JP2022094164A - Production method of compound, polymerizable composition, cured product, and compound - Google Patents

Abstract

To provide a production method of a compound having a thiohydantoin skeleton.SOLUTION: In a production method of a compound represented by formula (1), a compound represented by formula (2) is subjected to a ring-opening esterification reaction with 10-hydroxydecyl methacrylate or the like in the presence of an acid or base so as to obtain a compound represented by formula (1). In the formula, R1 is a hydrogen atom or the like; R2 is a divalent hydrocarbon group; and X is a (meth)acryloyloxy group or the like.SELECTED DRAWING: None

Description

The present disclosure relates to a method for producing a compound, a polymerizable composition, a cured product and a compound.

In the field of clinical medicine, in oral surgery and dentistry, the tooth substance is bonded to a metal inlay, an inlay, a crown, a bridge or other prosthesis, an abutment tooth post and core, or an orthodontic bracket. Sometimes. As described above, a compound having a thiohydantoin skeleton has been developed as an adhesive for adhering a metal and a dentin.
For example, Patent Document 1 describes a compound represented by a specific chemical structural formula.

International Publication No. 2020/032268

A compound having a thiohydantoin skeleton as described in Patent Document 1 is usually a method of hydrolyzing a compound represented by the formula (2) described later and then subjecting it to a dehydration condensation reaction with a compound having a hydroxy group. Can be obtained by
Since the carboxylic acid intermediate obtained by the above hydrolysis is also water-soluble, if an attempt is made to extract with an organic solvent in order to isolate from the aqueous solution after the reaction, the number of extractions must be repeated and a large amount of organic solvent is required. It becomes.
Therefore, this step often requires a large amount of organic solvent, a large amount of labor, and the like.
Further, since it is necessary to carry out the dehydration condensation reaction after performing the above hydrolysis reaction, a two-step reaction step is required for production.
From the above, there is a demand for a method capable of more easily producing a compound having a thiohydantoin skeleton.

This disclosure has been made in view of the above circumstances.
That is, an object of the present disclosure is to provide a method for producing a compound capable of easily producing a compound having a thiohydantoin skeleton, a polymerizable composition containing the compound produced by the above method for producing a compound, a cured product, and a compound. Is.

The means for solving the above problems include the following embodiments.
<1> A method for producing a compound represented by the following formula (1), wherein a compound represented by the following formula (2) and a compound represented by the following formula (3) are used in the presence of an acid or a base. A method for producing a compound, which comprises a step of obtaining a compound represented by the above formula (1) by reacting.

In formulas (1) to (3), R ¹ is a hydrogen atom, a monovalent hydrocarbon group or an alkali metal atom, R ² is a divalent hydrocarbon group, and X is a hydroxy group. It is a halogen atom or a (meth) acryloyloxy group.
<2> The method for producing a compound according to <1>, wherein the reaction between the compound represented by the formula (2) and the compound represented by the formula (3) is carried out in an organic solvent.
<3> The ^R2 in the formula (1) and the formula (3) is a divalent group represented by the following formula (4), an ether bond, a 1,4-phenylene group, and a 1,4-cyclohexyl. The method for producing a compound according to <1> or <2>, which comprises at least one group selected from the group consisting of a silene group and a divalent chain saturated hydrocarbon group.

In formula (4), Y ¹ and Y ² are independently oxygen atoms, a divalent group represented by -CH _2- or a divalent group represented by -NH-, and Y ³ is a divalent group. It is an oxygen atom or a sulfur atom.
<4> The method for producing a compound according to any one of <1> to <3>, wherein the R ² in the formula (1) and the formula (3) is an alkylene group having 2 to 20 carbon atoms. ..
<5> The method for producing a compound according to any one of <1> to <4>, wherein the X in the formula (1) and the formula (3) is a (meth) acryloyloxy group.
<6> A method for producing a compound represented by the formula (1A), which is represented by the above formula (1) by the method for producing a compound according to any one of <1> to <5>. A step of producing a compound in which X in the formula (1) is a hydroxy group, a compound represented by the formula (1) and in which X in the formula (1) is a hydroxy group, and (meth A method for producing a compound, comprising a step of reacting an acrylic acid halide, (meth) acrylic acid or anhydrous (meth) acrylic acid to obtain a compound represented by the formula (1A).

In formula (1A), R ^1A is a hydrogen atom, a monovalent hydrocarbon group or an alkali metal atom, R ^2A is a divalent hydrocarbon group, and X ^A is a (meth) acryloyloxy group. be.
<7> A method for producing a compound represented by the following formula (1B), which is represented by the above formula (1) by the method for producing a compound according to any one of <1> to <5>. In addition, a step of producing a compound in which X in the formula (1) is a halogen atom, a compound represented by the formula (1) and in which X in the formula (1) is a halogen atom, and ( A method for producing a compound, which comprises a step of reacting a meta) acrylic acid salt with a compound represented by the formula (1B) to obtain a compound represented by the formula (1B).

In formula (1B), R ^1B is a hydrogen atom, a monovalent hydrocarbon group or an alkali metal atom, R ^2B is a divalent hydrocarbon group, and X ^B is a (meth) acryloyloxy group. be.
<8> A polymerizable composition containing a compound represented by the following formula (1) and a compound represented by the following formula (5).

In formula (1), R ¹ is a hydrogen atom, a monovalent hydrocarbon group or an alkali metal atom, R ² is a divalent hydrocarbon group, and X is a hydroxy group, a halogen atom or (meth). ) Acryloyloxy group.

In formula (5), R ^1C is a hydrogen atom, a monovalent hydrocarbon group or an alkali metal atom, R ^2C is a divalent hydrocarbon group, and X ^C is a hydroxy group, a halogen atom or ( Meta) Acryloyloxy group.
<9> The content of the compound represented by the formula (1) is 60% by mass with respect to the total content of the compound represented by the formula (1) and the compound represented by the formula (5). The polymerizable composition according to <8>, which is ~ 95% by mass.
<10> The polymerizable composition according to <8> or <9> used as an adhesive.
<11> A cured product of the polymerizable composition according to any one of <8> to <10>.
<12> A compound represented by the following formula (5).

In formula (5), R ^1C is a hydrogen atom, a monovalent hydrocarbon group or an alkali metal atom, R ^2C is a divalent hydrocarbon group, and X ^C is a hydroxy group, a halogen atom or ( Meta) Acryloyloxy group.
<13> A method for producing a compound represented by the following formula (5), wherein a compound represented by the following formula (2) and a compound represented by the following formula (3) are used in the presence of an acid or a base. A method for producing a compound, which comprises a step of obtaining a compound represented by the above formula (5) by reacting.

In formula (5), R ^1C is a hydrogen atom, a monovalent hydrocarbon group or an alkali metal atom, R ^2C is a divalent hydrocarbon group, and X ^C is a hydroxy group, a halogen atom or ( Meta) Acryloyloxy group.

In formula (2), R ¹ is a hydrogen atom, a monovalent hydrocarbon group or an alkali metal atom.

In the formula (3), R ² is a divalent hydrocarbon group, and X is a hydroxy group, a halogen atom or a (meth) acryloyloxy group.

According to one embodiment of the present disclosure, there is provided a method for producing a compound capable of easily producing a compound having a thiohydantoin skeleton, a polymerizable composition containing the compound produced by the above method for producing a compound, a cured product, and a compound. can do.

In the present disclosure, the numerical range represented by using "-" means a range including the numerical values before and after "-" as the lower limit value and the upper limit value.
In the present disclosure, the term "process" is included in this term not only as an independent process but also as long as the intended purpose of the process is achieved even if it cannot be clearly distinguished from other processes. ..
In the present disclosure, the amount of each component contained in the composition is the total amount of the plurality of substances present in the composition unless otherwise specified, when a plurality of substances corresponding to each component are present in the composition. Means.
In the numerical range described stepwise in the present disclosure, the upper limit value or the lower limit value described in one numerical range may be replaced with the upper limit value or the lower limit value of the numerical range described in another stepwise description. .. Further, in the numerical range described in the present disclosure, the upper limit value or the lower limit value of the numerical range may be replaced with the value shown in the examples.
In the present disclosure, the (meth) acryloyloxy group represents an acryloyloxy group or a metaacryloyloxy group, and the (meth) acrylate represents an acrylate or a methacrylate.

<< Method for producing the compound represented by the formula (1) >>
The method for producing a compound represented by the formula (1) of the present disclosure is a method for producing a compound represented by the following formula (1) (also referred to as a compound (1)) in the presence of an acid or a base. , The compound represented by the following formula (2) (also referred to as compound (2)) and the compound represented by the following formula (3) (also referred to as compound (3)) are reacted to form the above formula (1). ) Is included (also referred to as a “compound manufacturing step” in the present disclosure).

In formulas (1) to (3), R ¹ is a hydrogen atom, a monovalent hydrocarbon group or an alkali metal atom, R ² is a divalent hydrocarbon group, and X is a hydroxy group. It is a halogen atom or a (meth) acryloyloxy group.

The method for producing the compound (1) can easily produce a compound having a thiohydantoin skeleton by including the above-mentioned compound production step.
As described above, a compound having a thiohydantoin skeleton such as compound (1) is usually obtained by a method of hydrolyzing compound (2) and then dehydrating and condensing it with a compound having a hydroxy group.
However, the method using the dehydration condensation often requires a large amount of organic solvent, a large amount of labor, and the like.
On the other hand, if the method for producing the compound (1) includes the above-mentioned compound production step, the compound (1) can be produced without including other steps.
That is, since the compound (1) can be produced without performing many steps over multiple steps in order to produce the compound (1), the labor for production can be reduced.

Further, in the above method using dehydration condensation, an active ester is generated as a reaction intermediate by a condensation reaction of a carboxyl group, and this active ester group reacts with the nitrogen atom of the amide in the molecule to form the original compound ( The reaction returning to 2) can occur as a competitive reaction. As a result, the yield of the target product, compound (1), may be significantly reduced.

On the other hand, in the method for producing the compound (1), the dehydration condensation reaction does not occur, so that the yield of the compound (1) can be further improved.
That is, in the method for producing compound (1), a hydrolysis step that requires a great deal of labor and an esterification step that has a low yield can be performed in one step. Furthermore, the method for producing compound (1) can produce compound (1) in high yield without using a special reagent such as a dehydration condensing agent.

<Compound manufacturing process>
The compound manufacturing step in the present disclosure is a step of reacting the compound (2) with the compound (3) in the presence of an acid or a base to obtain the compound (1).

In the compound manufacturing step, when the compound (2) and the compound (3) are reacted, the compound (1) can be obtained without going through a plurality of steps.
That is, in the compound manufacturing step, the compound (1) can be obtained in one step by reacting the compound (2) with the compound (3) in the presence of an acid or a base.

Specifically, the compound manufacturing step is a step of mixing an acid or a base, a compound (2) and a compound (3) to obtain a mixture, and a reaction of the compound (2) and the compound (3) in the above mixture. It may include a step of obtaining the compound (1).

The acid and base are not particularly limited.
Examples of the acid used include sulfonic acids such as methanesulfonic acid, paratoluenesulfonic acid, and camphor-sulfonic acid;
Carvones such as trichloroacetic acid, trifluoroacetic acid, formic acid, citric acid, oxalic acid;
Mineral acids such as hydrochloric acid, sulfuric acid, nitric acid;
Phosphoric acids such as phosphoric acid and pyrophosphate; Lewis acids such as tetraisopropyl orthotitanium acid, aluminum isopropoxide, boron trifluoride ethyl ether complex, silver trifluoromethanesulfonate, copper trifluoromethanesulfonate;
And so on.
Among the above, the acid used is preferably methanesulfonic acid or p-toluenesulfonic acid.

The base used is not particularly limited as long as it is a base exhibiting deprotonation ability with respect to the substrate. For example, carbonates of alkali metals such as sodium carbonate and potassium carbonate;
Bicarbonates of alkali metals such as sodium hydrogen carbonate and potassium hydrogen carbonate;
Organic bases such as triethylamine, N, N-dimethylaniline, pyridine;
Metal hydrides such as sodium hydride and potassium hydride;
Metal alkoxides such as sodium methoxide, sodium ethoxide, potassium tert-butoxide; and the like.
Among the above, the base used is preferably an organic base, and more preferably sodium methoxide.

<Solvent>
Examples of the solvent used in the reaction include water and organic solvents.

(Organic solvent)
In the compound manufacturing process of the present disclosure, it is preferable that the reaction between the compound (2) and the compound (3) is carried out in an organic solvent.
As described above, since it is not necessary to use the hydrolysis reaction as described above, it is preferable that the solvent mainly used is an organic solvent.
The organic solvent is not particularly limited, but is preferably an aprotic solvent.
Specific examples of the aprotic solvent include ketone solvents such as acetone, methyl ethyl ketone, methyl propyl ketone, and methyl butyl ketone;
Dimethyl ether, methyl ethyl ether, diethyl ether, methyl-t-butyl ether, 1,2-dimethoxyethane, tetrahydrofuran, 1-methyltetrahydrofuran,
Ethereal solvent such as 1,4-dioxane;
Hydrocarbon-based solvents such as n-pentane, n-hexane, n-heptane, and cyclohexane. Aromatic hydrocarbon solvents such as toluene, xylene, chlorobenzene, and dichlorobenzene;
Halogenated carbons such as dichloromethane, dichloroethane, chloroform;
Nitrile-based solvents such as acetonitrile and propionitrile;
Ester solvents such as methyl acetate, ethyl acetate, butyl acetate;
Examples thereof include amide-based solvents such as dimethylformamide, dimethylacetamide, and 1,3-dimethylimidazolidinone.

In the compound production step, the content of the organic solvent is preferably 90% by mass or more, more preferably 95% by mass or more, still more preferably 100% by mass, based on the total mass of the solvent. ..
The content of the organic solvent may be 100% by mass or less, or 99% by mass or less, based on the total mass of the solvent.

(water)
Since the method for producing the compound (1) does not require the use of a hydrolysis reaction as described above, it does not require the use of water.
In the compound production step, the water content is preferably less than 5% by mass, more preferably less than 1% by mass, and less than 0.1% by mass, based on the total mass of the solvent. More preferred.
The content of the organic solvent may be more than 0% by mass or 0.01% by mass or more with respect to the total mass of the solvent.

In the compound manufacturing process in the present disclosure, the following compound (2) and the compound (3) are reacted in the presence of an acid or a base to obtain the following compound (1).

In formula (1), R ¹ is a hydrogen atom, a monovalent hydrocarbon group or an alkali metal atom, R ² is a divalent hydrocarbon group, and X is a hydroxy group, a halogen atom or (meth). ) Acryloyloxy group.

In the formula (1), R ¹ preferably has a hydrogen atom or a monovalent hydrocarbon group, and more preferably a hydrogen atom.
In the formula (1), X is preferably a hydroxy group or a (meth) acryloyloxy group, and more preferably a (meth) acryloyloxy group.

In formula (2), R ¹ is a hydrogen atom, a monovalent hydrocarbon group or an alkali metal atom.
In the formula (2), R ¹ preferably has a hydrogen atom or a monovalent hydrocarbon group, and more preferably a hydrogen atom.

In the formula (3), R ² is a divalent hydrocarbon group, and X is a hydroxy group, a halogen atom or a (meth) acryloyloxy group.
In the formula (3), X is preferably a hydroxy group or a (meth) acryloyloxy group, and more preferably a (meth) acryloyloxy group.

It is preferable that X in the formula (1) and the formula (3) is a (meth) acryloyloxy group.

The monovalent hydrocarbon group in ^R1 in the formulas (1) and (2) may be a saturated hydrocarbon group or an unsaturated hydrocarbon group.
The monovalent hydrocarbon group in ^R1 in the formulas (1) and (2) may or may not have a cyclic structure (for example, an aromatic structure, an alicyclic structure, etc.). ..

In the formula (1) and the formula (2), examples of the alkali metal atom in R ¹ include lithium, sodium and potassium.

The number of carbon atoms of the divalent hydrocarbon group in ^R2 in the formulas (1) and (3) may be, for example, 1 to 30 or 2 to 30.

The divalent hydrocarbon group in R ² in the formulas (1) and (3) may be a saturated hydrocarbon group or an unsaturated hydrocarbon group.
The divalent hydrocarbon group in R ² in the formulas (1) and (3) may or may not have a cyclic structure (for example, an aromatic structure, an alicyclic structure, etc.). ..

^R2 in the formula (1) and the formula (3) is a divalent group represented by the following formula (4), an ether bond, a 1,4-phenylene group, a 1,4-cyclohexylene group, and a divalent group. It is preferable to contain at least one group selected from the group consisting of the chain saturated hydrocarbon group of the above, and it is composed of a divalent group represented by the following formula (4) and a divalent chain saturated hydrocarbon group. It is more preferred to include at least one group selected from the group.

In formula (4), Y ¹ and Y ² are independently oxygen atoms, a divalent group represented by -CH _2- or a divalent group represented by -NH-, and Y ³ is a divalent group. It is an oxygen atom or a sulfur atom.

As the divalent group represented by the formula (4), for example, the divalent group represented by -NH-C (= O) -O-, -OC (= O) -CH _2- A divalent group represented by -OC (= O) -O-, a divalent group represented by -NH-C (= O) -NH-, and a divalent group represented by -NH-C (= O) -NH-. Among these groups, a divalent group in which "= O" is replaced with "= S" can be mentioned.
Among these, a divalent group represented by —O—C (= O) _—CH2- is preferable.

In the case of a divalent group represented by -OC (= O) -CH _2- , -OC (= S) _-CH2- , _-CH2- faces the thiohydantoin skeleton side. It is preferable that they are bonded in such a manner. In the case of a divalent group represented by -NH-C (= O) -O- and -NH-C (= S) -O-, -O- is bound so as to face the thiohydantoin skeleton side. It is preferable to have.

It is also preferable that R ² in the formula (1) and the formula (3) is an alkylene group having 2 to 20 carbon atoms.

Specific examples of the compound (1) include the following compounds. However, the compound (1) in the present disclosure is not limited to the following specific examples.

The yield of compound (1) is preferably 50% by mass or more, more preferably 55% by mass or more, and further preferably 60% by mass or more.
The yield (%) of the compound is obtained by dividing the isolated yield (mass) of the compound by the theoretical yield (mass) of the compound and multiplying by 100.
The yield of compound (1) can be measured using ¹ H-NMR or HPLC.

In the present disclosure, the method for producing a compound includes a method for producing a compound represented by the following formula (1A) and a method for producing a compound represented by the following formula (1B).
The method for producing the compound represented by the formula (1A) and the method for producing the compound represented by the formula (1B) are the formula (1) using the compound (1) produced by the above-mentioned production method of the compound (1). A compound represented by 1A) and a compound represented by the formula (1B) can be obtained.

<Method for producing the compound represented by the formula (1A)>
The method for producing the compound represented by the formula (1A) is a method for producing the compound represented by the formula (1A), which is represented by the formula (1) and is represented by the formula (1) according to the method for producing the compound (1). (1) A step of producing a compound in which X is a hydroxy group,
A compound represented by the formula (1) and in which X in the formula (1) is a hydroxy group is reacted with a (meth) acrylic acid halide, (meth) acrylic acid or anhydrous (meth) acrylic acid. The step of obtaining the compound represented by the formula (1A) is included.

In formula (1A), R ^1A is a hydrogen atom, a monovalent hydrocarbon group or an alkali metal atom, R ^2A is a divalent hydrocarbon group, and X ^A is a (meth) acryloyloxy group. be.
The preferred embodiment of R ^1A and the preferred embodiment of R ^2A are the same as the preferred embodiment of R ¹ and the preferred embodiment of R ² in the formula (1).

<Method for producing the compound represented by the formula (1B)>
The method for producing a compound represented by the formula (1B) is a method for producing a compound represented by the following formula (1B), which is represented by the formula (1) and is represented by the method for producing a compound of the present disclosure. A step of producing a compound in which X in the formula (1) is a halogen atom,
A step of reacting a compound represented by the formula (1) and in which X in the formula (1) is a halogen atom with a (meth) acrylate to obtain a compound represented by the formula (1B). And, including.

In formula (1B), R ^1B is a hydrogen atom, a monovalent hydrocarbon group or an alkali metal atom, R ^2B is a divalent hydrocarbon group, and X ^B is a (meth) acryloyloxy group. be.
The preferred embodiment of R ^1B and the preferred embodiment of R ^2B are the same as the preferred embodiment of R ¹ and the preferred embodiment of R ² in the formula (1).

<< Method for producing the compound represented by the formula (5) >>
The method for producing a compound represented by the formula (5) is a method for producing a compound represented by the following formula (5) (also referred to as a compound (5)), and the following compound is produced in the presence of an acid or a base. This includes a step of reacting (2) with the following compound (3) to obtain a compound represented by the above formula (5).

In formula (5), R ^1C is a hydrogen atom, a monovalent hydrocarbon group or an alkali metal atom, R ^2C is a divalent hydrocarbon group, and X ^C is a hydroxy group, a halogen atom or ( Meta) Acryloyloxy group.

In formula (2), R ¹ is a hydrogen atom, a monovalent hydrocarbon group or an alkali metal atom.
In the formula (2), the preferred embodiment of R ¹ is the same as the preferred embodiment of R ¹ described in the above-mentioned section of the formula (2).

In the formula (3), R ² is a divalent hydrocarbon group, and X is a hydroxy group, a halogen atom or a (meth) acryloyloxy group.
In the formula (3), the preferred embodiment of R ² is the same as the preferred embodiment of R ² described in the above-mentioned section of the formula (3).

Similar to the above-mentioned method for producing the compound (1), the compound (5) can also be obtained by reacting the compound (2) with the compound (3) in the presence of an acid or a base.
At this time, both the compound (5) and the compound (1) can be obtained by reacting the compound (2) with the compound (3) in the presence of an acid or a base.

The following compound (5) can be obtained by the method for producing the compound (5).

In formula (5), R ^1C is a hydrogen atom, a monovalent hydrocarbon group or an alkali metal atom, R ^2C is a divalent hydrocarbon group, and X ^C is a hydroxy group, a halogen atom or ( Meta) Acryloyloxy group.
In the formula (5), the preferred embodiment of R ^1C , the preferred embodiment of R ^2C , and the preferred embodiment of X ^C are the preferred embodiment of R ¹ and the preferred embodiment of R ² described in the above-mentioned section of the formula (1). And X are the same as the preferred embodiments.

The compound represented by the formula (5) can be used as a polymerizable monomer in combination with the compound represented by the formula (1).
In particular, the compound represented by the formula (5) can be produced at the same time as the compound represented by the formula (1). That is, when both are used in combination, they can be manufactured separately and used without new addition, which is useful in terms of convenience.
Further, the compound represented by the formula (5) does not easily suppress the adhesive performance of the compound represented by the formula (1).

<< Polymerizable composition >>
The polymerizable composition of the present disclosure contains the compound (1) in the present disclosure.
The polymerizable composition of the present disclosure has a high adhesiveness and an adhesion promoting effect on metals, particularly noble metals such as gold, silver, platinum, and palladium, or alloys containing noble metals (hereinafter, also referred to as "precious metal alloys"). ..
Here, the "adhesion promoting effect" means an effect of enhancing the adhesiveness of the adhesive used when the polymerizable composition of the present disclosure is used as a primer described below.

The polymerizable compositions of the present disclosure are suitably used in medical or dental applications. The polymerizable composition of the present disclosure is useful as, for example, an adhesive, a primer, a bone cement, a bonding material, a sealant, a cement, a filler, a backing layer material, an abutment structure, a rocking tooth fixing material, and a root canal filler. be.
Among these, the polymerizable composition of the present disclosure is suitably used as an adhesive.
The polymerizable composition of the present disclosure includes an adhesive between an adherend such as a dentin and a noble metal or a noble metal alloy, an adhesive between a noble metal or a noble metal alloy, and an adhesion between an adherend such as a dentin and a noble metal or a noble metal alloy. It is useful as a primer (pretreatment material) to be applied to the adherend surface of a noble metal or a noble metal alloy for promotion or for promoting adhesion between noble metals or noble metal alloys.

Further, although the polymerizable composition of the present disclosure contains the compound (1), the compound (1) has little adverse effect such as causing a large decrease in adhesive force to the dentin surface or the surface of ceramics such as zirconium oxide. Further, even if the compound (1) is contained in the conventional adhesive, the adverse effect of the adhesive force on the dentin surface or the ceramic surface of the adhesive is small.

Examples of the bonding target made of the precious metal or the precious metal alloy include prostheses such as inlays, onlays, crowns, bridges, and dentures.

The polymerizable composition of the present disclosure can be sufficiently used as an adhesive in a field requiring adhesion between an organic material and a noble metal or a noble metal alloy (for example, precision machinery, jewelry industry, etc.). That is, the polymerizable composition of the present disclosure is a highly versatile polymerizable composition.
Specifically, the polymerizable composition of the present disclosure can be used as a general industrial adhesive, an arts and crafts adhesive, a jewelry adhesive, and a paint, a gap filler, a building adhesive, and a covering material. It can be used by adding it to the above.

The polymerizable composition of the present disclosure may be a one-component type or a one-paste type, or may be a multi-agent type such as a two-component type, a powder / liquid type, and a paste & paste type.
In the case of the multi-drug type, for example, each component stored in a state of being divided into a plurality of components can be mixed immediately before use.

The polymerizable composition of the present disclosure preferably contains a compound represented by the following formula (1) and a compound represented by the following formula (5).

In formula (1), R ¹ is a hydrogen atom, a monovalent hydrocarbon group or an alkali metal atom, R ² is a divalent hydrocarbon group, and X is a hydroxy group, a halogen atom or (meth). ) Acryloyloxy group.

In formula (5), R ^1C is a hydrogen atom, a monovalent hydrocarbon group or an alkali metal atom, R ^2C is a divalent hydrocarbon group, and X ^C is a hydroxy group, a halogen atom or ( Meta) Acryloyloxy group.

When the polymerizable composition of the present disclosure contains a compound represented by the following formula (1) and a compound represented by the following formula (5), the total of the compound (1) and the compound (5). The content of the compound (1) is preferably 60% by mass to 95% by mass, more preferably 70% by mass to 95% by mass, based on the content.

The polymerizable composition of the present disclosure may contain other components other than the above-mentioned compound (1) and compound (5).
The polymerizable composition of the present disclosure has, as other components, a radically polymerizable monomer (B), a silane coupling agent (C), a filler (D), a polymerization initiator (E), and a reducing compound (F). , At least one selected from the organic solvent (G) and water (H) can be further contained.
The radically polymerizable monomer (B), the silane coupling agent (C), the filler (D), the polymerization initiator (E), the reducing compound (F), the organic solvent (G) and the water (H) in the present disclosure. For specific examples and preferred embodiments of the above, the radically polymerizable monomer (B), the silane coupling agent (C), the filler (D), the polymerization initiator (E), which is described in International Publication No. 2020/032268. The same applies to the specific examples and preferred embodiments of the reducing compound (F), the organic solvent (G) and the water (H).

The cured product of the present disclosure is a cured product of the polymerizable composition of the present disclosure.
By applying the polymerizable composition to the object to be bonded and then curing the polymerizable composition, the cured product and the object to be adhered are fixed in contact with each other.
Further, by applying the polymerizable composition between the objects to be bonded and then curing the polymerizable composition, the objects to be bonded can be fixed in a bonded state.

Hereinafter, embodiments according to the present disclosure will be described in detail with reference to Examples. The invention of the present disclosure is not limited to the description of these examples.
In this example, the yield (%) of the compound was determined by dividing the isolated yield (mass) of the compound by the theoretical yield (mass) of the compound and multiplying by 100.

(Example 1)
<Synthesis of bicyclic compound (a1) by cyclization reaction of 2-pyrrolidone-5-carboxylic acid and ammonium thiocyanate>
As represented by the following reaction formula, the bicyclic compound (a1) was synthesized by a cyclization reaction of 2-pyrrolidone-5-carboxylic acid and ammonium thiocyanate.

Specifically, first, 100 g (775 mmol) of 2-pyrrolidone-5-carboxylic acid (compound (a6)), 237 g (2.32 mol) of acetic anhydride, 93 g (1.55 mmol) in a 1000 mL 4-diameter flask. Acetic anhydride and 64.8 g of ammonium thiocyanate were charged to prepare a suspension. The resulting suspension was stirred at 100 ° C. for 2 hours.
Next, the obtained mixed solution was allowed to cool to 60 ° C. or lower, 756 mL of a mixed solvent (ethyl acetate: hexane = 1: 1) was added, and the mixture was stirred. Then, the mixture was ice-cooled to 5 ° C. or lower and stirred for 1 hour. This suspension was filtered cold using filter paper (No. 5C, manufactured by Kiriyama Glass Co., Ltd.), and a total of 700 mL of a mixed solvent (ethyl acetate: hexane = 1: 1) was added in 3 portions and washed. As a brown solid, 70.3 g of compound (a1) was obtained (yield 53%).
Here, the yield (%) of the compound (a1) was determined by dividing the isolated yield (mass) of the compound (a1) by the theoretical yield (mass) of the compound (a1) and multiplying by 100.
The NMR analysis results of compound (a1) are shown below.
^{1 1} H-NMR (270 MHz, DMSO-d6) δ: 12.4 (1H, brand.s), 4.91 (1H, t, J = 8.9 Hz), 2.85 (1H, m), 2. 52 (1H, m), 2.13-2.38 (2H, m).

<Synthesis of thiohydantoin compounds (a2) and (a3) by ring-opening esterification of compound (a1) and 10-hydroxydecyl methacrylate>
As represented by the following reaction formula, the thiohydantoin compounds (a2) and (a3) were synthesized by the ring-opening esterification reaction of the compound (a1) and 10-hydroxydecyl methacrylate.

Specifically, first, 70.2 g (413 mmol) of the compound (a1) and 105 g (433 mmol) of 10-hydroxydecylmethacrylate, 3.97 g (41.3 mmol, the compound (a5)) were placed in a 1000 mL 4-diameter flask. Methanesulfonic acid and 0.735 g of 2,6-di-tert-butyl-p-cresol were charged, and 351 g of toluene was added thereto to dissolve them. The resulting solution was stirred at 100 ° C. for 2 hours.
Next, the obtained mixed solution was purified by silica gel column chromatography (column: silica gel C-100 1020 g, elution solvent: ethyl acetate-hexane based gradient (ethyl acetate 25% → 33%)) to obtain a pale yellow solid. , 82.2 g (yield 60%) of the compound (a2) and 13.7 g (yield 10%) of the compound (a3) were obtained.
The yield of the compound (a2) and the compound (a3) is the yield with respect to the compound (a1).
Further, the yield (%) of the mixture of the compound (a2) and the compound (a3) is the isolated yield (mass) of the mixture of the compound (a2) and the compound (a3) as the isolated yield (mass) of the compound (a2) and the compound (a3). It was determined by dividing by the theoretical yield (mass) of the mixture and multiplying by 100.
The NMR analysis results of the compound (a2) and the compound (a3) are shown below.
Compound (a2) ^{1 1} H-NMR (270 MHz, DMSO-d ₆ ) δ: 11.7 (1H, brd.s), 10.0 (1H, brd.s), 5.99 (1H, s), 5 .65 (1H, s), 4.21 (1H, m), 3.90-4.15 (2H, m), 2.41 (2H, t, J = 7.6Hz), 1.69-2 .04 (4H, m), 1.86 (3H, s), 1.47-1.65 (4H, m), 1.17-1.38 (12H, m).
Compound (a3) ^{1 1} H-NMR (270 MHz, DMSO-d ₆ ) δ: 9.63 (1H, brd.s), 9.58 (1H, brd.s), 6.00 (1H, s), 6 .65 (1H, s), 5.10 (1H, d, J = 9.6Hz), 3.96-4.22 (2H, m), 2.35 (1H, m), 1.86 (1H) , M), 1.86 (3H, s), 1.47-1.68 (4H, m), 1.15-1.42 (12H, m).

(Comparative Example 1)
<Synthesis of carboxylic acid (a4) by hydrolyzing dicyclic compound (a1)>
As represented by the following reaction formula, the carboxylic acid compound (a4) was synthesized by hydrolyzing the compound (a1).

Specifically, first, 43.78 g (0.257 mol) of the bicyclic compound (a1) and 386 mL of 2N hydrochloric acid (0.772 mol) were added to a 500 mL eggplant flask, and the mixture was stirred at 75 ° C. for 4 hours. did. The obtained solution was concentrated under reduced pressure to obtain 55.75 g of an oil.
Next, the oil was dissolved in 200 mL of ethyl acetate and transferred to a separating funnel. After washing with water (200 mL), the ethyl acetate layer was separated. 20 g of salt was added to the obtained aqueous layer to dissolve it, and the mixture was extracted with ethyl acetate (150 mL). This extraction operation was repeated 6 times. After combining the respective ethyl acetate layers, the organic layer was concentrated under reduced pressure. Ethyl acetate (150 mL) and n-hexane (50 mL) were added to the obtained semi-solid substance, and the mixture was heated to 60 ° C. with stirring and then gradually cooled to room temperature. The resulting crystals were collected by filtration and then dried under reduced pressure to give 36.9 g (yield 76%) of compound (a4) as a white solid.
The NMR analysis results of the obtained compound (a4) are shown below.
^{1 1} H-NMR (270 MHz, CDCl ₃ ) δ: 12.2 (1H, blend.s), 11.1 (1H, blend.s), 10.1 (1H, blend.s), 4.23 (1H) , T, J = 6.3), 2.34 (2H, t, J = 7.6), 1.94 (1H, m), 1.76 (1H, m).

<Synthesis of thiohydantoin compound (a2) by condensation of carboxylic acid compound (a4) and 10-hydroxydecylmethacrylate>
As expressed by the reaction formula below,
A thiohydantoin compound (a2) was synthesized by a condensation reaction between a carboxylic acid compound (a4) and 10-hydroxydecylmethacrylate.

Specifically, first, in a nitrogen atmosphere, 4.45 g (23.6 mmol) of the compound (a4) and 6.88 g (28.4 mmol) of 10-hydroxydecylmethacrylate (compound (a5)) were placed in a 300 mL 4-diameter flask. )), 7.0 mg of 2,6-di-tert-butyl-4-methylphenol, and 0.58 g (4.73 mmol) of 4-dimethylaminopyridine, and 90 mL of tetrahydrofuran is added to dissolve them. I let you. A solution of 5.82 g (24.8 mmol) of dicyclohexylcarbodiimide in 30 mL of tetrahydrofuran was added dropwise to the flask at room temperature, and the mixture was stirred at room temperature for 4.5 hours. Then, 150 mL of ethyl acetate and 30 mL of hexane were added to the reaction solution in the flask, and the mixture was stirred for 10 minutes. The mixture that became a white slurry in the flask was filtered through cerite, and the filtrate was concentrated under reduced pressure to obtain an oil.
Next, the obtained oil was purified twice by silica gel chromatography (column: Biotage SNAP KP-SilCartridge 100 g; elution solvent: ethyl acetate-hexane-based gradient: ethyl acetate 5% → 100%), and the compound (a2) was purified. ) Was obtained as a colorless oily substance in an amount of 4.79 g (yield: 49%).
The yield of the compound (a2) is the yield with respect to the compound (a4).
The NMR analysis results of the obtained compound (a2) are shown below.
^{1 1} H-NMR (270 MHz, CDCl ₃ ) δ: 8.45 (1H, blend.s), 7.53 (1H, blend.s), 6.10 (1H, m), 5.55 (1H, m) ), 4.26 (1H, dd, J = 6.9, 4.9Hz), 4.14 (2H, t, J = 6.9Hz), 4.10 (2H, t, J = 6.9Hz) , 2.53 (2H, t, J = 6.9Hz), 2.34-2.21 (1H, m), 2.17-2.01 (1H, m), 1.95 (3H, m) , 1.72-1.60 (4H, m), 1.43-1.26 (12H, m).

As described above, the compound (2) (that is, the compound (a1)) and the compound (3) (that is, the compound (a5)) are reacted in the presence of an acid or a base to cause the compound (1) (that is, the compound (a2)). In Example 1 using the method for producing a compound including the step of obtaining)), since the compound (1) could be produced from the compound (2) and the compound (3) in one step, thiohydantoin could be easily performed. A compound having a skeleton could be produced.
On the other hand, the compound (2) (that is, the compound (a1)) is once hydrolyzed to obtain a hydrolyzed compound (that is, the compound (a4)), and then the hydrolyzed compound and the compound (3) (that is, the compound (a5)). In Comparative Example 1 in which compound (1) (that is, compound (a2)) was obtained as a dehydration condensate by reacting with each other, compound (1) was produced from compound (2) and compound (3) in one step. It was not possible to easily produce a compound having a thiohydantoin skeleton.
In addition, Example 1 was superior in yield of compound (a2) as compared with Comparative Example 1.

Claims (13)

A method for producing a compound represented by the following formula (1).
Including a step of reacting a compound represented by the following formula (2) with a compound represented by the following formula (3) in the presence of an acid or a base to obtain a compound represented by the above formula (1). Method for producing a compound.

In formulas (1) to (3), R ¹ is a hydrogen atom, a monovalent hydrocarbon group or an alkali metal atom, R ² is a divalent hydrocarbon group, and X is a hydroxy group. It is a halogen atom or a (meth) acryloyloxy group. The method for producing a compound according to claim 1, wherein the reaction between the compound represented by the formula (2) and the compound represented by the formula (3) is carried out in an organic solvent. The R ² in the formula (1) and the formula (3) is a divalent group represented by the following formula (4), an ether bond, a 1,4-phenylene group, a 1,4-cyclohexylene group, and the like. The method for producing a compound according to claim 1 or claim 2, which comprises at least one group selected from the group consisting of a divalent chain saturated hydrocarbon group.

In formula (4), Y ¹ and Y ² are independently oxygen atoms, a divalent group represented by -CH _2- or a divalent group represented by -NH-, and Y ³ is a divalent group. It is an oxygen atom or a sulfur atom. The method for producing a compound according to any one of claims 1 to 3, wherein the R ² in the formula (1) and the formula (3) is an alkylene group having 2 to 20 carbon atoms. The method for producing a compound according to any one of claims 1 to 4, wherein the X in the formula (1) and the formula (3) is a (meth) acryloyloxy group. A method for producing a compound represented by the formula (1A).
A step of producing a compound represented by the formula (1) and in which X in the formula (1) is a hydroxy group by the method for producing a compound according to any one of claims 1 to 5. When,
A compound represented by the formula (1) and in which X in the formula (1) is a hydroxy group, and a (meth) acrylic acid halide, (meth) acrylic acid or anhydrous (meth) acrylic acid. A method for producing a compound, which comprises a step of reacting to obtain a compound represented by the formula (1A).

In formula (1A), R ^1A is a hydrogen atom, a monovalent hydrocarbon group or an alkali metal atom, R ^2A is a divalent hydrocarbon group, and X ^A is a (meth) acryloyloxy group. be. A method for producing a compound represented by the following formula (1B).
A step of producing a compound represented by the formula (1) and in which X in the formula (1) is a halogen atom by the method for producing a compound according to any one of claims 1 to 5. When,
A compound represented by the formula (1) and represented by the formula (1B) is obtained by reacting a compound in which X in the formula (1) is a halogen atom with a (meth) acrylate salt. A step of obtaining and a method for producing a compound containing.

In formula (1B), R ^1B is a hydrogen atom, a monovalent hydrocarbon group or an alkali metal atom, R ^2B is a divalent hydrocarbon group, and X ^B is a (meth) acryloyloxy group. be. A polymerizable composition containing a compound represented by the following formula (1) and a compound represented by the following formula (5).

In formula (1), R ¹ is a hydrogen atom, a monovalent hydrocarbon group or an alkali metal atom, R ² is a divalent hydrocarbon group, and X is a hydroxy group, a halogen atom or (meth). ) Acryloyloxy group.

In formula (5), R ^1C is a hydrogen atom, a monovalent hydrocarbon group or an alkali metal atom, R ^2C is a divalent hydrocarbon group, and X ^C is a hydroxy group, a halogen atom or ( Meta) Acryloyloxy group. The content of the compound represented by the formula (1) is 60% by mass to 95% by mass with respect to the total content of the compound represented by the formula (1) and the compound represented by the formula (5). The polymerizable composition according to claim 8. The polymerizable composition according to claim 8 or 9, which is used as an adhesive. The cured product of the polymerizable composition according to any one of claims 8 to 10. A compound represented by the following formula (5).

In formula (5), R ^1C is a hydrogen atom, a monovalent hydrocarbon group or an alkali metal atom, R ^2C is a divalent hydrocarbon group, and X ^C is a hydroxy group, a halogen atom or ( Meta) Acryloyloxy group. A method for producing a compound represented by the following formula (5).
Including a step of reacting a compound represented by the following formula (2) with a compound represented by the following formula (3) in the presence of an acid or a base to obtain a compound represented by the above formula (5). Method for producing a compound.

In formula (5), R ^1C is a hydrogen atom, a monovalent hydrocarbon group or an alkali metal atom, R ^2C is a divalent hydrocarbon group, and X ^C is a hydroxy group, a halogen atom or ( Meta) Acryloyloxy group.

In formula (2), R ¹ is a hydrogen atom, a monovalent hydrocarbon group or an alkali metal atom.

In the formula (3), R ² is a divalent hydrocarbon group, and X is a hydroxy group, a halogen atom or a (meth) acryloyloxy group.