (1A-R), (1B-Z In R) and (1C—R), R represents a hydrogen atom or a hydrocarbon group, and these are the same as the groups in R ^{1 and the} like in the formula (1). Ring Y ^a , R ^{6a and the} like are the same as described above. The above formulas (1A-Z) and (1A-R) are imine-type adamantane derivatives containing three imines in the molecule, and the above formulas (1B-Z) and (1B-R) are three amides in the molecule. It represents an amide type adamantane derivative containing a bond. The compounds represented by the above formulas (1C-Z) and (1C-R) represent oxazole-type adamantane derivatives in which three rings such as oxazole are formed in the molecule, and the above-mentioned imine-type adamantane derivatives and amide-type compounds. It can be derived from an adamantane derivative or the like.

  The amino group-containing adamantane derivative of the present invention is obtained by a reaction between a carbonyl group-containing adamantane derivative represented by the above formula (3) and a dihydroxydiamine derivative represented by the above formula (4).

In the formula (3), X ¹ , X ² , X ³ and X ⁴ are the same or different and each represents a single bond or a divalent aromatic or non-aromatic cyclic group, and R ^a , R ^b , R ^c and R ^d are the same or different and each represents a hydrogen atom, a hydrocarbon group, a carboxyl group or an acyl group which may be protected with a protecting group. However, at least three of R ^a , R ^b , R ^c and R ^d are the same or different and represent a carboxyl group or an acyl group which may be protected with a protecting group. The adamantane skeleton in the formula (3) may have a substituent as long as the properties of the reaction and the crosslinked polymer are not impaired.

The divalent aromatic or non-aromatic cyclic group in X ¹ , X ² , X ³ , and X ⁴ and the hydrocarbon group in R ^a , R ^b , R ^c , and R ^d are represented by the above formula ( X ¹ etc. and R ^a etc. in 1) are the same as those exemplified.

Examples of the carbonyl group-containing adamantane derivative represented by the formula (3) include compounds represented by the following formulas (3A) and (3B).

In the formulas (3A) and (3B), Z ¹ , Z ² , Z ³ and Z ⁴ are the same or different and each represents a carboxyl group or an acyl group which may be protected with a protecting group, and R represents a hydrogen atom. Alternatively, hydrocarbon groups are shown, and those exemplified as ^{Ra and the} like in formula (3) can be used for these groups. X ^{1 and the} like are the same as in equation (3). In the present specification, the compound represented by the above formula (3A) may be referred to as “tetrafunctional adamantane derivative”, and the compound represented by formula (3B) may be referred to as “trifunctional adamantane derivative”. 3 or 4 of R ^a , R ^b , R ^c and R ^d in formula (3) [in formulas (3A) and (3B), 3 or ^{3 of} Z ¹ , Z ² , Z ³ and Z ⁴ 4] is a carboxyl group or haloformyl group which may be protected with a protecting group as a “carboxyl”, a compound as a formyl group is an “aldehyde”, and an acyl group excluding a formyl group and a haloformyl group. The compound may be referred to as “ketones”.

  Representative examples of the carbonyl group-containing adamantane derivative represented by the formula (3A) include, for example, 1,3,5,7-adamantanetetracarboxylic acid, 1,3,5,7-tetrakis (4-carboxyphenyl) Adamantane, 1,3,5,7-adamantanetetracarboxylic acid tetrachloride, 1,3,5,7-tetrakis (4-chloroformylphenyl) adamantane, 1-carboxy-3,5,7-tricarboxyphenyladamantane, etc. Carboxylic acids of 1,3,5,7-adamantane tetraaldehyde, aldehydes such as 1,3,5,7-adamantane tetrakisbenzaldehyde, phenyladamantyl ketone (1,3,5,7-tetrabenzoyladamantane), etc. Examples include ketones.

  Representative examples of the carbonyl group-containing adamantane derivative represented by the formula (3B) include, for example, 1,3,5-adamantanetricarboxylic acid, 1,3,5-tricarboxy-7-methyladamantane, 1,3,5, Carboxylic acids such as 5-tris (4-carboxyphenyl) adamantane, 1,3,5-adamantanetricarboxylic acid chloride, 1,3,5-tris (4-chloroformylphenyl) adamantane, etc., 1-carboxy-3- Carboxylic acids such as carboxyphenyl-5-methyladamantane; Aldehydes such as 1,3,5-adamantane trialdehyde, 1,3,5-triformyl-4-methyladamantane, 1,3,5-adamantane trisbenzaldehyde; 1 , 3,5-trisbenzoyladamantane) and the like It is.

  These carbonyl group-containing adamantane derivatives can be used alone or in combination of two or more. Among them, the carbonyl group-containing adamantane derivative (tetrafunctional adamantane derivative) represented by the formula (3A) has a bulky structure, and can efficiently form sparse vacancies due to steric hindrance during the reaction. Preferably used.

  Further, when an aldehyde (for example, 1,3,5-adamantane tetrakisbenzaldehyde, 1,3,5,7-adamantanetetrakisbenzaldehyde, etc.) is used as the carbonyl group-containing adamantane derivative, the reaction with the dihydroxydiamine derivative can be easily controlled, This is advantageous in that the amino group-containing adamantane derivative represented by the formula (1) can be efficiently produced.

  The carbonyl group-containing adamantane derivative represented by the formula (3) (3A and 3B) can be obtained by a known method, or a known organic synthesis reaction, a known method for introducing a protective group into a carboxyl group (for example, esterification, Etc.) and the like.

In the formula (4), ring Y represents a monocyclic or polycyclic aromatic or non-aromatic ring, and R ^e , R ^f , R ^g and R ^h are substituents bonded to ring Y. And the same or different, two of them represent an amino group which may be protected with a protecting group, and the other two represent a hydroxyl group which may be protected with a protecting group. The polycyclic aromatic or non-aromatic ring in ring Y, the amino group optionally protected with a protecting group in R ^{g and the} like, and the hydroxyl group optionally protected with a protecting group are each represented by the above formula ( The ring Y and R ⁵ in 1) are the same as those exemplified.

In terms of ease of cyclization, a pair of a hydroxyl group which may be protected with a protecting group in R ^e , R ^f , R ^g and R ^h and an amino group which may be protected with a protecting group are The ring Y is preferably bonded to the position of the 1,2-position (α-position) or 1,3-position (β-position) of the constituent atoms of the ring Y. The pair of groups can form a ring such as oxazole with a compound having one carboxyl group (for example, a carbonyl group-containing adamantane derivative represented by the formula (3)).

As the dihydroxydiamine derivative represented by the formula (4), (i) any amino group that may be protected by two protecting groups of R ^e , R ^f , R ^g , and R ^h is an amino group. A compound, (ii) a compound in which at least one of R ^e , R ^f , R ^g , and R ^h is an amino group protected with an alkylidene group (that is, an imine derivative), (iii) R ^e , R ^f , R ^g , A compound in which at least one of R ^h is an acylamino group (ie, an amide derivative), (iv) an amino in which at least one of R ^e , R ^f , R ^g , R ^h is protected with an alkoxycarbonyl group or an aralkyloxycarbonyl group Examples thereof include a compound that is a group (that is, a carbamate derivative), (v) a compound in which at least one of R ^e , R ^f , R ^g , and R ^h is a mono-substituted amino group.

  As typical compounds of the dihydroxydiamine derivatives exemplified in the above (i) to (v), the ring Y is limited to a benzene ring, and the number of protecting groups in the case of having a protecting group is also a 4-substituent or Although the compound limited to 2 substitution body is illustrated below, it is not restricted to these. That is, when ring Y is a biphenyl ring or the like, compounds corresponding to the following compounds are exemplified.

As a representative example of a compound in which (i) the amino group optionally protected by two protecting groups out of R ^e , R ^f , R ^g and R ^h is an amino group, 1,4- Diamino-2,5-dihydroxybenzene, 1,5-diamino-2,4-dihydroxybenzene, 1,4-diamino-2,5-dimethyloxybenzene, 1,5-diamino-2,4-dimethyloxyxybenzene Etc.

As a representative example of the compound (ii) in which at least one of R ^e , R ^f , R ^g and R ^h is an amino group protected with an alkylidene group (that is, an imine derivative), a compound represented by the following formula: Etc.

In the imine derivative, R ^e and R ^h in the formula (4) are both amino groups protected with an alkylidene group, and N, N ″ -diisopropylidene-1,4-diamino-2,5-dihydroxy Benzene, N, N ″ -diisopropylidene-1,5-diamino-2,4-dihydroxybenzene, N, N ″ -dicyclohexylidene-1,4-diamino-2,5-dihydroxybenzene, N, N "-Dicyclohexylidene-1,5-diamino-2,4-dihydroxybenzene, N, N" -dibenzylidene-1,4-diamino-2,5-dihydroxybenzene, N, N "-dibenzylidene-1 , 5-diamino-2,4-dihydroxybenzene and the like, and R ^g and R ^h are both hydroxyl groups; N, N ″ -diisopropylidene-1,4-diamino-2, 5-dimethyloxybenzene, N, N ″ -diisopropylidene-1,5-diamino-2,4-dimethyloxybenzene, N, N ″ -dicyclohexylidene-1,4-diamino-2,5-dimethyl Oxybenzene, N, N ″ -dicyclohexylidene-1,5-diamino-2,4-dimethyloxymethyloxybenzene, N, N ″ -dibenzylidene-1,4-diamino-2,5-dimethyloxybenzene N, N ″ -dibenzylidene-1,5-diamino-2,4-dimethyloxybenzene and the like, and R ^g and R ^h are both hydroxyl groups protected by a protecting group.

Examples of the compound (iii) in which at least one of R ^e , R ^f , R ^g , and R ^h is an acylamino group (that is, an amide derivative) include compounds represented by the following formula.

In the amide derivative, R ^e and R ^h in the formula (4) are both acylamino groups, and 1,4-bis (acetamino) -2,5-dihydroxybenzene, 1,5-bis (acetamino) -2 Amide derivatives in which R ^f and R ^g are both hydroxyl groups, such as 1,4-dihydroxybenzene; 1,4-bis (acetamino) -2,5-diacetylbenzene, 1,5-bis (acetamino) -2,4- Examples include amide derivatives such as diacetylbenzene in which R ^f and R ^g are both hydroxyl groups protected by a protecting group.

Examples of the compound (iv) wherein at least one of R ^e , R ^f , R ^g , R ^h is an amino group protected with an alkoxycarbonyl group or an aralkyloxycarbonyl group (that is, a carbamic acid ester derivative) Examples of the compound are represented.

In the carbamic acid ester derivative, R ^e and R ^h in the formula (4) are both alkoxycarbonyl groups, and 1,4-bis (methoxycarbonylamino) -2,5-dihydroxybenzene, 1,5-bis (Methoxycarbonylamino) -2,4-dihydroxybenzene and the like carbamate derivatives in which R ^f and R ^g are both hydroxyl groups; 1,4-bis (methoxycarbonylamino) -2,5-dimethoxycarbonyloxybenzene, 1 include carbamate derivatives which are 5-bis R ^f, hydroxyl groups R ^g is protected both by a protecting group such as (methoxycarbonylamino) -2,4-dimethoxy carbonyl oxybenzene.

As a typical example of the compound (v) in which at least one of R ^e , R ^f , R ^g and R ^h is a mono-substituted amino group, R ^e and R ^h in the formula (4) are both mono-substituted amino groups. 1,4-dihydroxy-2,5-bis (methylamino) benzene, 1,5-dihydroxy-2,4-bis (methylamino) benzene, 1,4-dihydroxy-2,5-bis ( Compounds in which R ^f and R ^g are hydroxyl groups, such as phenylamino) benzene and 1,5-dihydroxy-2,4-bis (phenylamino) benzene; 1,4-dimethoxy-2,5-bis (methylamino) Benzene, 1,5-dimethoxy-2,4-bis (methylamino) benzene, 1,4-dimethoxy-2,5-bis (phenylamino) benzene, 1,5-dimethoxy-2,4-bis (phenylamino) ) R ^f, such as benzene, R ^g is a hydroxyl group protected by a protective group compound.

In addition to the above, the dihydroxydiamine derivative represented by the formula (4) includes a compound in which at least two of R ^e , R ^f , R ^g and R ^h are bonded to each other to form a ring with adjacent atoms. included. Examples of such dihydroxydiamine derivatives include compounds in which an amino group in the molecule is protected with a protecting group (polyfunctional protecting group) capable of simultaneously protecting the plurality of amino groups. As a typical example of such a compound, a compound in which 1,4-dihydroxy-2,5-diaminobenzene is protected with two oxalyl groups [in the formula (4), ring Z ¹ is a benzene ring, , R ^e and R ^f , R ^g and R ^h are each an amino group protected with an oxalyl group], 1,4-dihydroxy-2,5-diaminobenzene is two butane-2,3-diylidene groups [In Formula (4), Ring Z is a benzene ring, and R ^e and R ^f , R ^g and R ^h are each an amino group protected with a butane-2,3-diylidene group. Compound] and the like.

  These dihydroxydiamine derivatives can be used alone or in combination of two or more.

  The dihydroxydiamine derivative represented by the above formula (4) can be obtained by a known method, or a known organic synthesis reaction, a method for introducing a protecting group to a known amino group (for example, a method by acylation, iminolation, alkylation). Etc.) can be obtained by utilizing a known method for introducing a protecting group into a hydroxyl group.

  The reaction of the carbonyl group-containing adamantane derivative represented by the formula (3) and the dihydroxydiamine derivative represented by the formula (4) includes general amidation reaction, imine derivative (Schiff base) formation reaction, oxazole ring formation reaction. It can carry out according to etc. As such a reaction, for example, Terashima, M. et al. Synthesis, 484-485 (1982) describes a reaction for forming an oxazole ring via an amide bond forming reaction by a reaction between carboxylic acid and aminophenol. Described in Y. Kawashita et al. Org. Lett. 3713-3715 (2003) as a reaction to form an oxazole ring via a Schiff base by reaction of aldehyde and aminophenol. A cyclization reaction by oxidation of a Schiff base can be used. Moreover, you may use the oxazole ring formation reaction by another oxidation.

  The reaction is usually performed in a solvent. Any solvent may be used as long as it dissolves the raw materials and does not inhibit the reaction. Examples thereof include amides such as N, N-dimethylformamide, N, N-dimethylacetamide (DMAc), N-methyl-2-pyrrolidone; Cyclic aminoacetals such as imidazolidine and dimethylimidazolidinone (dimethylimidazolidine-dione); Sulfoxides such as dimethyl sulfoxide; Sulfones; Nitriles such as acetonitrile, propionitrile, benzonitrile; Acetone, Methyl ethyl ketone, Diethyl ketone , Ketones such as methyl isobutyl ketone, cyclopentanone, cyclohexanone; formate ester, acetate ester, propionate ester, benzoate ester, γ-butyrolactone, propylene glycol monomethyl ether acetate Esters such as PGMEA); ethers such as dioxane, tetrahydrofuran, diethyl ether, ethylene glycol diethyl ether; halogenated hydrocarbons such as dichloromethane, dichloroethane, chloroform, carbon tetrachloride, chlorobenzene; benzene, toluene, xylene, Examples thereof include aromatic hydrocarbons such as ethylbenzene and mesitylene; alicyclic hydrocarbons such as cyclohexane and methylcyclohexane; aliphatic hydrocarbons such as hexane, heptane and octane. These solvents can be used alone or in admixture of two or more.

  Of these, aprotic polar solvents such as amides, cyclic aminoacetals, and sulfones are preferable, and in particular, N, N-dimethylformamide, N, N-dimethylacetamide (DMAc), N-methyl-2-pyrrolidone, and the like. Amides; cyclic aminoacetals such as dimethylimidazolidine, dimethylimidazolidinone (dimethylimidazolidine-dione); and mixed solvents thereof are preferably used.

The dissolution is performed, for example, in an air atmosphere as long as the dihydroxydiamine derivative or the like is not oxidized, and preferably in an inert gas atmosphere such as nitrogen or argon. Further, as a carbonyl group-containing adamantane derivative, when at least one of R ^a , R ^b , R ^c , and R ^d in formula (3) is an acyl group (for example, formyl group), oxygen is supplied into the reaction system. It is preferable to do this. As the oxygen, a mixed gas (such as air) diluted with an inert gas such as nitrogen or argon can be used.

  The reaction temperature varies depending on the type of the carbonyl group-containing adamantane derivative represented by the formula (3), the type of the dihydroxydiamine derivative represented by the formula (4), etc., but generally it is appropriately selected within the range of 0 ° C to 200 ° C. it can. The reaction temperature may be constant or may be changed continuously or sequentially. For example, when the carbonyl group-containing adamantane derivative is adamantane tetrakisbenzaldehyde and the dihydroxydiamine derivative is an amine having no protecting group, the reaction temperature is about −10 ° C. to 150 ° C.

  The ratio of the carbonyl group-containing adamantane derivative and dihydroxydiamine derivative can be selected within a wide range, and both may be used in an equivalent amount, or one of them may be used in an excess amount. In the present invention, an excess of the dihydroxydiamine derivative exceeding the stoichiometric amount relative to the carbonyl group-containing adamantane derivative is preferably used. According to this method, gelation accompanying high molecular weight (polymerization consisting of a crosslinked structure) can be suppressed, and the desired compound can be obtained in good yield. The amount of the dihydroxydiamine derivative to be charged is, for example, 0.1 to 1000 equivalents, preferably 1 to 800 equivalents, more preferably 20 equivalents or more (particularly 20 to 500 equivalents) with respect to the carbonyl group-containing adamantane derivative. If the amount of the dihydroxydiamine derivative used is too small, the number of molecules of the dihydroxydiamine derivative bound to one molecule of the carbonyl group-containing adamantane derivative may decrease, and the dihydroxydiamine bonded to the bridgehead position of the carbonyl group-containing adamantane derivative may be reduced. A reaction in which the diamine derivative forms an amide bond with another carbonyl group-containing adamantane derivative easily proceeds, and it tends to be difficult to obtain the amino group-containing adamantane derivative represented by the formula (1). On the other hand, when the amount of the dihydroxydiamine derivative used is too large, separation and purification of the unreacted residual amine and the carbonyl group-containing adamantane derivative represented by the formula (1) tend to be inefficient and economical.

