Method for producing a hydroxyalkyl carboxamide compound and hydroxyalkyl carboxamide compound

Abstract

To provide a method for producing a hydroxyalkylcarboxamide compound that can produce a compound having a block isocyanato group and a hydroxy group without using a compound including halogen.SOLUTION: The method for producing a hydroxyalkylcarboxamide compound includes a first step of synthesizing a compound by reacting either one or both of a carbamic acid ester and a cyclized product of a carbamic acid ester with a blocking agent including a pyrazole ring in the presence of a solvent.SELECTED DRAWING: None

Description

Technical Field

[0001] The present invention relates to a method for producing a hydroxyalkyl carboxamide compound having a blocked isocyanato group and a hydroxy group, and a hydroxyalkyl carboxamide compound.

Background Art

[0002] Among carbamic acid esters, those generally called blocked isocyanates are synthesized by a method of reacting an isocyanate with a blocking agent for an isocyanato group (-NCO). Conventionally, as a blocking agent for an isocyanato group, a compound that adds active hydrogen to the isocyanato group, such as pyrazoles and ketoximes, has been used. The carbamic acid ester obtained from pyrazoles or ketoximes dissociates the blocking agent and regenerates the isocyanato group when heated, becoming an isocyanate. Such a carbamic acid ester is widely used as a compound having a blocked isocyanato group in which the isocyanato group is protected by a blocking agent.

[0003] As a compound having a blocked isocyanato group, a highly versatile one that can be used as a material for various compounds is required. Examples of such a compound include a compound having a blocked isocyanato group and a hydroxy group in the molecule. A compound having a blocked isocyanato group and a hydroxy group can perform various reactions using the hydroxy group and react with various compounds. Moreover, since a compound having a blocked isocyanato group and a hydroxy group can form a urethane bond (-NH-CO-O-) when the blocking agent dissociates, it can self-polymerize.

[0004] As a method for synthesizing a compound having a blocked isocyanato group and a hydroxy group, for example, there are the methods described in Patent Document 1 and Patent Document 2. Patent Document 1 and Patent Document 2 describe methods for synthesizing a compound having a blocked isocyanato group and a hydroxy group using phosgene or a chloroformic acid compound as a raw material.

Prior Art Documents

Patent Documents

[0005]

Patent Document 1

Patent Document 2

Summary of the Invention

Problems to be Solved by the Invention

[0006] However, in the method for producing a compound having a blocked isocyanato group and a hydroxy group described in Patent Document 1 and Patent Document 2, phosgene or a chloroformic acid compound is used as a raw material. Phosgene and chloroformic acid are toxic substances and are difficult to handle. In addition, phosgene and chloroformic acid compounds are compounds containing halogen. If a compound containing halogen remains as an impurity in a compound used in an electronic component, it may cause problems to the electronic component. For this reason, it is desirable not to use a compound containing halogen as a raw material for a compound used in an electronic component.

[0007] In addition, as a method for synthesizing a compound having a blocked isocyanato group and a hydroxy group without using a compound containing halogen, it is conceivable to use a method of synthesizing an isocyanate having a hydroxy group and protecting the isocyanato group with a blocking agent.

[0008] However, isocyanato groups have high reactivity with hydroxy groups. Therefore, it is difficult to have both isocyanato groups and hydroxy groups present in a compound. Also, the reactivity between isocyanato groups and hydroxy groups is higher than the reactivity between isocyanato groups and the active hydrogen of a blocking agent. For these reasons, it is difficult to synthesize an isocyanate having a hydroxy group and protect its isocyanato group with a blocking agent to synthesize a compound having a blocked isocyanato group and a hydroxy group.

[0009] Therefore, in the prior art, it was difficult to synthesize a compound having a blocked isocyanato group and a hydroxy group without using a halogen-containing compound. Also, a novel hydroxyalkyl carboxamide compound having a blocked isocyanato group and a hydroxy group and capable of being produced without using a halogen-containing compound has been desired.

[0010] The present invention has been made in view of the above circumstances, and an object thereof is to provide a method for producing a hydroxyalkyl carboxamide compound that synthesizes a hydroxyalkyl carboxamide compound having a blocked isocyanato group and a hydroxy group without using a halogen-containing compound, and the hydroxyalkyl carboxamide compound.

Means for Solving the Problems

[0011] The present inventors intensively studied to solve the above problems. As a result, it has been found that a hydroxyalkyl carboxamide compound can be obtained without using a halogen-containing compound by reacting a specific carbamic acid ester (and / or its cyclized form) with a specific blocking agent in the presence of a solvent, and the present invention has been conceived. That is, the present invention relates to the following matters.

[0012] [1] In the presence of a solvent, by reacting either one or both of a carbamate represented by the following general formula (3) and a cyclic form of a carbamate represented by the following general formula (4) with a blocking agent containing a pyrazole ring represented by the following general formula (5), a method for producing a hydroxyalkylcarboxamide compound, characterized by including a first step of synthesizing a compound represented by the following general formula (6).

