JP2009029801A - Naphthohydroquinone mono(meth)acrylate and method for producing the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a mono(meth)acrylate of a naphthohydroquinone compound and to provide a method for producing the mono(meth)acrylate. <P>SOLUTION: The naphthohydroquinone mono(meth)acrylate is represented by formula (I) (wherein, R represents a hydrogen atom or a methyl group; and X and Y may each be same or different and represent each any of a hydrogen atom, an alkyl group, a halogen atom, a hydroxy group, an alkoxy group, an alkylthio group, an arylthio group, a carboxy group, a sulfonic acid group and a nitro group). The method for its production comprises a step of reacting naphthohydroquinone with an acid halide in the presence of an inorganic base. <P>COPYRIGHT: (C)2009,JPO&amp;INPIT

Description

  The present invention relates to naphthohydroquinone mono (meth) acrylate and a method for producing the same.

  In the present invention, unless otherwise specified, 1,4-dihydroxynaphthalene is referred to as “naphthohydroquinone”.

  In the present invention, unless otherwise specified, “acrylate” and “methacrylate” are collectively referred to as “(meth) acrylate”, and “acrylic acid” and “methacrylic acid” are collectively referred to as “(meth) acrylic acid”. To do. The same applies to these derivatives.

  In recent years, lightweight and highly refractive plastic materials have been used in the fields of LCD panels, color filters, spectacle lenses, full-lens lenses, lenticular lenses, prism lens sheets for TFT, aspheric lenses, optical disks, optical fibers, and optical waveguides. Has been. As a method for increasing the refractive index of an organic compound, it is already well known that it is useful to introduce a halogen atom or a sulfur compound into the molecular structure. Or an unpleasant odor peculiar to sulfur may occur (see Patent Document 1 and Patent Document 2).

  In addition, it is known to introduce an aromatic ring as another method for increasing the refractive index of an organic compound. However, generally, when a high refractive index resin composition having many aromatic rings is applied to a glass substrate or the like by a spin coating method or the like, the familiarity between the high refractive index resin composition and the substrate tends to decrease. Accordingly, it is desired to provide a compound for a high refractive index resin composition that can solve these problems.

  On the other hand, a method for synthesizing a compound (hydroquinone monoacrylate) in which only one of hydroxyl groups of hydroquinone is esterified with acrylic acid is known (see Non-Patent Document 1, Non-Patent Document 2, etc.). These hydroquinone monoacrylates are known to be used for polymer liquid crystal monomers, antibiotic raw materials and the like.

JP 05-170702 A JP 2002-20433 A Indian Journal of Chemistry Section B, 1999, 38 (11), 1237-1241 Journal of Agricultural and Food Chemistry, 2004, 52, 7480-7383

  However, a method for synthesizing mono (meth) acrylate of a naphthohydroquinone compound has not been known so far. This mono (meth) acrylate of a naphthohydroquinone compound can be used as a polymer liquid crystal monomer or an antibiotic raw material, and as a result of intensive studies on a method for efficiently producing this compound, the present invention has been completed. is there.

  That is, an object of the present invention is to provide a mono (meth) acrylate of a naphthohydroquinone compound and a method for producing the same.

  As a result of intensive studies to solve the above problems, the present inventors have made it possible to synthesize naphthohydroquinone mono (meth) acrylate by reacting naphthohydroquinone and acid halide in the presence of an inorganic base. And found the present invention.

（式（Ｉ）において、Ｒは水素原子またはメチル基を示し、Ｘ，Ｙは同一でも異なっていてもよく、水素原子、アルキル基、ハロゲン原子、水酸基、アルコキシ基、アルキルチオ基、アリールチオ基、カルボキシル基、スルホン酸基、ニトロ基のいずれかを示す。） That is, the gist of the present invention resides in naphthohydroquinone mono (meth) acrylate, which is represented by the following formula (I) (Claim 1).

(In the formula (I), 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 alkylthio group, an arylthio group, a carboxyl group. Group, sulfonic acid group, or nitro group.)

  Another gist of the present invention is a method for producing the above-mentioned naphthohydroquinone mono (meth) acrylate, characterized by having a step of reacting naphthohydroquinone and acid halide in the presence of an inorganic base. And naphthohydroquinone mono (meth) acrylate production method (claim 2).

    Here, the molar ratio of acid halide to naphthohydroquinone is preferably less than 2 (claim 3).

  Moreover, it is preferable to use a (meth) acrylic acid halide as the acid halide.

  It is also preferable to use at least a 3-halogenated propionic acid halide as the acid halide. In this case, naphthohydroquinone monoacrylate is obtained.

  It is also preferable to use at least 3-halogenated-2-methylpropionic acid chloride as the acid halide. In this case, naphthohydroquinone monomethacrylate is obtained.

  The reaction is preferably carried out in a two-phase system composed of an aqueous phase and an organic phase.

  According to the present invention, it is possible to obtain a naphthohydroquinone mono (meth) acrylate whose synthesis method has not been known so far.

    Hereinafter, the present invention will be described in detail, but the present invention is not limited to the following description, and various modifications can be made within the scope of the gist of the present invention.

（式（Ｉ）において、Ｒは水素原子またはメチル基を示し、Ｘ，Ｙは同一でも異なっていてもよく、水素原子、アルキル基、ハロゲン原子、水酸基、アルコキシ基、アルキルチオ基、アリールチオ基、カルボキシル基、スルホン酸基、ニトロ基のいずれかを示す。） [I. Naphthohydroquinone mono (meth) acrylate]
The naphthohydroquinone mono (meth) acrylate of the present invention is a compound having a structure represented by the following formula (I).

(In the formula (I), 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 alkylthio group, an arylthio group, a carboxyl group. Group, sulfonic acid group, or nitro group.)

（式（Ｉａ）及び式（Ｉｂ）において、Ｘ，Ｙは同一でも異なっていてもよく、水素原子、アルキル基、ハロゲン原子、水酸基、アルコキシ基、アルキルチオ基、アリールチオ基、カルボキシル基、スルホン酸基、ニトロ基のいずれかを示す。） That is, the naphthohydroquinone mono (meth) acrylate of the present invention is specifically a compound having a structure represented by the following formula (Ia) or (Ib).

(In the formula (Ia) and the formula (Ib), 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 alkylthio group, an arylthio group, a carboxyl group, a sulfonic acid group. Or any of nitro groups.)

  Examples of the alkyl group represented by X and Y in the formula (I) (that is, the formula (Ia) and the formula (Ib)) include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, and an n-butyl group. I-butyl group, amyl group, 2-ethylhexyl group and the like. 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, an n-butoxy group, a hexyloxy group, and a 2-phenoxyethoxy group. Examples of the alkylthio group include a methylthio group, an ethylthio group, a propylthio group, a butylthio group, and a hexylthio group. Examples of the arylthio group include a phenylthio group, an o-tolylthio group, an m-tolylthio group, a p-tolylthio group, and a p-hydroxyphenylthio group.

  Examples of the compound represented by the structural formula (I) (that is, the formula (Ia) and the formula (Ib)) include the following. That is, 4-hydroxy-1-naphthyl acrylate, 4-hydroxy-1-naphthyl methacrylate, 3-methyl-4-hydroxy-1-naphthyl acrylate, 3-methyl-4-hydroxy-1-naphthyl methacrylate, 3-ethyl- 4-hydroxy-1-naphthyl acrylate, 3-ethyl-4-hydroxy-1-naphthyl methacrylate, 3-chloro-4-hydroxy-1-naphthyl acrylate, 3-chloro-4-hydroxy-1-naphthyl methacrylate, 3- Bromo-4-hydroxy-1-naphthyl acrylate, 3-bromo-4-hydroxy-1-naphthyl methacrylate, 3-methoxy-4-hydroxy-1-naphthyl acrylate, 3-methoxy-4-hydroxy-1-naphthyl methacrylate, 3-methylthio- -Hydroxy-1-naphthyl acrylate, 3-methylthio-4-hydroxy-1-naphthyl methacrylate, 2-phenylthio-4-hydroxy-1-naphthyl acrylate, 3-phenylthio-4-hydroxy-1-naphthyl methacrylate, 7-chloro -4-hydroxy-1-naphthyl acrylate, 7-nitro-4-hydroxy-1-naphthyl acrylate, 7-carboxy-4-hydroxy-1-naphthyl acrylate, and the like. Representative compound structural formulas are shown below.

In the following description, the compound having the structure represented by the formula (Ia) may be referred to as naphthohydroquinone monoacrylate or naphthalenediol mono (meth) acrylate.
In addition, the compound having the structure represented by the formula (Ib) may be referred to as naphthohydroquinone monomethacrylate or 1,4-dihydroxynaphthalene mono (meth) acrylate.

[II. Method for producing naphthohydroquinone mono (meth) acrylate]
The method for producing naphthohydroquinone mono (meth) acrylate of the present invention (hereinafter sometimes abbreviated as “production method of the present invention”) produces naphthohydroquinone mono (meth) acrylate represented by the above formula (I). The method includes at least a step of reacting naphthohydroquinone with an acid halide in the presence of an inorganic base.

The main two aspects of the production method of the present invention include the following two.
A mode in which (meth) acrylic acid halide is used as the acid halide (this may be hereinafter referred to as “(meth) acrylic acid halide method” or “first mode”).
A mode in which 3-halogenated propionic acid halide or 3-halogenated-2-methylpropionic acid halide is used as the acid halide to obtain naphthohydroquinone monoacrylate or naphthohydroquinone monomethacrylate (hereinafter referred to as “halogenated propionic acid halide method”) Alternatively, it may be referred to as “second aspect”).

  In the following description, first, the first aspect ((meth) acrylic acid halide method) will be described. Next, the second aspect (halogenated propionic acid halide method) will be described focusing on the differences from the first aspect.

[IIα. First Aspect]
<IIα-1. Raw material>
In the first embodiment, naphthohydroquinone and (meth) acrylic acid halide are used as raw materials.

(I) Naphthohydroquinone:
Naphthohydroquinone (1,4-dihydroxynaphthalene) is a compound having a structure represented by the following formula (i). In formula (i), X and Y are the same as X and Y described in formula (I).

  Naphthohydroquinone can be used as it is or after being appropriately purified. It is also distributed as an industrial product.

(Ii) (Meth) acrylic acid halide:
Acrylic acid halide is a compound having a structure represented by the following formula (ia), and methacrylic acid halide is a compound having a structure represented by the following formula (iib).

  In the above formulas (ia) and (iib), X ′ represents a halogen atom. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, and a chlorine atom is particularly preferable from the viewpoint of ease of production. That is, acrylic acid chloride is particularly preferable as the acrylic acid halide, and methacrylic acid chloride is particularly preferable as the methacrylic acid halide.

  If acrylic acid halide is used as a raw material, naphthohydroquinone monoacrylate is obtained. On the other hand, if methacrylic acid halide is used as a raw material, naphthohydroquinone monomethacrylate can be obtained. Therefore, what is necessary is just to select the (meth) acrylic acid halide used as a raw material according to the kind of target naphthohydroquinone mono (meth) acrylate.

  In addition, although only a single kind of (meth) acrylic acid halide may be used, two or more kinds of (meth) acrylic acid halides having different halogen atoms may be used in combination. Moreover, if acrylic acid halide and methacrylic acid halide are used in combination, a mixture of naphthohydroquinone monoacrylate and naphthohydroquinone monomethacrylate is obtained.

As the (meth) acrylic acid halide, a commercially available reagent can be used as it is or after being appropriately purified.
Prior to the monoesterification reaction of naphthohydroquinone, (meth) acrylic acid halide is synthesized from (meth) acrylic acid and thionyl halide for the purpose of monoesterification by the so-called in situ method, and this is isolated. It is also possible to use for esterification reaction, without using. This reaction will be described later.

(Iii) Ratio of naphthohydroquinone to (meth) acrylic acid halide:
The use ratio of naphthohydroquinone and (meth) acrylic acid halide is not particularly limited, but the molar ratio of (meth) acrylic acid halide to naphthohydroquinone is usually 0.5 or more, particularly 0.8 or more. Moreover, it is usually preferable to be in the range of less than 2 and especially 1.5 or less. If the ratio of (meth) acrylic acid halide is too low, the amount of unreacted naphthohydroquinone increases, and treatment such as raw material recovery may be required. On the other hand, if the ratio of (meth) acrylic acid halide is too high, the amount of diester by-product tends to increase.

<IIα-2. Inorganic base>
The kind of inorganic base is not particularly limited. Examples include sodium hydroxide (NaOH), potassium hydroxide (KOH), sodium carbonate (Na ₂ CO ₃ ), potassium carbonate (K ₂ CO ₃ ), and the like. Of these, sodium hydroxide and potassium hydroxide are preferable, and sodium hydroxide is more preferable. Any one of these inorganic bases may be used alone, or two or more thereof may be used in any combination and ratio.

  The use ratio of the inorganic base is not particularly limited, but the equivalent ratio of the inorganic base to naphthohydroquinone is usually 1.0 equivalent or more, especially 1.2 equivalents or more, and usually 3.0 equivalents or less, A range of 2.0 equivalents or less is preferable. If the ratio of the inorganic base is too low, the pH of the aqueous layer becomes acidic during the dropping of the acid halide, and the selectivity may be significantly reduced. On the other hand, if the ratio of the inorganic base is too high, decomposition of the acid halide may increase.

<IIα-3. Reaction solvent>
The reaction of naphthohydroquinone and (meth) acrylic acid halide is usually carried out in the presence of a reaction solvent.
The type of the reaction solvent is not particularly limited, but usually water, an organic solvent or the like is used.
Examples of the use form of the reaction solvent include a one-phase system consisting of only an aqueous phase, a one-phase system consisting of only an organic phase, and a two-phase system consisting of an aqueous phase and an organic phase. Among these, it is preferable to carry out the reaction in a two-phase system consisting of an aqueous phase and an organic phase.

  When the reaction is carried out in a one-phase system comprising an aqueous phase, water is usually used alone as the reaction solvent. In addition to water, it may contain one or more organic solvents miscible with water, but even in that case, the ratio of the organic solvent to the whole aqueous phase is usually 10% by volume or less, preferably 5% by volume. % Or less is preferable.

  When the reaction is carried out in a one-phase system comprising an aqueous phase, the concentration of naphthohydroquinone relative to the reaction solvent (aqueous phase) is usually 0.01 g / ml or more, particularly 0.04 g / ml or more, and usually 0.5 g / ml. In the following, it is preferable that the range be 0.3 g / ml or less. If the concentration of naphthohydroquinone is too low, production efficiency may be reduced. On the other hand, if the concentration of naphthohydroquinone is too high, it may be difficult to stir the slurry solution with the precipitated solid.

  When the reaction is performed in a one-phase system composed of an organic phase, one or two or more organic solvents are used as a reaction solvent. Although the kind in particular of organic solvent is not restrict | limited, What can melt | dissolve an inorganic salt is preferable. Specific examples of such an organic solvent include acetonitrile, acetone, tetrahydrofuran (THF), 1,2-dimethoxyethane, N, N-dimethylformamide (DMF) and the like. Of these, acetonitrile is particularly preferable in view of reaction results and ease of post-treatment.

  When the reaction is carried out in a one-phase system comprising an organic phase, the concentration of naphthohydroquinone relative to the reaction solvent (organic phase) is usually 0.02 g / ml or more, particularly 0.05 g / ml or more, and usually 0.5 g / ml. In the following, it is preferable that the range be 0.3 g / ml or less. If the concentration of naphthohydroquinone is too low, production efficiency may be reduced. On the other hand, if the concentration of naphthohydroquinone is too high, it may be difficult to stir the slurry solution with the precipitated solid. In addition, the selectivity may decrease.

When the reaction is performed in a two-phase system composed of an aqueous phase and an organic phase, usually, water and one or more organic solvents that form the organic phase are used in combination as a reaction 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 such organic solvents include aromatic hydrocarbon solvents such as toluene, xylene and decalin; aliphatic hydrocarbon solvents such as heptane and cyclohexane; Any of these may be used alone, or two or more of these may be used in combination in any combination and ratio. Of these, toluene, xylene and heptane are preferable, and it is particularly preferable to use toluene alone or mixed with heptane.

  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 usually 50% or more, particularly 75% or more, and usually 95%. Below, it is preferable that it is 90% or less of the range. If the proportion of the aqueous phase is too low or too high, the selectivity of the monoester tends to decrease.

  The concentration of naphthohydroquinone with respect to the total amount of the aqueous phase and the organic phase is usually 0.005 g / ml or more, especially 0.03 g / ml or more, and usually 0.5 g / ml or less, especially 0.3 g / ml or less. It is preferable that If the concentration of naphthohydroquinone is too low, production efficiency may be reduced. On the other hand, if the concentration of naphthohydroquinone is too high, the selectivity may decrease. Further, it may be difficult to stir the slurry solution with the precipitated solid.

<IIα-4. Reaction procedure, reaction conditions, etc.>
Details of the procedure, conditions, etc. of the esterification reaction of naphthohydroquinone in the first embodiment are as follows.

Although the reaction system is not limited, the reaction is usually carried out in a batch system.
Since naphthohydroquinone is easily oxidized, it may be oxidized to become a quinone structure and be colored when exposed to oxygen in the air. Therefore, the reaction is usually performed in an inert atmosphere.
Specifically, it is preferable to perform the reaction using a sealable reaction vessel and replacing the inside of the reaction vessel with an inert gas (nitrogen, argon, etc.).

Although the method of reaction is not limited, the reaction is usually carried out by bringing naphthohydroquinone and (meth) acrylic acid halide into contact with each other in the presence of an inorganic base in a reaction solvent.
From the viewpoint of controlling the reaction temperature and improving the selectivity, a method of dropping (meth) acrylic acid halide is preferred.
In particular, when the reaction is carried out in a two-phase system comprising an aqueous phase and an organic phase, naphthohydroquinone is dissolved in a two-phase solvent of the aqueous phase and the organic phase, and mixed in a container by a technique such as stirring ( It is preferable to react by dropping a (meth) acrylic acid halide.

The temperature of the reaction system is not limited, but it is preferable to carry out the reaction while cooling the reaction system. Specifically, the temperature of the reaction system is usually 10 ° C. or lower, and preferably 5 ° C. or lower. If the temperature during the reaction is too high, the selectivity tends to decrease, and hydrolysis of the reaction product ester (naphthohydroquinone mono (meth) acrylate) may occur. On the other hand, the lower limit of the reaction temperature is not particularly limited as long as it is higher than the temperature at which the aqueous phase solidifies.
The pressure during the reaction is not limited and may be normal pressure, increased pressure, or reduced pressure. Usually, the reaction is carried out under normal pressure conditions.

  Although the dropping speed of the (meth) acrylic acid halide is not limited, it is desirable to adjust the dropping speed so as to maintain the above-described appropriate reaction temperature (5 to 10 ° C. or lower). The dropping time is not limited, but is usually about 1 to 2 hours. If the dropping speed of the (meth) acrylic acid halide is too slow, the reaction time may be too long and the productivity may decrease. On the other hand, when the dropping speed of the (meth) acrylic acid halide is too high, the reaction temperature becomes high and the selectivity may be lowered.

Although the reaction time is not limited, it is usually in the range of usually 30 minutes or more, particularly 60 minutes or more, and usually 5 hours or less, especially 2 hours or less.
In particular, when the reaction is carried out while dropping the (meth) acrylic acid halide under the two-phase condition as described above, the reaction has almost reached the end point at the end of the (meth) acrylic acid halide, but the dropping is completed. Stirring may be continued while cooling for a certain time (for example, about 20 to 30 minutes).
However, if the reaction time is too long, the product (ester) may be hydrolyzed, and the resulting product may be colored.
Therefore, it is preferable to quench the reaction as soon as possible after the above reaction time has elapsed (that is, to make the reaction system acidic by adding dilute hydrochloric acid or the like).

  The completion of the reaction can be confirmed, for example, by analyzing the organic phase by gas chromatography (hereinafter sometimes referred to as “GC”) and examining the amount of the product. Of course, this procedure is unnecessary when the reaction time is known.

<IIα-5. Post-processing>
After completion of the reaction, post-treatment such as quenching (stopping) the reaction, crude purification, recrystallization purification, etc. may be performed as necessary.

  The reaction is quenched (stopped) by, for example, adding an acid such as dilute hydrochloric acid (about 1 to 3 N) or dilute sulfuric acid (about 1 to 3 N) to the reaction system (aqueous phase) to make it acidic.

The crude purification of the reaction product can be performed, for example, by the following procedure.
For example, an extraction solvent such as ethyl acetate is added to the reaction system and mixed to perform two-layer separation. The organic phase is washed with water, a drying agent such as magnesium sulfate (MgSO ₄ ) is added and dried, and then the solvent is distilled off to obtain a crude product.

The recrystallized purification of the crude purified product is performed, for example, by adding the crude purified product to a recrystallization solvent and dissolving it by heating, then allowing to cool and recrystallizing.
As the solvent for recrystallization, for example, toluene, a mixed solvent of toluene and ethyl acetate, a mixed solvent of toluene and ethanol, or the like can be used.

[IIβ. Second Aspect]
<IIβ-1. Raw material>
In the second embodiment, naphthohydroquinone and 3-halogenated propionic acid halide or 3-halogenated-2-methylpropionic acid halide (hereinafter collectively referred to as “3-halogenated (methyl) propionic acid halide”) as raw materials .) And use.

(I) Naphthohydroquinone:
About naphthohydroquinone (1,4-dihydroxynaphthalene), it is the same as that of the 1st aspect, The details are the said [II (alpha). <IIα-1. Raw material>, as described in the column of “(i) naphthohydroquinone”.

(Ii) 3-halogenated (methyl) propionic acid halide:
The 3-halogenated propionic acid halide is a compound having a structure represented by the following formula (iic), and the 3-halogenated-2-methylpropionic acid halide is a compound having a structure represented by the following formula (iid).

  In the above formulas (iic) and (iiid), X ″ represents a halogen atom. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, and a fluorine atom or a chlorine atom is preferable. An atom is particularly preferred, that is, an acrylic acid chloride is particularly preferred as the acrylic acid halide, and a methacrylic acid chloride is particularly preferred as the methacrylic acid halide. The two X ″ may be the same or different. From the viewpoint of availability of compounds, it is preferable that they are the same.

  If 3-halogenated propionic acid halide is used as a raw material, naphthohydroquinone monoacrylate is obtained. On the other hand, if 3-halogenated-2-methylpropionic acid halide is used as a raw material, naphthohydroquinone monomethacrylate is obtained. Therefore, what is necessary is just to select the 3-halogenated (methyl) propionic acid halide used as a raw material according to the kind of target naphthohydroquinone mono (meth) acrylate.

In the case of producing naphthohydroquinone monoacrylate, only 3-halogenated propionic acid halide may be used alone as a raw material, but 3-halogenated propionic acid halide and acrylic acid halide are combined in an arbitrary ratio. May be used.
Similarly, when producing naphthohydroquinone monomethacrylate, only 3-halogenated-2-methylpropionic acid halide may be used alone as a raw material, but 3-halogenated propionic acid halide and methacrylic acid halide May be used in combination at any ratio.

  As the 3-halogenated (methyl) propionic acid halide, a commercially available reagent can be used as it is or after being appropriately purified.

In addition, by reacting (meth) acrylic acid with thionyl halide, a mixture of 3-halogenated (methyl) propionic acid halide and (meth) acrylic acid halide was synthesized, and this was isolated without isolation. It is also possible to use for monoesterification reaction (so-called in situ method). Here, “thionyl halide” is a compound represented by the general formula SOX ″ ₂ (where X ″ is the same as X ″ in the above (iic) and (iid)), for example, thionyl chloride. (SOCl ₂ ).

The reaction formula of (meth) acrylic acid and thionyl halide is shown below.

  Although it is difficult to obtain 3-halogenated (2-methyl) propionic acid halide having a purity close to 100% by the reaction of (meth) acrylic acid and thionyl halide, 3-halogenated propionic acid halide and acrylic acid halide Or a mixture of 3-halogenated-2-methyl-propionic acid halide and methacrylic acid halide. As described above, naphthohydroquinone monoacrylate and naphthohydroquinone monomethacrylate can be obtained by a combination of these raw materials.

  The synthesis of acid halide (mixture of 3-halogenated (methyl) propionic acid halide and (meth) acrylic acid halide) by reaction of (meth) acrylic acid and thionyl halide is described in, for example, Helv. Chim. Acta, 42, 1653 (1959), or Compt. Rend. , C, 269, 1325 (1969) and the like.

(Iii) Ratio of naphthohydroquinone to 3-halogenated (methyl) propionic acid halide:
The use ratio of naphthohydroquinone and 3-halogenated (methyl) propionic acid halide is not particularly limited, but is usually 0.5 by mole ratio of 3-halogenated (methyl) propionic acid halide to naphthohydroquinone. Above all, it is preferably 0.8 or more, and usually less than 2, especially 1.5 or less. If the ratio of the 3-halogenated (methyl) propionic acid halide is too low, the amount of unreacted naphthohydroquinone increases, which may require treatment such as raw material recovery. On the other hand, when the ratio of 3-halogenated (methyl) propionic acid halide is too high, the amount of diester by-product tends to increase.

  In addition, when 3-halogenated propionic acid halide and acrylic acid halide are used in combination, and when 3-halogenated-2-methyl-propionic acid halide and methacrylic acid halide are used in combination, they are used in combination. So that the total amount of raw materials to satisfy the above range.

<IIβ-2. Inorganic base>
About the kind of inorganic base, it is the same as that of the case of a 1st aspect, The details are the said [II (alpha). <IIα-2. As described in the column “Inorganic base”.

The use ratio of the inorganic base is not limited, but is usually 1.2 equivalents or more, particularly 1.4 equivalents or more, and usually 3.0 equivalents or less, especially 2 in terms of the equivalent ratio of the inorganic base to naphthohydroquinone. It is preferable to make it into the range below 0.0 equivalent.
If the ratio of the inorganic base is too low, the pH of the aqueous phase becomes acidic during the dropwise addition of the acid halide, and the selectivity may be significantly reduced. This tendency becomes more prominent than when (meth) acrylic acid halide is used as the acid halide (first aspect). This is because dehydrochlorination occurs to some extent before and after 3-halogenated (methyl) propionic acid halide reacts with naphthohydroquinone, increasing the consumption of inorganic base.
On the other hand, if the ratio of the inorganic base is too high, decomposition of the acid halide may increase.

<IIβ-3. Reaction solvent>
About the reaction solvent, it is the same as that of the case of the 1st aspect, The details are the said [II (alpha). <IIα-3. As described in the column “Reaction solvent>.

<IIβ-4. Reaction procedure, reaction conditions, etc.>
The details of the procedure, conditions and the like of the esterification reaction of naphthohydroquinone are also the same as in the case of the first embodiment, and the details are described in [IIα. <IIα-4. As described in the column “Reaction procedure / reaction conditions”.

<IIβ-5. Post-processing>
In the second embodiment, a dehydrochlorination treatment is usually carried out after the esterification reaction of naphthohydroquinone. The preferred procedure is, for example, as follows.
That is, the crude product obtained by the esterification reaction is dissolved in a solvent such as acetonitrile. To this solution, 1 equivalent or less of potassium carbonate is added to the raw material naphthohydroquinone, and the mixture is stirred for about 1 hour at room temperature in an inert atmosphere such as nitrogen.

  Other post-treatments (quenching (stopping) reaction, rough purification, recrystallization purification, etc.) are the same as in the case of the first embodiment, and details thereof are described in [IIα. <IIα-5. As described in the column “Post-processing”.

[IIγ. Others]
According to the production method of the present invention described above, naphthohydroquinone mono (meth) acrylate can be obtained in high yield, high selectivity and high purity.
The yield, selectivity, and purity of naphthohydroquinone mono (meth) acrylate can be approximated based on the percentage of the peak area of the spectrum obtained by gas chromatography. However, when isolated as a crystal, the weight can be used to determine the yield.

  Specifically, the yield from the raw material (naphthohydroquinone) of naphthohydroquinone mono (meth) acrylate obtained by the production method of the present invention is not limited, but at the stage of the crude product after the esterification reaction. Usually, it is 30% or more, preferably 60% or more. In the stage after purification by recrystallization, it is usually 30% or more, preferably 50% or more.

  The selectivity of the naphthohydroquinone mono (meth) acrylate obtained by the production method of the present invention is not limited, but is usually 50% or more, preferably 70% or more.

The purity of the naphthohydroquinone mono (meth) acrylate obtained by the production method of the present invention is not limited, but is usually 90% or more, preferably 95% or more at the stage after purification by recrystallization. is there.
The naphthohydroquinone mono (meth) acrylate of the present invention gives a polymerizable composition by containing a thermal polymerization initiator and / or a photopolymerization initiator. At this time, it is also possible to mix a copolymerizable monomer having an ethylenically unsaturated double bond. Polymerization containing a polymerizable composition containing naphthohydroquinone mono (meth) acrylate and a thermal polymerization initiator and / or a photopolymerization initiator, or a copolymerizable monomer having an ethylenically unsaturated double bond. The composition can be polymerized by heat or light. The obtained polymer is useful as a high refractive index material.

  Examples of the copolymerizable monomer having an ethylenically unsaturated double bond include side chain alkyl-substituted styrene such as styrene and α-methylstyrene, nuclear alkyl-substituted styrene such as vinyltoluene, bromostyrene, and chlorostyrene. Examples thereof include halogenated styrene, divinylbenzene, vinyl naphthalene and the like. Examples of the vinyl cyanide monomer include acrylonitrile, methacrylonitrile, fumaronitrile, maleonitrile, α-chloroacrylonitrile and the like. (Meth) acrylic acid esters include methyl methacrylate, ethyl methacrylate, propylene methacrylate, butyl methacrylate, amyl methacrylate, hexyl methacrylate, phenyl methacrylate, methyl acrylate, ethyl acrylate, amyl acrylate, hexyl acrylate, octyl acrylate, 2-ethylhexyl acrylate Cyclohexyl acrylate, dodecyl acrylate, phenyl acrylate, benzyl acrylate, and the like. The polyfunctional acrylate for coating includes trimethylolpropane triacrylate, diethylene glycol diacrylate, tetraethylene glycol diacrylate, pentaerythritol triacrylate, 1,6-hexanediol diacrylate, tricyclodecane dimethanol diacrylate, epoxy acrylate , Urethane acrylate polyester acrylate, polybutadiene acrylate, polyol acrylate, polyether acrylate and the like.

  As the thermal polymerization initiator, either an organic peroxide or an azo compound can be used. Examples of the organic peroxide include t-hexylperoxyisopropyl monocarbonate, t-hexylperoxy-2-ethylhexanoate, t-butylperoxy-3,5,5-trimethylhexanoate, and t-butyl. Peroxyesters such as peroxyisopropyl carbonates, peroxyketals such as 1,1-bis (t-hexylperoxy) 3,3,5-trimethylcyclohexane, diacyl peroxides such as lauroyl peroxide, etc. Can be mentioned. Examples of the initiator of the azo compound include 2,2′-azobisisobutyronitrile, 2,2′-azobis (2-methylbutyronitrile), 1,1′-azobi (cyclohexane-1- Azonitriles such as carbonitrile)

  Next, as the photopolymerization initiator, for example, 2,2-dimethoxy-1,2-diphenylethane-1-one, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenylpropane-1 -One, 1- [4- (2-hydroxyethoxy) phenyl] -2-hydroxy-2-methylpropan-1-one, 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropane-1 -One, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butan-1-one, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis (2,4,6-trimethylbenzoyl) Examples include phenylphosphine oxide, 2-isopropylthioxanthone, 2-t-butylanthraquinone and the like. 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.

The composition ratio of the 4-hydroxy-1-naphthyl (meth) acrylate compound and the copolymerizable monomer having an ethylenically unsaturated double bond is often a copolymerizable monomer having an ethylenically unsaturated double bond. When the terms “above” and “below” are used differently, the weight ratio is usually 100: 1 or more, preferably 5: 1 or more, more preferably 2: 1 or more, and usually 1 : 100 or less, preferably 1: 5 or less, more preferably 1: 4 or less. When the composition ratio of the copolymerizable monomer having an ethylenically unsaturated double bond is too large, the refractive index of the obtained polymer does not increase, and when it is too small, the coating property tends to be lowered.
The amount of the polymerization initiator used relative to the total of the 4-hydroxy-1-naphthyl (meth) acrylate compound and the copolymerizable monomer having an ethylenically unsaturated double bond is usually 0.1% or more, preferably 0.3. % Or more, usually 5% or less, preferably 2% or less.

  The polymerization can be performed in the form of a film or in the form of a lump. In the case of curing in a film form, for example, a photocurable composition is applied to a glass substrate using a bar coater, and then irradiated with light. Examples of the light source used include a high-pressure mercury lamp, an ultra-high pressure mercury lamp, a metal halide lamp, a xenon lamp, an ultraviolet LED, a blue LED, a white LED, an H lamp, a D lamp, and a V lamp manufactured by Fusion. The use of sunlight is also possible. The light irradiation is desirably performed in the absence of oxygen. In the presence of oxygen, the surface of the coating is not easily sticky due to oxygen inhibition, and a large amount of initiator may be required. Examples of the curing method in the absence of oxygen include performing in an atmosphere such as nitrogen gas or helium gas. A method of photocuring with an oxygen-impermeable film is also effective.

  EXAMPLES Hereinafter, although this invention is demonstrated further in detail using an Example, this invention is not limited by a following example, unless the summary is exceeded. In the following description, the description of “parts” means “parts by weight”.

  Moreover, the yield, selectivity, and purity described below are values obtained based on the percentage of the peak area of the spectrum obtained by gas chromatography. However, when isolated as crystals, the weight was used to determine the yield.

[Example 1]
A reaction vessel was charged with 5.0 ml of water, 5.0 ml of toluene, and 250 mg of sodium hydroxide. After replacing the inside of the reaction vessel with nitrogen gas, 1.0 g of naphthohydroquinone was added to the reaction vessel with stirring in a nitrogen gas atmosphere, and then ice-cooled to 5 ° C. or lower.
Next, while cooling and stirring under a nitrogen gas atmosphere, 550 mg (6.1 mmol) of commercially available acrylic acid chloride was taken into a syringe and dropped into the mixture in the reaction vessel over 15 minutes. During this time, the internal temperature of the reaction vessel was kept at 5 ° C. or lower.
After completion of the dropwise addition, stirring was continued for 45 minutes while keeping the internal temperature at 5 ° C. or lower. Thereafter, dilute hydrochloric acid was added to adjust the pH of the reaction system (aqueous phase) to acidic, and the reaction was stopped.
Subsequently, ethyl acetate was added as an extraction solvent to separate into two layers, and the reaction product was recovered in the organic phase. The organic phase was washed with water and dried by adding magnesium sulfate. Further, the solvent was distilled off with a rotary evaporator to obtain 1.5 g of a dark brown solid product.

  When the obtained product was analyzed by gas chromatography (GC), the composition was 22.0% of naphthohydroquinone, 50.9% of naphthohydroquinone monoacrylate, and 24.9% of naphthohydroquinone diacrylate as the remaining raw materials. there were. Moreover, the selectivity of the naphthohydroquinone monoacrylate calculated | required from these values was 65.3%.

[Example 2]
The procedure of Example 1 was repeated except that 663 mg of sodium carbonate (Na ₂ CO ₃ ) was used instead of 250 mg of sodium hydroxide, whereby 1.0 g of a dark brown solid product was obtained. Got.

  When the obtained product was analyzed by gas chromatography (GC), the composition was 57.2% naphthohydroquinone, 27.9% naphthohydroquinone monoacrylate, and 14.8% naphthohydroquinone diacrylate as the remaining raw materials. there were. Further, the selectivity of naphthohydroquinone monoacrylate determined from these values was 65.2%.

[Example 3]
The procedure of Example 1 was repeated except that 10.0 ml of water was used instead of 5.0 ml of water and 5.0 ml of toluene, and 863 mg of potassium carbonate (K ₂ CO ₃ ) was used instead of 250 mg of sodium hydroxide. In the same manner as in Example 1, 1.0 g of a dark brown oily product was obtained.

  When the obtained product was analyzed by gas chromatography (GC), the composition was 30.8% of naphthohydroquinone, 40.2% of naphthohydroquinone monoacrylate, and 29.1% of naphthohydroquinone diacrylate as the remaining raw materials. there were. Moreover, the selectivity of the naphthohydroquinone monoacrylate calculated | required from these values was 58.1%.

[Example 4]
The procedure of Example 1 was repeated except that 5.0 ml of ethyl acetate was used instead of 5.0 ml of toluene, whereby 1.0 g of a reddish brown solid product was obtained.

  When the obtained product was analyzed by gas chromatography (GC), the composition was as follows: the remaining raw materials were naphthohydroquinone 29.9%, naphthohydroquinone monoacrylate 40.2%, naphthohydroquinone diacrylate 30.5%. there were. The selectivity of naphthohydroquinone monoacrylate determined from these values was 56.7%.

[Example 5]
The procedure of Example 1 was repeated except that 5.0 ml of heptane was used instead of 5.0 ml of toluene to obtain 1.3 g of a reddish brown solid product.

  When the obtained product was analyzed by gas chromatography (GC), the composition was 35.7% naphthohydroquinone, 30.8% naphthohydroquinone monoacrylate, and 33.2% naphthohydroquinone diacrylate as the remaining raw materials. there were. The selectivity of naphthohydroquinone monoacrylate determined from these values was 47.9%.

[Example 6]
In the procedure of Example 1, except that 5.0 ml of acetonitrile was used instead of 5.0 ml of toluene, the product was recovered in the organic phase by performing the same operation as in Example 1.

  When the obtained organic phase was analyzed by gas chromatography (GC), the composition of the reaction product contained in the organic phase was 31.9% naphthohydroquinone monoacrylate, 27.9% naphthohydroquinone monoacrylate, It was 40.0% of naphthohydroquinone diacrylate. The selectivity of naphthohydroquinone monoacrylate determined from these values was 41.0%.

[Example 7]
By performing the same operation as in Example 1, except that the amount of water used was changed from 5.0 ml to 10.0 ml and the amount of sodium hydroxide used was changed from 250 mg to 625 mg in the procedure of Example 1. The product was recovered in the organic phase.

  When the obtained organic phase was analyzed by gas chromatography (GC), the composition of the reaction product contained in the organic phase was as follows: naphthohydroquinone 42.4%, naphthohydroquinone monoacrylate 48.7%, Naphthhydroquinone diacrylate was 7.6%. Further, the selectivity of naphthohydroquinone monoacrylate determined from these values was 84.5%.

[Comparative Example 1]
In the same procedure as in Example 1, 10.0 ml of acetonitrile, 1.0 g of triethylamine, and 1.0 g of naphthohydroquinone were charged in a reaction vessel.
Next, while cooling and stirring under nitrogen gas flow, 660 mg (7.3 mmol) of commercially available acrylic acid chloride was taken into a syringe and dropped into the mixture in the reaction vessel over 42 minutes. During this time, the internal temperature of the reaction vessel was kept at 5 ° C. or lower.
After completion of the dropwise addition, stirring was continued for another 30 minutes while maintaining the internal temperature at 5 ° C. or lower. Thereafter, dilute hydrochloric acid was added to make the pH of the reaction system (aqueous phase) acidic, and the reaction was stopped.
Subsequently, ethyl acetate was added as an extraction solvent to separate into two layers, and the reaction product was recovered in the organic phase. The organic phase was washed with water and dried by adding magnesium sulfate.

  When the obtained organic phase was analyzed by GC, the composition of the reaction product contained in the organic phase was as follows: naphthohydroquinone 31.7%, naphthohydroquinone monoacrylate 13.5%, naphthohydroquinone diacrylate 55 0.0%. The selectivity of naphthohydroquinone monoacrylate determined from these values was 19.8%.

[Example 8]
In the same procedure as in Example 1, 5.0 ml of water, 5.0 ml of toluene, 250 mg of sodium hydroxide, and 1.0 g of naphthohydroquinone were charged into a reaction vessel.
Next, while cooling and stirring under a nitrogen gas atmosphere, 635 mg of methacrylic acid chloride obtained by re-distilling the commercially available product was taken into a syringe and added dropwise to the mixture in the reaction vessel over 15 minutes. During this time, the internal temperature of the reaction vessel was kept at 5 ° C. or lower.
After completion of the dropwise addition, stirring was continued for 45 minutes while keeping the internal temperature at 5 ° C. or lower. Thereafter, dilute hydrochloric acid was added to adjust the pH of the reaction system (aqueous phase) to acidic, and the reaction was stopped.
Subsequently, ethyl acetate was added as an extraction solvent to separate into two layers, and the reaction product was recovered in the organic phase. The organic phase was washed with water and dried by adding magnesium sulfate. Furthermore, the solvent was distilled off with a rotary evaporator, and the product was recovered in the organic phase.

  When the obtained organic phase was analyzed by gas chromatography (GC), the composition of the reaction product contained in the organic phase was 17.4% naphthohydroquinone as the remaining raw material, 62.6% naphthohydroquinone monomethacrylate, It was 16.7% of naphthohydroquinone dimethacrylate. The selectivity of naphthohydroquinone monomethacrylate determined from these values was 75.8%.

[Example 9]
In the same procedure as in Example 1, 30.0 ml of water, 800 mg of sodium hydroxide and 2.0 g of naphthohydroquinone were charged into a reaction vessel.
Next, while cooling and stirring under a nitrogen gas atmosphere, 1.4 g (13.1 mmol) of methacrylic acid chloride obtained by re-distilling the commercial product was taken into a syringe and dropped into the mixture in the reaction vessel over 20 minutes. During this time, the internal temperature of the reaction vessel was kept at 5 ° C. or lower. From the middle of dropping, a large amount of crystals was observed.
After completion of the dropping, stirring was continued for another 10 minutes while keeping the internal temperature of the reaction vessel at 5 ° C. or lower. Thereafter, dilute hydrochloric acid was added to make the pH of the reaction system (aqueous phase) acidic, and the reaction was stopped.
Subsequently, ethyl acetate was added as an extraction solvent to separate into two layers, and the reaction product was recovered in the organic phase. The organic phase was washed with water and dried by adding magnesium sulfate.

  When the obtained organic phase was analyzed by gas chromatography (GC), the composition of the reaction product contained in the organic phase was 15.3% of naphthohydroquinone as the remaining raw material, 65.6% of naphthohydroquinone monomethacrylate, Naphthhydroquinone dimethacrylate was 19.1%. The selectivity for naphthohydroquinone monomethacrylate determined from these values was 77.4%.

[Example 10]
In the procedure of Example 8, 5.0 ml of a mixed solvent of heptane and toluene (volume ratio of heptane / toluene = 1/3) was used instead of 5.0 ml of toluene, and the amount of sodium hydroxide used was changed from 250 mg to 400 mg. The product was recovered in the organic phase by performing the same operation as in Example 8, except that the amount of methacrylic acid chloride was changed from 635 mg to 917 mg.

  When the obtained organic phase was analyzed by gas chromatography (GC), the composition was 5.9% naphthohydroquinone, 66.7% naphthohydroquinone monomethacrylate, and 23.8% naphthohydroquinone dimethacrylate as the remaining raw materials. there were. Moreover, the selectivity of the naphthohydroquinone monomethacrylate calculated | required from these values was 70.8%.

  When this organic phase was concentrated with a rotary evaporator, a large amount of crystals precipitated during the concentration. This was collected by filtration and vacuum-dried to obtain 410 mg of off-white crystals. When this crystal was analyzed by GC, it was confirmed to be a monomethacrylate body having a purity of 91.3%.

[Example 11]
According to the same procedure as in Example 1, 75.0 ml of water, 15.0 ml of toluene, 1.2 g of sodium hydroxide, and 5.0 g of naphthohydroquinone were charged in a reaction vessel.
Next, while cooling and stirring under a nitrogen gas atmosphere, 3.5 g (33.0 mmol) of methacrylic acid chloride obtained by re-distilling the commercial product was dropped into the mixture in the reaction vessel over 85 minutes using a dropping funnel. did. During this time, the internal temperature of the reaction vessel was kept at 5 ° C. or lower. From the middle of dropping, a large amount of crystals was observed.
After completion of the dropping, stirring was continued for another 30 minutes while keeping the internal temperature of the reaction vessel at 5 ° C. or lower. Thereafter, dilute hydrochloric acid was added to make the pH of the reaction system (aqueous phase) acidic, and the reaction was stopped.
Subsequently, ethyl acetate was added as an extraction solvent to separate into two layers, and the reaction product was recovered in the organic phase. The organic phase was washed with water and dried by adding magnesium sulfate. Further, the solvent was distilled off with a rotary evaporator to obtain 7.4 g of a black solid crude product.

  When the crude product was analyzed by GC, the composition was 87.8% naphthohydroquinone monomethacrylate and 6.7% naphthohydroquinone dimethacrylate.

  To this crude product was added 23.0 ml of toluene, and the mixture was heated on an oil bath at 90 to 100 ° C. with stirring and dissolved. Next, the mixture was allowed to cool, and the precipitated crystals were collected by filtration and dried to obtain 6.0 g of off-white crystals. When this crystal was analyzed by GC, it was confirmed to be naphthohydroquinone monomethacrylate having a purity of 93.4%.

The obtained crystals were recrystallized using toluene in the same procedure, and 5.3 g of off-white crystals were obtained. When this crystal was analyzed by GC, it was confirmed to be naphthohydroquinone monomethacrylate having a purity of 97.5%.
The yield of naphthohydroquinone monomethacrylate through this example (yield from the raw material naphthohydroquinone) was 74.0%.

[Comparative Example 2]
In the procedure of Comparative Example 1, except that 680 mg of methacrylic acid chloride obtained by redistilling the commercially available product was used instead of 660 mg of the commercially available acrylic acid chloride, the reaction product was contained by performing the same operation as Comparative Example 1. An organic phase was obtained.

  When the obtained organic phase was analyzed by gas chromatography (GC), the composition of the reaction product contained in the organic phase was 27.8% naphthohydroquinone as the remaining raw material, 17.2% naphthohydroquinone monomethacrylate, Naphthhydroquinone dimethacrylate was 55.0%. The selectivity of naphthohydroquinone monomethacrylate determined from these values was 23.8%.

[Example 12]
In the same procedure as in Example 1, 5.0 ml of water, 5.0 ml of toluene, 520 mg (13.1 mmol) of sodium hydroxide, and 1.0 g (6.2 mmol) of naphthohydroquinone were charged into a reaction vessel.
Next, while cooling and stirring under nitrogen gas flow, 790 mg of commercially available 3-chloropropionic acid chloride taken in a syringe was added dropwise over 35 minutes. During this time, the internal temperature of the reaction vessel was kept at 5 ° C. or lower.
After completion of the dropwise addition, stirring was further continued for 2 hours while keeping the internal temperature of the reaction vessel at 5 ° C. or lower. Thereafter, dilute hydrochloric acid was added to make the pH of the reaction system (aqueous phase) acidic, and the reaction was stopped.
Subsequently, 10 ml of ethyl acetate was added as an extraction solvent to separate into two layers, and the reaction product was recovered in the organic phase. The organic phase was washed with water and dried by adding magnesium sulfate.

  When the obtained organic phase was analyzed by gas chromatography (GC), the composition of the reaction product contained in the organic phase was naphthohydroquinone 12.4%, naphthohydroquinone monoacrylate 59.0%, naphthohydroquinone mono ( 3-chloropropionate) 3.4%, three diesters of naphthohydroquinone {diacrylate, acrylate- (3-chloropropionate) mixed ester, di (3-chloropropionate)} The total was 25.2%. The total of monoester body of naphthohydroquinone {monoacrylate body and mono (3-chloropropionate) body} is 62.4%, and the selectivity of monoester body of naphthohydroquinone based on this is 71.2%. %Met.

[Example 13]
An organic phase containing a reaction product was obtained by performing the same operation as in Example 12 except that the amount of water used was changed from 5.0 ml to 15.0 ml in the procedure of Example 12.

  When the obtained organic phase was analyzed by gas chromatography (GC), the composition of the reaction product contained in the organic phase was 11.8% of naphthohydroquinone as a residual raw material, monoester of naphthohydroquinone {monoacrylate 71.1% in total and mono (3-chloropropionate)}, diester of naphthohydroquinone {diacrylate, acrylate- (3-chloropropionate) mixed ester, di (3-chloropropionate)} The total amount of the pioneate body} was 17.1%. Moreover, the selectivity of the monoester body of the naphthohydroquinone calculated | required from these values was 80.6%.

[Example 14]
[Esterification treatment]
According to the same procedure as in Example 1, 45.0 ml of water, 15.0 ml of toluene, 1.2 g (30.0 mmol) of sodium hydroxide, and 3.0 g (18.7 mmol) of naphthohydroquinone were charged into a reaction vessel.
Next, while cooling and stirring under a nitrogen gas atmosphere, 2.7 g (21.5 mmol) of commercially available 3-chloropropionic acid chloride was dropped into the mixture in the reaction vessel over 85 minutes using a dropping funnel. did. During this time, the internal temperature was kept below 5 ° C.
After completion of the dropwise addition, dilute hydrochloric acid was added to acidify the pH of the reaction system (aqueous phase) to stop the reaction. Subsequently, ethyl acetate was added as an extraction solvent to separate into two layers, and the reaction product was recovered in the organic phase. The organic phase was washed with water and dried by adding magnesium sulfate. Furthermore, the solvent was distilled off with a rotary evaporator to obtain 5.1 g of a crude product as a dark brown liquid.

  When this crude product was analyzed by gas chromatography (GC), the composition was as follows: naphthohydroquinone monoacrylate 37.8%, mono (3-chloropropionate) 42.7%, three diesters The total amount of {diacrylate body, acrylate- (3-chloropropionate) mixed ester body, di (3-chloropropionate) body} was 16.7%.

[Dehydrochlorination]
5.1 g of this crude product was dissolved in 20 ml of acetonitrile, 2.1 g (15.2 mmol) of potassium carbonate was added to the resulting solution, and the mixture was stirred at room temperature for 1 hour while flowing nitrogen gas. Thereafter, dilute hydrochloric acid was added to acidify the reaction system, and the reaction was stopped.

  Subsequently, ethyl acetate was added as an extraction solvent to separate into two layers, and the reaction product was recovered in the organic phase. The organic phase was washed with water and dried by adding magnesium sulfate. Furthermore, the solvent was distilled off with a rotary evaporator to obtain 4.2 g of a crudely purified product as a dark purple liquid. When this crude product was analyzed by gas chromatography, it was confirmed to be naphthohydroquinone monoacrylate having a purity of 79.5%.

[Recrystallization purification treatment]
To 4.2 g of this crude product, 10.0 ml of toluene was added and dissolved by heating on an oil bath at 90 to 100 ° C. while stirring. Next, the mixture was allowed to cool, and the precipitated crystals were suction filtered and dried to obtain 1.8 g of light brown crystals. When this crystal was analyzed by gas chromatography (GC), it was confirmed to be naphthohydroquinone monoacrylate having a purity of 98.0%.

  The yield of naphthohydroquinone monoacrylate throughout this example (yield from the starting naphthohydroquinone) was 44.1%.

[Example 15]
[Acid chloride synthesis]
Under a nitrogen gas stream, 4.0 g (55.8 mmol) of acrylic acid, 6.6 g (55.8 mmol) of thionyl chloride, 87 μl of dimethylformamide, and 12.0 ml of toluene were charged into the reactor at 33 to 36 ° C. for 80 minutes. Stir. Subsequently, it cooled so that the temperature of a reaction liquid might be 5 degrees C or less, nitrogen gas was blown in in the reactor, the gas component (hydrogen chloride and sulfur dioxide) was driven off, and it collected with alkaline water. When the temperature rise of the alkaline water disappeared, the reaction solution was analyzed by ¹ H NMR. As a result, the composition was 36.9 mmol of acrylic acid chloride and 17.5 mmol of 3-chloropropionic acid chloride.

[Esterification reaction]
In a separate reaction vessel, 100 ml of water, 21.0 ml of toluene, 2.7 g of sodium hydroxide and 6.7 g (41.8 mmol) of naphthohydroquinone were charged according to the same procedure as in Example 1.
Next, the toluene solution of the acrylic acid chloride and 3-chloropropionic acid chloride obtained by the said procedure was dripped at said mixture over 50 minutes using the syringe, cooling and stirring under nitrogen gas atmosphere. During this time, the reaction temperature was kept below 5 ° C.
After completion of the dropwise addition, stirring was continued for another 10 minutes while maintaining the internal temperature at 5 ° C. or lower. Next, dilute hydrochloric acid was added to acidify the reaction system to stop the reaction.
Subsequently, ethyl acetate was added as an extraction solvent to separate into two layers, and the reaction product was recovered in the organic phase. The organic phase was washed with water and dried by adding magnesium sulfate. Furthermore, the solvent was distilled off by a rotary evaporator to obtain 10.1 g of a brown liquid crude purified product.

  When this crude product was analyzed by gas chromatography (GC), the composition was 2.6% of naphthohydroquinone, 67.9% of monoacrylate of naphthohydroquinone, and mono (3-chloropropionate) of 10. It was 9%, dimethacrylate body 10.3%, acrylate- (3-chloropropionate) mixed ester body 6.6%, di (3-chloropropionate) body 0.3%.

[Dehydrochlorination process]
10.1 g of this crude product was dissolved in 50.0 ml of acetonitrile, 1.7 g (12.5 mmol) of potassium carbonate was added to the resulting solution, and the mixture was stirred at room temperature for 80 minutes in a nitrogen gas atmosphere. Thereafter, dilute hydrochloric acid was added to acidify the reaction system, and the reaction was stopped. Subsequently, ethyl acetate was added as an extraction solvent to separate into two layers, and the reaction product was recovered in the organic phase. The organic phase was washed with water and dried by adding magnesium sulfate. Furthermore, the solvent was distilled off with a rotary evaporator to obtain 9.1 g of a brown liquid crude purified product. When the obtained crude product was analyzed by gas chromatography (GC), it was confirmed to be naphthohydroquinone monoacrylate having a purity of 78.0%.

[Recrystallization purification treatment]
To 9.1 g of this crude product, 15.0 ml of a mixed solvent of hexane and toluene (hexane / toluene volume ratio = 3/7) was added, seed crystals of naphthohydroquinone monoacrylate were added, and the mixture was stirred at room temperature for about 1 hour. Crystals gradually precipitated during stirring. After completion of the stirring, the mixture was allowed to stand in an environment of 5 ° C. or lower, and the precipitated crystals were collected by filtration and dried to obtain 5.1 g of light brown crystals. When this crystal was analyzed by gas chromatography (GC), it was confirmed to be naphthohydroquinone monoacrylate having a purity of 98.7%.
To 5.1 g of the above crystals, 6.0 ml of a mixed solution of 10% by volume methanol in a mixed solvent of hexane and toluene (hexane / toluene volume ratio = 3/7) was added on an oil bath at 90 to 100 ° C. It was heated and dissolved with stirring. After allowing to cool, the precipitated crystals were collected by filtration and dried to obtain 3.7 g of light brown crystals.

When this crystal was analyzed by gas chromatography (GC), it was confirmed to be naphthohydroquinone monoacrylate having a purity of 99.5%.
The isolation yield of naphthohydroquinone monoacrylate (the yield from naphthohydroquinone as a raw material) throughout this example was 41.2%.

[Example 16]
[Acid chloride synthesis]
Under a nitrogen gas stream, 3.1 g (35.4 mmol) of methacrylic acid, 4.2 g (35.4 mmol) of thionyl chloride, 55 μl of dimethylformamide and 14.0 ml of toluene were charged into the reactor and stirred at 40 to 45 ° C. for 70 minutes. did. Next, nitrogen gas was blown into the reactor while cooling so that the temperature of the reaction solution was 5 ° C. or less, and gas components (hydrogen chloride and sulfur dioxide) were driven off and collected with alkaline water. When the temperature of the alkaline water disappeared, the reaction solution was analyzed by ¹ H NMR. As a result, the composition was 97.0 mol% methacrylic acid chloride and 3.0 mol% 3-chloro-2-methylpropionic acid chloride. It was.

[Esterification reaction]
In another reaction vessel, 75.0 ml of water, 11.0 ml of toluene, 2.0 g of sodium hydroxide and 5.0 g (31.2 mmol) of naphthohydroquinone were charged in the same procedure as in Example 1.
Next, while cooling and stirring under a nitrogen gas atmosphere, the toluene solution of methacrylic acid chloride and 3-chloro-2-methylpropionic acid chloride obtained in the above procedure is added to the mixture in the reaction vessel using a syringe. It was added dropwise over 80 minutes. During this time, the temperature in the reaction vessel was kept at 5 ° C. or lower.
After completion of the dropping, stirring was further continued for 40 minutes while maintaining the temperature of the reaction solution at 5 ° C. or lower. Next, dilute hydrochloric acid was added to acidify the reaction system to stop the reaction.
Subsequently, ethyl acetate was added as an extraction solvent to separate into two layers, and the reaction product was recovered in the organic phase. The organic phase was washed with water and dried by adding magnesium sulfate. Further, the solvent was distilled off with a rotary evaporator to obtain 7.0 g of a dark brown solid crude purified product.

  When this crude product was analyzed by gas chromatography (GC), the composition of the reaction product contained in the organic phase was 87.7% monomethacrylate of naphthohydroquinone, mono (3-chloro-2-methylpropyl). Pionate) body 1.3%, dimethacrylate body 3.9%, di (3-chloro-2-methylpropionate) body 0.5%.

[Recrystallization purification treatment]
To 7.0 g of this crude product, 20.0 ml of toluene was added and dissolved by heating on an oil bath at 90 to 100 ° C. while stirring. After allowing to cool, the precipitated crystals were collected by filtration and dried to obtain 5.8 g of light brown crystals. When this crystal was analyzed by gas chromatography (GC), it was confirmed to be naphthohydroquinone monomethacrylate having a purity of 93%.
19.0 ml of a mixed solution of methanol and toluene (methanol / toluene volume ratio = 1/9) was added to 5.8 g of the above crystals, and the mixture was heated and dissolved in an oil bath at 90 to 100 ° C. with stirring. After allowing to cool, the precipitated crystals were collected by filtration and dried to obtain 3.0 g of grayish white crystals.

When this crystal was analyzed by gas chromatography (GC), it was confirmed to be naphthohydroquinone monomethacrylate having a purity of 99.5%.
The yield of naphthohydroquinone monomethacrylate through this example (yield from the raw material naphthohydroquinone) was 41.7%.

[Example 17]
In the same procedure as in Example 1, 30.0 ml of water, 4.0 ml of toluene, 800 mg (20.0 mmol) of sodium hydroxide, and 2.0 g (12.5 mmol) of naphthohydroquinone were charged into a reaction vessel.
Next, while cooling and stirring under a nitrogen gas atmosphere, 1.4 g (15.0 mmol) of commercially available acrylic acid chloride was added dropwise to the mixture in the reaction vessel over 60 minutes using a syringe. During this time, the internal temperature was kept below 5 ° C. At this time, seed crystals of naphthohydroquinone monoacrylate were added to the reaction solution in two steps before dropping of acrylic acid chloride and when dropping 30% of acrylic acid chloride. When about 40% of acid chloride was dropped, a considerable amount of precipitate was observed.
After completion of the dropping, stirring was continued for 15 minutes while maintaining the internal temperature at 5 ° C. or lower. Thereafter, dilute hydrochloric acid was added to make the pH of the reaction system (aqueous phase) acidic, and the reaction was stopped.

Subsequently, ethyl acetate was added as an extraction solvent to separate into two layers, and the reaction product was recovered in the organic phase. The organic phase was washed with water and dried by adding magnesium sulfate.
When the obtained organic phase was analyzed by gas chromatography (GC), the composition was as follows: the remaining raw materials were naphthohydroquinone 5.5%, naphthohydroquinone monoacrylate 70.2%, naphthohydroquinone dimethacrylate 23.6%. there were. Moreover, the selectivity of the naphthohydroquinone monomethacrylate calculated | required from these values was 74.3%.

[Example 18]
The procedure of Example 17 was repeated except that the amount of sodium hydroxide used was changed from 800 mg (20.0 mmol) to 700 mg (17.5 mmol). 2.8 g of a crude product was obtained.
When the obtained crude purified product was analyzed by gas chromatography (GC), the composition was as follows: naphthohydroquinone 3.4%, naphthohydroquinone monoacrylate 73.9%, naphthohydroquinone dimethacrylate 21.8% as residual raw materials. Met. The selectivity for naphthohydroquinone monomethacrylate determined from these values was 76.5%.
To this crude product, 6.0 ml of toluene was added and dissolved by heating on an oil bath at 90 to 100 ° C. while stirring. Next, the mixture was allowed to cool, and the precipitated crystals were collected by filtration and dried to obtain 1.2 g of off-white crystals.

When this crystal was analyzed by gas chromatography (GC), it was confirmed to be naphthohydroquinone monoacrylate having a purity of 97.0%.
The yield of naphthohydroquinone monoacrylate throughout this example (yield from the starting naphthohydroquinone) was 42.8%.

[Example 19]
According to the same procedure as in Example 1, 30.0 ml of water, 10.0 ml of toluene, 800 mg (20.0 mmol) of sodium hydroxide, and 2.0 g (12.5 mmol) of naphthohydroquinone were charged into a reaction vessel.
Next, while cooling and stirring under a nitrogen gas atmosphere, 1.4 g (13.1 mmol) of methacrylic acid chloride obtained by re-distilling the commercial product is dropped into the mixture in the reaction vessel over 48 minutes using a dropping funnel. did. During this time, the internal temperature was kept below 5 ° C. When about 30% of the total amount of methacrylic acid chloride was dropped, clear crystal precipitation was observed.
After completion of the dropwise addition, stirring was continued for another 30 minutes while maintaining the internal temperature at 5 ° C. or lower. Thereafter, the precipitated crystals were collected by filtration, washed with n-hexane and dried to obtain 1.6 g of white crystals.

When the obtained crystal was analyzed by gas chromatography (GC), it was confirmed to be naphthohydroquinone monomethacrylate having a purity of 97.4%.
The yield of naphthohydroquinone monomethacrylate through this example (yield from the starting naphthohydroquinone) was 53.0%.

[Physicochemical properties of naphthohydroquinone monoacrylate]
When the physicochemical properties of the naphthohydroquinone monoacrylate obtained in Example 15 were analyzed, the results were as follows.
Melting point: 108.5-109.4 ° C
Mass spectrum (EI): 214 (M ⁺ ), 160, 55
¹ H-NMR (CDCl ₃ , 400 MHz):
8.05 (bd, 1H), 7.74 (bd, 1H), 7.49 (bdd, 1H),
7.4 (bdd, 1H), 6.97 (d, 1H), 6.73 (bd, 1H),
6.48 (dd, 1H), 6.47 (d, 1H), 6.10 (bd, 1H),
5.98 (bs, 1H)
IR (KBr): 3260 cm ⁻¹ (OH), 1712 cm ⁻¹ (C═O)

[Physicochemical properties of naphthohydroquinone monomethacrylate]
When the physicochemical properties of the naphthohydroquinone monomethacrylate obtained in Example 11 were analyzed, the results were as follows.
Melting point: 151.0-151.7 ° C
Mass spectrum (EI): 228 (M ⁺ ), 159, 69
¹ H-NMR (CDCl ₃ , 400 MHz):
8.04 (bd, 1H), 7.74 (bd, 1H), 7.49 (bdd, 1H),
7.43 (bdd, 1H), 6.95 (d, 1H), 6.53 (bs, 1H),
6.46 (d, 1H), 5.95 (bs, 1H), 5.86 (bs, 1H),
2.16 (bs, 3H)
IR (KBr): 3380 cm ⁻¹ (OH), 1705 cm ⁻¹ (C═O)

[Refractive index]
The refractive index (n _D ) of naphthohydroquinone monoacrylate (4-hydroxy-1-naphthyl acrylate) obtained in Example 1 was measured. The results are shown in [Table 1].

[Comparative Example 3]
As Comparative Example 3, the refractive index (n _D ) of a commercially available alkyl acrylate (specifically, trimethylolpropane triacrylate was used) was measured. The results are shown in [Table 1].

[Comparative Example 4]
As Comparative Example 4, the refractive index (n _D ) of a commercially available aromatic acrylate (specifically, 2-phenoxyethyl acrylate was used) was measured. The results are shown in [Table 1].

The results of the refractive index (n _D ) of [Example 1], [Comparative Example 3], and [Comparative Example 4] are shown in [Table 1] below. From these results, it was found that the naphthohydroquinone monoacrylate obtained in Synthesis Example 1 showed a high refractive index with respect to the commercially available alkyl acrylate and aromatic acrylate.

[Example 20]
Copolymerization of trimethylolpropane triacrylate (hereinafter sometimes referred to as “TMPTA”) and 4-hydroxy-1-naphthyl acrylate 50 parts by weight of trimethylolpropane and 50 parts by weight of 4-hydroxy-1-naphthyl acrylate are photopolymerized. As an initiator, 1 part by weight of Irgacure 819 manufactured by Ciba was added to obtain a photocured composition. This was applied on a polyester film (Toray Lumirror, film thickness 100 μm) to a film thickness of 12 μm using a bar coater. Subsequently, ultraviolet LED (optical center wavelength of 395 nm, irradiation intensity of 3 mw / cm ² ) was irradiated for 30 minutes in a nitrogen atmosphere. As a result, the film-like application was cured completely. After applying a 1cm line of streaks to the application surface with a knife, adhesive tape (trade name: Cellotape (registered trademark), manufactured by Nichiban Co., Ltd.) was applied to the application. The adhesive tape was peeled off, and the adhesion of the coated product was determined based on whether or not the film-shaped coated product was peeled off. The results are shown in [Table 2].

[Example 21]
Except for using a glass substrate instead of a polyester film as the substrate, a photocuring test was conducted in the same manner as in Example 20 to determine the adhesion. The results are shown in [Table 2].

[Comparative Example 5]
Copolymerization of trimethylolpropane triacrylate and 4-methoxy-1-naphthyl methacrylate 50 parts by weight of trimethylolpropane triacrylate and 50 parts by weight of 4-methoxy-1-naphthyl acrylate, Irgacure 819 manufactured by Ciba as a photopolymerization initiator 1 part by weight was added to obtain a photocured composition. This was applied on a polyester film (Toray Lumirror, film thickness 100 μm) to a film thickness of 12 μm using a bar coater. Subsequently, ultraviolet LED (optical center wavelength of 395 nm, irradiation intensity of 3 mw / cm ² ) was irradiated for 30 minutes in a nitrogen atmosphere. As a result, since the film-like coating material was cured beautifully, adhesion was determined in the same manner as in Example 20. The results are shown in [Table 2].

[Comparative Example 6]
A photo-curing test was conducted in the same manner as in Comparative Example 5 except that a glass substrate was used instead of the polyester film as the substrate, and the adhesion was determined. The results are shown in [Table 2].

The naphthohydroquinone mono (meth) acrylate of the present invention has a naphthalene skeleton, a hydroxyl group and a (meth) acryl group in one molecule, is easy to use as a monomer, and is promising as a raw material for pharmaceuticals and engineering plastics.
In particular, since it has a naphthalene skeleton, it can be used as a raw material for heat-resistant resins, high refractive index resins, high-hardness resins, hydrophobic resins, etc., and the adhesion of film-like coatings obtained by photocuring is extremely high. It is an industrially useful compound.

Claims (7)

A naphthohydroquinone mono (meth) acrylate represented by the following formula (I):

(In the above formula (I), 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 alkylthio group, an arylthio group. Represents any of carboxyl group, sulfone group and nitro group.) A method for producing a naphthohydroquinone mono (meth) acrylate according to claim 1, comprising a step of reacting naphthohydroquinone and acid halide in the presence of an inorganic base. Method for producing acrylate. The method for producing naphthohydroquinone mono (meth) acrylate according to claim 2, wherein the molar ratio of the acid halide to naphthohydroquinone is less than 2. (Meth) acrylic acid halide is used as an acid halide. The manufacturing method of the naphthohydroquinone mono (meth) acrylate of Claim 2 or Claim 3 characterized by the above-mentioned. A naphthohydroquinone monoacrylate is obtained by using at least a 3-halogenated propionic acid halide as an acid halide. The production of naphthohydroquinone mono (meth) acrylate according to any one of claims 2 to 4, Method. The naphthohydroquinone monomethacrylate according to any one of claims 2 to 4, wherein naphthohydroquinone monomethacrylate is obtained by using at least 3-halogenated-2-methylpropionic acid halide as the acid halide. ) A process for producing acrylates. The method for producing naphthohydroquinone mono (meth) acrylate according to any one of claims 2 to 6, wherein the reaction is carried out in a two-phase system comprising an aqueous phase and an organic phase.