  The reaction can be performed by a conventional method such as a batch system, a semi-batch system, or a continuous system. In the present invention, preferably, a method of sequentially adding a carbonyl group-containing adamantane derivative into a solution obtained by dissolving a dihydroxydiamine derivative in a solvent is performed. Sequentially add a carbonyl group-containing adamantane derivative to a solution of excess dihydroxydiamine derivative exceeding the stoichiometric amount.

  For the reaction, depending on the type of carbonyl group-containing adamantane derivative and dihydroxydiamine derivative used as a raw material, an appropriate catalyst (base catalyst, acid catalyst, etc.), a reactive agent, a trap agent (base, Dehydrating agents, etc.), condensing agents (polyphosphoric acid, etc.) may be used.

In this way, the carboxyl group or acyl group which may be protected with a protecting group in R ^a , R ^b , R ^c and R ^d of the carbonyl group-containing adamantane derivative, and R ^e and R ^f of the dihydroxydiamine derivative. The amino group-containing adamantane derivative represented by the formula (1) is generated by reaction with an amino group which may be protected with a protecting group in R ^g and R ^h . Specifically, depending on the type of R ^a or the like in Formula (3), for example, when R ^a or the like is an acyl group excluding a haloformyl group, it is represented by Formula (2A) by an imine (Schiff base) generation reaction. An imine-type adamantane derivative having a group is formed. In the case where R ^a or the like is ^a carboxyl group and / or a haloformyl group which may be protected with a protecting group, an amide type adamantane derivative having a group represented by the formula (2B) is generated by an amidation reaction. These imine-type adamantane derivatives and amide-type adamantane derivatives further generate oxazole-type adamantane derivatives having a group represented by the formula (2C) by further progress of the cyclization reaction in imine and amide.

  The molecular weight of the amino group-containing adamantane derivative to be generated is, for example, about 500 to 30000, preferably 700 to 10000, and more preferably about 1100 to 1500. The molecular weight of the amino group-containing adamantane derivative is approximately the same as the molecular weight of the starting carbonyl group-containing adamantane derivative and the sum of 3 to 4 times the molecular weight of the dihydroxydiamine derivative, and can be adjusted by appropriately selecting these raw materials. .

  The produced amino group-containing adamantane derivative can be isolated by separation and purification means such as precipitation, reprecipitation, crystallization, recrystallization, filtration, extraction, and drying.

  The amino group-containing adamantane derivative includes (i) a formula (1A) or a compound obtained by a reaction between a tetrafunctional adamantane derivative represented by the formula (3A) and a dihydroxydiamine derivative represented by the formula (4). An imine type compound represented by (1A-Z), an amide type compound represented by formula (1B) or (1B-Z), an oxazole type compound represented by formula (1C) or (1C-Z), and (Ii) an imine-type trifunctional compound represented by the formula (1A-R) obtained by reacting the trifunctional adamantane derivative represented by the formula (3B) with the dihydroxydiamine derivative represented by the formula (4) Amide type trifunctional compound represented by (1B-R) and oxazole type trifunctional compound represented by (1C-R).

  The amino group-containing adamantane derivative of the present invention is soluble in a solvent. Examples of such solvents include amides such as N, N-dimethylformamide, N, N-dimethylacetamide, and N-methyl-2-pyrrolidone; dimethylimidazolidine, dimethylimidazolidinone (dimethylimidazolidine-dione), and the like. Cyclic aminoacetals; sulfoxides such as dimethyl sulfoxide; sulfones; nitriles such as acetonitrile, propionitrile, and benzonitrile; ketones such as acetone, methyl ethyl ketone, diethyl ketone, methyl isobutyl ketone, cyclopentanone, and cyclohexanone; Esters such as formate ester, acetate ester, propionate ester, benzoate ester, ethyl lactate, γ-butyrolactone, propylene glycol monomethyl ether acetate (PGMEA); Ethers such as ethylene, tetrahydrofuran, diethyl ether, ethylene glycol monoethyl ether, ethylene glycol diethyl ether, propylene glycol monomethyl ether (PGME); alcohols such as methanol, ethanol, propanol, butanol, ethylene glycol, propylene glycol Halogenated hydrocarbons such as dichloromethane, dichloroethane, chloroform, carbon tetrachloride and chlorobenzene; nitro compounds such as nitromethane; aromatic hydrocarbons such as benzene, toluene, xylene, ethylbenzene and mesitylene; alicyclics such as cyclohexane and methylcyclohexane Hydrocarbons; aliphatic hydrocarbons such as hexane, heptane, and octane; and mixed solvents thereof. These solvents can be used alone or in admixture of two or more.

  The insulating film forming material is a polymerizable composition obtained by dissolving an amino group-containing adamantane derivative represented by the formula (1) and a carbonyl group-containing adamantane derivative represented by the formula (3) in a solvent. Can be configured. The amino group-containing adamantane derivative and the carbonyl group-containing adamantane derivative constitute a monomer component, and each component may be used alone or in combination of a plurality of types. Any solvent may be used as long as it can dissolve the amino group-containing adamantane derivative and does not inhibit polymerization, cyclization reaction, and the like. For example, the solvents exemplified above can be used. Of these, aprotic polar solvents such as amides, cyclic aminoacetals, and sulfones are preferable, and in particular, N, N-dimethylformamide, N, N-dimethylacetamide (DMAc), N-methyl-2-pyrrolidone, and the like. Amides; cyclic aminoacetals such as dimethylimidazolidine, dimethylimidazolidinone (dimethylimidazolidine-dione); and mixed solvents thereof are preferably used.

  The amino group-containing adamantane derivative can obtain a polymer crosslinked product having a high molecular weight by reaction with the carbonyl group-containing adamantane derivative. The use amount ratio (molar ratio) of the amino group-containing adamantane derivative and the carbonyl group-containing adamantane derivative is, for example, 1/99 to 99/1, preferably 10/90 to 90/10, more preferably 20/80 to 80 /. It is about 20 and can also be used in an equivalent amount.

  The insulating film forming material may contain other components as necessary. Examples of such components include components used as raw materials for amino group-containing adamantane derivatives (carbonyl group-containing adamantane derivatives and / or dihydroxydiamine derivatives). As other components other than the above, for example, a catalyst for promoting the polymerization reaction may be added. Typical examples of the catalyst include acid catalysts such as sulfuric acid, methanesulfonic acid, and p-toluenesulfonic acid. The usage-amount of a catalyst is 0-10 mol% with respect to the total amount of the said monomer component (Adamantane polycarboxylic acid and aromatic polyamine), Preferably it is about 0-5 mol%.

