JP2006232730A - Substituted aminoaryladamantane derivative and method for producing the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a new substituted aminoaryladamantane derivative capable of being simply produced from an easily available compound and capable of being easily induced into an aminoaryladamantane derivative useful as a raw material, etc., for a highly functional material. <P>SOLUTION: This substituted aminoaryladamantane derivative is expressed by formula (1) [R<SP>1</SP>, R<SP>2</SP>, R<SP>3</SP>, R<SP>4</SP>, R<SP>5</SP>and R<SP>6</SP>are identical to or different from one another and are each hydrogen, an aromatic cyclic group expressed by formula (2) (Z is an aromatic ring, R<SP>7</SP>is a hydrolyzable protecting group, R<SP>8</SP>is hydrogen, a hydrocarbon group or a hydrolyzable protecting group, and p is an integer of not less than 1, provided that two or more R<SP>7</SP>'s and R<SP>8</SP>'s are identical to or different from one another, when p is two or more, and the aromatic ring may have a substituent other than a substituent specified in the above) or a substituent other than the group expressed by formula (2), provided that at least one of R<SP>1</SP>, R<SP>2</SP>, R<SP>3</SP>, R<SP>4</SP>, R<SP>5</SP>and R<SP>6</SP>is a group expressed by formula (2)] or the like. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a novel substituted aminoaryladamantane derivative useful as a raw material for a functional material such as a highly functional polymer 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, since a compound having an amino group can be easily derived into a polymer, it is an industrially extremely important compound.

  Macro. Chem. Phys. 199, 963 (1998) discloses a method for producing 1,3-bis (4-aminophenyl) adamantane from 1,3-bis (4-nitrophenyl) adamantane. However, this method generally requires a large number of steps to obtain the desired product from readily available raw materials, and is not necessarily an industrially advantageous method. Zhurnal Organicheskoi Kimii (1991), 27 (1), 108-12 is reacted with 3-acylaminotoluene and adamantane bromide to give 4-adamantyl-3-acylaminotoluene or 6-adamantyl-3-acyl. A method for synthesizing aminotoluene is disclosed. In addition, Chem. Ber. , 1964, 97, 3488-3492 disclose a process for producing 4-adamantyl-acetanilide by reacting adamantane bromide with acetanilide. However, the compounds disclosed in these documents cannot be said to have sufficient characteristics in terms of functionality when used as polymer raw materials. There is also a need for adamantane derivatives that are raw materials for highly functional materials that are more excellent in properties such as heat resistance than ever.

Macro. Chem. Phys. 199, 963 (1998) Zhurnal Organicheskoi Kimii (1991), 27 (1), 108-12 Chem. Ber. , 1964, 97, 3488-3492

An object of the present invention is to provide a novel substituted aminoaryladamantane derivative that can be easily produced from an easily available compound and that can be easily derived into an aminoaryladamantane derivative useful as a raw material for a highly functional material, and its efficient production To provide a law.
Another object of the present invention is to provide a novel substituted aminoaryladamantane derivative useful as a raw material for functional materials having excellent electrical properties, thermal properties, mechanical properties, optical properties, physical properties, and the like, and an efficient production method thereof. There is to do.

  As a result of intensive studies to achieve the above object, the present inventors have found a novel substituted aminoaryladamantane derivative having an amino group protected by a hydrolyzable protecting group on an aromatic ring bonded to an adamantane ring, 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）

（式中、環Ｚは芳香環を示し、Ｒ⁷は加水分解性保護基を示し、Ｒ⁸は、水素原子、炭化水素基又は加水分解性保護基を示す。ｐは１以上の整数を示す。ｐが２以上の場合、複数個のＲ⁷、Ｒ⁸は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ている置換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）で表される基である。ｋは０〜３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。但し、ｋ＝０の場合には、Ｒ¹、Ｒ²、Ｒ³、Ｒ⁵のうち少なくとも２つは式（２）で表される基である。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］
で表される置換アミノアリールアダマンタン誘導体を提供する。 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)

(In the formula, ring Z represents an aromatic ring, R ⁷ represents a hydrolyzable protecting group, R ⁸ represents a hydrogen atom, a hydrocarbon group or a hydrolyzable protecting group. P represents an integer of 1 or more. When p is 2 or more, a plurality of R ⁷ and R ⁸ may be the same or different, and the aromatic ring may have a substituent other than the substituents shown in the formula Good)
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). k represents an integer of 0 to 3. When k is 2 or 3, the plurality of R ⁴ and R ⁶ may be the same or different. However, when k = 0, at least two of R ¹ , R ² , R ³ and R ⁵ are groups represented by the formula (2). The adamantane ring may have a substituent at a site other than the bridge head position]
The substituted aminoaryladamantane derivative represented by these is provided.

［式中、Ｘ¹、Ｘ²、Ｘ³、Ｘ⁴、Ｘ⁵、Ｘ⁶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基、又はその他の置換基を示す。但し、Ｘ¹、Ｘ²、Ｘ³、Ｘ⁴、Ｘ⁵、Ｘ⁶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基である。ｋは０〜３の整数を示す。ｋが２又は３の場合、複数個のＸ⁴、Ｘ⁶はそれぞれ同一であっても異なっていてもよい。但し、ｋ＝０の場合には、Ｘ¹、Ｘ²、Ｘ³、Ｘ⁵のうち少なくとも２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基である。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］
で表されるアダマンタン誘導体と、下記式（４）

（式中、環Ｚは芳香環を示し、Ｒ⁷は加水分解性保護基を示し、Ｒ⁸は、水素原子、炭化水素基又は加水分解性保護基を示す。ｐは１以上の整数を示す。ｐが２以上の場合、複数個のＲ⁷、Ｒ⁸は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ている置換基以外の置換基を有していてもよい）
で表される芳香族化合物とを反応させて、下記式（１）

［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）

（式中、環Ｚは芳香環を示し、Ｒ⁷は加水分解性保護基を示し、Ｒ⁸は、水素原子、炭化水素基又は加水分解性保護基を示す。ｐは１以上の整数を示す。ｐが２以上の場合、複数個のＲ⁷、Ｒ⁸は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ている置換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）で表される基である。ｋは０〜３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。但し、ｋ＝０の場合には、Ｒ¹、Ｒ²、Ｒ³、Ｒ⁵のうち少なくとも２つは式（２）で表される基である。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］
で表される置換アミノアリールアダマンタン誘導体を得ることを特徴とする置換アミノアリール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 (3):

[Wherein, X ¹ , X ² , X ³ , X ⁴ , X ⁵ , X ⁶ are the same or different, a hydrogen atom, a group capable of leaving to form a carbocation in the adamantane skeleton, or other substituents Indicates. However, at least one of X ¹ , X ² , X ³ , X ⁴ , X ⁵ and X ⁶ is a group capable of leaving and generating a carbocation in the adamantane skeleton. k represents an integer of 0 to 3. When k is 2 or 3, the plurality of X ⁴ and X ⁶ may be the same or different. However, when k = 0, at least two of X ¹ , X ² , X ³ and X ⁵ are groups capable of leaving to generate a carbocation in the adamantane skeleton. The adamantane ring may have a substituent at a site other than the bridge head position]
And an adamantane derivative represented by the following formula (4):

(In the formula, ring Z represents an aromatic ring, R ⁷ represents a hydrolyzable protecting group, R ⁸ represents a hydrogen atom, a hydrocarbon group or a hydrolyzable protecting group. P represents an integer of 1 or more. When p is 2 or more, a plurality of R ⁷ and R ⁸ may be the same or different, and the aromatic ring may have a substituent other than those shown in the formula Good)
Is reacted with an aromatic compound represented by 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)

(In the formula, ring Z represents an aromatic ring, R ⁷ represents a hydrolyzable protecting group, R ⁸ represents a hydrogen atom, a hydrocarbon group or a hydrolyzable protecting group. P represents an integer of 1 or more. When p is 2 or more, a plurality of R ⁷ and R ⁸ may be the same or different, and the aromatic ring may have a substituent other than those shown in the formula Good)
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). k represents an integer of 0 to 3. When k is 2 or 3, the plurality of R ⁴ and R ⁶ may be the same or different. However, when k = 0, at least two of R ¹ , R ² , R ³ and R ⁵ are groups represented by the formula (2). The adamantane ring may have a substituent at a site other than the bridge head position]
And a method for producing a substituted aminoaryladamantane derivative, characterized in that the substituted aminoaryladamantane derivative represented by the formula:

  According to the present invention, there is provided a novel substituted aminoaryladamantane derivative that can be easily produced from an easily available compound and can be easily derived into an aminoaryladamantane derivative useful as a raw material for a highly functional material. In addition, a novel substituted aminoaryladamantane derivative useful as a raw material for a functional material excellent in electrical characteristics, thermal characteristics, mechanical characteristics, optical characteristics, physical characteristics and the like is provided. According to the production method of the present invention, such highly useful substituted aminoaryladamantane derivatives can be efficiently produced in one step from readily available raw materials such as adamantane halide derivatives and adamantanol derivatives.

The substituted aminoaryladamantane derivative 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 group represented by the formula (2), or other The substituent of 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). k represents an integer of 0 to 3. When k is 2 or 3, the plurality of R ⁴ and R ⁶ may be the same or different. However, when k = 0, at least two of R ¹ , R ² , R ³ and R ⁵ are groups represented by the formula (2). The adamantane ring may have a substituent at a site other than the bridge head position. In formula (2), ring Z represents an aromatic ring. R ⁷ and R ⁸ are substituents bonded to a nitrogen atom, R ⁷ is a hydrolyzable protecting group (protecting group for amino group), and R ⁸ is a hydrogen atom, a hydrocarbon group or a hydrolysable protecting group. (Protecting group for amino group). R ⁷ and R ⁸ may together form a hydrolyzable protecting group. p represents an integer of 1 or more. When p is 2 or more, a plurality of R ⁷ and R ⁸ may be the same or different. The aromatic ring may have a substituent other than the substituents shown in the formula. Note that k and p each represent the number of groups in parentheses.

In the compound represented by the formula (1), the —NR ⁷ R ⁸ group bonded to the aromatic ring Z can be easily converted into an amino group or a monohydrocarbon group-substituted amino group by hydrolysis. Therefore, among the compounds represented by the formula (1), the compound having one aromatic cyclic group represented by the formula (2) has a —NR ⁷ R ⁸ group as an amino group or a monohydrocarbon group-substituted amino group. Then, by introducing a polymerizable group into the amino group or monohydrocarbon group-substituted amino group, it can be used as a monomer raw material for a polymer having an adamantane ring in the side chain (pendant type). In addition, after the —NR ⁷ R ⁸ group is converted to an amino group or a monohydrocarbon group-substituted amino group, these groups are used to form an adamantane ring on the side chain of the polymer having a group capable of reacting with these groups. It can also be introduced. On the other hand, a compound having two aromatic cyclic groups represented by the formula (2) (in particular, a compound having one aromatic cyclic group at each of the adamantane rings at both ends) is represented by the group —NR ⁷ R ^8. This is very important because it can be derived into a polymer (main chain type) by a condensation reaction using an amino group to be converted or a monohydrocarbon group-substituted amino group. Furthermore, a compound having three or more aromatic cyclic groups represented by the formula (2) can be used as a raw material for a high-order polymer having a three-dimensional network structure. Further, when k is 1 or more, since a structure in which a plurality of adamantane rings are directly bonded is adopted, characteristics such as heat resistance are remarkably improved when induced to a polymer.

  Examples of the aromatic ring in the aromatic cyclic group represented by the formula (2) include aromatic carbocycles such as benzene ring, naphthalene ring, anthracene ring, phenanthrene ring, triphenylene ring; pyridine ring, pyrazine ring, pyrimidine ring And aromatic heterocyclic rings such as pyridazine ring, quinoline ring, acridine ring, naphthyridine ring, quinoxaline ring, furan ring, benzofuran ring, and 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 hydrolyzable protecting group for R ⁷ may be any protecting group for an amino group that can be removed by hydrolysis, such as an acyl group, a sulfonyl group (benzenesulfonyl, p-toluenesulfonyl, methylsulfonyl, trifluoromethyl). Sulfonyl groups, etc.), groups that form aminoacetals with adjacent nitrogen atoms (methoxymethyl, 2-chloroethoxymethyl, 2-tetrahydropyranyl groups, etc.), groups that form urea with adjacent nitrogen atoms (piperidinylcarbonyl) , P-toluenesulfonylaminocarbonyl, phenylaminocarbonyl, methylaminocarbonyl group, etc.), phosphinyl group (diphenylphosphinyl group, etc.), phosphoryl group (diethylphosphoryl, diphenylphosphoryl group, etc.), silyl group (trimethylsilyl group, etc.), etc. Is mentioned. In addition, examples of the hydrolyzable protecting group in which R ⁷ and R ⁸ are integrally formed include groups that form an imine with an adjacent nitrogen atom (dimethylaminomethylene, isopropylidene, benzylidene, diphenylmethylene group, etc.). Can be mentioned. Examples of the acyl group include aliphatic acyl groups such as formyl, acetyl, propionyl, butyryl, isobutyryl, pivaloyl, hexanoyl, octanoyl, decanoyl group (eg, C _1-20 aliphatic acyl group); acetoacetyl group; Aromatic acyl groups such as benzoyl groups (eg, C _7-20 aromatic acyl groups); cycloaliphatic carboxylic acid acyl groups such as cyclopentanecarbonyl and cyclohexanecarbonyl groups (eg, C _4-20 alicyclic carboxylic acyls) Group). As the acyl group, a C _1-6 aliphatic acyl group such as an acetyl group is particularly preferable. The acyl group may be protected with a protecting group. As the protecting group for the acyl group, a protecting group commonly used in the field of organic synthesis can be used. Examples of the protected form of the acyl group include acetal (including hemiacetal). As the hydrolyzable protecting group for R ^7, an acyl group is particularly preferred.

Examples of the hydrocarbon group for R ⁸ include alkyl groups such as methyl, ethyl, propyl, isopropyl and butyl groups (particularly C _1-4 alkyl groups); alkenyl groups such as allyl groups (particularly C _2-4 alkenyls). Groups); cycloalkyl groups such as cyclopentyl and cyclohexyl groups (particularly 3 to 6-membered cycloalkyl groups); aryl groups such as phenyl groups and naphthyl groups; groups in which a plurality of these groups are bonded (benzyl groups and the like) and the like. . The hydrocarbon group may have a substituent (for example, a halogen atom such as a fluorine atom, a hydroxyl group, an alkoxy group, a carboxyl group, etc.). The hydrolyzable protecting group for R ⁸ is the same as the hydrolyzable protecting group for R ⁷ . R ⁸ is more preferably a hydrogen atom, a C _1-4 alkyl group, a phenyl group, and particularly preferably a hydrogen atom.

The aromatic ring (ring Z) may have a substituent other than the —NR ⁷ R ⁸ 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. Hydroxy (halo) alkyl group which may be protected with, amino group which may be protected with a protecting group other than hydrolyzable protecting group, acyl group which may be protected with protecting group, cyano group, aryl group Etc. 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 amino-protecting group include an alkyl group, an aralkyl group, and an alkoxycarbonyl group exemplified as the hydroxyl-protecting group. Examples of the protecting group for the acyl group include groups capable of forming an acetal with the acyl group. Examples of the aryl group include a phenyl group and a naphthyl group.

In the formula (2), the substitution position of the —NR ⁷ R ⁸ group is not particularly limited. For example, when the aromatic ring is a benzene ring, any of ortho-position, meta-position and para-position may be used. It can be appropriately selected depending on the situation. When the aromatic ring is a benzene ring, the ortho position and the para position are easy to synthesize in terms of orientation, and the para position is particularly useful as a polymerization monomer. When the aromatic ring is polycyclic, the substitution position can be selected according to the case of the benzene ring.

  The adamantane ring represented by formula (1) may have a substituent other than the group represented by formula (2) in order to impart or improve solvent solubility, heat resistance, and other functions. 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 substituent of the ring Z. 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, an alkyl group that may have a halogen atom is preferable because it has a function of significantly improving solvent solubility, and in particular, it has 1 to 6 carbon atoms. Or an alkyl group having 1 to 6 carbon atoms is preferred. 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 substituted aminoaryladamantane derivative represented by the formula (1) can form a salt when it has an acidic group or a basic group in the molecule. The compounds of the present invention also include such salts. 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.

  Representative examples of the compound represented by the formula (1) include 1,3-bis (4-acetylaminophenyl) adamantane, 1,3-bis (4-acetylamino-3-methylphenyl) adamantane, 1, 3-bis (4-acetylamino-3-methoxyphenyl) adamantane, 1,3-bis (4-acetylamino-3-hydroxyphenyl) adamantane, 1,3-bis (3-acetylamino-4-hydroxyphenyl) Adamantane, 1,3-bis (4-propionylaminophenyl) adamantane, 1,3-bis (4-acetylaminophenyl) -5,7-diethyladamantane, 1,3-bis (4-acetylaminophenyl) -5 , 7-dimethyladamantane, 1,3-bis (4-acetylaminophenyl) -5,7-dibutyladamantane, Bis (acylaminophenyl) adamantane derivatives such as 3-bis (4-acetylaminophenyl) -5,7-bis (trifluoromethyl) adamantane; 3- (4-acetylaminophenyl) -1,1′-biadamantane 3- (4-acetylamino-3-methylphenyl) -1,1′-biadamantane, 3- (4-acetylamino-3-methoxyphenyl) -1,1′-biadamantane, 3- (4- Acetylamino-3-hydroxyphenyl) -1,1′-biadamantane, 3- (3-acetylamino-4-hydroxyphenyl) -1,1′-biadamantane, 3- (4-propionylaminophenyl) -1 , 1′-biadamantane, 3- (4-acetylaminophenyl) -5,7-dimethyl-1,1′-biadamantane, 3- (4- Cetylaminophenyl) -5 ', 7'-dimethyl-1,1'-biadamantane, 3- (4-acetylaminophenyl) -5,5', 7,7'-tetramethyl-1,1'-bi Adamantane, 3- (4-acetylaminophenyl) -5,5 ', 7,7'-tetraethyl-1,1'-biadamantane, 3- (4-acetylaminophenyl) -5,5', 7,7 Acylamino such as '-tetrabutyl-1,1'-biadamantane, 3- (4-acetylaminophenyl) -5,5', 7,7'-tetrakis (trifluoromethyl) -1,1'-biadamantane Phenylbiadamantane derivatives; 3,3′-bis (4-acetylaminophenyl) -1,1′-biadamantane, 3,3′-bis (4-acetylamino-3-methylphenyl) -1,1′- Beer Damantane, 3,3′-bis (4-acetylamino-3-methoxyphenyl) -1,1′-biadamantane, 3,3′-bis (4-acetylamino-3-hydroxyphenyl) -1,1 ′ -Biadamantane, 3,3'-bis (3-acetylamino-4-hydroxyphenyl) -1,1'-biadamantane, 3,3'-bis (4-propionylamino-3-methylphenyl) -1, 1'-biadamantane, 3,3'-bis (4-acetylaminophenyl) -5,7-dimethyl-1,1'-biadamantane, 3,3'-bis (4-acetylaminophenyl) -5 ' , 7'-dimethyl-1,1'-biadamantane, 3,3'-bis (4-acetylaminophenyl) -5,5 ', 7,7'-tetramethyl-1,1'-biadamantane, 3, , 3'-bis 4-acetylaminophenyl) -5,5 ', 7,7'-tetraethyl-1,1'-biadamantane, 3,3'-bis (4-acetylaminophenyl) -5,5', 7,7 ' -Tetrabutyl-1,1'-biadamantane, 3,3'-bis (4-acetylaminophenyl) -5,5 ', 7,7'-tetrakis (trifluoromethyl) -1,1'-biadamantane, 3,3′-bis (4-acetylaminophenyl) -5,5 ′, 7,7′-tetrahydroxy-1,1′-biadamantane, 3,3′-bis (4-acetylaminophenyl) -5 , 5 ', 7,7'-tetraamino-1,1'-biadamantane, 3,3'-bis [3,4-bis (acetylamino) phenyl] -1,1'-biadamantane, 3,3 '-Bis [3,4-bis (acetylamino) Bis (acylamino) phenylbiadamantane derivatives such as phenyl] -5,7-dimethyl-1,1'-biadamantane; 3- (4-acetylaminophenyl) -1,1 ': 3', 1 "-tri Adamantane, 3- (4-acetylamino-3-methylphenyl) -1,1 ′: 3 ′, 1 ″ -triadamantane, 3- (4-acetylamino-3-methoxyphenyl) -1,1 ′: 3 ', 1 "-triadamantane, 3- (4-acetylamino-3-hydroxyphenyl) -1,1': 3 ', 1" -triadamantane, 3- (3-acetylamino-4-hydroxyphenyl)- 1,1 ′: 3 ′, 1 ″ -triadamantane, 3- (4-propionylaminophenyl) -1,1 ′: 3 ′, 1 ″ -triadamantane, 3- (4-acetylaminophenyl)- 5,5 ′, 5 ″, 7,7 ′, 7 ″ -hexamethyl-1,1 ′: 3 ′, 1 ″ -triadamantane, 3- (4-acetylaminophenyl) -5,5 ′, 5 ′ ', 7,7', 7 "-hexaethyl-1,1 ': 3', 1" -triadamantane, 3- (4-acetylaminophenyl) -5,5 ', 5 ", 7,7', 7 ″ -hexabutyl-1,1 ′: 3 ′, 1 ″ -triadamantane, 3- (4-acetylaminophenyl) -5,5 ′, 5 ″, 7,7 ′, 7 ″ -hexakis (trifluoro Acylaminophenyltriadamantane derivatives such as methyl) -1,1 ′: 3 ′, 1 ″ -triadamantane; 3,3 ″ -bis (4-acetylaminophenyl) -1,1 ′: 3 ′, 1 ″- Triadamantane, 3,3 ″ -bis (4-acetylamino-3-methylpheny ) -1,1 ′: 3 ′, 1 ″ -triadamantane, 3,3 ″ -bis (4-acetylamino-3-methoxyphenyl) -1,1 ′: 3 ′, 1 ″ -triadamantane, 3, 3 ″ -bis (4-acetylamino-3-hydroxyphenyl) -1,1 ′: 3 ′, 1 ″ -triadamantane, 3,3 ″ -bis (3-acetylamino-4-hydroxyphenyl) -1, 1 ': 3', 1 "-triadamantane, 3,3" -bis (4-propionylaminophenyl) -1,1 ': 3', 1 "-triadamantane, 3,3" -bis (4-acetyl) Aminophenyl) -5,5 ′, 5 ″, 7,7 ′, 7 ″ -hexamethyl-1,1 ′: 3 ′, 1 ″ -triadamantane, 3,3 ″ -bis (4-acetylaminophenyl) -5,5 ', 5 ", 7,7', 7" -hexaethyl 1,1 ′: 3 ′, 1 ″ -triadamantane, 3,3 ″ -bis (4-acetylaminophenyl) -5,5 ′, 5 ″, 7,7 ′, 7 ″ -hexabutyl-1,1 ': 3', 1 "-triadamantane, 3,3" -bis (4-acetylaminophenyl) -5,5 ', 5 ", 7,7', 7" -hexakis (trifluoromethyl) -1 , 1 ′: 3 ′, 1 ″ -triadamantane and other bis (acylaminophenyl) triadamantane derivatives; 3- (4-acetylaminophenyl) -1,1 ′: 3 ′, 1 ″: 3 ″, 1 ′ ″ ″ -Tetraadamantane, 3- (4-acetylamino-3-methylphenyl) -1,1 ′: 3 ′, 1 ″: 3 ″, 1 ″ ″-tetraadamantane, 3- (4-acetylamino- 3-methoxyphenyl) -1,1 ': 3', 1 ": 3", 1 ' ″ ″ -Tetraadamantane, 3- (4-acetylamino-3-hydroxyphenyl) -1,1 ′: 3 ′, 1 ″: 3 ″, 1 ″ ″-tetraadamantane, 3- (3-acetylamino- 4-hydroxyphenyl) -1,1 ′: 3 ′, 1 ″: 3 ″, 1 ″ ″-tetraadamantane, 3- (4-propionylaminophenyl) -1,1 ′: 3 ′, 1 ″: 3 ″, 1 ″ ″-tetraadamantane, 3- (4-acetylaminophenyl) -5,5 ′, 5 ″, 5 ″ ″, 7,7 ′, 7 ″, 7 ″ ″-octamethyl-1, 1 ': 3', 1 ": 3", 1 "'-tetraadamantane, 3- (4-acetylaminophenyl) -5,5', 5", 5 "", 7,7 ', 7 " 7 ′ ″-octaethyl-1,1 ′: 3 ′, 1 ″: 3 ″, 1 ″ ″-tetraadamantane, 3 (4-acetylaminophenyl) -5,5 ′, 5 ″, 5 ″ ′, 7,7 ′, 7 ″, 7 ″ ″-octabutyl-1,1 ′: 3 ′, 1 ″: 3 ″, 1 ″ ″-tetraadamantane, 3- (4-acetylaminophenyl) -5,5 ′, 5 ″, 5 ″ ″, 7,7 ′, 7 ″, 7 ″ ″-octakis (trifluoromethyl) -1,1 ': 3', 1 ": 3", acylaminophenyltetraadamantane derivatives such as 1 "'-tetraadamantane; 3,3"'-bis (4-acetylaminophenyl) -1,1 ': 3', 1 ": 3", 1 "'-tetraadamantane, 3,3"'-bis (4-acetylamino-3-methylphenyl) -1, 1 ': 3', 1 ": 3 ″, 1 ″ ″-tetraadamantane, 3,3 ″ ″-bis (4-acetylamino-3-methoxy Phenyl) -1,1 ′: 3 ′, 1 ″: 3 ″, 1 ″ ″-tetraadamantane, 3,3 ″ ″-bis (4-acetylamino-3-hydroxyphenyl) -1,1 ′: 3 ′, 1 ″: 3 ″, 1 ″ ″-tetraadamantane, 3,3 ″ ″-bis (3-acetylamino-4-hydroxyphenyl) -1,1 ′: 3 ′, 1 ″: 3 ″ , 1 ″ ″-tetraadamantane, 3,3 ″ ″-bis (4-propionylaminophenyl) -1,1 ′: 3 ′, 1 ″: 3 ″, 1 ″ ″-tetraadamantane, 3,3 ′ ″ -Bis (4-acetylaminophenyl) -5,5 ′, 5 ″, 5 ′ ″, 7,7 ′, 7 ″, 7 ″ ″-octamethyl-1,1 ′: 3 ′, 1 ": 3", 1 "'-tetraadamantane, 3,3"'-bis (4-acetylaminophenyl) -5,5 ', 5 ″, 5 ″ ″, 7, 7 ′, 7 ″, 7 ″ ″-octaethyl-1, 1 ′: 3 ′, 1 ″: 3 ″, 1 ″ ″-tetraadamantane, 3, 3 ″ ′ -Bis (4-acetylaminophenyl) -5,5 ', 5 ", 5" ", 7,7", 7 ""-octabutyl-1,1': 3 ', 1 ": 3 ″, 1 ″ ″-tetraadamantane, 3,3 ″ ″-bis (4-acetylaminophenyl) -5,5 ′, 5 ″, 5 ″ ″, 7,7 ′, 7 ″, 7 ″ Bis (acylaminophenyl) tetraadamantane derivatives such as '-octakis (trifluoromethyl) -1,1': 3 ', 1 ": 3", 1 "'-tetraadamantane; 3,3'-bis (4 -Acetylaminonaphthalen-1-yl) -1,1'-biadamantane and the like Adamantane derivative having an acyl amino naphthyl group corresponding to lanthanum derivatives.

  The substituted aminoaryladamantane derivatives and salts thereof of the present invention have an adamantane skeleton, which is a very stable and symmetric carbon skeleton, and can be used as a reactive functional group by hydrolysis. It has a group that can be easily converted to a hydrogen-substituted amino 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 such as an optical material, an aerospace material, a vehicle material, or a raw material or additive thereof.

  The substituted aminoaryl adamantane derivative represented by the formula (1) of the present invention is obtained by, for example, reacting the adamantane derivative represented by the formula (3) and the aromatic compound represented by the formula (4). Can be manufactured.

In formula (3), X ¹ , X ² , X ³ , X ⁴ , X ⁵ , and X ⁶ are the same or different and are a hydrogen atom, a group capable of leaving to form a carbocation in the adamantane skeleton, or other Indicates a substituent. However, at least one of X ¹ , X ² , X ³ , X ⁴ , X ⁵ and X ⁶ is a group capable of leaving and generating a carbocation in the adamantane skeleton. k represents an integer of 0 to 3. When k is 2 or 3, the plurality of X ⁴ and X ⁶ may be the same or different. However, when k = 0, at least two of X ¹ , X ² , X ³ and X ⁵ are groups capable of leaving to generate a carbocation in the adamantane skeleton. 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 X ¹ , X ² , X ³ , X ⁴ , X ⁵ , X ⁶ and the substituents that may be present at sites other than the bridge head position of the adamantane ring are R ¹ in formula (1), This is the same as the other substituents in R ² , R ³ , R ⁴ , R ⁵ and R ⁶ and the substituents that may be present at sites other than the bridge head position of the adamantane ring in formula (1). In addition, other substituents in X ¹ , X ² , X ³ , X ⁴ , X ⁵ , and X ⁶ , and the substituents that may be present at sites other than the bridge head position of the adamantane ring are represented by the formula (2). The group represented may be sufficient. In the preferred compound represented by the formula (3), at least one (more preferably 2 or more) of X ¹ , X ² , X ³ , X ⁴ , X ⁵ , X ⁶ 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.

  As typical examples of the compound represented by the formula (3), for example, 1,3-dibromoadamantane, 1,3-dibromo-5,7-dimethyladamantane, 1,3-dibromo-5,7-diethyladamantane 1,3-dibromo-5,7-dibutyladamantane, dibromoadamantane derivatives such as 1,3-dibromo-5,7-bis (trifluoromethyl) adamantane; 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'-biadamantane, 3-bromo-5,5', 7,7'-tetrakis (trifluoromethyl) -1,1'-biadamanta Bromobiadamantane derivatives such as 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', 7,7'-tetrabutyl-1,1 ' Dibromobiadamantane derivatives such as -biadamantane, 3,3'-dibromo-5,5 ', 7,7'-tetrakis (trifluoromethyl) -1,1'-biadamantane; 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, Bromotriadamantane derivatives such as 3-bromo-5,5 ′, 5 ″, 7,7 ′, 7 ″ -hexakis (trifluoromethyl) -1,1 ′: 3 ′, 1 ″ -triadamantane; 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 "-triadamantane, 3,3" -Dibromo-5,5 ', 5 ", 7,7', 7" -hexabutyl-1,1 ': 3', 1 "-triadamantane Dibromotriadamantane derivatives such as 3,3 "-dibromo-5,5 ', 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 ″ ″-tetraadamantane Tetraadamantane derivatives; 3,3 ″ ″-dibromo-1,1 ′: 3 ′, 1 ″: 3 ″, 1 ″ ″-tetraadamantane, 3,3 ″ ″-dibromo-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 ″ ″-octakis (trifluoromethyl) -1, 1 ′: 3 ′, 1 ″: 3 ″, dibromotetraadamantane derivatives such as 1 ′ ″-tetraadamantane; and 3-hydroxy-1,1′-biadamantane, 3-nitrooxy-1,1′-biadamantane Examples thereof include hydroxyadamantane derivatives and nitrooxyadamantane derivatives corresponding to the bromoadamantane derivatives.

