(Meth)acrylamide compound production method

Abstract

A production method for a (meth)acrylamide compound that includes a step for reacting (meth)acrylic acid with a primary amine compound in the presence of a condensing agent to synthesize a (meth)acrylamide compound (X).

Description

Technical Field

[0001] The present disclosure relates to a method for producing a (meth)acrylamide compound.

Background Art

[0002] (Meth)acrylate compounds are widely used as monomers in curable compositions. For example, Patent Document 1 discloses a (meth)acrylate (D) as a monomer capable of providing a cured product having both high toughness and rigidity. The (meth)acrylate (D) in this document is a reaction product of a thiol compound (A) having two or more mercapto groups, an iso(thio)cyanate compound (B) having two or more iso(thio)cyanate groups, and a hydroxy(meth)acrylate compound (C) having one or more polymerizable groups. This document also discloses a composition containing the (meth)acrylate (D).

[0003] Patent Document 1: International Publication No. 2019 / 107323

Summary of the Invention

Problems to be Solved by the Invention

[0004] (Meth)acrylate compounds are known as monomers exhibiting polymerizability. For example, (meth)acrylate compounds may be used as monomers contained in monomer compositions for dental materials. (Meth)acrylate compounds are monomers used in various applications, and are required to be produced by a simple production method.

[0005] One problem to be solved by an aspect of the present disclosure is to provide a simple method for producing a (meth)acrylamide compound.

Means for Solving the Problems

[0006] Means for solving the above problems include the following aspects. <1> A method for producing a (meth)acrylamide compound, comprising a step of reacting (meth)acrylic acid with a primary amine compound in the presence of a condensing agent to synthesize a (meth)acrylamide compound (X). <2> The method for producing a (meth)acrylamide compound according to <1>, wherein the condensing agent is a carbodiimide compound represented by the following formula (Z) or a hydrochloride of a carbodiimide compound containing an amino group among the carbodiimide compounds represented by the following formula (Z).

[0007]

Chemical formula

[0008] In formula (Z), R 1Z and R 2Z are each independently a hydrocarbon group having 1 to 10 carbon atoms which may be substituted with an amino group. <3> The method for producing a (meth)acrylamide compound according to <1> or <2>, wherein the condensing agent is a carbodiimide compound represented by the following formula (Z1) or a hydrochloride thereof.

[0009]

Chemical formula

[0010] <4> The method for producing a (meth)acrylamide compound according to any one of <1> to <3>, wherein the primary amine compound is a diamine compound. <5> The step of synthesizing is a step of obtaining a composition containing the (meth)acrylamide compound (X). After the step of synthesizing, the method for producing a (meth)acrylamide compound according to any one of <1> to <4> includes a step of performing acid washing and alkali washing on the composition containing the (meth)acrylamide compound (X).

Advantages of the Invention

[0011] According to one aspect of the present disclosure, a simple method for producing a (meth)acrylamide compound can be provided.

BEST MODE FOR CARRYING OUT THE INVENTION

[0012] In the present disclosure, a numerical range represented by "~" means a range including the numerical values described before and after "~" as the lower limit value and the upper limit value. In the present disclosure, the term "step" includes not only an independent step but also a step in which, even if it cannot be clearly distinguished from other steps, the intended purpose of the step is achieved. In the present disclosure, the amount of each component in the composition means the total amount of the plurality of substances present in the composition when there are a plurality of substances corresponding to each component in the composition, unless otherwise specified. In the numerical ranges described step by step 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 other step-by-step descriptions. Further, in the numerical ranges 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, "light" is a concept including active energy rays such as ultraviolet rays and visible light. In the present disclosure, "(meth)acrylic compound" means an acrylic compound or a methacrylic compound, "(meth)acrylate" means an acrylate or a methacrylate, and "(meth)acrylic acid" means acrylic acid or methacrylic acid.

[0013] ≪METHOD FOR PRODUCING (METH)ACRYLAMIDE COMPOUND≫ The method for producing a (meth)acrylamide compound of the present disclosure (also simply referred to as the production method of the present disclosure) includes a step of reacting (meth)acrylic acid with a primary amine compound in the presence of a condensing agent to synthesize a (meth)acrylamide compound (X) (also referred to as a synthesis step).

[0014] Conventionally, as a method for producing a (meth)acrylamide compound, for example, an acid chloride method in which a (meth)acrylic acid chloride is reacted with a primary amine compound has often been used. In the case of the acid chloride method, there are problems such as time-consuming purification to obtain a (meth)acrylamide compound with high purity and the need to use a column for purification, which is laborious. In contrast, the production method of the present disclosure is a method of subjecting (meth)acrylic acid and a primary amine to a condensation reaction in the presence of a condensing agent. As the condensing agent, for example, carbodiimide is preferably used. By using the production method of the present disclosure, a (meth)acrylamide compound can be easily produced. The production method of the present disclosure can also suppress the coloring of a composition containing a (meth)acrylamide compound (X) obtained by reacting (meth)acrylic acid with a primary amine compound. Further, the production method of the present disclosure does not necessarily require a complicated purification treatment (for example, column purification) for the composition containing the obtained (meth)acrylamide compound (X). In the production method of the present disclosure, for example, purification can also be performed by washing with water. This is one of the factors that improve the simplicity in the production method of the present disclosure. Further, since the production method of the present disclosure does not require a complicated purification treatment, the yield of the product (meth)acrylamide compound is also excellent.

[0015] <Synthesis step> The synthesis step is a step of synthesizing a (meth)acrylamide compound (X) by reacting (meth)acrylic acid with a primary amine compound in the presence of a condensing agent. By the synthesis step, a composition containing a (meth)acrylamide compound (X) may be obtained.

[0016] The reaction time for reacting (meth)acrylic acid with a primary amine compound is preferably 3 hours to 20 hours, more preferably 5 hours to 15 hours, and even more preferably 6 hours to 10 hours.

[0017] The reaction temperature for reacting (meth)acrylic acid with a primary amine compound is preferably from 0°C to 50°C, more preferably from 5°C to 40°C, and even more preferably from 10°C to 40°C.

[0018] (Condensing agent) The production method of the present disclosure uses a condensing agent. The condensing agent in the present disclosure is not particularly limited. For example, carbodiimide-based condensing agents such as N,N'-dicyclohexylcarbodiimide, imidazole-based condensing agents such as N,N'-carbonyldiimidazole, triazine-based condensing agents such as 4-(4,6-dimethoxy-1,3,5-triazin-2-yl)-4-methylmorpholinium chloride n-hydrate, phosphonium-based condensing agents such as 1H-benzotriazol-1-yloxytris(dimethylamino)phosphonium hexafluorophosphate, uronium-based condensing agents such as o-(benzotriazol-1-yl)-N,N,N',N'-tetramethyluronium hexafluorophosphate, and hauronium-based condensing agents such as 2-chloro-1,3-dimethylimidazolinium hexafluorophosphate, etc. can be mentioned. The condensing agent may be in the form of a salt (for example, hydrochloride). For example, as the condensing agent in the present disclosure, it is preferably a carbodiimide-based condensing agent.

[0019] The condensing agent is preferably a carbodiimide compound represented by the following formula (Z) or a hydrochloride of a carbodiimide compound containing an amino group among the carbodiimide compounds represented by the following formula (Z).

[0020] [Chemical formula]

[0021] In formula (Z), R 1Z and R 2Z are each independently a hydrocarbon group having 1 to 10 carbon atoms which may be substituted with an amino group.

[0022] The above amino group is a concept that includes both substituted amino groups and unsubstituted amino groups. The amino group in the present disclosure includes, for example, a monoalkylamino group, a dialkylamino group, and the like.

[0023] "The carbodiimide compound containing an amino group among the carbodiimide compounds represented by formula (Z)" specifically refers to a carbodiimide compound represented by formula (Z), where in formula (Z), R 1Z and R 2Z are each independently a hydrocarbon group having 1 to 10 carbon atoms which may be substituted with an amino group, and at least one of R 1Z and R 2Z may be a carbodiimide compound substituted with an amino group. "The hydrochloride of the carbodiimide compound containing an amino group among the carbodiimide compounds represented by formula (Z)" means the hydrochloride of the above "carbodiimide compound containing an amino group among the carbodiimide compounds represented by formula (Z)".

[0024] R 1Z and R 2Z In, the number of carbon atoms of the hydrocarbon group means the total number of carbon atoms contained in R 1Z and R 2Z For example, when the substituted amino group is contained in R For example, R 1Z and R 2Z when a substituted amino group is contained, in R 1Z and R 2Z the number of carbon atoms of the hydrocarbon group also includes the number of carbon atoms of the substituted amino group.