  Moreover, in order to improve applicability | paintability, you may add the thickener which raises the viscosity of a solution to an insulating film formation material. Typical examples of the thickener include alkylene glycols such as ethylene glycol, diethylene glycol, triethylene glycol, and polyethylene glycol, and polyalkylene glycols. The usage-amount of a thickener is 0-20 weight% with respect to the whole insulating film forming material, for example, Preferably it is about 0-10 weight%. Furthermore, monocarboxylic acids for adjusting the molecular weight after polymerization and / or dicarboxylic acids for adjusting the degree of crosslinking after polymerization may be added to the insulating film forming material. Representative examples of monocarboxylic acids include monocarboxylic acids such as adamantane carboxylic acid and benzoic acid; monocarboxylic acid derivatives such as adamantane carboxylic acid methyl ester and benzoic acid methyl ester, and the like. Examples include dicarboxylic acids such as terephthalic acid; dicarboxylic acid derivatives such as dimethyl terephthalate. The amount of monocarboxylic acid used is, for example, 0 to 10 mol%, preferably 0 to 5 mol%, based on the total amount of monomer components (amino group-containing adamantane derivative and carbonyl group-containing adamantane derivative) constituting the insulating film forming material. The amount of dicarboxylic acids used is, for example, 0 to 100 mol%, preferably 0 to 50 mol, based on the total amount of monomer components (amino group-containing adamantane derivative and carbonyl group-containing adamantane derivative) constituting the prepolymer. %.

  You may add the adhesion promoter for improving the board | substrate adhesiveness of the insulating film formed to an insulating film formation material. Typical examples of the adhesion promoter include trimethoxyvinylsilane, hexamethyldisilazane, γ-aminopropyltriethoxysilane, aluminum monoethylacetoacetate diisopropylate, and the like. The amount of the adhesion promoter used is, for example, about 0 to 10% by weight, preferably about 0 to 5% by weight, based on the total amount of the monomer components.

  The dissolution is performed, for example, in an air atmosphere, and preferably in an inert gas atmosphere such as nitrogen or argon, as long as the amino group-containing adamantane derivative or the like is not oxidized. The temperature to dissolve is not particularly limited, and may be heated according to the solubility and stability of the monomer component (amino group-containing adamantane derivative and carbonyl group-containing adamantane derivative), the boiling point of the solvent. Preferably it is about 10-150 degreeC.

  The insulating film is composed of a polymer (polymer crosslinked product) formed from the amino group-containing adamantane derivative and the carbonyl group-containing adamantane derivative. The insulating film is formed, for example, by applying an insulating film forming material made of a polymerizable composition on a substrate and then heating to cause a polymerization reaction. Examples of the base material include a silicon wafer, a metal substrate, and a ceramic substrate. The application method is not particularly limited, and conventional methods such as spin coating, dip coating, and spraying can be used.

  The heating temperature is not particularly limited as long as the polymerizable component to be used is polymerized, and is, for example, room temperature (about 25 ° C.) to 500 ° C., preferably about room temperature (about 25 ° C.) to 400 ° C. A temperature gradient may be applied. The stepwise temperature gradient may be a simple temperature rise (continuous temperature rise) or a multistage (discontinuous) temperature change. The heating may be performed, for example, in an air atmosphere as long as the performance of the formed thin film is not affected, and is preferably performed in an inert gas (nitrogen, argon, etc.) atmosphere or a vacuum atmosphere.

  By heating, the amino group-containing adamantane derivative “amino group optionally having a protecting group (amino groups)” contained in the insulating film forming material and the carbonyl group-containing adamantane derivative “having a protecting group Polymerization reaction proceeds by bonding with “good carboxyl group or acyl group (carbonyl-containing group)”. More specifically, the amino groups of the amino group-containing adamantane derivative and the carbonyl-containing groups of the carbonyl group-containing adamantane derivative are polycondensed with elimination of a protective group as necessary, and adamantane is obtained as a polymerization product. Skeletal-containing polybenzoxazoles are formed. For example, a combination of one carbonyl-containing group of a carbonyl group-containing adamantane derivative and two amino groups bonded to the 1,2- or 1,3-position carbon atoms of the amino group-containing adamantane derivative, etc. A 5-membered or 6-membered ring having two nitrogen atoms is formed.

In particular, in the present invention, since a decrease in density can be prevented during the polymerization reaction due to steric hindrance between the monomer components, a polymer having a macromolecular pore structure can be obtained. That is, the amino group-containing adamantane derivative represented by the formula (1) used for one monomer component is a tetrahedron (almost) centered on the central adamantane skeleton and having R ¹ , R ² , R ³ , and R ⁴ as vertices. A tetrahedron in which at least three of R ¹ , R ² , R ³ , and R ⁴ are composed of groups represented by any one of formulas (2A), (2B), and (2C) It is a macromolecule having a bulky structure (structure with a large volume). The carbonyl group-containing adamantane derivative represented by the formula (3) used for the other monomer component is a tetrahedron (substantially regular tetrahedron centered on the central adamantane skeleton and having apexes R ^a , R ^b , R ^c , R ^d. Body). In the polymerization reaction using these as monomer components, a giant tetrahedron having R ¹ , R ² , R ³ , and R ⁴ as vertices of the amino group-containing adamantane derivative represented by formula (1), and formula (3) The tetrahedron having R ^a , R ^b , R ^c , and R ^d as vertices in the carbonyl group-containing adamantane derivative represented by the formula is prevented from penetrating into the space of each other's tetrahedral structure due to extremely large steric hindrance, Furthermore, the intrusion of oligomers, polymers, etc. during elongation is limited. For this reason, the tetrahedral structure inherent to both monomer components is maintained, and a polymer having a low density structure in which pores having a size corresponding to the volume of these tetrahedra are regularly arranged can be formed.

  The insulating film thus obtained is composed of a polymer having a hole structure as described above. As described above, since a large number of macromolecular vacancies are uniformly dispersed therein, an extremely excellent relative dielectric constant is exhibited.

