JP5682853B2 - 10-acyloxy-1,2,3,4-tetrahydroanthracen-9-yl- (meth) acrylate compound, a production method thereof, and a polymer obtained by polymerizing the (meth) acrylate compound. - Google Patents

Description

  The present invention relates to a 10-acyloxy-1,2,3,4-tetrahydroanthracen-9-yl- (meth) acrylate compound, a production method thereof and a polymer obtained by polymerizing the (meth) acrylate compound.

  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 properties, but have a drawback that they easily become thick because their refractive index is lower than that of inorganic glass. 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 used as the raw material. In order to obtain a plastic with a high refractive index, the monomer constituting the plastic needs to have a high refractive index.

  As a method for increasing the refractive index of a monomer, it is already widely known to introduce a halogen atom (excluding fluorine), a sulfur atom, and further 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, the halogenation significantly deteriorates the light resistance of the obtained polymer and has a disadvantage of high specific gravity. 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 the monomer composition having a sulfur atom has a high refractive index and excellent impact resistance, the light resistance of the polymer obtained in the same manner is remarkably inferior, and there are problems such as giving off an unpleasant odor peculiar to sulfur. there were. Furthermore, when plastics using a monomer composition having sulfur atoms are treated as waste, there is a concern that harmful gases and sulfur compounds are generated.

  On the other hand, as a method for increasing the refractive index of a monomer, it is conventionally known to introduce a benzene ring or a biphenyl ring. A plastic material having a benzene ring and a biphenyl ring is lightweight, excellent in transparency, and has a relatively high refractive index (Patent Document 3 and the like). However, when a benzene ring is used, it is difficult to obtain a monomer that does not contain a halogen atom or a sulfur atom and has a refractive index exceeding 1.54.

  In addition, as a method for increasing the refractive index of a monomer, there has been reported an acrylate compound into which a naphthalene ring is introduced (Patent Documents 4 and 5). However, since an acrylate compound containing a naphthalene ring has UV absorption in the vicinity of 350 nm, when the most common high-pressure mercury lamp is used as a light source in the case of photocuring, light around 366 nm of the high-pressure mercury lamp is absorbed. Since it has a so-called internal filtering effect, there is a drawback that the photocuring is slow. For this reason, conventionally, an ultraviolet LED lamp having a wavelength of around 400 nm is used to light using a phosphine oxide-based photoradical polymerization initiator such as Irgacure 819 or Darocur TPO (Irgacure, Darocur is a registered trademark of Ciba Specialty Chemicals). It is cured (Patent Document 5).

  However, the ultraviolet LED lamp has not yet spread as a light source for photocuring, and has a drawback that it is difficult to produce a large industrial device. Further, the phosphine oxide-based photoradical polymerization initiator has a drawback of being expensive because it contains a phosphorus compound.

  In addition, in order to obtain a higher refractive index, development of a monomer having an anthracene ring and a fluorene ring has been studied (Patent Documents 6, 7, and 8). Furthermore, an attempt has been made to introduce an anthracene ring, a fluorene ring or the like into a polymer by transesterification (Patent Document 9).

  However, the introduction of an anthracene ring or fluorene ring can give a plastic material with a high refractive index. is there. In addition, when an anthracene ring is introduced, the anthracene ring emits fluorescence, so that there is a problem that application in the field of optical materials is difficult.

  Furthermore, an example of the synthesis of an acrylate compound having a 1,2,3,4-tetrahydroanthracene ring having an intermediate structure between a naphthalene ring and an anthracene ring has been reported, but nothing has been said about the refractive index. (Patent Document 10).

JP 05-170702 A JP 2002-20433 A JP 2003-064296 A JP 2001-276687 A JP 2008-81682 A JP 2004-083855 A Japanese Patent Laid-Open No. 06-220131 JP 2007-99637 A JP 2006-312709 A JP 2008-169324 A

  Therefore, there is no problem of absorption and fluorescence in the ultraviolet region as seen in anthracene and fluorene rings, excellent transparency, and acrylate that can be polymerized with a light source such as a general and most widely used high-pressure mercury lamp. Development of compounds is desired.

  As a result of intensive studies on the structure and photocurability of polycyclic aromatic compounds, the present inventor has found that 10-acyloxy-1,2,3,4-tetrahydroanthracene- having a 1,2,3,4-tetrahydroanthracene skeleton is present. Even though the 9-yl- (meth) acrylate compound is a tricyclic aromatic compound, it does not absorb ultraviolet rays as seen in an anthracene ring, has excellent transparency, and can be easily obtained by a high-pressure mercury lamp. The present invention was completed by polymerizing and finding that the obtained polymer had a high refractive index.

  That is, the gist of the present invention is the gist of the following. The first invention provides a 10-acyloxy-1,2,3,4-tetrahydroanthracen-9-yl- (meth) acrylate compound represented by the general formula (1).

In the general formula (1), R represents a hydrogen atom or a methyl group, Z represents an alkyl group (excluding those having an unsaturated double bond) or an aryl group, and X and Y are the same. May be different and each represents a hydrogen atom, an alkyl group, a halogen atom, an alkoxy group, an aryloxy group, an alkylthio group or an arylthio group.

  The second invention is the above 10-acyloxy-, which is obtained by acylating a 10-hydroxy-1,2,3,4-tetrahydroanthracen-9-yl- (meth) acrylate compound represented by the general formula (2). To provide a method for producing a 1,2,3,4-tetrahydroanthracen-9-yl- (meth) acrylate compound.

  In general formula (2), R represents a hydrogen atom or a methyl group, X and Y may be the same or different, and a hydrogen atom, an alkyl group, a halogen atom, a hydroxyl group, an alkoxy group, an aryloxy group, It represents either an alkylthio group or an arylthio group.

  A third invention is a 10-acyloxy according to the first invention, which is obtained by (meth) acryloylating a 10-acyloxy-1,2,3,4-tetrahydro-9-anthranol compound represented by the general formula (3). To provide a method for producing a -1,2,3,4-tetrahydroanthracen-9-yl- (meth) acrylate compound.

In the general formula (3), Z represents an alkyl group (excluding those having an unsaturated double bond) or an aryl group, and X and Y may be the same or different, a hydrogen atom, An alkyl group, a halogen atom, an alkoxy group, an aryloxy group, an alkylthio group or an arylthio group is shown.

  In the fourth invention, a radically polymerizable composition containing a 10-acyloxy-1,2,3,4-tetrahydroanthracen-9-yl- (meth) acrylate compound represented by the general formula (1) and a polymerization initiator. To provide.

  The fifth invention provides a polymer obtained by polymerizing the radically polymerizable composition according to the fourth invention.

  The sixth invention provides a high refractive index material containing the polymer according to the fifth invention.

  In the present invention, (meth) acrylate represents acrylate or methacrylate, (meth) acryloyl represents acryloyl or methacryloyl, and (meth) acryl represents acryl or methacryl.

  The 10-acyloxy-1,2,3,4-tetrahydroanthracen-9-yl- (meth) acrylate compound of the present invention is a novel compound and can be easily obtained by a high-pressure mercury lamp which is the most common light source. Polymerize. Moreover, the polymer obtained by the polymerization is an industrially useful compound having a high refractive index.

  The 10-acyloxy-1,2,3,4-tetrahydroanthracen-9-yl- (meth) acrylate compound of the present invention is a compound having a structure represented by the general formula (1).

  In the general formula (1), R represents a hydrogen atom or a methyl group, Z represents an alkyl group or an aryl group, X and Y may be the same or different, and a hydrogen atom, an alkyl group, or a halogen atom , A hydroxyl group, an alkoxy group, an aryloxy group, an alkylthio group, or an arylthio group.

In the general formula (1), examples of the alkyl group represented by Z include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, a sec-butyl group, a cyclohexyl group, and a benzyl group. Examples of the aryl group include a phenyl group and a naphthyl group. These groups may have a substituent, but when Z is an alkyl group, those having an unsaturated bond are excluded .

  In general formula (1), examples of the alkyl group represented by X and Y include a methyl group, an ethyl group, an n-propyl group, and an n-butyl group. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Examples of the alkoxy group include a methoxy group, an ethoxy group, an n-propoxy group, and an n-butoxy group. Examples of the aryloxy group include a phenoxy group, a p-tolyloxy group, an m-tolyloxy group, an o-tolyloxy group, a 1-naphthyloxy group, and a 2-naphthyloxy group. Examples of the alkylthio group include a methylthio group, an ethylthio group, an n-propylthio group, and an n-butylthio group. Examples of the arylthio group include a phenylthio group, a 1-naphthylthio group, and a 2-naphthylthio group.

  Examples of the 10-acyloxy-1,2,3,4-tetrahydroanthracen-9-yl- (meth) acrylate compound represented by the general formula (1) include the following compounds. That is, 10-acetyloxy-1,2,3,4-tetrahydroanthracen-9-yl-acrylate, 10-acetyloxy-1,2,3,4-tetrahydroanthracen-9-yl-methacrylate, 10-propanoyl Oxy-1,2,3,4-tetrahydroanthracen-9-yl-acrylate, 10-propanoyloxy-1,2,3,4-tetrahydroanthracen-9-yl-methacrylate, 10-n-butanoyloxy- 1,2,3,4-tetrahydroanthracen-9-yl-acrylate, 10-n-butanoyloxy-1,2,3,4-tetrahydroanthracen-9-yl-methacrylate, 10-benzoyloxy-1,2 , 3,4-Tetrahydroanthracen-9-yl-acrylate, 10-benzo Ruoxy-1,2,3,4-tetrahydroanthracen-9-yl-methacrylate, 10- (2-naphthylcarbonyloxy) -1,2,3,4-tetrahydroanthracen-9-yl-acrylate, 10- (2 -Naphtylcarbonyloxy) -1,2,3,4-tetrahydroanthracen-9-yl-methacrylate and the like.

  Furthermore, as a compound in which an alkyl group is substituted on the 1,2,3,4-tetrahydroanthracene ring, 2-methyl-10-acetyloxy-1,2,3,4-tetrahydroanthracen-9-yl-acrylate, 2-methyl-10-acetyloxy-1,2,3,4-tetrahydroanthracen-9-yl-methacrylate, 2-methyl-10-propanoyloxy-1,2,3,4-tetrahydroanthracen-9-yl -Acrylate, 2-methyl-10-propanoyloxy-1,2,3,4-tetrahydroanthracen-9-yl-methacrylate, 2-methyl-10-n-butanoyloxy-1,2,3,4 Tetrahydroanthracen-9-yl-acrylate, 2-methyl-10-n-butanoyloxy-1,2,3,4-te Lahydroanthracen-9-yl-methacrylate, 2-methyl-10-benzoyloxy-1,2,3,4-tetrahydroanthracen-9-yl-acrylate, 2-methyl-10-benzoyloxy-1,2,3 , 4-Tetrahydroanthracen-9-yl-methacrylate, 2-methyl-10- (2-naphthylcarbonyloxy) -1,2,3,4-tetrahydroanthracen-9-yl-acrylate, 2-methyl-10- ( 2-naphthylcarbonyloxy) -1,2,3,4-tetrahydroanthracen-9-yl-methacrylate, 3-methyl-10-acetyloxy-1,2,3,4-tetrahydroanthracen-9-yl-acrylate, 3-Methyl-10-acetyloxy-1,2,3,4-tetrahydroanthrace -9-yl-methacrylate, 3-methyl-10-propanoyloxy-1,2,3,4-tetrahydroanthracen-9-yl-acrylate, 3-methyl-10-propanoyloxy-1,2,3 4-tetrahydroanthracen-9-yl-methacrylate, 3-methyl-10-n-butanoyloxy-1,2,3,4-tetrahydroanthracen-9-yl-acrylate, 3-methyl-10-n-butanoyl Oxy-1,2,3,4-tetrahydroanthracen-9-yl-methacrylate, 3-methyl-10-benzoyloxy-1,2,3,4-tetrahydroanthracen-9-yl-acrylate, 3-methyl-10 -Benzoyloxy-1,2,3,4-tetrahydroanthracen-9-yl-methacrylate, 3-methyl Ru-10- (2-naphthylcarbonyloxy) -1,2,3,4-tetrahydroanthracen-9-yl-acrylate, 3-methyl-10- (2-naphthylcarbonyloxy) -1,2,3,4 -Tetrahydroanthracen-9-yl-methacrylate, 6-methyl-10-acetyloxy-1,2,3,4-tetrahydroanthracen-9-yl-acrylate, 6-methyl-10-acetyloxy-1,2,3 , 4-tetrahydroanthracen-9-yl-methacrylate, 6-methyl-10-propanoyloxy-1,2,3,4-tetrahydroanthracen-9-yl-acrylate, 6-methyl-10-propanoyloxy-1 , 2,3,4-Tetrahydroanthracen-9-yl-methacrylate, 6-methyl-10-n-butyl Noyloxy-1,2,3,4-tetrahydroanthracen-9-yl-acrylate, 6-methyl-10-n-butanoyloxy-1,2,3,4-tetrahydroanthracen-9-yl-methacrylate, 6- Methyl-10-benzoyloxy-1,2,3,4-tetrahydroanthracen-9-yl-acrylate, 6-methyl-10-benzoyloxy-1,2,3,4-tetrahydroanthracen-9-yl-methacrylate, 6-methyl-10- (2-naphthylcarbonyloxy) -1,2,3,4-tetrahydroanthracen-9-yl-acrylate, 6-methyl-10- (2-naphthylcarbonyloxy) -1,2,3 , 4-Tetrahydroanthracen-9-yl-methacrylate, 2,6-dimethyl-10-acetyl Xyl-1,2,3,4-tetrahydroanthracen-9-yl-acrylate, 2,6-dimethyl-10-acetyloxy-1,2,3,4-tetrahydroanthracen-9-yl-methacrylate, 2,6 -Dimethyl-10-propanoyloxy-1,2,3,4-tetrahydroanthracen-9-yl-acrylate, 2,6-dimethyl-10-propanoyloxy-1,2,3,4-tetrahydroanthracene-9 -Yl-methacrylate, 2,6-dimethyl-10-n-butanoyloxy-1,2,3,4-tetrahydroanthracen-9-yl-acrylate, 2,6-dimethyl-10-n-butanoyloxy- 1,2,3,4-tetrahydroanthracen-9-yl-methacrylate, 2,6-dimethyl-10-benzoyloxy Ci-1,2,3,4-tetrahydroanthracen-9-yl-acrylate, 2,6-dimethyl-10-benzoyloxy-1,2,3,4-tetrahydroanthracen-9-yl-methacrylate, 2,6 -Dimethyl-10- (2-naphthylcarbonyloxy) -1,2,3,4-tetrahydroanthracen-9-yl-acrylate, 2,6-dimethyl-10- (2-naphthylcarbonyloxy) -1,2, 3,4-tetrahydroanthracen-9-yl-methacrylate and the like.

  Furthermore, as a compound in which a halogen atom is substituted on the 1,2,3,4-tetrahydroanthracene ring, 2-chloro-10-acetyloxy-1,2,3,4-tetrahydroanthracene-9-yl-acrylate, 2-chloro-10-acetyloxy-1,2,3,4-tetrahydroanthracen-9-yl-methacrylate, 2-chloro-10-propanoyloxy-1,2,3,4-tetrahydroanthracen-9-yl -Acrylate, 2-chloro-10-propanoyloxy-1,2,3,4-tetrahydroanthracen-9-yl-methacrylate, 2-chloro-10-n-butanoyloxy-1,2,3,4 Tetrahydroanthracen-9-yl-acrylate, 2-chloro-10-n-butanoyloxy-1,2,3,4- Trahydroanthracen-9-yl-methacrylate, 2-chloro-10-benzoyloxy-1,2,3,4-tetrahydroanthracen-9-yl-acrylate, 2-chloro-10-benzoyloxy-1,2,3 , 4-Tetrahydroanthracen-9-yl-methacrylate, 2-chloro-10- (2-naphthylcarbonyloxy) -1,2,3,4-tetrahydroanthracen-9-yl-acrylate, 2-chloro-10- ( 2-naphthylcarbonyloxy) -1,2,3,4-tetrahydroanthracen-9-yl-methacrylate, 3-chloro-10-acetyloxy-1,2,3,4-tetrahydroanthracen-9-yl-acrylate, 3-chloro-10-acetyloxy-1,2,3,4-tetrahydroanthra 9-yl-methacrylate, 3-chloro-10-propanoyloxy-1,2,3,4-tetrahydroanthracen-9-yl-acrylate, 3-chloro-10-propanoyloxy-1,2,3 , 4-Tetrahydroanthracen-9-yl-methacrylate, 3-chloro-10-n-butanoyloxy-1,2,3,4-tetrahydroanthracen-9-yl-acrylate, 3-chloro-10-n-buta Noyloxy-1,2,3,4-tetrahydroanthracen-9-yl-methacrylate, 3-chloro-10-benzoyloxy-1,2,3,4-tetrahydroanthracen-9-yl-acrylate, 3-chloro- 10-benzoyloxy-1,2,3,4-tetrahydroanthracen-9-yl-methacrylate, 3-c Loro-10- (2-naphthylcarbonyloxy) -1,2,3,4-tetrahydroanthracen-9-yl-acrylate, 3-chloro-10- (2-naphthylcarbonyloxy) -1,2,3,4 -Tetrahydroanthracen-9-yl-methacrylate, 2,6-dichloro-10-acetyloxy-1,2,3,4-tetrahydroanthracen-9-yl-acrylate, 2,6-dichloro-10-acetyloxy-1 , 2,3,4-Tetrahydroanthracen-9-yl-methacrylate, 2,6-dichloro-10-propanoyloxy-1,2,3,4-tetrahydroanthracen-9-yl-acrylate, 2,6-dichloro -10-propanoyloxy-1,2,3,4-tetrahydroanthracen-9-yl-methacrylate 2,6-dichloro-10-n-butanoyloxy-1,2,3,4-tetrahydroanthracen-9-yl-acrylate, 2,6-dichloro-10-n-butanoyloxy-1,2,3 , 4-tetrahydroanthracen-9-yl-methacrylate, 2,6-dichloro-10-benzoyloxy-1,2,3,4-tetrahydroanthracen-9-yl-acrylate, 2,6-dichloro-10-benzoyloxy -1,2,3,4-tetrahydroanthracen-9-yl-methacrylate, 2,6-dichloro-10- (2-naphthylcarbonyloxy) -1,2,3,4-tetrahydroanthracen-9-yl-acrylate 2,6-dichloro-10- (2-naphthylcarbonyloxy) -1,2,3,4-tetrahydroanthrace -9-yl-methacrylate, 2-methyl-6-chloro-10-acetyloxy-1,2,3,4-tetrahydroanthracen-9-yl-acrylate, 2-methyl-6-chloro-10-acetyloxy- 1,2,3,4-tetrahydroanthracen-9-yl-methacrylate, 2-methyl-6-chloro-10-propanoyloxy-1,2,3,4-tetrahydroanthracen-9-yl-acrylate, 2- Methyl-6-chloro-10-propanoyloxy-1,2,3,4-tetrahydroanthracen-9-yl-methacrylate, 2-methyl-6-chloro-10-n-butanoyloxy-1,2,3 , 4-Tetrahydroanthracen-9-yl-acrylate, 2-methyl-6-chloro-10-n-butanoyloxy-1,2, 3,4-tetrahydroanthracen-9-yl-methacrylate, 2-methyl-6-chloro-10-benzoyloxy-1,2,3,4-tetrahydroanthracen-9-yl-acrylate, 2-methyl-6-chloro -10-benzoyloxy-1,2,3,4-tetrahydroanthracen-9-yl-methacrylate, 2-methyl-6-chloro-10- (2-naphthylcarbonyloxy) -1,2,3,4-tetrahydro Anthracen-9-yl-acrylate, 2-methyl-6-chloro-10- (2-naphthylcarbonyloxy) -1,2,3,4-tetrahydroanthracen-9-yl-methacrylate, 2-chloro-6-methyl -10-acetyloxy-1,2,3,4-tetrahydroanthracen-9-yl-acrylate, 2 Chloro-6-methyl-10-acetyloxy-1,2,3,4-tetrahydroanthracen-9-yl-methacrylate, 2-chloro-6-methyl-10-propanoyloxy-1,2,3,4 Tetrahydroanthracen-9-yl-acrylate, 2-chloro-6-methyl-10-propanoyloxy-1,2,3,4-tetrahydroanthracen-9-yl-methacrylate, 2-chloro-6-methyl-10- n-butanoyloxy-1,2,3,4-tetrahydroanthracen-9-yl-acrylate, 2-chloro-6-methyl-10-n-butanoyloxy-1,2,3,4-tetrahydroanthracene- 9-yl-methacrylate, 2-chloro-6-methyl-10-benzoyloxy-1,2,3,4-tetrahydroant Sen-9-yl-acrylate, 2-chloro-6-methyl-10-benzoyloxy-1,2,3,4-tetrahydroanthracen-9-yl-methacrylate, 2-chloro-6-methyl-10- (2 -Naphthylcarbonyloxy) -1,2,3,4-tetrahydroanthracen-9-yl-acrylate, 2-chloro-6-methyl-10- (2-naphthylcarbonyloxy) -1,2,3,4-tetrahydro And anthracene-9-yl-methacrylate.

  Furthermore, as a compound in which a hydroxyl group is substituted on the 1,2,3,4-tetrahydroanthracene ring, 5-hydroxy-10-acetyloxy-1,2,3,4-tetrahydroanthracen-9-yl-acrylate, 5 -Hydroxy-10-acetyloxy-1,2,3,4-tetrahydroanthracen-9-yl-methacrylate, 5-hydroxy-10-propanoyloxy-1,2,3,4-tetrahydroanthracen-9-yl- Acrylate, 5-hydroxy-10-propanoyloxy-1,2,3,4-tetrahydroanthracen-9-yl-methacrylate, 5-hydroxy-10-n-butanoyloxy-1,2,3,4-tetrahydro Anthracen-9-yl-acrylate, 5-hydroxy-10-n-butanoyloxy 1,2,3,4-tetrahydroanthracen-9-yl-methacrylate, 5-hydroxy-10-benzoyloxy-1,2,3,4-tetrahydroanthracen-9-yl-acrylate, 5-hydroxy-10-benzoyl Oxy-1,2,3,4-tetrahydroanthracen-9-yl-methacrylate, 5-hydroxy-10- (2-naphthylcarbonyloxy) -1,2,3,4-tetrahydroanthracen-9-yl-acrylate, 5-hydroxy-10- (2-naphthylcarbonyloxy) -1,2,3,4-tetrahydroanthracen-9-yl-methacrylate, 2-methyl-5-hydroxy-10-acetyloxy-1,2,3 4-tetrahydroanthracen-9-yl-acrylate, 2-methyl-5-hydride Xyl-10-acetyloxy-1,2,3,4-tetrahydroanthracen-9-yl-methacrylate, 2-methyl-5-hydroxy-10-propanoyloxy-1,2,3,4-tetrahydroanthracene-9 -Yl-acrylate, 2-methyl-5-hydroxy-10-propanoyloxy-1,2,3,4-tetrahydroanthracen-9-yl-methacrylate, 2-methyl-5-hydroxy-10-n-butanoyl Oxy-1,2,3,4-tetrahydroanthracen-9-yl-acrylate, 2-methyl-5-hydroxy-10-n-butanoyloxy-1,2,3,4-tetrahydroanthracen-9-yl- Methacrylate, 2-methyl-5-hydroxy-10-benzoyloxy-1,2,3,4-tetrahydroa Nthracen-9-yl-acrylate, 2-methyl-5-hydroxy-10-benzoyloxy-1,2,3,4-tetrahydroanthracen-9-yl-methacrylate, 2-methyl-5-hydroxy-10- (2 -Naphthylcarbonyloxy) -1,2,3,4-tetrahydroanthracen-9-yl-acrylate, 2-methyl-5-hydroxy-10- (2-naphthylcarbonyloxy) -1,2,3,4-tetrahydro Anthracen-9-yl-methacrylate, 2-chloro-5-hydroxy-10-acetyloxy-1,2,3,4-tetrahydroanthracen-9-yl-acrylate, 2-chloro-5-hydroxy-10-acetyloxy -1,2,3,4-tetrahydroanthracen-9-yl-methacrylate, 2-c Rho-5-hydroxy-10-propanoyloxy-1,2,3,4-tetrahydroanthracen-9-yl-acrylate, 2-chloro-5-hydroxy-10-propanoyloxy-1,2,3,4 -Tetrahydroanthracen-9-yl-methacrylate, 2-chloro-5-hydroxy-10-n-butanoyloxy-1,2,3,4-tetrahydroanthracen-9-yl-acrylate, 2-chloro-5-hydroxy -10-n-butanoyloxy-1,2,3,4-tetrahydroanthracene-9-yl-methacrylate, 2-chloro-5-hydroxy-10-benzoyloxy-1,2,3,4-tetrahydroanthracene- 9-yl-acrylate, 2-chloro-5-hydroxy-10-benzoyloxy-1,2,3,4 Tetrahydroanthracen-9-yl-methacrylate, 2-chloro-5-hydroxy-10- (2-naphthylcarbonyloxy) -1,2,3,4-tetrahydroanthracen-9-yl-acrylate, 2-chloro-5- Examples include hydroxy-10- (2-naphthylcarbonyloxy) -1,2,3,4-tetrahydroanthracen-9-yl-methacrylate.

  Furthermore, as a compound in which an alkoxy group is substituted on the 1,2,3,4-tetrahydroanthracene ring, 5-methoxy-10-acetyloxy-1,2,3,4-tetrahydroanthracene-9-yl-acrylate, 5-methoxy-10-acetyloxy-1,2,3,4-tetrahydroanthracen-9-yl-methacrylate, 5-methoxy-10-propanoyloxy-1,2,3,4-tetrahydroanthracen-9-yl -Acrylate, 5-methoxy-10-propanoyloxy-1,2,3,4-tetrahydroanthracen-9-yl-methacrylate, 5-methoxy-10-n-butanoyloxy-1,2,3,4 Tetrahydroanthracen-9-yl-acrylate, 5-methoxy-10-n-butanoyloxy-1, , 3,4-tetrahydroanthracen-9-yl-methacrylate, 5-methoxy-10-benzoyloxy-1,2,3,4-tetrahydroanthracen-9-yl-acrylate, 5-methoxy-10-benzoyloxy-1 , 2,3,4-Tetrahydroanthracen-9-yl-methacrylate, 5-methoxy-10- (2-naphthylcarbonyloxy) -1,2,3,4-tetrahydroanthracen-9-yl-acrylate, 5-methoxy -10- (2-naphthylcarbonyloxy) -1,2,3,4-tetrahydroanthracen-9-yl-methacrylate, 2-methyl-5-methoxy-10-acetyloxy-1,2,3,4-tetrahydro Anthracen-9-yl-acrylate, 2-methyl-5-methoxy-10-acetate Ruoxy-1,2,3,4-tetrahydroanthracen-9-yl-methacrylate, 2-methyl-5-methoxy-10-propanoyloxy-1,2,3,4-tetrahydroanthracen-9-yl-acrylate, 2-methyl-5-methoxy-10-propanoyloxy-1,2,3,4-tetrahydroanthracen-9-yl-methacrylate, 2-methyl-5-methoxy-10-n-butanoyloxy-1,2 , 3,4-tetrahydroanthracen-9-yl-acrylate, 2-methyl-5-methoxy-10-n-butanoyloxy-1,2,3,4-tetrahydroanthracen-9-yl-methacrylate, 2-methyl -5-methoxy-10-benzoyloxy-1,2,3,4-tetrahydroanthracen-9-yl-acryl 2-methyl-5-methoxy-10-benzoyloxy-1,2,3,4-tetrahydroanthracen-9-yl-methacrylate, 2-methyl-5-methoxy-10- (2-naphthylcarbonyloxy)- 1,2,3,4-tetrahydroanthracen-9-yl-acrylate, 2-methyl-5-methoxy-10- (2-naphthylcarbonyloxy) -1,2,3,4-tetrahydroanthracen-9-yl- Methacrylate, 2-chloro-5-methoxy-10-acetyloxy-1,2,3,4-tetrahydroanthracen-9-yl-acrylate, 2-chloro-5-methoxy-10-acetyloxy-1,2,3 , 4-Tetrahydroanthracen-9-yl-methacrylate, 2-chloro-5-methoxy-10-propanoyl Xyl-1,2,3,4-tetrahydroanthracen-9-yl-acrylate, 2-chloro-5-methoxy-10-propanoyloxy-1,2,3,4-tetrahydroanthracen-9-yl-methacrylate, 2-chloro-5-methoxy-10-n-butanoyloxy-1,2,3,4-tetrahydroanthracen-9-yl-acrylate, 2-chloro-5-methoxy-10-n-butanoyloxy-1 , 2,3,4-Tetrahydroanthracen-9-yl-methacrylate, 2-chloro-5-methoxy-10-benzoyloxy-1,2,3,4-tetrahydroanthracen-9-yl-acrylate, 2-chloro- 5-methoxy-10-benzoyloxy-1,2,3,4-tetrahydroanthracen-9-yl-methacrylate 2-chloro-5-methoxy-10- (2-naphthylcarbonyloxy) -1,2,3,4-tetrahydroanthracen-9-yl-acrylate, 2-chloro-5-methoxy-10- (2-naphthyl) Carbonyloxy) -1,2,3,4-tetrahydroanthracen-9-yl-methacrylate and the like.

  Furthermore, as a compound in which an aryloxy group is substituted on the 1,2,3,4-tetrahydroanthracene ring, 5-phenoxy-10-acetyloxy-1,2,3,4-tetrahydroanthracen-9-yl-acrylate 5-phenoxy-10-acetyloxy-1,2,3,4-tetrahydroanthracen-9-yl-methacrylate, 5-phenoxy-10-propanoyloxy-1,2,3,4-tetrahydroanthracene-9- Yl-acrylate, 5-phenoxy-10-propanoyloxy-1,2,3,4-tetrahydroanthracen-9-yl-methacrylate, 5-phenoxy-10-n-butanoyloxy-1,2,3,4 -Tetrahydroanthracen-9-yl-acrylate, 5-phenoxy-10-n-butano Luoxy-1,2,3,4-tetrahydroanthracen-9-yl-methacrylate, 5-phenoxy-10-benzoyloxy-1,2,3,4-tetrahydroanthracen-9-yl-acrylate, 5-phenoxy-10 -Benzoyloxy-1,2,3,4-tetrahydroanthracen-9-yl-methacrylate, 5-phenoxy-10- (2-naphthylcarbonyloxy) -1,2,3,4-tetrahydroanthracen-9-yl- Acrylate, 5-phenoxy-10- (2-naphthylcarbonyloxy) -1,2,3,4-tetrahydroanthracen-9-yl-methacrylate, 2-methyl-5-phenoxy-10-acetyloxy-1,2, 3,4-tetrahydroanthracen-9-yl-acrylate, 2-methyl 5-phenoxy-10-acetyloxy-1,2,3,4-tetrahydroanthracen-9-yl-methacrylate, 2-methyl-5-phenoxy-10-propanoyloxy-1,2,3,4-tetrahydroanthracene -9-yl-acrylate, 2-methyl-5-phenoxy-10-propanoyloxy-1,2,3,4-tetrahydroanthracen-9-yl-methacrylate, 2-methyl-5-phenoxy-10-n- Butanoyloxy-1,2,3,4-tetrahydroanthracen-9-yl-acrylate, 2-methyl-5-phenoxy-10-n-butanoyloxy-1,2,3,4-tetrahydroanthracene-9- Yl-methacrylate, 2-methyl-5-phenoxy-10-benzoyloxy-1,2,3,4-teto Lahydroanthracen-9-yl-acrylate, 2-methyl-5-phenoxy-10-benzoyloxy-1,2,3,4-tetrahydroanthracen-9-yl-methacrylate, 2-methyl-5-phenoxy-10- (2-Naphthylcarbonyloxy) -1,2,3,4-tetrahydroanthracen-9-yl-acrylate, 2-methyl-5-phenoxy-10- (2-naphthylcarbonyloxy) -1,2,3,4 -Tetrahydroanthracen-9-yl-methacrylate, 2-chloro-5-phenoxy-10-acetyloxy-1,2,3,4-tetrahydroanthracen-9-yl-acrylate, 2-chloro-5-phenoxy-10- Acetyloxy-1,2,3,4-tetrahydroanthracen-9-yl-methacrylate 2-chloro-5-phenoxy-10-propanoyloxy-1,2,3,4-tetrahydroanthracen-9-yl-acrylate, 2-chloro-5-phenoxy-10-propanoyloxy-1,2, 3,4-tetrahydroanthracen-9-yl-methacrylate, 2-chloro-5-phenoxy-10-n-butanoyloxy-1,2,3,4-tetrahydroanthracen-9-yl-acrylate, 2-chloro- 5-phenoxy-10-n-butanoyloxy-1,2,3,4-tetrahydroanthracen-9-yl-methacrylate, 2-chloro-5-phenoxy-10-benzoyloxy-1,2,3,4 Tetrahydroanthracen-9-yl-acrylate, 2-chloro-5-phenoxy-10-benzoyloxy-1, , 3,4-Tetrahydroanthracen-9-yl-methacrylate, 2-chloro-5-phenoxy-10- (2-naphthylcarbonyloxy) -1,2,3,4-tetrahydroanthracen-9-yl-acrylate, 2, -Chloro-5-phenoxy-10- (2-naphthylcarbonyloxy) -1,2,3,4-tetrahydroanthracen-9-yl-methacrylate and the like.

  Further, as a compound in which an alkylthio group is substituted on the 1,2,3,4-tetrahydroanthracene ring, 6-methylthio-10-acetyloxy-1,2,3,4-tetrahydroanthracen-9-yl-acrylate, 6-methylthio-10-acetyloxy-1,2,3,4-tetrahydroanthracen-9-yl-methacrylate, 6-methylthio-10-propanoyloxy-1,2,3,4-tetrahydroanthracen-9-yl -Acrylate, 6-methylthio-10-propanoyloxy-1,2,3,4-tetrahydroanthracen-9-yl-methacrylate, 6-methylthio-10-n-butanoyloxy-1,2,3,4 Tetrahydroanthracen-9-yl-acrylate, 6-methylthio-10-n-butanoy Oxy-1,2,3,4-tetrahydroanthracen-9-yl-methacrylate, 6-methylthio-10-benzoyloxy-1,2,3,4-tetrahydroanthracen-9-yl-acrylate, 6-methylthio-10 -Benzoyloxy-1,2,3,4-tetrahydroanthracen-9-yl-methacrylate, 6-methylthio-10- (2-naphthylcarbonyloxy) -1,2,3,4-tetrahydroanthracen-9-yl- Acrylate, 6-methylthio-10- (2-naphthylcarbonyloxy) -1,2,3,4-tetrahydroanthracen-9-yl-methacrylate, 2-methyl-6-methylthio-10-acetyloxy-1,2, 3,4-tetrahydroanthracen-9-yl-acrylate, 2-methyl- -Methylthio-10-acetyloxy-1,2,3,4-tetrahydroanthracen-9-yl-methacrylate, 2-methyl-6-methylthio-10-propanoyloxy-1,2,3,4-tetrahydroanthracene- 9-yl-acrylate, 2-methyl-6-methylthio-10-propanoyloxy-1,2,3,4-tetrahydroanthracen-9-yl-methacrylate, 2-methyl-6-methylthio-10-n-buta Noyloxy-1,2,3,4-tetrahydroanthracen-9-yl-acrylate, 2-methyl-6-methylthio-10-n-butanoyloxy-1,2,3,4-tetrahydroanthracen-9-yl -Methacrylate, 2-methyl-6-methylthio-10-benzoyloxy-1,2,3,4-tetra Hydroanthracen-9-yl-acrylate, 2-methyl-6-methylthio-10-benzoyloxy-1,2,3,4-tetrahydroanthracen-9-yl-methacrylate, 2-methyl-6-methylthio-10- ( 2-naphthylcarbonyloxy) -1,2,3,4-tetrahydroanthracen-9-yl-acrylate, 2-methyl-6-methylthio-10- (2-naphthylcarbonyloxy) -1,2,3,4 Tetrahydroanthracen-9-yl-methacrylate, 2-chloro-6-methylthio-10-acetyloxy-1,2,3,4-tetrahydroanthracen-9-yl-acrylate, 2-chloro-6-methylthio-10-acetyl Oxy-1,2,3,4-tetrahydroanthracen-9-yl-methacrylate 2-chloro-6-methylthio-10-propanoyloxy-1,2,3,4-tetrahydroanthracen-9-yl-acrylate, 2-chloro-6-methylthio-10-propanoyloxy-1,2,3 , 4-tetrahydroanthracen-9-yl-methacrylate, 2-chloro-6-methylthio-10-n-butanoyloxy-1,2,3,4-tetrahydroanthracen-9-yl-acrylate, 2-chloro-6 -Methylthio-10-n-butanoyloxy-1,2,3,4-tetrahydroanthracen-9-yl-methacrylate, 2-chloro-6-methylthio-10-benzoyloxy-1,2,3,4-tetrahydro Anthracen-9-yl-acrylate, 2-chloro-6-methylthio-10-benzoyloxy-1,2 3,4-tetrahydroanthracen-9-yl-methacrylate, 2-chloro-6-methylthio-10- (2-naphthylcarbonyloxy) -1,2,3,4-tetrahydroanthracen-9-yl-acrylate, 2- And chloro-6-methylthio-10- (2-naphthylcarbonyloxy) -1,2,3,4-tetrahydroanthracen-9-yl-methacrylate.

  Furthermore, as a compound in which an arylthio group is substituted on the 1,2,3,4-tetrahydroanthracene ring, 6-phenylthio-10-acetyloxy-1,2,3,4-tetrahydroanthracen-9-yl-acrylate, 6-phenylthio-10-acetyloxy-1,2,3,4-tetrahydroanthracen-9-yl-methacrylate, 6-phenylthio-10-propanoyloxy-1,2,3,4-tetrahydroanthracen-9-yl -Acrylate, 6-phenylthio-10-propanoyloxy-1,2,3,4-tetrahydroanthracen-9-yl-methacrylate, 6-phenylthio-10-n-butanoyloxy-1,2,3,4 Tetrahydroanthracen-9-yl-acrylate, 6-phenylthio-10- -Butanoyloxy-1,2,3,4-tetrahydroanthracen-9-yl-methacrylate, 6-phenylthio-10-benzoyloxy-1,2,3,4-tetrahydroanthracen-9-yl-acrylate, 6- Phenylthio-10-benzoyloxy-1,2,3,4-tetrahydroanthracen-9-yl-methacrylate, 6-phenylthio-10- (2-naphthylcarbonyloxy) -1,2,3,4-tetrahydroanthracene-9 -Yl-acrylate, 6-phenylthio-10- (2-naphthylcarbonyloxy) -1,2,3,4-tetrahydroanthracen-9-yl-methacrylate, 2-methyl-6-phenylthio-10-acetyloxy-1 , 2,3,4-Tetrahydroanthracen-9-yl-ac 2-methyl-6-phenylthio-10-acetyloxy-1,2,3,4-tetrahydroanthracen-9-yl-methacrylate, 2-methyl-6-phenylthio-10-propanoyloxy-1,2, 3,4-tetrahydroanthracen-9-yl-acrylate, 2-methyl-6-phenylthio-10-propanoyloxy-1,2,3,4-tetrahydroanthracen-9-yl-methacrylate, 2-methyl-6 Phenylthio-10-n-butanoyloxy-1,2,3,4-tetrahydroanthracen-9-yl-acrylate, 2-methyl-6-phenylthio-10-n-butanoyloxy-1,2,3,4 -Tetrahydroanthracen-9-yl-methacrylate, 2-methyl-6-phenylthio-10-benzo Yloxy-1,2,3,4-tetrahydroanthracen-9-yl-acrylate, 2-methyl-6-phenylthio-10-benzoyloxy-1,2,3,4-tetrahydroanthracen-9-yl-methacrylate, 2 -Methyl-6-phenylthio-10- (2-naphthylcarbonyloxy) -1,2,3,4-tetrahydroanthracen-9-yl-acrylate, 2-methyl-6-phenylthio-10- (2-naphthylcarbonyloxy) ) -1,2,3,4-tetrahydroanthracen-9-yl-methacrylate and the like.

  Of these compounds, 10-acetyloxy-1,2,3,4-tetrahydroanthracen-9-yl-acrylate, 10-propanoyloxy-1,2,3,4-tetrahydroanthracen-9-yl-acrylate 10-propanoyloxy-1,2,3,4-tetrahydroanthracen-9-yl-methacrylate is particularly preferred because it is easy to synthesize and the resulting product has a high refractive index.

(Production method)
Next, a method for producing the 10-acyloxy-1,2,3,4-tetrahydroanthracen-9-yl- (meth) acrylate compound of the present invention will be described. The 10-acyloxy-1,2,3,4-tetrahydroanthracen-9-yl- (meth) acrylate compound of the present invention can be synthesized by two synthetic routes as shown in the figure below. One is route A in which 1,2,3,4-tetrahydroanthracene-9,10-diol compound is first mono (meth) acryloylated and then monoacylated, and the other is mono (meth) acryloylation reaction. In this route, the order of the monoacylation reaction is reversed, and first, 1,2,3,4-tetrahydroanthracene-9,10-diol compound is monoacylated and then mono (meth) acryloylated.

<Route A>
First, a manufacturing method according to the route A will be described. In route A, the 10-acyloxy-1,2,3,4-tetrahydroanthracen-9-yl- (meth) acrylate compound of the present invention is used as a starting material 1,2,3,4-tetrahydroanthracene-9, 10-diol compound was mono- (meth) acryloylated to give a first reaction with 10-hydroxy-1,2,3,4-tetrahydroanthracen-9-yl- (meth) acrylate compound, and 10 -Hydroxy-1,2,3,4-tetrahydroanthracen-9-yl- (meth) acrylate compound is monoacylated to give 10-acyloxy-1,2,3,4-tetrahydroanthracen-9-yl- ( It can be synthesized by a second reaction with a meth) acrylate compound.

  The first reaction will be described. In the first reaction, 1,2-3,4-tetrahydroanthracene-9,10-diol compound and (meth) acryloylating agent are reacted in the presence of an inorganic base to produce 10-hydroxy-1,2,3. , 4-tetrahydroanthracen-9-yl- (meth) acrylate compound can be obtained.

  Examples of the 1,2,3,4-tetrahydroanthracene-9,10-diol compound used in the first reaction include the following compounds. That is, 1,2,3,4-tetrahydroanthracene-9,10-diol, 2-methyl-1,2,3,4-tetrahydroanthracene-9,10-diol, 3-methyl-1,2,3, 4-tetrahydroanthracene-9,10-diol, 6-methyl-1,2,3,4-tetrahydroanthracene-9,10-diol, 2,6-dimethyl-1,2,3,4-tetrahydroanthracene-9 , 10-diol, 2-chloro-1,2,3,4-tetrahydroanthracene-9,10-diol, 3-chloro-1,2,3,4-tetrahydroanthracene-9,10-diol, 6-chloro -1,2,3,4-tetrahydroanthracene-9,10-diol, 2,6-dichloro-1,2,3,4-tetrahydroanthracene-9,10- All, 2-methyl-6, chloro-1,2,3,4-tetrahydroanthracene-9,10-diol, 5-hydroxy-1,2,3,4-tetrahydroanthracene-9,10-diol, 2- Methyl-5-hydroxy-1,2,3,4-tetrahydroanthracene-9,10-diol, 2-chloro-5-hydroxy-1,2,3,4-tetrahydroanthracene-9,10-diol, 5- Methoxy-1,2,3,4-tetrahydroanthracene-9,10-diol, 2-methyl-5-methoxy-1,2,3,4-tetrahydroanthracene-9,10-diol, 2-chloro-5 Methoxy-1,2,3,4-tetrahydroanthracene-9,10-diol, 5-phenoxy-1,2,3,4-tetrahydroanthracene-9 10-diol, 2-methyl-5-phenoxy-1,2,3,4-tetrahydroanthracene-9,10-diol, 2-chloro-5-phenoxy-1,2,3,4-tetrahydroanthracene-9, 10-diol, 6-methylthio-1,2,3,4-tetrahydroanthracene-9,10-diol, 2-methyl-6-methylthio-1,2,3,4-tetrahydroanthracene-9,10-diol, 2-chloro-6-methylthio-1,2,3,4-tetrahydroanthracene-9,10-diol, 6-phenylthio-1,2,3,4-tetrahydroanthracene-9,10-diol, 2-methyl- 6-phenylthio-1,2,3,4-tetrahydroanthracene-9,10-diol, 2-chloro-6-phenylthio-1,2,3 , 4-tetrahydroanthracene-9,10-diol and the like.

  As the (meth) acryloylating agent that can be used in the first reaction, halogenated (meth) acryloyl is suitably used. When the halogen atom is a chlorine atom, it is acryloyl chloride or methacryloyl chloride, and when the halogen atom is a bromine atom, it is acryloyl bromide or methacryloyl bromide. Among them, acryloyl chloride or methacryloyl chloride is particularly preferable because the target product can be obtained with high yield. When 1,2,3,4-tetrahydroanthracene-9,10-diol compound is reacted with acryloyl chloride, 10-hydroxy-1,2,3,4-tetrahydroanthracen-9-yl-acrylate compound is obtained. On the other hand, when methacryloyl chloride is reacted, 10-hydroxy-1,2,3,4-tetrahydroanthracen-9-yl-methacrylate compound is obtained.

  In the first reaction, the addition amount of the halogenated (meth) acryloyl used is usually 0.5 mol times or more and 2.0 mol per mol of the 1,2,3,4-tetrahydroanthracene-9,10-diol compound. 2 times or less, preferably 0.8 mol times or more and 1.5 mol times or less. When the amount is less than 0.5 mol times, the raw material 1,2,3,4-tetrahydroanthracene-9,10-diol compound remains unreacted, whereas it is more than 2.0 mol times. In this case, the halogenated (meth) acryloyl is partially polymerized, and the purity of the obtained 10-hydroxy-1,2,3,4-tetrahydroanthracen-9-yl- (meth) acrylate compound is reduced. Neither is preferred.

  Examples of the base to be used in the first reaction include sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate and the like. In particular, sodium hydroxide and potassium hydroxide are preferable, and sodium hydroxide is more preferable.

  The addition amount of the base used is usually 1.0 mol times or more and 1.5 mol times or less with respect to 1 mol of the halogenated (meth) acryloyl. If the amount of the base used is too small, the pH of the aqueous layer becomes acidic during the dropwise addition of the halogenated (meth) acryloyl, and the selectivity may decrease. On the other hand, if the amount of the base used is too large, the halogenated (meth) acryloyl may decompose, which is not preferable.

  In the first reaction, the reaction between the 1,2,3,4-tetrahydroanthracene-9,10-diol compound and the halogenated (meth) acryloyl is usually carried out in the presence of a solvent. The type of the solvent is not particularly limited, but the reaction is preferably performed in a two-phase system composed of an aqueous phase and an organic phase.

  In the case of (meth) acryloylation in a two-phase system composed of an aqueous phase and an organic phase, it is usually preferable to use water and one or more organic solvents forming the organic phase in combination as a solvent. The type of the organic solvent that forms the organic phase is not particularly limited, but it is preferable to use an organic solvent that exhibits relatively low polarity and is not miscible with water. Examples of the organic solvent that can be used include aromatic hydrocarbon solvents such as toluene and xylene, and aliphatic hydrocarbon solvents such as heptane, cyclohexane, and decalin. These organic solvents may be used independently and may use 2 or more types together by arbitrary combinations and a ratio. When used alone, toluene is preferable. As a combination of two or more organic solvents, a combination of toluene and xylene or toluene and heptane is preferable.

  The mixing ratio of the aqueous phase and the organic phase is not particularly limited. However, when the total of the aqueous phase and the organic phase is 100 vol%, the volume ratio of the aqueous phase is usually 50 vol% or more and 95 vol% or less. A range is preferable. If the volume ratio of the aqueous phase is less than 50 vol% or too high than 95 vol%, the selectivity of the resulting 10-hydroxy-1,2,3,4-tetrahydroanthracen-9-yl- (meth) acrylate compound is increased. Neither is preferred because it tends to decrease. The concentration of the 1,2,3,4-tetrahydroanthracene-9,10-diol compound relative to the total of the aqueous phase and the organic phase is usually 0.005 g / ml or more and 0.5 g / ml or less, particularly 0.03 g / ml or more. A range of 0.3 g / ml or less is preferable. 10-hydroxy-1,2,3,4-tetrahydroanthracen-9-yl- (meth) acrylate compound obtained when the concentration of 1,2,3,4-tetrahydroanthracene-9,10-diol compound is too low The yield of is reduced. On the other hand, if the concentration of 1,2,3,4-tetrahydroanthracene-9,10-diol compound is too high, the resulting 10-hydroxy-1,2,3,4-tetrahydroanthracen-9-yl- (meth) is obtained. The selectivity of the acrylate compound may decrease. In addition, the 1,2,3,4-tetrahydroanthracene-9,10-diol compound becomes difficult to dissolve in the solvent, and stirring of the slurry solution may be difficult, which is not preferable.

  In the first reaction, from the viewpoint of controlling the reaction temperature and improving the selectivity, the raw material (halogenated) (meth) acryloyl is converted into a 1,2,3,4-tetrahydroanthracene-9,10-diol compound and an organic solvent or the like. A method of dropping into the solution while stirring is preferred.

  In the first reaction, the (meth) acryloylation reaction is preferably performed while cooling. Specifically, the reaction temperature is usually 10 ° C. or lower, preferably 5 ° C. or lower, and preferably the temperature at which the aqueous phase does not solidify. If the reaction temperature is too high due to exotherm, the selectivity of the resulting 10-hydroxy-1,2,3,4-tetrahydroanthracen-9-yl- (meth) acrylate compound tends to decrease and is obtained. The 10-hydroxy-1,2,3,4-tetrahydroanthracen-9-yl- (meth) acrylate compound may be hydrolyzed, which is not preferable.

  In the first reaction, the time required for the (meth) acryloylation reaction is not particularly limited, but is usually in the range of 0.5 to 5 hours, particularly 1 to 2 hours. After completion of the reaction, it is preferable to quench (stop) the reaction as soon as possible.

  In the first reaction, the method for quenching the reaction is, for example, dilute hydrochloric acid (concentration: 1 to 3 mol / L), dilute sulfuric acid (concentration: 0.5 to 1.5 mol / L) in the reaction system (aqueous phase). It is performed by adding an acid to make it acidic. After completion of the reaction, post-treatment such as rough purification and recrystallization purification may be performed as necessary.

  Next, the second reaction will be described. In the second reaction, the 10-hydroxy-1,2,3,4-tetrahydroanthracen-9-yl- (meth) acrylate compound obtained in the first reaction is acylated in the presence or absence of a base. This reaction is to obtain the corresponding 10-acyloxy-1,2,3,4-tetrahydroanthracen-9-yl- (meth) acrylate compound by using an agent.

  Examples of the 10-hydroxy-1,2,3,4-tetrahydroanthracen-9-yl- (meth) acrylate compound used in the second reaction include the following compounds. 10-hydroxy-1,2,3,4-tetrahydroanthracen-9-yl-acrylate, 10-hydroxy-1,2,3,4-tetrahydroanthracen-9-yl-methacrylate, etc. in the first reaction (meth) Examples thereof include compounds obtained by acryloylation.

  Examples of acylating agents that can be used in the second reaction include aliphatic carboxylic acid halides such as acetyl chloride, acetyl bromide, propanoyl chloride, and butanoyl chloride, and aliphatic carboxylic acids such as acetic anhydride, propionic anhydride, and butyric anhydride. Specific examples include acid anhydrides, aromatic carboxylic acid halides such as benzoyl chloride, benzoyl bromide, 1-naphthoyl chloride, and 2-naphthoyl chloride, and aromatic carboxylic acid anhydrides such as benzoic acid anhydride.

  When the acylating agent is a carboxylic acid halide, the amount of the acylating agent used is 1 mol of 10-hydroxy-1,2,3,4-tetrahydroanthracen-9-yl- (meth) acrylate compound. Usually, it is 1 mol or more and 2 mol or less, preferably 1.1 mol or more and 1.3 mol or less. If it is less than 1 mol, unreacted 10-hydroxy-1,2,3,4-tetrahydroanthracen-9-yl- (meth) acrylate compound remains, and if it exceeds 2 mol, acylation Since the agent remains in the reaction product and the reaction product is difficult to crystallize, neither is preferable.

  On the other hand, when the acylating agent is a carboxylic acid anhydride, it is usually 1 mole or more per mole of 10-hydroxy-1,2,3,4-tetrahydroanthracen-9-yl- (meth) acrylate compound. Although it is preferable to add more than 2 molar times, there is no adverse effect on the reaction, and when the carboxylic acid anhydride is liquid at the reaction temperature, it may be added in a large excess as a solvent.

  Examples of the base that can be used in the second reaction include trimethylamine, triethylamine, tributylamine, pyridine, α-picoline, β-picoline, γ-picoline, and piperidine.

  The amount of the base used is 1 mol or more and 3 mol or less with respect to 1 mol of the starting 10-hydroxy-1,2,3,4-tetrahydroanthracen-9-yl- (meth) acrylate compound.

  In the second reaction, the monoacylation reaction is usually performed in a solvent. Solvents used include aromatic hydrocarbon solvents such as benzene, toluene, xylene and chlorobenzene, halogenated hydrocarbon solvents such as methylene chloride, dichloroethane and dichloroethylene, and ketones such as acetone, methyl ethyl ketone and methyl isobutyl ketone. Solvents, amide solvents such as N-methylpyrrolidone and dimethylformamide, and ether solvents such as tetrahydrofuran and 1,4-dioxane are preferably used. When it is liquid at the reaction temperature, an acylating agent can be used as a reaction solvent. The concentration of 10-hydroxy-1,2,3,4-tetrahydroanthracen-9-yl- (meth) acrylate compound in the solvent is usually preferably 0.2 mol / L or more.

  In the second reaction, the reaction temperature is preferably 0 ° C. or higher and 80 ° C. or lower, particularly preferably 0 ° C. or higher and 20 ° C. or lower. If the reaction temperature is too low, the reaction takes time. On the other hand, if the reaction temperature is too high, a by-product is generated. In the second reaction, the time required for the reaction is preferably 15 minutes or longer and 3 hours or shorter.

<Route B>
Next, route B will be described. In route B, the 10-acyloxy-1,2,3,4-tetrahydroanthracen-9-yl- (meth) acrylate compound represented by the general formula (1) of the present invention is a starting material 1,2,3. , 4-tetrahydroanthracene-9,10-diol compound is converted to a 10-acyloxy-1,2,3,4-tetrahydro-9-anthranol compound represented by the following general formula (3). The tri-reaction and the resulting 10-acyloxy-1,2,3,4-tetrahydro-9-anthranol compound are mono (meth) acryloylated to give 10-acyloxy-1,2,3,4-tetrahydro It can be synthesized by a fourth reaction with anthracene-9-yl- (meth) acrylate compound.

（一般式（３）中、Ｚはアルキル基（但し、不飽和二重結合を有するものを除く。）又はアリール基を示し、Ｘ及びＹは同一であっても異なっていても良く、水素原子、アルキル基、ハロゲン原子、アルコキシ基、アリールオキシ基、アルキルチオ基又はアリールチオ基のいずれかを示す。）

(In general formula (3), Z represents an alkyl group (excluding those having an unsaturated double bond) or an aryl group, and X and Y may be the same or different, and may be a hydrogen atom. , An alkyl group, a halogen atom, an alkoxy group, an aryloxy group, an alkylthio group or an arylthio group.

  In the general formula (3), examples of the alkyl group represented by X and Y include a methyl group, an ethyl group, an n-propyl group, and an n-butyl group. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Examples of the alkoxy group include a methoxy group, an ethoxy group, an n-propoxy group, and an n-butoxy group. Examples of the aryloxy group include a phenoxy group and a naphthyloxy group. Examples of the alkylthio group include a methylthio group and an ethylthio group. Examples of the arylthio group include a phenylthio group and a naphthylthio group.

  First, the third reaction will be described. The third reaction consists of reacting a 1,2,3,4-tetrahydroanthracene-9,10-diol compound with an acylating agent in the presence of a base to give 10-acyloxy-1,2,3,4-tetrahydro. This is a reaction for obtaining a -9-anthranol compound.

  The 1,2,3,4-tetrahydroanthracene-9,10-diol compound used in the third reaction is the same as the compound that can be used in the first reaction.

  Examples of the 10-acyloxy-1,2,3,4-tetrahydro-9-anthranol compound obtained in the third reaction include the following compounds. That is, 10-acetyloxy-1,2,3,4-tetrahydro-9-anthranol, 10-propanoyloxy-1,2,3,4-tetrahydro-9-anthranol, 10-n-butanoyloxy -1,2,3,4-tetrahydro-9-anthranol, 10-i-butanoyloxy-1,2,3,4-tetrahydro-9-anthranol, 10-benzoyloxy-1,2,3 4-tetrahydro-9-anthranol, 10- (1-naphthylcarbonyloxy) -1,2,3,4-tetrahydro-9-anthranol, 10- (2-naphthylcarbonyloxy) -1,2,3 4-tetrahydro-9-anthanol etc. are mentioned.

Furthermore, an alkyl group is substituted on the 1,2,3,4-tetrahydroanthracene ring.
Methyl-10-acetyloxy-1,2,3,4-tetrahydro-9-anthranol, 2-methyl-10-propanoyloxy-1,2,3,4-tetrahydro-9-anthranol, 2-methyl -10-n-butanoyloxy-1,2,3,4-tetrahydro-9-anthranol, 2-methyl-10-i-butanoyloxy-1,2,3,4-tetrahydro-9-anthranol 2-methyl-10-benzoyloxy-1,2,3,4-tetrahydro-9-anthranol, 2-methyl-10- (1-naphthylcarbonyloxy) -1,2,3,4-tetrahydro-9 Anthanol, 2-methyl-10- (2-naphthylcarbonyloxy) -1,2,3,4-tetrahydro-9-anthranol, 3-methyl-10-acetylo Ci-1,2,3,4-tetrahydro-9-anthranol, 3-methyl-10-propanoyloxy-1,2,3,4-tetrahydro-9-anthranol, 3-methyl-10-n- Butanoyloxy-1,2,3,4-tetrahydro-9-anthranol, 3-methyl-10-i-butanoyloxy-1,2,3,4-tetrahydro-9-anthranol, 3-methyl- 10-benzoyloxy-1,2,3,4-tetrahydro-9-anthranol, 3-methyl-10- (1-naphthylcarbonyloxy) -1,2,3,4-tetrahydro-9-anthranol, 3 -Methyl-10- (2-naphthylcarbonyloxy) -1,2,3,4-tetrahydro-9-anthranol, 6-methyl-10-acetyloxy-1,2,3,4-te Lahydro-9-anthranol, 6-methyl-10-propanoyloxy-1,2,3,4-tetrahydro-9-anthranol, 6-methyl-10-n-butanoyloxy-1,2,3 4-tetrahydro-9-anthranol, 6-methyl-10-i-butanoyloxy-1,2,3,4-tetrahydro-9-anthranol, 6-methyl-10-benzoyloxy-1,2,3 , 4-Tetrahydro-9-anthranol, 6-methyl-10- (1-naphthylcarbonyloxy) -1,2,3,4-tetrahydro-9-anthranol, 6-methyl-10- (2-naphthylcarbonyl) Oxy) -1,2,3,4-tetrahydro-9-anthranol, 2,6-dimethyl-10-acetyloxy-1,2,3,4-tetrahydro-9-an Tolanol, 2,6-dimethyl-10-propanoyloxy-1,2,3,4-tetrahydro-9-anthranol, 2,6-dimethyl-10-n-butanoyloxy-1,2,3,4 -Tetrahydro-9-anthranol, 2,6-dimethyl-10-i-butanoyloxy-1,2,3,4-tetrahydro-9-anthranol, 2,6-dimethyl-10-benzoyloxy-1, 2,3,4-tetrahydro-9-anthranol, 2,6-dimethyl-10- (1-naphthylcarbonyloxy) -1,2,3,4-tetrahydro-9-anthranol, 2,6-dimethyl- 10- (2-naphthylcarbonyloxy) -1,2,3,4-tetrahydro-9-anthranol and the like can be mentioned.

 Furthermore, 2-chloro-10-acetyloxy-1,2,3,4-tetrahydro-9-anthranol, 2-chloro-10-, wherein a halogen atom is substituted on the 1,2,3,4-tetrahydroanthracene ring, Propanoyloxy-1,2,3,4-tetrahydro-9-anthranol, 2-chloro-10-n-butanoyloxy-1,2,3,4-tetrahydro-9-anthranol, 2-chloro- 10-i-butanoyloxy-1,2,3,4-tetrahydro-9-anthranol, 2-chloro-10-benzoyloxy-1,2,3,4-tetrahydro-9-anthranol, 2-chloro -10- (1-naphthylcarbonyloxy) -1,2,3,4-tetrahydro-9-anthranol, 2-chloro-10- (2-naphthylcarbonyloxy) 1,2,3,4-tetrahydro-9-anthranol, 3-chloro-10-acetyloxy-1,2,3,4-tetrahydro-9-anthranol, 3-chloro-10-propanoyloxy-1 , 2,3,4-tetrahydro-9-anthranol, 3-chloro-10-n-butanoyloxy-1,2,3,4-tetrahydro-9-anthranol, 3-chloro-10-i-butane Noyloxy-1,2,3,4-tetrahydro-9-anthranol, 3-chloro-10-benzoyloxy-1,2,3,4-tetrahydro-9-anthranol, 3-chloro-10- (1 -Naphtylcarbonyloxy) -1,2,3,4-tetrahydro-9-anthranol, 3-chloro-10- (2-naphthylcarbonyloxy) -1,2,3,4-tetra Dro-9-anthranol, 6-chloro-10-acetyloxy-1,2,3,4-tetrahydro-9-anthranol, 6-chloro-10-propanoyloxy-1,2,3,4-tetrahydro -9-anthranol, 6-chloro-10-n-butanoyloxy-1,2,3,4-tetrahydro-9-anthranol, 6-chloro-10-i-butanoyloxy-1,2,3 , 4-Tetrahydro-9-anthranol, 6-chloro-10-benzoyloxy-1,2,3,4-tetrahydro-9-anthranol, 6-chloro-10- (1-naphthylcarbonyloxy) -1, 2,3,4-tetrahydro-9-anthranol, 6-chloro-10- (2-naphthylcarbonyloxy) -1,2,3,4-tetrahydro-9-anthranol 2,6-dichloro-10-acetyloxy-1,2,3,4-tetrahydro-9-anthranol, 2,6-dichloro-10-propanoyloxy-1,2,3,4-tetrahydro-9 Anthranol, 2,6-dichloro-10-n-butanoyloxy-1,2,3,4-tetrahydro-9-anthranol, 2,6-dichloro-10-i-butanoyloxy-1,2 , 3,4-tetrahydro-9-anthranol, 2,6-dichloro-10-benzoyloxy-1,2,3,4-tetrahydro-9-anthranol, 2,6-dichloro-10- (1-naphthyl) Carbonyloxy) -1,2,3,4-tetrahydro-9-anthranol, 2,6-dichloro-10- (2-naphthylcarbonyloxy) -1,2,3,4-tetrahydro- -Anthranol, 2-chloro-6-methyl-10-acetyloxy-1,2,3,4-tetrahydro-9-anthranol, 2-chloro-6-methyl-10-propanoyloxy-1,2, 3,4-tetrahydro-9-anthranol, 2-chloro-6-methyl-10-n-butanoyloxy-1,2,3,4-tetrahydro-9-anthranol, 2-chloro-6-methyl- 10-i-butanoyloxy-1,2,3,4-tetrahydro-9-anthranol, 2-chloro-6-methyl-10-benzoyloxy-1,2,3,4-tetrahydro-9-anthranol 2-chloro-6-methyl-10- (1-naphthylcarbonyloxy) -1,2,3,4-tetrahydro-9-anthranol, 2-chloro-6-methyl-10- (2 Naphthylcarbonyl oxy) -1,2,3,4-tetrahydro-9-Antoranoru the like.

  Furthermore, 5-methoxy-10-acetyloxy-1,2,3,4-tetrahydro-9-anthranol, 5-methoxy-10-, wherein an alkoxy group is substituted on the 1,2,3,4-tetrahydroanthracene ring, Propanoyloxy-1,2,3,4-tetrahydro-9-anthranol, 5-methoxy-10-n-butanoyloxy-1,2,3,4-tetrahydro-9-anthranol, 5-methoxy- 10-i-butanoyloxy-1,2,3,4-tetrahydro-9-anthranol, 5-methoxy-10-benzoyloxy-1,2,3,4-tetrahydro-9-anthranol, 5-methoxy -10- (1-naphthylcarbonyloxy) -1,2,3,4-tetrahydro-9-anthranol, 5-methoxy-10- (2-naphthylcal Nyloxy) -1,2,3,4-tetrahydro-9-anthranol, 2-methyl-5-methoxy-10-acetyloxy-1,2,3,4-tetrahydro-9-anthranol, 2-methyl- 5-methoxy-10-propanoyloxy-1,2,3,4-tetrahydro-9-anthranol, 2-methyl-5-methoxy-10-n-butanoyloxy-1,2,3,4-tetrahydro -9-anthranol, 2-methyl-5-methoxy-10-i-butanoyloxy-1,2,3,4-tetrahydro-9-anthranol, 2-methyl-5-methoxy-10-benzoyloxy- 1,2,3,4-tetrahydro-9-anthranol, 2-methyl-5-methoxy-10- (1-naphthylcarbonyloxy) -1,2,3,4-tetrahydride -9-anthranol, 2-methyl-5-methoxy-10- (2-naphthylcarbonyloxy) -1,2,3,4-tetrahydro-9-anthranol, 2-chloro-5-methoxy-10-acetyl Oxy-1,2,3,4-tetrahydro-9-anthranol, 2-chloro-5-methoxy-10-propanoyloxy-1,2,3,4-tetrahydro-9-anthranol, 2-chloro- 5-methoxy-10-n-butanoyloxy-1,2,3,4-tetrahydro-9-anthranol, 2-chloro-5-methoxy-10-i-butanoyloxy-1,2,3,4 -Tetrahydro-9-anthranol, 2-chloro-5-methoxy-10-benzoyloxy-1,2,3,4-tetrahydro-9-anthranol, 2-chloro-5-methol Xyl-10- (1-naphthylcarbonyloxy) -1,2,3,4-tetrahydro-9-anthranol, 2-chloro-5-methoxy-10- (2-naphthylcarbonyloxy) -1,2,3 , 4-tetrahydro-9-anthranol and the like.

  Furthermore, 5-phenoxy-10-acetyloxy-1,2,3,4-tetrahydro-9-anthranol, 5-phenoxy-10 in which an aryloxy group is substituted on the 1,2,3,4-tetrahydroanthracene ring -Propanoyloxy-1,2,3,4-tetrahydro-9-anthranol, 5-phenoxy-10-n-butanoyloxy-1,2,3,4-tetrahydro-9-anthranol, 5-phenoxy -10-i-butanoyloxy-1,2,3,4-tetrahydro-9-anthranol, 5-phenoxy-10-benzoyloxy-1,2,3,4-tetrahydro-9-anthranol, 5- Phenoxy-10- (1-naphthylcarbonyloxy) -1,2,3,4-tetrahydro-9-anthranol, 5-phenoxy-10- 2-naphthylcarbonyloxy) -1,2,3,4-tetrahydro-9-anthranol, 2-methyl-5-phenoxy-10-acetyloxy-1,2,3,4-tetrahydro-9-anthranol, 2-methyl-5-phenoxy-10-propanoyloxy-1,2,3,4-tetrahydro-9-anthranol, 2-methyl-5-phenoxy-10-n-butanoyloxy-1,2,3 , 4-Tetrahydro-9-anthranol, 2-methyl-5-phenoxy-10-i-butanoyloxy-1,2,3,4-tetrahydro-9-anthranol, 2-methyl-5-phenoxy-10 -Benzoyloxy-1,2,3,4-tetrahydro-9-anthranol, 2-methyl-5-phenoxy-10- (1-naphthylcarbonyloxy -1,2,3,4-tetrahydro-9-anthranol, 2-methyl-5-phenoxy-10- (2-naphthylcarbonyloxy) -1,2,3,4-tetrahydro-9-anthranol, 2 -Chloro-5-phenoxy-10-acetyloxy-1,2,3,4-tetrahydro-9-anthranol, 2-chloro-5-phenoxy-10-propanoyloxy-1,2,3,4-tetrahydro -9-anthranol, 2-chloro-5-phenoxy-10-n-butanoyloxy-1,2,3,4-tetrahydro-9-anthranol, 2-chloro-5-phenoxy-10-i-buta Noyloxy-1,2,3,4-tetrahydro-9-anthranol, 2-chloro-5-phenoxy-10-benzoyloxy-1,2,3,4-tetrahydro -9-anthranol, 2-chloro-5-phenoxy-10- (1-naphthylcarbonyloxy) -1,2,3,4-tetrahydro-9-anthranol, 2-chloro-5-phenoxy-10- ( 2-naphthylcarbonyloxy) -1,2,3,4-tetrahydro-9-anthranol and the like.

  Further, 6-methylthio-10-acetyloxy-1,2,3,4-tetrahydro-9-anthranol, 6-methylthio-10- substituted with an alkylthio group on the 1,2,3,4-tetrahydroanthracene ring. Propanoyloxy-1,2,3,4-tetrahydro-9-anthranol, 6-methylthio-10-n-butanoyloxy-1,2,3,4-tetrahydro-9-anthranol, 6-methylthio- 10-i-butanoyloxy-1,2,3,4-tetrahydro-9-anthranol, 6-methylthio-10-benzoyloxy-1,2,3,4-tetrahydro-9-anthranol, 6-methylthio -10- (1-naphthylcarbonyloxy) -1,2,3,4-tetrahydro-9-anthranol, 6-methylthio-10- ( -Naphthylcarbonyloxy) -1,2,3,4-tetrahydro-9-anthranol, 2-methyl-6-methylthio-10-acetyloxy-1,2,3,4-tetrahydro-9-anthranol, 2 -Methyl-6-methylthio-10-propanoyloxy-1,2,3,4-tetrahydro-9-anthranol, 2-methyl-6-methylthio-10-n-butanoyloxy-1,2,3 4-tetrahydro-9-anthranol, 6-methylthio-10-i-butanoyloxy-1,2,3,4-tetrahydro-9-anthranol, 2-methyl-6-methylthio-10-benzoyloxy-1 , 2,3,4-Tetrahydro-9-anthranol, 2-methyl-6-methylthio-10- (1-naphthylcarbonyloxy) -1,2,3 4-tetrahydro-9-anthranol, 2-methyl-6-methylthio-10- (2-naphthylcarbonyloxy) -1,2,3,4-tetrahydro-9-anthranol, 2-chloro-6-methylthio- 10-acetyloxy-1,2,3,4-tetrahydro-9-anthranol, 2-chloro-6-methylthio-10-propanoyloxy-1,2,3,4-tetrahydro-9-anthranol, 2 -Chloro-6-methylthio-10-n-butanoyloxy-1,2,3,4-tetrahydro-9-anthranol, 6-methylthio-10-i-butanoyloxy-1,2,3,4 Tetrahydro-9-anthranol, 2-chloro-6-methylthio-10-benzoyloxy-1,2,3,4-tetrahydro-9-anthranol, 2- Chloro-6-methylthio-10- (1-naphthylcarbonyloxy) -1,2,3,4-tetrahydro-9-anthranol, 2-chloro-6-methylthio-10- (2-naphthylcarbonyloxy) -1 2,3,4-tetrahydro-9-anthranol and the like.

  Further, 6-phenylthio-10-acetyloxy-1,2,3,4-tetrahydro-9-anthranol, 6-phenylthio-10- substituted with an arylthio group on the 1,2,3,4-tetrahydroanthracene ring. Propanoyloxy-1,2,3,4-tetrahydro-9-anthranol, 6-phenylthio-10-n-butanoyloxy-1,2,3,4-tetrahydro-9-anthranol, 6-phenylthio- 10-i-butanoyloxy-1,2,3,4-tetrahydro-9-anthranol, 6-phenylthio-10-benzoyloxy-1,2,3,4-tetrahydro-9-anthranol, 6-phenylthio -10- (1-naphthylcarbonyloxy) -1,2,3,4-tetrahydro-9-anthranol, 6-phenyl O-10- (2-naphthylcarbonyloxy) -1,2,3,4-tetrahydro-9-anthranol, 2-methyl-6-phenylthio-10-acetyloxy-1,2,3,4-tetrahydro- 9-anthranol, 2-methyl-6-phenylthio-10-propanoyloxy-1,2,3,4-tetrahydro-9-anthranol, 2-methyl-6-phenylthio-10-n-butanoyloxy- 1,2,3,4-tetrahydro-9-anthranol, 2-methyl-6-phenylthio-10-i-butanoyloxy-1,2,3,4-tetrahydro-9-anthranol, 2-methyl- 6-phenylthio-10-benzoyloxy-1,2,3,4-tetrahydro-9-anthranol, 2-methyl-6-phenylthio-10- (1- Phthalylcarbonyloxy) -1,2,3,4-tetrahydro-9-anthranol, 2-methyl-6-phenylthio-10- (2-naphthylcarbonyloxy) -1,2,3,4-tetrahydro-9 -Anthranol, 2-chloro-6-phenylthio-10-acetyloxy-1,2,3,4-tetrahydro-9-anthranol, 2-chloro-6-phenylthio-10-propanoyloxy-1,2, 3,4-tetrahydro-9-anthranol, 2-chloro-6-phenylthio-10-n-butanoyloxy-1,2,3,4-tetrahydro-9-anthranol, 2-chloro-6-phenylthio- 10-i-butanoyloxy-1,2,3,4-tetrahydro-9-anthranol, 2-chloro-6-phenylthio-10-benzoyl Oxy-1,2,3,4-tetrahydro-9-anthranol, 2-chloro-6-phenylthio-10- (1-naphthylcarbonyloxy) -1,2,3,4-tetrahydro-9-anthranol, Examples include 2-chloro-6-phenylthio-10- (2-naphthylcarbonyloxy) -1,2,3,4-tetrahydro-9-anthranol.

  Examples of acylating agents that can be used in the third reaction include aliphatic carboxylic acid halides such as acetyl chloride, acetyl bromide, propanoyl chloride, and butanoyl chloride, benzoyl chloride, benzoyl bromide, -1-naphthoyl chloride, and chloride. And aromatic carboxylic acid halides such as -2-naphthoyl.

  In the third reaction, the amount of the carboxylic acid halide to be used is usually 0.5 mol or more and 2 mol or less, and particularly preferably 0. 1 mol per 1 mol of the 1,2,3,4-tetrahydroanthracene-9,10-diol compound. The range is preferably 8 mol or more and 1.5 mol or less. If the amount of carboxylic acid halide used is too small, unreacted 1,2,3,4-tetrahydroanthracene-9,10-diol compound remains, and processing such as raw material recovery may be required. On the other hand, if the amount of carboxylic acid halide used is too large, a diester in which the two hydroxyl groups of the 1,2,3,4-tetrahydroanthracene-9,10-diol compound are acylated is by-produced, and the yield of the desired product Decreases, which is not preferable.

  Examples of the base that can be used in the third reaction include sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate and the like. In particular, sodium hydroxide and potassium hydroxide are preferable, and sodium hydroxide is more preferable.

  In the third reaction, the amount of the base to be used is usually 1.0 mol or more and 3.0 mol or less, particularly 1. mol. It is preferable to be in the range of 2 mol or more and 2.0 mol or less. If the amount of the base used is too small, the pH of the aqueous layer becomes acidic during the dropwise addition of the carboxylic acid halide, and the selectivity of the resulting 10-acyloxy-1,2,3,4-tetrahydro-9-anthranol compound is high. On the other hand, if the ratio of the base is too large, the carboxylic acid halide may be decomposed, which is not preferable.

  In the third reaction, the monoacylation reaction is usually performed in the presence of a solvent. The type of the solvent is not particularly limited, but it is preferable to carry out the reaction in a two-phase system composed of an aqueous phase and an organic phase, as in the first reaction in Route A. The type of the organic solvent that forms the organic phase is not particularly limited, but it is preferable to use an organic solvent that exhibits relatively low polarity and is not miscible with water. Examples of the organic solvent that can be used include aromatic hydrocarbon solvents such as toluene and xylene, and aliphatic hydrocarbon solvents such as heptane, cyclohexane, and decalin. These organic solvents may be used alone or in combination of two or more in any combination and ratio. When used alone, toluene is preferable. As a combination of two or more organic solvents, a combination of toluene and xylene or toluene and heptane is preferable.

  The ratio of the aqueous phase and the organic phase is not particularly limited, but the volume ratio of the aqueous phase to the total amount of the aqueous phase and the organic phase is preferably in the range of usually 50 vol% or more and 95 vol% or less. . If the volume ratio of the aqueous phase is less than 50 vol% or more than 95 vol%, the selectivity of the 10-acyloxy-1,2,3,4-tetrahydro-9-anthranol compound tends to decrease. Neither is preferred. The concentration of the 1,2,3,4-tetrahydroanthracene-9,10-diol compound relative to the total amount of the aqueous phase and the organic phase is usually 0.005 g / ml or more, 0.5 g / ml or less, particularly 0.03 g / ml. It is preferable to be in the range of not less than ml and not more than 0.3 g / ml. If the concentration of 1,2,3,4-tetrahydroanthracene-9,10-diol compound is too low, the efficiency is poor, while the concentration of 1,2,3,4-tetrahydroanthracene-9,10-diol compound is low. If it is too high, the selectivity is lowered, and it may be difficult to stir the slurry solution with the precipitated solid.

  In the third reaction, the reaction temperature is preferably a method in which a carboxylic acid halide is dropped from the viewpoint of improving the selectivity of the target product. In particular, when the reaction is carried out in a two-phase system composed of an aqueous phase and an organic phase, the 1,2,3,4-tetrahydroanthracene-9,10-diol compound is dissolved in the two-phase solvent of the aqueous phase and the organic phase. The carboxylic acid halide is dropped and reacted while mixing in a container by a technique such as stirring.

  In the third reaction, the monoacylation reaction is preferably performed while cooling. Specifically, it is preferable that the reaction temperature is usually 10 ° C. or lower, particularly 5 ° C. or lower, and the temperature at which the aqueous layer does not solidify. If the reaction temperature is too high due to heat generation, the selectivity tends to decrease, and the resulting 10-acyloxy-1,2,3,4-tetrahydro-9-anthranol compound will hydrolyze, Neither is preferred.

  In the third reaction, the time required for the reaction is usually in the range of 0.5 to 5 hours, particularly 1 to 2 hours. It is preferable to quench (stop) the reaction as soon as possible after the reaction time has elapsed.

  The reaction is quenched by adding an acid such as dilute hydrochloric acid (concentration 1 to 3 mol / L) or dilute sulfuric acid (concentration 0.5 to 1.5 mol / L) to the reaction system (aqueous phase), for example. To do. After completion of the reaction, post-treatment such as rough purification and recrystallization purification may be performed as necessary.

  Next, the fourth reaction will be described. In the fourth reaction, the 10-acyloxy-1,2,3,4-tetrahydro-9-anthranol compound obtained in the third reaction is used in the presence or absence of a base with a (meth) acryloylating agent. (Meth) acryloylation to obtain 10-acyloxy-1,2,3,4-tetrahydroanthracen-9-yl- (meth) acrylate compound.

  As the (meth) acryloylating agent that can be used in the fourth reaction, halogenated (meth) acryloyl is preferably used in the same manner as the (meth) acryloylating agent that can be used in the first reaction in Route A. When the halogen atom is a chlorine atom, it is acryloyl chloride or methacryloyl chloride, and when the halogen atom is a bromine atom, it is acryloyl bromide or methacryloyl bromide. Among them, acryloyl chloride or methacryloyl chloride is particularly preferable because the target product can be obtained with high yield. When 10-acyloxy-1,2,3,4-tetrahydro-9-anthranol compound is reacted with acryloyl chloride, 10-acyloxy-1,2,3,4-tetrahydroanthracen-9-yl-acrylate compound is obtained. It is done. On the other hand, when methacryloyl chloride is reacted, 10-acyloxy-1,2,3,4-tetrahydroanthracen-9-yl-methacrylate compound is obtained.

  In the fourth reaction, the amount of the (meth) acryloylating agent added to 1 mol of the 10-acyloxy-1,2,3,4-tetrahydro-9-anthranol compound is 1 mol times or more and 2 mol times or less. 1 mol times or more and 1.3 mol times or less are preferable. If the amount is less than 1 mol, unreacted 10-acyloxy-1,2,3,4-tetrahydro-9-anthranol compound remains, whereas if it is more than 2 mol, (meth) acryloyl Since a large amount of the agent remains in the reaction product, the resulting 10-acyloxy-1,2,3,4-tetrahydroanthracen-9-yl- (meth) acrylate compound is difficult to crystallize.

  In the fourth reaction, as the base that can be used in the second reaction in Route A, for example, trimethylamine, triethylamine, tributylamine, pyridine, α-picoline, β-picoline, γ-picoline, And piperidine.

  In the fourth reaction, the amount of the base used is usually preferably 1 mol or more and 3 mol or less with respect to 1 mol of the starting 10-acyloxy-1,2,3,4-tetrahydro-9-anthranol compound.

  In the fourth reaction, the reaction between the 10-acyloxy-1,2,3,4-tetrahydro-9-anthranol compound and the halogenated (meth) acryloyl is usually carried out in the presence of a solvent. Solvents used include aromatic hydrocarbon solvents such as benzene, toluene, xylene and chlorobenzene, halogenated hydrocarbon solvents such as methylene chloride, dichloroethane and dichloroethylene, and ketones such as acetone, methyl ethyl ketone and methyl isobutyl ketone. Solvents, amide solvents such as N-methylpyrrolidone and dimethylformamide, and ether solvents such as tetrahydrofuran and 1,4-dioxane are preferably used. An acylating agent can also be used as a solvent. The concentration of the 10-acyloxy-1,2,3,4-tetrahydro-9-anthranol compound in the solvent is usually preferably 0.2 mol / L or more.

  In the fourth reaction, from the viewpoint of controlling the reaction temperature and improving the selectivity, the starting material (halogenated) (meth) acryloyl is converted to a 10-acyloxy-1,2,3,4-tetrahydro-9-anthranol compound and an organic solvent, etc. The method of dropping into the solution with stirring is preferred.

  In the fourth reaction, the (meth) acryloylation reaction is preferably performed while cooling. Specifically, the reaction temperature is 0 ° C. or higher and 80 ° C. or lower, preferably 0 ° C. or higher and 20 ° C. or lower. If the reaction temperature is too low, the reaction takes time, and if it is higher than 80 ° C., the selectivity of the 10-acyloxy-1,2,3,4-tetrahydroanthracen-9-yl- (meth) acrylate compound decreases. There is a tendency and is not preferred. In the fourth reaction, the time required for the (meth) acryloylation reaction is about 15 minutes to 3 hours.

(Radically polymerizable composition)
The 10-acyloxy-1,2,3,4-tetrahydroanthracen-9-yl- (meth) acrylate compound of the present invention can be made into a radical polymerizable composition by mixing a radical polymerization initiator. The radical polymerization initiator that can be used includes a photo radical polymerization initiator and a thermal radical polymerization initiator. Photoradical polymerization using active energy rays such as ultraviolet rays and visible rays is fast and can provide a highly transparent polymer with high efficiency, particularly when the polymerizable composition of the present invention is used for optical applications. It is preferable to use photo radical polymerization.

  Examples of the photo radical polymerization initiator include the following compounds. That is, 2,2-dimethoxy-1,2-diphenylethane-1-one, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1- [4- (2 -Hydroxyethoxy) phenyl] -2-hydroxy-2-methylpropan-1-one, 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one, 2-benzyl-2-dimethyl Amino-1- (4-morpholinophenyl) butan-1-one, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide, 2-isopropylthioxanthone, 2 -T-butylanthraquinone etc. are mentioned. Examples of actual industrial products include Irgacure 651, Irgacure 184, Darocur 1173, Irgacure 907, Irgacure 369, Darocur TPO and Irgacure 819 manufactured by Ciba Specialty Chemicals (Irgacure and Darocur are registered trademarks of Ciba Specialty Chemicals).

  In the radical polymerizable composition of the present invention, a 10-acyloxy-1,2,3,4-tetrahydroanthracen-9-yl- (meth) acrylate compound can be used alone as a radical polymerizable monomer for polymerization. On the other hand, copolymerization is performed using 10-acyloxy-1,2,3,4-tetrahydroanthracen-9-yl- (meth) acrylate compound and one or more other radical polymerizable monomers. You can also.

  Examples of the radical polymerizable monomer to be copolymerized include the following compounds. That is, tetraethylene glycol diacrylate, trimethylolpropane triacrylate, pentaerythritol triacrylate, epoxy acrylate, urethane acrylate polyester acrylate, polybutadiene acrylate, polyol acrylate, polyether acrylate, silicone resin acrylate, imide acrylate, styrene, vinyl acetate , Acrylic acid, methacrylic acid, acrylonitrile, methacrylonitrile, acrylamide, acrylic ester, methacrylic ester, phenyl acrylate, phenyl methacrylate, p-tolyl acrylate, p-tolyl methacrylate, m-tolyl acrylate, m-tolyl methacrylate, o -Tolyl acrylate, o-tolyl methacrylate 2-phenoxyethyl acrylate, 2-phenoxyethyl methacrylate, biphenyl-4-yl-acrylate, biphenyl-4-yl-methacrylate, 4-phenoxyphenyl acrylate, 4-phenoxyphenyl methacrylate, 2-phenoxyphenyl acrylate, 2-phenoxy Examples include phenyl methacrylate, 2- (biphenyl-2-yloxy) ethyl acrylate, and 2- (biphenyl-2-yloxy) ethyl methacrylate.

  10-Acyloxy-1,2,3,4-tetrahydroanthracen-9-yl- (meth) acrylate compound of the present invention and 10-acyloxy-1,2,3,4-tetrahydroanthracen-9-yl- (meth) ) By copolymerizing with other radical polymerizable monomer having a refractive index lower than that of the acrylate compound, it is low other than 10-acyloxy-1,2,3,4-tetrahydroanthracen-9-yl- (meth) acrylate compound. Compared with the case where a radically polymerizable monomer having a refractive index is polymerized alone, not only the refractive index of the resulting polymer is improved, but also solvent resistance, hardness, oxygen impermeability, and the like can be improved. The radical polymerizable composition obtained by adding the 10-acyloxy-1,2,3,4-tetrahydroanthracen-9-yl- (meth) acrylate compound of the present invention to the radical polymerizable monomer has a relatively low viscosity. There is also an advantage that it is easy to handle.

  In the radical polymerizable composition containing the 10-acyloxy-1,2,3,4-tetrahydroanthracen-9-yl- (meth) acrylate compound of the present invention, the concentration of the radical polymerization initiator used is 10-acyloxy. −1,2,3,4-tetrahydroanthracen-9-yl- (meth) acrylate compound and 0.1 wt% or more and 5 wt% or less based on the total weight of the radical polymerizable monomer used in combination as necessary. A range of 0.5 wt% or more and 2 wt% or less is particularly preferable. If the amount is less than 0.1% by weight, the polymerization rate is slow. On the other hand, if the amount is more than 5% by weight, the physical properties of the resulting polymer are deteriorated.

  The radical polymerizable composition containing the 10-acyloxy-1,2,3,4-tetrahydroanthracen-9-yl- (meth) acrylate compound of the present invention includes not only radical photopolymerization but also a thermal radical polymerization initiator. It can also be used for thermal radical polymerization.

  Examples of the thermal radical polymerization initiator include organic peroxides and azo compounds, and both can be used. Examples of the organic peroxide include t-hexylperoxyisopropyl monocarbonate, t-hexylperoxy-2-ethylhexanoate, t-butylperoxy-3,5,6-trimethylhexanoate, t-butyl. Peroxyesters such as peroxyisopropyl carbonates, peroxyketals such as 1,1-bis (t-hexylperoxy) -3,3,6-trimethylcyclohexane, diacyl peroxides such as lauroyl peroxide, etc. Is mentioned. Examples of the polymerization initiator for the azo compound include 2,2′-azobisisobutyronitrile, 2,2′-azobis (2-methylbutyronitrile), 1,1′-azobi (cyclohexane-1 And azonitriles such as (carbonitrile).

  The radical polymerizable composition containing the 10-acyloxy-1,2,3,4-tetrahydroanthracen-9-yl- (meth) acrylate compound of the present invention includes a diluent, as long as the effects of the present invention are not impaired. Various resin additives such as colorants, organic or inorganic fillers, leveling agents, surfactants, antifoaming agents, thickeners, flame retardants, antioxidants, stabilizers, lubricants, plasticizers, etc. Good.

(Polymerization method)
When polymerizing a radical polymerizable composition containing the 10-acyloxy-1,2,3,4-tetrahydroanthracen-9-yl- (meth) acrylate compound of the present invention, it can be cured in the form of a film, It can also be hardened in a lump. In the case of curing in the form of a film, the liquid radically polymerizable composition is applied to a substrate such as a polyester film so as to have a film thickness of 5 to 300 μm using a bar coater or the like. As the film thickness, not only a thin film of several μm but also a thick film of several mm can be used.

  The coating film thus prepared can be polymerized by irradiating it with active energy rays. As a light source that can be used, a light source that can irradiate active energy rays having a wavelength of 250 to 500 nm is used, although it varies depending on the radical photopolymerization initiator used. Specifically, a light source such as a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a halogen lamp, a metal halide lamp, a UV-LED, a blue LED, or a white LED can be used. Natural light such as sunlight can also be used. In particular, the polymerizable composition containing the 10-acyloxy-1,2,3,4-tetrahydroanthracen-9-yl- (meth) acrylate compound of the present invention is a light source most widely used as a UV curing apparatus. Since it can be polymerized even with a certain high-pressure mercury lamp (wavelength 366 nm), it is an industrially very useful compound.

  When polymerizing a radical polymerizable composition containing the 10-acyloxy-1,2,3,4-tetrahydroanthracen-9-yl- (meth) acrylate compound of the present invention, the determination of radical polymerization is, for example, tack-free. It can be performed based on a test (a finger touch test). The tack-free test is a method for measuring the time until tacking (stickiness) of the application surface of the radically polymerizable composition can be removed by light irradiation.

  The polymer obtained by polymerizing the radical polymerizable composition containing the 10-acyloxy-1,2,3,4-tetrahydroanthracen-9-yl- (meth) acrylate compound of the present invention exhibits a high refractive index. In addition, from its chemical structure, it can be expected to have ultraviolet absorption, high heat resistance, high hardness, high gloss, and the like.

  The high refractive index material containing the polymer of the present invention can be widely used for applications such as plastic lenses, prisms, optical fibers, information recording substrates, colored filters, and infrared absorption filters.

  The present invention is illustrated by the following examples which are not intended to limit the scope of the invention. Unless otherwise noted, all parts and percentages are on a weight basis.

The structure of the compound obtained in the examples was confirmed by measurement with the following equipment.
(1) Melting point: Melting point measuring device manufactured by Gelen Camp, model MFB-595 (conforms to JIS K0064)
(2) Refractive index: Abbe refractometer: manufactured by Elmer, model ER-7MW-H
(3) Infrared (IR) spectrophotometer: manufactured by JASCO Corporation, model IR-810
(4) Nuclear magnetic resonance apparatus (NMR): manufactured by JEOL Ltd., model GSX FT NMR Spectrometer
(5) Mass spectrum: manufactured by Shimadzu Corporation, mass spectrometer, model GCMS-QP5000
(6) Gas chromatograph: GC-1700 manufactured by Shimadzu Corporation, Column: CBP1-W25-500
(7) High performance liquid chromatography; JASCO Corporation 880-Pu (pump), UV-970 (detector), 860-CO (column oven), column; Inertosyl ODS-2

(Synthesis Example 1) Synthesis of 10-hydroxy-1,2,3,4-tetrahydroanthracen-9-yl-acrylate In a nitrogen atmosphere, 30.0 ml of water, 18.0 ml of toluene, 670 mg of sodium hydroxide ( 16.8 mmol), and 2.0 g (9.3 mmol) of 9,10-dihydroxy-1,2,3,4-tetrahydroanthracene. Next, while cooling and stirring, a solution prepared by dissolving 1.3 g (14 mmol) of commercially available acryloyl chloride in 2 ml of toluene was added dropwise to the mixture in the reaction vessel with a syringe over 30 minutes. During the dropping, the temperature of the reaction vessel was kept at 4-6 ° C. From the middle of dropping, a large amount of crystals was observed. After completion of the dropping, stirring was continued for another 5 minutes while keeping the temperature of the reaction vessel at 5 ° C. or lower. Thereafter, ethyl acetate was added as an extraction solvent, and further dilute hydrochloric acid was added to acidify the pH of the reaction system (aqueous phase) to stop the reaction. The two layers were then separated and the reaction product was extracted into the organic phase. The organic phase was washed with saturated sodium bicarbonate water and water in this order. Then, the solvent was distilled off from the organic phase with a rotary evaporator to obtain 2.8 g of a crudely brown solid purified product. The crude product was analyzed by gas chromatograph (GC-1700, manufactured by Shimadzu Corporation, column: CBP1-W25-500). As a result, the composition was 14.3% unreacted raw material in terms of peak area ratio, 10-hydroxy-1,2,3,4-tetrahydroanthracen-9-yl-acrylate 53.7%, 1,2,3,4-tetrahydroanthracene-9, 10-yl-diacrylate 20.7% Met. To this crude product, 10 ml of toluene was added and heated on an oil bath at 90 to 100 ° C. while stirring to dissolve. Next, the mixture was allowed to cool, and the precipitated crystals were separated by filtration and dried to obtain 870 mg (3.2 mmol) of light brown crystals. When this crystal was analyzed by gas chromatography, 10-hydroxy-1,2,3,4-tetrahydroanthracen-9-yl-acrylate having a peak area ratio of 96.6% was obtained. The isolated yield based on the raw material 9,10-dihydroxy-1,2,3,4-tetrahydroanthracene was 34 mol%.

The physicochemical properties of this product are shown below.
Melting point: 171-172 ° C

Refractive index n _D = 1.641

IR (KBr, cm ⁻¹ ): 3440, 2940, 1723, 1632, 1595, 1572, 1504, 1408, 1390, 1302, 1222, 1172, 1180, 1167, 1068, 1038, 922, 808, 762

¹ H-NMR (400 MHz, CDCl ₃ ): δ 7.90-8.07 (m, 1H), 7.48-7.65 (m, 1H), 7.28-7.47 (m, 2H), 6.74 (d, 1H), 6.49 (dd, 1H), 6.12 (d, 1H), 5.23-5.40 (m, 1H), 2.27-2.95 (m, 4H), 1.52-2.95 (m, 4H)

(Synthesis Example 2) Synthesis of 10-hydroxy-1,2,3,4-tetrahydroanthracen-9-yl-methacrylate In a nitrogen atmosphere, 30.0 ml of water, 1.6 ml of toluene, 933 mg of sodium hydroxide ( 23.3 mmol), and 2.0 g (9.3 mmol) of 9,10-dihydroxy-1,2,3,4-tetrahydroanthracene. Next, with cooling and stirring, 9.2 g of a toluene solution of methacryloyl chloride synthesized in advance from methacrylic acid and thionyl chloride was weighed. This toluene solution contains 2.24 g (21.4 mmol) of methacryloyl chloride and 8.2 ml of toluene. This solution was added dropwise to the mixture in the reaction vessel with a syringe over 40 minutes. During the dropping, the temperature of the reaction vessel was kept at 5 to 10 ° C. From the middle of dropping, a large amount of crystals was observed. After completion of the dropwise addition, ethyl acetate was added as an extraction solvent, and further dilute hydrochloric acid was added to acidify the pH of the reaction system (aqueous phase) to stop the reaction. The two layers were then separated and the reaction product was recovered in the organic phase. The organic phase was washed with saturated sodium bicarbonate water and water in this order. Then, the solvent was distilled off with a rotary evaporator to obtain 2.3 g of a crude product as a tan solid. The crude product was analyzed by gas chromatograph (GC-1700, manufactured by Shimadzu Corporation, column: CBP1-W25-500), and the composition was 8.7% of unreacted raw material in terms of peak area ratio, 10 of the target product. -Hydroxy-1,2,3,4-tetrahydroanthracen-9-yl-methacrylate 85.3%, 1,2,3,4-tetrahydroanthracene-9,10-yl-dimethacrylate 0.2% . To this crude product was added 5 ml of toluene and 5 ml of hexane, and the mixture was heated and dissolved in an oil bath at 80 to 90 ° C. with stirring. Next, the mixture was allowed to cool, and the precipitated crystals were collected by filtration and dried to obtain 1.5 g (5.3 mmol) of pale yellow crystals. When this crystal was analyzed by high performance liquid chromatography (LC), the purity of 10-hydroxy-1,2,3,4-tetrahydroanthracen-9-yl-methacrylate was 97.6% in peak area ratio. . The isolated yield based on the starting 9,10-dihydroxy-1,2,3,4-tetrahydroanthracene was 57 mol%.

The physicochemical properties of this product are shown below.
Melting point: 140-141 ° C

Refractive index n _D = 1.626

IR (KBr, cm ⁻¹ ): 3460, 2940, 1742, 1600, 1572, 1390, 1370, 1295, 1224, 1180, 1068, 1044, 760

¹ H-NMR (400 MHz, CDCl ₃ ): δ 7.92-8.00 (m, 1H), 7.56-7.61 (m, 1H), 7.27-7.42 (m, 2H), 6.53 (s, 1H), 5.85 (s, 1H), 5.52 (bs, 1H), 2.30-2.91 (m, 4H), 2.17 (s, 3H), 1 .52-1.88 (m, 4H)

Synthesis Example 3 Synthesis of 10-acetyloxy-1,2,3,4-tetrahydro-9-anthranol In a nitrogen atmosphere, 20.0 ml of water, 18 ml of toluene, 930 mg of sodium hydroxide (23.3) Mmol), and 2.0 g (9.3 mmol) of 9,10-dihydroxy-1,2,3,4-tetrahydroanthracene. Next, while cooling and stirring, a solution obtained by dissolving 1.69 g (21.5 mmol) of commercially available acetyl chloride in 2 ml of toluene was added dropwise over 20 minutes while stirring the mixture in the reaction vessel with a syringe. During the dropping, the temperature of the reaction vessel was kept at 7 to 10 ° C. From the middle of dropping, a large amount of crystals was observed. After completion of the dropwise addition, ethyl acetate was added as an extraction solvent, and further dilute hydrochloric acid was added to acidify the pH of the reaction system (aqueous phase) to stop the reaction. The two layers were then separated and the reaction product was recovered in the organic phase. The organic phase was washed with saturated sodium bicarbonate water and water in this order. Then, the solvent was distilled off with a rotary evaporator to obtain 2.1 g of a yellow solid crude product. When this crude product was analyzed by liquid chromatography, the composition was as follows: unreacted raw material 0.6% in peak area ratio, 10-acetyloxy-1,2,3,4-tetrahydro-9 as the target product. -Anthranol 72.1%, 1,2,3,4-tetrahydroanthracene-9, 10-yl-diacetate 21.4%. To this crude product, 8 ml of toluene was added and heated on an oil bath at 80 to 90 ° C. with stirring to dissolve. Next, the mixture was allowed to cool, and the precipitated crystals were collected by filtration and dried to obtain 0.87 g (3.4 mmol) of pale yellow crystals. When this crystal was analyzed by high performance liquid chromatography (LC), the purity of 10-propanoyloxy-1,2,3,4-tetrahydro-9-anthranol was 84.7% in peak area ratio. . The isolated yield based on the starting 9,10-dihydroxy-1,2,3,4-tetrahydroanthracene was 37 mol%.

The physicochemical properties of this product are shown below.
Melting point: 161-162 ° C

Refractive index n _D = 1.628

IR (KBr, cm ⁻¹ ): 3460, 2940, 1742, 1600, 1572, 1390, 1370, 1295, 1224, 1180, 1044, 760

¹ H-NMR (400 MHz, CDCl ₃ ): δ 7.94-8.02 (m, 1H), 7.56-7.65 (m, 1H), 7.30-7.46 (m, 2H), 5.32 (bs, 1H), 2.39-2.89 (m, 7H), 1.60-1.88 (bs, 4H)

Synthesis Example 4 Synthesis of 10-propanoyloxy-1,2,3,4-tetrahydro-9-anthranol In a nitrogen atmosphere, 20.0 ml of water, 18 ml of toluene, 930 mg of sodium hydroxide (23. 3 mmol), and 2.0 g (9.3 mmol) of 9,10-dihydroxy-1,2,3,4-tetrahydroanthracene. Next, while cooling and stirring, a solution prepared by dissolving 2.0 g (21.6 mmol) of commercially available propionyl chloride in 2 ml of toluene was added dropwise over 20 minutes while stirring the mixture in the reaction vessel with a syringe. During the dropping, the temperature of the reaction vessel was kept at 5 to 10 ° C. From the middle of dropping, a large amount of crystals was observed. After completion of the dropwise addition, ethyl acetate was added as an extraction solvent, and further dilute hydrochloric acid was added to acidify the pH of the reaction system (aqueous phase) to stop the reaction. The two layers were then separated and the reaction product was recovered in the organic phase. The organic phase was washed with saturated sodium bicarbonate water and water in this order. Then, the solvent was distilled off by a rotary evaporator to obtain 1.7 g of a crude product as a tan solid. The crude purified product was analyzed by gas chromatograph (GC-1700, manufactured by Shimadzu Corporation, column: CBP1-W25-500). As a result, the composition was 1.6% unreacted raw material by peak area ratio, and 10 of the target product. -Propanoyloxy-1,2,3,4-tetrahydro-9-anthranol 85.8%, 1,2,3,4-tetrahydroanthracene-9,10-yl-dipropionate 6.6%. To this crude product, 8 ml of toluene was added and heated on an oil bath at 80 to 90 ° C. with stirring to dissolve. Next, the mixture was allowed to cool, and the precipitated crystals were collected by filtration and dried to obtain 1.50 g (5.56 mmol) of pale yellow crystals. When this crystal was analyzed by high performance liquid chromatography (LC), the purity of 10-propanoyloxy-1,2,3,4-tetrahydro-9-anthranol was 95.4% in peak area ratio. . The isolated yield based on the starting 9,10-dihydroxy-1,2,3,4-tetrahydroanthracene was 60 mol%.

The physicochemical properties of this product are shown below.
Melting point: 143-144 ° C

Refractive index n _D = 1.614

IR (KBr, cm ⁻¹ ): 3450, 2940, 1734, 1600, 1572, 1500, 1460, 1420, 1390, 1358, 1296, 1222, 1162, 1080, 1080, 922, 760, 702

¹ H-NMR (400 MHz, CDCl ₃ ): δ 7.96-8.10 (m, 1H), 7.53-7.62 (m, 1H), 7.30-7.42 (m, 2H), 5.25-5.38 (m, 1H), 2.40-2.89 (m, 6H), 1.58-1.90 (bs, 4H), 1.38 (t, 3H)

Mass spectrum: (EI-MS) m / z = 270 (M ⁺ )

Example 1 Synthesis of 10-acetyloxy-1,2,3,4-tetrahydro-anthracen-9-yl-acrylate (Route B)
Under a nitrogen gas atmosphere, 9 ml of acetonitrile, 510 mg (5.0 mmol) of triethylamine and 650 mg of 10-acetyloxy-1,2,3,4-tetrahydro-9-anthranol synthesized in the same manner as in Synthesis Example 3 were placed in a reaction vessel. (2.54 mmol) was charged. Next, while cooling and stirring, a solution prepared by dissolving 370 mg (4.1 mmol) of commercially available acryloyl chloride in 1 ml of acetonitrile was added dropwise to the mixture in the reaction vessel with a syringe over 15 minutes. During the dropping, the temperature in the reaction vessel was kept at 10 to 15 ° C or lower. After completion of the dropwise addition, the temperature was returned to room temperature and stirring was continued for another 20 minutes. Thereafter, water and ethyl acetate were added, and two layers were separated to obtain an organic phase. The organic phase was washed with saturated aqueous sodium hydrogencarbonate and then with water, and then the solvent was distilled off with a rotary evaporator to obtain 0.74 g of a yellow solid crude product. When the crude product was analyzed by high performance liquid chromatography, the purity of 10-acetyloxy-1,2,3,4-tetrahydro-anthracen-9-yl-acrylate was 91.3% in peak area ratio. . The crude product was recrystallized with a toluene solvent to obtain 0.43 g (1.4 mmol) of pale yellow crystals. When analyzed by high performance liquid chromatography (LC), the purity of 10-acetyloxy-1,2,3,4-tetrahydro-anthracen-9-yl-acrylate was 94.8% in terms of peak area ratio. The isolated yield based on the starting 10-acetyloxy-1,2,3,4-tetrahydro-9-anthranol was 55 mol%.

The physicochemical properties of this product are shown below.
Melting point: 158-160 ° C

Refractive index n _D = 1.606

IR (KBr, cm ⁻¹ ): 2949, 1756, 1742, 1368, 1246, 1212, 1180, 1160, 1058, 980, 760

¹ H-NMR (400 MHz, CDCl ₃ ): δ 7.64-7.73 (m, 2H), 7.39-7.48 (m, 2H), 6.73 (d, 1H), 6.48 ( dd, 1H), 6.10 (d, 1H), 2.55-2.95 (bs, 4H), 2.47 (s, 3H), 1.72-1.91 (bs, 4H)

Mass spectrum: (EI-MS) m / z = 310 (M ⁺ )

Example 2 Synthesis of 10-acetyloxy-1,2,3,4-tetrahydro-anthracen-9-yl-acrylate (Route A)
In a reaction vessel, 8 ml of acetonitrile, 1.41 g (14.0 mmol) of triethylamine and 0.99 g of 10-hydroxy-1,2,3,4-tetrahydroanthracen-9-yl-acrylate synthesized in the same manner as in Synthesis Example 1. (3.7 mmol) was charged. Next, while cooling and stirring under a nitrogen gas atmosphere, a solution obtained by dissolving 550 mg (7.0 mmol) of commercially available acetyl chloride in 2 ml of acetonitrile is added to the mixture in the reaction vessel with a syringe over 15 minutes. It was dripped. During the dropping, the temperature in the reaction vessel was kept at around 10 ° C. After completion of the dropwise addition, the temperature was returned to room temperature, and stirring was further continued for 10 minutes. Thereafter, water and ethyl acetate were added, and two layers were separated to obtain an organic phase. The organic phase was washed with saturated aqueous sodium bicarbonate and then with water, and the solvent was distilled off to obtain 1.03 g of a yellowish brown crude product. This was recrystallized with a methanol solvent to obtain 0.64 g (2.1 mmol) of light brown crystals. This was the same as the 10-acetyloxy-1,2,3,4-tetrahydro-anthracen-9-yl-acrylate obtained in Example 1, and the starting 10-hydroxy-1,2,3 The isolated yield based on 1,4-tetrahydroanthracen-9-yl-acrylate was 57 mol%.

Example 3 Synthesis of 10-propanoyloxy-1,2,3,4-tetrahydro-anthracen-9-yl-methacrylate (Route A)
In a reaction vessel, 8 ml of acetonitrile, 1.43 g (14.2 mmol) of triethylamine and 1.0 g of 10-hydroxy-1,2,3,4-tetrahydroanthracen-9-yl-methacrylate synthesized in the same manner as in Synthesis Example 2. (3.5 mmol) was charged. Next, while cooling and stirring under a nitrogen gas atmosphere, a solution obtained by dissolving 660 mg (7.1 mmol) of commercially available propionyl chloride in 2 ml of acetonitrile is added to the mixture in the reaction vessel with a syringe over 15 minutes. It was dripped. During the dropping, the temperature in the reaction vessel was kept at around 10 ° C. After completion of the dropwise addition, the temperature was returned to room temperature, and stirring was further continued for 10 minutes. Thereafter, water and ethyl acetate were added, and two layers were separated to obtain an organic phase. The organic phase was washed with a saturated aqueous sodium bicarbonate solution and then with water, and then the solvent was distilled off to obtain 1.10 g of a yellowish brown crude product. When the crude product was analyzed by high performance liquid chromatography (LC), the purity of 10-propanoyloxy-1,2,3,4-tetrahydro-anthracen-9-yl-methacrylate was 92.1 in peak area ratio. %Met. The crude product was recrystallized with a methanol solvent to obtain 0.57 g (1.7 mmol) of light brown crystals. When analyzed by high performance liquid chromatography (LC), the purity of 10-propanoyloxy-1,2,3,4-tetrahydro-anthracen-9-yl-methacrylate was 97.2% in terms of peak area ratio. . The isolated yield based on the starting 10-propanoyloxy-1,2,3,4-tetrahydro-9-anthranol was 49 mol%.

The physicochemical properties of this product are shown below.
Melting point: 149-151 ° C

Refractive index n _D = 1.592

IR (KBr, cm ⁻¹ ): 2950, 1750, 1736, 1635, 1460, 1362, 1298, 1204, 1162, 1132, 1090, 1040, 760

¹ H-NMR (400 MHz, CDCl ₃ ): δ 7.63-7.72 (m, 2H), 7.40-7.47 (m, 2H), 6.51 (s, 1H), 5.85 ( s, 1H), 2.50-3.02 (m, 6H), 2.15 (s, 3H), 1.82 (bs, 4H), 1.38 (t, 3H)

Example 4 Synthesis of 10-propanoyloxy-1,2,3,4-tetrahydro-anthracen-9-yl-acrylate (Route B)
Under a nitrogen gas atmosphere, 9 ml of acetonitrile, 1.4 g (13.9 mmol) of triethylamine and 10-propanoyloxy-1,2,3,4-tetrahydro-9- synthesized in the same manner as in Synthesis Example 4 were placed in a reaction vessel. Anthranol 1.0 g (3.7 mmol) was charged. Next, while cooling and stirring under a nitrogen gas atmosphere, a solution prepared by dissolving 680 mg (7.5 mmol) of commercially available acryloyl chloride in 1 ml of acetonitrile is dropped into the mixture in the reaction vessel with a syringe over 20 minutes. did. During the dropping, the internal temperature was kept at 9 to 15 ° C or lower. After completion of the dropwise addition, the temperature was returned to room temperature, and stirring was further continued for 40 minutes. Thereafter, water and ethyl acetate were added, and two layers were separated to obtain an organic phase. The organic phase was washed with saturated aqueous sodium hydrogencarbonate and then with water, and then the solvent was distilled off to obtain 1.40 g of a crude purified product as a yellow solid. When yellow solid was analyzed by high performance liquid chromatography (LC), the purity of 10-propanoyloxy-1,2,3,4-tetrahydro-anthracen-9-yl-acrylate was 80.0% in peak area ratio. Met. The crude product was recrystallized with a toluene solvent to obtain 0.46 g (1.4 mmol) of pale yellow crystals. When analyzed by high performance liquid chromatography (LC), the purity of 10-propanoyloxy-1,2,3,4-tetrahydro-anthracen-9-yl-acrylate was 95.3% in terms of peak area ratio. . The isolated yield based on 10-propanoyloxy-1,2,3,4-tetrahydro-9-anthranol as a raw material was 38 mol%.

The physicochemical properties of this product are shown below.
Melting point: 149-151 ° C

Refractive index n _D = 1.592

IR (KBr, cm ⁻¹ ): 2950, 1750, 1736, 1635, 1572, 1460, 1362, 1298, 1204, 1132, 1090, 1040, 760

¹ H-NMR (400 MHz, CDCl ₃ ): δ 7.66-7.74 (m, 2H), 7.38-7.48 (m, 2H), 6.71 (d, 1H), 6.49 ( dd, 1H), 6.12 (d, 1H), 2.56-2.89 (m, 6H), 1.70-1.92 (bs, 4H), 1.39 (t, 3H)

Mass spectrum: (EI-MS) m / z = 324 (M ⁺ )

(Example 5)
Photocopolymerization of 10-propanoyloxy-1,2,3,4-tetrahydro-anthracen-9-yl-acrylate and trimethylolpropane triacrylate 10-propanoyloxy-1 synthesized in the same manner as in Example 4. , 2,3,4-Tetrahydro-anthracen-9-yl-acrylate, 100 parts of trimethylolpropane triacrylate, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide (manufactured by Ciba Specialty) Irgacure 819) 1 part was mixed and immersed in an oil bath at 60 ° C. to melt. The obtained polymerizable composition was coated on a polyester film (Toray Lumirror) so that the film thickness was 0.2 mm, and then the surface was irradiated with ultraviolet rays while keeping the film at 50 ° C. in a nitrogen atmosphere. An LED (irradiation intensity at a wavelength of 395 nm was 10 mw / cm 2) was irradiated for 1 minute to obtain a photopolymerized product. The refractive index of the obtained polymer was nD = 1.525.

(Example 6)
Photocopolymerization of 10-propanoyloxy-1,2,3,4-tetrahydro-anthracen-9-yl-methacrylate and trimethylolpropane triacrylate 10-propanoyloxy-1 synthesized in the same manner as in Example 3. , 2,3,4-Tetrahydro-anthracen-9-yl-methacrylate, 100 parts of trimethylolpropane triacrylate, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide (manufactured by Ciba Specialty) Irgacure 819) 1 part was mixed and immersed in an oil bath at 60 ° C. to melt. The obtained polymerizable composition was coated on a polyester film (Toray Lumirror) so that the film thickness was 0.2 mm, and then the surface was irradiated with ultraviolet rays while keeping the film at 50 ° C. in a nitrogen atmosphere. An LED (irradiation intensity at a wavelength of 395 nm was 10 mw / cm 2) was irradiated for 1 minute to obtain a photopolymerized product. The refractive index of the obtained polymer was nD = 1.521.

(Comparative Example 1)
Photopolymerization of trimethylolpropane triacrylate 100 parts of trimethylolpropane triacrylate was mixed with 1 part of bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide (Irgacure 819 manufactured by Ciba Specialty) and 60 ° C. It was immersed in an oil bath and melted. The obtained polymerizable composition was coated on a polyester film (Toray Lumirror) so that the film thickness was 0.2 mm, and then the surface was irradiated with ultraviolet rays while keeping the film at 50 ° C. in a nitrogen atmosphere. An LED (irradiation intensity at a wavelength of 395 nm was 10 mw / cm 2) was irradiated for 1 minute to obtain a photopolymerized product. The refractive index of the obtained polymer was nD = 1.512.

  The following is clear from Examples 5 and 6 and Comparative Example 1. That is, 10-propanoyloxy-1,2,3,4-tetrahydro-anthracen-9-yl- (meth) acrylate is copolymerized with trimethylolpropane triacrylate to give a homopolymer of trimethylolpropane triacrylate. The copolymer using 10-propanoyloxy-1,2,3,4-tetrahydro-anthracen-9-yl- (meth) acrylate has the effect of increasing the refractive index. I understand that.

Claims (6)

A 10-acyloxy-1,2,3,4-tetrahydroanthracen-9-yl- (meth) acrylate compound represented by the general formula (1).

(In the general formula (1), R represents a hydrogen atom or a methyl group, Z represents an alkyl group (excluding those having an unsaturated double bond) or an aryl group, and X and Y are the same. Or may be different, and represents a hydrogen atom, an alkyl group, a halogen atom, an alkoxy group, an aryloxy group, an alkylthio group or an arylthio group.) The 10-acyloxy-1, 2-acetyl-1,2-3,4-tetrahydroanthracen-9-yl- (meth) acrylate compound represented by the general formula (2) is acylated. A method for producing 2,3,4-tetrahydroanthracen-9-yl- (meth) acrylate compound.

(In the general formula (2), R represents a hydrogen atom or a methyl group, X and Y may be the same or different, and a hydrogen atom, an alkyl group, a halogen atom, an alkoxy group, an aryloxy group, an alkylthio group. Represents either a group or an arylthio group.) The 10-acyloxy-1,2, 2 compound according to claim 1, which comprises (meth) acryloylating a 10-acyloxy-1,2,3,4-tetrahydro-9-anthranol compound represented by the general formula (3). Method for producing 3,4-tetrahydroanthracen-9-yl- (meth) acrylate compound.

(In general formula (3), Z represents an alkyl group (excluding those having an unsaturated double bond) or an aryl group, and X and Y may be the same or different, and may be a hydrogen atom. , An alkyl group, a halogen atom, an alkoxy group, an aryloxy group, an alkylthio group or an arylthio group. A radical polymerizable composition comprising the 10-acyloxy-1,2,3,4-tetrahydroanthracen-9-yl- (meth) acrylate compound according to claim 1 and a radical polymerization initiator. A polymer obtained by polymerizing the radically polymerizable composition according to claim 4. A high refractive index material containing the polymer according to claim 5.