JP2009256275A - New mono(meth)acrylate compound having 9,10-ethanoanthracene skeleton - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a new polymerizable mono(meth)acrylate compound that has a high refractive index and excellent transparency free from problems of ultraviolet absorption and fluorescence. <P>SOLUTION: The industrially useful mono(meth)acrylate compound having a 9,10-ethanoanthracene skeleton is a transparent compound that has a high refractive index and no UV absorption in a high-wavelength side of ≥250 nm, and is a polymerizable compound which contains a radically polymerizable group. Its polymer is useful as an optical material having a high refractive index. The method for producing the same is provided. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to an acrylate compound, and more particularly to an acrylate compound useful as a monomer for a polymer material having a high refractive index and a method for producing the same.

  The mono (meth) acrylate compound having a 9,10-ethanoanthracene skeleton of the present invention is a compound having both a 9,10-ethanoanthracene skeleton having a high refractive index and a polymerizable acrylate group. A polymer compound obtained by polymerizing the compound having a high refractive index also has a high refractive index, and is expected as a useful material particularly in the optical field.

  In recent years, plastic has been actively used as a glass substitute material in the optical field. For example, polycarbonate and polymethyl methacrylate are well known. These plastic materials have light weight, safety, and design, but have a disadvantage that they are lower in refractive index than inorganic glass and easily become thick. Therefore, in recent years, there has been an increasing demand for plastic materials having a high refractive index. In particular, the advancement of high refractive index plastic materials to optical products has been remarkable, such as liquid crystal display panels, color filters, spectacle lenses, Fresnel lenses, lenticular lenses, prism lens sheets for TFT, aspherical lenses, optical disks, holograms, and optical fibers. Studies on optical waveguides and the like have been actively conducted.

There is a positive correlation between the refractive index of the plastic and the refractive index of the monomer as the raw material, and in order to obtain a plastic with a high refractive index, the monomer part constituting the polymer must have a high refractive index. is necessary.

As a method for increasing the refractive index of an organic compound as a monomer, it is already well known that it is useful to introduce a halogen atom (excluding fluorine), a sulfur atom and an aromatic ring into the molecular structure. For example, a high refractive index polymer in which a halogen atom is introduced into a biphenyl ring using a high intrinsic refractive index of a halogen atom has been reported (Patent Document 1). However, due to halogenation, the light resistance is remarkably deteriorated and the specific gravity is high. In addition to the halogen, a monomer composition having a sulfur atom having a high intrinsic refractive index has also been reported (Patent Document 2). However, although these have a high refractive index and excellent impact resistance, the light resistance of the obtained polymer is remarkably inferior, and there is a disadvantage that an unpleasant odor peculiar to sulfur becomes a problem. Moreover, when plastics using these are treated as waste, there is a concern that harmful gases and compounds are generated.

On the other hand, high refractive index materials having a benzene ring and a biphenyl ring have been known for introduction of an aromatic ring, and these are light and excellent in transparency and have a well-balanced high refractive index material (Patent Document 3). etc). However, when these benzene rings are used, it is difficult to obtain a monomer that does not contain a halogen atom or sulfur atom and has a refractive index of more than 1.55. In the case of a compound having a biphenyl ring, for example, 2- (biphenyl-2-yloxy) ethyl acrylate is a high refractive index compound having a refractive index of 1.576. When absorbing and photoradically polymerizing this compound, depending on the light source used, it may overlap with the absorption wavelength of the photopolymerization initiator, which has the disadvantage that the photopolymerization reaction is not performed efficiently. Furthermore, in order to obtain a high refractive index, introduction of an anthracene ring and a fluorene ring, which are polycyclic compounds containing an aromatic group, has been studied (Patent Document 4). Attempts have also been made to introduce a polycyclic compound group containing an aromatic ring such as an anthracene group or a fluorene group into a polymer by a polymer reaction (Patent Document 5).

However, introduction of anthracene ring or fluorene ring can yield a polymer with a relatively high refractive index. However, when a fluorene ring is introduced, it absorbs in the ultraviolet region and is easily colored by light irradiation, which causes problems with light resistance. Comes out. In addition, when an anthracene ring is introduced, the anthracene ring emits fluorescence, so that there are problems such as difficulty in application in the field of optical materials.

Therefore, the development of a polymerizable monomer having a high refractive index, an aromatic polycyclic compound, and a compound group with excellent transparency that does not have the problem of absorption and fluorescence in the ultraviolet region as seen in anthracene and fluorene groups Is desired.

On the other hand, it is known that an anthracene compound and Diels-Alder reaction with dienophile, and a compound having a 9,10-ethanoanthracene skeleton is synthesized by this Diels-Alder reaction. For example, it is known that unsubstituted anthracene reacts with a Dielsophile such as maleic anhydride, maleimide, maleic ester, acrolein, acrylonitrile, benzoquinone, and Diels-Alder reaction to give a 9,10-ethanoanthracene compound (non-patented). Literature 1, 2, 3 etc.).

However, there is no example synthesized for the acrylate compound containing the 9,10-ethanoanthracene skeleton of the present invention, and it includes the 9,10-ethanoanthracene skeleton obtained by the Diels-Alder reaction of the anthracene compound of the present invention and dienophile. There are no examples of acrylate compounds studied as monomers for synthesizing polymers or as raw material monomers for optical materials.

JP 05-170702 A JP 2002-20433 A JP 2003-064296 A JP 2004-083855 A JP 2006-312709 A “Journal of American Chemical Society (J. Am. Chem. Soc.)” (USA), 1948, 70, p. 1458 “Journal of Organic Chemistry (J. Org. Chem.), (USA), 1939, vol. 4, p. "Chemiche Berichte", (Germany), 1931, 64, p. 1676.

In view of such circumstances, the present inventors have intensively studied to provide a technique that eliminates these drawbacks, and as a result, have completed the present invention. That is, the object of the present invention is as follows.
It is to provide a novel mono (meth) acrylate compound having a high refractive index, having no problem of absorption and fluorescence in the ultraviolet region and excellent in transparency, and providing an industrially advantageous production method of the compound That is.

In order to achieve the above object, the first invention provides a novel mono (meth) acrylate compound having a 9,10-ethanoanthracene skeleton represented by the general formula (1).

In the general formula (1), n represents an integer of 0 or more and less than 10, X represents a nitrogen atom to which a hydrogen atom, an alkyl group or an aryl group is bonded, or an oxygen atom, and Y ¹ and Y ² are the same. Or a hydrogen atom, an alkyl group, a halogen atom, a hydroxyl group, an alkoxy group or an aryloxy group, R ¹ represents a hydrogen atom or a methyl group, and either R ² or R ³ represents hydrogen. An atom, the other represents a hydrogen atom, a methyl group or an ethyl group, and R ⁴ represents a hydrogen atom or a methyl group;

In the description of the present invention, the (meth) acrylate compound represents an acrylate compound or a methacrylate compound. Moreover, (meth) acrylation represents acrylation or methacrylation.

In the description of the present invention, the 9,10-ethanoanthracene skeleton represents the skeleton of the following structural formula (10).

In the second invention, the 9,10-ethanoanthracene skeleton represented by the general formula (1) is characterized in that the anthracene compound represented by the general formula (2) and the dienophile represented by the general formula (3) are subjected to Diels-Alder reaction. The manufacturing method of the mono (meth) acrylate compound which has this.

In Formula (2), n represents an integer of 0 or more and less than 10, R ¹ represents a hydrogen atom or a methyl group, one of R ² or R ³ represents a hydrogen atom, and the other represents a hydrogen atom or a methyl group. Alternatively, it represents an ethyl group, and Y ¹ and Y ² may be the same or different and each represents a hydrogen atom, an alkyl group, a halogen atom, a hydroxyl group, an alkoxy group or an aryloxy group.

In the general formula (3), R ⁴ represents a hydrogen atom or a methyl group, and X represents a nitrogen atom to which a hydrogen atom, an alkyl group or an aryl group is bonded, or an oxygen atom.

Furthermore, in the third invention, a hydroxy compound containing a 9,10-ethanoanthracene skeleton represented by the general formula (4) is (meth) acrylated, and the 9,10-ethano represented by the general formula (1) is characterized. A method for producing a mono (meth) acrylate compound having an anthracene skeleton is provided.

In the general formula (4), n represents an integer of 0 or more and less than 10, X represents a nitrogen atom to which a hydrogen atom, an alkyl group or an aryl group is bonded, or an oxygen atom, and Y ¹ and Y ² are the same. May be different from each other, and represents a hydrogen atom, an alkyl group, a halogen atom, a hydroxyl group, an alkoxy group or an aryloxy group, one of R ^{2 and} R ³ represents a hydrogen atom, and the other represents a hydrogen atom, a methyl group Alternatively, it represents an ethyl group, and R ⁴ represents a hydrogen atom or a methyl group.

The present invention is as described in detail below, and has the following particularly advantageous effects, and its industrial utility value is extremely large.
The mono (meth) acrylate compound containing the 9,10-ethanoanthracene skeleton of the present invention is a novel compound, a high refractive index, a transparent compound having no UV absorption at 250 nm or more, and a high refractive index. It is an industrially useful compound as a refractive index optical material.

Hereinafter, the present invention will be described in detail.
The compound according to the first aspect of the present invention is a novel mono (meth) acrylate compound having a 9,10-ethanoanthracene skeleton represented by the following general formula (1).

In the general formula (1), n represents an integer of 0 or more and less than 10, X represents a nitrogen atom to which a hydrogen atom, an alkyl group or an aryl group is bonded, or an oxygen atom, and Y ¹ and Y ² are the same. Or a hydrogen atom, an alkyl group, a halogen atom, a hydroxyl group, an alkoxy group or an aryloxy group, R ¹ represents a hydrogen atom or a methyl group, and either R ² or R ³ represents hydrogen. An atom, the other represents a hydrogen atom, a methyl group or an ethyl group, and R ⁴ represents a hydrogen atom or a methyl group;

In general formula (1), the alkyl group bonded to the nitrogen atom in the nitrogen atom to which the hydrogen atom, alkyl group or aryl group represented by X is bonded includes a methyl group, an ethyl group, an n-propyl group, and an n-dodecyl group. , A cyclohexyl group, a 2-carboxyethyl group, a benzyl group, and the like. As an aryl group bonded to a nitrogen atom, a halogen-substituted phenyl group such as a phenyl group or a p-chlorophenyl group, or an alkyl-substituted phenyl such as a p-tolyl group. Group, alkoxyphenyl group such as p-hydroxyphenyl group and p-methoxyphenyl group, p-carboxyphenyl group, naphthyl group and the like. In particular, a compound in which an aryl group is bonded to a nitrogen atom is preferable because of its high refractive index.

Examples of the alkyl group represented by Y ¹ and Y ² include methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, t-butyl group, amyl group, 2 -Ethylhexyl group etc. are mentioned, As a halogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom is mentioned, As an alkoxy group, a methoxy group, an ethoxy group, n-propoxy group, n-butoxy group, n- Hexyloxy group, 2-ethylhexyloxy group and the like are mentioned. As the aryloxy group, phenoxy group, p-methylphenoxy group, o-methylphenoxy group, p-chlorophenoxy group, o-chlorophenoxy group, p-hydroxy A phenoxy group, o-hydroxyphenoxy group, etc. are mentioned.

In the general formula (1), when n is 0, X is an oxygen atom, and Y ¹ and Y ² are hydrogen atoms, 9,10-ethanoanthracene-11,12- shown in the general formula (5) It becomes a dicarboxylic acid anhydride compound.

In the general formula (5), R ¹ and R ⁴ may be the same or different and each represents a hydrogen atom or a methyl group.

In the general formula (1), when n is 1, X is an oxygen atom, and Y ¹ and Y ² are hydrogen atoms, 9,10-ethanoanthracene-11 shown in the general formula (6) , 12-dicarboxylic anhydride compound.

In the general formula (6), R ¹ and R ⁴ may be the same or different and each represents a hydrogen atom or a methyl group, either R ² or R ³ represents a hydrogen atom, and the other represents hydrogen. An atom, a methyl group or an ethyl group is shown.

In the general formula (1), when n is 0, X is a nitrogen atom to which an aryl group is bonded, R ⁴ is a hydrogen atom, and Y ¹ and Y ² are hydrogen atoms, The 9,10-ethanoanthracene-11,12-maleimide compound represented by formula (7) is obtained.

In the general formula (7), Ar represents an aryl group, and R ¹ represents a hydrogen atom or a methyl group. In the general formula (7), the aryl group represented by Ar includes a phenyl group, a p-tolyl group, an m-tolyl group, an o-tolyl group, a p-chlorophenyl group, an m-chlorophenyl group, and a p-hydroxyphenyl group. , P-methoxyphenyl group, p-carboxyphenyl group, 1-naphthyl group, 2-naphthyl group and the like.

Furthermore, in the general formula (1), when n is 1, X is a nitrogen atom to which an aryl group is bonded, R ⁴ is a hydrogen atom, and Y ¹ and Y ² are hydrogen atoms, The 9,10-ethanoanthracene-11,12-maleimide compound represented by the general formula (8) is obtained.

In the general formula (8), Ar represents an aryl group, R ¹ represents a hydrogen atom or a methyl group, one of R ² or R ³ represents a hydrogen atom, and the other represents a hydrogen atom, a methyl group or an ethyl group. Indicates. The aryl group represented by Ar in the general formula (8) is the same as in the compound of the general formula (7).

Examples of the compound represented by the general formula (5) include the following compounds.
9,10-dihydro-9-acryloyloxy-9,10-ethanoanthracene-11,12-dicarboxylic anhydride (compound of the following structural formula (5-1)), 9,10-dihydro-9-methacryloyloxy- 9,10-ethanoanthracene-11,12-dicarboxylic anhydride (compound of the following structural formula (5-2)), 9,10-dihydro-9-acryloyloxy-12-methyl-9,10-ethanoanthracene- 11,12-dicarboxylic anhydride, 9,10-dihydro-9-methacryloyloxy-12-methyl-9,10-ethanoanthracene-11,12-dicarboxylic anhydride.

Examples of the compound represented by the general formula (6) include the following compounds. 9,10-dihydro-9- (2-acryloyloxyethoxy) -9,10-ethanoanthracene-11,12-dicarboxylic anhydride, 9,10-dihydro-9- (2-methacryloyloxyethoxy) -9, 10-ethanoanthracene-11,12-dicarboxylic acid anhydride, 9,10-dihydro-9- (2-acryloyloxyethoxy) -12-methyl-9,10-ethanoanthracene-11,12-dicarboxylic acid anhydride ( Compound of the following structural formula (6-1)), 9,10-dihydro-9- (2-methacryloyloxyethoxy) -12-methyl-9,10-ethanoanthracene-11,12-dicarboxylic anhydride, 9, 10-dihydro-9- (2-acryloyloxypropoxy) -9,10-ethanoanthracene-11,12-dicarboxylic acid Anhydride, 9,10-Dihydro-9- (1-methyl-2-acryloyloxyethoxy) -9,10-ethanoanthracene-11,12-dicarboxylic anhydride, 9,10-dihydro-9- (2- Methacryloyloxypropoxy) -9,10-ethanoanthracene-11,12-dicarboxylic anhydride, 9,10-dihydro-9- (1-methyl-2-methacryloyloxyethoxy) -9,10-ethanoanthracene-11 12-dicarboxylic anhydride, 9,10-dihydro-9- (2-acryloyloxypropoxy) -12-methyl-9,10-ethanoanthracene-11,12-dicarboxylic anhydride, 9,10-dihydro-9 -(1-methyl-2-acryloyloxyethoxy) -12-methyl-9,10-ethanoanthracene-11, 2-dicarboxylic anhydride, 9,10-dihydro-9- (2-methacryloyloxypropoxy) -12-methyl-9,10-ethanoanthracene-11,12-dicarboxylic anhydride, 9,10-dihydro-9 -(1-methyl-2-methacryloyloxyethoxy) -12-methyl-9,10-ethanoanthracene-11,12-dicarboxylic acid anhydride and the like.

In the exemplified compounds, 9,10-dihydro-9- (2-acryloyloxypropoxy) -9,10-ethanoanthracene-11,12-dicarboxylic anhydride and 9,10-dihydro-9- (1-methyl- 2-acryloyloxyethoxy) -9,10-ethanoanthracene-11,12-dicarboxylic anhydride, 9,10-dihydro-9- (2-methacryloyloxypropoxy) -9,10-ethanoanthracene-11,12- A compound such as dicarboxylic acid anhydride and 9,10-dihydro-9- (1-methyl-2-methacryloyloxyethoxy) -9,10-ethanoanthracene-11,12-dicarboxylic acid anhydride is 9,10-ethanoic acid. It is a substituent in the hydroxyethylene group that binds the anthracene skeleton and the (meth) acryloxy group Position of the methyl group are different isomers. Hereinafter, the compound having this relationship is also referred to as an isomer in a hydroxyethylene group, including the case where the substituent is an ethyl group.

Furthermore, the following are mentioned as compounds having a substituent on the 9,10-ethanoanthracene skeleton of the compound of the general formula (5) or the general formula (6). As a compound substituted with a t-butyl group, 9,10-dihydro-2-t-butyl-9-acryloyloxy-9,10-ethanoanthracene-11,12-dicarboxylic anhydride, 9,10-dihydro- 2-t-butyl-9-methacryloyloxy-9,10-ethanoanthracene-11,12-dicarboxylic anhydride, 9,10-dihydro-2-t-butyl-9-acryloyloxy-12-methyl-9, 10-ethanoanthracene-11,12-dicarboxylic anhydride, 9,10-dihydro-2-t-butyl-9-methacryloyloxy-12-methyl-9,10-ethanoanthracene-11,12-dicarboxylic anhydride 9,10-dihydro-2-t-butyl-9- (2-acryloyloxyethoxy) -9,10-ethanoanthracene-1 , 12-dicarboxylic anhydride, 9,10-dihydro-2-t-butyl-9- (2-methacryloyloxyethoxy) -9,10-ethanoanthracene-11,12-dicarboxylic anhydride, 9,10- Dihydro-2-t-butyl-9- (2-acryloyloxyethoxy) -12-methyl-9,10-ethanoanthracene-11,12-dicarboxylic anhydride, 9,10-dihydro-2-t-butyl- 9- (2-Methacryloyloxyethoxy) -12-methyl-9,10-ethanoanthracene-11,12-dicarboxylic anhydride, 9,10-dihydro-2-t-butyl-9- (2-acryloyloxypropoxy) ) -9,10-ethanoanthracene-11,12-dicarboxylic anhydride, 9,10-dihydro-2-tert-butyl-9- (2-meta) Acryloyloxypropoxy) -9,10-ethanoanthracene-11,12-dicarboxylic anhydride, 9,10-dihydro-2-t-butyl-9- (2-acryloyloxypropoxy) -12-methyl-9, 10-ethanoanthracene-11,12-dicarboxylic anhydride, 9,10-dihydro-2-tert-butyl-9- (2-methacryloyloxypropoxy) -12-methyl-9,10-ethanoanthracene-11,12 -Dicarboxylic acid anhydrides, and isomers of hydroxyethylene groups of these compounds.

Further, as a compound substituted with a methyl group, 9,10-dihydro-2-methyl-9-acryloyloxy-9,10-ethanoanthracene-11,12-dicarboxylic anhydride, 9,10-dihydro-2 -Methyl-9-methacryloyloxy-9,10-ethanoanthracene-11,12-dicarboxylic anhydride, 9,10-dihydro-2-methyl-9-acryloyloxy-12-methyl-9,10-ethanoanthracene- 11,12-dicarboxylic anhydride, 9,10-dihydro-2-methyl-9-methacryloyloxy-12-methyl-9,10-ethanoanthracene-11,12-dicarboxylic anhydride, 9,10-dihydro- 2-Methyl-9- (2-acryloyloxyethoxy) -9,10-ethanoanthracene-11,12- Carboxylic anhydride, 9,10-dihydro-2-methyl-9- (2-methacryloyloxyethoxy) -9,10-ethanoanthracene-11,12-dicarboxylic anhydride, 9,10-dihydro-2-methyl -9- (2-acryloyloxyethoxy) -12-methyl-9,10-ethanoanthracene-11,12-dicarboxylic anhydride, 9,10-dihydro-2-methyl-9- (2-methacryloyloxyethoxy) -12-methyl-9,10-ethanoanthracene-11,12-dicarboxylic anhydride, 9,10-dihydro-2-methyl-9- (2-acryloyloxypropoxy) -9,10-ethanoanthracene-11 12-dicarboxylic anhydride, 9,10-dihydro-2-methyl-9- (2-methacryloyloxypropoxy)- 9,10-ethanoanthracene-11,12-dicarboxylic anhydride, 9,10-dihydro-2-methyl-9- (2-acryloyloxypropoxy) -12-methyl-9,10-ethanoanthracene-11,12 -Dicarboxylic anhydride, 9,10-dihydro-2-methyl-9- (2-methacryloyloxypropoxy) -12-methyl-9,10-ethanoanthracene-11,12-dicarboxylic anhydride, and compounds thereof Isomers of the hydroxyethylene group.

Further, as a compound substituted with a chloro group, 9,10-dihydro-2-chloro-9-acryloyloxy-9,10-ethanoanthracene-11,12-dicarboxylic anhydride, 9,10-dihydro-2- Chlor-9-methacryloyloxy-9,10-ethanoanthracene-11,12-dicarboxylic anhydride, 9,10-dihydro-2-chloro-9-acryloyloxy-12-methyl-9,10-ethanoanthracene-11 , 12-dicarboxylic anhydride, 9,10-dihydro-2-chloro-9-methacryloyloxy-12-methyl-9,10-ethanoanthracene-11,12-dicarboxylic anhydride, 9,10-dihydro-2 -Chloro-9- (2-acryloyloxyethoxy) -9,10-ethanoanthracene-11,12-dicar Acid anhydride, 9,10-dihydro-2-chloro-9- (2-methacryloyloxyethoxy) -9,10-ethanoanthracene-11,12-dicarboxylic acid anhydride, 9,10-dihydro-2-chloro -9- (2-acryloyloxyethoxy) -12-methyl-9,10-ethanoanthracene-11,12-dicarboxylic anhydride, 9,10-dihydro-2-chloro-9- (2-methacryloyloxyethoxy) -12-methyl-9,10-ethanoanthracene-11,12-dicarboxylic anhydride, 9,10-dihydro-2-chloro-9- (2-acryloyloxypropoxy) -9,10-ethanoanthracene-11 12-dicarboxylic anhydride, 9,10-dihydro-2-chloro-9- (2-methacryloyloxypropoxy) -9,1 Ethanoanthracene-11,12-dicarboxylic anhydride, 9,10-dihydro-2-chloro-9- (2-acryloyloxypropoxy) -12-methyl-9,10-ethanoanthracene-11,12-dicarboxylic acid Anhydride, 9,10-dihydro-2-chloro-9- (2-methacryloyloxypropoxy) -12-methyl-9,10-ethanoanthracene-11,12-dicarboxylic anhydride, and hydroxyethylene of these compounds And isomers in the group.

In the general formula (1), the compound in which n is 2 or more, X is an oxygen atom, and Y ¹ and Y ² are hydrogen atoms is 9,10-dihydro-9- [2- (Acryloyloxyethoxy) ethoxy] -9,10-ethanoanthracene-11,12-dicarboxylic anhydride, 9,10-dihydro-9- [2- (methacryloyloxyethoxy) ethoxy] -9,10-ethanoanthracene- 11,12-dicarboxylic anhydride, 9,10-dihydro-9- [2- (acryloyloxyethoxy) ethoxy] -12-methyl-9,10-ethanoanthracene-11,12-dicarboxylic anhydride, 10-dihydro-9- [2- (methacryloyloxyethoxy) ethoxy] -12-methyl-9,10-ethanoanthracene-11,12- Carboxylic anhydride, 9,10-dihydro-9- [2- (acryloyloxypropoxy) propoxy] -9,10-ethanoanthracene-11,12-dicarboxylic anhydride, 9,10-dihydro-9- [2 -(Methacryloyloxypropoxy) propoxy] -9,10-ethanoanthracene-11,12-dicarboxylic anhydride, 9,10-dihydro-9- [2- (acryloyloxypropoxy) propoxy] -12-methyl-9, 10-ethanoanthracene-11,12-dicarboxylic anhydride, 9,10-dihydro-9- [2- (methacryloyloxypropoxy) propoxy] -12-methyl-9,10-ethanoanthracene-11,12-dicarboxylic acid Anhydride, 9,10-dihydro-9- {2- [2- (2-acryloyloxyate) C) Ethoxy] ethoxy} -9,10-ethanoanthracene-11,12-dicarboxylic anhydride, 9,10-dihydro-9- {2- [2- (2-acryloyloxyethoxy) ethoxy] ethoxy} -9 , 10-ethanoanthracene-11,12-dicarboxylic anhydride, and isomers of these compounds in the hydroxyethylene group.

Similarly, in the general formula (1), n is 2 or more, X is an oxygen atom, and Y ¹ and Y ² are hydrogen atoms. Examples include compounds substituted at the position with a t-butyl group, a methyl group or a chloro group.

Next, the following compound is mentioned as an example of a compound represented by General formula (7).
9,10-dihydro-9-acryloyloxy-9,10-ethanoanthracene-11,12-dicarboxylic acid-N-phenylimide, 9,10-dihydro-9-methacryloyloxy-9,10-ethanoanthracene-11 12-dicarboxylic acid-N-phenylimide (compound of the following structural formula (7-1)), 9,10-dihydro-9-acryloyloxy-9,10-ethanoanthracene-11,12-dicarboxylic acid-N- ( p-tolyl) imide, 9,10-dihydro-9-methacryloyloxy-9,10-ethanoanthracene-11,12-dicarboxylic acid-N-tolylimide, 9,10-dihydro-9-acryloyloxy-9,10- Ethanoanthracene-11,12-dicarboxylic acid-N- (p-chlorophenyl) imide, 9,10-di Mud-9-methacryloyloxy-9,10 ethanolate anthracene-11,12-N-dicarboxylic acid (p- methoxyphenyl) imide.

Moreover, the following compound is mentioned as an example of a compound represented by General formula (8). 9,10-dihydro-9- (2-acryloyloxyethoxy) -9,10-ethanoanthracene-11,12-dicarboxylic acid-N-phenylimide, 9,10-dihydro-9- (2-methacryloyloxyethoxy) -9,10-ethanoanthracene-11,12-dicarboxylic acid-N-phenylimide, 9,10-dihydro-9- (2-acryloyloxyethoxy) -9,10-ethanoanthracene-11,12-dicarboxylic acid N-phenylimide, 9,10-dihydro-9- (2-methacryloyloxyethoxy) -9,10-ethanoanthracene-11,12-dicarboxylic acid-N-phenylimide, 9,10-dihydro-9- (2 -Acryloyloxypropoxy) -9,10-ethanoanthracene-11,12-dicarboxylic acid- -Phenylimide, 9,10-dihydro-9- (2-methacryloyloxypropoxy) -9,10-ethanoanthracene-11,12-dicarboxylic acid-N-phenylimide, 9,10-dihydro-9- (2- (Acryloyloxypropoxy) -9,10-ethanoanthracene-11,12-dicarboxylic acid-N-phenylimide, 9,10-dihydro-9- (2-methacryloyloxypropoxy) -9,10-ethanoanthracene-11,12 -Dicarboxylic acid-N-phenylimide and isomers of hydroxyethylene groups of these compounds.

Furthermore, the following are mentioned as compounds having a substituent on the 9,10-ethanoanthracene skeleton of the compound of the general formula (7) or the general formula (8). As a compound substituted with a t-butyl group, 9,10-dihydro-2-t-butyl-9-acryloyloxy-9,10-ethanoanthracene-11,12-dicarboxylic acid-N-phenylimide, 9,10 -Dihydro-2-t-butyl-9-methacryloyloxy-9,10-ethanoanthracene-11,12-dicarboxylic acid-N-phenylimide, 9,10-dihydro-2-t-butyl-9-acryloyloxy- 9,10-ethanoanthracene-11,12-dicarboxylic acid-N-tolylimide, 9,10-dihydro-2-t-butyl-9-methacryloyloxy-9,10-ethanoanthracene-11,12-dicarboxylic acid-N -Phenylimide, 9,10-dihydro-2-t-butyl-9- (2-acryloyloxyethoxy) -9,1 Ethanoanthracene-11,12-dicarboxylic acid-N-phenylimide, 9,10-dihydro-2-tert-butyl-9- (2-methacryloyloxyethoxy) -9,10-ethanoanthracene-11,12-dicarboxylic Acid-N-phenylimide, 9,10-dihydro-2-t-butyl-9- (2-acryloyloxyethoxy) -9,10-ethanoanthracene-11,12-dicarboxylic acid-N-phenylimide, 10-dihydro-2-t-butyl-9- (2-methacryloyloxyethoxy) -9,10-ethanoanthracene-11,12-dicarboxylic acid-N-phenylimide, 9,10-dihydro-2-t-butyl -9- (2-acryloyloxypropoxy) -9,10-ethanoanthracene-11,12-dicarboxylic acid-N Phenylimide, 9,10-dihydro-2-t-butyl-9- (2-methacryloyloxypropoxy) -9,10-ethanoanthracene-11,12-dicarboxylic acid-N-phenylimide, 9,10-dihydro- 2-t-butyl-9- (2-acryloyloxypropoxy) -9,10-ethanoanthracene-11,12-dicarboxylic acid-N-phenylimide, 9,10-dihydro-2-t-butyl-9- ( 2-methacryloyloxypropoxy) -9,10-ethanoanthracene-11,12-dicarboxylic acid-N-phenylimide, and isomers of these compounds in the hydroxyethylene group.

Furthermore, as a compound substituted with a methyl group, 9,10-dihydro-2-methyl-9-acryloyloxy-9,10-ethanoanthracene-11,12-dicarboxylic acid-N-phenylimide, 9,10- Dihydro-2-methyl-9-methacryloyloxy-9,10-ethanoanthracene-11,12-dicarboxylic acid-N-phenylimide, 9,10-dihydro-2-methyl-9-acryloyloxy-9,10-ethano Anthracene-11,12-dicarboxylic acid-N-tolylimide, 9,10-dihydro-2-methyl-9-methacryloyloxy-9,10-ethanoanthracene-11,12-dicarboxylic acid-N-phenylimide, 9,10 -Dihydro-2-methyl-9- (2-acryloyloxyethoxy) -9,10-ethano Nthracene-11,12-dicarboxylic acid-N-phenylimide, 9,10-dihydro-2-methyl-9- (2-methacryloyloxyethoxy) -9,10-ethanoanthracene-11,12-dicarboxylic acid-N- Phenylimide, 9,10-dihydro-2-methyl-9- (2-acryloyloxyethoxy) -9,10-ethanoanthracene-11,12-dicarboxylic acid-N-phenylimide, 9,10-dihydro-2- Methyl-9- (2-methacryloyloxyethoxy) -9,10-ethanoanthracene-11,12-dicarboxylic acid-N-phenylimide, 9,10-dihydro-2-methyl-9- (2-acryloyloxypropoxy) -9,10-ethanoanthracene-11,12-dicarboxylic acid-N-phenylimide, 9,10 Dihydro-2-methyl-9- (2-methacryloyloxypropoxy) -9,10-ethanoanthracene-11,12-dicarboxylic acid-N-phenylimide, 9,10-dihydro-2-methyl-9- (2- (Acryloyloxypropoxy) -9,10-ethanoanthracene-11,12-dicarboxylic acid-N-phenylimide, 9,10-dihydro-2-methyl-9- (2-methacryloyloxypropoxy) -9,10-ethanoanthracene -11,12-dicarboxylic acid-N-phenylimide, and isomers of hydroxyethylene groups of these compounds.

Furthermore, as a compound substituted with a chloro group, 9,10-dihydro-2-chloro-9-acryloyloxy-9,10-ethanoanthracene-11,12-dicarboxylic acid-N-phenylimide, 9,10-dihydro 2-Chloro-9-methacryloyloxy-9,10-ethanoanthracene-11,12-dicarboxylic acid-N-phenylimide, 9,10-dihydro-2-chloro-9-acryloyloxy-9,10-ethanoanthracene -11,12-dicarboxylic acid-N-tolylimide, 9,10-dihydro-2-chloro-9-methacryloyloxy-9,10-ethanoanthracene-11,12-dicarboxylic acid-N-phenylimide, 9,10- Dihydro-2-chloro-9- (2-acryloyloxyethoxy) -9,10-ethanoant Sen-11,12-dicarboxylic acid-N-phenylimide, 9,10-dihydro-2-chloro-9- (2-methacryloyloxyethoxy) -9,10-ethanoanthracene-11,12-dicarboxylic acid-N- Phenylimide, 9,10-dihydro-2-chloro-9- (2-acryloyloxyethoxy) -9,10-ethanoanthracene-11,12-dicarboxylic acid-N-phenylimide, 9,10-dihydro-2- Chlor-9- (2-methacryloyloxyethoxy) -9,10-ethanoanthracene-11,12-dicarboxylic acid-N-phenylimide, 9,10-dihydro-2-chloro-9- (2-acryloyloxypropoxy) -9,10-ethanoanthracene-11,12-dicarboxylic acid-N-phenylimide, 9,10-dihy Ro-2-chloro-9- (2-methacryloyloxypropoxy) -9,10-ethanoanthracene-11,12-dicarboxylic acid-N-phenylimide, 9,10-dihydro-2-chloro-9- (2- (Acryloyloxypropoxy) -9,10-ethanoanthracene-11,12-dicarboxylic acid-N-phenylimide, 9,10-dihydro-2-chloro-9- (2-methacryloyloxypropoxy) -9,10-ethanoanthracene -11,12-dicarboxylic acid-N-phenylimide, and isomers of hydroxyethylene groups of these compounds.

In the general formula (1), when n is 2 or more, X is a nitrogen atom to which an aryl group is bonded, and Y ¹ and Y ² are hydrogen atoms, 9,10-dihydro -9- [2- (acryloyloxyethoxy) ethoxy] -9,10-ethanoanthracene-11,12-dicarboxylic acid-N-phenylimide, 9,10-dihydro-9- [2- (methacryloyloxyethoxy) ethoxy ] -9,10-ethanoanthracene-11,12-dicarboxylic acid-N-phenylimide, 9,10-dihydro-9- [2- (acryloyloxyethoxy) ethoxy] -9,10-ethanoanthracene-11,12 -Dicarboxylic acid-N-phenylimide, 9,10-dihydro-9- [2- (methacryloyloxyethoxy) ethoxy] -9,1 Ethanoanthracene-11,12-dicarboxylic acid-N-phenylimide, 9,10-dihydro-9- [2- (acryloyloxypropoxy) propoxy] -9,10-ethanoanthracene-11,12-dicarboxylic acid-N -Phenylimide, 9,10-dihydro-9- [2- (methacryloyloxypropoxy) propoxy] -9,10-ethanoanthracene-11,12-dicarboxylic acid-N-phenylimide, 9,10-dihydro-9- [2- (Acryloyloxypropoxy) propoxy] -9,10-ethanoanthracene-11,12-dicarboxylic acid-N-phenylimide, 9,10-dihydro-9- [2- (methacryloyloxypropoxy) propoxy] -9 , 10-Ethanoanthracene-11,12-dicarboxylic acid-N-fur Enylimide, 9,10-dihydro-9- {2- [2- (2-acryloyloxyethoxy) ethoxy] ethoxy} -9,10-ethanoanthracene-11,12-dicarboxylic acid-N-phenylimide, 9,10 -Dihydro-9- {2- [2- (2-acryloyloxyethoxy) ethoxy] ethoxy} -9,10-ethanoanthracene-11,12-dicarboxylic acid-N-tolylimide, and the hydroxyethylene group of these compounds Examples include isomers.

Furthermore, similarly, in the general formula (1), n is 2 or more, X is a nitrogen atom to which an aryl group is bonded, and 9, 10 of the exemplary compounds in the case where Y ¹ and Y ² are hydrogen atoms -A compound substituted at the 2-position of the ethanoanthracene skeleton with a t-butyl group, a methyl group, a chloro group or the like can be mentioned.

Next, a method for producing a mono (meth) acrylate compound having a 9,10-ethanoanthracene skeleton of the general formula (1) will be described. As shown in FIG. 1, there are two synthesis routes of A route and B route. Is possible.

In the method shown in Route A, a hydroxy compound having an anthracene skeleton represented by general formula (9) is first (meth) acrylated to obtain a (meth) acrylate compound having an anthracene skeleton represented by general formula (2), and then a dienophile and In this method, a (meth) acrylate compound having a 9,10-ethanoanthracene skeleton represented by the general formula (1) is obtained by the Diels-Alder reaction. Next, in the method shown in Route B, first, a hydroxy compound having an anthracene skeleton represented by general formula (9) is reacted with Genophyl and Diels-Alder to have a 9,10-ethanoanthracene skeleton represented by general formula (4). This is a method for obtaining a (meth) acrylate compound having a 9,10-ethanoanthracene skeleton represented by the general formula (1) by making a hydroxy compound and then (meth) acrylating this.

First, a hydroxy compound having an anthracene skeleton represented by the general formula (9), which is a starting material for both routes, can be synthesized as follows.

In the general formula (9), n represents an integer of 0 or more and less than 10, and Y ¹ and Y ² may be the same or different, and may be a hydrogen atom, an alkyl group, a halogen atom, a hydroxyl group, an alkoxy group or An aryloxy group, wherein either R ² or R ³ represents a hydrogen atom, and the other represents a hydrogen atom, a methyl group or an ethyl group;

First, in the general formula (9), when n is 0, a 9-anthanol compound is obtained. This can be synthesized by isomerizing the corresponding 9-anthrone compound. Since the 9-anthrone compound can be synthesized from the 9,10-anthraquinone compound, the 9-anthranol compound is an industrially easily available compound among the anthracene compound group in which the hydroxyl group is substituted.

In general, as an agent used for isomerization of 9-anthrone compounds, both acids and bases can be used. Examples of the acid include inorganic acids such as hydrochloric acid, sulfuric acid and nitric acid, organic acids such as methanesulfonic acid and p-toluenesulfonic acid, and solid acids such as aluminum oxide and acidic ion exchange resins. Examples of the base include alkali metal salts such as sodium hydroxide and potassium hydroxide, and organic bases such as pyridine, piperidine and triethylamine. The isomerization reaction is usually performed in the presence of a solvent. Solvents include nitrile solvents such as acetonitrile, ketone solvents such as acetone, methyl ethyl ketone, methyl-i-butyl ketone and cyclohexanone, alcohol solvents such as methanol, ethanol and propanol, amide solvents such as dimethylformamide and dimethylacetamide, Examples include basic solvents such as pyridine and N-methylpyrrolidone. Usually, the isomerization of the 9-anthrone compound to the 9-anthranol compound is completed by heating at 80 ° C. to 120 ° C. for 30 minutes to 2 hours. The 9-anthranol compound thus obtained is used in the next reaction without isolation.

Next, n is a compound having 1 or more, which can be synthesized by reacting a 9-anthanol compound with ethylene oxide, propylene oxide or butylene oxide.

In this reaction, alkylene oxide such as ethylene oxide is ring-opened in the presence of an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide, and etherified with a 9-anthanol compound. Solvents used in this etherification reaction include water, alcohol solvents such as methanol, ethanol, propyl alcohol, ethylene glycol, and propylene glycol, protic solvents such as dimethylformamide and diethylformamide, or methyl ethyl ketone and methyl isobutyl ketone. Ketone solvents and water-soluble ether solvents such as tetrahydrofuran are used. Moreover, these mixed solvents may be sufficient.

The reaction between the 9-anthanol compound and the alkylene oxide depends on the kind and amount of the alkali to be added and other conditions, but the preferred reaction temperature is 10 ° C. or more and 80 ° C. or less, and the reaction time is 1 hour or more. 5 hours or less. The reaction pressure is 0.2 MPa or more and 0.5 MPa or less.

In the reaction with alkylene oxide, when obtaining a compound with n = 1, the amount of alkylene oxide used varies depending on the reaction conditions, but is preferably 1 to 5 moles per 9-anthranol compound. Usually, the compound of n = 1 is mainly produced, and the compound of n = 2 and n = 3 and the compound having a large number of n begin to be produced as the alkylene oxide is excessively added. The compound of n = 1 and the compound of n = 2 or more have different solubility in the reaction solvent, and the compound of n = 2 or more dissolves well in the reaction solvent. Therefore, by filtering the dissolved compound of n = 2 or more, , N = 1 and n = 2 or more can be separated. When alkylene oxide is used in a large excess amount of 5 moles or more, the formation of an addition reaction product of n = 2 or more becomes dominant, and the product becomes a mixture of compounds having different values of n. From the solution containing the adduct of n = 2 or more, the compound of n = 2 or more can be further separated by recrystallization or column treatment.

When propylene oxide or butylene oxide is used as the alkylene oxide, R ² in the general formula (9) becomes a hydrogen atom and R ³ becomes a methyl group or an ethyl group depending on the reaction position of the 9-anthranol compound and the alkylene oxide. And a compound in which R ² is a methyl group or an ethyl group and R ³ is a hydrogen atom. In general, since the oxygen anion attacks a carbon atom having a small steric hindrance in the alkylene oxide, a compound in which R ² is a methyl group or an ethyl group and R ³ is a hydrogen atom is mainly produced. Any of these isomers can be used as a raw material for synthesizing the mono (meth) acrylate compound having the 9,10-ethanoanthracene skeleton of the present invention. Moreover, it is also possible to use it as a raw material for synthesizing a mono (meth) acrylate compound having a 9,10-ethanoanthracene skeleton without separating these isomers. A mixture of mono (meth) acrylate compounds having a 9,10-ethanoanthracene skeleton also shows a high refractive index, does not have UV absorption at 250 nm or more, and becomes a radically polymerizable compound.

Next, a method for producing the compound of the general formula (1) via route A will be described. In this route, first, an anthracene compound represented by general formula (9) is reacted with acryloyl chloride or methacryloyl chloride in the presence or absence of a base to synthesize a compound of general formula (2).

In the general formula (2), n represents an integer of 0 or more and less than 10, R ¹ represents either a hydrogen atom or a methyl group, either R ² or R ³ represents a hydrogen atom, and the other represents hydrogen. An atom, a methyl group or an ethyl group is shown, Y ¹ and Y ² may be the same or different and each represents a hydrogen atom, an alkyl group, a halogen atom, a hydroxyl group, an alkoxy group or an aryloxy group.

Examples of the alkyl group represented by Y ¹ and Y ² in the general formula (2) include a methyl group, an ethyl group, a t-butyl group, and an i-amyl group, and the halogen atom includes a fluorine atom, a chlorine atom, Examples of the alkoxy group include methoxy group, ethoxy group, n-propoxy group, and n-butoxy group. Examples of the aryloxy group include phenoxy group, p-tolyloxy group, and p-chloro group. A phenoxy group etc. are mentioned.

  Examples of the compound represented by the general formula (2) include the following. 9-acryloyloxyanthracene, 9-methacryloyloxyanthracene, 9- (2-acryloyloxyethoxy) anthracene, 9- (2-acryloyloxypropoxy) anthracene, 9- (2-acryloyloxybutoxy) anthracene, 9- (2-methacryloyloxyethoxy) anthracene, 9- (2-methacryloyloxypropoxy) anthracene, 9- (2-methacryloyloxybutoxy) anthracene, 9- [2- (2-acryloyloxyethoxy) ethoxy] anthracene, 9- [ 2- (2-methacryloyloxyethoxy) ethoxy] anthracene and isomers of these compounds in the hydroxyethylene group.

Furthermore, examples of the compound substituted at the 2-position of the anthracene skeleton with a t-butyl group include 2-t-butyl-9-acryloyloxyanthracene, 2-t-butyl-9-methacryloyloxyanthracene, 2-t -Butyl-9- (2-acryloyloxyethoxy) anthracene, 2-t-butyl-9- (2-acryloyloxypropoxy) anthracene, 2-t-butyl-9- (2-acryloyloxybutoxy) anthracene, 2- t-butyl-9- (2-methacryloyloxyethoxy) anthracene, 2-t-butyl-9- (2-methacryloyloxypropoxy) anthracene, 2-t-butyl-9- (2-methacryloyloxybutoxy) anthracene, 2 -T-Butyl-9- [2- (2-acryloyloxyethoxy) ester Carboxymethyl] anthracene, and isomers, and the like in the hydroxyethylene group of these compounds.

Further, as a compound substituted with a methyl group, 2-methyl-9-acryloyloxyanthracene, 2-methyl-9-methacryloyloxyanthracene, 2-methyl-9- (2-acryloyloxyethoxy) anthracene, 2- Methyl-9- (2-acryloyloxypropoxy) anthracene, 2-methyl-9- (2-acryloyloxybutoxy) anthracene, 2-methyl-9- (2-methacryloyloxyethoxy) anthracene, 2-methyl-9- ( 2-Methacryloyloxypropoxy) anthracene, 2-methyl-9- (2-methacryloyloxybutoxy) anthracene, 2-methyl-9- [2- (2-acryloyloxyethoxy) ethoxy] anthracene, and hydroxyethylene of these compounds Based on That isomers, and the like.

Further, examples of the compound substituted with a methyl group include 2-chloro-9-acryloyloxyanthracene, 2-chloro-9-methacryloyloxyanthracene, 2-chloro-9- (2-acryloyloxyethoxy) anthracene, 2- Chlor-9- (2-acryloyloxypropoxy) anthracene, 2-chloro-9- (2-acryloyloxybutoxy) anthracene, 2-chloro-9- (2-methacryloyloxyethoxy) anthracene, 2-chloro-9- ( 2-Methacryloyloxypropoxy) anthracene, 2-chloro-9- (2-methacryloyloxybutoxy) anthracene, 2-chloro-9- [2- (2-acryloyloxyethoxy) ethoxy] anthracene, and hydroxyethylenes of these compounds Based on That isomers, and the like.

Examples of the base that can be used when the anthracene compound represented by the general formula (9) is reacted with acryloyl chloride or methacryloyl chloride include, for example, trimethylamine, triethylamine, tributylamine, pyridine, α-picoline, β-picoline, and γ-picoline. , Piperidine and the like. The reaction is generally carried out in a solvent. Examples of the solvent used include aromatic solvents such as benzene, toluene, xylene and chlorobenzene, halogenated carbon solvents such as methylene chloride, dichloroethane and dichloroethylene, acetone. A ketone solvent such as methyl ethyl ketone and methyl isobutyl ketone, an amide solvent such as N-methylpyrrolidone and dimethylformamide, and an ether solvent such as tetrahydrofuran and 1,4-dioxane are preferably used. The addition amount of acryloyl chloride or methacryloyl chloride to the anthracene compound represented by the general formula (9) is 1 to 6 times, preferably 1.2 to 4 times. The reaction temperature is 0 ° C to 80 ° C, preferably 0 ° C to 20 ° C. This reaction is exothermic and requires cooling. The reaction time is about 15 to 60 minutes. After completion of the reaction, water or methanol is added to hydrate the unreacted acryloyl chloride or methacryloyl chloride, and then the hydrochloride is removed by filtration. Then, water is added to the filtrate to crystallize, Crystals can be isolated by filtration.

Next, the compound of the general formula (1) can be obtained by subjecting the compound of the general formula (2) thus obtained and the dienophile represented by the general formula (3) to a Diels-Alder reaction.

In the general formula (3), R ⁴ represents a hydrogen atom or a methyl group, and X represents a nitrogen atom to which a hydrogen atom, an alkyl group or an aryl group is bonded, or an oxygen atom.

Examples of the dienophile represented by the general formula (3) include maleic anhydride and citraconic anhydride when X is an oxygen atom. When X is a nitrogen atom to which a hydrogen atom, an alkyl group or an aryl group is bonded, a maleimide compound is obtained, and a maleimide having a hydrogen atom bonded thereto, an N-methylmaleimide having an alkyl group bonded thereto, N-ethylmaleimide, N-propylmaleimide N-dodecylmaleimide, N-cyclohexylmaleimide, N- (2-carboxyethyl) maleimide, N-benzylmaleimide and the like, and N-phenylmaleimide, N-tolylmaleimide, N- (p-chlorophenyl) to which an aryl group is bonded. ) Maleimide, N- (p-methoxyphenyl) maleimide and the like.

The Diels-Alder reaction between an acrylate compound containing an anthracene skeleton represented by general formula (2) and a maleic anhydride, citraconic anhydride or maleimide compound, which is a dienophile of general formula (3), is generally carried out in a solvent. The Examples of the solvent include aromatic solvents such as benzene, toluene and xylene, alcohol solvents such as methanol, ethanol, n-propyl alcohol and n-butyl alcohol, and ether solvents such as tetrahydrofuran and 1,4-dioxane. Nitrile solvents such as acetonitrile and propionitrile, ketone solvents such as acetone, methyl ethyl ketone and cyclohexaneone, amide solvents such as dimethylformamide and dimethylacetamide, and organic acid solvents such as acetic acid, propionic acid and butyric acid are suitable. Can be used. Of course, a reaction without solvent is also possible.

The reaction temperature is preferably 80 ° C. or higher and 160 ° C. or lower, more preferably 100 ° C. or higher and 130 ° C. or lower. If it is less than 80 degreeC, advancing of reaction is slow, and a raw material remains, and when it exceeds 160 degreeC, a side reaction will arise and the purity of a product will fall, and it is not preferable.

The addition ratio of the dienophile such as maleic anhydride, citraconic anhydride or maleimide compound to the anthracene compound is generally 1 mol times or more and 4 mol times or less. If it is less than 1 mol, the raw material anthracene compound remains, and if it exceeds 4 mol, dienophile is mixed into the product and the purity of the product is lowered, which is not preferable.

When the reaction rate of the Diels-Alder reaction is slow, a catalyst can be used to increase the reaction rate. As the catalyst, boron trifluoride or the like is preferably used. The concentration of the catalyst is preferably 0.1% by weight or more and 20% by weight or less based on the anthracene compound. More preferably, it is 2% by weight or more and 10% by weight or less. If the amount is less than 0.1% by weight, the reaction rate is slow and it takes too much time to complete the reaction. If the amount exceeds 20% by weight, coloring or the like proceeds and the purity of the product decreases.

In the Diels-Alder reaction, a polymerization inhibitor may be present in order to prevent polymerization reaction of acryloyl group or methacryloyl group. As the polymerization inhibitor, hydroquinone, 4-methoxyphenol (methoquinone) or the like is used. The addition amount of the polymerization inhibitor is preferably 0.1 to 5% by weight based on the anthracene compound.

After completion of the reaction, the reaction solution is cooled, and then a poor solvent such as methanol, ethanol, n-hexane or the like is added and concentrated to give a 9,10-ethanoanthracene skeleton represented by the general formula (1). Colorless to white-yellow crystals of the mono (meth) acrylate compound can be obtained. As a result of measuring the refractive index of the obtained mono (meth) acrylate compound having a 9,10-ethanoanthracene skeleton with an Atago refractometer T1, it was found to have a higher refractive index than commercially available acrylates.

Next, a method for producing the compound of the general formula (1) via route B will be described. In this route, first, an anthracene compound represented by the general formula (9) is reacted with a dienophile of the above general formula (3) and a Diels-Alder reaction to synthesize a compound of the general formula (4).

In the general formula (4), n represents an integer of 0 or more and less than 10, X represents a nitrogen atom to which a hydrogen atom, an alkyl group or an aryl group is bonded, or an oxygen atom, and Y ¹ and Y ² are the same. May be different from each other, and represents a hydrogen atom, an alkyl group, a halogen atom, a hydroxyl group, an alkoxy group or an aryloxy group, one of R ^{2 and} R ³ represents a hydrogen atom, and the other represents a hydrogen atom, a methyl group Alternatively, it represents an ethyl group, and R ⁴ represents a hydrogen atom or a methyl group.

Examples of the dienophile represented by the general formula (3) include maleic anhydride and citraconic anhydride when X is an oxygen atom. When X is a nitrogen atom to which a hydrogen atom, an alkyl group or an aryl group is bonded, a maleimide compound is obtained, and a maleimide having a hydrogen atom bonded thereto, an N-methylmaleimide having an alkyl group bonded thereto, N-ethylmaleimide, N-propylmaleimide N-dodecylmaleimide, N-cyclohexylmaleimide, N- (2-carboxyethyl) maleimide, N-benzylmaleimide and the like, and N-phenylmaleimide, N-tolylmaleimide, N- (p-chlorophenyl) to which an aryl group is bonded ) Maleimide, N- (p-methoxyphenyl) maleimide and the like.

The Diels-Alder reaction of an acrylate compound containing an anthracene skeleton represented by general formula (9) and a maleic anhydride, citraconic anhydride or maleimide compound, which is a dienophile of general formula (3), is generally carried out in a solvent. . Examples of the solvent include aromatic solvents such as benzene, toluene and xylene, alcohol solvents such as methanol, ethanol, n-propyl alcohol and n-butyl alcohol, and ether solvents such as tetrahydrofuran and 1,4-dioxane. Nitrile solvents such as acetonitrile and propionitrile, ketone solvents such as acetone, methyl ethyl ketone and cyclohexaneone, amide solvents such as dimethylformamide and dimethylacetamide, and organic acid solvents such as acetic acid, propionic acid and butyric acid are suitable. Can be used. Of course, a reaction without a solvent is also possible.

The reaction temperature is preferably 80 ° C. or higher and 160 ° C. or lower, more preferably 100 ° C. or higher and 130 ° C. or lower. If it is less than 80 degreeC, advancing of reaction is slow, and a raw material remains, and when it exceeds 160 degreeC, a side reaction will arise and the purity of a product will fall, and it is not preferable.

The addition ratio of the dienophile such as maleic anhydride, citraconic anhydride or maleimide compound to the anthracene compound is generally 1 mol times or more and 4 mol times or less. If it is less than 1 mol, the raw material anthracene compound remains, and if it exceeds 4 mol, dienophile is mixed into the product and the purity of the product is lowered, which is not preferable.

When the reaction rate of the Diels-Alder reaction is slow, a catalyst can be used to increase the reaction rate. As the catalyst, boron trifluoride or the like is preferably used. The concentration of the catalyst is preferably 0.1% by weight or more and 20% by weight or less based on the anthracene compound. More preferably, it is 2% by weight or more and 10% by weight or less. If the amount is less than 0.1% by weight, the reaction rate is slow and it takes too much time to complete the reaction. If the amount exceeds 20% by weight, coloring or the like proceeds and the purity of the product decreases.

After completion of the reaction, the reaction solution is cooled, and then a poor solvent such as methanol, ethanol, n-hexane or the like is added and concentrated to give a 9,10-ethanoanthracene skeleton represented by the general formula (4). Colorless to white-yellow crystals of the hydroxy compound can be obtained.

In the general formula (4), examples of the alkyl group represented by Y ¹ or Y ² include methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, and t-butyl. Group, amyl group, 2-ethylhexyl and the like, halogen atom includes fluorine atom, chlorine atom, bromine atom and iodine atom, and alkoxy group includes methoxy group, ethoxy group, n-propoxy group, n- Examples include butoxy group and n-hexyloxy group. As aryloxy group, phenoxy group, p-methylphenoxy group, o-methylphenoxy group, p-chlorophenoxy group, o-chlorophenoxy group, p-hydroxyphenoxy group , O-hydroxyphenoxy group and the like.

Examples of the compound represented by the general formula (4) include the following. That is, first, when X is an oxygen atom and Y ¹ and Y ² are hydrogen atoms, 9,10-dihydro-9-hydroxy-9,10-ethanoanthracene-11,12-dicarboxylic acid anhydride, 9,10-dihydro-9-hydroxy-12-methyl-9,10-ethanoanthracene-11,12-dicarboxylic anhydride, 9,10-dihydro-9- (2-hydroxyethoxy) -9,10-ethano Anthracene-11,12-dicarboxylic anhydride, 9,10-dihydro-9- (2-hydroxyethoxy) -12-methyl-9,10-ethanoanthracene-11,12-dicarboxylic anhydride, 9,10- Dihydro-9- (2-hydroxypropoxy) -9,10-ethanoanthracene-11,12-dicarboxylic anhydride, 9,10-dihydro-9- 2-hydroxypropoxy) -12-methyl-9,10-ethanoanthracene-11,12-dicarboxylic anhydride, 9,10-dihydro-9- (2-hydroxybutoxy) -9,10-ethanoanthracene-11 12-dicarboxylic anhydride, 9,10-dihydro-9- (2-hydroxybutoxy) -12-methyl-9,10-ethanoanthracene-11,12-dicarboxylic anhydride, 9,10-dihydro-9- [2- (2-hydroxyethoxy) ethoxy] -9,10-ethanoanthracene-11,12-dicarboxylic anhydride, 9,10-dihydro-9- [2- (2-hydroxyethoxy) ethoxy] -12 Methyl-9,10-ethanoanthracene-11,12-dicarboxylic anhydride and the difference in hydroxyethylene group of these compounds Body, and the like.

Next, X is a nitrogen atom to which a hydrogen atom, an alkyl group or an aryl group is bonded, and Y ¹ and Y ² are hydrogen atoms. -9-hydroxy-9,10-ethanoanthracene-11,12-dicarboxylic acid-N-methylimide, 9,10-dihydro-9-hydroxy-9,10-ethanoanthracene-11,12-dicarboxylic acid-N-ethylimide 9,10-dihydro-9-hydroxy-9,10-ethanoanthracene-11,12-dicarboxylic acid-N-propylimide, 9,10-dihydro-9-hydroxy-9,10-ethanoanthracene-11,12 -Dicarboxylic acid-N-cyclohexylimide, 9,10-dihydro-9-hydroxy-9,10-ethanoanthracene-1 , 12-dicarboxylic acid-N-dodecylimide, 9,10-dihydro-9-hydroxy-9,10-ethanoanthracene-11,12-dicarboxylic acid-N-benzylimide, 9,10-dihydro-9-hydroxy- 9,10-ethanoanthracene-11,12-dicarboxylic acid-N-phenylimide, 9,10-dihydro-9-hydroxy-9,10-ethanoanthracene-11,12-dicarboxylic acid-N- (p-tolyl) Imido, 9,10-dihydro-9-hydroxy-9,10-ethanoanthracene-11,12-dicarboxylic acid-N- (p-chlorophenyl) imide, 9,10-dihydro-9-hydroxy-9,10-ethano And anthracene-11,12-dicarboxylic acid-N- (p-methoxyphenyl) imide.

Furthermore, 9,10-dihydro-9- (2-hydroxyethoxy) -9,10-ethanoanthracene-11,12-dicarboxylic acid-N-methylimide, wherein the 9-position is a 2-hydroxyethoxy group, 9,10 -Dihydro-9- (2-hydroxyethoxy) -9,10-ethanoanthracene-11,12-dicarboxylic acid-N-ethylimide, 9,10-dihydro-9- (2-hydroxyethoxy) -9,10-ethano Anthracene-11,12-dicarboxylic acid-N-propylimide, 9,10-dihydro-9- (2-hydroxyethoxy) -9,10-ethanoanthracene-11,12-dicarboxylic acid-N-cyclohexylimide, 10-dihydro-9- (2-hydroxyethoxy) -9,10-ethanoanthracene-11,12-dicarboxylic acid -N-dodecylimide, 9,10-dihydro-9- (2-hydroxyethoxy) -9,10-ethanoanthracene-11,12-dicarboxylic acid-N-benzylimide, 9,10-dihydro-9- (2 -Hydroxyethoxy) -9,10-ethanoanthracene-11,12-dicarboxylic acid-N-phenylimide, 9,10-dihydro-9- (2-hydroxyethoxy) -9,10-ethanoanthracene-11,12- Dicarboxylic acid-N- (p-tolyl) imide, 9,10-dihydro-9- (2-hydroxyethoxy) -9,10-ethanoanthracene-11,12-dicarboxylic acid-N- (p-chlorophenyl) imide, 9,10-dihydro-9- (2-hydroxyethoxy) -9,10-ethanoanthracene-11,12-dicarboxylic acid-N (P- methoxyphenyl) imide.

Furthermore, 9,10-dihydro-9- (2-hydroxypropoxy) -9,10-ethanoanthracene-11,12-dicarboxylic acid-N-methylimide, wherein the 9-position is a 2-hydroxypropoxy group, 9,10 -Dihydro-9- (2-hydroxypropoxy) -9,10-ethanoanthracene-11,12-dicarboxylic acid-N-ethylimide, 9,10-dihydro-9- (2-hydroxypropoxy) -9,10-ethano Anthracene-11,12-dicarboxylic acid-N-propylimide, 9,10-dihydro-9- (2-hydroxypropoxy) -9,10-ethanoanthracene-11,12-dicarboxylic acid-N-cyclohexylimide, 9, 10-dihydro-9- (2-hydroxypropoxy) -9,10-ethanoanthracene-11,12 Dicarboxylic acid-N-dodecylimide, 9,10-dihydro-9- (2-hydroxypropoxy) -9,10-ethanoanthracene-11,12-dicarboxylic acid-N-benzylimide, 9,10-dihydro-9- (2-hydroxypropoxy) -9,10-ethanoanthracene-11,12-dicarboxylic acid-N-phenylimide, 9,10-dihydro-9- (2-hydroxypropoxy) -9,10-ethanoanthracene-11 12-dicarboxylic acid-N- (p-tolyl) imide, 9,10-dihydro-9- (2-hydroxypropoxy) -9,10-ethanoanthracene-11,12-dicarboxylic acid-N- (p-chlorophenyl) Imide, 9,10-dihydro-9- (2-hydroxypropoxy) -9,10-ethanoanthracene-11 -N-2-dicarboxylic acid (p- methoxyphenyl) imide, and isomers thereof in the hydroxyethylene group of these compounds.

Furthermore, 9,10-dihydro-9- (2-hydroxybutoxy) -9,10-ethanoanthracene-11,12-dicarboxylic acid-N-methylimide, wherein the 9-position is a 2-hydroxybutoxy group, 9,10 -Dihydro-9- (2-hydroxybutoxy) -9,10-ethanoanthracene-11,12-dicarboxylic acid-N-ethylimide, 9,10-dihydro-9- (2-hydroxybutoxy) -9,10-ethano Anthracene-11,12-dicarboxylic acid-N-propylimide, 9,10-dihydro-9- (2-hydroxybutoxy) -9,10-ethanoanthracene-11,12-dicarboxylic acid-N-cyclohexylimide, 9, 10-dihydro-9- (2-hydroxybutoxy) -9,10-ethanoanthracene-11,12-dicarboxylic acid -N-dodecylimide, 9,10-dihydro-9- (2-hydroxybutoxy) -9,10-ethanoanthracene-11,12-dicarboxylic acid-N-benzylimide, 9,10-dihydro-9- (2 -Hydroxybutoxy) -9,10-ethanoanthracene-11,12-dicarboxylic acid-N-phenylimide, 9,10-dihydro-9- (2-hydroxybutoxy) -9,10-ethanoanthracene-11,12- Dicarboxylic acid-N- (p-tolyl) imide, 9,10-dihydro-9- (2-hydroxybutoxy) -9,10-ethanoanthracene-11,12-dicarboxylic acid-N- (p-chlorophenyl) imide, 9,10-dihydro-9- (2-hydroxybutoxy) -9,10-ethanoanthracene-11,12-dicarboxylic acid-N (P- methoxyphenyl) imide, and isomers thereof in the hydroxyethylene group of these compounds.

In addition, 9,10-dihydro-9- [2- (2-hydroxyethoxy) ethoxy] -9,10-ethanoanthracene-11,12-dicarboxylic acid-N-phenylimide, 9,10-dihydro-9- [ 2- (2-hydroxyethoxy) ethoxy] -9,10-ethanoanthracene-11,12-dicarboxylic acid-N- (p-tolyl) imide, 9,10-dihydro-9- {2- [2- (2 -Hydroxyethoxy) ethoxy] ethoxy} -9,10-ethanoanthracene-11,12-dicarboxylic acid-N-phenylimide, 9,10-dihydro-9- {2- [2- (2-hydroxyethoxy) ethoxy] Ethoxy} -9,10-ethanoanthracene-11,12-dicarboxylic acid-N- (p-tolyl) imide and the like.

Then, the obtained hydroxy compound having a 9,10-ethanoanthracene skeleton represented by the general formula (4) is reacted with acryloyl chloride or methacryloyl chloride in the presence or absence of a base to give a general formula (1 A mono (meth) acrylate compound having a 9,10-ethanoanthracene skeleton represented by formula (1) can be synthesized.

Examples of the base that can be used when the hydroxy compound having a 9,10-ethanoanthracene skeleton represented by the general formula (4) is reacted with acryloyl chloride or methacryloyl chloride include, for example, trimethylamine, triethylamine, tributylamine, pyridine, α- Examples include picoline, β-picoline, γ-picoline, piperidine and the like. The reaction is generally carried out in a solvent. Examples of the solvent used include aromatic solvents such as benzene, toluene, xylene and chlorobenzene, halogenated carbon solvents such as methylene chloride, dichloroethane and dichloroethylene, acetone. A ketone solvent such as methyl ethyl ketone and methyl isobutyl ketone, an amide solvent such as N-methylpyrrolidone and dimethylformamide, and an ether solvent such as tetrahydrofuran and 1,4-dioxane are preferably used. The addition amount of acryloyl chloride or methacryloyl chloride to the anthracene compound represented by the general formula (4) is 1 to 6 times, preferably 1.2 to 4 times. The reaction temperature is 0 ° C to 80 ° C, preferably 0 ° C to 20 ° C. This reaction is exothermic and requires cooling. The reaction time is about 15 to 60 minutes. After completion of the reaction, water or methanol is added to hydrate the unreacted acryloyl chloride or methacryloyl chloride, and then the hydrochloride is removed by filtration. Then, water is added to the filtrate to crystallize, By filtering, a crystal of a mono (meth) acrylate compound having a 9,10-ethanoanthracene skeleton represented by the general formula (1) can be isolated.

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.

Confirmation and physical properties of the product were measured by the following equipment.
(1) Melting point: Melting point measuring device manufactured by Gelen Camp, model MFB-595 (conforms to JIS K0064)
(2) Infrared (IR) spectrophotometer: Model IR-810 manufactured by JASCO Corporation
(3) Nuclear magnetic resonance apparatus (NMR): manufactured by JEOL Ltd., model GSX FT NMR Spectrometer, 270 MHz
(4) Mass spectrum: manufactured by Shimadzu Corporation, mass spectrometer, model GCMS-QP5000

Example 1 Synthesis of 9-acryloyloxyanthracene A 300 ml three-necked flask equipped with a stirrer and a thermometer was charged with 10 g (52 mmol) of 9-anthrone, 80 ml of acetonitrile, and 9 g (89 mmol) of triethylamine, and then 2 at a bath temperature of 80 ° C. Heated for hours. Next, the reaction liquid was cooled, and while cooling with an ice-water bath, a solution of 7 g (74 mmol) of acryloyl chloride in 24 ml of o-xylene was added over 1 hour, and further stirred at room temperature for 1 hour. 50 g of water was added and stirred well, and the aqueous layer was discarded. Washing with water was repeated three times to obtain a light khaki xylene solution. Next, the xylene layer was concentrated, and the produced crystals were suction filtered. The obtained wet cake was reslurried in 20 ml of methanol and then suction filtered and dried to obtain 9.1 g (37 mmol) of 9-acryloyloxyanthracene yellow powder. The yield of the product with respect to 9-anthrone was 71 mol%.

(1) Melting point: 157-158 ° C
(2) IR (KBr, cm ⁻¹ ): 3050, 1732, 1660, 1622, 1395, 1340, 1290, 1235, 1140, 1060, 980, 882, 772, 730, 540.
(3) ¹ H-NMR (CDCl ₃ , ppm): δ = 6.22 (d, J = 10 Hz, 1H), 6.64 (dd, J ₁ = 10 Hz, J ₂ = 17 Hz, 1H), 6. 86 (d, J = 17 Hz, 1H), 7.42-7.53 (m, 4H), 7.89-7.98 (m, 2H), 7.98-8.06 (m, 2H), 8.38 (s, 1H).

Example 2 Synthesis of 9-methacryloyloxyanthracene
A 300 ml three-necked flask equipped with a stirrer and a thermometer was charged with 15 g (77 mmol) of 9-anthrone, 90 ml of acetonitrile and 13 g (128 mmol) of triethylamine, and then heated at a bath temperature of 80 ° C. for 2 hours. Next, the reaction solution was cooled, and while cooling with an ice water bath, a solution of 12 g (124 mmol) of methacryloyl chloride in 35 ml of o-xylene was added over 1 hour, and further stirred at room temperature for 1 hour. 80 g of water was added and stirred well, and the aqueous layer was discarded. Washing with water was repeated three times to obtain a light khaki xylene solution. Next, the xylene layer was concentrated, and the produced crystals were suction filtered. The obtained wet cake was reslurried in 35 ml of methanol, and then suction filtered and dried to obtain 12 g (46 mmol) of 9-methacryloyloxyanthracene yellow powder. The yield of the product with respect to 9-anthrone was 59 mol%.

(1) Melting point: 131-132 ° C
(2) IR (KBr, cm ⁻¹ ): 3050, 1732, 1660, 1620, 1440, 1400, 1340, 1308, 1290, 1128, 1044, 950, 880, 828, 770, 718, 538.
(3) ¹ H-NMR (CDCl ₃ , ppm): δ = 2.23 (s, 3H), 5.95 (s, 1H), 6.67 (s, 1H), 7.39-7.52 (M.4H), 7.86-8.04 (m, 4H), 8.36 (s, 1H).

Example 3 Synthesis of 9- (2-hydroxyethoxy) anthracene In a nitrogen box, 4.9 g (25 mmol) of 9-anthrone was dispersed in 25 ml of methanol in an autoclave equipped with a stirrer, and 20% by weight of sodium hydroxide. 20 g of aqueous solution (4 g of sodium hydroxide, 100 mmol) was added and sealed. After heating at 60 ° C. for 20 minutes to change 9-anthrone to 9-anthranol, the temperature of the reaction solution was lowered to 45 ° C. Thereto, 5.5 g (125 mmol) of ethylene oxide was introduced over 60 minutes while maintaining the temperature not exceeding 50 ° C. and the pressure not exceeding 0.3 MPa. Furthermore, the reaction was continued for 3 hours while maintaining the reaction temperature at 40 ° C. After completion of the reaction, the reaction mixture was cooled to room temperature and neutralized with a 5 wt% aqueous sulfuric acid solution. As the crystals were precipitated as a result of neutralization, the crystals were filtered by suction, and the obtained crystals were filtered and washed with water. By drying at 80 ° C., 3.5 g (15 mmol) of 9- (2-hydroxyethoxy) anthracene was obtained. The yield of the product with respect to 9- (2-hydroxyethoxy) anthracene was 60 mol%.

(1) Melting point: 115-116 ° C
(2) IR (KBr, cm ⁻¹ ): 3240, 3040, 2910, 2860, 1615, 1410, 1330, 1272, 1100, 1080, 1060, 1024, 880, 832, 782, 720, 698, 650, 546.
(3) ¹ H-NMR (CDCl ₃ , ppm): δ = 2.48 (t, J = 7 Hz, 1H), 4.20 (t, J = 7 Hz, 2H), 4.35 (t, J = 7 Hz, 2H), 7.35-7.58 (m, 4H), 7.90-8.06 (m, 2H), 8.26 (s, 1H), 8.30-8.39 (m, 2H).

Example 4 Synthesis of 9- (2-acryloyloxyethoxy) anthracene
9- (2-Hydroxyethoxy) anthracene synthesized in the same manner as in Example 3 (2.0 g, 8.4 mmol), acetonitrile (40 ml), triethylamine (2.3 g, 23 mmol) were charged, and the contents of the flask were stirred and stirred at room temperature. After mixing, a solution of 1.9 g (21 mmol) of acryloyl chloride dissolved in 10 ml of acetonitrile was added, and stirring was continued at room temperature for 1 hour. After adding 10 ml of pure water to the flask and continuing stirring for 10 minutes, 10 ml of saturated saline and 40 ml of ethyl acetate were further added. The obtained reaction product was washed with 10 ml of pure water, and this washing operation was repeated three times. The organic layer was separated from the liquid after washing with pure water. The oily substance obtained by concentrating the separated organic layer was purified by silica gel column chromatography using hexane and ethyl acetate as developing solvents, and 1.5 g of orange oily 9- (2-acryloxyethoxy) anthracene ( 5.1 mmol). The yield of the product based on 9- (2-hydroxyethoxy) anthracene was 61 mol%.

(1) Melting point: Water syrup at room temperature (2) IR (neat, cm ⁻¹ ): 730, 1060, 1094, 1161, 1188, 1265, 1290, 1335, 1402, 1720.
(3) ¹ H-NMR (CDCl ₃ , ppm): δ = 4.44-4.47 (m, 2H), 4.66-4.68 (m, 2H), 5.92 (dd, 1H) , 6.26 (dd, 1H), 6.48 (dd, 1H), 7.38-7.54 (m, 4H), 8.2 (s, 1H), 7.90-8.36 (m , 5H).
(4) Mass spectrum: (EI-MS) m / z = 292 (M ⁺ ).

Example 5 Synthesis of 9- (2-methacryloyloxyethoxy) anthracene
After mixing 2.0 g (8.4 mmol) of 9- (2-hydroxyethoxy) anthracene synthesized in the same manner as in Example 3 with 40 ml of acetonitrile and 2.3 g (23 mmol) of triethylamine, 2.2 g (methacryloyl chloride) at room temperature ( 21 mmol) in 10 mL of acetonitrile was added and stirred for 1 hour. After adding 10 ml of pure water and stirring for 10 minutes, 10 mL of saturated brine and 40 ml of ethyl acetate were added, and the mixture was washed 3 times with 10 ml of pure water. After concentration of the washed organic layer, the obtained oily substance was purified by silica gel column chromatography using hexane and ethyl acetate as developing solvents, and 1.3 g (4 of yellow crystalline 9- (2-methacryloyloxyethoxy) anthracene was obtained. .3 mmol) was obtained. The yield of the product based on 9- (2-hydroxyethoxy) anthracene was 51 mol%.

(1) Melting point: 49 ° C
(2) IR (KBr, cm ⁻¹ ): 731, 1085, 1155, 1292, 1318, 1339, 1383, 1715.
(3) ¹ H-NMR (CDCl ₃ , ppm): δ = 2.04 (s, 3H), 4.43-4.50 (m, 2H), 4.66-4.69 (m, 2H) , 5.66-5.82 (m, 1H), 6.19-6.26 (m, 1H), 7.39-7.54 (m, 4H), 7.77-8.37 (m, 5H).
(4) Mass spectrum: (EI-MS) m / z = 306 (M ⁺ )

Example 6 Synthesis of 9- (2-hydroxypropoxy) anthracene In a nitrogen box, 4.9 g (25 mmol) of 9-anthrone was dispersed in 25 ml of methanol in an autoclave equipped with a stirrer, and 20% by weight of sodium hydroxide. After adding 20 g of aqueous solution (4 g of sodium hydroxide, 100 mmol) and heating at 60 ° C. for 20 minutes, the temperature of the reaction solution was lowered to 45 ° C. Next, 7 g (120 mmol) of propylene oxide was added little by little, the temperature of the liquid was kept at about 50 ° C., and the mixture was heated as it was for 1 hour. Then, it cools to room temperature and neutralizes with 5 weight% sulfuric acid aqueous solution. As the crystals are precipitated as a result of neutralization, the crystals are suction filtered, dried, and then purified by silica gel column chromatography using hexane and ethyl acetate as developing solvents to obtain khaki powder. 2.7 g (11 mmol) of-(2-hydroxypropoxy) anthracene was obtained. The yield of the product based on 9- (2-hydroxypropoxy) anthracene was 43 mol%.

(1) Melting point: 127-128 ° C
(2) IR (KBr, cm ⁻¹ ): 3340, 3040, 2960, 2910, 2860, 1615, 1546, 1432, 1408, 1330, 1278, 1160, 1130, 1080, 996, 874, 840, 782, 730, 690, 652, 550.
(3) ¹ H-NMR (CDCl ₃ , ppm): δ = 1.40 (d, J = 8 Hz, 3H), 2.83 (d, J = 4 Hz, 1H), 4.11 (d, J = 8 Hz, 2H), 4.46-4.60 (m, 1H), 7.40-7.55 (m, 4H), 7.95-8.04 (m, 2H), 8.27 (s, 1H), 8.28-8.37 (m, 2H).

(Example 7) Synthesis of 9- (2-acryloyloxypropoxy) anthracene 2.0 g (8.0 mmol) of 9- (2-hydroxypropoxy) anthracene synthesized in the same manner as in Example 6, 40 ml of acetonitrile, triethylamine After charging 2 g (22 mmol) and mixing the contents of the flask at room temperature, a solution of 1.8 g (20 mmol) of acryloyl chloride in 10 ml of acetonitrile was added and stirring was continued for 1 hour. After adding 10 ml of pure water to the flask and continuing stirring for 10 minutes, 10 ml of saturated saline and 40 ml of ethyl acetate were further added. The obtained reaction product was washed with 10 ml of pure water, and this washing operation was repeated three times. The organic layer was separated from the liquid after washing with pure water. The oily substance obtained by concentrating the separated organic layer was purified by silica gel column chromatography using hexane and ethyl acetate as developing solvents, and 1.3 g of orange oily 9- (2-acryloxypropoxy) anthracene ( 4.3 mmol) was obtained. The yield of the product based on 9- (2-hydroxypropoxy) anthracene was 53 mol%.

(1) Melting point: Room temperature Varicella (2) IR (neat, cm ⁻¹ ): 732, 1090, 1195, 1342, 1405, 1720.
(3) ¹ H-NMR (CDCl ₃ , ppm): δ = 1.56 (d, 3H), 4.16-4.34 (m, 2H), 5.53-5.64 (m, 1H) 5.90 (dd, 1H), 6.25 (dd, 1H), 6.50 (dd, 1H), 7.39-7.50 (m, 4H), 7.93-8.36 (m , 5H).

(Example 8) Synthesis of 9- (2-methacryloyloxypropoxy) anthracene 2.0-g (8.0 mmol) of 9- (2-hydroxypropoxy) anthracene synthesized in the same manner as in Example 6, acetonitrile 40 ml, triethylamine 2. After charging 2 g (22 mmol) and mixing the contents of the flask at room temperature, a solution of 1.9 g (18 mmol) of methacryloyl chloride in 10 ml of acetonitrile was added, and stirring was continued for 1 hour. After adding 10 ml of pure water to the flask and continuing stirring for 10 minutes, 10 ml of saturated saline and 40 ml of ethyl acetate were further added. The obtained reaction product was washed with 10 ml of pure water, and this washing operation was repeated three times. The organic layer was separated from the liquid after washing with pure water. The oily substance obtained by concentrating the separated organic layer was purified by silica gel column chromatography using hexane and ethyl acetate as developing solvents, and 1.3 g of orange oily 9- (2-methacryloxypropoxy) anthracene ( 4.1 mmol) was obtained. The yield of the product based on 9- (2-hydroxypropoxy) anthracene was 51 mol%.

(1) Melting point: Room temperature Varicella (2) IR spectrum (neat, cm ⁻¹ ): 732, 1085, 1160, 1340, 1712.
(3) ¹ H-NMR (CDCl ₃ , ppm): δ = 1.55 (d, 3H), 2.00 (s, 3H), 5.64-5.81 (m, 1H), 6.22 -6.24 (m, 1H), 7.38-7.50 (m, 4H), 7.92-8.37 (m, 5H).
(4) Mass spectrum: (EI-MS) m / z = 320 (M ^<+> ).

Example 9 Synthesis of 9,10-dihydro-9-hydroxy-9,10-ethanoanthracene-11,12-dicarboxylic anhydride An 5.8 g of 9-anthrone was placed in a 300 ml three-necked flask equipped with a stirrer and a thermometer. (30 mmol), 5.0 g (51 mmol) of maleic anhydride and 100 mg of p-toluenesulfonic acid were added, and the mixture was heated in a bath temperature of 106 ° C. for 1 hour in 40 g of toluene. The color of the liquid changed from khaki to pale yellow. When the reaction solution was cooled with water, a large amount of colorless crystals precipitated. The obtained slurry was subjected to suction filtration, and then washed on the funnel twice with 10 ml of toluene. Finally, the wet cake was dried to obtain 7.9 g (27 mmol) of light yellow crystals of 9,10-dihydro-9-hydroxy-9,10-ethanoanthracene-11,12-dicarboxylic anhydride. The yield of the product based on 9-anthrone was 91 mol%.

(1) Melting point: 171-173 ° C
(2) IR (KBr, cm ⁻¹ ): 3480, 1852, 1822, 1770, 1456, 1230, 1220, 1070, 980, 930, 920, 760, 750, 721, 522.
(3) ¹ H-NMR (CDCl ₃ , ppm): δ = 3.44 (d, J = 9 Hz, 1H), 3.64 (dd, J ₁ = 3 Hz, J ₂ = 9 Hz, 1H), 4. 79 (d, J = 3 Hz, 1H), 7.15-7.41 (m, 6H), 7.53 (d, J = 8 Hz, 1H), 7.70 (d, J = 8 Hz, 1H).

Example 10 Synthesis of 9,10-dihydro-9-hydroxy-9,10-ethanoanthracene-11,12-dicarboxylic acid-N-phenylimide Into a 300 ml three-necked flask equipped with a stirrer and a thermometer, 9-anthrone was added. 7.8 g (40 mmol), 8.6 g (50 mmol) of N-phenylmaleimide and 200 mg of p-toluenesulfonic acid were added and dispersed in 40 g of toluene, and the slurry was heated at a bath temperature of 106 ° C. After 1 minute, it became a homogeneous solution. When heating was continued, a large amount of white crystals precipitated after 20 minutes. After heating for 1 hour, the reaction solution was water-cooled, and the resulting slurry was suction filtered, and then washed on the funnel twice with 10 ml of toluene. Finally, the wet cake was dried to obtain 14 g (38 mmol) of pure white powder of 9,10-dihydro-9-hydroxy-9,10-ethanoanthracene-11,12-dicarboxylic acid-N-phenylimide. The yield of the product with respect to 9-anthrone was 94 mol%.

(1) Melting point: 183-186 ° C
(2) IR (KBr, cm ⁻¹ ): 3420, 1700, 1498, 1462, 1382, 1300, 1275, 1248, 1180, 920, 770, 720, 690, 562.
(3) ¹ H-NMR (CDCl ₃ , ppm): δ = 3.10 (bs, 1H), 3.28 (d, J = 9 Hz, 1H), 3.50 (dd, J ₁ = 3 Hz, J ₂ = 9 Hz, 1H), 4.84 (d, J = 3 Hz, 1H), 6.48 (m, 2H), 7.16-7.38 (m, 8H), 7.42 (d, J = 8 Hz, 1H), 7.56 (d, J = 8 Hz, 1H), 7.74 (d, J = 8 Hz, 1H).

Example 11 9,10-Dihydro-9- (2-hydroxypropoxy) -9,10-ethanoanthracene-11,12-dicarboxylic anhydride and 9,10-dihydro-9- (1-methyl-2) -Hydroxyethoxy) -9,10-ethanoanthracene-11,12-dicarboxylic acid anhydride mixture synthesized in the same manner as in Example 6 in a 300 ml three-necked flask equipped with a stirrer and thermometer. Khaki powder 2.5 g (10 mmol) and maleic anhydride 3.0 g (31 mmol) were added, and the mixture was heated in 15 g of toluene at a bath temperature of 106 ° C. for 1 hour. The color of the liquid changed from khaki to pale yellow, and a large amount of colorless crystals precipitated. The obtained slurry was cooled and then suction filtered, and then washed on the funnel twice with 10 ml of toluene. Finally, the wet cake was dried to obtain 2.7 g (7.7 mmol) of colorless crystals. As a result of ¹ H-NMR measurement, this product was 9,10-dihydro-9- (2-hydroxypropoxy) -9,10-ethanoanthracene-11,12-dicarboxylic acid anhydride and its isomer 9, It was found to be a 2: 1 molar ratio mixture with 10-dihydro-9- (1-methyl-2-hydroxyethoxy) -9,10-ethanoanthracene-11,12-dicarboxylic anhydride. The yield of product was 77 mol%. This mixture was used for the next (meth) acrylation reaction without separation.

(1) Melting point: 241-242 ° C
(2) IR (KBr, cm ⁻¹ ): 3570, 3450, 3070, 2970, 1860, 1780, 1460, 1250, 1222, 1210, 1070, 940, 762, 758, 740, 534.
(3) ¹ H-NMR (CDCl ₃ , ppm):
The 9,10-dihydro-9- (2-hydroxypropoxy) -9,10-ethanoanthracene-11,12-dicarboxylic acid anhydride is as follows. δ = 1.50 (d, J = 8 Hz, 3H), 3.68 (dd, J ₁ = 2 Hz, J ₂ = 9 Hz, 1H), 3.87 (d, J = 9 Hz, 1H), 4.10 (T, J = 8 Hz, 1H), 4.28 (dd, J1 = 6 Hz, J2 = 8 Hz, 1H), 4.41-4.55 (m, 1H), 4.79 (d, J = 2 Hz, 1H), 7.16-7.35 (m, 5H), 7.40 (d, J = 8 Hz, 1H), 7.60-7.70 (m, 2H).
The isomer 9,10-dihydro-9- (1-methyl-2-hydroxyethoxy) -9,10-ethanoanthracene-11,12-dicarboxylic anhydride is as follows.
δ = 1.42 (d, J = 8 Hz, 3H), 3.68 (dd, J ₁ = 2 Hz, J ₂ = 9 Hz, 1H), 3.87 (d, J = 9 Hz, 1H), 4.30 -4.40 (m, 2H), 4.41-4.55 (m, 1H), 4.79 (d, J = 2Hz, 1H), 7.16-7.35 (m, 5H), 7 .60-7.70 (m, 1H), 7.78 (d, J = 8 Hz, 2H).

Example 12 Synthesis of 9,10-dihydro-9- (2-hydroxyethoxy) -9,10-ethanoanthracene-11,12-dicarboxylic acid-N-phenylimide 300 ml three-neck flask with stirrer and thermometer 4.8 g (20 mmol) of 9- (2-hydroxyethoxy) anthracene synthesized in the same manner as in Example 3 and 4.6 g (27 mmol) of N-phenylmaleimide were added. Heated for 5 hours. The color of the liquid changed from khaki to pale yellow. After cooling and concentrating the reaction solution, the obtained solid was reslurried with 20 ml of toluene and suction filtered. Finally, the wet cake was dried to obtain 6.1 g of light yellow crystals of 9,10-dihydro-9- (2-hydroxyethoxy) -9,10-ethanoanthracene-11,12-dicarboxylic acid-N-phenylimide. (15 mmol) was obtained. The yield of the product based on 9- (2-hydroxyethoxy) anthracene was 74 mol%.

(1) Melting point: 224-225 ° C
(2) IR (KBr, cm ⁻¹ ): 3430, 3030, 2920, 1776, 1700, 1590, 1460, 1452, 1382, 1300, 1261, 1200, 1094, 1066, 770, 742, 720, 680, 640, 618,544.
(3) ¹ H-NMR (CDCl ₃ , ppm): δ = 3.11 (t, J = 8 Hz, 1H), 3.52 (dd, J ₁ = 3H, J ₂ = 9 Hz, 1H), 3. _{78 (d, J-9Hz,} 1H), 4.17 (dt, J1 = 7Hz, J 2 = 8Hz, 2H), 4.45-4.53 (m, 1H), 4.55-4.64 ( m, 1H), 4.80 (d, J = 3 Hz, 1H), 6.45 (d, J = 8 Hz, 1H), 6.47 (d, J = 8 Hz, 1H), 7.15-7. 34 (m, 8H), 7.43 (d, J = 8 Hz, 1H), 7.68 (d, J = 8 Hz, 1H), 7.72 (d, J = 8 Hz, 1H).

Example 13 Synthesis of 9,10-dihydro-9-acryloyloxy-9,10-ethanoanthracene-11,12-dicarboxylic anhydride (A route)
To a 300 ml three-necked flask equipped with a stirrer and a thermometer, 13 g (52 mmol) of 9-acryloyloxyanthracene synthesized in the same manner as in Example 1 and 8.0 g (82 mmol) of maleic anhydride were added, and 40 g of toluene was added. Heated at a temperature of 106 ° C. for 3 hours. The reaction solution was cooled with water, 100 ml of methanol was added, and the mixture was allowed to stand overnight. Unreacted raw material 9-acryloyloxyanthracene crystals were precipitated and removed by filtration. The filtrate was then concentrated and separated into two layers. The upper colorless methanol layer was discarded, and the lower red solution was further washed twice with 40 ml of methanol to obtain 14.2 g of a khaki-colored water tank. . This is heated on a hot plate and is heated until the weight is constant, and light khaki of 9,10-dihydro-9-acryloyloxy-9,10-ethanoanthracene-11,12-dicarboxylic anhydride As a result, 12 g (35 mmol) of a glassy product was obtained. The yield of the product with respect to 9-acryloyloxyanthracene was 67 mol%.

(1) Melting point: 180-185 ° C
(2) IR (KBr, cm ⁻¹ ): 1870, 1788, 1740, 1640, 1460, 1408, 1252, 1230, 1180, 1080, 930, 764, 746, 540.
(3) ¹ H-NMR (CDCl ₃ , ppm): δ = 3.70 (dd, J ₁ = 3 Hz, J ₂ = 9 Hz, 1H), 4.8 (d, J = 3 Hz, 1H), 5. 01 (bs, 1H), 6.16 (d, J = 8 Hz, 1H), 6.58 (dd, J ₁ = 8 Hz, J ₂ = 17 Hz, 1H), 6.81 (d, J = 17 Hz, 1H) ), 7.0607.46 (m, 7H), 7.64 (d, J = 8 Hz, 1H).
(4) UV absorption: No absorption was observed at 250 nm or more.
(5) Refractive index: n _D = 1.62

Example 14 Synthesis of 9,10-dihydro-9-methacryloyloxy-9,10-ethanoanthracene-11,12-dicarboxylic anhydride (A route)
To a 300 ml three-necked flask equipped with a stirrer and a thermometer, 13 g (50 mmol) of 9-methacryloyloxyanthracene synthesized in the same manner as in Example 2 and 8.0 g (82 mmol) of maleic anhydride were added, and 40 g of toluene was added. Heated at a bath temperature of 106 ° C. for 1 hour. The color of the liquid changed from khaki to bright black-green. When the reaction solution was cooled with water, a large amount of pale yellow crystals were precipitated. The resulting slurry was suction filtered, and then washed on the funnel twice with 20 ml of toluene and twice with 20 ml of methanol. Finally, the wet cake was dried to obtain 13 g (35 mmol) of light yellow crystals of 9,10-dihydro-9-methacryloyloxy-9,10-ethanoanthracene-11,12-dicarboxylic anhydride. The yield of the product based on 9-methacryloyloxyanthracene was 71 mol%.

(1) Melting point: 246-247 ° C
(2) IR (KBr, cm ⁻¹ ): 3020, 3000, 2955, 2930, 1860, 1780, 1720, 1630, 1450, 1310, 1270, 1250, 1220, 1150, 1126, 1070, 1004, 946, 920, 902, 882, 762, 724, 642, 530.
(3) ¹ H-NMR (CDCl ₃ , ppm): δ = 2.26 (s, 3H), 3.72 (dd, J1 = 3H, J2 = 9 Hz, 1H), 4.81 (d, J = 3Hz, 1H), 5.04 (bs, 1H), 5.89 (s, 1H), 6.56 (s, 1H), 7.16-7.45 (m, 7H), 7.64 (d , J = 8 Hz, 1H).
(4) UV absorption: No absorption was observed at 250 nm or more.

Example 15 Synthesis of 9,10-dihydro-9-methacryloyloxy-9,10-ethanoanthracene-11,12-dicarboxylic acid-N-phenylmaleimide (A route)
To a 300 ml three-necked flask equipped with a stirrer and a thermometer, 5.2 g (20 mmol) of 9-methacryloyloxyanthracene synthesized in the same manner as in Example 2 and 6.8 g (39 mmol) of N-phenylmaleimide were added, and 20 mg of methoquinone was added. Thereafter, 50 g of toluene was added and heated at a bath temperature of 106 ° C. for 1.5 hours. The color of the liquid changed from khaki to bright yellow. When the reaction solution was cooled with water and 90 ml of methanol was added, a large amount of light yellow crystals were precipitated. The obtained slurry was subjected to suction filtration, and washed on the funnel twice with 40 ml of methanol. Finally, the wet cake was dried to obtain 7.1 g (15 mmol) of light yellow crystals of 9,10-dihydro-9-methacryloyloxy-9,10-ethanoanthracene-11,12-dicarboxylic acid-N-phenylmaleimide. It was. The yield of the product based on 9-methacryloyloxyanthracene was 75 mol%.

(1) Melting point: 244-245 ° C
(2) IR (KBr, cm ⁻¹ ): 1720, 1500, 1460, 1382, 1310, 1200, 1160, 770, 746, 730, 692, 620, 560.
(3) ¹ H-NMR (CDCl ₃ , ppm): δ = 2.24 (s, 3H), 3.57 (dd, J ₁ = 3 Hz, J ₂ = 9 Hz, 1H), 4.87 (d, J = 3 Hz, 1H), 4.92 (bs, 1H), 5.83 (s, 1H), 6.47 (s, 1H), 6.48-6.55 (m, 2H), 7.16 −7.36 (m, 8H), 7.36-7.49 (m, 2H), 7.66 (bs, 1H).
(4) UV absorption: No absorption was observed at 250 nm or more.

Example 16 Synthesis of 9,10-dihydro-9- (2-acryloyloxyethoxy) -9,10-ethanoanthracene-11,12-dicarboxylic anhydride (A route)
To a 300 ml three-necked flask equipped with a stirrer and a thermometer, 2.9 g (10 mmol) of 9- (2-acryloyloxyethoxy) anthracene synthesized in the same manner as in Example 4 and 3.0 g (31 mmol) of maleic anhydride were added. After adding 70 mg of methoquinone, 20 g of toluene was added and heated at a bath temperature of 106 ° C. for 1 hour. The color of the liquid changed from khaki to bright light yellow. The reaction solution was water-cooled, added with 80 ml of methanol, and concentrated to precipitate colorless crystals. The obtained slurry was subjected to suction filtration, and washed on the funnel twice with 15 ml of methanol. Finally, the wet cake was dried to obtain 2.1 g (5.4 mmol) of white crystals of 9,10-dihydro-9- (2-acryloyloxyethoxy) -9,10-ethanoanthracene-11,12-dicarboxylic anhydride. )Obtained. The yield of the product based on 9- (2-acryloyloxyethoxy) anthracene was 54 mol%.

(1) Melting point: 199-200 ° C
(2) IR (KBr, cm ⁻¹ ): 3080, 2980, 1860, 1780, 1730, 1680, 1640, 1460, 1410, 1290, 1264, 1230, 1209, 1100, 1074, 942, 770, 760, 690, 538.
(3) ¹ H-NMR (CDCl ₃ , ppm): δ = 3.69 (dd, J ₁ = 2 Hz, J ₂ = 9 Hz, ₁ H), 3.86 (d, J = 9 Hz, ₁ H), 4. 40-4.49 (m, 1H), 4.64-4.72 (m.2H), 4.76 (d, J = 2 Hz, 1H), 4.80-4.90 (m, 1H), 5.94 (d, J = 8 Hz, 1H), 6.29 (dd, J ₁ = 8 Hz, J ₂ = 17 Hz, 1H), 6.57 (d, J = 17 Hz, 1H), 7.16-7 .32 (m, 5H), 7.42 (d, J = 8 Hz, 1H), 7.60-7.69 (m, 2H).
(4) UV absorption: No absorption was observed at 250 nm or more.
(5) Refractive index: n _D = 1.595

Example 17 Synthesis of 9,10-dihydro-9- (2-methacryloyloxyethoxy) -9,10-ethanoanthracene-11,12-dicarboxylic anhydride (A route)
To a 300 ml three-necked flask equipped with a stirrer and a thermometer, 7.5 g (25 mmol) of 9- (2-methacryloyloxyethoxy) anthracene synthesized in the same manner as in Example 5 and 4.0 g (41 mmol) of maleic anhydride were added. After adding 70 mg of methoquinone, 30 g of toluene was added and heated at a bath temperature of 106 ° C. for 1 hour. The color of the liquid changed from khaki to bright yellowish green. When the reaction solution was cooled with water, 150 ml of methanol was added and concentrated, a large amount of colorless crystals were precipitated. The obtained slurry was subjected to suction filtration, and washed on the funnel twice with 20 ml of methanol. Finally, the wet cake was dried to obtain 6.5 g (16 mmol) of white crystals of 9,10-dihydro-9- (2-methacryloyloxyethoxy) -9,10-ethanoanthracene-11,12-dicarboxylic anhydride. It was. The yield of the product based on 9- (2-methacryloyloxyethoxy) anthracene was 66 mol%.

(1) Melting point: 167-168 ° C
(2) IR (KBr, cm ⁻¹ ): 3080, 2980, 1862, 1782, 1724, 1640, 1460, 1300, 1234, 1178, 1100, 1080, 942, 910, 772, 761, 742, 656, 540.
(3) ¹ H-NMR (CDCl ₃ , ppm): δ = 2.05 (s, 3H), 3.70 (dd, J ₁ = 2 Hz, J ₂ = 9 Hz, ₁ H), 3.86 (d, J = 9 Hz, 1H), 4.40-4.49 (m, 1H), 4.62-4.69 (m, 1H), 4.76 (d, J = 2 Hz, 1H), 4.68-. 4.88 (m, 2H), 5.67 (s, 1H), 6.28 (s, 1H), 7.16-7.32 (m, 5H), 7.40 (d, J = 8 Hz, 1H), 7.63-7.70 (m, 2H).
(4) UV absorption: No absorption was observed at 250 nm or more.
(5) Refractive index: n _D = 1.586

Example 18 9,10-Dihydro-9- (2-acryloyloxypropoxy) -9,10-ethanoanthracene-11,12-dicarboxylic anhydride and 9,10-dihydro-9- (1-methyl-) Synthesis of a mixture with 2-acryloyloxyethoxy) -9,10-ethanoanthracene-11,12-dicarboxylic anhydride (A route)
To a 200 ml three-necked flask equipped with a stirrer and a thermometer, 6.3 g (21 mmol) of an oil before column purification synthesized in the same manner as in Example 7 and 4.0 g (41 mmol) of maleic anhydride were added, and 70 mg of methoquinone was added. Thereafter, 25 g of toluene was added and heated at a bath temperature of 106 ° C. for 1 hour. The color of the liquid changed from khaki to bright yellowish green. When the reaction solution was cooled with water, 100 ml of methanol was added and concentrated, a large amount of colorless crystals were precipitated. The obtained slurry was subjected to suction filtration, and washed on the funnel twice with 20 ml of methanol. Finally, the wet cake was dried to obtain 3.6 g (9.0 mmol) of white crystals. As a result of ¹ H-NMR measurement, this was 9,10-dihydro-9- (2-acryloyloxypropoxy) -9,10-ethanoanthracene-11,12-dicarboxylic acid anhydride and its isomer 9 , 10-dihydro-9- (1-methyl-2-acryloyloxyethoxy) -9,10-ethanoanthracene-11,12-dicarboxylic anhydride was found to be a 5: 2 molar ratio mixture. The yield of product was 43 mol%. The mixture can be polymerized by radical polymerization into a high refractive index resin without separation.

(1) Melting point: 152-154 ° C.
(2) IR (KBr, cm ⁻¹ ): 3080, 2970, 1862, 1782, 1730, 1640, 1620, 1460, 276, 1230, 1200, 1100, 1080, 1048, 946, 770, 762, 650, 540.
(3) ¹ H-NMR (CDCl ₃ , ppm):
-About 9,10-dihydro-9- (2-acryloyloxypropoxy) -9,10-ethanoanthracene-11,12-dicarboxylic anhydride. δ = 1.68 (d, J = 8 Hz, 3H), 3.67 (dd, J ₁ = 2 Hz, J ₂ = 9 Hz, 1H), 3.87 (d, J = 9 Hz, 1H), 4.28 -4.35 (m, 1H), 4.47-4.54 (m, 1H), 4.74 (d, J = 2Hz, 1H), 5.64-5.74 (m, 1H), 5 .93 (d, J = 8 Hz, 1H), 6.28 (dd, J ₁ = 8 Hz, J ₂ = 17 Hz, 1H), 6.50 (d, J = 17 Hz, 1H), 7.16-7. 32 (m, 6H), 7.40 (d, J = 8 Hz, 1H), 7.64 (d, J = 8 Hz, 1H).
The isomer 9,10-dihydro-9- (1-methyl-2-acryloyloxyethoxy) -9,10-ethanoanthracene-11,12-dicarboxylic anhydride is as follows. δ = 1.57 (d.J = 8 Hz, 3H), 3.67 (dd, J ₁ = 2 Hz, J ₂ = 9 Hz, 1H), 3.83 (d, J = 9 Hz, 1H), 4.35 -4.41 (m, 1H), 4.47-4.54 (m, 1H), 4.74 (d, J = 2Hz, 1H), 5.53-5.61 (m, 1H), 5 .88 (d, J = 8 Hz, 1H), 6.21 (dd, J ₁ = 8 Hz, J ₂ = 17 Hz, 1H), 6.55 (d, J = 17 Hz, 1H), 7.16-7. 32 (m, 6H), 7.56 (d, J = 8 Hz, 1H), 7.70 (d, J = 8 Hz, 1H).
(4) UV absorption: No absorption was observed at 250 nm or more.
(5) Refractive index: n _D = 1.580

Example 19 9,10-Dihydro-9- (2-methacryloyloxypropoxy) -9,10-ethanoanthracene-11,12-dicarboxylic anhydride and 9,10-dihydro-9- (1-methyl-) Synthesis of a mixture of 2-methacryloyloxyethoxy) -9,10-ethanoanthracene-11,12-dicarboxylic anhydride (A route)
To a 200 ml three-necked flask equipped with a stirrer and a thermometer, 6.3 g (20 mmol) of an oil before column purification synthesized in the same manner as in Example 8 and 4.0 g (41 mmol) of maleic anhydride were added, and 70 mg of methoquinone was added. Thereafter, 25 g of toluene was added and heated at a bath temperature of 106 ° C. for 1 hour. The color of the liquid changed from khaki to bright yellowish green. When the reaction solution was cooled with water, 100 ml of methanol was added and concentrated, a large amount of colorless crystals were precipitated. The obtained slurry was subjected to suction filtration, and washed on the funnel twice with 20 ml of methanol. Finally, the wet cake was dried to obtain 3.6 g (8.7 mmol) of white crystals. This was 9,10-dihydro-9- (2-methallyloyloxypropoxy) -9,10-ethanoanthracene-11,12-dicarboxylic anhydride and its isomer as a result of ¹ H-NMR measurement. It was found to be a 5: 2 molar ratio mixture with 9,10-dihydro-9- (1-methyl-2-methacryloyloxyethoxy) -9,10-ethanoanthracene-11,12-dicarboxylic anhydride. . The yield of product was 44 mol%. The mixture can be polymerized by radical polymerization into a high refractive index resin without separation.

(1) Melting point: 176 ° C
(2) IR (KBr, cm ⁻¹ ): 3080, 2970, 1864, 1790, 1720, 1638, 1462, 1300, 1230, 1192, 1100, 1080, 942, 760, 650, 540.
(3) ¹ H-NMR (CDCl ₃ , ppm):
The 9,10-dihydro-9- (2-methacryloyloxypropoxy) -9,10-ethanoanthracene-11,12-dicarboxylic acid anhydride is as follows. δ = 1.70 (d, J = 8 Hz, 3H), 2.07 (s, 3H), 3.68 (dd, J ₁ = 2 Hz, J ₂ = 9 Hz, 1H), 3.85 (d, J = 9 Hz, 1H), 4.28-4.34 (m, 2H), 4.75 (d, J = 2 Hz, 1H), 5.50-5.60 (m, 1H), 5.68 (s). , 1H), 6.30 (s, 1H), 7.11-7.32 (m, 5H), 7.40 (d, J = 8 Hz, 1H), 7.60-7.68 (m, 2H) ).
The isomer 9,10-dihydro-9- (1-methyl-2-methacryloyloxyethoxy) -9,10-ethanoanthracene-11,12-dicarboxylic acid anhydride is as follows. δ = 1.59 (d, J = 8 Hz, 3H), 2.00 (s, 3H), 3.68 (dd, J ₁ = 2 Hz, J ₂ = 9 Hz, ₁ H), 3.85 (d, J = 9 Hz, 1H), 4.34-4.42 (m, 1H), 4.48-4.55 (m, 2H), 5.62 (s, 1H), 6.24 (s, 1H), 7.11-7.32 (m, 5H), 7.52-7.59 (m, 2H), 7.70 (d, J = 8 Hz, 1H).
(4) UV absorption: No absorption was observed at 250 nm or more.
(5) Refractive index: n _D = 1.575

Example 20 Synthesis of 9,10-dihydro-9- (2-methacryloyloxyethoxy) -9,10-ethanoanthracene-11,12-dicarboxylic acid-N-phenylmaleimide (A route)
To a 300 ml three-necked flask equipped with a stirrer and a thermometer, 10 g (34 mmol) of 9- (2-methacryloyloxyethoxy) anthracene synthesized in the same manner as in Example 5 and 6.9 g (40 mmol) of N-phenylmaleimide were added, and methoquinone. After 80 mg was added, 80 g of toluene was added and heated at a bath temperature of 106 ° C. for 1 hour. The color of the liquid changed from khaki to bright yellow. The reaction solution was cooled with water, 300 ml of methanol was added, and the mixture was concentrated to give a colorless syrup. The obtained chickenpox was cooled in a refrigerator, and 15 g (31 mmol) of white powder of 9,10-dihydro-9- (2-methacryloyloxyethoxy) -9,10-ethanoanthracene-11,12-dicarboxylic acid-N-phenylmaleimide was obtained. )Obtained. The yield of the product based on 9- (2-methacryloyloxyethoxy) anthracene was 92 mol%.

(1) Melting point: 45 ° C
(2) IR (KBr, cm ⁻¹ ): 3060, 2955, 1776, 1718, 1632, 1592, 1495, 1458, 1380, 1294, 1194, 1166, 1132, 1092, 1042, 940, 762, 748, 718, 682,544.
(3) ¹ H-NMR (CDCl ₃ , ppm): δ = 2.06 (s, 1H), 3.54 (dd, J ₁ = 3 Hz, J ₂ = 9 Hz, 1H), 3.72 (d, J = 9 Hz, 1H), 4.41-4.52 (m, 1H), 4.62-4.72 (m, 1H), 4.72-4.86 (m, 2H), 4.82 ( d, J = 3 Hz, 1H), 5.66 (s, 1H), 6.28 (s, 1H), 6.48 (d, J = 8 Hz, 1H), 6.51 (d, J = 8 Hz, 1H), 6.87 (s, 1H), 7.16-7.37 (m, 6H), 7.37-7.50 (m, 2H), 7.66-7.78 (m, 2H) .
(4) UV absorption: No absorption was observed at 250 nm or more.
(5) Refractive index: n _D = 1.608

Example 21 9,10-Dihydro-9- (2-acryloxypropoxy) -9,10-ethanoanthracene-11,12-dicarboxylic anhydride and 9,10-dihydro-9- (1-methyl-) Synthesis of a mixture with 2-acryloyloxyethoxy) -9,10-ethanoanthracene-11,12-dicarboxylic anhydride (B route)
9,10-dihydro-9- (2-hydroxypropoxy) -9,10-ethanoanthracene-11,12-dicarboxylic acid anhydride synthesized in the same manner as in Example 11 in a 200 ml three-necked flask equipped with a stirrer and a thermometer And a isomer of 9,10-dihydro-9- (1-methyl-2-hydroxyethoxy) -9,10-ethanoanthracene-11,12-dicarboxylic anhydride in a 2: 1 molar ratio mixture To a solution of 1.8 g (5.0 mmol) and acryloyl chloride 1.8 g (20 mmol) in acetone 30 ml, triethylamine 1.5 g (15 mmol) in acetone 4 ml was added with water cooling. A white precipitate immediately formed. Stirring was continued for 1 hour. 4 ml of water was added to the resulting slurry to dissolve the precipitate. Furthermore, when 10 ml of water was added, the reaction solution became cloudy, so it was stored in a freezer. The next morning, a white solid had precipitated, so suction filtration, washing with water, and drying were performed to obtain 1.1 g (2.6 mmol) of a white powder. As a result of ¹ H-NMR measurement, this product was subjected to 9,10-dihydro-9- (2-acryloyloxypropoxy) -9,10-ethanoanthracene-11,12-dicarboxylic anhydride as in Example 18. 2: 1 molar ratio of the product and its isomer, 9,10-dihydro-9- (1-methyl-2-acryloyloxyethoxy) -9,10-ethanoanthracene-11,12-dicarboxylic anhydride It turned out to be a mixture. The product 9,10-dihydro-9- (2-hydroxypropoxy) -9,10-ethanoanthracene-11,12-dicarboxylic anhydride and its isomer 9,10-dihydro-9- (1- The yield based on the mixture with methyl-2-hydroxyethoxy) -9,10-ethanoanthracene-11,12-dicarboxylic anhydride was 52 mol%.

Example 22 Synthesis of 9,10-dihydro-9- (2-methacryloyloxyethoxy) -9,10-ethanoanthracene-11,12-dicarboxylic acid-N-phenylmaleimide (B route)
9,10-Dihydro-9- (2-hydroxyethoxy) -9,10-ethanoanthracene-11,12-dicarboxylic acid- synthesized in the same manner as in Example 12 in a 200 ml three-necked flask equipped with a stirrer and a thermometer To a solution of N-phenylmaleimide (2.1 g, 5.0 mmol) and methacryloyl chloride (2.1 g, 20 mmol) in acetone (30 ml) was added triethylamine (1.5 g, 15 mmol) in acetone (4 ml) with water cooling. A white precipitate immediately formed. Stirring was continued for 1 hour. 4 ml of water was added to the resulting slurry to dissolve the precipitate. Furthermore, when 10 ml of water was added, the reaction solution became cloudy, so it was stored in a freezer. The next morning, a white solid had precipitated, so suction filtration, washing with water, and drying were performed to obtain 1.2 g (2.4 mmol) of a white powder. From the measurement results of IR and ¹ H-NMR, this was the same 9,10-dihydro-9- (2-methacryloyloxyethoxy) -9,10-ethanoanthracene-11 as the compound obtained in Example 20. , 12-dicarboxylic acid-N-phenylmaleimide. The yield of the product with respect to 9,10-dihydro-9- (2-hydroxyethoxy) -9,10-ethanoanthracene-11,12-dicarboxylic acid-N-phenylmaleimide was 48 mol%.

Table 1 shows refractive index measurements of mono (meth) acrylate compounds having 9,10-ethanoanthracene skeletons obtained in Example 13, Example 16, Example 17, Example 18, Example 19 and Example 20. The result and the refractive index of 2-phenoxyethyl acrylate which is a commercially available aromatic monoacrylate compound were compared and described. From Table 1, the following is clear. That is, the mono (meth) acrylate compound having the 9,10-ethanoanthracene skeleton of the present invention has a refractive index of 1.55 or more, and is a commercially available aromatic monoacrylate compound 2-phenoxyethyl acrylate. It can be said that it has a higher refractive index.

The acrylate compound of the present invention can be suitably used as a polymerizable monomer for producing an optical member that requires a high refractive index and a high light transmittance. Examples of its use are “2008 Optical Functional Materials and Product Market Overview (First Volume, Second Volume)” (Fuji Keizai Co., Ltd., 2008), “Front Line of Transparent Plastics” (NTT Corporation, 2006) Year) Polymer Materials / Technology Directory Editorial Committee “Polymer Materials / Technology Guide” (Industrial Technology Service Center, 2004), Optical Application Technology / Material Dictionary Editorial Committee “Optical Application Technology / Material Dictionary” (( It is disclosed in publications such as Industrial Technology Service Center Co., Ltd. (2006).

Specifically, UV resist, Deep UV resist, liquid solder resist, electrodeposition resist, dry film resist for printed circuit boards, photoresist for TFT, black resist, color resist, FDP (flat display panel) and PDP (plasma display panel) Resist such as dry film resist, tapes such as dicing tape, back grind tape, overcoat agent for color filter, buffer coating agent, PDP electrode moisture proof coating material, PDP electrode material, etc. in electronics field, UV paint, coating, etc. Paints and coatings, UV curable inks, UV curable ink jets, optical fiber coatings and other inks, optical disc coatings, UV curable adhesives and other coating / coating related fields, contact Agents, sealant such, spectacle lenses, Fresnel lenses, it is possible to use lenticular lenses, prism lens sheets TFT, and aspheric lenses, lens such as a microlens, the field of optical materials such as a color filter.

It is the figure which showed that there exist two types of synthetic routes, A route and B route, about the manufacturing method of the mono (meth) acrylate compound which has 9,10-ethanoanthracene skeleton of General formula (1).

Claims (7)

A mono (meth) acrylate compound having a 9,10-ethanoanthracene skeleton represented by the general formula (1).
(In General Formula (1), n represents an integer of 0 or more and less than 10, X represents a nitrogen atom to which a hydrogen atom, an alkyl group or an aryl group is bonded, or an oxygen atom, and Y ¹ and Y ² are the same. Or a hydrogen atom, an alkyl group, a halogen atom, a hydroxyl group, an alkoxy group or an aryloxy group, R ¹ represents a hydrogen atom or a methyl group, and either R ² or R ³ represents A hydrogen atom, the other represents a hydrogen atom, a methyl group or an ethyl group, and R ⁴ represents a hydrogen atom or a methyl group.) ^{2. The} mono (meth) acrylate compound having a 9,10-ethanoanthracene skeleton according to claim 1, wherein in the general formula (1), n is 0 and Y ¹ and Y ² are hydrogen atoms. ^{2. The} mono (meth) acrylate compound having a 9,10-ethanoanthracene skeleton according to claim 1, wherein in the general formula (1), n is 1, and Y ¹ and Y ² are hydrogen atoms. The mono (meth) acrylate compound having a 9,10-ethanoanthracene skeleton according to any one of claims 1 to 3, wherein in the general formula (1), X is an oxygen atom. The 9,10-ethano according to any one of claims 1 to 3, wherein, in the general formula (1), X is a nitrogen atom to which an aryl group is bonded, and R ⁴ is a hydrogen atom. A mono (meth) acrylate compound having an anthracene skeleton. The mono (meth) acrylate compound having a 9,10-ethanoanthracene skeleton according to claim 1, wherein the anthracene compound represented by the general formula (2) is reacted with a dienophile represented by the general formula (3) and a Diels-Alder reaction. Manufacturing method.
(In Formula (2), n represents an integer of 0 or more and less than 10, R ¹ represents a hydrogen atom or a methyl group, either R ² or R ³ represents a hydrogen atom, and the other represents a hydrogen atom or methyl. And Y ¹ and Y ² may be the same or different and each represents a hydrogen atom, an alkyl group, a halogen atom, a hydroxyl group, an alkoxy group or an aryloxy group.
(In general formula (3), R ⁴ represents a hydrogen atom or a methyl group, and X represents a nitrogen atom to which a hydrogen atom, an alkyl group or an aryl group is bonded, or an oxygen atom.) 2. A mono (meth) acrylate having a 9,10-ethanoanthracene skeleton according to claim 1, wherein a hydroxy compound containing the 9,10-ethanoanthracene skeleton represented by the general formula (4) is (meth) acrylated. Compound manufacturing method.
(In General Formula (4), n represents an integer of 0 or more and less than 10, X represents a nitrogen atom to which a hydrogen atom, an alkyl group or an aryl group is bonded, or an oxygen atom, and Y ¹ and Y ² are the same. May be different from each other, and represents a hydrogen atom, an alkyl group, a halogen atom, a hydroxyl group, an alkoxy group or an aryloxy group, one of R ^{2 and} R ³ represents a hydrogen atom, the other represents a hydrogen atom, methyl A group or an ethyl group, and R ⁴ represents a hydrogen atom or a methyl group.)