  The thickness of the insulating film formed by heating can be appropriately set depending on the application, but is generally 50 nm or more (about 50 to 2000 nm), preferably 100 nm or more (about 100 to 2000 nm), more preferably 300 nm or more (300 About 2000 nm). If the film thickness is less than 50 nm, problems such as adverse effects on electrical characteristics such as the occurrence of leakage current, and difficulty in planarizing the film by chemical mechanical polishing (CMP) in the semiconductor manufacturing process are likely to occur. Particularly, it is not suitable for use as an interlayer insulating film.

  In addition, it is conceivable to form an insulating film by applying a polymer (polymer crosslinked product) prepared in advance on a substrate. Such a high molecular weight polymer has a very low solubility in a solvent. Therefore, when forming a thin film by coating, defective coating such as coating unevenness due to the influence of undissolved components appears remarkably. In order to prevent such poor coating, a process for removing undissolved components such as strict filtration is required at the time of preparing the coating solution, and the process itself is likely to be economically disadvantageous because it requires a lot of labor. . It is also conceivable to form an insulating film by applying a solution of monomer components (carbonyl group-containing adamantane derivative and dihydroxydiamine derivative) dissolved in a solvent on the substrate. At that time, since the monomer component enters the pores of the high molecular weight polymer generated or the newly generated polymer chain penetrates through the pores of the formed high molecular weight polymer, the pores are likely to be blocked. Porosity tends to decrease.

  On the other hand, a prepolymer obtained by partially polymerizing the monomer component (a polymer having a weight average molecular weight of about 8000 or more: for example, a prepolymer described in JP-A-2005-139271) and a monomer component are combined into a solvent. When an insulating film is formed by applying a dissolved solution on a substrate, from the viewpoint of reactivity, the difference in molecular size between the prepolymer and the monomer component is so large that the prepolymer mainly forms a solid state (prepolymer). In the solid phase composed of a polymer, there is a problem that diffusion of monomer components due to thermal motion is inhibited, the frequency of collision of functional groups is reduced, and the reaction of functional groups is difficult to proceed (reaction rate 20-30%). ). Moreover, from the viewpoint of the three-dimensional structure, a certain degree of dielectric constant reduction can be achieved because the prepolymer has a portion in which steric hindrance is formed and large vacancies are retained, but the prepolymer has a low bulk structure. Sites are also included, and the monomer component easily enters such sites, and pores are likely to be blocked by penetrating the polymer chain, so that the reduction in porosity is easily impaired.

  On the other hand, according to the combination of the amino group-containing adamantane derivative of the present invention and the monomer component, the molecular size difference is much smaller, and the frequency of collision of molecules due to thermal motion is sufficiently increased. The rate can be increased (for example, a reaction rate of 60% or more), and a film having excellent film quality and mechanical properties can be formed. Further, from the viewpoint of the steric structure, the amino group-containing adamantane derivative of the present invention is a macromolecule having a bulky structure, and the monomer component into the pores by a polymerization reaction with the monomer component also having steric hindrance Intrusion and penetration of polymer chains are suppressed. Therefore, it is possible to easily construct a highly ordered pore structure in which a large number of uniform and large-sized pores are dispersed inside. The insulating film made of the polymer formed in this manner has a high porosity and thus has a low relative dielectric constant, has sufficient heat resistance and mechanical strength due to crosslinking, and has an advantage that the diffusion of copper from the wiring is extremely small. Have

  Moreover, the amino group-containing adamantane derivative of the present invention can have an oxazole ring in the molecule, and can produce a polymer having the oxazole ring as a structural unit by a polymerization reaction. A compound having an oxazole ring has a lower basicity than a compound having an imidazole ring and tends to decrease hydrophilicity. Presumed to stabilize.

  Since the insulating film is composed of the polymer having the above-described pore structure, the dielectric constant (K value) is, for example, less than 3 (preferably less than 2.8, more preferably less than 2.3). A low dielectric constant can be exhibited.

  Since the insulating film exhibits a low dielectric constant and high heat resistance, it can be used, for example, as an insulating film in electronic material parts such as semiconductor devices, and is particularly useful as an interlayer insulating film.

  Hereinafter, the present invention will be described in more detail based on examples, but the present invention is not limited to these examples. The film thickness of the polymer film is measured using an ellipsometer, the density of the polymer film is obtained by analysis of X-ray reflectivity measurement, and the relative dielectric constant of the polymer film is formed by forming an Al electrode on the surface of the film. And measured. Infrared absorption spectrum was measured using a thin film transmission method. The weight average molecular weight is a value in terms of polystyrene. The density is a value of 25 ° C.

反応容器（３口フラスコ）に、上記式（2-1）で表される３，３’―シヒドロキシベンジジン７８．３ｇ（３６２ｍｍｏｌ）、Ｎ，Ｎ−ジメチルアセトアミド（ＤＭＡｃ）３００ｇを加えて溶解させた後、活性炭１００ｇ（Darco KB, Aldrich, Inc社製）を仕込み、氷浴で０℃以下に保った。
この反応容器へ、上記式（3A-1）で表されるアダマンタンテトラキスベンズアルデヒド４．０ｇ（７．２ｍｍｏｌ）をＤＭＡｃ ５００ｇに溶解させた溶液を、滴下ロートを用いて、流速約６ｍｌ／ｍｉｎで、反応容器内の液温が０℃を越えないように注意しながら滴下させた。滴下終了後のロート内は、１０５ｇのＤＭＡｃにより洗浄し、反応容器内に滴下した。反応液に、テフロン（登録商標）チューブを用いて酸素濃度５モル％の酸素窒素混合ガスを導入しながら、反応容器をオイルバスにより加熱し、液温を１２０℃に保ち、９時間反応させた。反応終了後、反応容器の反応液をろ過して不溶分を取り除いた後、９．１ｋｇのメタノールに滴下し、沈殿と上澄みとから成るスラリーを、滴下終了後約１時間攪拌した。撹拌中、アミンの酸化を防止するため、反応液に窒素をバブリングさせた。得られた沈殿物を濾別し、反応容器に再度移し、メタノール１．８３ｋｇを加えて、窒素雰囲気下、加熱還流を３０分施すことにより、加熱洗浄を行った。左記洗浄操作を５回繰り返した後、再度固形分を濾別し、真空乾燥機で乾燥させた。
乾燥させた生成物について、赤外線吸収スペクトルとＮＭＲを測定したところ、下記のスペクトルデータにより上記式(1C-1)で表されるアミノ基含有アダマンタン誘導体が形成されていることを確認した。アミノ基含有アダマンタン誘導体の収量は０．８２ｇ、収率は１２％であった。
［ＮＭＲスペクトルデータ］
¹Ｈ−ＮＭＲ（ＤＭＳＯ−ｄ₆） δ（ｐｐｍ）：２．３２（１２Ｈ＜−ＣＨ₂−＞）， ４．６０（１６Ｈ＜−ＮＨ₂＞），６．６２−６．９７（１２Ｈ＜芳香環プロトン＞）， ７．５３−７．７８（１２Ｈ＜芳香環プロトン＞），７．８７（８Ｈ），８．２４（８Ｈ） ９．０５（４Ｈ＜−ＯＨ＞）
［赤外線吸収スペクトルデータ（ｃｍ^-1）］
３４４０（Ｏ−Ｈ＜伸縮振動＞），３４２５（Ｎ−Ｈ＜伸縮振動＞），２９３０（−ＣＨ₂−のＣ−Ｈ＜伸縮振動＞），１６０２（−Ｃ＝Ｎ−＜伸縮振動＞），１４２０−１５２０（芳香環＜面内振動＞），１２８０（芳香族−ＮＨ₂＜伸縮振動＞） Example 1
Synthesis of an amino group-containing adamantane derivative represented by the following formula (1C-1)

In a reaction vessel (3-neck flask), 78.3 g (362 mmol) of 3,3′-sihydroxybenzidine represented by the above formula (2-1) and 300 g of N, N-dimethylacetamide (DMAc) are added and dissolved. Thereafter, 100 g of activated carbon (Darco KB, Aldrich, Inc.) was charged and kept at 0 ° C. or lower in an ice bath.
A solution prepared by dissolving 4.0 g (7.2 mmol) of adamantanetetrakisbenzaldehyde represented by the above formula (3A-1) in 500 g of DMAc into this reaction vessel at a flow rate of about 6 ml / min using a dropping funnel, The solution was added dropwise with care so that the liquid temperature in the reaction vessel did not exceed 0 ° C. The inside of the funnel after the dropping was washed with 105 g of DMAc and dropped into the reaction vessel. The reaction vessel was heated with an oil bath while introducing an oxygen / nitrogen mixed gas having an oxygen concentration of 5 mol% into the reaction solution using a Teflon (registered trademark) tube, and the reaction temperature was maintained at 120 ° C. for 9 hours. . After completion of the reaction, the reaction solution in the reaction vessel was filtered to remove insolubles, and then added dropwise to 9.1 kg of methanol, and the slurry consisting of the precipitate and the supernatant was stirred for about 1 hour after the completion of the addition. During the stirring, nitrogen was bubbled through the reaction solution to prevent oxidation of the amine. The obtained precipitate was separated by filtration, transferred again to the reaction vessel, added with 1.83 kg of methanol, and heated and refluxed under a nitrogen atmosphere for 30 minutes for heating and washing. After the washing operation described above was repeated 5 times, the solid content was again filtered and dried with a vacuum dryer.
When the infrared absorption spectrum and NMR of the dried product were measured, it was confirmed that the amino group-containing adamantane derivative represented by the above formula (1C-1) was formed from the following spectral data. The yield of the amino group-containing adamantane derivative was 0.82 g, and the yield was 12%.
[NMR spectral data]
¹ H-NMR (DMSO-d ₆ ) δ (ppm): 2.32 (12H <—CH ₂ —>), 4.60 (16H <—NH ₂ >), 6.62-6.97 (12H < Aromatic ring proton>), 7.53-7.78 (12H <aromatic ring proton>), 7.87 (8H), 8.24 (8H) 9.05 (4H <-OH>)
[Infrared absorption spectrum data (cm ⁻¹ )]
3440 (O—H <stretching vibration>), 3425 (N—H <stretching vibration>), 2930 (—CH ₂ —CH <stretching vibration>), 1602 (—C = N— <stretching vibration>) , 1420-1520 (aromatic <plane vibration>), 1280 (aromatic -NH ₂ <stretching vibration>)

Example 2
A stirring bar was placed in a 30 ml flask equipped with a three-way cock, and while introducing nitrogen into the container, 500 mg of the amino group-containing adamantane derivative obtained in Example 1, 258 mg of adamantanetetrakisbenzoic acid, and N, N-dimethylacetamide ( Add a mixed solvent [DMAc) and dimethylimidazolidinone (DMI) [mixing ratio 1: 1 (weight ratio)] and stir at 60 ° C. for 1 hour to dissolve the substrate and apply a solid content of 10% by weight. A liquid was prepared.
The coating liquid returned to room temperature was filtered through a Teflon (registered trademark) filter having a pore size of 0.2 μm, and then dropped on an 8-inch silicon wafer, and spin-coated at a rotational speed of 100 to 3000 rpm. This was heated and fired at room temperature to 400 ° C. for 120 minutes in a quartz chamber in a nitrogen atmosphere to form a film. When the infrared absorption spectrum of the polymer film thus obtained was measured, it was confirmed from the following infrared absorption spectrum data that the target crosslinked polybenzoxazole film was formed. The film thickness of the obtained film was 180 nm. The density of the film was 1.1 g / cm ³ and the relative dielectric constant was 2.1.
[Infrared absorption spectrum data (cm ⁻¹ )]
_{2925 (-CH 2 - <C-} H stretching vibration>), 1615 (-C = N-<stretching vibration>), 1425 to 1540 (aromatic ring <plane vibration>), 1280 (aromatic -NH ₂ <stretch Vibration>), 803 (aromatic ring <out-of-plane expansion>)

Comparative Example 1
5.37 g (20 mmol) of 1,3,5-adamantane tricarboxylic acid and 6.43 g (30 mmol) of 3,3′-diaminobenzidine were converted to N-methyl-2-pyrrolidone (NMP) at room temperature under a nitrogen atmosphere. By dissolving, a coating solution having a concentration of 25% by weight was prepared. The coating solution was passed through a filter having a pore size of 0.2 μm and then spin-coated on an 8-inch silicon wafer. This was heated and fired at room temperature to 400 ° C. for 120 minutes in a nitrogen atmosphere to form a film. When the infrared absorption spectrum of the polymer film thus obtained was measured, it was confirmed from the following infrared absorption spectrum data that the target crosslinked polybenzimidazole film was formed. The film thickness of the obtained film was 550 nm. The density of the film was 1.24 g / cm ³ and the relative dielectric constant was 2.8.
[Infrared absorption spectrum data (cm ⁻¹ )]
805 (m), 1280 (m), 1403 (m), 1450 (s), 1522 (w), 1625 (w), 2857 (s), 2928 (s), 3419 (w)

Comparative Example 2
1.03 g (4 mmol) of 1,3,5-adamantanetricarboxylic acid and 1.30 g (6 mmol) of 3,3′-dihydroxybenzidine were dissolved in propylene glycol monomethyl ether at room temperature under a nitrogen atmosphere. A coating solution having a concentration of 2.3% by weight was prepared. This coating solution was passed through a filter having a pore diameter of 0.1 μm and then spin-coated on an 8-inch silicon wafer. This was heated at 300 ° C. for 30 minutes in a nitrogen atmosphere, and further heated and fired at 400 ° C. for 30 minutes to form a film. When the infrared absorption spectrum of the polymer film thus obtained was measured, it was confirmed that the target crosslinked polybenzoxazole film was formed. The film thickness of the obtained film was 20 nm. The density of the film was 1.26 g / cm ³ and the relative dielectric constant was 2.7.

Claims (2)

The following formula (3 ' )

Wherein X ¹ , X ² , X ³ and X ⁴ are the same or different and each represents a single bond , a benzene ring, a biphenyl ring or a naphthalene ring , and R ^a , R ^b , R ^c and R ^d are The same or different, a hydrogen atom , an alkyl group having 1 to 20 carbon atoms , an alkenyl group having 2 to 20 carbon atoms , an alkynyl group having 2 to 20 carbon atoms, a 3 to 20 membered cycloalkyl group, and a 3 to 20 membered cyclo An alkenyl group, a bridged cyclic carbocycle having 2 to 4 rings, an aromatic hydrocarbon group having 6 to 20 carbon atoms, a C _3-20 cycloalkyl-C _1-4 alkyl group, a C _7-18 aralkyl group, C _{1 A} group selected from a phenyl group substituted with a _-4 alkyl group, a naphthyl group substituted with a C _1-4 alkyl group, and a formyl group, provided that at least 3 of R ^a , R ^b , R ^c and R ^d Represents a formyl group )
And a carbonyl group-containing adamantane derivative represented by the following formula (4 ′ ):

(In the formula, ring Y represents a ring selected from a benzene ring, naphthalene ring, anthracene ring, phenanthrene ring, triphenylene ring, pyrene ring, biphenyl ring, biphenylene ring, fluorene ring, and stilbene ring , and R ^e , R ^f , R ^g and R ^h are substituents bonded to the ring Y and are the same or different, and two of them are a C _1-6 aliphatic acyl group, a C _6-20 aromatic acyl group, a C _{1-4 an} alkoxy-carbonyl group, a C _7-20 aralkyloxycarbonyl group, an aliphatic alkylidene group, an amino group which may be protected with a protecting group selected from an aromatic alkylidene group, the remaining two are C _{1- 6} alkyl group, 3-15 membered cycloalkyl group, C _7-20 aralkyl groups, methoxymethyl group, benzyloxymethyl group, t-butoxymethyl group, 2-methoxyethoxymethyl group, 1-ethoxy Butyl group, 1-methyl-1-methoxyethyl group, C _1-10 aliphatic acyl group, C _4-20 cycloaliphatic acyl group, C _7-20 aromatic acyl group, C _1-4 alkoxy - carbonyl group, A hydroxyl group optionally protected with a protecting group selected from a C _7-20 aralkyloxy-carbonyl group)
By the reaction with a dihydroxydiamine derivative represented by the following formula (1 ′)

[Wherein, X ¹ , X ² , X ³ and X ⁴ are the same as above. R ¹ , R ² , R ³ , and R ⁴ are adamantane rings or substituents bonded to the rings X ¹ , X ² , X ³ , and X ⁴ , and they are the same or different and have a hydrogen atom, carbon number of 1 ˜20 alkyl group, C 2-20 alkenyl group, C 2-20 alkynyl group, 3-20 membered cycloalkyl group, 3-20 membered cycloalkenyl group, 2-4 bridged ring A carbocyclic ring, an aromatic hydrocarbon group having 6 to 20 carbon atoms, a C _3-20 cycloalkyl-C _1-4 alkyl group, a C _7-18 aralkyl group, a phenyl group substituted by a C _1-4 alkyl group, C _1-4 alkyl group substituted naphthyl group, formyl group, or the following formula (2A ′), (2B ′) or (2C ′)

(In formulas (2A ′), (2B ′) and (2C ′), ring Y is the same as defined above. R ⁵ and R ⁶ are the same or different and are each a C _1-6 alkyl group, a 3- to 15-membered cyclohexane. Alkyl group, C _7-20 aralkyl group, methoxymethyl group, benzyloxymethyl group, t-butoxymethyl group, 2-methoxyethoxymethyl group, 1-ethoxyethyl group, 1-methyl-1-methoxyethyl group, C _{1 -10} protecting group selected from aliphatic acyl group, C _4-20 alicyclic acyl group, C _7-20 aromatic acyl group, C _1-4 alkoxy-carbonyl group, C _7-20 aralkyloxy-carbonyl group R ⁷ is a C _1-6 aliphatic acyl group, a C _6-20 aromatic acyl group, a C _1-4 alkoxy-carbonyl group, a C _7-20 aralkyloxy group. Selected from carbonyl group, aliphatic alkylidene group, and aromatic alkylidene group An amino group which may be protected by a selected protecting group, and R ′ represents a hydrogen atom)
The group represented by these is shown. However, at least three of R ¹ , R ² , R ³ and R ⁴ are the same or different and represent a group represented by the formula (2A ′), (2B ′) or (2C ′)]
The manufacturing method of the amino group containing adamantane derivative which obtains the amino group containing adamantane derivative represented by these . A carbonyl group-containing adamantane derivative, an excess of the manufacturing method of the amino group-containing adamantane derivative according to claim 1, wherein the sequentially added to a solution of dihydroxy diamine derivative in excess of the stoichiometric amount.