[0025] It is more preferable that the condensing agent is a carbodiimide compound represented by the following formula (Z1) or a hydrochloride thereof.

[0026]

Chemical formula

[0027] More specific examples of the condensing agent include, for example, 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide (also referred to as EDC), 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride (also referred to as EDC·HCl), N,N'-dicyclohexylcarbodiimide, N,N'-diisopropylcarbodiimide, and the like. Among these, as the condensing agent, 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide and 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride are preferred.

[0028] (Primary amine compound) The production method of the present disclosure uses a primary amine compound. The primary amine compound in the present disclosure is not particularly limited.

[0029] The primary amine compound in the present disclosure may be a monoamine compound or a diamine compound, but a diamine compound is preferred. As the diamine compound, for example, it may or may not contain a cyclic structure, but it preferably contains a cyclic structure.

[0030] From the viewpoint of being able to suppress water absorption when the synthesized (meth)acrylamide compound (X) is cured, the primary amine compound in the present disclosure is more preferably a primary amine compound containing two amino groups and a cyclic structure. When the primary amine compound in the present disclosure contains a cyclic structure, the cyclic structure is not particularly limited. For example, the cyclic structure may be an alicyclic structure or an aromatic structure, but an alicyclic structure is preferred. The number of carbon atoms in the cyclic structure is preferably 4 to 15, and more preferably 6 to 13. The primary amine compound may contain only one cyclic structure or two or more cyclic structures. In the primary amine compound, the cyclic structure and the two amino groups may be directly bonded or bonded via a divalent linking group. Examples of the divalent linking group include a methylene group, an ethylene group, etc., and a methylene group is preferred.

[0031] It is preferable that the primary amine compound contains a compound represented by any one of the following formulas (1-1) to (1-7).

[0032]

Chemical formula

[0033] <(Meth)acrylamide compound (X)> The (meth)acrylamide compound (X) in the present disclosure is synthesized by reacting (meth)acrylic acid with a primary amine compound. The (meth)acrylamide compound (X) preferably contains a cyclic structure and a (meth)acrylamide group. Since the (meth)acrylamide compound (X) has the above structure, a cured product with an increased water absorption rate can be suppressed. As a result, a cured product with a maintained flexural strength can be obtained. Since the cured product in the present disclosure maintains a good flexural strength, for example, the elastic modulus and breaking strength of the cured product can be maintained well.

[0034] The (meth)acrylamide compound (X) is preferably a compound represented by the following formula (1).

[0035]

Chemical formula

[0036] In formula (1), R 1 and R 2 are each independently a hydrogen atom or a methyl group, and R 3 is a divalent group containing two amino groups and a cyclic structure. In formula (1), details such as specific embodiments of the primary amine compound containing two amino groups and a cyclic structure are the same as the details of the specific embodiments of the above primary amine compound.

[0037] R in formula (1) 3 is preferably a group represented by the following formula (1a).

[0038]

Chemical formula

[0039] In formula (1a), X 1 and X 2 are each independently a single bond or a methylene group, Y is a divalent linking group having 6 to 13 carbon atoms containing an alicyclic structure or an aromatic structure, and the two * each represent a bonding position.

[0040] In formula (1a), the divalent linking group in Y preferably has 6 to 10 carbon atoms, more preferably 6 to 8 carbon atoms.

[0041] (Meth)acrylamide compound (X) preferably has a molecular weight of 150 to 500, more preferably 200 to 400, and even more preferably 200 to 350.

[0042] The (meth)acrylamide compound (X) of the present disclosure contains two (meth)acrylamide groups and a divalent alicyclic hydrocarbon group, and it is more preferable that the nitrogen atoms in the two (meth)acrylamide groups are both bonded to the divalent alicyclic hydrocarbon group via a methylene group. The above (meth)acrylamide compound (X) can be produced, for example, by reacting at least one (meth)acrylic compound (X) selected from the group consisting of (meth)acrylic acid and halides of (meth)acrylic acid with a primary amine compound (Y1) containing two amino groups and a divalent alicyclic hydrocarbon group, and in which the nitrogen atoms in the two amino groups are both bonded to the divalent alicyclic hydrocarbon group via a methylene group.

[0043] ≪Monomer composition≫ In the synthesis process of the present disclosure, in the presence of a condensing agent, (meth)acrylic acid and a primary amine compound are reacted to synthesize a (meth)acrylamide compound (X), and a composition containing the above (meth)acrylamide compound (X) (also referred to as a monomer composition) may be obtained.

[0044] The monomer composition in the present disclosure may contain components other than the (meth)acrylamide compound, but preferably substantially does not contain components other than the (meth)acrylamide compound. Thereby, the timing of starting polymerization can be adjusted. That is, when the monomer composition substantially does not contain components other than the (meth)acrylamide compound, curing does not start, and polymerization can be started by adding a polymerization initiator at a desired time.

[0045] From the above viewpoints, for example, in the monomer composition of the present disclosure, the content of the (meth)acrylamide compound (X) is preferably 90% by mass or more, more preferably 95% by mass or more, based on the total mass of the monomer composition. In the monomer composition of the present disclosure, the content of the (meth)acrylamide compound (X) may be 100% by mass or less, or may be 99% by mass or less, based on the total mass of the monomer composition.

[0046] [Purification] The production method of the present disclosure is such that the above synthesis step (i.e., the synthesis process) is a step of obtaining a composition containing the (meth)acrylamide compound (X), and after the above synthesis step, a step of purifying the composition containing the (meth)acrylamide compound (X) may be included. Since the production method of the present disclosure does not require complicated purification such as column purification, the above purification can be a simple purification. Examples of the simple purification include purification by washing with water. Purification by washing with water may specifically be the following embodiment.

[0047] The manufacturing method of the present disclosure is such that the above synthesis step is a step of obtaining a composition containing the (meth)acrylamide compound (X), and after the above synthesis step, it is preferable to include a step of performing acid washing and alkali washing (also referred to as a water washing step) on the composition containing the (meth)acrylamide compound (X). Since the manufacturing method of the present disclosure includes a water washing step, the (meth)acrylamide compound (X) can be purified without performing complicated purification such as column purification, so that the simplicity can be improved.

[0048] In the water washing step, acid washing and alkali washing may each be independently performed one or more times, or two or more times.

[0049] The monomer composition of the present disclosure is preferably for dental materials. Examples of dental materials include dental restorative materials, denture base resins, denture base liners, impression materials, luting materials (resin cements, resin-added glass ionomer cements, etc.), dental adhesives (orthodontic adhesives, cavity coating adhesives, etc.), dental fissure sealants, CAD / CAM resin blocks, temporary crowns, artificial tooth materials, and the like. Examples of dental restorative materials include composite resins for crowns, composite resins for filling carious cavities, composite resins for building abutments, and composite resins for filling and restoration.

Examples

[0050] Hereinafter, the present disclosure will be described more specifically with reference to examples, but the present disclosure is not limited to the following examples. The abbreviations of the compounds used in the examples of the present disclosure are shown below. EDC·HCl: 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride Salt D CM: Dichloromethane TEA: Triethylamine MACl: Methacrylic acid chloride AcOEt: Ethyl acetate MeOH: Methanol NBDA: Bis(aminomethyl)norbornane XDA: m-Xylylenediamine DODA: 1,2-Bis(2-aminoethoxy)ethane H6XDA: 1,3-Bis(aminomethyl)cyclohexane IPDA: Isophoronediamine ン (This "ン" seems to be an incomplete or incorrect character. It might be a misprint. Without more context, it's hard to provide a more meaningful translation for it. For now, it remains as "ン".)

[0051] The structural formulas of the above NBDA, H6XDA, IPDA, XDA, D-400, D-2000, and DODA are as follows.

[0052] [Chemical formula]

[0053] [Chemical formula]

[0054] [HPLC measurement method] The HPLC chart spectrum of the (meth)acrylamide compound obtained in each example or comparative example was measured using an HPLC device: LC-20AT manufactured by Shimadzu Corporation. After dissolving the (meth)acrylamide compound obtained in each example or comparative example in CH3CN, the measurement was performed with an eluent of CH3CN / H2O = 90 / 10 for the above (meth)acrylamide compound.

[0055] [IR spectrum measurement method] The IR spectrum of the (meth)acrylamide compound obtained in each production example was measured using a Fourier transform infrared spectrometer, Spectrum Two / UATR (Universal Attenuated Total Reflectance), manufactured by PerkinElmer Japan Co., Ltd. After allowing the obtained (meth)acrylamide compound to stand at 20°C for 24 hours, the infrared absorption spectrum of the (meth)acrylamide compound was measured at 20°C.

[0056] [Example 1: Condensation of NBDA + Methacrylic Acid] 17.22 parts by mass of methacrylic acid and 100 parts by mass of DCM were charged into a 300 mL four-necked flask equipped with a sufficiently dried stirring blade and a thermometer, and dissolved. Then, the solution was cooled to 10 °C, and 38.34 parts by mass of EDC·HCl was charged in portions so that the internal temperature did not exceed 10 °C. After dissolution to form a homogeneous solution, the reaction was carried out at 10 °C for 0.5 hour. 15.43 parts by mass of NBDA was added dropwise to the solution over 0.5 hour. Since the internal temperature rose due to the heat of reaction during the dropwise addition, the dropwise addition amount was controlled so that it was 30 °C or lower. After the total amount was added dropwise, the reaction temperature was maintained at 30 °C, and the reaction was carried out for 6 hours. The reaction mass was a colorless transparent liquid. At this time, the progress of the reaction was traced by HPLC analysis to confirm the end point of the reaction. 50 parts by mass of a 5% aqueous citric acid solution was added to the flask, stirred for 10 minutes, and then the aqueous layer was discharged. The same operation was carried out in the order of distilled water, 5% aqueous sodium carbonate solution, and distilled water. The treatment time for the water washing step was 1 hour. The remaining DCM layer was distilled off with an evaporator for 2 hours to obtain methacrylamide (1) as a white solid. The total treatment time was 3 hours. The yield by this production method was 21.0 g. The yield, purity, reaction time, and treatment time are summarized in Table 1. IR spectrum of methacrylamide (1) was measured, and the attenuation of the peak intensity of the amino group at 3200 cm -1 ~3500 cm -1 was confirmed. The structure of methacrylamide (1) was confirmed to be the following structure.

[0057] [Chemical formula]

[0058] [Example 2: Condensation of XDA + Methacrylic Acid Product] 17.22 parts by mass of methacrylic acid and 100 parts by mass of DCM were charged into a 300 mL four-necked flask equipped with a well-dried stirring blade and a thermometer and dissolved. Then, the solution was cooled to 10 °C, and 38.34 parts by mass of EDC·HCl were charged in portions so that the internal temperature did not exceed 10 °C. After dissolution to form a homogeneous solution, the reaction was carried out at 10 °C for 0.5 hour. 13.62 parts by mass of XDA were added dropwise to the solution over 0.5 hour. Since the internal temperature rose due to the heat of reaction during the dropwise addition, the dropping rate was controlled so that the temperature would be 30 °C or lower. After the total amount was dropped, the reaction temperature was maintained at 30 °C and the reaction was carried out for 5 hours. The reaction mass was a pale yellow transparent liquid. At this time, the progress of the reaction was traced by HPLC analysis to confirm the end point of the reaction. 50 parts by mass of a 5% aqueous citric acid solution were added to the flask, stirred for 10 minutes, and then the aqueous layer was drained. The same operation was carried out in the order of distilled water, 5% aqueous sodium carbonate solution, and distilled water. The treatment time for the water washing step was 1.5 hours. The remaining DCM layer was distilled off with an evaporator for 2 hours to obtain methacrylamide (2) as a white solid. The total treatment time was 3.5 hours. The yield by this production method was 21.1 g. The yield, purity, reaction time, and treatment time were summarized in Table 1. The IR spectrum of methacrylamide (2) was measured, and the attenuation of the peak intensity of the amino group at 3200 cm -1 ~3500 cm -1 was confirmed. The structure of methacrylamide (2) was confirmed to be the following structure.

