JP4364783B2 - Tetraadamantane derivative and process for producing the same - Google Patents

Description

  The present invention relates to a tetraadamantane 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 high-functional polymers with excellent physical properties, and its industrial use is expected to increase in the future.

  Research on biadamantane derivatives in which two molecules of adamantane are bonded has been actively conducted. For example, U.S. Pat. No. 3,342,880 discloses various 1,1′-biadamantane derivatives and methods for producing the same. Japanese Patent Laid-Open No. 2001-253853 discloses 3,3′-dialkoxycarbonyl-1,1′biadamantane excellent in heat resistance, water resistance and optical properties and a method for producing the same. However, polymers obtained from these adamantane derivatives do not always have sufficiently high functionality depending on applications, etc., and a novel adamantane derivative useful as a raw material for polymers exhibiting higher functionality is desired. It has been.

U.S. Pat. No. 8,342,880 JP 2001-253853 A

  Accordingly, an object of the present invention is to provide a novel adamantane 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, and a method for producing the same.

  As a result of intensive studies to achieve the above object, the present inventors have found a novel tetraadamantane derivative in which a halogen atom or a hydroxyl group is bonded to at least one of the four adamantane rings, thereby completing the present invention.

（式中、Ｒ¹、Ｒ²、Ｒ³、Ｒ⁴、Ｒ⁵、Ｒ⁶、Ｒ⁷、Ｒ⁸、Ｒ⁹、Ｒ¹⁰は、同一又は異なって、水素原子、ハロゲン原子を有していてもよいアルキル基、ハロゲン原子を有していてもよいアルコキシ基、ハロゲン原子又はヒドロキシル基を示す。但し、Ｒ¹、Ｒ²、Ｒ³、Ｒ⁴、Ｒ⁵、Ｒ⁶、Ｒ⁷、Ｒ⁸、Ｒ⁹、Ｒ¹⁰のうち少なくとも１つはハロゲン原子又はヒドロキシル基である）
で表されるテトラアダマンタン誘導体を提供する。 That is, the present invention provides the following formula (1):

(In the formula, R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ are the same or different and have a hydrogen atom or a halogen atom. An alkyl group which may have a halogen atom, a halogen atom or a hydroxyl group, provided that R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ and R ¹⁰ are each a halogen atom or a hydroxyl group)
The tetraadamantane derivative represented by these is provided.

（式中、Ｘ¹、Ｘ²、Ｘ³、Ｘ⁴、Ｘ⁵、Ｘ⁶、Ｘ⁷、Ｘ⁸、Ｘ⁹、Ｘ¹⁰は、同一又は異なって、水素原子、ハロゲン原子を有していてもよいアルキル基、ハロゲン原子を有していてもよいアルコキシ基、ハロゲン原子又はヒドロキシル基を示す。但し、Ｘ¹、Ｘ²、Ｘ³、Ｘ⁴、Ｘ⁵、Ｘ⁶、Ｘ⁷、Ｘ⁸、Ｘ⁹、Ｘ¹⁰のうち少なくとも１つは水素原子である）
で表されるテトラアダマンタン誘導体にハロゲン化剤を反応させて、下記式（1a）

（式中、Ｒ^1a、Ｒ^2a、Ｒ^3a、Ｒ^4a、Ｒ^5a、Ｒ^6a、Ｒ^7a、Ｒ^8a、Ｒ^9a、Ｒ^10aは、同一又は異なって、水素原子、ハロゲン原子を有していてもよいアルキル基、ハロゲン原子を有していてもよいアルコキシ基、ハロゲン原子又はヒドロキシル基を示す。但し、Ｒ^1a、Ｒ^2a、Ｒ^3a、Ｒ^4a、Ｒ^5a、Ｒ^6a、Ｒ^7a、Ｒ^8a、Ｒ^9a、Ｒ^10aのうち少なくとも１つはハロゲン原子である）
で表されるテトラアダマンタンハライド誘導体を得ることを特徴とするテトラ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 (2a)

(In the formula, X ¹ , X ² , X ³ , X ⁴ , X ⁵ , X ⁶ , X ⁷ , X ⁸ , X ⁹ , X ¹⁰ are the same or different and have a hydrogen atom or a halogen atom. An alkyl group which may have a halogen atom, a halogen atom or a hydroxyl group, provided that X ¹ , X ² , X ³ , X ⁴ , X ⁵ , X ⁶ , X ⁷ , X ⁸ , X ⁹ or X ¹⁰ is a hydrogen atom)
A tetraadamantane derivative represented by the formula (1a)

(In the formula, R ^1a , R ^2a , R ^3a , R ^4a , R ^5a , R ^6a , R ^7a , R ^8a , R ^9a , R ^10a are the same or different and have a hydrogen atom or a halogen atom. An alkyl group which may have a halogen atom, a halogen atom or a hydroxyl group, provided that R ^1a , R ^2a , R ^3a , R ^4a , R ^5a , R ^6a , R ^7a , R ^8a , R ^9a or R ^10a is a halogen atom)
A tetraadamantane halide derivative represented by the following formula is obtained.

（式中、Ｒ^1a、Ｒ^2a、Ｒ^3a、Ｒ^4a、Ｒ^5a、Ｒ^6a、Ｒ^7a、Ｒ^8a、Ｒ^9a、Ｒ^10aは、同一又は異なって、水素原子、ハロゲン原子を有していてもよいアルキル基、ハロゲン原子を有していてもよいアルコキシ基、ハロゲン原子又はヒドロキシル基を示す。但し、Ｒ^1a、Ｒ^2a、Ｒ^3a、Ｒ^4a、Ｒ^5a、Ｒ^6a、Ｒ^7a、Ｒ^8a、Ｒ^9a、Ｒ^10aのうち少なくとも１つはハロゲン原子である）
で表されるテトラアダマンタンハライド誘導体を加水分解して、下記式（1b）

（式中、Ｒ^1b、Ｒ^2b、Ｒ^3b、Ｒ^4b、Ｒ^5b、Ｒ^6b、Ｒ^7b、Ｒ^8b、Ｒ^9b、Ｒ^10bは、同一又は異なって、水素原子、ハロゲン原子を有していてもよいアルキル基、ハロゲン原子を有していてもよいアルコキシ基、ハロゲン原子又はヒドロキシル基を示す。但し、Ｒ^1b、Ｒ^2b、Ｒ^3b、Ｒ^4b、Ｒ^5b、Ｒ^6b、Ｒ^7b、Ｒ^8b、Ｒ^9b、Ｒ^10bのうち少なくとも１つはヒドロキシル基である）
で表されるヒドロキシテトラアダマンタン誘導体を得ることを特徴とするテトラアダマンタン誘導体の製造法を提供する。 The present invention further includes the following formula (1a):

(In the formula, R ^1a , R ^2a , R ^3a , R ^4a , R ^5a , R ^6a , R ^7a , R ^8a , R ^9a , R ^10a are the same or different and have a hydrogen atom or a halogen atom. An alkyl group which may have a halogen atom, a halogen atom or a hydroxyl group, provided that R ^1a , R ^2a , R ^3a , R ^4a , R ^5a , R ^6a , R ^7a , R ^8a , R ^9a or R ^10a is a halogen atom)
Hydrolysis of a tetraadamantane halide derivative represented by the following formula (1b)

(In the formula, R ^1b , R ^2b , R ^3b , R ^4b , R ^5b , R ^6b , R ^7b , R ^8b , R ^9b , R ^10b are the same or different and have a hydrogen atom or a halogen atom. Or an alkyl group optionally having a halogen atom, a halogen atom or a hydroxyl group, provided that R ^1b , R ^2b , R ^3b , R ^4b , R ^5b , R ^6b , R ^7b , R ^8b , R ^9b and R ^10b are at least one hydroxyl group)
A method for producing a tetraadamantane derivative, characterized in that a hydroxytetraadamantane derivative represented by the formula:

  ADVANTAGE OF THE INVENTION According to this invention, the novel adamantane derivative useful as a raw material of a functional material excellent in an electrical property, a thermal property, a mechanical property, an optical property, a physical property etc., and its efficient manufacturing method are provided.

The tetraadamantane derivative of the present invention is represented by the formula (1). In formula (1), R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ are the same or different and have a hydrogen atom or a halogen atom. An alkyl group that may be present, an alkoxy group that may have a halogen atom, a halogen atom, or a hydroxyl group. However, at least ^one of R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ is a halogen atom or a hydroxyl group.

Examples of the alkyl group optionally having a halogen atom in R ^{1 to} R ¹⁰ include carbon numbers such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, s-butyl, t-butyl, pentyl, hexyl and the like. An alkyl group having about 1 to 15 (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 and pentafluoroethyl groups (preferably C _1-10 haloalkyl group, more preferably C _1-6 haloalkyl group) and the like. 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 halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

The tetraadamantane derivative of the present invention also includes a compound in which at least one of R ^{1 to} R ¹⁰ is a halogen atom and at least one is a hydroxyl group. Further, the tetraadamantane derivative of the present invention includes a mixture of a plurality of compounds having different numbers and / or positions of halogen atoms and hydroxyl groups present in the molecule.

In the tetraadamantane derivative of the present invention, as a typical example of a tetraadamantane derivative (tetraadamantane halide derivative; halotetraadamantane derivative) in which at least one of R ^{1 to} R ¹⁰ is a halogen atom, for example, 3-bromo-1 1 ′: 3 ′, 1 ″: 3 ″, 1 ″ ″-tetraadamantane, 3-bromo-5,5 ′, 5 ″, 3 ″ ″-tetramethyl-1,1 ′: 3 ′, 1 ": 3", 1 "'-tetraadamantane, 3-bromo-5,7,5', 7 ', 5", 7 ", 3"",5""-octamethyl-1,1': Tetraadamantane halide derivatives in which one of R ^{1 to} R ¹⁰ is a halogen atom, such as 3 ′, 1 ″: 3 ″, 1 ′ ″-tetraadamantane and the corresponding 3-chloro derivatives; 3 "'-Dibro -1,1 ': 3', 1 ": 3", 1 ""-tetraadamantane, 3,3 ""-dibromo-5,5 ', 5 ", 5""-tetramethyl-1, 1 ': 3', 1 ": 3", 1 ""-tetraadamantane, 3,3 ""-dibromo-5,7,5 ', 7', 5 ", 7", 5 "", 7 ″ ″-octamethyl-1,1 ′: 3 ′, 1 ″: 3 ″, 1 ″ ″-tetraadamantane, 3,3 ″ ″-dibromo-5,7,5 ′, 7 ′, 5 ″ , 7 ", 5"",7""-octaethyl-1,1':3',1": 3 ", 1""-tetraadamantane,3,3""-dibromo-5,7 , 5 ', 7', 5 ", 7", 5 "", 7 ""-octabutyl-1, 1 ': 3', 1 ": 3", 1 ""-tetraadamantane and the like 3,3 ""-dichroic Such derivatives, two of tetra adamantane halide derivative is a halogen atom of ^{R 1 ~R 10; 3,5 ',} 3''' - tribromo-1,1 ': 3', 1 ": 3", 1 '"-Tetraadamantane, 3,5', 3"'-tribromo-5,7', 5 ", 5""-tetramethyl-1,1':3',1": 3 ", 1 Tetraadamantane halide derivatives in which three of R ^{1 to} R ¹⁰ are halogen atoms, such as ′ ″ -tetraadamantane and the corresponding 3,5 ′, 3 ′ ″-trichloro derivatives; , 5 ", 3""-tetrabromo-1,1':3',1": 3 ", 1""-tetraadamantane, 3,5 ', 5", 3 ""-tetrabromo-5 7 ', 7 ", 5""-tetramethyl-1,1': 3 ', 1": 3 ", 1""- Examples thereof include tetraadamantane halide derivatives in which four of R ^{1 to} R ¹⁰ are halogen atoms, such as tetraadamantane and the corresponding 3,5 ′, 5 ″, 3 ′ ″-tetrachloro derivatives.

In addition, as a typical example of a tetraadamantane derivative (hydroxytetraadamantane derivative) in which at least one of R ^{1 to} R ¹⁰ is a hydroxyl group in the tetraadamantane derivative of the present invention, 3-hydroxy-5,5 ′, 5 ″, 3 ″ ″-tetramethyl-1,1 ′: 3 ′, 1 ″: 3 ″, 1 ″ ″-tetraadamantane, 3-hydroxy-5,7,5 ′, 7 ′, 5 ″, 7 ″, 3 ″ ″, 5 ″ ″-octamethyl-1,1 ′: 3 ′, 1 ″: 3 ″, one of R ^{1 to} R ¹⁰ such as 1 ′ ″-tetraadamantane is a hydroxyl group A hydroxytetraadamantane derivative; 3,3 ′ ″-dihydroxy-1,1 ′: 3 ′, 1 ″: 3 ″, 1 ′ ″-tetraadamantane, 3,3 ″ ″-dihydroxy-5,5 ', 5 ", 5"'-Tet Methyl-1,1 ′: 3 ′, 1 ″: 3 ″, 1 ″ ″-tetraadamantane, 3,3 ″ ″-dihydroxy-5,7,5 ′, 7 ′, 5 ″, 7 ″, 5 ′ ″, 7 ′ ″-octamethyl-1,1 ′: 3 ′, 1 ″: 3 ″, 1 ″ ″-tetraadamantane, 3,3 ″ ″-dihydroxy-5,7,5 ′, 7 ', 5 ", 7", 5 "", 7 ""-octaethyl-1,1': 3 ', 1 ": 3", 1 ""-tetraadamantane, 3,3 ""-dihydroxy -5,7,5 ', 7', 5 ", 7", 5 "", 7 ""-octabutyl-1,1 ': 3', 1 ": 3", 1 ""-tetraadamantane such as, two of hydroxy tetramethyl adamantane derivative is a hydroxyl group of ^{R 1 ~R 10; 3,5 ',} 3''' - trihydroxy-1,1 ': 3', 1 " 3 ″, 1 ″ ″-tetraadamantane, 3,5 ′, 3 ″ ″-trihydroxy-5,7 ′, 5 ″, 5 ″ ″-tetramethyl-1,1 ′: 3 ′, 1 ″ : A tetraadamantane halide derivative in which three of R ^{1 to} R ¹⁰ are hydroxyl groups, such as 3 ″, 1 ′ ″-tetraadamantane; 3,5 ′, 5 ″, 3 ′ ″-tetrahydroxy-1 , 1 ': 3', 1 ": 3", 1 "'-tetraadamantane, 3, 5', 5", 3 "'-tetrahydroxy-5, 7', 7", 5 "'- Examples thereof include hydroxytetraadamantane derivatives in which four of R ^{1 to} R ¹⁰ are hydroxyl groups, such as tetramethyl-1,1 ′: 3 ′, 1 ″: 3 ″, 1 ′ ″-tetraadamantane.

In the tetraadamantane derivative of the present invention, the tetraadamantane derivative in which at least one of R ^{1 to} R ¹⁰ is a halogen atom is obtained by, for example, reacting a tetraadamantane derivative represented by the formula (2a) with a halogenating agent. Can be manufactured. In the formula (2a), X ¹ , X ² , X ³ , X ⁴ , X ⁵ , X ⁶ , X ⁷ , X ⁸ , X ⁹ , X ¹⁰ are the same or different and have a hydrogen atom or a halogen atom. An alkyl group that may be present, an alkoxy group that may have a halogen atom, a halogen atom, or a hydroxyl group. However, at least ^one of X ¹ , X ² , X ³ , X ⁴ , X ⁵ , X ⁶ , X ⁷ , X ⁸ , X ⁹ and X ¹⁰ is a hydrogen atom. The alkyl group which may have the above halogen atom, the alkoxy group which may have a halogen atom, and the halogen atom are the same as the alkyl group which may have a halogen atom in R ^{1 to} R ¹⁰ . It is.

  As typical examples of the tetraadamantane derivative represented by the formula (2a), for example, 1,1 ′: 3 ′, 1 ″: 3 ″, 1 ′ ″-tetraadamantane (= tetraadamantane), 3, 7 ′, 7 ″, 5 ″ ″-tetramethyl-1,1 ′: 3 ′, 1 ″: 3 ″, 1 ″ ″-tetraadamantane, 3,5,5 ′, 7 ′, 5 ″, 7 ", 3" ', 5 "'-octamethyl-1,1 ': 3', 1": 3 ", 1" "-tetraadamantane, 3,5,5 ', 7', 5", 7 ", 3" ', 5 "'-octaethyl-1,1 ': 3', 1": 3 ", 1" "-tetraadamantane, 3,5,5 ', 7', 5", 7 ″, 3 ″ ″, 5 ″ ″-octabutyl-1,1 ′: 3 ′, 1 ″: 3 ″, 1 ″ ″-tetraadamantane and the like.

Examples of the halogenating agent include fluorine (F ₂ ), chlorine (Cl ₂ ), bromine (Br ₂ ), iodine (I ₂ ) halogens; tertiary alkyl halides (eg, t-butyl bromide, t- Butyl chloride, t-amyl bromide, t-amyl chloride, etc.), N-bromosuccinimide, boron tribromide, carbon tetrabromide, sulfolane, and the like. The reaction between the tetraadamantane derivative represented by the formula (2a) and the halogenating agent is performed in the presence or absence of a solvent inert to the reaction. As the solvent, for example, halogenated hydrocarbons such as methylene chloride, chloroform, carbon tetrachloride, 1,2-dichloroethane, methylene bromide, dibromopropane, dibromobutane, bromochloromethane, and bromochloroethane are preferably used. In order to improve the reaction rate and selectivity, a catalyst can be used together with the halogenating agent. Examples of the catalyst include anhydrous ferric chloride, anhydrous ferric bromide, anhydrous aluminum chloride, anhydrous aluminum bromide, anhydrous zinc chloride, anhydrous zinc bromide, anhydrous titanium tetrachloride, and other Lewis acids, phosphorus pentoxide ( P ₂ O _5), phosphorus pentachloride compounds such as phosphorus trichloride (PCl _5), and the like boron compounds such boron tribromide (BBr _3).

The amount of halogenating agent used varies depending on the type of halogenating agent and the number of halogen atoms introduced into the tetraadamantane derivative. When halogen is used as the halogenating agent, the amount is generally about 0.8 to 100 mol with respect to 1 mol of the tetraadamantane derivative represented by the formula (2a), and even if a large excess of halogen is used. Good. In particular, when one halogen atom is introduced into each of four adamantane rings, the amount of halogen used is X ¹ , X ² , X ³ , X ⁴ among the tetraadamantane derivatives represented by the formula (2a). Is preferably about 4 to 100 mol, more preferably about 8 to 60 mol, per 1 mol of a compound in which all are hydrogen atoms. The amount of catalyst in the case of using a catalyst such as Lewis acid together with halogen can be appropriately selected from a range of about 0.01 to 50% by weight with respect to the tetraadamantane derivative represented by the formula (2a), for example. The reaction temperature at the time of reacting the tetraadamantane derivative represented by the formula (2a) with halogen is, for example, -20 ° C to 150 ° C, preferably about 0 to 80 ° C.

  The reaction between the tetraadamantane derivative represented by the formula (2a) and the halogenating agent may be carried out by any system such as a batch system, a semi-batch system, and a continuous system.

By the above reaction, a tetraadamantane halide represented by the formula (1a) in which at least one hydrogen atom at the bridge head position (X ^{1 to} X ¹⁰ ) of the adamantane ring of the compound represented by the formula (2a) is replaced by a halogen atom A derivative is formed. The halogen atom (introduced halogen atom) in R ^{1a to} R ^10a in the formula (1a) is a halogen atom corresponding to the halogenating agent used, and is a fluorine atom, a chlorine atom, a bromine atom or an iodine atom. The alkyl group and alkoxy group which may have a halogen atom in R ^{1a to} R ^10a in the formula (1a) are the same as the alkyl group which may have a halogen atom in R ^{1 to} R ¹⁰ . After completion of the reaction, the reaction product is decomposed by reducing the remaining halogenating agent as necessary, and then general separation and purification such as liquidity adjustment, extraction, crystallization, washing, recrystallization, column chromatography, etc. Separation and purification can be carried out by applying the means.

  The number of halogen atoms introduced into the adamantane ring of the tetraadamantane derivative is not only the amount of the halogenating agent, but also the type of halogenating agent, the type and amount of catalyst, the presence or absence of a solvent, the substrate concentration, the reaction temperature and the reaction time. Etc. can be adjusted. The substitution of the hydrogen atom at the bridge head position of the adamantane ring with a halogen atom is usually assumed to occur advantageously from the adamantane rings at both ends of the four adamantane rings.

  The tetraadamantane derivative represented by the formula (2a) can be obtained by a coupling reaction (including a cross-coupling reaction) of a halobiadamantane derivative, and the halobiadamantane derivative is a halomonoadamantane derivative. It can be produced by halogenating a biadamantane derivative obtained by a coupling reaction (including a cross coupling reaction) of a derivative. The coupling reaction and the halogenation reaction can be performed by known methods.

In the tetraadamantane derivative of the present invention, the tetraadamantane derivative in which at least one of R ^{1 to} R ¹⁰ is a hydroxyl group can be produced, for example, by hydrolyzing the tetraadamantane halide derivative represented by the formula (1a). .

  For the hydrolysis, a conventionally performed hydrolysis method such as acid hydrolysis or alkali hydrolysis can be employed. Examples of acids used in the acid hydrolysis include inorganic acids such as hydrochloric acid and sulfuric acid, sulfonic acids such as p-toluenesulfonic acid, benzenesulfonic acid, naphthalenesulfonic acid, methanesulfonic acid, and trifluoromethanesulfonic acid, and strong acidic cations. Exchange resin etc. are mentioned. Examples of the alkali used in the alkali hydrolysis include alkali metal-containing compounds such as alkali metal hydroxides such as sodium hydroxide and potassium hydroxide. The amount of alkali used and the amount of water used can be appropriately selected depending on the number of hydroxyl groups introduced. A catalytic amount of the acid may be used. The reaction is carried out in the presence of water, but an organic solvent may be added to the reaction system in order to increase the solubility of the reaction components. Examples of the organic solvent include water-soluble organic solvents such as alcohols such as methanol and ethanol and amides such as N, N-dimethylformamide. The reaction temperature is, for example, about 30 to 110 ° C.

Hydrolysis may be performed by any method such as a batch method, a semi-batch method, and a continuous method. In such a hydrolysis reaction, in the formula (1b), at least one halogen atom in the bridge head position (R ^{1a to} R ^10a ) of the adamantane ring of the tetraadamantane halide derivative represented by the formula (1a) is replaced with a hydroxyl group. The hydroxytetraadamantane derivative represented is produced. The reaction product can be separated and purified by general separation and purification means such as liquidity adjustment, extraction, crystallization, washing, recrystallization, column chromatography and the like.

  The hydroxytetraadamantane derivative represented by the formula (1b) is also produced by oxidizing a tetraadamantane derivative having at least one hydrogen atom at the bridge head position of the adamantane ring represented by the formula (2a). You can also.

  As the oxidizing agent, for example, oxygen, chromic acid or the like can be used. When oxygen is used as the oxidizing agent, pure oxygen (molecular oxygen) may be used as oxygen, or oxygen or air diluted with an inert gas such as nitrogen may be used. The amount of oxygen used varies depending on the amount of hydroxyl group introduced and the like, but is usually 0.25 mol or more per 1 mol of the tetraadamantane derivative represented by the formula (2a). When oxygen is used as the oxidizing agent, the oxidation reaction is usually performed in the presence of a catalyst. The catalyst is not particularly limited as long as it exhibits a catalytic action for the oxidation reaction at the bridge head position of the adamantane ring, and examples thereof include cobalt catalysts such as cobalt naphthenate, manganese catalysts such as manganese naphthenate, and combinations thereof. It is done. The usage-amount of a catalyst can be selected in a wide range, for example, is 0.0000001-1 mol with respect to 1 mol of tetraadamantane derivatives represented by Formula (2a), Preferably it is about 0.000001-0.5 mol. .

  The oxidation reaction is performed in the presence or absence of a solvent. Examples of the solvent include aromatic hydrocarbons such as benzene; halogenated hydrocarbons such as methylene chloride, chloroform, 1,2-dichloroethane and dichlorobenzene; alcohols such as t-butanol and t-amyl alcohol; acetonitrile, benzo Nitriles such as nitrile; carboxylic acids such as acetic acid and propionic acid; amides such as N, N-dimethylformamide; and mixed solvents thereof.

  The reaction temperature is, for example, about 30 to 250 ° C, preferably about 60 to 200 ° C. In order to increase the reaction rate, the reaction may be performed under pressure. The oxidation reaction may be performed by any system such as a batch system, a semi-batch system, and a continuous system.

By the above reaction, the hydroxytetraadamantane represented by the formula (1b) in which at least one hydrogen atom at the bridge head position (X ^{1 to} X ¹⁰ ) of the adamantane ring of the compound represented by the formula (2a) is replaced with a hydroxyl group A derivative is formed. After completion of the reaction, the reaction product can be separated and purified by general separation and purification means such as liquidity adjustment, extraction, crystallization, washing, recrystallization, column chromatography and the like.

  In the tetraadamantane derivative of the present invention, in a compound having an alkyl group which may have a halogen atom or an alkoxy group which may have a halogen atom together with a halogen atom or a hydroxyl group in the adamantane ring, The introduction of the substituent may be performed at any stage for producing the tetraadamantane derivative of the present invention. That is, for example, a monoadamantane derivative is halogenated to form a halomonoadamantane derivative, the halomonoadamantane derivative is subjected to a coupling reaction to obtain a biadamantane derivative, the biadamantane derivative is halogenated to form a halobiadamantane derivative, Further, the halobiadamantane derivative is subjected to a coupling reaction to obtain a tetraadamantane derivative having a hydrogen atom at the bridge head position of the adamantane ring, and the tetraadamantane derivative is halogenated as described above to produce a halotetraadamantane derivative, When the hydroxyadadamantane derivative is produced by hydrolyzing the halotetraadamantane derivative or oxidizing the tetraadamantane derivative having a hydrogen atom at the bridge head position of the adamantane ring, Tan derivatives, biadamantane derivatives, tetra adamantane derivative, may be introduced the substituent at any stage, such as halo or hydroxy tetra adamantane derivative. These substituents can be introduced by using a known method or a known reaction.

  In the tetraadamantane derivative represented by the formula (1), four adamantane skeletons, which are very stable and excellent in symmetry, are directly bonded, and a halogen atom or a hydroxyl group which is a reactive functional group is bonded. For example, it is possible to easily introduce a polymerizable group or the like by utilizing the reactivity, and thus, such as heat resistance, water resistance, optical characteristics, light transmittance, low dielectric constant, water absorption, adhesion, etc. It can be used as a raw material (for example, a precursor of a monomer) of a functional material such as various high-functional polymers having excellent properties, thermal properties, mechanical properties, optical properties, physical properties, and the like.

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

Production Example 1
Under a nitrogen atmosphere, a mixed solution of 11.2 g (31.9 mmol) of 3-bromo-1,1′-biadamantane, 44.6 g of n-octane, and 0.22 g (9.6 mmol) of sodium was heated and stirred at 120 ° C. . After 2 hours, 0.66 g (28.7 mmol) of sodium was added little by little over 8 hours, and then heated and stirred for 2 hours. The reaction mixture was cooled to 60 ° C., 22 g of ethanol was added and stirred for 30 minutes, and then filtered hot. The obtained crystal and 60 g of toluene were heated and stirred at 80 ° C. for 1 hour, and then subjected to hot filtration, and the obtained crystal was dried. As a result, 6.0 g of tetraadamantane (= 1,1 ′: 3 ′, 1 ″: 3 ″, 1 ′ ″-tetraadamantane) was obtained with a yield of 70%. Identification was performed by IR, melting point, and DI-MS (direct mass, direct sample introduction method) (Reference: Tetrahedron Letter, Vol. 42, 2001, pages 8645-8647).
DI-MS-spectrometry: 537, 403, 269, 135 m / z [M -] [CI Method]

Production Example 2
Under a nitrogen atmosphere, 3-bromo-5,5 ′, 7,7′-tetramethyl-1,1′-biadamantane 55 g (0.14 mol), n-octane 440 g, sodium 1.2 g (0.05 mol) The mixed solution was heated and stirred at 110 ° C. After 2 hours, 3.5 g (0.15 mol) of sodium was added little by little over 8 hours, and then heated and stirred for 2 hours. The reaction mixture was cooled to 60 ° C., 55 g of ethanol was added and stirred for 30 minutes, filtered hot and washed with ethanol. The obtained crystals and 200 g of water were heated and stirred at 60 ° C. for 1 hour, filtered hot, and washed with ethanol. The crystals and 525 g of toluene were heated and stirred at 60 ° C., and then filtered hot to dry the crystals. As a result, tetra (dimethyladamantane) (= 3, 5, 5 ′, 7 ′, 5 ″, 7 ″, 3 ′ ″, 5 ′ ″-octamethyl-1, 1 ′: 3 ′, 1 ″: 3 ″, 1 ″ ″-tetraadamantane) was obtained with a yield of 64%.
IR (KBr): 1336, 1359, 1454, 2846, 2894, 2940 (cm ^-1 )
DI-MS-spectrometry: 649, 487, 325, 163 m / z [M -] [EI method]

Example 1
Under a nitrogen atmosphere, a mixed solution of 2.0 g (3.7 mmol) of tetraadamantane and 16.6 g (103.9 mmol) of bromine was heated and stirred at 50 ° C. for 8 hours. The reaction mixture was cooled to 5 ° C., water was added, and sodium hydrogen sulfite was slowly added to reduce excess bromine. Thereafter, the precipitate was filtered, washed successively with a saturated aqueous solution of sodium bicarbonate, water and acetone and dried. As a result, tetrabromotetraadamantane (= 3,5 ′, 5 ″, 3 ″ ″-tetrabromo-1,1 ′: 3 ′, 1 ″: 3 ″, 1 ″ ″-tetra represented by the following formula: Adamantane) was obtained in an amount of 2.3 g (2.7 mmol) in a yield of 73%.
IR (KBr): 684, 821 (C-Br), 1022, 1330, 1344, 1448, 2857, 2908, 2935 (cm ^-1 )
DI-MS-spectrometry: 856, 776, 696, 616, 538, 404, 269, 135 m / z [CI method]

Example 2
Under a nitrogen atmosphere, a mixed solution of 2.0 g (3.7 mmol) of tetraadamantane and 16.6 g (103.9 mmol) of bromine was heated and stirred at 50 ° C. for 3 hours. The reaction mixture was cooled to 5 ° C., water was added, and sodium hydrogen sulfite was slowly added to reduce excess bromine. Thereafter, the precipitate was filtered, washed successively with a saturated aqueous solution of sodium bicarbonate, water and acetone and dried. As a result, 2.1 g of a mixture of dibromotetraadamantane, tribromotetraadamantane and tetrabromotetraadamantane as main components was obtained.
IR (KBr): 684, 821 (C-Br), 1022, 1330, 1344, 1448, 2857, 2908, 2935 (cm ^-1 )
[Dibromotetraadamantane]
DI-MS-spectrometry: 696, 617, 536, 404, 269, 135 m / z [CI method]
[Tribromotetraadamantane]
DI-MS-spectrometry: 776, 696, 617, 536, 404, 269, 135 m / z [CI method]

Example 3
Under a nitrogen atmosphere, a mixed solution of 2.0 g (3.0 mmol) of tetra (dimethyladamantane) and 13.7 g (86.0 mmol) of bromine was heated and stirred at 50 ° C. for 8 hours. The reaction mixture was cooled to 5 ° C., water was added, and sodium hydrogen sulfite was slowly added to reduce excess bromine. Thereafter, the precipitate was filtered, washed successively with a saturated aqueous solution of sodium bicarbonate, water and acetone and dried. As a result, dibromotetra (dimethyladamantane) represented by the following formula (= 3,3 ′ ″-dibromo-5,7,5 ′, 7 ′, 5 ″, 7 ″, 5 ″ ″, 7 ″) ′ -Octamethyl-1,1 ′: 3 ′, 1 ″: 3 ″, 1 ″ ″-tetraadamantane) was obtained in an amount of 2.0 g (2.4 mmol) in a yield of 79%.
IR (KBr): 736, 838 (C-Br), 931, 1338, 1359, 1455, 2850, 2894, 2942 (cm ^-1 )
DI-MS-spectrometry: 808, 728, 649, 487, 325, 161 m / z [CI method]

Example 4
Under a nitrogen atmosphere, a mixed solution of 2.0 g (3.0 mmol) of tetra (dimethyladamantane) and 13.7 g (86.0 mmol) of bromine was heated and stirred at 50 ° C. for 2 hours. The reaction mixture was cooled to 5 ° C., water was added, and sodium hydrogen sulfite was slowly added to reduce excess bromine. Thereafter, the precipitate was filtered, washed successively with a saturated aqueous solution of sodium bicarbonate, water and acetone and dried. As a result, 1.9 g of a mixture of monobromotetra (dimethyladamantane) as a main component and other dibromotetra (dimethyladamantane) was obtained.
IR (KBr): 736, 838, 931, 1338, 1359, 1455, 2850, 2894, 2942 (cm ^-1 )
DI-MS-spectrometry: 728, 649, 487, 325, 161 m / z [CI method]

Claims (3)

Following formula (1)

(In the formula, R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ are the same or different and have a hydrogen atom or a halogen atom. An alkyl group which may have a halogen atom, a halogen atom or a hydroxyl group, provided that R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ and R ¹⁰ are each a halogen atom or a hydroxyl group)
A tetraadamantane derivative represented by: Following formula (2a)

(In the formula, X ¹ , X ² , X ³ , X ⁴ , X ⁵ , X ⁶ , X ⁷ , X ⁸ , X ⁹ , X ¹⁰ are the same or different and have a hydrogen atom or a halogen atom. An alkyl group which may have a halogen atom, a halogen atom or a hydroxyl group, provided that X ¹ , X ² , X ³ , X ⁴ , X ⁵ , X ⁶ , X ⁷ , X ⁸ , X ⁹ or X ¹⁰ is a hydrogen atom)
A tetraadamantane derivative represented by the formula (1a)

(In the formula, R ^1a , R ^2a , R ^3a , R ^4a , R ^5a , R ^6a , R ^7a , R ^8a , R ^9a , R ^10a are the same or different and have a hydrogen atom or a halogen atom. An alkyl group which may have a halogen atom, a halogen atom or a hydroxyl group, provided that R ^1a , R ^2a , R ^3a , R ^4a , R ^5a , R ^6a , R ^7a , R ^8a , R ^9a or R ^10a is a halogen atom)
A process for producing a tetraadamantane derivative represented by the formula: The following formula (1a)

(In the formula, R ^1a , R ^2a , R ^3a , R ^4a , R ^5a , R ^6a , R ^7a , R ^8a , R ^9a , R ^10a are the same or different and have a hydrogen atom or a halogen atom. An alkyl group which may have a halogen atom, a halogen atom or a hydroxyl group, provided that R ^1a , R ^2a , R ^3a , R ^4a , R ^5a , R ^6a , R ^7a , R ^8a , R ^9a or R ^10a is a halogen atom)
Hydrolysis of a tetraadamantane halide derivative represented by the following formula (1b)

(In the formula, R ^1b , R ^2b , R ^3b , R ^4b , R ^5b , R ^6b , R ^7b , R ^8b , R ^9b , R ^10b are the same or different and have a hydrogen atom or a halogen atom. Or an alkyl group optionally having a halogen atom, a halogen atom or a hydroxyl group, provided that R ^1b , R ^2b , R ^3b , R ^4b , R ^5b , R ^6b , R ^7b , R ^8b , R ^9b and R ^10b are at least one hydroxyl group)
A process for producing a tetraadamantane derivative characterized by obtaining a hydroxytetraadamantane derivative represented by the formula: