JP2013234128A - Epoxy compound, method of producing the same, epoxy resin composition, and cured product thereof - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method of producing an aromatic polyfunctional epoxy compound having a high refraction index, being liquid at room temperature, and giving a cured product excellent in heat resistance.SOLUTION: An epoxy compound is obtained by glycidylating a 1,2,3,4-tetrahydro-1,4-methanoanthracene-9,10-diol compound represented by formula (2) in the presence of a specific basic compound. (In the formula: R, R, R, Rand Rmay be the same or different mutually and each represents a hydrogen atom or a methyl group; and X represents a hydrogen atom, a halogen atom or the like).

Description

  The present invention relates to a novel epoxy compound that provides a cured product excellent in heat resistance, a method for producing the same, an epoxy resin composition, and a cured product thereof.

  Epoxy resins have various excellent properties such as adhesion, heat resistance and mechanical properties, and are used in electrical / electronic materials, paints, adhesives, various composite materials, civil engineering and building materials. Especially with the rapid development of IT field in recent years, as an epoxy resin for electric and electronic materials, it has excellent heat resistance, flame retardancy, low water absorption, dimensional stability, etc. Epoxy resins are craved. In general, it has been found that introducing an aromatic ring into the structure of the curing agent is effective for improving the heat resistance of the epoxy resin. Among these, novolak type epoxy resins containing polyfunctional aromatic compounds are mainly used in fields where high heat resistance is required. The novolak type epoxy resin has a structure in which several molecules of a phenol compound and an aldehyde compound are polycondensed. In order to obtain a cured product having high heat resistance, it is necessary to increase the degree of polymerization of the polycondensation. However, when the degree of polymerization is increased, the melt viscosity of the epoxy resin is increased and the fluidity is lost, causing a problem in workability. For example, a novolak type epoxy resin composition in which a polyglycidyl ether compound obtained by glycidyl etherification of a part of a plurality of hydroxyl groups derived from dihydroxynaphthalene of a novolak resin derived from a dihydroxynaphthalene compound and an aldehyde compound such as formaldehyde is proposed. (Patent Document 1). However, such a polyfunctional novolac type epoxy resin composition has a high heat resistance, but is a solid at room temperature, and it must be heated and melted or dissolved in a solvent to be cured. There is a problem in workability.

  On the other hand, an aliphatic epoxy compound such as trimethylolpropane triglycidyl ether is known as a representative example of a polyfunctional epoxy resin composition that is liquid at room temperature. However, such an aliphatic epoxy compound is liquid at room temperature and thus has good workability, but has a problem in heat resistance. Moreover, although it is a small number, the aromatic polyfunctional epoxy compound which is liquid at normal temperature has been reported (for example, patent document 2). However, its heat resistance is not satisfactory.

Epoxy resins are also preferably used in the field of optical component materials such as lenses. Epoxy resins can easily form parts with relatively complicated shapes, are lighter than glass, have toughness, and are difficult to break. However, in the field of optical component materials such as lenses, a lens having a high refractive index can be made thin when manufactured using a material having a high refractive index. Cured products of alicyclic epoxy compounds such as 3,4-epoxycyclohexylmethyl (3,4-epoxy) cyclohexanecarboxylate used in optical component materials are excellent in transparency, but their refractive index is There is a problem that the refractive index is low because it does not reach 1.5, while naphthalene diglycidyl ether whose refractive index reaches 1.62 is solid, so that it can be cured by heating or dissolving in a solvent. There was a problem in workability.

  Thus, a liquid aromatic polyfunctional epoxy compound excellent in heat resistance and workability and having a refractive index exceeding 1.6 is not yet proposed.

JP-A-61-69826 Japanese Patent Laid-Open No. 8-311154

  Accordingly, an object of the present invention is to provide an aromatic polyfunctional epoxy compound that has a high refractive index, is liquid at room temperature, and provides a cured product having excellent heat resistance, a method for producing the epoxy compound, and the epoxy compound as an essential component. It is providing the epoxy resin composition and the hardened | cured material which hardened the said epoxy resin composition.

  As a result of intensive studies in view of the above problems, the present inventor has obtained an epoxy compound obtained by glycidylating a 1,2,3,4-tetrahydro-1,4-methanoanthracene-9,10-diol compound. The inventors have found that a cured product having a high refractive index, liquid at normal temperature, and excellent heat resistance can be obtained, and the present invention has been completed.

  That is, the first gist of the present invention resides in an epoxy compound represented by the following general formula (1).

(In the general formula (1), R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ may be the same or different from each other, and represent a hydrogen atom or a methyl group, and X is hydrogen Indicates an atom, halogen atom, alkyl group, alkoxy group or aryloxy group.)

  The second gist of the present invention is to provide a 1,2,3,4-tetrahydro-1,4-methanoanthracene-9,10-diol compound represented by the following general formula (2) in the presence of a basic compound. It exists in the manufacturing method of the epoxy compound as described in the 1st summary characterized by making it react with the epihalohydrin compound represented by following General formula (3).

(In the general formula (2), R ¹ , R ² , R ³ , R ⁴ and R ⁵ may be the same or different from each other, and represent a hydrogen atom or a methyl group, and X represents a hydrogen atom, a halogen atom, (Atom, alkyl group, alkoxy group, or aryloxy group is shown.)

(In general formula (3), R ⁶ represents either a hydrogen atom or a methyl group, and Y represents a halogen atom.)

  The third gist of the present invention resides in an epoxy resin composition comprising the epoxy compound described in the first gist as a component.

The fourth aspect of the present invention resides in a cured product obtained by curing the epoxy resin composition described in the third aspect.

In the description of the present invention, the position numbers of the substituents in the 1,2,3,4-tetrahydro-1,4-methanoanthracene skeleton are given as follows.

  According to the present invention, an aromatic polyfunctional epoxy compound that exhibits a high refractive index, is liquid at room temperature, and gives a cured product having excellent heat resistance, a method for producing the epoxy compound, and an epoxy resin composition containing the epoxy compound as an essential component And a cured product obtained by curing the epoxy resin composition are provided.

  Hereinafter, the present invention will be described in detail.

(Epoxy compound)
The epoxy compound of the present invention is represented by the following general formula (1).

(In the general formula (1), R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ may be the same or different from each other, and represent a hydrogen atom or a methyl group, and X is hydrogen Indicates an atom, halogen atom, alkyl group, alkoxy group or aryloxy group.)

  Specific examples of the halogen atom represented by X in the general formula (1) are as follows. That is, for example, a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Specific examples of the alkyl group are as follows. That is, methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, n-pentyl group, n-hexyl group, cyclohexyl group, n-heptyl group, 2-ethylhexyl, Such as dodecyl group. Furthermore, specific examples of the alkoxy group are as follows. That is, a methoxy group, an ethoxy group, an n-propoxy group, an n-butoxy group, an n-hexyloxy group, and the like. Finally, specific examples of the aryloxy group are as follows. That is, a phenoxy group, a p-methylphenoxy group, an o-methylphenoxy group, a p-chlorophenoxy group, an o-chlorophenoxy group, and the like.

  Examples of the compound represented by the general formula (1) include the following.

First, as examples of compounds in which X is a hydrogen atom, 1,2,3,4-tetrahydro-1,4-methanoanthracene-9,10-diglycidyl ether, 1,2,3,4-tetrahydro-1 , 4-methanoanthracene-9,10-bis (2-methylglycidyl) ether, 1-methyl-1,2,3,4-tetrahydro-1,4-methanoanthracene-9,10-diglycidyl ether, 1- Methyl-1,2,3,4-tetrahydro-1,4-methanoanthracene-9,10-bis (2-methylglycidyl) ether, 2-methyl-1,2,3,4-tetrahydro-1,4- Methanoanthracene-9,10-diglycidyl ether, 2-methyl-1,2,3,4-tetrahydro-1,4-methanoanthracene-9,10-bis (2-methyl group) Sidyl) ether, 11-methyl-1,2,3,4-tetrahydro-1,4-methanoanthracene-9,10-diglycidyl ether, 11-methyl-1,2,3,4-tetrahydro-1,4 -Methanoanthracene-9,10-bis (2-methylglycidyl) ether and the like.

Next, examples of X being a halogen atom include 5-fluoro-1,2,3,4-tetrahydro-1,4-methanoanthracene-9,10-diglycidyl ether, 5-chloro-1,2,3. , 4-tetrahydro-1,4-methanoanthracene-9,10-diglycidyl ether, 5-bromo-1,2,3,4-tetrahydro-1,4-methanoanthracene-9,10-diglycidyl ether, 5 -Iodo-1,2,3,4-tetrahydro-1,4-methanoanthracene-9,10-diglycidyl ether, 6-fluoro-1,2,3,4-tetrahydro-1,4-methanoanthracene-9 , 10-diglycidyl ether, 6-chloro-1,2,3,4-tetrahydro-1,4-methanoanthracene-9,10-diglycidyl ether, 6-bromo-1 2,3,4-tetrahydro-1,4-methanoanthracene-9,10-diglycidyl ether, 6-iodo-1,2,3,4-tetrahydro-1,4-methanoanthracene-9,10-diglycidyl Ether, 1-methyl-5-fluoro-1,2,3,4-tetrahydro-1,4-methanoanthracene-9,10-diglycidyl ether, 1-methyl-5-chloro-1,2,3,4 -Tetrahydro-1,4-methanoanthracene-9,10-diglycidyl ether, 1-methyl-5-bromo-1,2,3,4-tetrahydro-1,4-methanoanthracene-9,10-diglycidyl ether 1-methyl-5-iodo-1,2,3,4-tetrahydro-1,4-methanoanthracene-9,10-diglycidyl ether, 1-methyl-6-thio Oro-1,2,3,4-tetrahydro-1,4-methanoanthracene-9,10-diglycidyl ether, 1-methyl-6-chloro-1,2,3,4-tetrahydro-1,4-methano Anthracene-9,10-diglycidyl ether, 1-methyl-6-bromo-1,2,3,4-tetrahydro-1,4-methanoanthracene-9,10-diglycidyl ether, 1-methyl-6-iodo -1,2,3,4-tetrahydro-1,4-methanoanthracene-9,10-diglycidyl ether, 2-methyl-5-fluoro-1,2,3,4-tetrahydro-1,4-methanoanthracene -9,10-diglycidyl ether, 2-methyl-5-chloro-1,2,3,4-tetrahydro-1,4-methanoanthracene-9,10-diglycidyl ether 2-methyl-5-bromo-1,2,3,4-tetrahydro-1,4-methanoanthracene-9,10-diglycidyl ether, 2-methyl-5-iodo-1,2,3,4 Tetrahydro-1,4-methanoanthracene-9,10-diglycidyl ether, 2-methyl-6-fluoro-1,2,3,4-tetrahydro-1,4-methanoanthracene-9,10-diglycidyl ether, 2-methyl-6-chloro-1,2,3,4-tetrahydro-1,4-methanoanthracene-9,10-diglycidyl ether, 2-methyl-6-bromo-1,2,3,4-tetrahydro -1,4-methanoanthracene-9,10-diglycidyl ether, 2-methyl-6-iodo-1,2,3,4-tetrahydro-1,4-methanoanthracene-9,10- Glycidyl ether, 5-fluoro-1,2,3,4-tetrahydro-1,4-methanoanthracene-9,10-bis (2-methylglycidyl) ether, 5-chloro-1,2,3,4-tetrahydro -1,4-methanoanthracene-9,10-bis (2-methylglycidyl) ether, 5-bromo-1,2,3,4-tetrahydro-1,4-methanoanthracene-9,10-bis (2- Methyl glycidyl) ether, 5-iodo-1,2,3,4-tetrahydro-1,4-methanoanthracene-9,10-bis (2-methylglycidyl) ether, 6-fluoro-1,2,3,4 -Tetrahydro-1,4-methanoanthracene-9,10-bis (2-methylglycidyl) ether, 6-chloro-1,2,3,4-tetrahydro-1,4- Tanoanthracene-9,10-bis (2-methylglycidyl) ether, 6-bromo-1,2,3,4-tetrahydro-1,4-methanoanthracene-9,10-bis (2-methylglycidyl) ether, 6-iodo-1,2,3,4-tetrahydro-1,4-methanoanthracene-9,10-bis (2-methylglycidyl) ether, 1-methyl-5-fluoro-1,2,3,4 Tetrahydro-1,4-methanoanthracene-9,10-bis (2-methylglycidyl) ether, 1-methyl-5-chloro-1,2,3,4-tetrahydro-1,4-methanoanthracene-9,10 -Bis (2-methylglycidyl) ether, 1-methyl-5-bromo-1,2,3,4-tetrahydro-1,4-methanoanthracene-9,10-bis (2- Methyl glycidyl) ether, 1-methyl-5-iodo-1,2,3,4-tetrahydro-1,4-methanoanthracene-9,10-bis (2-methylglycidyl) ether, 1-methyl-6-fluoro -1,2,3,4-tetrahydro-1,4-methanoanthracene-9,10-bis (2-methylglycidyl) ether, 1-methyl-6-chloro-1,2,3,4-tetrahydro-1 , 4-Methanoanthracene-9,10-bis (2-methylglycidyl) ether, 1-methyl-6-bromo-1,2,3,4-tetrahydro-1,4-methanoanthracene-9,10-bis ( 2-methylglycidyl) ether, 1-methyl-6-iodo-1,2,3,4-tetrahydro-1,4-methanoanthracene-9,10-bis (2-methylglycidyl) ) Ether, 2-methyl-5-fluoro-1,2,3,4-tetrahydro-1,4-methanoanthracene-9,10-bis (2-methylglycidyl) ether, 2-methyl-5-chloro-1 , 2,3,4-Tetrahydro-1,4-methanoanthracene-9,10-bis (2-methylglycidyl) ether, 2-methyl-5-bromo-1,2,3,4-tetrahydro-1,4 -Methanoanthracene-9,10-bis (2-methylglycidyl) ether, 2-methyl-5-iodo-1,2,3,4-tetrahydro-1,4-methanoanthracene-9,10-bis (2- Methyl glycidyl) ether, 2-methyl-6-fluoro-1,2,3,4-tetrahydro-1,4-methanoanthracene-9,10-bis (2-methylglycidyl) ether 2-methyl-6-chloro-1,2,3,4-tetrahydro-1,4-methanoanthracene-9,10-bis (2-methylglycidyl) ether, 2-methyl-6-bromo-1,2, 3,4-tetrahydro-1,4-methanoanthracene-9,10-bis (2-methylglycidyl) ether, 2-methyl-6-iodo-1,2,3,4-tetrahydro-1,4-methanoanthracene -9,10-bis (2-methylglycidyl) ether and the like.

Furthermore, examples of X as an alkyl group include 5-methyl-1,2,3,4-tetrahydro-1,4-methanoanthracene-9,10-diglycidyl ether, 5-ethyl-1,2,3, 4-tetrahydro-1,4-methanoanthracene-9,10-diglycidyl ether, 5- (n-propyl) -1,2,3,4-tetrahydro-1,4-methanoanthracene-9,10-diglycidyl Ether, 5- (i-propyl) -1,2,3,4-tetrahydro-1,4-methanoanthracene-9,10-diglycidyl ether, 5- (n-butyl) -1,2,3,4 -Tetrahydro-1,4-methanoanthracene-9,10-diglycidyl ether, 5- (i-butyl) -1,2,3,4-tetrahydro-1,4-methanoanthracene-9,10-digly Dil ether, 5- (n-pentyl) -1,2,3,4-tetrahydro-1,4-methanoanthracene-9,10-diglycidyl ether, 5- (n-hexyl) -1,2,3 4-tetrahydro-1,4-methanoanthracene-9,10-diglycidyl ether, 5- (n-heptyl) -1,2,3,4-tetrahydro-1,4-methanoanthracene-9,10-diglycidyl Ether, 5- (2-ethylhexyl) -1,2,3,4-tetrahydro-1,4-methanoanthracene-9,10-diglycidyl ether, 5- (n-dodecyl) -1,2,3,4 -Tetrahydro-1,4-methanoanthracene-9,10-diglycidyl ether, 5-cyclohexyl-1,2,3,4-tetrahydro-1,4-methanoanthracene-9,1 -Diglycidyl ether, 6-methyl-1,2,3,4-tetrahydro-1,4-methanoanthracene-9,10-diglycidyl ether, 6-ethyl-1,2,3,4-tetrahydro-1, 4-methanoanthracene-9,10-diglycidyl ether, 6- (n-propyl) -1,2,3,4-tetrahydro-1,4-methanoanthracene-9,10-diglycidyl ether, 6- (i -Propyl) -1,2,3,4-tetrahydro-1,4-methanoanthracene-9,10-diglycidyl ether, 6- (n-butyl) -1,2,3,4-tetrahydro-1,4 -Methanoanthracene-9,10-diglycidyl ether, 6- (i-butyl) -1,2,3,4-tetrahydro-1,4-methanoanthracene-9,10-diglycidyl ether Ter, 6- (n-pentyl) -1,2,3,4-tetrahydro-1,4-methanoanthracene-9,10-diglycidyl ether, 6- (n-hexyl) -1,2,3,4 -Tetrahydro-1,4-methanoanthracene-9,10-diglycidyl ether, 6- (n-heptyl) -1,2,3,4-tetrahydro-1,4-methanoanthracene-9,10-diglycidyl ether , 6- (2-ethylhexyl) -1,2,3,4-tetrahydro-1,4-methanoanthracene-9,10-diglycidyl ether, 6- (n-dodecyl) -1,2,3,4 Tetrahydro-1,4-methanoanthracene-9,10-diglycidyl ether, 6-cyclohexyl-1,2,3,4-tetrahydro-1,4-methanoanthracene-9,10-digly Dil ether, 5-methyl-1,2,3,4-tetrahydro-1,4-methanoanthracene-9,10-bis (2-methylglycidyl) ether, 5-ethyl-1,2,3,4-tetrahydro -1,4-methanoanthracene-9,10-bis (2-methylglycidyl) ether, 5- (n-propyl) -1,2,3,4-tetrahydro-1,4-methanoanthracene-9,10- Bis (2-methylglycidyl) ether, 5- (i-propyl) -1,2,3,4-tetrahydro-1,4-methanoanthracene-9,10-bis (2-methylglycidyl) ether, 5- ( n-butyl) -1,2,3,4-tetrahydro-1,4-methanoanthracene-9,10-bis (2-methylglycidyl) ether, 5- (i-butyl) -1,2,3 -Tetrahydro-1,4-methanoanthracene-9,10-bis (2-methylglycidyl) ether, 5- (n-pentyl) -1,2,3,4-tetrahydro-1,4-methanoanthracene-9, 10-bis (2-methylglycidyl) ether, 5- (n-hexyl) -1,2,3,4-tetrahydro-1,4-methanoanthracene-9,10-bis (2-methylglycidyl) ether, 5 -(N-heptyl) -1,2,3,4-tetrahydro-1,4-methanoanthracene-9,10-bis (2-methylglycidyl) ether, 5- (2-ethylhexyl) -1,2,3 , 4-Tetrahydro-1,4-methanoanthracene-9,10-bis (2-methylglycidyl) ether, 5- (n-dodecyl) -1,2,3,4-tetrahydro-1, 4-methanoanthracene-9,10-bis (2-methylglycidyl) ether, 5-cyclohexyl-1,2,3,4-tetrahydro-1,4-methanoanthracene-9,10-bis (2-methylglycidyl) Ether, 6-methyl-1,2,3,4-tetrahydro-1,4-methanoanthracene-9,10-bis (2-methylglycidyl) ether, 6-ethyl-1,2,3,4-tetrahydro- 1,4-methanoanthracene-9,10-bis (2-methylglycidyl) ether, 6- (n-propyl) -1,2,3,4-tetrahydro-1,4-methanoanthracene-9,10-bis (2-Methylglycidyl) ether, 6- (i-propyl) -1,2,3,4-tetrahydro-1,4-methanoanthracene-9,10-bis (2-methyl) Glycidyl) ether, 6- (n-butyl) -1,2,3,4-tetrahydro-1,4-methanoanthracene-9,10-bis (2-methylglycidyl) ether, 6- (i-butyl)- 1,2,3,4-tetrahydro-1,4-methanoanthracene-9,10-bis (2-methylglycidyl) ether, 6- (n-pentyl) -1,2,3,4-tetrahydro-1, 4-methanoanthracene-9,10-bis (2-methylglycidyl) ether, 6- (n-hexyl) -1,2,3,4-tetrahydro-1,4-methanoanthracene-9,10-bis (2 -Methylglycidyl) ether, 6- (n-heptyl) -1,2,3,4-tetrahydro-1,4-methanoanthracene-9,10-bis (2-methylglycidyl) ether, 6- ( -Ethylhexyl) -1,2,3,4-tetrahydro-1,4-methanoanthracene-9,10-bis (2-methylglycidyl) ether, 6- (n-dodecyl) -1,2,3,4 Tetrahydro-1,4-methanoanthracene-9,10-bis (2-methylglycidyl) ether, 6-cyclohexyl-1,2,3,4-tetrahydro-1,4-methanoanthracene-9,10-bis (2 -Methyl glycidyl ether), 1-methyl-5-methyl-1,2,3,4-tetrahydro-1,4-methanoanthracene-9,10-diglycidyl ether, 1-methyl-5-ethyl-1,2 , 3,4-Tetrahydro-1,4-methanoanthracene-9,10-diglycidyl ether, 1-methyl-5- (n-propyl) -1,2,3,4-tetrahi Dro-1,4-methanoanthracene-9,10-diglycidyl ether, 1-methyl-5- (i-propyl) -1,2,3,4-tetrahydro-1,4-methanoanthracene-9,10- Diglycidyl ether, 1-methyl-5- (n-butyl) -1,2,3,4-tetrahydro-1,4-methanoanthracene-9,10-diglycidyl ether, 1-methyl-5- (i- Butyl) -1,2,3,4-tetrahydro-1,4-methanoanthracene-9,10-diglycidyl ether, 1-methyl-5- (n-pentyl) -1,2,3,4-tetrahydro- 1,4-methanoanthracene-9,10-diglycidyl ether, 1-methyl-5- (n-hexyl) -1,2,3,4-tetrahydro-1,4-methanoanthracene-9,10-digly Dil ether, 1-methyl-5- (n-heptyl) -1,2,3,4-tetrahydro-1,4-methanoanthracene-9,10-diglycidyl ether, 1-methyl-5- (2-ethylhexyl) ) -1,2,3,4-tetrahydro-1,4-methanoanthracene-9,10-diglycidyl ether, 1-methyl-5- (n-dodecyl) -1,2,3,4-tetrahydro-1 , 4-methanoanthracene-9,10-diglycidyl ether, 1-methyl-5-cyclohexyl-1,2,3,4-tetrahydro-1,4-methanoanthracene-9,10-diglycidyl ether, 1-methyl -6-methyl-1,2,3,4-tetrahydro-1,4-methanoanthracene-9,10-diglycidyl ether, 1-methyl-6-ethyl-1,2,3 -Tetrahydro-1,4-methanoanthracene-9,10-diglycidyl ether, 1-methyl-6- (n-propyl) -1,2,3,4-tetrahydro-1,4-methanoanthracene-9,10 -Diglycidyl ether, 1-methyl-6- (i-propyl) -1,2,3,4-tetrahydro-1,4-methanoanthracene-9,10-diglycidyl ether, 1-methyl-6- (n -Butyl) -1,2,3,4-tetrahydro-1,4-methanoanthracene-9,10-diglycidyl ether, 1-methyl-6- (i-butyl) -1,2,3,4-tetrahydro -1,4-methanoanthracene-9,10-diglycidyl ether, 1-methyl-6- (n-pentyl) -1,2,3,4-tetrahydro-1,4-methanoanthracene-9,1 0-diglycidyl ether, 1-methyl-6- (n-hexyl) -1,2,3,4-tetrahydro-1,4-methanoanthracene-9,10-diglycidyl ether, 1-methyl-6- ( n-heptyl) -1,2,3,4-tetrahydro-1,4-methanoanthracene-9,10-diglycidyl ether, 1-methyl-6- (2-ethylhexyl) -1,2,3,4 Tetrahydro-1,4-methanoanthracene-9,10-diglycidyl ether, 1-methyl-6- (n-dodecyl) -1,2,3,4-tetrahydro-1,4-methanoanthracene-9,10- Diglycidyl ether, 1-methyl-6-cyclohexyl-1,2,3,4-tetrahydro-1,4-methanoanthracene-9,10-diglycidyl ether, 1-methyl-5- Til-1,2,3,4-tetrahydro-1,4-methanoanthracene-9,10-bis (2-methylglycidyl) ether, 1-methyl-5-ethyl-1,2,3,4-tetrahydro- 1,4-methanoanthracene-9,10-bis (2-methylglycidyl) ether, 1-methyl-5- (n-propyl) -1,2,3,4-tetrahydro-1,4-methanoanthracene-9 , 10-bis (2-methylglycidyl) ether, 1-methyl-5- (i-propyl) -1,2,3,4-tetrahydro-1,4-methanoanthracene-9,10-bis (2-methyl) Glycidyl) ether, 1-methyl-5- (n-butyl) -1,2,3,4-tetrahydro-1,4-methanoanthracene-9,10-bis (2-methylglycidyl) ether, Tyl-5- (i-butyl) -1,2,3,4-tetrahydro-1,4-methanoanthracene-9,10-bis (2-methylglycidyl) ether, 1-methyl-5- (n-pentyl) ) -1,2,3,4-tetrahydro-1,4-methanoanthracene-9,10-bis (2-methylglycidyl) ether, 1-methyl-5- (n-hexyl) -1,2,3 4-tetrahydro-1,4-methanoanthracene-9,10-bis (2-methylglycidyl) ether, 1-methyl-5- (n-heptyl) -1,2,3,4-tetrahydro-1,4- Methanoanthracene-9,10-bis (2-methylglycidyl) ether, 1-methyl-5- (2-ethylhexyl) -1,2,3,4-tetrahydro-1,4-methanoanthracene-9,10-bis ( 2-methylglycidyl) ether, 1-methyl-5- (n-dodecyl) -1,2,3,4-tetrahydro-1,4-methanoanthracene-9,10-bis (2-methylglycidyl) ether, 1 -Methyl-5-cyclohexyl-1,2,3,4-tetrahydro-1,4-
Methanoanthracene-9,10-bis (2-methylglycidyl) ether, 1-methyl-6-methyl-1,2,3,4-tetrahydro-1,4-methanoanthracene-9,10-bis (2-methyl) Glycidyl) ether, 1-methyl-6-ethyl-1,2,3,4-tetrahydro-1,4-methanoanthracene-9,10-bis (2-methylglycidyl) ether, 1-methyl-6- (n -Propyl) -1,2,3,4-tetrahydro-1,4-methanoanthracene-9,10-bis (2-methylglycidyl) ether, 1-methyl-6- (i-propyl) -1,2, 3,4-tetrahydro-1,4-methanoanthracene-9,10-bis (2-methylglycidyl) ether, 1-methyl-6- (n-butyl) -1,2,3,4-tetrahydride -1,4-methanoanthracene-9,10-bis (2-methylglycidyl) ether, 1-methyl-6- (i-butyl) -1,2,3,4-tetrahydro-1,4-methanoanthracene- 9,10-bis (2-methylglycidyl) ether, 1-methyl-6- (n-pentyl) -1,2,3,4-tetrahydro-1,4-methanoanthracene-9,10-bis (2- Methyl glycidyl) ether, 1-methyl-6- (n-hexyl) -1,2,3,4-tetrahydro-1,4-methanoanthracene-9,10-bis (2-methylglycidyl) ether, 1-methyl -6- (n-heptyl) -1,2,3,4-tetrahydro-1,4-methanoanthracene-9,10-bis (2-methylglycidyl) ether, 1-methyl-6- (2-ethyl) Xyl) -1,2,3,4-tetrahydro-1,4-methanoanthracene-9,10-bis (2-methylglycidyl) ether, 1-methyl-6- (n-dodecyl) -1,2,3 , 4-Tetrahydro-1,4-methanoanthracene-9,10-bis (2-methylglycidyl) ether, 1-methyl-6-cyclohexyl-1,2,3,4-tetrahydro-1,4-methanoanthracene- 9,10-bis (2-methylglycidyl) ether and the like can be mentioned.

Furthermore, examples of X being an alkoxy group or an aryloxy group include 5-methoxy-1,2,3,4-tetrahydro-1,4-methanoanthracene-9,10-diglycidyl ether, 5-ethoxy-1 , 2,3,4-Tetrahydro-1,4-methanoanthracene-9,10-diglycidyl ether, 5- (n-propoxy) -1,2,3,4-tetrahydro-1,4-methanoanthracene-9 , 10-diglycidyl ether, 5- (n-butoxy) -1,2,3,4-tetrahydro-1,4-methanoanthracene-9,10-diglycidyl ether, 5- (n-hexyloxy) -1 , 2,3,4-tetrahydro-1,4-methanoanthracene-9,10-diglycidyl ether, 5-phenoxy-1,2,3,4-tetrahydro-1,4-me Noanthracene-9,10-diglycidyl ether, 5- (p-methylphenoxy) phenoxy-1,2,3,4-tetrahydro-1,4-methanoanthracene-9,10-diglycidyl ether, 5- (p -Chlorophenoxy) -1,2,3,4-tetrahydro-1,4-methanoanthracene-9,10-diglycidyl ether, 5- (o-chlorophenoxy) -1,2,3,4-tetrahydro-1 , 4-methanoanthracene-9,10-diglycidyl ether, 6-methoxy-1,2,3,4-tetrahydro-1,4-methanoanthracene-9,10-diglycidyl ether, 6-ethoxy-1,2 , 3,4-Tetrahydro-1,4-methanoanthracene-9,10-diglycidyl ether, 6- (n-propoxy) -1,2,3,4 Tetrahydro-1,4-methanoanthracene-9,10-diglycidyl ether, 6- (n-butoxy) -1,2,3,4-tetrahydro-1,4-methanoanthracene-9,10-diglycidyl ether, 6- (n-hexyloxy) -1,2,3,4-tetrahydro-1,4-methanoanthracene-9,10-diglycidyl ether, 6-phenoxy-1,2,3,4-tetrahydro-1, 4-methanoanthracene-9,10-diglycidyl ether, 6- (p-methylphenoxy) phenoxy-1,2,3,4-tetrahydro-1,4-methanoanthracene-9,10-diglycidyl ether, 6- (P-chlorophenoxy) -1,2,3,4-tetrahydro-1,4-methanoanthracene-9,10-diglycidyl ether, 6- ( o-chlorophenoxy) -1,2,3,4-tetrahydro-1,4-methanoanthracene-9,10-diglycidyl ether, 5-methoxy-1,2,3,4-tetrahydro-1,4-methano Anthracene-9,10-bis (2-methylglycidyl) ether, 5-ethoxy-1,2,3,4-tetrahydro-1,4-methanoanthracene-9,10-bis (2-methylglycidyl) ether, 5 -(N-propoxy) -1,2,3,4-tetrahydro-1,4-methanoanthracene-9,10-bis (2-methylglycidyl) ether, 5- (n-butoxy) -1,2,3 , 4-Tetrahydro-1,4-methanoanthracene-9,10-bis (2-methylglycidyl) ether, 5- (n-hexyloxy) -1,2,3,4-tetrahydride -1,4-methanoanthracene-9,10-bis (2-methylglycidyl) ether, 5-phenoxy-1,2,3,4-tetrahydro-1,4-methanoanthracene-9,10-bis (2- Methyl glycidyl) ether, 5- (p-methylphenoxy) phenoxy-1,2,3,4-tetrahydro-1,4-methanoanthracene-9,10-bis (2-methylglycidyl) ether, 5- (p- Chlorophenoxy) -1,2,3,4-tetrahydro-1,4-methanoanthracene-9,10-bis (2-methylglycidyl) ether, 5- (o-chlorophenoxy) -1,2,3,4 -Tetrahydro-1,4-methanoanthracene-9,10-bis (2-methylglycidyl) ether, 6-methoxy-1,2,3,4-tetrahydro-1 4-methanoanthracene-9,10-bis (2-methylglycidyl) ether, 6-ethoxy-1,2,3,4-tetrahydro-1,4-methanoanthracene-9,10-bis (2-methylglycidyl) Ether, 6- (n-propoxy) -1,2,3,4-tetrahydro-1,4-methanoanthracene-9,10-bis (2-methylglycidyl) ether, 6- (n-butoxy) -1, 2,3,4-tetrahydro-1,4-methanoanthracene-9,10-bis (2-methylglycidyl) ether, 6- (n-hexyloxy) -1,2,3,4-tetrahydro-1,4 -Methanoanthracene-9,10-bis (2-methylglycidyl) ether, 6-phenoxy-1,2,3,4-tetrahydro-1,4-methanoanthracene-9,10 -Bis (2-methylglycidyl) ether, 6- (p-methylphenoxy) phenoxy-1,2,3,4-tetrahydro-1,4-methanoanthracene-9,10-bis (2-methylglycidyl) ether, 6- (p-chlorophenoxy) -1,2,3,4-tetrahydro-1,4-methanoanthracene-9,10-bis (2-methylglycidyl) ether, 6- (o-chlorophenoxy) -1, 2,3,4-tetrahydro-1,4-methanoanthracene-9,10-bis (2-methylglycidyl) ether, 1-methyl-5-methoxy-1,2,3,4-tetrahydro-1,4- Methanoanthracene-9,10-diglycidyl ether, 1-methyl-5-ethoxy-1,2,3,4-tetrahydro-1,4-methanoanthracene-9,10 Diglycidyl ether, 1-methyl-5- (n-propoxy) -1,2,3,4-tetrahydro-1,4-methanoanthracene-9,10-diglycidyl ether, 1-methyl-5- (n- Butoxy) -1,2,3,4-tetrahydro-1,4-methanoanthracene-9,10-diglycidyl ether, 1-methyl-5- (n-hexyloxy) -1,2,3,4-tetrahydro -1,4-methanoanthracene-9,10-diglycidyl ether, 1-methyl-5-phenoxy-1,2,3,4-tetrahydro-1,4-methanoanthracene-9,10-diglycidyl ether, 1 -Methyl-5- (p-methylphenoxy) phenoxy-1,2,3,4-tetrahydro-1,4-methanoanthracene-9,10-diglycidyl ether, 1 Methyl-5- (p-chlorophenoxy) -1,2,3,4-tetrahydro-1,4-methanoanthracene-9,10-diglycidyl ether, 1-methyl-5- (o-chlorophenoxy) -1 , 2,3,4-Tetrahydro-1,4-methanoanthracene-9,10-diglycidyl ether, 1-methyl-6-methoxy-1,2,3,4-tetrahydro-1,4-methanoanthracene-9 , 10-diglycidyl ether, 1-methyl-6-ethoxy-1,2,3,4-tetrahydro-1,4-methanoanthracene-9,10-diglycidyl ether, 1-methyl-6- (n-propoxy) ) -1,2,3,4-tetrahydro-1,4-methanoanthracene-9,10-diglycidyl ether, 1-methyl-6- (n-butoxy) -1,2,3,4 -Tetrahydro-1,4-methanoanthracene-9,10-diglycidyl ether, 1-methyl-6- (n-hexyloxy) -1,2,3,4-tetrahydro-1,4-methanoanthracene-9, 10-diglycidyl ether, 1-methyl-6-phenoxy-1,2,3,4-tetrahydro-1,4-methanoanthracene-9,10-diglycidyl ether, 1-methyl-6- (p-methylphenoxy) ) Phenoxy-1,2,3,4-tetrahydro-1,4-methanoanthracene-9,10-diglycidyl ether, 1-methyl-6- (p-chlorophenoxy) -1,2,3,4-tetrahydro -1,4-methanoanthracene-9,10-diglycidyl ether, 1-methyl-6- (o-chlorophenoxy) -1,2,3,4-tetrahydride 1,4-methanoanthracene-9,10-diglycidyl ether 1-methyl-5-methoxy-1,2,3,4-tetrahydro-1,4-methanoanthracene-9,10-bis (2-methylglycidyl ) Ether, 1-methyl-5-ethoxy-1,2,3,4-tetrahydro-1,4-methanoanthracene-9,10-bis (2-methylglycidyl) ether, 1-methyl-5- (n- Propoxy) -1,2,3,4-tetrahydro-1,4-methanoanthracene-9,10-bis (2-methylglycidyl) ether, 1-methyl-5- (n-butoxy) -1,2,3 , 4-Tetrahydro-1,4-methanoanthracene-9,10-bis (2-methylglycidyl) ether, 1-methyl-5- (n-hexyloxy) -1,2,3,4-te Lahydro-1,4-methanoanthracene-9,10-bis (2-methylglycidyl) ether, 1-methyl-5-phenoxy-1,2,3,4-tetrahydro-1,4-methanoanthracene-9,10 -Bis (2-methylglycidyl) ether, 1-methyl-5- (p-methylphenoxy) phenoxy-1,2,3,4-tetrahydro-1,4-methanoanthracene-9,10-bis (2-methyl) Glycidyl) ether, 1-methyl-5- (p-chlorophenoxy) -1,2,3,4-tetrahydro-1,4-methanoanthracene-9,10-bis (2-methylglycidyl) ether, 1-methyl -5- (o-chlorophenoxy) -1,2,3,4-tetrahydro-1,4-methanoanthracene-9,10-bis (2-methylglycidyl) Ether, 1-methyl-6-methoxy-1,2,3,4-tetrahydro-1,4-methanoanthracene-9,10-bis (2-methylglycidyl) ether, 1-methyl-6-ethoxy-1, 2,3,4-tetrahydro-1,4-methanoanthracene-9,10-bis (2-methylglycidyl) ether, 1-methyl-6- (n-propoxy) -1,2,3,4-tetrahydro- 1,4-methanoanthracene-9,10-bis (2-methylglycidyl) ether, 1-methyl-6- (n-butoxy) -1,2,3,4-tetrahydro-1,4-methanoanthracene-9 , 10-bis (2-methylglycidyl) ether, 1-methyl-6- (n-hexyloxy) -1,2,3,4-tetrahydro-1,4-methanoanthracene-9,10-bis 2-methylglycidyl) ether, 1-methyl-6-phenoxy-1,2,3,4-tetrahydro-1,4-methanoanthracene-9,10-bis (2-methylglycidyl) ether, 1-methyl-6 -(P-methylphenoxy) phenoxy-1,2,3,4-tetrahydro-1,4-methanoanthracene-9,10-bis (2-methylglycidyl) ether, 1-methyl-6- (p-chlorophenoxy) ) -1,2,3,4-tetrahydro-1,4-methanoanthracene-9,10-bis (2-methylglycidyl) ether, 1-methyl-6- (o-chlorophenoxy) -1,2,3 , 4-tetrahydro-1,4-methanoanthracene-9,10-bis (2-methylglycidyl) ether, and the like.

  Among these exemplified compounds, 1,2,3,4-tetrahydro-1,4-methanoanthracene-9,10-diglycidyl ether, 1,2,3, because of ease of synthesis and high heat resistance. 4-Tetrahydro-1,4-methanoanthracene-9,10-bis (2-methylglycidyl) ether is preferred, and in particular, 1,2,3,4-tetrahydro-1,4- from the viewpoint of availability of raw materials. Methanoanthracene-9,10-diglycidyl ether is preferred.

(Method for producing epoxy compound)
The method for producing an epoxy compound of the present invention comprises a 1,2,3,4-tetrahydro-1,4-methanoanthracene-9,10-diol compound represented by the following general formula (2) in the presence of a basic compound. Is reacted with an epihalohydrin compound represented by the following general formula (3).

(In the general formula (2), R ¹ , R ² , R ³ , R ⁴ and R ⁵ may be the same or different from each other, and represent a hydrogen atom or a methyl group, and X represents a hydrogen atom, a halogen atom, (Atom, alkyl group, alkoxy group, or aryloxy group is shown.)

(In general formula (3), R ⁶ represents either a hydrogen atom or a methyl group, and Y represents a halogen atom.)

Specific examples of the halogen atom represented by X in the general formula (2) are as follows. That is, for example, a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Specific examples of the alkyl group are as follows. That is, methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, n-pentyl group, n-hexyl group, cyclohexyl group, n-heptyl group, 2-ethylhexyl, Such as dodecyl group. Furthermore, specific examples of the alkoxy group are as follows. That is, a methoxy group, an ethoxy group, an n-propoxy group, an n-butoxy group, an n-hexyloxy group, and the like. Finally, specific examples of the aryloxy group are as follows. That is, a phenoxy group, a p-methylphenoxy group, an o-methylphenoxy group, a p-chlorophenoxy group, an o-chlorophenoxy group, and the like.

Specific examples of the halogen atom represented by Y in the general formula (3) are as follows. That is, for example, a chlorine atom, a bromine atom, and an iodine atom.

  The 1,2,3,4-tetrahydro-1,4-methanoanthracene-9,10-diol compound represented by the general formula (2) is, for example, a Diels-Alder reaction of a 1,4-naphthoquinone compound and a cyclopentadiene compound. 1,4,4a, 9a-tetrahydro-1,4-methanoanthracene-9,10-dione compound obtained by reduction of 1,2,3,4,4a, 9a-hexahydro-1,4-methano Anthracene-9,10-dione can be obtained and then enolized with an acid or alkali.

That is, the epoxy compound of the present invention is a first reaction in which a 1,4-naphthoquinone compound and cyclopentadiene are reacted, and 1,4,4a, 9a-tetrahydro-1,4-methanoanthracene-9 obtained by the first reaction. , 10-dione compound hydrogenation, 1,2,3,4,4a, 9a-hexahydro-1,4-methanoanthracene-9,10-dione obtained in the second reaction is enolized Third reaction, fourth reaction in which the 1,2,3,4-tetrahydro-1,4-methanoanthracene-9,10-diol compound obtained in the third reaction is reacted with an epihalohydrin compound in the presence of a basic compound Is obtained.

In the first reaction formula, R ¹ , R ² , R ³ , R ⁴ and R ⁵ may be the same or different from each other, and each represents a hydrogen atom or a methyl group, and X represents a hydrogen atom, a halogen atom, An alkyl group, an alkoxy group, or an aryloxy group is shown.

In the second reaction formula, R ¹ , R ² , R ³ , R ⁴ and R ⁵ may be the same or different from each other, and each represents a hydrogen atom or a methyl group, and X represents a hydrogen atom, a halogen atom, An alkyl group, an alkoxy group, or an aryloxy group is shown.

In the third reaction formula, R ¹ , R ² , R ³ , R ⁴ and R ⁵ may be the same or different from each other, and each represents a hydrogen atom or a methyl group, and X represents a hydrogen atom, a halogen atom, An alkyl group, an alkoxy group, or an aryloxy group is shown.

In the fourth reaction formula, R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ may be the same as or different from each other, and each represents a hydrogen atom or a methyl group, X represents a hydrogen atom, One of a halogen atom, an alkyl group, an alkoxy group, and an aryloxy group is shown. Y represents a halogen atom.

Specific examples of the halogen atom, alkyl group, alkoxy group and aryloxy group represented by each X in the above-mentioned first reaction formula, second reaction formula, third reaction formula and fourth reaction formula are all represented by the formula (1 It is the same as X in).

Specific examples of the halogen atom represented by Y in the fourth reaction formula are the same as Y in formula (3).

(First reaction)
The following are mentioned as a naphthoquinone compound used as a raw material in a 1st reaction. 1,4-naphthoquinone, 5-fluoro-1,4-naphthoquinone, 5-chloro-1,4-naphthoquinone, 5-bromo-1,4-naphthoquinone, 5-iodo-1,4-naphthoquinone, 6- Fluoro-1,4-naphthoquinone, 6-chloro-1,4-naphthoquinone, 6-bromo-1,4-naphthoquinone, 6-iodo-1,4-naphthoquinone, 5-methyl-1,4-naphthoquinone, 5- Ethyl-1,4-naphthoquinone, 5- (n-propyl) -1,4-naphthoquinone, 5- (i-propyl) -1,4-naphthoquinone, 5- (n-butyl) -1,4-naphthoquinone, 5- (i-butyl) -1,4-naphthoquinone, 5- (n-pentyl) -1,4-naphthoquinone, 5- (n-hexyl) -1,4-naphthoquinone, 5- (n-heptyl)- 1,4- Phtoquinone, 5- (2-ethylhexyl) -1,4-naphthoquinone, 5- (n-dodecyl) -1,4-naphthoquinone, 5-cyclohexyl-1,4-naphthoquinone, 6-methyl-1,4-naphthoquinone, 6-ethyl-1,4-naphthoquinone, 6- (n-propyl) -1,4-naphthoquinone, 6- (i-propyl) -1,4-naphthoquinone, 6- (n-butyl) -1,4- Naphthoquinone, 6- (i-butyl) -1,4-naphthoquinone, 6- (n-pentyl) -1,4-naphthoquinone, 6- (n-hexyl) -1,4-naphthoquinone, 6- (n-heptyl) ) -1,4-naphthoquinone, 6- (2-ethylhexyl) -1,4-naphthoquinone, 6- (n-dodecyl) -1,4-naphthoquinone, 6-cyclohexyl-1,4-naphthoquinone, 5-metho Si-1,4-naphthoquinone, 5-ethoxy-1,4-naphthoquinone, 5- (n-propoxy) -1,4-naphthoquinone, 5- (n-butoxy) -1,4-naphthoquinone, 5- (n -Hexyloxy) -1,4-naphthoquinone, 5-phenoxy-1,4-naphthoquinone, 5- (p-methylphenoxy) phenoxy-1,4-naphthoquinone, 5- (p-chlorophenoxy) -1,4- Naphthoquinone, 5- (o-chlorophenoxy) -1,4-naphthoquinone, 6-methoxy-1,4-naphthoquinone, 6-ethoxy-1,4-naphthoquinone, 6- (n-propoxy) -1,4-naphthoquinone , 6- (n-butoxy) -1,4-naphthoquinone, 6- (n-hexyloxy) -1,4-naphthoquinone, 6-phenoxy-1,4-naphthoquinone, 6- (p- Examples thereof include methylphenoxy) phenoxy-1,4-naphthoquinone, 6- (p-chlorophenoxy) -1,4-naphthoquinone, 6- (o-chlorophenoxy) -1,4-naphthoquinone and the like.

Examples of the cyclopentadiene compound used in the first reaction include cyclopentadiene and methylcyclopentadiene. These cyclopentadiene compounds are obtained by thermal decomposition of dicyclopentadiene compounds in C4-C5 fraction obtained by thermal decomposition of naphtha. These cyclopentadiene compounds can be used alone or in combination. The cyclopentadiene compound may be used by heating the corresponding dicyclopentadiene compound and decomposing it into a cyclopentadiene compound.

For example, when dicyclopentadiene is heated to 150 ° C. or more, it is thermally decomposed into cyclopentadiene. By cooling this, cyclopentadiene can be isolated. Similarly, methylcyclopentadiene can be obtained by thermally decomposing methyldicyclopentadiene. The cyclopentadiene or methylcyclopentadiene thus obtained is preferably dimerized again at room temperature, so that it is preferably used immediately in the next reaction. When cyclopentadiene or methylcyclopentadiene is mixed with a naphthoquinone compound, heat is generated and a Diels-Alder reaction occurs to produce a cyclic adduct. When methylcyclopentadiene is a mixture of isomers with different substitution positions of the methyl group, the Diels-Alder reaction product is often a low melting point product compared to when cyclopentadiene is used. The hydrogenation reaction, enolization reaction, and fourth reaction can be carried out by substantially the same reaction operation, and the epoxy compound of the present invention can be synthesized.

In the first reaction, for example, cyclopentadiene obtained by thermal decomposition of a naphthoquinone compound and dicyclopentadiene is converted into an aromatic solvent such as toluene or xylene, an alcohol solvent such as methanol, ethanol or propyl alcohol, tetrahydrofuran, or 1,4-dioxane. 1,4,4a, 9a-tetrahydro-1,4-methanoanthracene-9, by heating in an ether solvent such as acetone, a ketone solvent such as acetone or methyl ethyl ketone, or an amide solvent such as dimethylacetamide or dimethylformamide. A 10-dione compound is obtained.

Examples of the 1,4,4a, 9a-tetrahydro-1,4-methanoanthracene-9,10-dione compound obtained by the first reaction include the following compounds. That is, 1,4,4a, 9a-tetrahydro-1,4-methanoanthracene-9,10-dione, 1-methyl-1,4,4a, 9a-tetrahydro-1,4-methanoanthracene-9,10- Dione, 2-methyl-1,4,4a, 9a-tetrahydro-1,4-methanoanthracene-9,10-dione, 11-methyl-1,4,4a, 9a-tetrahydro-1,4-methanoanthracene- 9,10-dione and the like.

5-fluoro-1,4,4a, 9a-tetrahydro-1,4-methanoanthracene-9,10-dione, 5-chloro-1,4,4a, 9a-tetrahydro-1,4-methanoanthracene- 9,10-dione, 5-bromo-1,4,4a, 9a-tetrahydro-1,4-methanoanthracene-9,10-dione, 5-iodo-1,4,4a, 9a-tetrahydro-1,4 -Methanoanthracene-9,10-dione, 6-fluoro-1,4,4a, 9a-tetrahydro-1,4-methanoanthracene-9,10-dione, 6-chloro-1,4,4a, 9a-tetrahydro 1,4-methanoanthracene-9,10-dione, 6-bromo-1,4,4a, 9a-tetrahydro-1,4-methanoanthracene-9,10-dione, 6-iodo- , 4,4a, 9a-tetrahydro-1,4-methanoanthracene-9,10-dione, 1-methyl-5-fluoro-1,4,4a, 9a-tetrahydro-1,4-methanoanthracene-9,10 -Dione, 1-methyl-5-chloro-1,4,4a, 9a-tetrahydro-1,4-methanoanthracene-9,10-dione, 1-methyl-5-bromo-1,4,4a, 9a- Tetrahydro-1,4-methanoanthracene-9,10-dione, 1-methyl-5-iodo-1,4,4a, 9a-tetrahydro-1,4-methanoanthracene-9,10-dione, 1-methyl- 6-fluoro-1,4,4a, 9a-tetrahydro-1,4-methanoanthracene-9,10-dione, 1-methyl-6-chloro-1,4,4a, 9a-tetrahydro-1, -Methanoanthracene-9,10-dione, 1-methyl-6-bromo-1,4,4a, 9a-tetrahydro-1,4-methanoanthracene-9,10-dione, 1-methyl-6-iodo-1 4,4a, 9a-tetrahydro-1,4-methanoanthracene-9,10-dione and the like.

Furthermore, 5-methyl-1,4,4a, 9a-tetrahydro-1,4-methanoanthracene-9,10-dione, 5-ethyl-1,4,4a, 9a-tetrahydro-1,4-methanoanthracene -9,10-dione, 5- (n-propyl) -1,4,4a, 9a-tetrahydro-1,4-methanoanthracene-9,10-dione, 5- (i-propyl) -1,4 4a, 9a-tetrahydro-1,4-methanoanthracene-9,10-dione, 5- (n-butyl) -1,4,4a, 9a-tetrahydro-1,4-methanoanthracene-9,10-dione, 5- (i-butyl) -1,4,4a, 9a-tetrahydro-1,4-methanoanthracene-9,10-dione, 5- (n-pentyl) -1,4,4a, 9a-tetrahydro-1 , 4-meta Anthracene-9,10-dione, 5- (n-hexyl) -1,4,4a, 9a-tetrahydro-1,4-methanoanthracene-9,10-dione, 5- (n-heptyl) -1,4 , 4a, 9a-tetrahydro-1,4-methanoanthracene-9,10-dione, 5- (2-ethylhexyl) -1,4,4a, 9a-tetrahydro-1,4-methanoanthracene-9,10-dione 5- (n-dodecyl) -1,4,4a, 9a-tetrahydro-1,4-methanoanthracene-9,10-dione, 5-cyclohexyl-1,4,4a, 9a-tetrahydro-1,4- Methanoanthracene-9,10-dione, 6-methyl-1,4,4a, 9a-tetrahydro-1,4-methanoanthracene-9,10-dione, 6-ethyl-1,4,4a, a-tetrahydro-1,4-methanoanthracene-9,10-dione, 6- (n-propyl) -1,4,4a, 9a-tetrahydro-1,4-methanoanthracene-9,10-dione, 6- (I-propyl) -1,4,4a, 9a-tetrahydro-1,4-methanoanthracene-9,10-dione, 6- (n-butyl) -1,4,4a, 9a-tetrahydro-1,4 -Methanoanthracene-9,10-dione, 6- (i-butyl) -1,4,4a, 9a-tetrahydro-1,4-methanoanthracene-9,10-dione, 6- (n-pentyl) -1 , 4,4a, 9a-tetrahydro-1,4-methanoanthracene-9,10-dione, 6- (n-hexyl) -1,4,4a, 9a-tetrahydro-1,4-methanoanthracene-9,10 - ON, 6- (n-heptyl) -1,4,4a, 9a-tetrahydro-1,4-methanoanthracene-9,10-dione, 6- (2-ethylhexyl) -1,4,4a, 9a-tetrahydro -1,4-methanoanthracene-9,10-dione, 6- (n-dodecyl) -1,4,4a, 9a-tetrahydro-1,4-methanoanthracene-9,10-dione, 6-cyclohexyl-1 , 4,4a, 9a-tetrahydro-1,4-methanoanthracene-9,10-dione, 1-methyl-5-methyl-1,4,4a, 9a-tetrahydro-1,4-methanoanthracene-9,10 -Dione, 1-methyl-5-ethyl-1,4,4a, 9a-tetrahydro-1,4-methanoanthracene-9,10-dione, 1-methyl-5- (n-propyl) -1,4 4a, 9a-tetrahydro-1,4-methanoanthracene-9,10-dione, 1-methyl-5- (i-propyl) -1,4,4a, 9a-tetrahydro-1,4-methanoanthracene-9, 10-dione, 1-methyl-5- (n-butyl) -1,4,4a, 9a-tetrahydro-1,4-methanoanthracene-9,10-dione, 1-methyl-5- (i-butyl) -1,4,4a, 9a-tetrahydro-1,4-methanoanthracene-9,10-dione, 1-methyl-5- (n-pentyl) -1,4,4a, 9a-tetrahydro-1,4- Methanoanthracene-9,10-dione, 1-methyl-5- (n-hexyl) -1,4,4a, 9a-tetrahydro-1,4-methanoanthracene-9,10-dione, 1-methyl-5 (N-hep ) -1,4,4a, 9a-tetrahydro-1,4-methanoanthracene-9,10-dione, 1-methyl-5- (2-ethylhexyl) -1,4,4a, 9a-tetrahydro-1, 4-methanoanthracene-9,10-dione, 1-methyl-5- (n-dodecyl) -1,4,4a, 9a-tetrahydro-1,4-methanoanthracene-9,10-dione, 1-methyl- 5-cyclohexyl-1,4,4a, 9a-tetrahydro-1,4-methanoanthracene-9,10-dione, 1-methyl-6-methyl-1,4,4a, 9a-tetrahydro-1,4-methano Anthracene-9,10-dione, 1-methyl-6-ethyl-1,4,4a, 9a-tetrahydro-1,4-methanoanthracene-9,10-dione, 1-methyl-6- (n-pro Pyr) -1,4,4a, 9a-tetrahydro-1,4-methanoanthracene-9,10-dione, 1-methyl-6- (i-propyl) -1,4,4a, 9a-tetrahydro-1, 4-methanoanthracene-9,10-dione, 1-methyl-6- (n-butyl) -1,4,4a, 9a-tetrahydro-1,4-methanoanthracene-9,10-dione, 1-methyl- 6- (i-Butyl) -1,4,4a, 9a-tetrahydro-1,4-methanoanthracene-9,10-dione, 1-methyl-6- (n-pentyl) -1,4,4a, 9a -Tetrahydro-1,4-methanoanthracene-9,10-dione, 1-methyl-6- (n-hexyl) -1,4,4a, 9a-tetrahydro-1,4-methanoanthracene-9,10-dione 1-methyl- -(N-heptyl) -1,4,4a, 9a-tetrahydro-1,4-methanoanthracene-9,10-dione, 1-methyl-6- (2-ethylhexyl) -1,4,4a, 9a- Tetrahydro-1,4-methanoanthracene-9,10-dione, 1-methyl-6- (n-dodecyl) -1,4,4a, 9a-tetrahydro-1,4-methanoanthracene-9,10-dione, Examples include 1-methyl-6-cyclohexyl-1,4,4a, 9a-tetrahydro-1,4-methanoanthracene-9,10-dione.

5-methoxy-1,4,4a, 9a-tetrahydro-1,4-methanoanthracene-9,10-dione, 5-ethoxy-1,4,4a, 9a-tetrahydro-1,4-methanoanthracene -9,10-dione, 5- (n-propoxy) -1,4,4a, 9a-tetrahydro-1,4-methanoanthracene-9,10-dione, 5- (n-butoxy) -1,4 4a, 9a-tetrahydro-1,4-methanoanthracene-9,10-dione, 5- (n-hexyloxy) -1,4,4a, 9a-tetrahydro-1,4-methanoanthracene-9,10-dione 5-phenoxy-1,4,4a, 9a-tetrahydro-1,4-methanoanthracene-9,10-dione, 5- (p-methylphenoxy) phenoxy-1,4,4a, 9 -Tetrahydro-1,4-methanoanthracene-9,10-dione, 5- (p-chlorophenoxy) -1,4,4a, 9a-tetrahydro-1,4-methanoanthracene-9,10-dione, 5- (O-chlorophenoxy) -1,4,4a, 9a-tetrahydro-1,4-methanoanthracene-9,10-dione, 6-methoxy-1,4,4a, 9a-tetrahydro-1,4-methanoanthracene -9,10-dione, 6-ethoxy-1,4,4a, 9a-tetrahydro-1,4-methanoanthracene-9,10-dione, 6- (n-propoxy) -1,4,4a, 9a- Tetrahydro-1,4-methanoanthracene-9,10-dione, 6- (n-butoxy) -1,4,4a, 9a-tetrahydro-1,4-methanoanthracene-9,1 -Dione, 6- (n-hexyloxy) -1,4,4a, 9a-tetrahydro-1,4-methanoanthracene-9,10-dione, 6-phenoxy-1,4,4a, 9a-tetrahydro-1 , 4-methanoanthracene-9,10-dione, 6- (p-methylphenoxy) phenoxy-1,4,4a, 9a-tetrahydro-1,4-methanoanthracene-9,10-dione, 6- (p- Chlorophenoxy) -1,4,4a, 9a-tetrahydro-1,4-methanoanthracene-9,10-dione, 6- (o-chlorophenoxy) -1,4,4a, 9a-tetrahydro-1,4- Methanoanthracene-9,10-dione, 1-methyl-5-methoxy-1,4,4a, 9a-tetrahydro-1,4-methanoanthracene-9,10-dione, 1-methyl Tyl-5-ethoxy-1,4,4a, 9a-tetrahydro-1,4-methanoanthracene-9,10-dione, 1-methyl-5- (n-propoxy) -1,4,4a, 9a-tetrahydro -1,4-methanoanthracene-9,10-dione, 1-methyl-5- (n-butoxy) -1,4,4a, 9a-tetrahydro-1,4-methanoanthracene-9,10-dione, -Methyl-5- (n-hexyloxy) -1,4,4a, 9a-tetrahydro-1,4-methanoanthracene-9,10-dione, 1-methyl-5-phenoxy-1,4,4a, 9a -Tetrahydro-1,4-methanoanthracene-9,10-dione, 1-methyl-5- (p-methylphenoxy) phenoxy-1,4,4a, 9a-tetrahydro-1,4-methanoanthra -9,10-dione, 1-methyl-5- (p-chlorophenoxy) -1,4,4a, 9a-tetrahydro-1,4-methanoanthracene-9,10-dione, 1-methyl-5 (O-chlorophenoxy) -1,4,4a, 9a-tetrahydro-1,4-methanoanthracene-9,10-dione, 1-methyl-6-methoxy-1,4,4a, 9a-tetrahydro-1, 4-methanoanthracene-9,10-dione, 1-methyl-6-ethoxy-1,4,4a, 9a-tetrahydro-1,4-methanoanthracene-9,10-dione, 1-methyl-6- (n -Propoxy) -1,4,4a, 9a-tetrahydro-1,4-methanoanthracene-9,10-dione, 1-methyl-6- (n-butoxy) -1,4,4a, 9a-tetrahydro-1 4-methanoanthracene-9,10-dione, 1-methyl-6- (n-hexyloxy) -1,4,4a, 9a-tetrahydro-1,4-methanoanthracene-9,10-dione, 1-methyl -6-phenoxy-1,4,4a, 9a-tetrahydro-1,4-methanoanthracene-9,10-dione, 1-methyl-6- (p-methylphenoxy) phenoxy-1,4,4a, 9a- Tetrahydro-1,4-methanoanthracene-9,10-dione, 1-methyl-6- (p-chlorophenoxy) -1,4,4a, 9a-tetrahydro-1,4-methanoanthracene-9,10-dione 1-methyl-6- (o-chlorophenoxy) -1,4,4a, 9a-tetrahydro-1,4-methanoanthracene-9,10-dione and the like.

(Second reaction)
In the second reaction, the 1,4,4a, 9a-tetrahydro-1,4-methanoanthracene-9,10-dione compound obtained in the first reaction is reduced to 1,2,3,4, 4a, 9a-hexahydro-1,4-methanoanthracene-9,10-dione compound. For the reduction reaction, hydrogen reduction using a noble metal as a catalyst is used. Usable noble metal catalysts include palladium on activated carbon, palladium on alumina, platinum on activated carbon and the like. In particular, 5% palladium / carbon is preferably used.

  The solvent to be used is not particularly limited, but alcohol solvents such as methanol and ethanol; ketone solvents such as acetone and methyl isobutyl ketone; ether solvents such as tetrahydrofuran and 1,4-dioxane; aromatics such as toluene and xylene Group solvents; halogen solvents such as dichloromethane and chloroform; amide solvents such as dimethylformamide and dimethylacetamide; water and the like. Two or more of these solvents may be used in combination.

  The pressure of hydrogen used for hydrogen reduction is usually 2 to 10 atm, preferably 3 to 7 atm. If the hydrogen pressure is too low, the reaction time for hydrogen reduction becomes long, and if the hydrogen pressure is too high, hydrogenation of the aromatic ring may occur as a side reaction.

Examples of the 1,2,3,4,4a, 9a-hexahydro-1,4-methanoanthracene-9,10-dione compound obtained by the second reaction include the following. That is, 1,2,3,4,4a, 9a-hexahydro-1,4-methanoanthracene-9,10-dione, 1-methyl-1,2,3,4,4a, 9a-hexahydro-1,4 -Methanoanthracene-9,10-dione, 2-methyl-1,2,3,4,4a, 9a-hexahydro-1,4-methanoanthracene-9,10-dione, 11-methyl-1,2,3 4,4a, 9a-hexahydro-1,4-methanoanthracene-9,10-dione and the like.

Also, 5-fluoro-1,2,3,4,4a, 9a-hexahydro-1,4-methanoanthracene-9,10-dione, 5-chloro-1,2,3,4,4a, 9a-hexahydro -1,4-methanoanthracene-9,10-dione, 5-bromo-1,2,3,4,4a, 9a-hexahydro-1,4-methanoanthracene-9,10-dione, 5-iodo-1 , 2,3,4,4a, 9a-hexahydro-1,4-methanoanthracene-9,10-dione, 6-fluoro-1,2,3,4,4a, 9a-hexahydro-1,4-methanoanthracene -9,10-dione, 6-chloro-1,2,3,4,4a, 9a-hexahydro-1,4-methanoanthracene-9,10-dione, 6-bromo-1,2,3,4 4a, 9a-hexahydro-1 4-methanoanthracene-9,10-dione, 6-iodo-1,2,3,4,4a, 9a-hexahydro-1,4-methanoanthracene-9,10-dione, 1-methyl-5-fluoro- 1,2,3,4,4a, 9a-hexahydro-1,4-methanoanthracene-9,10-dione, 1-methyl-5-chloro-1,2,3,4,4a, 9a-hexahydro-1 , 4-Methanoanthracene-9,10-dione, 1-methyl-5-bromo-1,2,3,4,4a, 9a-hexahydro-1,4-methanoanthracene-9,10-dione, 1-methyl -5-iodo-1,2,3,4,4a, 9a-hexahydro-1,4-methanoanthracene-9,10-dione, 1-methyl-6-fluoro-1,2,3,4,4a, 9a-hexahydro-1, -Methanoanthracene-9,10-dione, 1-methyl-6-chloro-1,2,3,4,4a, 9a-hexahydro-1,4-methanoanthracene-9,10-dione, 1-methyl-6 -Bromo-1,2,3,4,4a, 9a-hexahydro-1,4-methanoanthracene-9,10-dione, 1-methyl-6-iodo-1,2,3,4,4a, 9a- And hexahydro-1,4-methanoanthracene-9,10-dione.

Furthermore, 5-methyl-1,2,3,4,4a, 9a-hexahydro-1,4-methanoanthracene-9,10-dione, 5-ethyl-1,2,3,4,4a, 9a- Hexahydro-1,4-methanoanthracene-9,10-dione, 5- (n-propyl) -1,2,3,4,4a, 9a-hexahydro-1,4-methanoanthracene-9,10-dione, 5- (i-propyl) -1,2,3,4,4a, 9a-hexahydro-1,4-methanoanthracene-9,10-dione, 5- (n-butyl) -1,2,3,4 , 4a, 9a-hexahydro-1,4-methanoanthracene-9,10-dione, 5- (i-butyl) -1,2,3,4,4a, 9a-hexahydro-1,4-methanoanthracene-9 , 10-dione, 5- (n-pentyl) 1,2,3,4,4a, 9a-hexahydro-1,4-methanoanthracene-9,10-dione, 5- (n-hexyl) -1,2,3,4,4a, 9a-hexahydro-1 , 4-Methanoanthracene-9,10-dione, 5- (n-heptyl) -1,2,3,4,4a, 9a-hexahydro-1,4-methanoanthracene-9,10-dione, 5- ( 2-ethylhexyl) -1,2,3,4,4a, 9a-hexahydro-1,4-methanoanthracene-9,10-dione, 5- (n-dodecyl) -1,2,3,4,4a, 9a-hexahydro-1,4-methanoanthracene-9,10-dione, 5-cyclohexyl-1,2,3,4,4a, 9a-hexahydro-1,4-methanoanthracene-9,10-dione, 6- Methyl-1,2,3 4,4a, 9a-hexahydro-1,4-methanoanthracene-9,10-dione, 6-ethyl-1,2,3,4,4a, 9a-hexahydro-1,4-methanoanthracene-9,10- Dione, 6- (n-propyl) -1,2,3,4,4a, 9a-hexahydro-1,4-methanoanthracene-9,10-dione, 6- (i-propyl) -1,2,3 , 4,4a, 9a-Hexahydro-1,4-methanoanthracene-9,10-dione, 6- (n-butyl) -1,2,3,4,4a, 9a-hexahydro-1,4-methanoanthracene -9,10-dione, 6- (i-butyl) -1,2,3,4,4a, 9a-hexahydro-1,4-methanoanthracene-9,10-dione, 6- (n-pentyl)- 1,2,3,4,4a, 9a-hex Sahydro-1,4-methanoanthracene-9,10-dione, 6- (n-hexyl) -1,2,3,4,4a, 9a-hexahydro-1,4-methanoanthracene-9,10-dione, 6- (n-heptyl) -1,2,3,4,4a, 9a-hexahydro-1,4-methanoanthracene-9,10-dione, 6- (2-ethylhexyl) -1,2,3,4 , 4a, 9a-hexahydro-1,4-methanoanthracene-9,10-dione, 6- (n-dodecyl) -1,2,3,4,4a, 9a-hexahydro-1,4-methanoanthracene-9 , 10-dione, 6-cyclohexyl-1,2,3,4,4a, 9a-hexahydro-1,4-methanoanthracene-9,10-dione, 1-methyl-5-methyl-1,2,3 4,4a, 9a-hex Hydro-1,4-methanoanthracene-9,10-dione, 1-methyl-5-ethyl-1,2,3,4,4a, 9a-hexahydro-1,4-methanoanthracene-9,10-dione, 1-methyl-5- (n-propyl) -1,2,3,4,4a, 9a-hexahydro-1,4-methanoanthracene-9,10-dione, 1-methyl-5- (i-propyl) -1,2,3,4,4a, 9a-hexahydro-1,4-methanoanthracene-9,10-dione, 1-methyl-5- (n-butyl) -1,2,3,4,4a, 9a-Hexahydro-1,4-methanoanthracene-9,10-dione, 1-methyl-5- (i-butyl) -1,2,3,4,4a, 9a-hexahydro-1,4-methanoanthracene- 9,10-dione, 1-methyl-5 (N-pentyl) -1,2,3,4,4a, 9a-hexahydro-1,4-methanoanthracene-9,10-dione, 1-methyl-5- (n-hexyl) -1,2,3 , 4,4a, 9a-Hexahydro-1,4-methanoanthracene-9,10-dione, 1-methyl-5- (n-heptyl) -1,2,3,4,4a, 9a-hexahydro-1, 4-methanoanthracene-9,10-dione, 1-methyl-5- (2-ethylhexyl) -1,2,3,4,4a, 9a-hexahydro-1,4-methanoanthracene-9,10-dione, 1-methyl-5- (n-dodecyl) -1,2,3,4,4a, 9a-hexahydro-1,4-methanoanthracene-9,10-dione, 1-methyl-5-cyclohexyl-1,2 , 3,4,4a, 9a-hexa Hydro-1,4-methanoanthracene-9,10-dione, 1-methyl-6-methyl-1,2,3,4,4a, 9a-hexahydro-1,4-methanoanthracene-9,10-dione, 1-methyl-6-ethyl-1,2,3,4,4a, 9a-hexahydro-1,4-methanoanthracene-9,10-dione, 1-methyl-6- (n-propyl) -1,2 , 3,4,4a, 9a-Hexahydro-1,4-methanoanthracene-9,10-dione, 1-methyl-6- (i-propyl) -1,2,3,4,4a, 9a-hexahydro- 1,4-methanoanthracene-9,10-dione, 1-methyl-6- (n-butyl) -1,2,3,4,4a, 9a-hexahydro-1,4-methanoanthracene-9,10- Dione, 1-methyl-6- (i-bu ) -1,2,3,4,4a, 9a-hexahydro-1,4-methanoanthracene-9,10-dione, 1-methyl-6- (n-pentyl) -1,2,3,4 4a, 9a-Hexahydro-1,4-methanoanthracene-9,10-dione, 1-methyl-6- (n-hexyl) -1,2,3,4,4a, 9a-hexahydro-1,4-methano Anthracene-9,10-dione, 1-methyl-6- (n-heptyl) -1,2,3,4,4a, 9a-hexahydro-1,4-methanoanthracene-9,10-dione, 1-methyl -6- (2-ethylhexyl) -1,2,3,4,4a, 9a-hexahydro-1,4-methanoanthracene-9,10-dione, 1-methyl-6- (n-dodecyl) -1, 2,3,4,4a, 9a-hexahydro- , 4-methanoanthracene-9,10-dione, 1-methyl-6-cyclohexyl-1,2,3,4,4a, 9a-hexahydro-1,4-methanoanthracene-9,10-dione and the like. .

5-methoxy-1,2,3,4,4a, 9a-hexahydro-1,4-methanoanthracene-9,10-dione, 5-ethoxy-1,2,3,4,4a, 9a- Hexahydro-1,4-methanoanthracene-9,10-dione, 5- (n-propoxy) -1,2,3,4,4a, 9a-hexahydro-1,4-methanoanthracene-9,10-dione, 5- (n-butoxy) -1,2,3,4,4a, 9a-hexahydro-1,4-methanoanthracene-9,10-dione, 5- (n-hexyloxy) -1,2,3 4,4a, 9a-hexahydro-1,4-methanoanthracene-9,10-dione, 5-phenoxy-1,2,3,4,4a, 9a-hexahydro-1,4-methanoanthracene-9,10- Dione, 5- (p Methylphenoxy) phenoxy-1,2,3,4,4a, 9a-hexahydro-1,4-methanoanthracene-9,10-dione, 5- (p-chlorophenoxy) -1,2,3,4,4a , 9a-hexahydro-1,4-methanoanthracene-9,10-dione, 5- (o-chlorophenoxy) -1,2,3,4,4a, 9a-hexahydro-1,4-methanoanthracene-9, 10-dione, 6-methoxy-1,2,3,4,4a, 9a-hexahydro-1,4-methanoanthracene-9,10-dione, 6-ethoxy-1,2,3,4,4a, 9a -Hexahydro-1,4-methanoanthracene-9,10-dione, 6- (n-propoxy) -1,2,3,4,4a, 9a-Hexahydro-1,4-methanoanthracene-9,10-di 6- (n-butoxy) -1,2,3,4,4a, 9a-hexahydro-1,4-methanoanthracene-9,10-dione, 6- (n-hexyloxy) -1,2, 3,4,4a, 9a-hexahydro-1,4-methanoanthracene-9,10-dione, 6-phenoxy-1,2,3,4,4a, 9a-hexahydro-1,4-methanoanthracene-9, 10-dione, 6- (p-methylphenoxy) phenoxy-1,2,3,4,4a, 9a-hexahydro-1,4-methanoanthracene-9,10-dione, 6- (p-chlorophenoxy)- 1,2,3,4,4a, 9a-hexahydro-1,4-methanoanthracene-9,10-dione, 6- (o-chlorophenoxy) -1,2,3,4,4a, 9a-hexahydro- 1,4-methano Anthracene-9,10-dione, 1-methyl-5-methoxy-1,2,3,4,4a, 9a-hexahydro-1,4-methanoanthracene-9,10-dione, 1-methyl-5-ethoxy -1,2,3,4,4a, 9a-hexahydro-1,4-methanoanthracene-9,10-dione, 1-methyl-5- (n-propoxy) -1,2,3,4,4a, 9a-Hexahydro-1,4-methanoanthracene-9,10-dione, 1-methyl-5- (n-butoxy) -1,2,3,4,4a, 9a-hexahydro-1,4-methanoanthracene- 9,10-dione, 1-methyl-5- (n-hexyloxy) -1,2,3,4,4a, 9a-hexahydro-1,4-methanoanthracene-9,10-dione, 1-methyl- 5-phenoxy-1, , 3,4,4a, 9a-Hexahydro-1,4-methanoanthracene-9,10-dione, 1-methyl-5- (p-methylphenoxy) phenoxy-1,2,3,4,4a, 9a- Hexahydro-1,4-methanoanthracene-9,10-dione, 1-methyl-5- (p-chlorophenoxy) -1,2,3,4,4a, 9a-hexahydro-1,4-methanoanthracene-9 , 10-dione, 1-methyl-5- (o-chlorophenoxy) -1,2,3,4,4a, 9a-hexahydro-1,4-methanoanthracene-9,10-dione, 1-methyl-6 -Methoxy-1,2,3,4,4a, 9a-hexahydro-1,4-methanoanthracene-9,10-dione, 1-methyl-6-ethoxy-1,2,3,4,4a, 9a- Hexahydro , 4-Methanoanthracene-9,10-dione, 1-methyl-6- (n-propoxy) -1,2,3,4,4a, 9a-hexahydro-1,4-methanoanthracene-9,10-dione 1-methyl-6- (n-butoxy) -1,2,3,4,4a, 9a-hexahydro-1,4-methanoanthracene-9,10-dione, 1-methyl-6- (n-hexyl) Oxy) -1,2,3,4,4a, 9a-hexahydro-1,4-methanoanthracene-9,10-dione, 1-methyl-6-phenoxy-1,2,3,4,4a, 9a- Hexahydro-1,4-methanoanthracene-9,10-dione, 1-methyl-6- (p-methylphenoxy) phenoxy-1,2,3,4,4a, 9a-hexahydro-1,4-methanoanthracene- 9, 10- Dione, 1-methyl-6- (p-chlorophenoxy) -1,2,3,4,4a, 9a-hexahydro-1,4-methanoanthracene-9,10-dione, 1-methyl-6- (o -Chlorophenoxy) -1,2,3,4,4a, 9a-hexahydro-1,4-methanoanthracene-9,10-dione and the like.

(Third reaction)
In the third reaction, the 1,2,3,4,4a, 9a-hexahydro-1,4-methanoanthracene-9,10-dione compound obtained in the second reaction is heated in a solvent in the presence of an acid or a base. By enolization, a 1,2,3,4-tetrahydro-1,4-methanoanthracene-9,10-diol compound is obtained.

First, an enolization method using an acid catalyst will be described. 1,2,3,4,4a, 9a-Hexahydro-1,4-methanoanthracene-9,10-dione compounds are enolated by 1,2,3,4,4a, 9a-hexahydro-1,4- This is carried out by heating the methanoanthracene-9,10-dione compound and the acid catalyst in a solvent. Examples of the acid catalyst that can be used include mineral acids such as sulfuric acid, hydrogen chloride, and nitric acid, and organic acids such as p-toluenesulfonic acid, methanesulfonic acid, and acetic acid.

In the enolization using an acid catalyst, a solvent that can be used is not particularly limited, but an aromatic solvent such as toluene and xylene, a ketone solvent such as methyl ethyl ketone, an ether such as tetrahydrofuran and 1,4-dioxane. A system solvent is preferably used. In particular, when an aromatic solvent is used, a 1,2,3,4-tetrahydro-1,4-methanoanthracene-9,10-diol compound precipitates when the reaction solution is cooled after the completion of the reaction. Particularly desirable.

The enolization temperature using an acid catalyst is preferably 50 ° C. or higher and 150 ° C. or lower, more preferably 80 ° C. or higher and 120 ° C. or lower. At 50 ° C. or lower, the reaction time is too long, and at 150 ° C. or higher, the purity of the product is lowered. The enolization reaction time depends on the reaction temperature, but is usually about 30 minutes to 3 hours. After completion of the reaction, the reaction solution is cooled or poured into a poor solvent such as n-hexane to precipitate a 1,2,3,4-tetrahydro-1,4-methanoanthracene-9,10-diol compound. To do.

Next, the enolization method using an inorganic base will be described. As the base used for the enolization reaction, an inorganic base such as sodium hydroxide, potassium hydroxide, sodium carbonate, or potassium carbonate, or an organic base such as triethylamine, piperidine, or pyridine is used. Among these, sodium hydroxide is most preferably used.

When using a base, the 1,2,3,4,4a, 9a-hexahydro-1,4-methanoanthracene-9,10-dione compound in a base aqueous solution is heated to form an alkali salt aqueous solution, By neutralization, a 1,2,3,4-tetrahydro-1,4-methanoanthracene-9,10-diol compound represented by the general formula (2) is obtained. The reaction temperature is usually from 50 ° C to 80 ° C.

Examples of the 1,2,3,4-tetrahydro-1,4-methanoanthracene-9,10-diol compound obtained by the third reaction include the following compounds. That is, 1,2,3,4-tetrahydro-1,4-methanoanthracene-9,10-diol, 1-methyl-1,2,3,4-tetrahydro-1,4-methanoanthracene-9,10- Diol, 2-methyl-1,2,3,4-tetrahydro-1,4-methanoanthracene-9,10-diol, 11-methyl-1,2,3,4-tetrahydro-1,4-methanoanthracene- 9,10-diol and the like.

Further, 5-fluoro-1,2,3,4-tetrahydro-1,4-methanoanthracene-9,10-diol, 5-chloro-1,2,3,4-tetrahydro-1,4-methanoanthracene- 9,10-diol, 5-bromo-1,2,3,4-tetrahydro-1,4-methanoanthracene-9,10-diol, 5-iodo-1,2,3,4-tetrahydro-1,4 -Methanoanthracene-9,10-diol, 6-fluoro-1,2,3,4-tetrahydro-1,4-methanoanthracene-9,10-diol, 6-chloro-1,2,3,4-tetrahydro -1,4-methanoanthracene-9,10-diol, 6-bromo-1,2,3,4-tetrahydro-1,4-methanoanthracene-9,10-diol, 6-iodo-1,2,3 , 4 Tetrahydro-1,4-methanoanthracene-9,10-diol, 1-methyl-5-fluoro-1,2,3,4-tetrahydro-1,4-methanoanthracene-9,10-diol, 1-methyl- 5-chloro-1,2,3,4-tetrahydro-1,4-methanoanthracene-9,10-diol, 1-methyl-5-bromo-1,2,3,4-tetrahydro-1,4-methano Anthracene-9,10-diol, 1-methyl-5-iodo-1,2,3,4-tetrahydro-1,4-methanoanthracene-9,10-diol, 1-methyl-6-fluoro-1,2 , 3,4-tetrahydro-1,4-methanoanthracene-9,10-diol, 1-methyl-6-chloro-1,2,3,4-tetrahydro-1,4-methanoanthracene-9,1 -Diol, 1-methyl-6-bromo-1,2,3,4-tetrahydro-1,4-methanoanthracene-9,10-diol, 1-methyl-6-iodo-1,2,3,4 And tetrahydro-1,4-methanoanthracene-9,10-diol.

Furthermore, 5-methyl-1,2,3,4-tetrahydro-1,4-methanoanthracene-9,10-diol, 5-ethyl-1,2,3,4-tetrahydro-1,4-methanoanthracene -9,10-diol, 5- (n-propyl) -1,2,3,4-tetrahydro-1,4-methanoanthracene-9,10-diol, 5- (i-propyl) -1,2, 3,4-tetrahydro-1,4-methanoanthracene-9,10-diol, 5- (n-butyl) -1,2,3,4-tetrahydro-1,4-methanoanthracene-9,10-diol, 5- (i-butyl) -1,2,3,4-tetrahydro-1,4-methanoanthracene-9,10-diol, 5- (n-pentyl) -1,2,3,4-tetrahydro-1 , 4-Methanoanthracene- , 10-diol, 5- (n-hexyl) -1,2,3,4-tetrahydro-1,4-methanoanthracene-9,10-diol, 5- (n-heptyl) -1,2,3 4-tetrahydro-1,4-methanoanthracene-9,10-diol, 5- (2-ethylhexyl) -1,2,3,4-tetrahydro-1,4-methanoanthracene-9,10-diol, 5- (N-dodecyl) -1,2,3,4-tetrahydro-1,4-methanoanthracene-9,10-diol, 5-cyclohexyl-1,2,3,4-tetrahydro-1,4-methanoanthracene- 9,10-diol, 6-methyl-1,2,3,4-tetrahydro-1,4-methanoanthracene-9,10-diol, 6-ethyl-1,2,3,4-tetrahydro-1,4 −Me Noanthracene-9,10-diol, 6- (n-propyl) -1,2,3,4-tetrahydro-1,4-methanoanthracene-9,10-diol, 6- (i-propyl) -1, 2,3,4-tetrahydro-1,4-methanoanthracene-9,10-diol, 6- (n-butyl) -1,2,3,4-tetrahydro-1,4-methanoanthracene-9,10- Diol, 6- (i-butyl) -1,2,3,4-tetrahydro-1,4-methanoanthracene-9,10-diol, 6- (n-pentyl) -1,2,3,4-tetrahydro -1,4-methanoanthracene-9,10-diol, 6- (n-hexyl) -1,2,3,4-tetrahydro-1,4-methanoanthracene-9,10-diol, 6- (n- Heptyl) -1,2,3 4-tetrahydro-1,4-methanoanthracene-9,10-diol, 6- (2-ethylhexyl) -1,2,3,4-tetrahydro-1,4-methanoanthracene-9,10-diol, 6- (N-dodecyl) -1,2,3,4-tetrahydro-1,4-methanoanthracene-9,10-diol, 6-cyclohexyl-1,2,3,4-tetrahydro-1,4-methanoanthracene- 9,10-diol, 1-methyl-5-methyl-1,2,3,4-tetrahydro-1,4-methanoanthracene-9,10-diol, 1-methyl-5-ethyl-1,2,3 , 4-Tetrahydro-1,4-methanoanthracene-9,10-diol, 1-methyl-5- (n-propyl) -1,2,3,4-tetrahydro-1,4-methanoanthracene- , 10-diol, 1-methyl-5- (i-propyl) -1,2,3,4-tetrahydro-1,4-methanoanthracene-9,10-diol, 1-methyl-5- (n-butyl) ) -1,2,3,4-tetrahydro-1,4-methanoanthracene-9,10-diol, 1-methyl-5- (i-butyl) -1,2,3,4-tetrahydro-1,4 -Methanoanthracene-9,10-diol, 1-methyl-5- (n-pentyl) -1,2,3,4-tetrahydro-1,4-methanoanthracene-9,10-diol, 1-methyl-5 -(N-hexyl) -1,2,3,4-tetrahydro-1,4-methanoanthracene-9,10-diol, 1-methyl-5- (n-heptyl) -1,2,3,4 Tetrahydro-1,4-methanoanthracene 9,10-diol, 1-methyl-5- (2-ethylhexyl) -1,2,3,4-tetrahydro-1,4-methanoanthracene-9,10-diol, 1-methyl-5- (n- Dodecyl) -1,2,3,4-tetrahydro-1,4-methanoanthracene-9,10-diol, 1-methyl-5-cyclohexyl-1,2,3,4-tetrahydro-1,4-methanoanthracene -9,10-diol, 1-methyl-6-methyl-1,2,3,4-tetrahydro-1,4-methanoanthracene-9,10-diol, 1-methyl-6-ethyl-1,2, 3,4-tetrahydro-1,4-methanoanthracene-9,10-diol, 1-methyl-6- (n-propyl) -1,2,3,4-tetrahydro-1,4-methanoanthracene-9, 10- Diol, 1-methyl-6- (i-propyl) -1,2,3,4-tetrahydro-1,4-methanoanthracene-9,10-diol, 1-methyl-6- (n-butyl) -1 , 2,3,4-Tetrahydro-1,4-methanoanthracene-9,10-diol, 1-methyl-6- (i-butyl) -1,2,3,4-tetrahydro-1,4-methanoanthracene -9,10-diol, 1-methyl-6- (n-pentyl) -1,2,3,4-tetrahydro-1,4-methanoanthracene-9,10-diol, 1-methyl-6- (n -Hexyl) -1,2,3,4-tetrahydro-1,4-methanoanthracene-9,10-diol, 1-methyl-6- (n-heptyl) -1,2,3,4-tetrahydro-1 , 4-Methanoanthracene-9,10 Diol, 1-methyl-6- (2-ethylhexyl) -1,2,3,4-tetrahydro-1,4-methanoanthracene-9,10-diol, 1-methyl-6- (n-dodecyl) -1 , 2,3,4-tetrahydro-1,4-methanoanthracene-9,10-diol, 1-methyl-6-cyclohexyl-1,2,3,4-tetrahydro-1,4-methanoanthracene-9,10 -Diol etc. are mentioned.

And 5-methoxy-1,2,3,4-tetrahydro-1,4-methanoanthracene-9,10-diol, 5-ethoxy-1,2,3,4-tetrahydro-1,4-methanoanthracene -9,10-diol, 5- (n-propoxy) -1,2,3,4-tetrahydro-1,4-methanoanthracene-9,10-diol, 5- (n-butoxy) -1,2, 3,4-tetrahydro-1,4-methanoanthracene-9,10-diol, 5- (n-hexyloxy) -1,2,3,4-tetrahydro-1,4-methanoanthracene-9,10-diol 5-phenoxy-1,2,3,4-tetrahydro-1,4-methanoanthracene-9,10-diol, 5- (p-methylphenoxy) phenoxy-1,2,3,4-tetrahydro 1,4-methanoanthracene-9,10-diol, 5- (p-chlorophenoxy) -1,2,3,4-tetrahydro-1,4-methanoanthracene-9,10-diol, 5- (o- Chlorophenoxy) -1,2,3,4-tetrahydro-1,4-methanoanthracene-9,10-diol, 6-methoxy-1,2,3,4-tetrahydro-1,4-methanoanthracene-9, 10-diol, 6-ethoxy-1,2,3,4-tetrahydro-1,4-methanoanthracene-9,10-diol, 6- (n-propoxy) -1,2,3,4-tetrahydro-1 , 4-Methanoanthracene-9,10-diol, 6- (n-butoxy) -1,2,3,4-tetrahydro-1,4-methanoanthracene-9,10-diol, 6- (n-hex Ruoxy) -1,2,3,4-tetrahydro-1,4-methanoanthracene-9,10-diol, 6-phenoxy-1,2,3,4-tetrahydro-1,4-methanoanthracene-9,10 -Diol, 6- (p-methylphenoxy) phenoxy-1,2,3,4-tetrahydro-1,4-methanoanthracene-9,10-diol, 6- (p-chlorophenoxy) -1,2,3 , 4-tetrahydro-1,4-methanoanthracene-9,10-diol, 6- (o-chlorophenoxy) -1,2,3,4-tetrahydro-1,4-methanoanthracene-9,10-diol, 1-methyl-5-methoxy-1,2,3,4-tetrahydro-1,4-methanoanthracene-9,10-diol, 1-methyl-5-ethoxy-1,2,3,4-te Trahydro-1,4-methanoanthracene-9,10-diol, 1-methyl-5- (n-propoxy) -1,2,3,4-tetrahydro-1,4-methanoanthracene-9,10-diol, 1-methyl-5- (n-butoxy) -1,2,3,4-tetrahydro-1,4-methanoanthracene-9,10-diol, 1-methyl-5- (n-hexyloxy) -1, 2,3,4-tetrahydro-1,4-methanoanthracene-9,10-diol, 1-methyl-5-phenoxy-1,2,3,4-tetrahydro-1,4-methanoanthracene-9,10- Diol, 1-methyl-5- (p-methylphenoxy) phenoxy-1,2,3,4-tetrahydro-1,4-methanoanthracene-9,10-diol, 1-methyl-5- (p-chloro Phenoxy) -1,2,3,4-tetrahydro-1,4-methanoanthracene-9,10-diol, 1-methyl-5- (o-chlorophenoxy) -1,2,3,4-tetrahydro-1 , 4-Methanoanthracene-9,10-diol, 1-methyl-6-methoxy-1,2,3,4-tetrahydro-1,4-methanoanthracene-9,10-diol, 1-methyl-6-ethoxy -1,2,3,4-tetrahydro-1,4-methanoanthracene-9,10-diol, 1-methyl-6- (n-propoxy) -1,2,3,4-tetrahydro-1,4- Methanoanthracene-9,10-diol, 1-methyl-6- (n-butoxy) -1,2,3,4-tetrahydro-1,4-methanoanthracene-9,10-diol, 1-methyl-6 ( -Hexyloxy) -1,2,3,4-tetrahydro-1,4-methanoanthracene-9,10-diol, 1-methyl-6-phenoxy-1,2,3,4-tetrahydro-1,4- Methanoanthracene-9,10-diol, 1-methyl-6- (p-methylphenoxy) phenoxy-1,2,3,4-tetrahydro-1,4-methanoanthracene-9,10-diol, 1-methyl- 6- (p-chlorophenoxy) -1,2,3,4-tetrahydro-1,4-methanoanthracene-9,10-diol, 1-methyl-6- (o-chlorophenoxy) -1,2,3 , 4-tetrahydro-1,4-methanoanthracene-9,10-diol, and the like.

(Fourth reaction)
In the fourth reaction, the space inside the reactor containing the 1,2,3,4-tetrahydro-1,4-methanoanthracene-9,10-diol compound solution obtained in the third reaction is passed through an inert gas. And is reacted with an epihalohydrin compound represented by the general formula (3) in the presence of a basic compound in the presence of a normal pressure, in the presence or absence of a solvent, to give the corresponding 1,2,3,4-tetrahydro A -1,4-methanoanthracene-9,10-bis (2-methylglycidyl) ether compound can be obtained.

  Examples of the epihalohydrin compound represented by the general formula (3) used in the fourth reaction include epichlorohydrin, epibromohydrin, 2-methylepichlorohydrin, 2-methylepibromohydrin, and the like. , Preferably epichlorohydrin or 2-methylepichlorohydrin, and more preferably epichlorohydrin because it is easily available. The epihalohydrin compound can also be used as a solvent.

  In the fourth reaction, the charged molar ratio of the epihalohydrin compound to the 1,2,3,4-tetrahydro-1,4-methanoanthracene-9,10-diol compound is usually 2.0 to 30, preferably 3.0 to 15. It is. When the latter charged molar ratio with respect to the former is less than 2.0, unreacted 1,2,3,4-tetrahydro-1,4-methanoanthracene-9,10-diol compound remains, and the charged molar ratio is When it exceeds 30, removal of the unreacted epihalohydrin compound takes time and is inefficient.

  Examples of basic compounds used as dehydrohalogenating agents in the fourth reaction include trimethylamine, triethylamine, tripropylamine, tributylamine, diethylamine, dibutylamine, piperidine, pyridine, α-picoline, and γ-picoline. Organic bases; inorganic bases such as sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium carbonate, sodium bicarbonate, potassium carbonate, and potassium bicarbonate. Among these, sodium hydroxide or potassium hydroxide is preferable because it is easily available.

  The usage-amount of a basic compound is 2.0-9 normally as a preparation molar ratio with respect to a 1,2,3,4-tetrahydro-1,4-methanoanthracene-9,10-diol compound. When the charged molar ratio is less than 2.0, the 1,2,3,4-tetrahydro-1,4-methanoanthracene-9,10-diol compound remains unreacted, while the basic compound is too much. When the amount is too large, the epihalohydrin compound or the epoxy group is polymerized or cleaved, resulting in rapid heat generation during the reaction and a decrease in product purity.

  In the fourth reaction, a solvent is used as necessary. Examples of the usable solvent include alcohol solvents such as ethanol and 2-propanol; ketone solvents such as acetone and methyl isobutyl ketone; ether solvents such as dioxane and tetrahydrofuran. Solvents; Amide solvents such as dimethylformamide, dimethylacetamide, N-methylpyrrolidone; Halogen solvents such as chloroform and dichloromethane. Two or more of these organic solvents may be combined.

  In the fourth reaction, a catalyst is used as necessary. Catalysts that can be used include quaternary ammonium salts such as tetramethylammonium chloride and tetrabutylammonium bromide; tertiary amines such as triethylamine and benzyldimethylamine; imidazoles such as 2-phenylimidazole; phosphines such as triphenylphosphine. Etc.

  Next, reaction conditions for the fourth reaction will be described. The reaction temperature of the fourth reaction is usually not higher than the boiling point of the solvent or epihalohydrin compound. For example, when epichlorohydrin is used, the temperature is in the range of 10 to 100 ° C. When adding an aqueous solution of an inorganic base as the dehydrohalogenating agent described above, it is preferable to add the aqueous solution of the inorganic base continuously or intermittently in small portions over 1 to 8 hours in order to prevent a rapid reaction.

  After completion of the reaction, the basic compound and by-product salt are removed by washing with water and / or filtered. Next, the epoxy compound of the present invention can be obtained by removing the solvent and unreacted epihalohydrin compound by distillation under reduced pressure.

(Epoxy resin composition)
The epoxy resin composition of the present invention is characterized by containing an epoxy compound represented by the following general formula (1) as a component.

(In the general formula (1), R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ may be the same or different from each other, and represent a hydrogen atom or a methyl group, and X is hydrogen Indicates an atom, halogen atom, alkyl group, alkoxy group or aryloxy group.)

  The epoxy resin composition of this invention can use another epoxy compound and an epoxy resin together as needed. Any epoxy compound or epoxy resin can be used as long as it has two or more epoxy groups in one molecule, but all conventionally known epoxy compounds and epoxy resins can be used. . For example, bisphenol A type, bisphenol F type, biphenyl type, phenol novolak type, cresol novolak type, bisphenol A novolak type, phenol aralkyl type, naphthalene type, epoxy resin, alicyclic epoxy compound, aliphatic epoxy compound, etc. Can be mentioned. Two or more of these epoxy compounds and epoxy resins may be used in combination.

  Furthermore, a hardening | curing agent can be used for the epoxy resin composition of this invention as needed. It does not specifically limit as a hardening | curing agent, All the compounds generally used as a hardening | curing agent of an epoxy resin can be used. For example, polyphenols such as bisphenol A, bisphenol F, bisphenol S, thiodiphenol, hydroquinone, biphenol, dihydroxynaphthalene; various aldehydes such as phenol novolac resin, cresol novolac resin, bisphenol A novolac resin, naphthol novolac resin Phenol resins obtained by condensation reaction of; acid anhydrides such as methyltetrahydrophthalic anhydride, hexahydrophthalic anhydride, pyrometic anhydride, and methylnadic acid; latent amine curing agents such as dicyandiamide, imidazole, and guanidine derivatives And aromatic amines such as metaphenylenediamine and xylylenediamine. Two or more of these curing agents may be used in combination.

  The blending ratio of the epoxy resin and the curing agent is not particularly limited, but is generally 0.3 to 2.0 equivalents, preferably 0.7 to the amount of the active hydrogen group of the curing agent with respect to 1 equivalent of the epoxy group in the epoxy resin. 1.2 equivalents.

  Furthermore, a curing accelerator can be used. The curing accelerator is not particularly limited, and all compounds generally used as an epoxy resin curing accelerator can be used. For example, phosphines such as triphenylphosphine and tributylphosphine; imidazoles such as 2-ethyl-4-methylimidazole and 2-methylimidazole; 4-dimethylaminopyridine, 2,4,6-tris (dimethylaminomethyl) phenol And diazabicyclo compounds such as 1,8-diazabicyclo [5,4,0] -7-undecene; Lewis acids, amine complex salts and the like. Two or more of these curing accelerators may be used in combination.

  The blending ratio of the epoxy resin and the curing accelerator is not particularly limited, but is usually 0.1 to 7.0% by weight, preferably 0.2 to 5.0% by weight with respect to the epoxy resin.

In the epoxy resin composition of the present invention, if necessary, a colorant, an antioxidant, a leveling agent, a surfactant, an ultraviolet absorber, a silane coupling agent, an inorganic filler, resin particles, a wettability improver, Additives such as antifoaming agents, light stabilizers and heat stabilizers; inorganic fillers such as calcium carbonate, talc, silica and barium sulfate can be used in combination.

[Cured product]
The cured product of the present invention can be obtained by curing the epoxy resin composition of the present invention. The curing means may be any of heat, light and the like.

In the method of curing using a curing agent such as an acid anhydride, the epoxy resin composition of the present invention blended with a curing agent is further blended with a curing accelerator, if necessary, and the mixture is heated. be able to.

The curing temperature is, for example, 30 to 240 ° C, preferably 50 to 200 ° C. Curing may be performed in two stages. For example, after primary curing at a temperature of 30 to 130 ° C. (preferably 50 to 130 ° C.) and then secondary curing at a temperature of 135 to 240 ° C. (preferably 135 to 200 ° C.), transparency and heat resistance are achieved. A cured product having good physical properties can be obtained.

As a specific method for forming the cured product, for example, the curable composition is uniformly mixed with a kneader, a roll, an extruder, etc., and molded using a transfer molding machine or a mold, and then 1 to 24 hours. A method of heating to a certain extent can be mentioned.

When a cationic polymerization initiator is used as the curing agent, it can be cured by irradiation with active energy rays. An active energy ray is a general term for electron beams, X-rays, ultraviolet rays, electron beams with high energy such as visible light in a low wavelength region, or electromagnetic waves, and ultraviolet rays are preferable because of the simplicity and spread of ordinary devices. There are many types of devices that can irradiate ultraviolet rays, but they can be arbitrarily selected. Moreover, it is also possible to use a blue LED as energy such as visible light on the low wavelength region side.

  EXAMPLES Hereinafter, although this invention is demonstrated in detail based on an Example, this invention is not limited to the following description examples, unless the meaning is exceeded.

The product was confirmed by measurement using the following equipment.
(1) Melting point: Melting point measuring device manufactured by Gelen Camp, model MFB-595 (conforms to JIS K0064)
(2) Refractive index: Abbe refractometer: manufactured by Elmer, model ER-7MW-H
(3) Infrared (IR) spectrophotometer: manufactured by JASCO Corporation, model IR-810
(4) Nuclear magnetic resonance apparatus (NMR): manufactured by JEOL Ltd., model GSX, FTNMR Spectrometer

“Synthesis Example 1” Synthesis of 1,4,4a, 9a-tetrahydro-1,4-methanoanthracene-9,10-dione 120 g of dicyclopentadiene (manufactured by Wako Pure Chemical Industries, Ltd.), a 300 ml eggplant-shaped flask and Friedrich A cyclopentadiene (distilling temperature of 40 ° C) is charged by distillation into a distillation apparatus equipped with a cooling pipe and heated in an oil bath at 185 ° C, and 60 g of methylene chloride (manufactured by Wako Pure Chemical Industries) is contained. The collected volume was collected in a 200 ml eggplant flask. The eggplant flask to be collected was cooled with dry ice / acetone. The methylene chloride solution of 64 g of cyclopentadiene collected by the above method was transferred to a four-necked flask having a volume of 500 ml and cooled to −60 ° C. with dry ice / acetone. Prepare a slurry of 128 g of 1,4-naphthoquinone (manufactured by Kawasaki Kasei Kogyo Co., Ltd.) and 200 g of methylene chloride (manufactured by Wako Pure Chemical Industries) in a separate container, and add the slurry to the methylene chloride solution of 64 g of cyclopentadiene over 15 minutes. did. When the cooling of dry ice / acetone was stopped after completion of the addition, the internal temperature rose to 45 ° C. due to an exothermic reaction. Stirring was continued until the internal temperature decreased, and when the internal temperature began to decrease, the bath temperature was adjusted to 35 ° C. and further stirred for 30 minutes. Thereafter, the reaction solution was transferred to a 1 L eggplant type flask, 300 ml of methanol (manufactured by Wako Pure Chemical Industries, Ltd.) was added thereto, 250 g of methylene chloride in the reaction solution was heated to 50 ° C. and distilled, and crystals were obtained. Crystallized. The precipitated crystals were suction filtered, and the obtained crystals were washed three times with 50 ml of methanol. The obtained crystals were 170 g of white crystals. When this crystal was identified, it was 1,4,4a, 9a-tetrahydro-1,4-methanoanthracene-9,10-dione. The yield based on the raw material 1,4-naphthoquinone was 94 mol%.

Synthesis Example 2 Synthesis of 1,2,3,4,4a, 9a-hexahydro-1,4-methanoanthracene-9,10-dione 1,4,4a, 9a obtained in the same manner as in Synthesis Example 1 -70 g of tetrahydro-1,4-methanoanthracene-9,10-dione was weighed into a glass autoclave having a volume of 300 ml, 150 g of orthoxylene (manufactured by Wako Pure Chemical Industries) as a solvent, 5% supported palladium carbon as a hydrogenation catalyst 1 g of (Pd / C) was added, and hydrogen was supplied under a condition of 0.2 MpaG to cause a hydrogenation reaction. After completion of the reaction, Pd / C was filtered, the reaction solution was concentrated under reduced pressure, 130 g of orthoxylene was distilled off, and 50 g of methanol was added for crystallization. The precipitated crystals were suction filtered, washed with 50 ml of methanol and dried to obtain 60 g of white crystals. When this crystal was identified, it was 1,2,3,4,4a, 9a-hexahydro-1,4-methanoanthracene-9,10-dione. The yield based on 1,4,4a, 9a-tetrahydro-1,4-methanoanthracene-9,10-dione was 85 mol%.

Melting point: 116-117 ° C
(1) IR (KBr, cm ⁻¹ ): 2980, 2960, 2880, 1670, 1590, 1478, 1452, 1322, 1302, 1262, 1168, 1050, 998, 900, 820, 757, 730, 540
(2) ¹ H-NMR (CDCl ₃ , 400 MHz): δ = 1.1-1.21 (2H, m), 1.41-1.46 (1H, m), 1.46-1.54 ( 2H, m), 1.58-1.65 (1H, m), 3.03 (2H, s), 3.20 (2H, s), 7.72-7.80 (2H, m), 8 .08-8.16 (2H, m).

“Synthesis Example 3” Synthesis of 1,2,3,4-tetrahydro-1,4-methanoanthracene-9,10-diol under acidic conditions in a three-necked flask with a volume of 100 ml equipped with a stirrer 1.65 g (25 mmol) of 1,2,3,4,4a, 9a-hexahydro-1,4-methanoanthracene-9,10-dione obtained in Example 2, 20 g of toluene and 50 mg of methanesulfonic acid were added. The reaction was conducted by heating at 105 ° C. for 1 hour under a nitrogen atmosphere. After cooling this reaction liquid, it poured into 200 ml of n-hexane, and white precipitation was obtained. This white precipitate was separated by suction filtration, and the obtained crystals were dried to obtain 4.09 g of a white powder of 1,2,3,4-tetrahydro-1,4-methanoanthracene-9,10-diol. . The yield based on 1,2,3,4,4a, 9a-hexahydro-1,4-methanoanthracene-9,10-dione as a raw material was 72 mol%.

(1) Melting point: 157-159 ° C
(2) IR (KBr, cm ⁻¹ ): 3260, 2970, 2880, 1612, 1450, 1390, 1320, 1296, 1272, 1224, 1172, 1158, 1083, 1040, 972, 928, 878, 772, 758, 645.
(3) ¹ H-NMR (CDCl ₃ , 400 MHz): δ = 1.30-1.37 (1H, m), 1.60-1.71 (2H, m), 1.78-1.85 ( 1H, m), 1.92-2.03 (2H, m), 3.62 (2H, s), 4.72 (2H, s), 7.39-7.48 (2H, m), 8 .01-8.09 (2H, m).

Synthesis Example 4 Synthesis of 1,2,3,4-tetrahydro-1,4-methanoanthracene-9,10-diol under alkaline conditions in a three-necked flask with a volume of 300 ml equipped with a stirrer Slurry thoroughly in 100 g of degassed 11.3 g (50 mmol) of 1,2,3,4,4a, 9a-hexahydro-1,4-methanoanthracene-9,10-dione obtained in Example 2 Turned into. A solution prepared by dissolving 6.0 g (150 mmol) of sodium hydroxide in 20 g of degassed water was added to the slurry. When the slurry which became light red by the addition of aqueous sodium hydroxide was heated at 60 ° C. for 30 minutes, a red solution was obtained. The solution was cooled with ice water and then added to 1000 ml of an acidic aqueous solution to make the pH of the reaction solution acidic. As a result, a large amount of white precipitate was produced. This precipitate was filtered by suction filtration, and the obtained crystals were dried to obtain 10.6 g of a white powder. The powder was identified and found to be 1,2,3,4-tetrahydro-1,4-methanoanthracene-9,10-diol. The yield based on 1,2,3,4,4a, 9a-hexahydro-1,4-methanoanthracene-9,10-dione as a raw material was 94 mol%.

"Example 1" 1,2,3,4-tetrahydro-1,4-methanoanthracene-9,10-diglycidyl ether synthesis thermometer, in a 200 ml three-necked flask equipped with a stirrer in a nitrogen atmosphere, as in Synthesis Example 4 1,2,3,4-tetrahydro-1,4-methanoanthracene-9,10-diol (Mw226) 4.52 g (20 mmol), dimethylacetamide 20 g, epichlorohydrin (Mw92.5) 4.6 g (50 mmol) was charged to give a colorless solution. Thereto was added a 10 g solution of 2.4 g (60 mmol) of caustic soda (Mw40) while cooling with ice water. The liquid color immediately turned red. When the mixture was stirred at room temperature for 6 hours, a colorless candy-like substance precipitated. When 10% sulfuric acid aqueous solution was added to make the pH of the solution slightly acidic, the amount of candy-like precipitates increased. Discard the supernatant, wash the syrup of the bottom well, dry it and dry it, 1,2,3,4-tetrahydro-1,4-methanoanthracene-9,10-diglycidyl ether, which is a light khaki syrup 4.07 g was obtained. The yield based on the raw material 1,2,3,4-tetrahydro-1,4-methanoanthracene-9,10-diol was 65 mol%.

(1) Melting point: room temperature liquid (2) Refractive index n _D = 1.604
(3) IR (neat, cm ⁻¹ ): 2960, 2880, 1660, 1646, 1455, 1360, 1334, 1305, 1280, 1176, 1082, 1048, 1012, 908, 860, 772.
(4) ¹ H-NMR (400 MHz, CDCl ₃ ): δ = 13-11-142 (m, 2H), 1.59-1.66 (m, 1H), 1.75-1.81 ( m, 1H), 1.96-2.06 (m, 2H), 2.72-2.80 (m, 2H), 2.87-2.94 (m, 2H), 3.40-3. 48 (m, 2H), 3.71-3.79 (m, 2H), 4.04 (dd, J ₁ = 18 Hz, J ₂ = 9 Hz, 2H), 4.28 (dd, J ₁ = 17 Hz, _{J 2 = 8Hz, 2H),} 7.36-7.47 (m, 2H), 8.04-8.17 (m, 2H).

"Example 2" 1,2,3,4-tetrahydro-1,4-methanoanthracene-9,10-diglycidyl ether curing method and evaluation of cured product 1,2,3 obtained in the same manner as in Example 1 Mixing 100 parts by weight of 3,4-tetrahydro-1,4-methanoanthracene-9,10-diglycidyl ether (Compound E-1, epoxy equivalent 157) with 50 parts by weight of methyltetrahydrophthalic anhydride as a curing agent, Furthermore, 1.0 part by weight of 4-dimethylaminopyridine was mixed as a curing accelerator to obtain an epoxy resin composition. Subsequently, it heated at 100 degreeC for 2 hours, 150 degreeC for 2 hours, and 180 degreeC for 2 hours, and obtained hardened | cured material. Table 1 shows the glass transition temperature (Tg) of the obtained cured product. Tg was measured by DSC according to JIS K 7121 (hereinafter the same).

Comparative Example 1 Curing Method of Trimethylolpropane Triglycidyl Ether and Evaluation of Cured Product In Example 2, instead of 1,2,3,4-tetrahydro-1,4-methanoanthracene-9,10-diglycidyl ether In the same manner as in Example 2, except that trimethylolpropane triglycidyl ether (Compound E-2, epoxy equivalent: 145 g / eq, Sigma-Aldrich Japan Co., Ltd. reagent) was used, an epoxy resin composition and a cured product were obtained. Got. Table 1 shows Tg of the obtained cured product.

From Example 1, 1,2,3,4-tetrahydro-1,4-methanoanthracene-9,10-diglycidyl ether, which is a compound of the present invention, has a very high refractive index of 1.6 or more, and It turns out to be liquid at room temperature and easy to handle. The following is clear from Example 2, Comparative Example 1 and Table 1. That is, the glass transition temperature of the cured product of 1,2,3,4-tetrahydro-1,4-methanoanthracene-9,10-diglycidyl ether of the present invention is the trimethylolpropane triglycidyl obtained in Comparative Example 1. Since it is higher than the glass transition temperature of the hardened | cured material of ether, it turns out that it is excellent in heat resistance.

Claims (4)

An epoxy compound represented by the general formula (1).

(In the general formula (1), R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ may be the same or different from each other, and represent a hydrogen atom or a methyl group, and X is hydrogen Indicates an atom, halogen atom, alkyl group, alkoxy group or aryloxy group.) In the presence of a basic compound, 1,2,3,4-tetrahydro-1,4-methanoanthracene-9,10-diol represented by the following general formula (2) is represented by the following general formula (3). The method for producing an epoxy compound according to claim 1, wherein the epoxy compound is reacted with an epihalohydrin compound.

(In the general formula (2), R ¹ , R ² , R ³ , R ⁴ and R ⁵ may be the same or different from each other, and represent a hydrogen atom or a methyl group, and X represents a hydrogen atom, a halogen atom, (Atom, alkyl group, alkoxy group, or aryloxy group is shown.)

(In general formula (3), R ⁶ represents either a hydrogen atom or a methyl group, and Y represents a halogen atom.)   An epoxy resin composition comprising the epoxy compound according to claim 1 as a component.   A cured product obtained by curing the epoxy resin composition according to claim 3.