In the formula (4), ring Z represents an aromatic ring, R ⁷ represents a hydrolyzable protecting group, and R ⁸ represents a hydrogen atom, a hydrocarbon group or a hydrolyzable protecting group. p represents an integer of 1 or more. When p is 2 or more, a plurality of R ⁷ and R ⁸ may be the same or different. The aromatic ring may have a substituent other than the substituents shown in the formula. Hydrolyzable protecting group in R ^7, the hydrocarbon group of R ^8, hydrolyzable protecting group, as a substituent on the aromatic ring other than the substituent shown in formula are the same as in the formula (1) . Representative examples of the aromatic compound represented by the formula (4) include acetylaminobenzene (= acetanilide), 1-acetylamino-2-methylbenzene, 1-acetylamino-2-methoxybenzene, 1-acetylamino. 2-hydroxybenzene, propionylaminobenzene, o-bis (acetylamino) benzene, m-bis (acetylamino) benzene, p-bis (acetylamino) benzene, 1-acetylaminonaphthalene, 2-acetylaminonaphthalene, 1 , 2-bis (acetylamino) naphthalene and the like.

  The reaction of the adamantane derivative represented by formula (3) and the aromatic compound represented by formula (4) is carried out 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 (4) is 0.8-30 mol with respect to 1 mol of adamantane derivatives represented by Formula (3), Preferably it is 1-20 mol, More preferably Is about 1.5 to 10 moles. A large excess of the aromatic compound represented by the formula (4) 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 adamantane derivative represented by the formula (3), the reaction rate is increased. The reaction is preferably carried out 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 adamantane derivatives represented by Formula (3), Preferably it is about 0.1-5 mol.

When a compound (adamantan halide derivative) in which a group capable of generating a carbocation in the adamantane skeleton is a halogen atom (adamantan halide derivative) is used as the adamantane derivative represented by the formula (3), the reaction is usually performed under heating. Do. At this time, the reaction may be performed in the presence of a suitable base in order to capture the by-produced hydrogen halide. In addition, when a compound in which a group capable of generating a carbocation in the adamantane skeleton is a halogen atom is used, the reaction (Friedelcraft reaction) may be performed in the presence of a Lewis acid. Examples of the Lewis acid include FeBr ₃ , FeCl ₃ , AlBr ₃ , AlCl ₃ , PF ₅ , PF ₃ , and SBCl ₅ . Among these, aluminum-based Lewis acids such as AlBr ₃ and AlCl ₃ are preferable. The usage-amount of a Lewis acid is 0.001-10 mol with respect to 1 mol of adamantane derivatives represented by Formula (3), for example, Preferably it is about 0.05-5 mol.

  The reaction temperature in the reaction between the adamantane derivative represented by the formula (3) and the aromatic compound represented by the formula (4) can be appropriately selected according to the kind of the reaction component. For example, when a compound (adamantanol derivative) in which a group capable of generating a carbocation in the adamantane skeleton and forming a carbocation is used as the adamantane derivative represented by the formula (3), 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 adamantane derivative represented by the formula (3) 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, by adjusting the usage-amount of the aromatic compound represented by Formula (4) [equivalent ratio with the adamantane derivative represented by Formula (3)] and other reaction conditions, it is represented by Formula (3). An amino group protected with a hydrolyzable protecting group in the molecule, leaving some of the halogen atom, hydroxyl group, etc. as a group capable of generating a carbocation in the adamantane skeleton by elimination from the adamantane derivative. The compound represented by Formula (1) which has a halogen atom, a hydroxy group, etc. with a group containing aromatic ring 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. When the reaction between the adamantane derivative represented by formula (3) and the aromatic compound represented by formula (4) is carried out in the presence of a Lewis acid, the adamantane derivative represented by formula (3) and the formula (4 The order of addition of the aromatic compound represented by) and the Lewis acid is not particularly limited, but in a mixture (usually including a solvent) of the adamantane derivative represented by Formula (3) and the Lewis acid at a predetermined temperature. When the aromatic compound represented by the formula (4) is added successively or intermittently, the yield of the target product is greatly improved.

  By the above reaction (dehydrohalogenation reaction, dehydration condensation reaction, etc.), the compound represented by formula (3) can be eliminated by the formula (2) at the bonding site of the group capable of generating a carbocation in the adamantane skeleton. A corresponding substituted aminoaryladamantane derivative represented by the formula (1) to which the group is bonded is produced. After completion of the reaction, the reaction product can be separated and purified by general separation and purification means such as liquid property adjustment, filtration, concentration, crystallization, washing, recrystallization, extraction, distillation, sublimation purification, column chromatography and the like.

  In the substituted aminoaryladamantane derivative represented by the formula (1) of the present invention, each substituent on the adamantane ring and each substituent on the aromatic ring of the aromatic cyclic group represented by the formula (2) The introduction may be performed at any stage for producing the substituted aminoaryladamantane derivative. For example, the substituent may be introduced as a pre-process (or a raw material production process) of the dehydrohalogenation reaction or dehydration condensation reaction shown above, or the substituent may be introduced as a post-process. Good. A compound having a plurality of adamantanes can be synthesized by utilizing a coupling reaction of adamantane. For example, a biadamantane derivative can be obtained by reacting a bromoadamantane derivative in the presence of sodium, and a triadamantane derivative can be obtained by reacting a bromoadamantane derivative with a bromobiadamantane derivative in the presence of sodium. The tetraadamantane derivative can be obtained by reacting the bromobiadamantane derivative in the presence of sodium.

  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, 10 g of 3,3′-dibromo-1,1′-biadamantane, 13.3 g of anhydrous aluminum chloride, and 50 g of chloroform were placed in a 100 ml three-necked flask, and the water was stirred up to 40 ° C. while stirring with a magnetic stirrer. The temperature rose on the bus. Thereafter, 60 g of acetanilide was added to the mixture in the flask over a period of about 30 minutes in the form of powder. After aging for 1 hour, 50 g of chloroform was added, and then 50 ml of water was added for liquid separation. When the lower layer was concentrated and the solvent was removed, a brown solid was obtained. To this, 30 ml of ethyl acetate and 30 ml of hexane were added, stirred at 50 ° C. for 3 hours, and then cooled to room temperature to obtain a white solid. The white solid was filtered and dried to give 3,3′-bis (4-acetylaminophenyl) -1,1′-biadamantane in 50% yield (6.3 g).
GC / MS: m / z = 536
FAB ⁺ / MS: m / z = 537, 403, 135

Reference example 1
Under a nitrogen atmosphere, 6.3 g of 3,3′-bis (4-acetylaminophenyl) -1,1′-biadamantane and 30 ml of concentrated hydrochloric acid were put into a 100 ml three-necked flask and stirred with a magnetic stirrer. The temperature was raised in an oil bath until refluxing. After aging for 15 hours, 5N aqueous sodium hydroxide solution was poured to pH 7, filtered and dried, yielding 95% yield of 3,3'-bis (4-aminophenyl) -1,1'-biadamantane. Obtained at a rate (5.0 g).
GC / MS: m / z = 452
¹ H-NMR (DMSO-d6, 500 MHz) δ: 1.3-2.2 (m, 28H), 7.33 (d, 4H), 7.48 (d, 4H)

Claims (2)

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)

(In the formula, ring Z represents an aromatic ring, R ⁷ represents a hydrolyzable protecting group, R ⁸ represents a hydrogen atom, a hydrocarbon group or a hydrolyzable protecting group. P represents an integer of 1 or more. When p is 2 or more, a plurality of R ⁷ and R ⁸ may be the same or different, and the aromatic ring may have a substituent other than the substituents shown in the formula Good)
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). k represents an integer of 0 to 3. When k is 2 or 3, the plurality of R ⁴ and R ⁶ may be the same or different. However, when k = 0, at least two of R ¹ , R ² , R ³ and R ⁵ are groups represented by the formula (2). The adamantane ring may have a substituent at a site other than the bridge head position]
A substituted aminoaryladamantane derivative represented by: Following formula (3)

[Wherein, X ¹ , X ² , X ³ , X ⁴ , X ⁵ , X ⁶ are the same or different, a hydrogen atom, a group capable of leaving to form a carbocation in the adamantane skeleton, or other substituents Indicates. However, at least one of X ¹ , X ² , X ³ , X ⁴ , X ⁵ and X ⁶ is a group capable of leaving and generating a carbocation in the adamantane skeleton. k represents an integer of 0 to 3. When k is 2 or 3, the plurality of X ⁴ and X ⁶ may be the same or different. However, when k = 0, at least two of X ¹ , X ² , X ³ and X ⁵ are groups capable of leaving to generate a carbocation in the adamantane skeleton. The adamantane ring may have a substituent at a site other than the bridge head position]
And an adamantane derivative represented by the following formula (4):

(In the formula, ring Z represents an aromatic ring, R ⁷ represents a hydrolyzable protecting group, R ⁸ represents a hydrogen atom, a hydrocarbon group or a hydrolyzable protecting group. P represents an integer of 1 or more. When p is 2 or more, a plurality of R ⁷ and R ⁸ may be the same or different, and the aromatic ring may have a substituent other than the substituents shown in the formula Good)
Is reacted with an aromatic compound represented by 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)

(In the formula, ring Z represents an aromatic ring, R ⁷ represents a hydrolyzable protecting group, R ⁸ represents a hydrogen atom, a hydrocarbon group or a hydrolyzable protecting group. P represents an integer of 1 or more. When p is 2 or more, a plurality of R ⁷ and R ⁸ may be the same or different, and the aromatic ring may have a substituent other than the substituents shown in the formula Good)
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). k represents an integer of 0 to 3. When k is 2 or 3, the plurality of R ⁴ and R ⁶ may be the same or different. However, when k = 0, at least two of R ¹ , R ² , R ³ and R ⁵ are groups represented by the formula (2). The adamantane ring may have a substituent at a site other than the bridge head position]
A method for producing a substituted aminoaryladamantane derivative characterized by obtaining a substituted aminoaryladamantane derivative represented by the formula: