JP6221610B2 - Polymerization inhibitor for carboxylic acid halide - Google Patents

Description

The present invention relates to a polymerization inhibitor for a carboxylic acid halide having a polymerizable group.

Carboxylic acid halides play an important role as raw materials and intermediates for the production of optical materials, pharmaceuticals, and agricultural chemicals. Particularly, acrylic acid chlorides and methacrylic acid chlorides having a polymerizable group are polymerizable groups in organic synthesis. Since it is useful as an acylating agent that can be easily imparted, there is a great demand.

In the process of producing a carboxylic acid halide having a polymerizable group such as acrylic acid chloride or methacrylic acid chloride, after reacting with a corresponding carboxylic acid and a halogenating agent such as thionyl chloride, phosgene, or phosphorus oxychloride in the presence of a catalyst. Distillation purification is performed. At that time, in order to prevent polymerization of the produced carboxylic acid halide having a polymerizable group, as a polymerization inhibitor, p-methoxyphenol, 1,4-hydroquinone having a monocyclic aromatic skeleton substituted with a phenolic OH group, di- t-Butyl-p-cresol or the like, or phenothiazine containing a hetero atom such as sulfur is used alone or in combination (Patent Document 1).

However, in the distillation purification of carboxylic acid halides having such a polymerizable group, etc., the polymerization inhibitor present in the system due to insufficient ability of the polymerization inhibitor used or entrainment due to the high vapor pressure of the polymerization inhibitor. As a result, polymerization of the carboxylic acid halide having a polymerizable group occurs, and coloring of the product, clogging of the distillation tower, and the like become problems.

In order to suppress such polymerization during distillation, a method of blowing oxygen into the distillation reactor without using a polymerization inhibitor has been proposed (Patent Document 2). However, it is not sufficient in terms of safety because it may reach the combustion limit.

In addition, a polymerization inhibitor is added to the produced carboxylic acid halide having a polymerizable group in order to suppress polymerization during storage or transfer. Examples of the polymerization inhibitor used at this time include p-methoxyphenol, 1,4-hydroquinone, and di-t-butyl-p-cresol in which a monocyclic aromatic skeleton is substituted with a phenolic OH group. The long-term polymerization inhibition effect was not sufficient.

Furthermore, polymerization inhibitors include those containing hetero atoms such as sulfur and those having high toxicity, and development of a new polymerization inhibitor is desired from the viewpoint of improvement in handling properties and reduction of environmental load.

On the other hand, it is already known that a compound having a condensed polycyclic aromatic skeleton used in the present invention has an action as a polymerization inhibitor (Patent Document 3). However, although it is described that it is effective for α, β-unsaturated carboxylic acid compounds, α, β-unsaturated carboxylic acid ester compounds, aromatic vinyl compounds, vinyl ester compounds or acrylic compounds, the polymerizable group is It is not described that it is used as a polymerization inhibitor of a polymerizable compound having a high reactivity with a hydroxyl group such as a carboxylic acid halide, and its inhibitory effect compared with a polymerization inhibitor having a conventional monocyclic aromatic skeleton It was not clear that was very strong.

JP 2003-277319 A JP 2000-290223 A JP 2012-111741 A

The present invention has been made in view of the above circumstances, and its first object is to produce a carboxylic acid halide having a polymerizable group, which has a high ability to inhibit polymerization at the time of distillation purification and is accompanied by droplets at a low vapor pressure. It is to provide a polymerization inhibitor with a small amount. A second object is to provide a polymerization inhibitor capable of imparting high storage stability to the produced carboxylic acid halide having a polymerizable group.

Therefore, as a result of intensive studies by the present inventors, by using a compound having a condensed polycyclic aromatic skeleton having a specific structural feature as a polymerization inhibitor, the knowledge that the above problem can be solved, The present invention has been completed.

That is, the first gist of the present invention resides in a polymerization inhibitor for a carboxylic acid halide having a polymerizable group, which has a condensed polycyclic aromatic skeleton represented by the following general formula (1).

(In the formula, n represents an integer of 1 to 4, R represents a hydrogen atom, an alkyl group, an aryl group, an aralkyl group, an alkoxyalkyl group, a glycidyl group, a hydroxyalkyl group, or an aryloxyalkyl group, and a plurality of OR groups. In some cases, R may be the same or different, and X, Y and Z may be the same or different, and each represents a hydrogen atom, a hydroxyl group, or a halogen atom. Represents an acyl group, an alkyl group, an aryl group, an aralkyl group, an alkoxyalkyl group, a glycidyl group, a hydroxyalkyl group or an aryloxyalkyl group, of which X and Y are bonded to each other to form a saturated or unsaturated ring. Or a ring may be formed across an oxygen atom.)

The second gist of the present invention resides in a polymerization inhibitor for a carboxylic acid halide having a polymerizable group, which has a condensed polycyclic aromatic skeleton represented by the following general formula (2).

(In the formula, R ¹ and R ² may be the same or different, and represent a hydrogen atom, an alkyl group, an aryl group, an aralkyl group, an alkoxyalkyl group, a glycidyl group, a hydroxyalkyl group or an aryloxyalkyl group. X, Y and Z may be the same or different and each represents a hydrogen atom, a hydroxyl group, a halogen atom, an acyl group, an alkyl group, an aryl group, an aralkyl group, an alkoxyalkyl group, or a glycidyl group. Represents a hydroxyalkyl group or an aryloxyalkyl group, among which X and Y may be bonded to each other to form a saturated or unsaturated ring, or a ring may be formed with an oxygen atom in between.

The third gist of the present invention resides in a polymerization inhibitor for a carboxylic acid halide having a polymerizable group, which has a condensed polycyclic aromatic skeleton represented by the following general formula (3).

(In the formula, X, Y and Z may be the same or different, and each is a hydrogen atom, a hydroxyl group, a halogen atom, an acyl group, an alkyl group, an aryl group, an aralkyl group, an alkoxyalkyl group, A glycidyl group, a hydroxyalkyl group or an aryloxyalkyl group, among which X and Y may be bonded to each other to form a saturated or unsaturated ring, or a ring may be formed with an oxygen atom in between. .)

A fourth gist of the present invention is a carboxylic acid halide having a polymerizable group according to any one of the first to third gist, wherein the halide in the carboxylic acid halide having a polymerizable group is chloride or bromide. It exists in the polymerization inhibitor.

According to a fifth aspect of the present invention, in any one of the first to fourth aspects, the carboxylic acid having a polymerizable group in the carboxylic acid halide having a polymerizable group is acrylic acid or methacrylic acid. It exists in the polymerization inhibitor for carboxylic acid halides which have a polymeric group.

According to a sixth aspect of the present invention, there is provided a carboxylic acid halide having a polymerizable group, which comprises the polymerization inhibitor according to any one of the first to fifth aspects and p-methoxyphenol. A polymerization inhibitor composition.

ADVANTAGE OF THE INVENTION According to this invention, in manufacture of the carboxylic acid halide which has a polymeric group, the polymerization inhibitory ability at the time of distillation refinement | purification is high, and the polymerization inhibitor with few amounts of entrainment with low vapor pressure can be provided. Moreover, the polymerization inhibitor which can provide high storage stability to the manufactured carboxylic acid halide which has a polymeric group can be provided.

The polymerization inhibitor for carboxylic acid halides of the present invention is a compound having a condensed polycyclic aromatic skeleton represented by the following general formula (1).

In the general formula (1), n represents an integer of 1 to 4, R represents a hydrogen atom, an alkyl group, an aryl group, an aralkyl group, an alkoxyalkyl group, a glycidyl group, a hydroxyalkyl group, or an aryloxyalkyl group, and OR When there are a plurality of groups, R may be the same or different. X, Y and Z may be the same or different, and each is a hydrogen atom, hydroxyl group, halogen atom, acyl group, alkyl group, aryl group, aralkyl group, alkoxy group, alkoxyalkyl group, glycidyl. Represents a group, a hydroxyalkyl group, an aryloxyalkyl group or an aryloxyalkyl group, of which X and Y may combine with each other to form a saturated or unsaturated ring, and form a ring with an oxygen atom in between You may do it.

Examples of the alkyl group represented by R in the general formula (1) include methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, tert-butyl group, and n-pentyl. Group, n-hexyl group, 2-ethylhexyl group, n-decyl group, n-dodecyl group and the like. Examples of the aryl group include a phenyl group, a p-tolyl group, an o-tolyl group, and a naphthyl group. Examples of the aralkyl group include benzyl group, phenethyl group, phenylpropyl group, naphthylmethyl group, naphthylethyl group and the like. Examples of the alkoxyalkyl group include 2-methoxyethyl group and 2-ethoxyethyl group. Examples of the glycidyl group include a glycidyl group and a 2-methylglycidyl group. Examples of the hydroxyalkyl group include a hydroxymethyl group, a 2-hydroxyethoxy group, a 2-hydroxypropyl group, a 3-hydroxypropyl group, a 2-hydroxybutyl group, and a 3-hydroxybutyl group. Examples of the aryloxyalkyl group include phenoxyethyl and triloxyethyl. In addition to those described above, there may be mentioned substituents containing oxygen, nitrogen and sulfur. However, a structure composed of carbon, oxygen, and hydrogen is desirable from the viewpoints of improving the handleability and reducing the environmental load.

Examples of the halogen atom represented by X, Y, and Z in the general formula (1) include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
An acetyl group, a propionyl group, etc. are mentioned, As an alkyl group, a methyl group, an ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, tert-butyl group, n-pentyl group N-hexyl group, 2-ethylhexyl group, n-decyl group, n-dodecyl group and the like. Examples of the aralkyl group include a benzyl group and a phenethyl group, and examples of the aryl group include a phenyl group, a p-tolyl group, an o-tolyl group, and a naphthyl group. Examples of the alkoxy group include a methoxy group, an ethoxy group, an n-propoxy group, an i-propoxy group, an n-butoxy group, an i-butoxy group, and a tert-butoxy group. As the alkoxyalkyl group, 2-methoxy An ethyl group, 2-ethoxyethyl group, etc. are mentioned, As a glycidyl group, a glycidyl group, 2-methylglycidyl group, etc. are mentioned. Examples of the hydroxyalkyl group include a hydroxymethyl group and 1-hydroxyethyl group, and examples of the aryloxyalkyl group include a phenoxymethyl group. In addition to those described above, there may be mentioned substituents containing oxygen, nitrogen and sulfur. However, a structure composed of carbon, oxygen, and hydrogen is desirable from the viewpoints of improving the handleability and reducing the environmental load.

In general formula (1), a compound in which n is 2 and two OR groups are substituted at positions 1 and 4 of the naphthalene skeleton is a compound represented by the following general formula (2).

In the general formula (2), R ¹ and R ^{2 each} represent a hydrogen atom, an alkyl group, an aryl group, an aralkyl group, an alkoxyalkyl group, a glycidyl group, a hydroxyalkyl group, or an aryloxyalkyl group, and R ¹ and R ² may be the same or different. X, Y and Z may be the same or different, and are each hydrogen atom, hydroxyl group, halogen atom, acyl group, alkyl group, aryl group, aralkyl group, alkoxyalkyl group, glycidyl group, hydroxy group Represents an alkyl group or an aryloxyalkyl group, which may be the same or different, and X and Y may combine with each other to form a saturated or unsaturated ring, and form a ring with an oxygen atom in between. May be.

Examples of the alkyl group represented by R ¹ and R ² in the general formula (2) include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, an i-butyl group, and a tert-butyl group. N-pentyl group, n-hexyl group, 2-ethylhexyl group, n-decyl group, n-dodecyl group and the like. Examples of the aryl group include a phenyl group, a p-tolyl group, an o-tolyl group, and a naphthyl group. Examples of the aralkyl group include benzyl group, phenethyl group, phenylpropyl group, naphthylmethyl group, naphthylethyl group and the like. Examples of the alkoxyalkyl group include 2-methoxyethyl group and 2-ethoxyethyl group. Examples of the glycidyl group include a glycidyl group and a 2-methylglycidyl group. Examples of the hydroxyalkyl group include a hydroxymethyl group, a 2-hydroxyethoxy group, a 2-hydroxypropyl group, a 3-hydroxypropyl group, a 2-hydroxybutyl group, and a 3-hydroxybutyl group. Examples of the aryloxyalkyl group include phenoxyethyl and triloxyethyl. In addition to those described above, there may be mentioned substituents containing oxygen, nitrogen and sulfur. However, a structure composed of carbon, oxygen, and hydrogen is desirable from the viewpoints of improving the handleability and reducing the environmental load.

Examples of the halogen atom represented by X, Y, and Z in the general formula (2) include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
An acetyl group, a propionyl group, etc. are mentioned, As an alkyl group, a methyl group, an ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, tert-butyl group, n-pentyl group N-hexyl group, 2-ethylhexyl group, n-decyl group, n-dodecyl group and the like. Examples of the aralkyl group include a benzyl group and a phenethyl group, and examples of the aryl group include a phenyl group, a p-tolyl group, an o-tolyl group, and a naphthyl group. Examples of the alkoxy group include a methoxy group, an ethoxy group, an n-propoxy group, an i-propoxy group, an n-butoxy group, an i-butoxy group, and a tert-butoxy group, and the alkoxyalkyl group includes 2-methoxyethyl. Group, 2-ethoxyethyl group and the like, and examples of the glycidyl group include glycidyl group and 2-methylglycidyl group. Examples of the hydroxyalkyl group include a hydroxymethyl group and 1-hydroxyethyl group, and examples of the aryloxyalkyl group include a phenoxymethyl group. In addition to those described above, there may be mentioned substituents containing oxygen, nitrogen and sulfur. However, a structure composed of carbon, oxygen, and hydrogen is desirable from the viewpoints of improving the handleability and reducing the environmental load.

Next, in the general formula (2), a compound having a quinone structure in which two C-OR groups are replaced with a ketone group is a compound of the general formula (3).

In the general formula (3), X, Y and Z may be the same or different, and each is a hydrogen atom, a hydroxyl group, a halogen atom, an acyl group, an alkyl group, an aryl group, an aralkyl group, an alkoxy group. Represents an alkyl group, a glycidyl group, a hydroxyalkyl group or an aryloxyalkyl group, and among them, X and Y may combine with each other to form a saturated or unsaturated ring, and form a ring with an oxygen atom in between. May be.

Examples of the halogen atom in the general formula (3) include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
An acetyl group, a propionyl group, etc. are mentioned, As an alkyl group, a methyl group, an ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, tert-butyl group, n-pentyl group N-hexyl group, 2-ethylhexyl group, n-decyl group, n-dodecyl group and the like. Examples of the aralkyl group include a benzyl group and a phenethyl group, and examples of the aryl group include a phenyl group, a p-tolyl group, an o-tolyl group, and a naphthyl group. Examples of the alkoxy group include a methoxy group, an ethoxy group, an n-propoxy group, an i-propoxy group, an n-butoxy group, an i-butoxy group, and a tert-butoxy group, and the alkoxyalkyl group includes 2-methoxyethyl. Group, 2-ethoxyethyl group and the like, and examples of the glycidyl group include glycidyl group and 2-methylglycidyl group. Examples of the hydroxyalkyl group include a hydroxymethyl group and 1-hydroxyethyl group, and examples of the aryloxyalkyl group include a phenoxymethyl group. In addition to those described above, there may be mentioned substituents containing oxygen, nitrogen and sulfur. However, a structure composed of carbon, oxygen, and hydrogen is desirable from the viewpoints of improving the handleability and reducing the environmental load.

Specific examples of the compound having a condensed polycyclic aromatic skeleton of the present invention include the following compounds.

In the general formula (1), a compound in which n is 2 and two OR groups are substituted at the 1- and 4-positions of the naphthalene skeleton is a compound represented by the general formula (2). The compound (2) will be exemplified.

In the general formula (2), specific examples in which the substituents R ¹ and / or R ² are hydrogen atoms and the substituents X, Y and Z are all hydrogen atoms include, for example, 1,4-dihydroxy Naphthalene, 1-hydroxy-4-methoxynaphthalene, 1-hydroxy-4-ethoxynaphthalene, 1-hydroxy-4-n-propoxynaphthalene, 1-hydroxy-4-isopropoxynaphthalene, 1-hydroxy-4-n-butoxy Naphthalene, 1-hydroxy-4-hexyloxynaphthalene, 1-hydroxy-4- (2-ethylhexyloxy) naphthalene, 1-hydroxy-4- (2-methoxyethoxy) naphthalene, 1-hydroxy-4- (2-phenoxy) Ethoxy) naphthalene, 1-hydroxy-4-glycidyloxynaphthalene, 1-hydroxy-4 (2-hydroxyethoxy) naphthalene, 1-hydroxy-4- (2-hydroxypropoxy) naphthalene.

And as an example in the case where the substituents X, Y and / or Z are not hydrogen atoms, and in the general formula (2), X and Y are not bonded to each other to form a ring, For example, 2-methyl-1,4-dihydroxynaphthalene, 1-hydroxy-2-methyl-4-methoxynaphthalene, 1-hydroxy-2-methyl-4-ethoxynaphthalene, 1-hydroxy-2-methyl-4-n -Propoxynaphthalene, 1-hydroxy-2-methyl-4-isopropoxynaphthalene, 1-hydroxy-2-methyl-4-n-butoxynaphthalene, 1-hydroxy-2-methyl-4-hexyloxynaphthalene, 1-hydroxy 2-Methyl-4- (2-ethylhexyloxy) naphthalene, 1-hydroxy-2-methyl-4- (2-methoxyethoxy) naphtha 1-hydroxy-2-methyl-4- (2-phenoxyethoxy) naphthalene, 1-hydroxy-2-methyl-4-glycidyloxynaphthalene, 1-hydroxy-2-methyl-4- (2-hydroxyethoxy) Naphthalene, 1-hydroxy-2-methyl-4- (2-hydroxypropoxy) naphthalene, 2-ethyl-1,4-dihydroxynaphthalene, 1-hydroxy-2-ethyl-4-methoxynaphthalene, 1-hydroxy-2- Ethyl-4-ethoxynaphthalene, 1-hydroxy-2-ethyl-4-n-propoxynaphthalene, 1-hydroxy-2-ethyl-4-isopropoxynaphthalene, 1-hydroxy-2-ethyl-4-n-butoxynaphthalene 1-hydroxy-2-ethyl-4-hexyloxynaphthalene, 1-hydro Ci-2-ethyl-4- (2-ethylhexyloxy) naphthalene, 1-hydroxy-2-ethyl-4- (2-methoxyethoxy) naphthalene, 1-hydroxy-2-ethyl-4- (2-phenoxyethoxy) Naphthalene, 1-hydroxy-2-ethyl-4-glycidyloxynaphthalene, 1-hydroxy-2-ethyl-4- (2-hydroxyethoxy) naphthalene, 1-hydroxy-2-ethyl-4- (2-hydroxypropoxy) Naphthalene, 6-methyl-1,4-dihydroxynaphthalene, 1-hydroxy-4-methoxy-6-methylnaphthalene, 1-hydroxy-4-ethoxy-6-methylnaphthalene, 1-hydroxy-4-n-propoxy-6 -Methylnaphthalene, 1-hydroxy-4-isopropoxy-6-methylnaphthalene, -Hydroxy-4-n-butoxy-6-methylnaphthalene, 1-hydroxy-4-hexyloxy-6-methylnaphthalene, 1-hydroxy-4- (2-ethylhexyloxy) -6-methylnaphthalene, 1-hydroxy- 4- (2-methoxyethoxy) -6-methylnaphthalene, 1-hydroxy-4- (2-phenoxyethoxy) -6-methylnaphthalene, 1-hydroxy-4-glycidyloxy-6-methylnaphthalene, 1-hydroxy- 4- (2-hydroxyethoxy) -6-methylnaphthalene, 1-hydroxy-4- (2-hydroxypropoxy) -6-methylnaphthalene, and the like.

And it is an example in case the substituent X, Y and / or Z is a group which is not a hydrogen atom, Comprising: In General formula (2), X and Y couple | bond together and form the saturated 6-membered ring. Specific examples of the case include 9,10-dihydroxy-1,2,3,4-tetrahydroanthracene, 9-hydroxy-10-methoxy-1,2,3,4-tetrahydroanthracene, 9-hydroxy-10-ethoxy. -1,2,3,4-tetrahydroanthracene, 9-hydroxy-10-n-propoxy-1,2,3,4-tetrahydroanthracene, 9-hydroxy-10-isopropoxy-1,2,3,4 Tetrahydroanthracene, 9-hydroxy-10-n-butoxy-1,2,3,4-tetrahydroanthracene, 9-hydroxy-10-hexyloxy-1,2,3,4 -Tetrahydroanthracene, 9-hydroxy-10- (2-ethylhexyloxy) -1,2,3,4-tetrahydroanthracene, 9-hydroxy-10- (2-methoxyethoxy) -1,2,3,4-tetrahydro Anthracene, 9-hydroxy-10- (2-phenoxyethoxy) -1,2,3,4-tetrahydroanthracene, 9-hydroxy-10-glycidyloxy-1,2,3,4-tetrahydroanthracene, 9-hydroxy- Examples thereof include 10- (2-hydroxyethoxy) -1,2,3,4-tetrahydroanthracene, 9-hydroxy-10- (2-hydroxypropoxy) -1,2,3,4-tetrahydroanthracene.

And it is an example in case the substituent X, Y and / or Z is a group which is not a hydrogen atom, Comprising: In General formula (2), X and Y couple | bond together and form an unsaturated 6-membered ring. Specific examples of the case where the 6-membered ring is non-aromatic include 9,10-dihydroxy-1,4-dihydroanthracene, 9-hydroxy-10-methoxy-1,4-dihydroanthracene, 9- Hydroxy-10-ethoxy-1,4-dihydroanthracene, 9-hydroxy-10-n-propoxy-1,4-dihydroanthracene, 9-hydroxy-10-isopropoxy-1,4-dihydroanthracene, 9-hydroxy- 10-n-butoxy-1,4-dihydroanthracene, 9-hydroxy-10-hexyloxy-1,4-dihydroanthracene, 9-hydroxy-10- ( 2-ethylhexyloxy) -1,4-dihydroanthracene, 9-hydroxy-10- (2-methoxyethoxy) -1,4-dihydroanthracene, 9-hydroxy-10- (2-phenoxyethoxy) -1,4- Dihydroanthracene, 9-hydroxy-10-glycidyloxy-1,4-dihydroanthracene, 9-hydroxy-10- (2-hydroxyethoxy) -1,4-dihydroanthracene, 9-hydroxy-10- (2-hydroxypropoxy) ) -1,4-dihydroanthracene.

And it is an example in case the substituent X, Y and / or Z is a group which is not a hydrogen atom, Comprising: In General formula (2), X and Y couple | bond together and form an unsaturated 6-membered ring. Specific examples of the case where the 6-membered ring is aromatic include 9,10-dihydroxyanthracene, 9-hydroxy-10-methoxyanthracene, 9-hydroxy-10-ethoxyanthracene, 9-hydroxy-10- n-propoxyanthracene, 9-hydroxy-10-isopropoxyanthracene, 9-hydroxy-10-n-butoxyanthracene, 9-hydroxy-10-hexyloxyanthracene, 9-hydroxy-10- (2-ethylhexyloxy) anthracene, 9-hydroxy-10- (2-methoxyethoxy) anthracene, 9-hydroxy-10- (2- Phenoxyethoxy) anthracene, 9-hydroxy-10-glycidyloxyanthracene, 9-hydroxy-10- (2-hydroxyethoxy) anthracene, 9-hydroxy-10- (2-hydroxypropoxy) anthracene and the like.

Next, in the general formula (2), specific examples of the case where the substituents R ¹ and R ² are groups that are not hydrogen atoms and X, Y, and Z are all hydrogen atoms include, for example, 1, 4 -Dimethoxynaphthalene, 1,4-diethoxynaphthalene, 1,4-di-n-propoxynaphthalene, 1,4-diisopropoxynaphthalene, 1,4-di-n-butoxynaphthalene, 1,4-dihexyloxynaphthalene 1,4-bis (2-ethylhexyloxy) naphthalene, 1,4-bis (2-methoxyethoxy) naphthalene, 1,4-bis (2-phenoxyethoxy) naphthalene, 1,4-diglycidyloxynaphthalene, , 4-bis (2-hydroxyethoxy) naphthalene, 1,4-bis (2-hydroxypropoxy) naphthalene, 1-methoxy-4-ethoxynaphtha Down, 1-methoxy-4-butoxy naphthalene.

As an example of the case where the substituents X, Y and / or Z are not a hydrogen atom, in the general formula (2), X and Y are not bonded to each other to form a ring. For example, 2-methyl-1,4-dimethoxynaphthalene, 2-methyl-1,4-diethoxynaphthalene, 2-methyl-1,4-di-n-propoxynaphthalene, 2-methyl-1,4-di Isopropoxynaphthalene, 2-methyl-1,4-di-n-butoxynaphthalene, 2-methyl-1,4-dihexyloxynaphthalene, 2-methyl-1,4-bis (2-ethylhexyloxy) naphthalene, 2- Methyl-1,4-bis (2-methoxyethoxy) naphthalene, 2-methyl-1,4-bis (2-phenoxyethoxy) naphthalene, 2-methyl-1,4-diglycidyloxynaphthalene 2-methyl-1,4-bis (2-hydroxyethoxy) naphthalene, 2-methyl-1,4-bis (2-hydroxypropoxy) naphthalene, 1-methoxy-2-methyl-4-ethoxynaphthalene, -Methoxy-2-methyl-4-butoxynaphthalene, 2-ethyl-1,4-dimethoxynaphthalene, 2-ethyl-1,4-diethoxynaphthalene, 2-ethyl-1,4-di-n-propoxynaphthalene, 2-ethyl-1,4-diisopropoxynaphthalene, 2-ethyl-1,4-di-n-butoxynaphthalene, 2-ethyl-1,4-dihexyloxynaphthalene, 2-ethyl-1,4-bis ( 2-ethylhexyloxy) naphthalene, 2-ethyl-1,4-bis (2-methoxyethoxy) naphthalene, 2-ethyl-1,4-bis (2-phenyl) Xyloxy) naphthalene, 2-ethyl-1,4-diglycidyloxynaphthalene, 2-ethyl-1,4-bis (2-hydroxyethoxy) naphthalene, 2-ethyl-1,4-bis (2-hydroxypropoxy) naphthalene 1-methoxy-2-ethyl-4-ethoxynaphthalene, 1-methoxy-2-ethyl-4-butoxynaphthalene, 2-hydroxy-1,4-dimethoxynaphthalene, 2-hydroxy-1,4-diethoxynaphthalene, 2-hydroxy-1,4-di-n-propoxynaphthalene, 2-hydroxy-1,4-diisopropoxynaphthalene, 2-hydroxy-1,4-di-n-butoxynaphthalene, 2-hydroxy-1,4 -Dihexyloxynaphthalene, 2-hydroxy-1,4-bis (2-hydroxyhexyloxy) Phthalene, 2-hydroxy-1,4-bis (2-methoxyethoxy) naphthalene, 2-hydroxy-1,4-bis (2-phenoxyethoxy) naphthalene, 2-hydroxy-1,4-diglycidyloxynaphthalene, 2 -Hydroxy-1,4-bis (2-hydroxyethoxy) naphthalene, 2-hydroxy-1,4-bis (2-hydroxypropoxy) naphthalene, 1-methoxy-2-hydroxy-4-ethoxynaphthalene, 1-methoxy- 2-hydroxy-4-butoxynaphthalene, 2-methoxy-1,4-dimethoxynaphthalene, 2-methoxy-1,4-diethoxynaphthalene, 2-methoxy-1,4-di-n-propoxynaphthalene, 2-methoxy -1,4-diisopropoxynaphthalene, 2-methoxy-1,4-di-n-butoxyna Phthalene, 2-methoxy-1,4-dihexyloxynaphthalene, 2-methoxy-1,4-bis (2-methoxyhexyloxy) naphthalene, 2-methoxy-1,4-bis (2-methoxyethoxy) naphthalene, 2, -Methoxy-1,4-bis (2-phenoxyethoxy) naphthalene, 2-methoxy-1,4-diglycidyloxynaphthalene, 2-methoxy-1,4-bis (2-hydroxyethoxy) naphthalene, 2-methoxy- Examples include 1,4-bis (2-hydroxypropoxy) naphthalene, 1-methoxy-2-methoxy-4-ethoxynaphthalene, 1-methoxy-2-methoxy-4-butoxynaphthalene and the like.

In the general formula (2), as specific examples in which X and Y are bonded to each other to form a saturated 6-membered ring, 9,10-dimethoxy-1,2,3,4-tetrahydroanthracene, 9 , 10-diethoxy-1,2,3,4-tetrahydroanthracene, 9,10-di-n-propoxy-1,2,3,4-tetrahydroanthracene, 9,10-diisopropoxy-1,2,3 , 4-tetrahydroanthracene, 9,10-di-n-butoxy-1,2,3,4-tetrahydroanthracene, 9,10-bis (2-ethylhexyloxy) -1,2,3,4-tetrahydroanthracene, 9,10-bis (2-methoxyethoxy) -1,2,3,4-tetrahydroanthracene, 9,10-bis (2-phenoxyethoxy) -1,2,3,4-tetrahydro Loanthracene, 9,10-bis (2-hydroxyethoxy) -1,2,3,4-tetrahydroanthracene, 9-methoxy-10-ethoxy-1,2,3,4-tetrahydroanthracene, 9-methoxy-10 -Butoxy-1,2,3,4-tetrahydroanthracene, 2-methyl-9,10-diethoxy-1,2,3,4-tetrahydroanthracene, 2-ethyl-9,10-diethoxy-1,2,3 , 4-tetrahydroanthracene, 9-hydroxy-10-methoxy-1,2,3,4-tetrahydroanthracene, 9-hydroxy-10-ethoxy-1,2,3,4-tetrahydroanthracene, 9-hydroxy-10- n-propoxy-1,2,3,4-tetrahydroanthracene, 9-hydroxy-10-isopropoxy-1 2,3,4-tetrahydroanthracene, 9-hydroxy-10-n-butoxy-1,2,3,4-tetrahydroanthracene, 9-hydroxy-10- (2-ethylhexyloxy) -1,2,3,4 -Tetrahydroanthracene, 9-hydroxy-10- (2-methoxyethoxy) -1,2,3,4-tetrahydroanthracene, 9-hydroxy-10- (2-phenoxyethoxy) -1,2,3,4-tetrahydro Anthracene, 9-hydroxy-10- (2-hydroxyethoxy) -1,2,3,4-tetrahydroanthracene, 2-methyl-9-hydroxy-10-ethoxy-1,2,3,4-tetrahydroanthracene, 2 -Ethyl-9-hydroxy-10-ethoxy-1,2,3,4-tetrahydroanthracene The

In the general formula (2), when X and Y are bonded to each other to form an unsaturated 6-membered ring and the 6-membered ring is non-aromatic, a specific example is 9,10-dimethoxy -1,4-dihydroanthracene, 9,10-diethoxy-1,4-dihydroanthracene, 9,10-di-n-propoxy-1,4-dihydroanthracene, 9,10-diisopropoxy-1,4- Dihydroanthracene, 9,10-di-n-butoxy-1,4-dihydroanthracene, 9,10-bis (2-ethylhexyloxy) -1,4-dihydroanthracene, 9,10-bis (2-methoxyethoxy) -1,4-dihydroanthracene, 9,10-bis (2-phenoxyethoxy) -1,4-dihydroanthracene, 9,10-bis (2-hydroxyethoxy) -1, -Dihydroanthracene, 9-methoxy-10-ethoxy-1,4-dihydroanthracene, 9-methoxy-10-butoxy-1,4-dihydroanthracene, 2-methyl-9,10-diethoxy-1,4-dihydroanthracene 2-ethyl-9,10-diethoxy-1,4-dihydroanthracene, 9-hydroxy-10-methoxy-1,4-dihydroanthracene, 9-hydroxy-10-ethoxy-1,4-dihydroanthracene, 9- Hydroxy-10-n-propoxy-1,4-dihydroanthracene, 9-hydroxy-10-isopropoxy-1,4-dihydroanthracene, 9-hydroxy-10-n-butoxy-1,4-dihydroanthracene, 9- Hydroxy-10- (2-ethylhexyloxy) -1,4-dihydride Anthracene, 9-hydroxy-10- (2-methoxyethoxy) -1,4-dihydroanthracene, 9-hydroxy-10- (2-phenoxyethoxy) -1,4-dihydroanthracene, 9-hydroxy-10- (2 -Hydroxyethoxy) -1,4-dihydroanthracene, 2-methyl-9-hydroxy-10-ethoxy-1,4-dihydroanthracene, 2-ethyl-9-hydroxy-10-ethoxy-1,4-dihydroanthracene, etc. Is mentioned.

In the general formula (2), when X and Y are bonded to each other to form an unsaturated 6-membered ring and the 6-membered ring is aromatic, a specific example is 9,10-dimethoxyanthracene 9,10-diethoxyanthracene, 9,10-di-n-propoxyanthracene, 9,10-diisopropoxyanthracene, 9,10-di-n-butoxyanthracene, 9,10-bis (2-ethylhexyloxy) ) Anthracene, 9,10-bis (2-methoxyethoxy) anthracene, 9,10-bis (2-phenoxyethoxy) anthracene, 9,10-bis (2-hydroxyethoxy) anthracene, 9-methoxy-10-ethoxyanthracene 9-methoxy-10-butoxyanthracene, 2-methyl-9,10-diethoxyanthracene, 2-ethy -9,10-diethoxyanthracene, 9-hydroxy-10-methoxyanthracene, 9-hydroxy-10-ethoxyanthracene, 9-hydroxy-10-n-propoxyanthracene, 9-hydroxy-10-isopropoxyanthracene, 9- Hydroxy-10-n-butoxyanthracene, 9-hydroxy-10- (2-ethylhexyloxy) anthracene, 9-hydroxy-10- (2-methoxyethoxy) anthracene, 9-hydroxy-10- (2-phenoxyethoxy) anthracene 9-hydroxy-10- (2-hydroxyethoxy) anthracene, 2-methyl-9-hydroxy-10-ethoxyanthracene, 2-ethyl-9-hydroxy-10-ethoxyanthracene and the like.

In the general formula (2), as a specific example in which X and Y are bonded to each other with an oxygen atom in between to form a ring, 3,4-dihydro-5,10-dimethoxy-2-methyl-2H -Naphtho [2,3-b] pyran-4-one, 4,9-dimethoxy-2,3-dihydronaphtho [2,3-b] furan, 2-methyl-4,9-dimethoxy-2,3- Dihydronaphtho [2,3-b] furan, 1,4-dimethoxy-2,3-methylenedioxynaphthalene, 9-methoxy-2,3-dihydronaphtho [2,3-b] furan-4-ol, 2 -Methyl-9-methoxy-2,3-dihydronaphtho [2,3-b] furan-4-ol and the like.

As specific examples of the compound represented by the general formula (1) other than the compound represented by the general formula (2) and n is 2, first, the substituents R ¹ and / or R ² are hydrogen atoms. In the case where all of the substituents X, Y and Z are hydrogen atoms, for example, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 1,7-dihydroxynaphthalene, 2,6 -Dihydroxynaphthalene, 2,7-dihydroxynaphthalene, 1-hydroxy-5-methoxynaphthalene, 1-hydroxy-6-methoxynaphthalene, 1-hydroxy-7-methoxynaphthalene, 2-hydroxy-6-methoxynaphthalene, 2-hydroxy -7-methoxynaphthalene, 1-hydroxy-5-ethoxynaphthalene, 1-hydroxy-6-ethoxynaphthalene, 1-hydride Xyl-7-ethoxynaphthalene, 2-hydroxy-6-ethoxynaphthalene, 2-hydroxy-7-ethoxynaphthalene, 1-hydroxy-5-n-propoxynaphthalene, 1-hydroxy-5-isopropoxynaphthalene, 1-hydroxy- 6-n-propoxynaphthalene, 1-hydroxy-6-isopropoxynaphthalene, 1-hydroxy-7-n-propoxynaphthalene, 1-hydroxy-7-isopropoxynaphthalene, 2-hydroxy-6-n-propoxynaphthalene, 2 -Hydroxy-6-isopropoxynaphthalene, 2-hydroxy-7-n-propoxynaphthalene, 2-hydroxy-7-isopropoxynaphthalene, 1-hydroxy-5-n-butoxynaphthalene, 1-hydroxy-6-n-butoxy Naphthalene, 1-hi Roxy-7-n-butoxynaphthalene, 2-hydroxy-6-n-butoxynaphthalene, 2-hydroxy-7-n-butoxynaphthalene, 1-hydroxy-5- (2-ethylhexyloxy) naphthalene, 1-hydroxy- 6- (2-ethylhexyloxy) naphthalene, 1-hydroxy-7- (2-ethylhexyloxy) naphthalene, 2-hydroxy-6- (2-ethylhexyloxy) naphthalene, 2,7-bis (2-ethyl) Hexyloxy) naphthalene, 1-hydroxy-5- (2-methoxyethoxy) naphthalene, 1-hydroxy-6- (2-methoxyethoxy) naphthalene, 1-hydroxy-7- (2-methoxyethoxy) naphthalene, 2-hydroxy -6- (2-methoxyethoxy) naphthalene, 2-hydroxy-7- (2- Methoxyethoxy) naphthalene, 1-hydroxy-5- (2-hydroxyethoxy) naphthalene, 1-hydroxy-6- (2-hydroxyethoxy) naphthalene, 1-hydroxy-7- (2-hydroxyethoxy) naphthalene, 2-hydroxy -6- (2-hydroxyethoxy) naphthalene, 2-hydroxy-7- (2-hydroxyethoxy) naphthalene, 1-hydroxy-5- (2-phenoxyethoxy) naphthalene, 1-hydroxy-6- (2-phenoxyethoxy) ) Naphthalene, 1-hydroxy-7- (2-phenoxyethoxy) naphthalene, 2-hydroxy-6- (2-phenoxyethoxy) naphthalene, 2-hydroxy-7- (2-phenoxyethoxy) naphthalene, 2-methyl-1 -Hydroxy-5-methoxynaphthalene, 2- Til-1-hydroxy-6-methoxynaphthalene, 2-methyl-1-hydroxy-7-methoxynaphthalene, 2-ethyl-1-hydroxy-5-ethoxynaphthalene, 2-ethyl-1-hydroxy-6-ethoxynaphthalene, Examples include 2-ethyl-1-hydroxy-7-ethoxynaphthalene.

Next, in the case where the compound represented by the general formula (1) other than the compound represented by the general formula (2) is a compound in which n is 2, and the substituents R ¹ and R ² are not a hydrogen atom In the case where X, Y and Z are all hydrogen atoms, for example, 1,5-dimethoxynaphthalene, 1,6-dimethoxynaphthalene, 1,7-dimethoxynaphthalene, 2,6-dimethoxynaphthalene, 2,7-dimethoxynaphthalene, 1,5-diethoxynaphthalene, 1,6-diethoxynaphthalene, 1,7-diethoxynaphthalene, 2,6-diethoxynaphthalene, 2,7-diethoxynaphthalene, 1,5 -Di-n-propoxynaphthalene, 1,5-diisopropoxynaphthalene, 1,6-di-n-propoxynaphthalene, 1,6-diisopropoxynaphthalene, 1,7-di- -Propoxynaphthalene, 1,7-diisopropoxynaphthalene, 2,6-di-n-propoxynaphthalene, 2,6-diisopropoxynaphthalene, 2,7-di-n-propoxynaphthalene, 2,7-diiso Propoxynaphthalene, 1,5-di-n-butoxynaphthalene, 1,6-di-n-butoxynaphthalene, 1,7-di-n-butoxynaphthalene, 2,6-di-n-butoxynaphthalene, 2,7 -Di-n-butoxynaphthalene, 1,5-bis (2-ethylhexyloxy) naphthalene, 1,6-bis (2-ethylhexyloxy) naphthalene, 1,7-bis (2-ethylhexyloxy) naphthalene, 2,6-bis (2-ethylhexyloxy) naphthalene, 2,7-bis (2-ethylhexyloxy) naphthalene, 1,5-bis (2- Methoxyethoxy) naphthalene, 1,6-bis (2-methoxyethoxy) naphthalene, 1,7-bis (2-methoxyethoxy) naphthalene, 2,6-bis (2-methoxyethoxy) naphthalene, 2,7-bis ( 2-methoxyethoxy) naphthalene, 1,5-bis (2-hydroxyethoxy) naphthalene, 1,6-bis (2-hydroxyethoxy) naphthalene, 1,7-bis (2-hydroxyethoxy) naphthalene, 2,6- Bis (2-hydroxyethoxy) naphthalene, 2,7-bis (2-hydroxyethoxy) naphthalene, 1,5-bis (2-phenoxyethoxy) naphthalene, 1,6-bis (2-phenoxyethoxy) naphthalene, 1, 7-bis (2-phenoxyethoxy) naphthalene, 2,6-bis (2-phenoxyethoxy) naphtha 2,7-bis (2-phenoxyethoxy) naphthalene, 1-methoxy-5-ethoxynaphthalene, 1-methoxy-6-ethoxynaphthalene, 1-methoxy-7-ethoxynaphthalene, 2-methoxy-6-ethoxynaphthalene 2-methoxy-7-ethoxynaphthalene, 1-methoxy-5-n-butoxynaphthalene, 1-methoxy-6-n-butoxynaphthalene, 1-methoxy-7-butoxynaphthalene, 2-methoxy-6-n-butoxy Naphthalene, 2-methoxy-7-n-butoxynaphthalene, 2-methyl-1,5-dimethoxynaphthalene, 2-methyl-1,6-dimethoxynaphthalene, 2-methyl-1,7-dimethoxynaphthalene, 2-ethyl- 1,5-diethoxynaphthalene, 2-ethyl-1,6-diethoxynaphthalene, 2- Chill-1,7-diethoxy naphthalene.

Furthermore, specific examples of the compound represented by the general formula (1), where n is 1, include, for example, 1-naphthol, 2-naphthol, 1-methoxynaphthalene, 1-ethoxynaphthalene, 1-n. -Propoxynaphthalene, 1-isopropoxynaphthalene, 1-n-butoxynaphthalene, 1- (2-ethylhexyloxy) naphthalene, 2-methoxynaphthalene, 2-ethoxynaphthalene, 2-n-propoxynaphthalene, 2-isopropoxynaphthalene, Examples include 2-n-butoxynaphthalene and 2- (2-ethylhexyloxy) naphthalene.

Furthermore, specific examples of the compound represented by the general formula (1) and n being 3 or more include, for example, 1,2,4-trimethoxynaphthalene, 1,2,4-triethoxynaphthalene, 1,2,4-tripropoxynaphthalene, 1,2,4-tributoxynaphthalene, 1,4,5-trimethoxynaphthalene, 1,4,5-triethoxynaphthalene, 1,4,5-tri-n- Propoxynaphthalene, 1,4,5-triisopropoxynaphthalene, 1,4,5-tri-n-butoxynaphthalene, 1,4,6-trimethoxynaphthalene, 1,4,6-triethoxynaphthalene, 1,4 , 6-Tri-n-propoxynaphthalene, 1,4,6-triisopropoxynaphthalene, 1,4,6-tri-n-butoxynaphthalene, 1,4,5,8-tetramethoxy Naphthalene, 1,4,5,8-tetraethoxynaphthalene, 1,4,5,8-tetra-n-propoxynaphthalene, 1,4,5,8-tetraisopropoxynaphthalene, 1,4,5,8- Tetra-n-butoxynaphthalene, 2-hydroxy-1,4-dimethoxynaphthalene, 2-hydroxy-1,4-diethoxynaphthalene, 2-hydroxy-1,4-dipropoxynaphthalene, 2-hydroxy-1,4- Dibutoxynaphthalene, 2,3-dihydroxy-1,4-dimethoxynaphthalene, 2,3-dihydroxy-1,4-diethoxynaphthalene, 2,3-dihydroxy-1,4-di-n-propoxynaphthalene, 2, 3-dihydroxy-1,4-diisopropoxynaphthalene, 2,3-dihydroxy-1,4-di-n-butoxynaphthalene And the like.

In addition to the compounds exemplified here, for example, compounds specifically disclosed in JP2012-111741A can be used.

Among these exemplified compounds, the compound of the general formula (2) in which the OR ¹ group and the OR ² group are substituted at the 1,4-positions of the naphthalene skeleton is preferable because of the high effect of the present invention, and R ¹ is a hydrogen atom and R ^A compound in which ² is an alkyl group and a compound in which R ¹ and R ² are both alkyl groups are preferred. Among these, compounds in which X, Y, and Z are hydrogen atoms are more preferable because they are highly effective and easy to produce. Specifically, 1-hydroxy-4-methoxynaphthalene and 1,4-diethoxynaphthalene are particularly preferable.

These exemplified compounds can be easily synthesized by a method of alkylating the corresponding hydroxynaphthalene compound with an alkylating agent such as dialkyl sulfuric acid.

Next, the compound of general formula (3) is illustrated. In the general formula (2), a compound having a quinone structure in which two C-OR groups are replaced with a ketone group is a compound of the general formula (3).

In the general formula (3), specific examples when the substituents R ¹ and / or R ² are hydrogen atoms and X, Y and Z are all hydrogen atoms include, for example, 1,4-naphthoquinone, 2 -Fluoro-1,4-naphthoquinone, 2-chloro-1,4-naphthoquinone, 2-bromo-1,4-naphthoquinone, 2-iodo-1,4-naphthoquinone, 2-methyl-1,4-naphthoquinone, 2 -Ethyl-1,4-naphthoquinone, 2-n-propyl-1,4-naphthoquinone, 2-i-propyl-1,4-naphthoquinone, 2-n-butyl-1,4-naphthoquinone, 2-i-butyl 1,4-naphthoquinone, 2-sec-butyl-1,4-naphthoquinone, 2-tert-butyl 1,4-naphthoquinone, 2-n-pentyl-1,4-naphthoquinone 2-n-hexyl-1,4 -Naphthoquinone, 2- (4-methyl Nthyl) -1,4-naphthoquinone, 2-n-heptyl-1,4-naphthoquinone, 2-n-octyl-1,4-naphthoquinone, 2-sec-octyl-1,4-naphthoquinone, 2-n-nonyl 1,4-naphthoquinone, 2-n-decyl-1,4-naphthoquinone, 2-n-undecyl-1,4-naphthoquinone, 2-n-dodecyl-1,4-naphthoquinone, 2-n-tridecyl-1 , 4-naphthoquinone, 2-n-tetradecyl-1,4-naphthoquinone, 2-n-pentadecyl-1,4-naphthoquinone, 2-cyclopropyl-1,4-naphthoquinone, 2-cyclopentyl-1,4-naphthoquinone, 2-cyclohexyl-1,4-naphthoquinone, 2-cyclopropylmethyl-1,4-naphthoquinone, 2-cyclopentylmethyl-1,4-naphthoquinone, 2-cyclohexylme 1,4-naphthoquinone, 2- (2-cyclopropylethyl) -1,4-naphthoquinone, 2- (2-cyclopentylethyl-1,4-naphthoquinone, 2- (2-cyclohexylethyl) -1,4 -Naphthoquinone etc. are mentioned.

Also, 2-benzyl-1,4-naphthoquinone, 2- (2-fluorobenzyl) -1,4-naphthoquinone, 2- (3-fluorobenzyl) -1,4-naphthoquinone, 2- (4-fluorobenzyl) 1,4-naphthoquinone, 2- (2-chlorobenzyl) -1,4-naphthoquinone, 2- (3-chlorobenzyl) -1,4-naphthoquinone, 2- (4-chlorobenzyl) -1,4- Naphthoquinone, 2- (2-methylbenzyl) -1,4-naphthoquinone, 2- (3-methylbenzyl) -1,4-naphthoquinone, 2- (4-methylbenzyl) -1,4-naphthoquinone, 2- ( 2-methoxybenzyl) -1,4-naphthoquinone, 2- (3-methoxybenzyl) -1,4-naphthoquinone, 2- (4-methoxybenzyl) -1,4-naphthoquinone, 2- (2-trifluoromethyl) Be Ndyl) -1,4-naphthoquinone, 2- (3-trifluoromethylbenzyl) -1,4-naphthoquinone, 2- (4-trifluoromethylbenzyl) -1,4-naphthoquinone, 2- (2-methylthiobenzyl) ) -1,4-naphthoquinone, 2- (3-methylthiobenzyl) -1,4-naphthoquinone, 2- (4-methylthiobenzyl) -1,4-naphthoquinone, 2- (2-nitrobenzyl) -1,4 -Naphthoquinone, 2- (3-nitrobenzyl) -1,4-naphthoquinone, 2- (4-nitrobenzyl) -1,4-naphthoquinone, 2- (2-phenethyl) -1,4-naphthoquinone, 2- ( 1-phenethyl) -1,4-naphthoquinone, 2- (3-phenylpropyl) -1,4-naphthoquinone, 2- (2-phenylpropyl) -1,4-naphthoquinone, 2- (1-phenylpropyl) (Lopyl) -1,4-naphthoquinone, 2-diphenylmethyl-1,4-naphthoquinone, 2- (1,1-diphenylethyl) -1,4-naphthoquinone, 2- (2,2-diphenylethyl) -1, 4-naphthoquinone, 2-chloromethyl-1,4-naphthoquinone, 2-bromomethyl-1,4-naphthoquinone, 2-iodomethyl-1,4-naphthoquinone, 2-trifluoromethyl-1,4-naphthoquinone, 2-dichloro Methyl-1,4-naphthoquinone, 2-trichloromethyl-1,4-naphthoquinone, 2- (2-chloroethyl) -1,4-naphthoquinone, 2- (2-bromoethyl) -1,4-naphthoquinone, 2-penta Fluoroethyl-1,4-naphthoquinone, 2-hydroxymethyl-1,4-naphthoquinone, 2- (1-hydroxyethyl) -1,4-naphthoquinone, 2- (2 Hydroxyethyl) -1,4-naphthoquinone, 2-methoxymethyl-1,4-naphthoquinone, 2-ethoxymethyl-1,4-naphthoquinone, 2-n-propoxymethyl-1,4-naphthoquinone, 2-i-propoxy Methyl-1,4-naphthoquinone, 2-n-butyloxymethyl-1,4-naphthoquinone, 2-i-butyloxymethyl-1,4-naphthoquinone, 2-sec-butyloxymethyl-1,4-naphthoquinone, 2-tert-butyloxymethyl-1,4-naphthoquinone, 2- (1-methoxyethyl) -1,4-naphthoquinone, 2- (2-methoxyethyl) -1,4-naphthoquinone, 2- (1-ethoxy Ethyl) -1,4-naphthoquinone, 2- (2-ethoxyethyl) -1,4-naphthoquinone, 2-dimethoxymethyl-1,4-naphthoquinone, 2-die Kishimechiru-1,4-naphthoquinone, and the like.

Furthermore, 2-mercaptomethyl-1,4-naphthoquinone, 2- (1-mercaptoethyl) -1,4-naphthoquinone, 2- (2-mercaptoethyl) -1,4-naphthoquinone, 2-methylthiomethyl 2- (1-mercaptoethyl) -1,4-naphthoquinone, 2-ethylthiomethyl-1,4-naphthoquinone, 2-n-propiothiomethyl-1,4-naphthoquinone, 2-i-propylthiomethyl-1, 4-naphthoquinone, 2-n-butylthiomethyl-1,4-naphthoquinone, 2-i-butylthiomethyl-1,4-naphthoquinone, 2-sec-butylthiomethyl-1,4-naphthoquinone, 2-tert- Butylthiomethyl-1,4-naphthoquinone, 2- (1-methylthioethyl) -1,4-naphthoquinone, 2- (2-methylthioethyl) -1,4-naphthoquinone, 2 -(1-ethylthioethyl) -1,4-naphthoquinone, 2- (2-ethylthioethyl) -1,4-naphthoquinone, 2-chloromethoxymethyl-1,4-naphthoquinone, 2-trifluoromethoxymethyl- 1,4-naphthoquinone, 2- (1-chloromethoxyethyl) -1,4-naphthoquinone, 2- (2-chloromethoxyethyl) -1,4-naphthoquinone, 2-chloromethylthiomethyl-1,4-naphthoquinone, 2-trifluoromethylthiomethyl-1,4-naphthoquinone, 2- (1-chloromethylthioethyl) -1,4-naphthoquinone, 2- (2-chloromethylthioethyl) -1,4-naphthoquinone, 2-phenoxymethyl- 1,4-naphthoquinone, 2- (1-phenoxyethyl) -1,4-naphthoquinone, 2- (2-phenoxyethyl) -1,4-naphthoquinone 2- (1-phenoxypropyl) -1,4-naphthoquinone, 2- (2-phenoxypropyl) -1,4-naphthoquinone, 2- (3-phenoxypropyl) -1,4-naphthoquinone, 2- (1 -Phenoxy-1-methylethyl) -1,4-naphthoquinone, 2- (2-chlorophenoxymethyl) -1,4-naphthoquinone, 2- (3-chlorophenoxymethyl) -1,4-naphthoquinone, 2- ( 4-chlorophenoxymethyl) -1,4-naphthoquinone, 2- (2-methylphenoxymethyl) -1,4-naphthoquinone, 2- (3-methylphenoxymethyl) -1,4-naphthoquinone, 2- (4- Methylphenoxymethyl) -1,4-naphthoquinone, 2- (2-fluorophenoxymethyl) -1,4-naphthoquinone, 2- (3-fluorophenoxymethyl) -1,4- Phtoquinone, 2- (4-fluorophenoxymethyl) -1,4-naphthoquinone, 2- (2-trifluoromethylphenoxymethyl) -1,4-naphthoquinone, 2- (3-trifluoromethylphenoxymethyl) -1, 4-naphthoquinone, 2- (4-trifluoromethylphenoxymethyl) -1,4-naphthoquinone, 2- (2-nitrophenoxymethyl) -1,4-naphthoquinone, 2- (3-nitrophenoxymethyl) -1, 4-naphthoquinone, 2- (4-nitrophenoxymethyl) -1,4-naphthoquinone, 2-benzyloxymethyl-1,4-naphthoquinone, 2- (2-fluorobenzyloxymethyl) -1,4-naphthoquinone, 2 -(3-Fluorobenzyloxymethyl) -1,4-naphthoquinone, 2- (4-Fluorobenzyloxymethyl) -1,4 -Naphthoquinone, 2- (2-chlorobenzyloxymethyl) -1,4-naphthoquinone, 2- (3-chlorobenzyloxymethyl) -1,4-naphthoquinone, 2- (4-chlorobenzyloxymethyl) -1, 4-naphthoquinone, 2- (2-methoxybenzyloxymethyl) -1,4-naphthoquinone, 2- (3-methoxybenzyloxymethyl) -1,4-naphthoquinone, 2- (4-methoxybenzyloxymethyl) -1 , 4-naphthoquinone, 2- (2-trifluoromethylbenzyloxymethyl) -1,4-naphthoquinone, 2- (3-trifluoromethylbenzyloxymethyl) -1,4-naphthoquinone, 2- (4-trifluoro Methylbenzyloxymethyl) -1,4-naphthoquinone, 2- (2-nitrobenzyloxymethyl) -1,4-naphthoquinone, 2 -(3-nitrobenzyloxymethyl) -1,4-naphthoquinone, 2- (4-nitrobenzyloxymethyl) -1,4-naphthoquinone, 2- (2-phenethyloxymethyl) -1,4-naphthoquinone, 2 -(1-phenethyloxymethyl) -1,4-naphthoquinone, 2- (1-benzyloxyethyl) -1,4-naphthoquinone, 2- (2-benzyloxyethyl) -1,4-naphthoquinone, 2- ( 1-benzyloxy-1-methylethyl) -1,4-naphthoquinone, 2-benzoyloxymethyl) -1,4-naphthoquinone, 2- (2-fluorobenzoyloxymethyl) -1,4-naphthoquinone, 2- ( 3-fluorobenzoyloxymethyl) -1,4-naphthoquinone, 2- (4-fluorobenzoyloxymethyl) -1,4-naphthoquinone, 2- (2-meso Rubenzoyloxymethyl) -1,4-naphthoquinone, 2- (3-methylbenzoyloxymethyl) -1,4-naphthoquinone, 2- (4-methylbenzoyloxymethyl) -1,4-naphthoquinone, 2- (2 -Chlorobenzoyloxymethyl) -1,4-naphthoquinone, 2- (3-chlorobenzoyloxymethyl) -1,4-naphthoquinone, 2- (4-chlorobenzoyloxymethyl) -1,4-naphthoquinone, 2- ( 2-trifluoromethylbenzoyloxymethyl) -1,4-naphthoquinone, 2- (3-trifluoromethylbenzoyloxymethyl) -1,4-naphthoquinone, 2- (4-trifluoromethylbenzoyloxymethyl) -1, 4-naphthoquinone, 2-acetoxymethyl-1,4-naphthoquinone, 2-propionyloxymethyl-1,4- Phtoquinone, 2-phenylthiomethyl-1,4-naphthoquinone, 2-benzylthiomethyl-1,4-naphthoquinone, 2-benzoylthiomethyl-1,4-naphthoquinone, 2-acetylthiomethyl-1,4-naphthoquinone, 2-carboxymethyl-1,4-naphthoquinone, 2-cyanomethyl-1,4-naphthoquinone, 2-methoxycarbonylmethyl-1,4-naphthoquinone, 2-ethoxycarbonylmethyl-1,4-naphthoquinone, 2-methylthiocarbonylmethyl -1,4-naphthoquinone, 2-vinyl-1,4-naphthoquinone, 2-allyl-1,4-naphthoquinone, 2- (2-butenyl) -1,4-naphthoquinone, 2- (3-methyl-2- Butenyl) -1,4-naphthoquinone, 2-ethyl-1,4-naphthoquinone, 2-propargyl-1,4-naphthoquinone, 2 Phenyl-1,4-naphthoquinone, 2- (2-fluorophenyl) -1,4-naphthoquinone, 2- (3-fluorophenyl) -1,4-naphthoquinone, 2- (4-fluorophenyl) -1,4 -Naphthoquinone, 2- (2-chlorophenyl) -1,4-naphthoquinone, 2- (3-chlorophenyl) -1,4-naphthoquinone, 2- (4-chlorophenyl) -1,4-naphthoquinone, 2- (2- Methylenyl) -1,4-naphthoquinone, 2- (3-methylenyl) -1,4-naphthoquinone, 2- (4-methylenyl) -1,4-naphthoquinone, 2- (2-trifluoromethylphenyl) -1, 4-naphthoquinone, 2- (2-trifluoromethylphenyl) -1,4-naphthoquinone, 2- (3-trifluoromethylphenyl) -1,4-naphthoquinone, 2- (4-trimethyl) Fluoromethylphenyl) -1,4-naphthoquinone, 2- (2-methoxyphenyl) -1,4-naphthoquinone, 2- (3-methoxyphenyl) -1,4-naphthoquinone, 2- (4-methoxyphenyl) 1,4-naphthoquinone, 2- (2-nitrophenyl) -1,4-naphthoquinone, 2- (3-nitrophenyl) -1,4-naphthoquinone, 2- (4-nitrophenyl) -1,4- Examples thereof include naphthoquinone and 2- (1 ′, 4′-naphthoquinone-2′-yl) -1,4-naphthoquinone.

In addition, 2-hydroxy-1,4-naphthoquinone, 2-methoxy-1,4-naphthoquinone, 2-ethoxy-1,4-naphthoquinone, 2-n-propoxy-1,4-naphthoquinone, 2-i-propoxy 1,4-naphthoquinone, 2-n-butoxy-1,4-naphthoquinone, 2-i-butoxy-1,4-naphthoquinone, 2-sec-butoxy-1,4-naphthoquinone, 2-i-butoxy-1 , 4-naphthoquinone, 2-tert-butoxy-1,4-naphthoquinone, 2- (2-hydroxyethoxy) -1,4-naphthoquinone, 2-cyclopropyloxy-1,4-naphthoquinone, 2-cyclopentyloxy-1 , 4-naphthoquinone, 2-cyclohexyl-1,4-naphthoquinone, 2-cyclopropylmethyloxy-1,4-naphthoquinone, 2-cyclopentylmethyl Xyl-1,4-naphthoquinone, 2-cyclohexylmethyloxy-1,4-naphthoquinone, 2-chloromethyloxy-1,4-naphthoquinone, 2-trifluoromethyloxy-1,4-naphthoquinone, 2-allyloxy-1 , 4-naphthoquinone, 2- (2-butenyloxy) -1,4-naphthoquinone, 2-propargyloxy-1,4-naphthoquinone, 2-phenoxy-1,4-naphthoquinone, 2- (4-fluorophenoxy) -1 , 4-naphthoquinone, 2- (4-chlorophenoxy) -1,4-naphthoquinone, 2- (4-methylphenoxy) -1,4-naphthoquinone, 2- (4-trifluoromethylphenoxy) -1,4- Naphthoquinone, 2- (4-methoxyphenoxy) -1,4-naphthoquinone, 2- (4-nitrophenoxy) -1,4-naphthoquinone, 2 -Benzyloxy-1,4-naphthoquinone, 2- (4-fluorobenzyloxy) -1,4-naphthoquinone, 2- (4-chlorobenzyloxy) -1,4-naphthoquinone, 2- (4-methylbenzyloxy) ) -1,4-naphthoquinone, 2- (4-methoxybenzyloxy) -1,4-naphthoquinone, 2- (4-trifluoromethylbenzyloxy) -1,4-naphthoquinone, 2- (4-methylthiobenzyloxy) ) -1,4-naphthoquinone, 2- (4-nitrobenzyloxy) -1,4-naphthoquinone, 2- (2-phenethyloxy) -1,4-naphthoquinone, 2-acetoxy-1,4-naphthoquinone and the like. Can be mentioned.

Furthermore, 2- (2-nitrophenyl) -1,4-naphthoquinone, 2-propionyloxy-1,4-naphthoquinone, 2-benzoyloxy-1,4-naphthoquinone, 2- (4-fluorobenzoyloxy) -1,4-naphthoquinone, 2- (4-methylbenzoyloxy) -1,4-naphthoquinone, 2- (4-chlorobenzoyloxy) -1,4-naphthoquinone, 2- (4-trifluoromethylbenzoyloxy) 1,4-naphthoquinone, 2-mercapto-1,4-naphthoquinone, 2-methylthio-1,4-naphthoquinone, 2-ethylthio-1,4-naphthoquinone, 2-n-propylthio-1,4-naphthoquinone, 2 -I-propylthio-1,4-naphthoquinone, 2-n-butylthio-1,4-naphthoquinone, 2-i-butylthio-1,4-naphthoquinone 2-sec-butylthio-1,4-naphthoquinone, 2-tert-butylthio-1,4-naphthoquinone, 2-cyclopropylthio-1,4-naphthoquinone, 2-cyclopentylthio-1,4-naphthoquinone, 2-cyclohexyl Thio-1,4-naphthoquinone, 2-cyclopropylmethylthio-1,4-naphthoquinone, 2-cyclopentylmethylthio-1,4-naphthoquinone, 2-cyclohexylmethylthio-1,4-naphthoquinone, 2-chloromethylthio-1,4 -Naphthoquinone, 2-trifluoromethylthio-1,4-naphthoquinone, 2-allylthio-1,4-naphthoquinone, 2- (2-butenylthio) -1,4-naphthoquinone, 2-propargylthio-1,4-naphthoquinone, 2-phenylthio-1,4-naphthoquinone, 2- (4-fluorophenylthio) 1,4-naphthoquinone, 2- (4-chlorophenylthio) -1,4-naphthoquinone, 2- (4-methylphenylthio) -1,4-naphthoquinone, 2- (4-trifluoromethylphenylthio) -1 , 4-naphthoquinone, 2- (4-methoxyphenylthio) -1,4-naphthoquinone, 2- (4-nitrophenylthio) -1,4-naphthoquinone, 2-benzylthio-1,4-naphthoquinone, 2- ( 4-fluorobenzylthio) -1,4-naphthoquinone, 2- (4-chlorobenzylthio) -1,4-naphthoquinone, 2- (4-methylbenzylthio) -1,4-naphthoquinone, 2- (4- Methoxybenzylthio) -1,4-naphthoquinone, 2- (4-trifluoromethylbenzylthio) -1,4-naphthoquinone, 2- (4-nitrobenzylthio) -1,4-naphthoquino 2- (2-phenethylthio) -1,4-naphthoquinone, 2-acetylthio-1,4-naphthoquinone, 2-propionylthio-1,4-naphthoquinone, 2-benzoylthio-1,4-naphthoquinone, 2- (4-fluorobenzoylthio) -1,4-naphthoquinone, 2- (4-methylbenzoylthio) -1,4-naphthoquinone, 2- (4-chlorobenzoylthio) -1,4-naphthoquinone, 2- (4 -Trifluoromethylbenzoylthio) -1,4-naphthoquinone, 2-methylsulfinyl-1,4-naphthoquinone, 2-ethylsulfinyl-1,4-naphthoquinone, 2-n-propylsulfinyl-1,4-naphthoquinone, 2 -I-propylsulfinyl-1,4-naphthoquinone, 2-n-butylsulfinyl-1,4-naphthoquinone, 2-i-butylsulfur Nyl-1,4-naphthoquinone, 2-sec-butylsulfinyl-1,4-naphthoquinone, 2-tert-butylsulfinyl-1,4-naphthoquinone, 2-cyclopropylsulfinyl-1,4-naphthoquinone, 2-cyclopentylsulfinyl 1,4-naphthoquinone, 2-cyclohexylsulfinyl-1,4-naphthoquinone, 2- (hydroxymethylsulfinyl) -1,4-naphthoquinone, 2- (hydroxyethylsulfinyl) -1,4-naphthoquinone, 2-phenylsulfinyl 1,4-naphthoquinone, 2-benzylsulfinyl-1,4-naphthoquinone, 2-methylsulfonyl-1,4-naphthoquinone, 2-ethylsulfonyl-1,4-naphthoquinone, 2-n-propylsulfonyl-1,4 -Naphthoquinone, 2-i-propylsulfonyl- 2,4-naphthoquinone, 2-n-butylsulfonyl-1,4-naphthoquinone, 2-i-butylsulfonyl-1,4-naphthoquinone, 2-sec-butylsulfonyl-1,4-naphthoquinone, 2-tert-butylsulfonyl 1,4-naphthoquinone, 2-cyclopropylsulfonyl-1,4-naphthoquinone, 2-cyclopentylsulfonyl-1,4-naphthoquinone, 2-cyclohexylsulfonyl-1,4-naphthoquinone, 2- (hydroxymethylsulfonyl) -1 2,4-naphthoquinone, 2- (hydroxyethylsulfonyl) -1,4-naphthoquinone, 2-phenylsulfonyl-1,4-naphthoquinone, 2-benzylsulfonyl-1,4-naphthoquinone, 2-acetyl-1,4-naphthoquinone 2-propanoyl-1,4-naphthoquinone, 2-chloroacetyl-1 , 4-naphthoquinone, 2-trifluoroacetyl-1,4-naphthoquinone, 2-methoxyacetyl-1,4-naphthoquinone, 2-benzoyl-1,4-naphthoquinone, 2- (2-fluorobenzoyl) -1,4 -Naphthoquinone, 2- (3-fluorobenzoyl) -1,4-naphthoquinone, 2- (4-fluorobenzoyl) -1,4-naphthoquinone, 2- (2-methylbenzoyl) -1,4-naphthoquinone, 2- (3-methylbenzoyl) -1,4-naphthoquinone, 2- (4-methylbenzoyl) -1,4-naphthoquinone, 2- (2-chlorobenzoyl) -1,4-naphthoquinone, 2- (3-chlorobenzoyl) ) -1,4-naphthoquinone, 2- (4-chlorobenzoyl) -1,4-naphthoquinone, 2- (2-trifluoromethylbenzoyl) -1,4-naphthoquino 2- (3-trifluoromethylbenzoyl) -1,4-naphthoquinone, 2- (4-trifluoromethylbenzoyl) -1,4-naphthoquinone, 2-carboxy-1,4-naphthoquinone, 2-methoxycarbonyl- 1,4-naphthoquinone, 2-ethoxycarbonyl-1,4-naphthoquinone, 2-carbamoyl-1,4-naphthoquinone, 2-dimethylaminocarbonyl-1,4-naphthoquinone, 2-cyano-1,4-naphthoquinone, 2 -Nitro-1,4-naphthoquinone and the like.

Furthermore, 2,3-dimethyl-1,4-naphthoquinone, 2,3-diethyl-1,4-naphthoquinone, 2-methyl-3-hydroxy-1,4-naphthoquinone, 2-methyl-3-methoxy- 1,4-naphthoquinone, 2,3-dihydroxy-1,4-naphthoquinone, 2,3-dimethoxy-1,4-naphthoquinone, 2,3-dichloro-1,4-naphthoquinone, 2-amino-3-chloro- 1,4-naphthoquinone, 2,3,6-trimethyl-1,4-naphthoquinone, 2,3,6,7-tetramethyl-1,4-naphthoquinone, 2,3-dimethyl-5-butyl-1,4 -Naphthoquinone, 2,3-dimethyl-6-butyl-1,4-naphthoquinone, 2,3-dimethyl-6,7-dibutyl-1,4-naphthoquinone, 2,3-dimethyl-5-pentyl-1,4 Naphthoquinone, 2,3-dimethyl-6-pentyl-1,4-naphthoquinone, 2,3-dimethyl-5-chloro-1,4-naphthoquinone, 2,3-dimethyl-6-chloro-1,4-naphthoquinone, 2,3-dimethyl-6,7-dichloro-1,4-naphthoquinone, 2,3-dimethyl-5-hydroxy-1,4-naphthoquinone, 2,3-dimethyl-6-hydroxy-1,4-naphthoquinone, 2,3-dimethyl-5,8-dihydroxy-1,4-naphthoquinone, 2,3-dimethyl-5,6,8-trihydroxy-1,4-naphthoquinone, 2,3-dimethyl-5-methoxy-1 , 4-naphthoquinone, 2,3-dimethyl-6-methoxy-1,4-naphthoquinone, 2,3-dimethyl-5,8-dimethoxy-1,4-naphthoquinone, 2,6-dimethyl-3-hi Roxy-1,4-naphthoquinone, 2,6,7-trimethyl-3-hydroxy-1,4-naphthoquinone, 2-methyl-3-hydroxy-5-butyl-1,4-naphthoquinone, 2-methyl-3- Hydroxy-6-butyl-1,4-naphthoquinone, 2-methyl-3-hydroxy-6,7-dibutyl-1,4-naphthoquinone, 2-methyl-3-hydroxy-5-pentyl-1,4-naphthoquinone, 2-methyl-3-hydroxy-6-pentyl-1,4-naphthoquinone, 2-methyl-3-hydroxy-5-chloro-1,4-naphthoquinone, 2-methyl-3-hydroxy-6-chloro-1, 4-naphthoquinone, 2-methyl-3-hydroxy-6,7-dichloro-1,4-naphthoquinone, 2-methyl-3,5-dihydroxy-1,4-naphthoquinone, 2-me Til-3,6-dihydroxy-1,4-naphthoquinone, 2-methyl-3,5,8-trihydroxy-1,4-naphthoquinone, 2-methyl-3,5,6,8-tetrahydroxy-1, 4-naphthoquinone, 2-methyl-3-hydroxy-5-methoxy-1,4-naphthoquinone, 2-methyl-3-hydroxy-6-methoxy-1,4-naphthoquinone, 2-methyl-3-hydroxy-5, 8-dimethoxy-1,4-naphthoquinone, 2,3-dichloro-6-methyl-1,4-naphthoquinone, 2,3-dichloro-6,7-dimethyl-1,4-naphthoquinone, 2,3-dichloro- 5-butyl-1,4-naphthoquinone, 2,3-dichloro-6-butyl-1,4-naphthoquinone, 2,3-dichloro-6,7-dibutyl-1,4-naphthoquinone, 2,3-dichloro 5-pentyl-1,4-naphthoquinone, 2,3-dichloro-6-pentyl-1,4-naphthoquinone, 2,3,5-trichloro-1,4-naphthoquinone, 2,3,6-trichloro-1, 4-naphthoquinone, 2,3,6,7-tetrachloro-1,4-naphthoquinone, 2,3-dichloro-5-hydroxy-1,4-naphthoquinone, 2,3-dichloro-6-hydroxy-1,4 -Naphthoquinone, 2,3-dichloro-5,8-dihydroxy-1,4-naphthoquinone, 2,3-dichloro-5,6,8-trihydroxy-1,4-naphthoquinone, 2,3-dichloro-5 Methoxy-1,4-naphthoquinone, 2,3-dichloro-6-methoxy-1,4-naphthoquinone, 2,3-dichloro-5,8-dimethoxy-1,4-naphthoquinone, 2-amino-3-chloro -6-methyl-1,4-naphthoquinone, 2-amino-3-chloro-6,7-dimethyl-1,4-naphthoquinone, 2-amino-3-chloro-5-butyl-1,4-naphthoquinone, 2 -Amino-3-chloro-6-butyl-1,4-naphthoquinone, 2-amino-3-chloro-6,7-dibutyl-1,4-naphthoquinone, 2-amino-3-chloro-5-pentyl-1 , 4-naphthoquinone, 2-amino-3-chloro-6-pentyl-1,4-naphthoquinone, 2-amino-3-chloro-5-chloro-1,4-naphthoquinone, 2-amino-3,6-dichloro -1,4-naphthoquinone, 2-amino-3,6,7-trichloro-1,4-naphthoquinone, 2-amino-3-chloro-5-hydroxy-1,4-naphthoquinone, 2-amino-3-chloro -6-hydroxy Ci-1,4-naphthoquinone, 2-amino-3-chloro-5,8-dihydroxy-1,4-naphthoquinone, 2-amino-3-chloro-5,6,8-trihydroxy-1,4-naphthoquinone 2-amino-3-chloro-5-methoxy-1,4-naphthoquinone, 2-amino-3-chloro-6-methoxy-1,4-naphthoquinone, 2-amino-3-chloro-5,8-dimethoxy -1,4-naphthoquinone and the like.

In the general formula (3), when X and Y are bonded to each other to form an unsaturated 6-membered ring and the 6-membered ring is aromatic, specific examples include 9,10-anthraquinone, 1 -Methylanthraquinone, 2-methylanthraquinone, 2-ethylanthraquinone, 1-methoxyanthraquinone, 1-methoxy-4-methylanthraquinone, 1,4-dihydro-9,10-anthraquinone, 1,4,4a, 9a-tetrahydro- 9,10-anthraquinone, 1,2,3,4-tetrahydro-9,10-anthraquinone, 1-methyl-9,10-anthraquinone, 2-methyl-9,10-anthraquinone, methyldihydro-9,10-anthraquinone 2-methyl-1,4-dihydro-9,10-anthraquinone, methyltetrahydro-9,10-anthraquinone, Examples thereof include 1-methyl-1,4,4a, 9a-tetrahydro-9,10-anthraquinone, 2-methyl-1,4,4a, 9a-tetrahydro-9,10-anthraquinone and the like.

Among these exemplified compounds, 1,4-naphthoquinone, 2-methyl-1,4-naphthoquinone, and 2-hydroxy-1,4-naphthoquinone are preferable because of their high effects and easy production.

The compound having a condensed polycyclic aromatic skeleton of the present invention has a vapor pressure lower than that of a conventionally used polymerization inhibitor having a monocyclic aromatic skeleton, and at the time of producing a carboxylic acid halide having a polymerizable group. It can be said that there is a low possibility of being taken out of the system accompanied by droplets during distillation purification.

Although it does not specifically limit as a carboxylic acid halide which has a polymeric group of this invention, For example, the (alpha), (beta)-unsaturated carboxylic acid halide represented by following General formula (4) is mentioned.

In the general formula (4), A, B, and C may be the same or different. In addition, a ring may be formed by bonding to A and B or B and C, or a ring may be formed with an oxygen atom interposed therebetween.

A, B and C are usually hydrogen atom, hydroxyl group, halogen atom, acyl group, alkyl group, aryl group, aralkyl group, alkoxyalkyl group, glycidyl group, hydroxyalkyl group or aryloxyalkyl group, oxygen, nitrogen And substituents containing sulfur. Preferred are a hydrogen atom, a hydroxyl group, a halogen atom, an acyl group and an alkyl group, and more preferred are a hydrogen atom, a hydroxyl group and an alkyl group.

In the general formula (4), examples of the halogen atom represented by A, B, and C include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Examples of the acyl group include an acetyl group and a propionyl group. Examples of the alkyl group include methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, tert-butyl group, n-pentyl group, n-hexyl group, and 2-ethylhexyl group. , N-decyl group, n-dodecyl group, 2-methoxyethyl group, 2-ethoxyethyl group and the like. Examples of the aralkyl group include a benzyl group and a phenethyl group, and examples of the aryl group include a phenyl group, a p-tolyl group, an o-tolyl group, and a naphthyl group. Examples of the alkoxy group include a methoxy group, an ethoxy group, an n-propoxy group, an i-propoxy group, an n-butoxy group, an i-butoxy group, and a tert-butoxy group, and the alkoxyalkyl group includes 2-methoxyethyl. Group, 2-ethoxyethyl group and the like, and examples of the glycidyl group include glycidyl group and 2-methylglycidyl group. Examples of the hydroxyalkyl group include a hydroxymethyl group and 1-hydroxyethyl group, and examples of the aryloxyalkyl group include a phenoxymethyl group.

D is a halogen atom, and examples thereof include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Preferred halogen atoms are chlorine atoms and bromine atoms, and more preferred halogen atoms are chlorine atoms.

Specifically, methacrylic acid chloride, methacrylic acid bromide, acrylic acid chloride, acrylic acid bromide, crotonic acid chloride, crotonic acid bromide and the like are preferable, and acrylic acid chloride and methacrylic acid chloride are particularly preferable.

The amount of the polymerization inhibitor used for the carboxylic acid halide of the present invention is not particularly limited, but when the carboxylic acid halide is 100 parts by weight, in distillation purification, it is usually 10 to 10,000 ppm, preferably 50 to 5000 ppm, more preferably Used in the range of 100 to 1000 ppm. At the time of storage and transfer of the product, it is usually used in the range of 10 to 5000 ppm, preferably 50 to 3000 ppm, more preferably 100 to 1000 ppm.

Examples of other polymerization inhibitors that can be used in combination with the polymerization inhibitor of the present invention include hydroquinone, such as hydroquinone, methylhydroquinone, 2-methylhydroquinone, and t-butylhydroquinone, p-benzoquinone, and methyl- Benzoquinones such as p-benzoquinone, catechols such as catechol and t-butylcatechol, phenols such as 2,6-di-t-butyl-4-methylphenol, p-methoxyphenol and cresol, phenothiazine, ferdazil, α , Α-diphenyl-β-picrylhydrazyl, 4-hydroxy-2,2,6,6-tetramethylpiperidine-1-oxyl and the like are known polymerization inhibitors. Two or more kinds of these polymerization inhibitors may be used together with the polymerization inhibitor of the present invention.

In particular, p-methoxyphenol is preferable in that it is highly effective when used in combination with the compound having a condensed polycyclic aromatic skeleton of the present invention.

Although the usage-amount of these polymerization inhibitors is not specifically limited, In addition to the polymerization inhibitor of this invention, it is 10-10000 ppm normally in distillation refinement | purification, Preferably it is 50-5000 ppm, More preferably, it uses in 100-1000 ppm. At the time of storage and transfer of the product, it is usually used in the range of 10 to 5000 ppm, preferably 50 to 3000 ppm, more preferably 100 to 1000 ppm. The weight ratio of the amount used with the polymerization inhibitor of the present invention is not particularly limited, but it is desirable to use a large amount of the polymerization inhibitor of the present invention.

The polymerization inhibitor of the present invention is used as an additive for the purpose of inhibiting polymerization during the chemical reaction using a carboxylic acid halide having a polymerizable group as well as during purification distillation during the production of a carboxylic acid halide having a polymerizable group. Can also be used.

EXAMPLES Hereinafter, specific embodiments of the present invention will be described in more detail by way of examples, but the present invention is not limited to the following.

Table 1 shows the types and abbreviations of the polymerization inhibitors used in the examples. In the table, NQ, LSN, MNT and DEN are compounds having the condensed polycyclic aromatic skeleton of the present invention, and HTEMPO, BQ, Pz, MEHQ and HQ are compounds used for comparison.

<Evaluation of storage stability of methacrylic acid chloride>
0.10 g of the polymerization inhibitor described in Table 1 was placed in a sample tube, and 9.9 g of a commercially available methacrylic acid chloride (Wako Pure Chemical Industries, Ltd., reagent grade 1, MEHQ 400 ppm contained as a polymerization inhibitor) was added. The change in viscosity and color of this sample over time was confirmed visually. In addition, evaluation of the viscosity was determined as follows.

Evaluation criteria for viscosity ○ No change △ Bubble breakage worsens, signs of thickening × Thickening is observed ×× Solidification

<Evaluation of stability during distillation purification of methacrylic acid chloride>
0.0030 g of the polymerization inhibitor described in Table 1 was placed in a sample tube, and 6.0 g of commercially available methacrylic acid chloride (Wako Pure Chemical Industries, Ltd., reagent grade 1, MEHQ 400 ppm contained as a polymerization inhibitor) was added. This sample was stored under air / nitrogen, and the change with time in viscosity and color was confirmed visually. The results stored in air are shown in Tables 3 and 4, and the results stored in a nitrogen atmosphere are shown in Tables 5 and 6.

From the above results, the following is mainly clear.

(1) Examples 1 to 4, which are long-term storage tests for 10 months, Comparative Examples 1 and 2, and Table 2 showing the test results clearly show that the condensed polycyclic aromatic skeleton of the present invention is used. NQ, DEN, and MNT that are compounds having no change in viscosity even after 10 months, whereas Comparative Example 1 using HQ that is a compound having a monocyclic aromatic skeleton, and HTEMPO having no aromatic skeleton In Comparative Example 2 using a solidified compound after 10 months, the compound having a condensed polycyclic aromatic skeleton of the present invention is compared with HQ which is a compound having a monocyclic aromatic skeleton and HTEMPO having no aromatic skeleton. It can be seen that the polymerization inhibiting ability is remarkably high, and it has a high effect as a polymerization inhibitor capable of imparting storage stability of a carboxylic acid halide having a polymerizable group.

(2) As is clear from Tables 3 and 4, NQ, LSN, DEN, and MNT, which are compounds having the condensed polycyclic aromatic skeleton of the present invention, are also used in the test of the short-term polymerization inhibition effect in air. In the case of Examples 4, 5, 6, and 7 used, even if the addition amount was reduced, Comparative Examples 5, 6, and 7 that are compounds of a monocyclic aromatic skeleton and Comparative Example 4 that is non-aromatic as in (1) It can be seen that the polymerization inhibition effect is equivalent to or better than that.

(3) As is clear from Tables 5 and 6, in the test of the short-term polymerization inhibition effect in a nitrogen atmosphere, NQ, LSN, DEN, and MNT, which are compounds having the condensed polycyclic aromatic skeleton of the present invention, are used. In the case of Examples 8, 9, 10, and 11 used, the ability to inhibit polymerization does not decrease even when stored in a nitrogen atmosphere, and Comparative Examples 10, 11, 12, and 13 that are compounds having a monocyclic aromatic skeleton. Compared with Comparative Example 10 which is non-aromatic, it has a polymerization inhibiting effect equal to or higher than that.

That is, the compound having a condensed polycyclic aromatic skeleton of the present invention is a compound having a polymerizable group and having a carboxylic acid halide in the presence of air or a nitrogen atmosphere as compared with a monocyclic aromatic skeleton compound which is a conventional polymerization inhibitor. The polymerization inhibiting ability is good under either of the following conditions. Therefore, it turns out that it is effective as a polymerization inhibitor at the time of the distillation refinement | purification of manufacture of the carboxylic acid halide which has a polymeric group.

Claims (5)

A polymerization inhibitor for a carboxylic acid halide having a polymerizable group, having a condensed polycyclic aromatic skeleton represented by the following general formula (2).

(Wherein, R ^1, R ^2, which may be the same or different and represent a hydrogen atom, an alkyl group, an aryl group, an aralkyl group, an alkoxyalkyl group, a hydroxycarboxylic alkyl group or an aryloxy group , X, Y and Z are identical or different, represent each a hydrogen atom, a hydroxyl group, an alkyl group, an a Turkey alkoxyalkyl group.) A polymerization inhibitor for a carboxylic acid halide having a polymerizable group, having a condensed polycyclic aromatic skeleton represented by the following general formula (3).

(Wherein, X, Y and Z are identical or different, represent each a hydrogen atom, a hydroxyl group, an alkyl group, an A Turkey alkoxyalkyl group.) The polymerization inhibitor for a carboxylic acid halide having a polymerizable group according to claim 1 or 2, wherein the halide in the carboxylic acid halide having a polymerizable group is chloride or bromide. The polymerization inhibitor for a carboxylic acid halide having a polymerizable group according to any one of claims 1 to 3 , wherein the carboxylic acid having a polymerizable group in the carboxylic acid halide having a polymerizable group is acrylic acid or methacrylic acid. . A polymerization inhibitor composition for a carboxylic acid halide having a polymerizable group, comprising the polymerization inhibitor according to any one of claims 1 to 4 and p-methoxyphenol.