[0059] [Chemical formula]

[0060] [Example 3: Condensation of DODA + Methacrylic Acid] 17.22 parts by mass of methacrylic acid and 100 parts by mass of DCM were charged into a 300 mL four-necked flask equipped with a well-dried stirring blade and a thermometer and dissolved. Then, the solution was cooled to 10 °C, and 38.34 parts by mass of EDC·HCl were charged in portions so that the internal temperature did not exceed 10 °C. After dissolution to form a homogeneous solution, the reaction was carried out at 10 °C for 0.5 hour. 14.82 parts by mass of DODA were added dropwise to the solution over 0.5 hour. Since the internal temperature increased due to the heat of reaction during the dropwise addition, the dropping rate was controlled so that the temperature was 30 °C or lower. After the total amount was added dropwise, the reaction temperature was maintained at 30 °C and the reaction was carried out for 6 hours. The reaction mass was a colorless transparent liquid. At this time, the progress of the reaction was traced by HPLC analysis to confirm the end point of the reaction. 50 parts by mass of a 5% aqueous citric acid solution were added to the flask, stirred for 10 minutes, and then the aqueous layer was drained. The same operation was carried out in the order of distilled water, 5% aqueous sodium carbonate solution, and distilled water. The treatment time for the water washing step was 1 hour. The remaining DCM layer was distilled off with an evaporator for 2 hours to obtain methacrylamide (3) as a pale yellow liquid. The total treatment time was 3 hours. The yield by this production method was 17.8 g. The yield, purity, reaction time, and treatment time are summarized in Table 1. IR spectrum measurement was performed on methacrylamide (3), and attenuation of the peak intensity of the amino group at 3200 cm -1 ~3500 cm -1 was confirmed. The structure of methacrylamide (3) was confirmed to be the following structure.

[0061] [Chemical formula]

[0062] [Comparative Example 1: Reaction of NBDA + Methacrylic Acid Chloride] Into a 300 mL four-necked flask equipped with a well-dried stirring blade and a thermometer, 15.43 parts by mass of NBDA, 30.36 parts by mass of TEA, and 100 parts by mass of DCM were charged and dissolved. Then, the solution was cooled to -10°C. 31.35 parts by mass of MACl was added dropwise to the solution over 0.5 hours. Since the internal temperature increased due to the heat of reaction during the addition, the dropping rate was controlled so that the temperature would be 10°C or lower. After the total amount was added dropwise, the reaction temperature was maintained at 10°C and the reaction was carried out for 5 hours. The reaction mass was a reddish-brown slurry. At this time, the progress of the reaction was monitored by HPLC analysis to confirm the end point of the reaction. After the reaction, triethylamine hydrochloride was filtered off. The processing time for the filtration step was 0.5 hours. The filtrate was evaporated in an evaporator for 2 hours to obtain a concentrated residue. The obtained concentrated residue was purified using silica gel column chromatography (developing solvent: AcOEt / MeOH = 3 / 1). The time required for column purification was 6 hours. After column purification, the solvent was evaporated in an evaporator for 2 hours to obtain methacrylamide (1) as a white solid. The total processing time was 10.5 hours. The yield by this production method was 5.7 g. The yield, purity, reaction time, and processing time are summarized in Table 1.

[0063] [Comparative Example 2: Reaction of XDA + Methacrylic Acid Chloride] Into a 300 mL four-necked flask equipped with a well-dried stirring blade and a thermometer, 13.62 parts by mass of XDA, 30.36 parts by mass of TEA, and 100 parts by mass of DCM were charged and dissolved. Then, the solution was cooled to -10°C. 31.35 parts by mass of MACl was added dropwise to the solution over 0.5 hours. Since the internal temperature rose due to the heat of reaction during the dropwise addition, the dropping rate was controlled so that the temperature would be 10°C or lower. After the entire amount was added dropwise, the reaction temperature was maintained at 10°C and the reaction was carried out for 4.5 hours. The reaction mass was a brownish slurry. At this time, the progress of the reaction was monitored by HPLC analysis to confirm the end point of the reaction. After the reaction, triethylamine hydrochloride was filtered off. The processing time for the filtration step was 0.5 hours. The filtrate was distilled off using an evaporator for 2 hours to obtain a concentrated residue. The obtained concentrated residue was purified using silica gel column chromatography (developing solvent: AcOEt / MeOH = 3 / 1). The time required for column purification was 7.5 hours. After column purification, the solvent was distilled off using an evaporator for 2 hours to obtain methacrylamide (2) as a white solid. The total processing time was 12 hours. The yield by this production method was 4.0 g. The yield, purity, reaction time, and processing time are summarized in Table 1.

[0064] [Comparative Example 3: Reaction of DODA + Methacrylic Acid Chloride] Into a 300 mL four-necked flask equipped with a well-dried stirring blade and a thermometer, 14.82 parts by mass of DODA, 30.36 parts by mass of TEA, and 100 parts by mass of DCM were charged Then, it was dissolved. Thereafter, the solution was cooled to -10°C. 1.35 parts by mass of MACl3 was added dropwise to the solution over 0.5 hours. Since the internal temperature rose due to the heat of reaction during the dropwise addition, the dropping rate was controlled so that the temperature would be 10°C or lower. After the total amount was added dropwise, the reaction temperature was maintained at 10°C and the reaction was carried out for 6 hours. The reaction mass was a reddish-brown slurry. At this time, the progress of the reaction was monitored by HPLC analysis to confirm the end point of the reaction. After the reaction, triethylamine hydrochloride was filtered off. The processing time for the filtration step was 0.5 hours. The filtrate was distilled off using an evaporator for 2 hours to obtain a concentrated residue. The obtained concentrated residue was purified using silica gel column chromatography (developing solvent: AcOEt / MeOH = 3 / 1). The time required for column purification was 5 hours. After column purification, the solvent was distilled off using an evaporator for 2 hours to obtain methacrylamide (3) as a pale yellow liquid. The total processing time was 9.5 hours. The yield by this production method was 4.0 g. The yields, purities, reaction times, and processing times are summarized in Table 1.

[0065]

Table 1

[0066] As shown in Table 1, in the examples using the production method of a (meth)acrylamide compound including a step of reacting (meth)acrylic acid with a primary amine compound in the presence of a condensing agent to synthesize a (meth)acrylamide compound (X), the (meth)acrylamide compound (X) could be obtained without performing complicated purification such as column purification. Therefore, the (meth)acrylamide compound could be produced by a simple method. On the other hand, in Comparative Examples 1 to 3 in which a (meth)acrylamide compound was synthesized by the acid chloride method instead of the condensation reaction, the (meth)acrylamide compound could be obtained, but column purification was performed, and the (meth)acrylamide compound could not be produced by a simple method. Furthermore, Example 1 was superior in purity compared to Comparative Example 1, Example 2 was superior in purity compared to Comparative Example 2, and Example 3 was superior in purity compared to Comparative Example 3. Example 1 was significantly superior in yield compared to Comparative Example 1, Example 2 was significantly superior in yield compared to Comparative Example 2, and Example 3 was significantly superior in yield compared to Comparative Example 3. Coloring was suppressed in Example 1 compared to Comparative Example 1, in Example 2 compared to Comparative Example 2, and in Example 3 compared to Comparative Example 3.

[0067] The disclosure of Japanese Patent Application No. 2021-152361 filed on September 17, 2021 is hereby incorporated by reference in its entirety. All documents, patent applications, and technical standards described in this specification are hereby incorporated by reference to the same extent as if each individual document, patent application, and technical standard was specifically and individually indicated to be incorporated by reference.

Claims

1. A process for synthesizing a (meth)acrylamide compound (X) by reacting (meth)acrylic acid with a primary amine compound in the presence of a condensing agent, wherein the primary amine compound is a diamine compound, wherein the diamine compound includes the following compound (1-1), compound (1-2), compound (1-3), compound (1-4), or compound DODA, A method for producing a (meth)acrylamide compound. 【Chemical Formula 1】

2. The method for producing a (meth)acrylamide compound according to claim 1, wherein the condensing agent is a carbodiimide compound represented by the following formula (Z), or a hydrochloride of a carbodiimide compound containing an amino group among the carbodiimide compounds represented by the following formula (Z). 【Chemical Formula 2】 In formula (Z), R １Ｚ and R ２Ｚ are each independently a hydrocarbon group having 1 to 10 carbon atoms which may be substituted with an amino group.

3. The method for producing a (meth)acrylamide compound according to claim 1, wherein the condensing agent is a carbodiimide compound represented by the following formula (Z1) or a hydrochloride thereof. 【Chemical Formula 3】

4. The step of synthesizing is a step of obtaining a composition containing the (meth)acrylamide compound (X), The method for producing a (meth)acrylamide compound according to claim 1, further comprising a step of performing acid washing and alkali washing on the composition containing the (meth)acrylamide compound (X) after the step of synthesizing.

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