Method for producing compound, polymerizable composition, cured product and compound

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

[Technical field]

[0001] The present disclosure relates to a method for producing a compound, a polymerizable composition, a cured product, and a compound. [Background technology]

[0002] In clinical medicine, oral surgery and dentistry involve bonding between dentin and metal prostheses such as inlays, onlays, crowns, and bridges, posts and cores of abutment teeth, or orthodontic brackets. Compounds with a thiohydantoin skeleton have been developed as adhesives for bonding metals and dentin. For example, Patent Document 1 describes a compound represented by a specific chemical structural formula. [Prior art documents] [Patent documents]

[0003] [Patent Document 1] International Publication No. 2020 / 032268 Summary of the Invention [Problem to be solved by the invention]

[0004] The compound having a thiohydantoin skeleton as described in Patent Document 1 can usually be obtained by a method in which a compound represented by the formula (2) described below is subjected to a hydrolysis reaction, and then a dehydration condensation reaction is carried out with a compound having a hydroxy group. Since the carboxylic acid intermediate obtained by the above hydrolysis is water-soluble, if extraction with an organic solvent is attempted in order to isolate it from the aqueous solution after the reaction, multiple extractions must be performed, which requires a large amount of organic solvent. Therefore, this process often requires a large amount of organic solvent, a great deal of labor, and the like. In addition, since a dehydration condensation reaction must be carried out after the hydrolysis reaction, the production requires two reaction steps. For these reasons, there is a demand for a method for more easily producing a compound having a thiohydantoin skeleton.

[0005] The present disclosure has been made in consideration of the above circumstances. In other words, an object of the present disclosure is to provide a compound production method capable of easily producing a compound having a thiohydantoin skeleton, and a polymerizable composition, a cured product, and a compound each containing the compound produced by the compound production method. [Means for solving the problem]

[0006] Means for solving the above problems include the following embodiments. <1> A method for producing a compound represented by the following formula (1), comprising 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 the compound represented by the formula (1).

[0007] [ka]

[0008] In formulas (1) to (3), R 1 is a hydrogen atom, a monovalent hydrocarbon group, or an alkali metal atom, and R 2 is a divalent hydrocarbon group, and X is a hydroxy group, a halogen atom, or a (meth)acryloyloxy group. <2> 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. <1> A method for producing the compound described in <3> The R in the formula (1) and the formula (3) 2 contains at least one group selected from the group consisting of 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 chain saturated hydrocarbon group: <1> or <2> A method for producing the compound described in

[0009] [ka]

[0010] In formula (4), Y 1 and Y 2 each independently represents an oxygen atom, a divalent group represented by -CH-, or a divalent group represented by -NH-; Y 3 is an oxygen atom or a sulfur atom. <4> The R in the formula (1) and the formula (3) 2 is an alkylene group having 2 to 20 carbon atoms <1> ~ <3> A method for producing the compound according to any one of the above. <5> In the formula (1) and the formula (3), X is a (meth)acryloyloxy group. <1> ~ <4> A method for producing the compound according to any one of the above. <6> A method for producing a compound represented by formula (1A), comprising the steps of: <1> ~ <5> and a step of reacting the compound represented by formula (1) and wherein X in formula (1) is a hydroxy group with a (meth)acrylic acid halide, (meth)acrylic acid, or (meth)acrylic anhydride to obtain a compound represented by formula (1A).

[0011] [ka]

[0012] In formula (1A), R 1A is a hydrogen atom, a monovalent hydrocarbon group, or an alkali metal atom, and R 2A is a divalent hydrocarbon group, and X A is a (meth)acryloyloxy group. <7> A method for producing a compound represented by the following formula (1B): <1> ~ <5> and reacting the compound represented by formula (1) and X in formula (1) where X is a halogen atom with a (meth)acrylate salt to obtain a compound represented by formula (1B).

[0013] [ka]

[0014] In formula (1B), R 1B is a hydrogen atom, a monovalent hydrocarbon group, or an alkali metal atom, and R 2B is a divalent hydrocarbon group, and X B is a (meth)acryloyloxy group. <8> A polymerizable composition comprising a compound represented by the following formula (1) and a compound represented by the following formula (5):

[0015] [ka]

[0016] In formula (1), R 1 is a hydrogen atom, a monovalent hydrocarbon group, or an alkali metal atom, and R 2 is a divalent hydrocarbon group, and X is a hydroxy group, a halogen atom, or a (meth)acryloyloxy group.

[0017] [ka]

[0018] In formula (5), R 1C is a hydrogen atom, a monovalent hydrocarbon group, or an alkali metal atom, and R 2C is a divalent hydrocarbon group, and X Cis a hydroxy group, a halogen atom or a (meth)acryloyloxy group. <9> The content of the compound represented by formula (1) is 60% by mass to 95% by mass based on the total content of the compound represented by formula (1) and the compound represented by formula (5). <8> The polymerizable composition according to claim 1. <10> Used as an adhesive <8> or <9> The polymerizable composition according to claim 1. <11> <8> ~ <10> 2. A cured product of the polymerizable composition according to claim 1. <12> A compound represented by the following formula (5):

[0019] [ka]

[0020] In formula (5), R 1C is a hydrogen atom, a monovalent hydrocarbon group, or an alkali metal atom, and R 2C is a divalent hydrocarbon group, and X C is a hydroxy group, a halogen atom or a (meth)acryloyloxy group. <13> A method for producing a compound represented by the following formula (5), comprising 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 the compound represented by the formula (5).

[0021] [ka]

[0022] In formula (5), R 1C is a hydrogen atom, a monovalent hydrocarbon group, or an alkali metal atom, and R 2C is a divalent hydrocarbon group, and X C is a hydroxy group, a halogen atom or a (meth)acryloyloxy group.

[0023] [ka]

[0024] In formula (2), R 1 is a hydrogen atom, a monovalent hydrocarbon group, or an alkali metal atom.

[0025] [ka]

[0026] In formula (3), R 2 is a divalent hydrocarbon group, and X is a hydroxy group, a halogen atom, or a (meth)acryloyloxy group. Effect of the Invention

[0027] According to one embodiment of the present disclosure, it is possible to provide a compound production method capable of easily producing a compound having a thiohydantoin skeleton, and a polymerizable composition, a cured product, and a compound each containing the compound produced by the compound production method. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0028] In the present disclosure, a numerical range expressed using "to" means a range that includes the numerical values ​​before and after "to" as the lower and upper limits. In the present disclosure, the term "step" refers not only to an independent step, but also to a step that cannot be clearly distinguished from other steps, as long as the intended purpose of the step is achieved. In the present disclosure, when a plurality of substances corresponding to each component are present in the composition, the amount of each component contained in the composition means the total amount of the plurality of substances present in the composition, unless otherwise specified. In the numerical ranges described in the present disclosure in stages, the upper or lower limit value described in one numerical range may be replaced with the upper or lower limit value of another numerical range described in stages. In addition, in the numerical ranges described in the present disclosure, the upper or lower limit value of the numerical range may be replaced with a value shown in the examples. In the present disclosure, a (meth)acryloyloxy group refers to an acryloyloxy group or a methacryloyloxy group, and a (meth)acrylate refers to an acrylate or a methacrylate.

[0029] <Method for producing compound represented by formula (1)> The method for producing a compound represented by formula (1) of the present disclosure is a method for producing a compound represented by the following formula (1) (also referred to as compound (1)), and includes a step of reacting a compound represented by the following formula (2) (also referred to as compound (2)) with a compound represented by the following formula (3) (also referred to as compound (3)) in the presence of an acid or a base to obtain the compound represented by formula (1) (also referred to as a "compound production step" in the present disclosure).

[0030] [ka]

[0031] In formulas (1) to (3), R 1 is a hydrogen atom, a monovalent hydrocarbon group, or an alkali metal atom, and R 2 is a divalent hydrocarbon group, and X is a hydroxy group, a halogen atom, or a (meth)acryloyloxy group.

[0032] The method for producing compound (1) includes the above-mentioned compound production steps, and thus can easily produce a compound having a thiohydantoin skeleton. As described above, a compound having a thiohydantoin skeleton such as compound (1) can usually be obtained, for example, by a method in which compound (2) is subjected to a hydrolysis reaction, and then the compound is subjected to a dehydration condensation reaction with a compound having a hydroxy group. However, the above-mentioned method using dehydration condensation often requires a large amount of organic solvent, a great deal of labor, and the like. In contrast, the method for producing compound (1) can produce compound (1) as long as it includes the above-mentioned compound production step, even if it does not include any other steps. That is, compound (1) can be produced without carrying out many steps spanning multiple stages, thereby reducing the labor required for production.

[0033] In the above-mentioned method using dehydration condensation, an active ester is generated as a reaction intermediate by the condensation reaction of a carboxyl group, but this active ester group may react with a nitrogen atom of an amide in the molecule to return to the original compound (2), which may occur as a competing reaction, and this may result in a significant decrease in the yield of the target product, compound (1).

[0034] In contrast, in the production method of compound (1), since no dehydration condensation reaction occurs, the yield of compound (1) can be further improved. That is, the method for producing compound (1) can perform the hydrolysis step, which requires a lot of labor, and the esterification step, which has a low yield, in a single step. Furthermore, the method for producing compound (1) can produce compound (1) in a high yield without using a special reagent such as a dehydration condensation agent.

[0035] <Compound manufacturing process> The compound production process in the present disclosure is a process in which compound (2) and compound (3) are reacted in the presence of an acid or a base to obtain compound (1).

[0036] In the compound production process, compound (1) can be obtained by reacting compound (2) with compound (3) without going through multiple steps. That is, in the compound production process, compound (1) can be obtained in one step by reacting compound (2) with compound (3) in the presence of an acid or a base.

[0037] Specifically, the compound production process may include a step of mixing an acid or a base, compound (2), and compound (3) to obtain a mixture, and a step of reacting compound (2) with compound (3) in the mixture to obtain compound (1).

[0038] The acid and base are not particularly limited. Examples of the acid to be used include sulfonic acids such as methanesulfonic acid, paratoluenesulfonic acid, and camphorsulfonic acid; Carboxylic acids such as trichloroacetic acid, trifluoroacetic acid, formic acid, citric acid, and oxalic acid; Mineral acids such as hydrochloric acid, sulfuric acid, and nitric acid; phosphoric acid, pyrophosphoric acid, and other phosphoric acids; Lewis acids, such as tetraisopropyl orthotitanate, aluminum isopropoxide, boron trifluoride ethyl ether complex, silver trifluoromethanesulfonate, and copper trifluoromethanesulfonate; etc. Of the above, the acid used is preferably methanesulfonic acid or paratoluenesulfonic acid.

[0039] The base to be used is not particularly limited as long as it has the ability to deprotonate the substrate. For example, alkali metal carbonates such as sodium carbonate and potassium carbonate; Alkali metal bicarbonates such as sodium bicarbonate and potassium bicarbonate; Organic bases such as triethylamine, N,N-dimethylaniline, and pyridine; Metal hydrides such as sodium hydride and potassium hydride; Metal alkoxides such as sodium methoxide, sodium ethoxide, potassium tert-butoxide, etc.; and the like. Among the above, the base to be used is preferably an organic base, and more preferably sodium methoxide.

[0040] <Solvent> The solvent used in the reaction includes water, an organic solvent, and the like.

[0041] (Organic solvent) In the compound production process of the present disclosure, the reaction between compound (2) and compound (3) is preferably carried out in an organic solvent. As described above, since there is no need to use a hydrolysis reaction, 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 aprotic solvents 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, Ether solvents such as 1,4-dioxane; Hydrocarbon solvents such as n-pentane, n-hexane, n-heptane, and cyclohexane Aromatic hydrocarbon solvents such as benzene, toluene, xylene, chlorobenzene, and dichlorobenzene; Halocarbons such as dichloromethane, dichloroethane, and chloroform; Nitrile solvents such as acetonitrile and propionitrile; Ester solvents such as methyl acetate, ethyl acetate, and butyl acetate; Amide solvents such as dimethylformamide, dimethylacetamide, and 1,3-dimethylimidazolidinone; and the like.

[0042] In the compound production process, the content of the organic solvent is preferably 90% by mass or more, more preferably 95% by mass or more, and even 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.

[0043] (water) As described above, the method for producing compound (1) does not require the use of a hydrolysis reaction, and therefore does not require the use of water. In the compound production process, the content of water is preferably less than 5% by mass, more preferably less than 1% by mass, and even more preferably less than 0.1% by mass, based on the total mass of the solvent. The content of the organic solvent may be more than 0 mass % or may be 0.01 mass % or more, based on the total mass of the solvent.

[0044] In the compound production process of the present disclosure, the following compound (2) is reacted with compound (3) in the presence of an acid or a base to obtain the following compound (1).

[0045] [ka]

[0046] In formula (1), R 1 is a hydrogen atom, a monovalent hydrocarbon group, or an alkali metal atom, and R 2 is a divalent hydrocarbon group, and X is a hydroxy group, a halogen atom, or a (meth)acryloyloxy group.

[0047] In formula (1), R 1 is preferably a hydrogen atom or a monovalent hydrocarbon group, and more preferably a hydrogen atom. In formula (1), X is preferably a hydroxy group or a (meth)acryloyloxy group, and more preferably a (meth)acryloyloxy group.

[0048] [ka]

[0049] In formula (2), R 1 is a hydrogen atom, a monovalent hydrocarbon group, or an alkali metal atom. In formula (2), R 1 is preferably a hydrogen atom or a monovalent hydrocarbon group, and more preferably a hydrogen atom.

[0050] [ka]

[0051] In formula (3), R 2 is a divalent hydrocarbon group, and X is a hydroxy group, a halogen atom, or a (meth)acryloyloxy group. In formula (3), X is preferably a hydroxy group or a (meth)acryloyloxy group, and more preferably a (meth)acryloyloxy group.

[0052] In formula (1) and formula (3), X is preferably a (meth)acryloyloxy group.

[0053] R in formula (1) and formula (2) 1 The monovalent hydrocarbon group in may be a saturated hydrocarbon group or an unsaturated hydrocarbon group. R in formula (1) and formula (2) 1 The monovalent hydrocarbon group in may or may not have a cyclic structure (eg, an aromatic structure, an alicyclic structure, etc.).

[0054] In formula (1) and formula (2), R 1 Examples of the alkali metal atom in the formula include lithium, sodium, and potassium.

[0055] R in formula (1) and formula (3) 2 The divalent hydrocarbon group may have, for example, 1 to 30 carbon atoms or 2 to 30 carbon atoms.

[0056] R in formula (1) and formula (3) 2 The divalent hydrocarbon group in may be a saturated hydrocarbon group or an unsaturated hydrocarbon group. R in formula (1) and formula (3) 2 The divalent hydrocarbon group in may or may not have a cyclic structure (eg, an aromatic structure, an alicyclic structure, etc.).

[0057] R in formula (1) and formula (3) 2preferably contains at least one group selected from the group consisting of 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 linear saturated hydrocarbon group, and more preferably contains at least one group selected from the group consisting of a divalent group represented by the following formula (4), and a divalent linear saturated hydrocarbon group:

[0058] [ka]

[0059] In formula (4), Y 1 and Y 2 each independently represents an oxygen atom, a divalent group represented by -CH-, or a divalent group represented by -NH-; Y 3 is an oxygen atom or a sulfur atom.

[0060] Examples of the divalent group represented by formula (4) include a divalent group represented by -NH-C(=O)-O-, a divalent group represented by -OC(=O)-CH2-, a divalent group represented by -OC(=O)-O-, a divalent group represented by -NH-C(=O)-NH-, and divalent groups in which "=O" is replaced with "=S" in these groups. Among these, a divalent group represented by -OC(=O)-CH2- is preferable.

[0061] In the case of a divalent group represented by -OC(=O)-CH2- or -OC(=S)-CH2-, it is preferable that -CH2- is bonded so as to face the thiohydantoin skeleton. In the case of a divalent group represented by -NH-C(=O)-O- or -NH-C(=S)-O-, it is preferable that -O- is bonded so as to face the thiohydantoin skeleton.

[0062] R in formula (1) and formula (3) 2 It is also preferable that the alkylene group has 2 to 20 carbon atoms.

[0063] Specific examples of compound (1) include the compounds shown below. However, compound (1) in the present disclosure is not limited to the specific examples below.

[0064] [ka]

[0065] [ka]

[0066] [ka]

[0067] The yield of compound (1) is preferably 50% by mass or more, more preferably 55% by mass or more, and even more preferably 60% by mass or more. The yield (%) of a compound is calculated by dividing the isolated yield (mass) of the compound by the theoretical yield (mass) of the compound and multiplying the result by 100. The yield of compound (1) is 1 It can be measured using H-NMR or HPLC.

[0068] 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 formula (1A) and the method for producing the compound represented by formula (1B) can obtain the compound represented by formula (1A) and the compound represented by formula (1B) by using compound (1) produced by the above-mentioned method for producing compound (1).

[0069] <Method for producing the compound represented by formula (1A)> The method for producing a compound represented by formula (1A) is a method for producing a compound represented by formula (1A), comprising the steps of: producing a compound represented by formula (1), in which X in formula (1) is a hydroxy group, by a method for producing compound (1); and reacting a compound represented by formula (1), in which X in formula (1) is a hydroxy group, with a (meth)acrylic acid halide, (meth)acrylic acid, or (meth)acrylic anhydride to obtain a compound represented by formula (1A).

[0070] [ka]

[0071] In formula (1A), R 1A is a hydrogen atom, a monovalent hydrocarbon group, or an alkali metal atom, and R 2A is a divalent hydrocarbon group, and X A is a (meth)acryloyloxy group. R 1A Preferred embodiments of and R 2A A preferred embodiment of the present invention is R 1 Preferred embodiments of and R 2 This is similar to the preferred embodiment of the above.

[0072] <Method for producing the compound represented by formula (1B)> The method for producing a compound represented by formula (1B) is a method for producing a compound represented by the following formula (1B), which includes the steps of producing a compound represented by formula (1) in which X in formula (1) is a halogen atom, by the method for producing a compound of the present disclosure; and reacting a compound represented by formula (1), in which X in formula (1) is a halogen atom, with a (meth)acrylate salt to obtain a compound represented by formula (1B).

[0073] [ka]

[0074] In formula (1B), R 1Bis a hydrogen atom, a monovalent hydrocarbon group, or an alkali metal atom, and R 2B is a divalent hydrocarbon group, and X B is a (meth)acryloyloxy group. R 1B Preferred embodiments of and R 2B A preferred embodiment of the present invention is R 1 Preferred embodiments of and R 2 This is similar to the preferred embodiment of the above.

[0075] <Method for producing compound represented by formula (5)> The method for producing a compound represented by formula (5) is a method for producing a compound represented by the following formula (5) (also referred to as compound (5)), and includes a step of reacting the following compound (2) with the following compound (3) in the presence of an acid or a base to obtain the compound represented by formula (5).

[0076] [ka]

[0077] In formula (5), R 1C is a hydrogen atom, a monovalent hydrocarbon group, or an alkali metal atom, and R 2C is a divalent hydrocarbon group, and X C is a hydroxy group, a halogen atom or a (meth)acryloyloxy group.

[0078] [ka]

[0079] In formula (2), R 1 is a hydrogen atom, a monovalent hydrocarbon group, or an alkali metal atom. In formula (2), R 1 A preferred embodiment of the formula is R 1 This is similar to the preferred embodiment of the above.

[0080] [ka]

[0081] In formula (3), R 2 is a divalent hydrocarbon group, and X is a hydroxy group, a halogen atom, or a (meth)acryloyloxy group. In formula (3), R 2 A preferred embodiment of the formula is R 2 This is similar to the preferred embodiment of the above.

[0082] Similarly to the above-mentioned method for producing compound (1), compound (5) can also be obtained by reacting compound (2) with compound (3) in the presence of an acid or a base. In this case, compound (5) and compound (1) can both be obtained by reacting compound (2) with compound (3) in the presence of an acid or a base.

[0083] According to the method for producing compound (5), the following compound (5) can be obtained.

[0084] [ka]

[0085] In formula (5), R 1C is a hydrogen atom, a monovalent hydrocarbon group, or an alkali metal atom, and R 2C is a divalent hydrocarbon group, and X C is a hydroxy group, a halogen atom or a (meth)acryloyloxy group. In formula (5), R 1C A preferred embodiment of R 2C Preferred embodiments of the formula: C A preferred embodiment of the formula is R 1 A preferred embodiment of R 2 The preferred embodiments are the same as those of the above and the preferred embodiments of X.

[0086] The compound represented by formula (5) can be used as a polymerizable monomer in combination with the compound represented by formula (1). In particular, the compound represented by formula (5) can be produced simultaneously with the compound represented by formula (1). That is, when both are used in combination, they can be produced separately and used without the need for additional addition, which is useful in terms of simplicity. In addition, the compound represented by formula (5) does not easily suppress the adhesive performance of the compound represented by formula (1).

[0087] ≪Polymerizable composition≫ The polymerizable composition of the present disclosure contains compound (1) of the present disclosure. The polymerizable composition of the present disclosure has high adhesiveness and adhesion-promoting effects to metals, particularly to precious metals such as gold, silver, platinum, and palladium, or alloys containing precious metals (hereinafter also referred to as "precious metal alloys"). Here, the "adhesion promoting effect" refers to the effect of enhancing the adhesiveness of an adhesive used when the polymerizable composition of the present disclosure is used as a primer as described below.

[0088] The polymerizable composition of the present disclosure is suitable for use in medical or dental applications. For example, the polymerizable composition of the present disclosure is useful as an adhesive, a primer, a bone cement, a bonding material, a sealant, a cement, a filling material, a lining material, a core structure, a material for fixing loose teeth, or a root canal filling material. Among these, the polymerizable composition of the present disclosure is suitably used as an adhesive. INDUSTRIAL APPLICABILITY The polymerizable composition of the present disclosure is useful as an adhesive between an adherend such as dentin and a precious metal or precious metal alloy, an adhesive between precious metals or precious metal alloys, or a primer (pretreatment material) applied to the adhesion surface of a precious metal or precious metal alloy to promote adhesion between an adherend such as dentin and a precious metal or precious metal alloy, or to promote adhesion between precious metals or precious metal alloys.

[0089] In addition, the polymerizable composition of the present disclosure contains compound (1), but compound (1) has little adverse effect such as a large decrease in adhesive strength to a tooth surface or a ceramic surface such as zirconium oxide. In addition, even if compound (1) is contained in a conventional adhesive, the adverse effect on the adhesive strength to a tooth surface or a ceramic surface is small.

[0090] Examples of the object to be bonded made of the above-mentioned precious metal or precious metal alloy include prosthetic devices such as inlays, onlays, crowns, bridges, and dentures.

[0091] The polymerizable composition of the present disclosure can be fully utilized as an adhesive in fields requiring adhesion between organic materials and precious metals or precious metal alloys (e.g., precision machinery, jewelry industry, etc.). In other words, 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, or a jewelry adhesive, and can also be added to paints, gap fillers, construction adhesives, coating materials, and the like.

[0092] The polymerizable composition of the present disclosure may be a one-part type or one-paste type, or may be a multi-part type such as a two-part type, a powder / liquid type, or a paste & paste type. In the case of a multi-drug type, for example, each component stored in a divided state can be mixed immediately before use.

[0093] 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).

[0094] [ka]

[0095] In formula (1), R 1 is a hydrogen atom, a monovalent hydrocarbon group, or an alkali metal atom, and R 2 is a divalent hydrocarbon group, and X is a hydroxy group, a halogen atom, or a (meth)acryloyloxy group.

[0096] [ka]

[0097] In formula (5), R1C is a hydrogen atom, a monovalent hydrocarbon group, or an alkali metal atom, and R 2C is a divalent hydrocarbon group, and X C is a hydroxy group, a halogen atom or a (meth)acryloyloxy group.

[0098] 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 content of compound (1) is preferably 60% by mass to 95% by mass, and more preferably 70% by mass to 95% by mass, based on the total content of compound (1) and compound (5).

[0099] The polymerizable composition of the present disclosure may contain components other than the above-mentioned compound (1) and compound (5). The polymerizable composition of the present disclosure may further contain, as other components, at least one selected from a radically polymerizable monomer (B), a silane coupling agent (C), a filler (D), a polymerization initiator (E), a reducing compound (F), an organic solvent (G), and water (H). Specific examples and preferred aspects of the radical polymerizable monomer (B), silane coupling agent (C), filler (D), polymerization initiator (E), reducing compound (F), organic solvent (G), and water (H) in the present disclosure are the same as the specific examples and preferred aspects of the radical polymerizable monomer (B), silane coupling agent (C), filler (D), polymerization initiator (E), reducing compound (F), organic solvent (G), and water (H) described in WO 2020 / 032268.

[0100] The cured product of the present disclosure is a cured product of the polymerizable composition of the present disclosure. After the polymerizable composition is applied to the object to be bonded, the polymerizable composition is cured, whereby the cured composition and the object to be bonded are fixed in contact with each other. Furthermore, by applying the polymerizable composition between objects to be bonded and then curing the polymerizable composition, the objects to be bonded can be fixed in an adhered state. EXAMPLES

[0101] Hereinafter, the embodiments of the present disclosure will be described in detail with reference to examples. Note that the present disclosure is not limited to the description of these examples. In the present examples, the yield (%) of a compound was calculated by dividing the isolated yield (mass) of the compound by the theoretical yield (mass) of the compound and multiplying the result by 100.

[0102] Example 1 <Synthesis of bicyclic compound (a1) by cyclization reaction of 2-pyrrolidone-5-carboxylic acid with ammonium thiocyanate> As shown in the following reaction scheme, the bicyclic compound (a1) was synthesized by the cyclization reaction of 2-pyrrolidone-5-carboxylic acid with ammonium thiocyanate.

[0103] [ka]

[0104] Specifically, 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) of acetic acid, and 64.8 g of ammonium thiocyanate were placed in a 1000 mL four-neck flask to prepare a suspension, which was then stirred at 100° C. for 2 hours. Next, the resulting mixture was allowed to cool to below 60°C, and 756mL of a mixed solvent (ethyl acetate:hexane = 1:1) was added and stirred. Then, it was ice-cooled to below 5°C and stirred for 1 hour. The suspension was filtered in the cold using filter paper (No. 5C, Kiriyama Seisakusho), and washed by adding a total of 700mL of a mixed solvent (ethyl acetate:hexane = 1:1) in three portions. 70.3g of compound (a1) was obtained as a brown solid (yield 53%). Here, the yield (%) of compound (a1) was calculated by dividing the isolated yield (mass) of compound (a1) by the theoretical yield (mass) of compound (a1) and multiplying the result by 100. The NMR analysis results of compound (a1) are shown below. 1H-NMR(270MHz,DMSO-d6)δ:12.4(1H,brd.s),4.91(1H,t,J=8.9Hz),2.85(1H,m),2.52(1H,m),2.13-2.38(2H,m).

[0105] <Synthesis of thiohydantoin compounds (a2) and (a3) ​​by ring-opening esterification of compound (a1) with 10-hydroxydecyl methacrylate> As shown in the following reaction formula, thiohydantoin compounds (a2) and (a3) ​​were synthesized by ring-opening esterification reaction of compound (a1) with 10-hydroxydecyl methacrylate.

[0106] [ka]

[0107] Specifically, 70.2 g (413 mmol) of compound (a1), 105 g (433 mmol) of 10-hydroxydecyl methacrylate, 3.97 g (41.3 mmol, compound (a5)) of methanesulfonic acid, and 0.735 g of 2,6-di-tert-butyl-p-cresol were placed in a 1000 mL four-neck flask, and 351 g of toluene was added to dissolve them. The resulting solution was stirred at 100° C. for 2 hours. Next, the resulting mixture was purified by silica gel column chromatography (column: silica gel C-100 1020 g, elution solvent: ethyl acetate-hexane gradient (ethyl acetate 25% to 33%)) to obtain 82.2 g (yield 60%) of compound (a2) and 13.7 g (yield 10%) of compound (a3) ​​as pale yellow solids. The yields of the above compounds (a2) and (a3) ​​are relative to the compound (a1). In addition, the yield (%) of the mixture of compound (a2) and compound (a3) ​​was obtained by dividing the isolated yield (mass) of the mixture of compound (a2) and compound (a3) ​​by the theoretical yield (mass) of the mixture of compound (a2) and compound (a3) ​​and multiplying the result by 100. The NMR analysis results of compound (a2) and compound (a3) ​​are shown below. compound (a2) 1 H-NMR(270MHz,DMSO-d6)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 H-NMR(270MHz,DMSO-d6)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).

[0108] Comparative Example 1 <Synthesis of Carboxylic Acid (a4) by Hydrolysis of Bicyclic Compound (a1)> As shown in the following reaction formula, the compound (a1) was hydrolyzed to synthesize the carboxylic acid compound (a4).

[0109] [ka]

[0110] 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 recovery flask, and the mixture was stirred for 4 hours at 75° C. The resulting solution was concentrated under reduced pressure to obtain 55.75 g of an oily product. Next, the oily material was dissolved in 200 mL of ethyl acetate and transferred to a separatory funnel. After washing with water (200 mL), the ethyl acetate layer was separated. 20 g of salt was added to the obtained aqueous layer and dissolved, and extracted with ethyl acetate (150 mL). This extraction operation was repeated six times. After combining the 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 material, 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 obtain 36.9 g (76% yield) of compound (a4) as a white solid. The NMR analysis results of the obtained compound (a4) are shown below. 1 H-NMR(270MHz,CDCl3)δ:12.2(1H,brd.s),11.1(1H,brd.s),10.1(1H,brd.s), 4.23(1H,t,J=6.3),2.34(2H,t,J=7.6),1.94(1H,m),1.76(1H,m).

[0111] <Synthesis of thiohydantoin compound (a2) by condensation of carboxylic acid compound (a4) with 10-hydroxydecyl methacrylate> As shown in the following reaction formula: The thiohydantoin compound (a2) was synthesized by the condensation reaction of the carboxylic acid compound (a4) with 10-hydroxydecyl methacrylate.

[0112] [ka]

[0113] Specifically, first, under a nitrogen atmosphere, 4.45 g (23.6 mmol) of compound (a4), 6.88 g (28.4 mmol) of 10-hydroxydecyl methacrylate (compound (a5)), 7.0 mg of 2,6-di-tert-butyl-4-methylphenol, and 0.58 g (4.73 mmol) of 4-dimethylaminopyridine were charged into a 300 mL four-neck flask, and 90 mL of tetrahydrofuran was added to dissolve them. At room temperature, a solution of 5.82 g (24.8 mmol) of dicyclohexylcarbodiimide dissolved in 30 mL of tetrahydrofuran was dropped into the flask and 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 stirred for 10 minutes. The mixture that became a white slurry in the flask was filtered through Celite, and the filtrate was concentrated under reduced pressure to obtain an oily product. Next, the obtained oily matter was purified twice by silica gel chromatography (column: Biotage SNAP KP-Sil Cartridge 100 g; elution solvent: ethyl acetate-hexane gradient: ethyl acetate 5% → 100%) to obtain 4.79 g of compound (a2) as a colorless oily matter (yield: 49%). The yield of the compound (a2) is the yield relative to the compound (a4). The NMR analysis results of the obtained compound (a2) are shown below. 1 H-NMR(270MHz,CDCl3)δ:8.45(1H,brd.s),7.53(1H,brd.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).

[0114] As described above, in Example 1, the compound production method including the step of reacting compound (2) (i.e., compound (a1)) with compound (3) (i.e., compound (a5)) in the presence of an acid or a base to obtain compound (1) (i.e., compound (a2)) was used, which enabled compound (1) to be produced from compound (2) and compound (3) in one step, thereby enabling the easy production of a compound having a thiohydantoin skeleton. On the other hand, in Comparative Example 1 in which compound (2) (i.e., compound (a1)) was first hydrolyzed to obtain a hydrolyzed compound (i.e., compound (a4)), and then the hydrolyzed compound was reacted with compound (3) (i.e., compound (a5)) to obtain compound (1) (i.e., compound (a2)) as a dehydration condensation product, it was not possible to produce compound (1) from compound (2) and compound (3) in one step, and it was not possible to simply produce a compound having a thiohydantoin skeleton. Moreover, Example 1 was superior to Comparative Example 1 in the yield of compound (a2).

Claims

1. A method for producing a compound represented by the following formula (1): A method for producing a compound, comprising the 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 formula (1): 【Chemistry 1】 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 or a divalent group containing at least one group selected from the group consisting of 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 linear saturated hydrocarbon group, When R 2 is a divalent group containing an ether bond, R 2 contains a divalent hydrocarbon group, X is a hydroxy group, a halogen atom or a (meth)acryloyloxy group. 【Chemistry 2】 In formula (4), Y 1 and Y 2 each independently represent an oxygen atom, a divalent group represented by —CH 2 —, or a divalent group represented by —NH—, and Y 3 represents an oxygen atom or a sulfur atom.

2. The method for producing the 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.

3. The R in the formula (1) and the formula (3) ２ The method for producing the compound according to claim 1 or 2, wherein is an alkylene group having 2 to 20 carbon atoms.

4. The method for producing a compound according to any one of claims 1 to 3, wherein X in the formula (1) and the formula (3) is a (meth)acryloyloxy group.

5. A method for producing a compound represented by formula (1A), comprising the steps of: A process for producing a compound represented by the formula (1) in which X in the formula (1) is a hydroxy group, by the process for producing a compound according to any one of claims 1 to 3; and a step of reacting a compound represented by formula (1), in which X in formula (1) is a hydroxy group, with a (meth)acrylic acid halide, (meth)acrylic acid, or (meth)acrylic anhydride to obtain a compound represented by formula (1A). 【Chemistry 3】 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 or a divalent group containing at least one group selected from the group consisting of a divalent group represented by formula (4), an ether bond, a 1,4-phenylene group, a 1,4-cyclohexylene group, and a divalent chain saturated hydrocarbon group, When R 2A is a divalent group containing an ether bond, R 2A contains a divalent hydrocarbon group, X Ａ is a (meth)acryloyloxy group.

6. A method for producing a compound represented by the following formula (1B): A process for producing a compound represented by the formula (1) in which X in the formula (1) is a halogen atom, by the process for producing a compound according to any one of claims 1 to 3; and a step of reacting a compound represented by formula (1), in which X in formula (1) is a halogen atom, with a (meth)acrylate salt to obtain a compound represented by formula (1B). 【Chemistry 4】 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 or a divalent group containing at least one group selected from the group consisting of a divalent group represented by formula (4), an ether bond, a 1,4-phenylene group, a 1,4-cyclohexylene group, and a divalent chain saturated hydrocarbon group, When R 2B is a divalent group containing an ether bond, R 2B contains a divalent hydrocarbon group, X Ｂ is a (meth)acryloyloxy group.

7. A polymerizable composition comprising a compound represented by the following formula (1) and a compound represented by the following formula (5): 【Chemistry 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 or a divalent group containing at least one group selected from the group consisting of 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 linear saturated hydrocarbon group, When R 2 is a divalent group containing an ether bond, R 2 contains a divalent hydrocarbon group, X is a hydroxy group, a halogen atom or a (meth)acryloyloxy group. 【Chemistry 6】 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 or a divalent group containing at least one group selected from the group consisting of 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 linear saturated hydrocarbon group, When R 2C is a divalent group containing an ether bond, R 2C contains a divalent hydrocarbon group, X Ｃ is a hydroxy group, a halogen atom or a (meth)acryloyloxy group. 【Chemistry 7】 In formula (4), Y 1 and Y 2 each independently represent an oxygen atom, a divalent group represented by —CH 2 —, or a divalent group represented by —NH—, and Y 3 represents an oxygen atom or a sulfur atom.

8. The polymerizable composition according to claim 7, wherein the content of the compound represented by formula (1) is 60% by mass to 95% by mass with respect to the total content of the compound represented by formula (1) and the compound represented by formula (5).

9. The polymerizable composition according to claim 7 or 8, which is used as an adhesive.

10. A cured product of the polymerizable composition according to any one of claims 7 to 9.

11. A compound represented by the following formula (5): 【Chemistry 8】 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 or a divalent group containing at least one group selected from the group consisting of 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 linear saturated hydrocarbon group, When R 2C is a divalent group containing an ether bond, R 2C contains a divalent hydrocarbon group, X Ｃ is a hydroxy group, a halogen atom or a (meth)acryloyloxy group. 【Chemistry 9】 In formula (4), Y 1 and Y 2 each independently represent an oxygen atom, a divalent group represented by —CH 2 —, or a divalent group represented by —NH—, and Y 3 represents an oxygen atom or a sulfur atom.

12. A method for producing a compound represented by the following formula (5): A method for producing a compound, comprising the 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 formula (5): 【Chemistry 10】 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 or a divalent group containing at least one group selected from the group consisting of 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 linear saturated hydrocarbon group, When R 2C is a divalent group containing an ether bond, R 2C contains a divalent hydrocarbon group, X Ｃ is a hydroxy group, a halogen atom or a (meth)acryloyloxy group. 【Chemistry 11】 In formula (2), R 1 is a hydrogen atom, a monovalent hydrocarbon group or an alkali metal atom. 【Chemistry 12】 In formula (3), R 2 is a divalent hydrocarbon group or a divalent group containing at least one group selected from the group consisting of 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 linear saturated hydrocarbon group, When R 2 is a divalent group containing an ether bond, R 2 contains a divalent hydrocarbon group, X is a hydroxy group, a halogen atom or a (meth)acryloyloxy group. 【Chemistry 13】 In formula (4), Y 1 and Y 2 each independently represent an oxygen atom, a divalent group represented by —CH 2 —, or a divalent group represented by —NH—, and Y 3 represents an oxygen atom or a sulfur atom.

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