[0013] [Chemical formula] (In formula (3), R 1 represents -CH 3 , -CH 2 -CH 3 . In formula (3), formula (4) and formula (6), R 2 represents a linear alkylene group having 2 to 6 carbon atoms or a cycloalkylene group having 4 to 6 carbon atoms. In formula (5) and formula (6), R 3 and R 5 each represent -H, -CH 3 or -CH 2 -CH 3 respectively, and R 4 represents -H. In formula (5), X represents either a hydrogen atom or an alkali metal atom.)

[0014] [2] Before the first step, by reacting a dialkyl carbonate represented by the following general formula (1) with a compound having an amino group and a hydroxy group represented by the following general formula (2), a method for producing a hydroxyalkylcarboxamide compound according to [1], characterized by performing a second step of synthesizing either one or both of a carbamate represented by the following general formula (3) and a cyclic form of a carbamate represented by the following general formula (4).

[0015] [Chemical formula] (In formula (1) and formula (3), R 1 represents -CH 3 , -CH2 -CH 3 is shown. The two Rs in formula (1) 1 are the same. In formulas (2) to (4), R 2 represents a linear alkylene group having 2 to 6 carbon atoms or a cycloalkylene group having 4 to 6 carbon atoms.)

[0016] [3] In formula (3), when R 1 represents -CH 3 , and in formulas (3), (4) and (6), when R 2 represents -CH 2 -CH 2 -, and in formulas (5) and (6), when R 3 and R 5 both represent -CH 3 , and R 4 represents -H, the method for producing a hydroxyalkyl carboxamide compound according to [1] or [2].

[0017] [4] In the first step, in the presence of an activator composed of a base compound, reacting either one or both of the carbamic acid ester and the cyclized product with the blocking agent, the method for producing a hydroxyalkyl carboxamide compound according to any one of [1] to [3].

[0018] [5] The method for producing a hydroxyalkyl carboxamide compound according to [4], wherein the activator is any one or two or more selected from hydrides of alkali metals, hydrides of alkaline earth metals, primary to tertiary alkoxides, hydroxides of alkali metals, and phosphates of alkali metals. [6] The method for producing a hydroxyalkyl carboxamide compound according to [4], wherein the activator is any one selected from lithium methoxide, sodium methoxide, and sodium tert-butoxide.

[0019] [7] In the first step, the method for producing a hydroxyalkyl carboxamide compound according to any one of [1] to [6], characterized in that either one or both of the carbamic acid ester and the cyclized product are reacted with the blocking agent in an amide solvent. [8] The method for producing a hydroxyalkyl carboxamide compound according to [7], characterized in that the amide solvent is N,N-dimethylformamide.

[0020] [9] A hydroxyalkyl carboxamide compound represented by the following general formula (60).

[0021] [Chemical formula] (In formula (60), R 20 represents -CH 2 -CH 2 -CH 2 -. R 30 and R 50 each represent -H, -CH 3 or -CH 2 -CH 3 respectively, and R 40 represents -H.) [Advantages of the Invention]

[0022] According to the method for producing a hydroxyalkyl carboxamide compound of the present invention, a hydroxyalkyl carboxamide compound having a blocked isocyanato group and a hydroxy group can be produced without using a halogen-containing compound. According to the present invention, a novel hydroxyalkyl carboxamide compound having a blocked isocyanato group and a hydroxy group can be provided. [Brief Description of the Drawings]

[0023]

Figure 1

Figure 2

Figure 3

Figure 4

Figure 5

Figure 6

Mode for Carrying Out the Invention

[0024] Hereinafter, the method for producing the compound of the present invention will be described in detail. Note that the present invention is not limited only to the embodiments shown below.

[0025] <Method for Producing Compound> The method for producing the hydroxyalkyl carboxamide compound of the present embodiment includes a carbamic acid ester synthesis step (corresponding to the "second step" in the claims) and a carboxamide compound synthesis step (corresponding to the "first step" in the claims).

[0026] The carbamic acid ester synthesis step can be, for example, the steps shown below. First, a dialkyl carbonate represented by the following general formula (1) is reacted with a compound having an amino group and a hydroxy group represented by the following general formula (2). Thereby, either one or both of a carbamic acid ester represented by the following general formula (3) and a cyclized product of a carbamic acid ester represented by the following general formula (4) are synthesized.

[0027]

Chemical Formula

[0028] In the carboxamide compound synthesis step, in the presence of a solvent, either one or both of the carbamic acid ester represented by the formula (3) and the cyclized product represented by the formula (4) are reacted with a blocking agent containing a pyrazole ring represented by the following general formula (5). Thereby, a hydroxyalkyl carboxamide compound represented by the following general formula (6) is synthesized.

[0029] [Chemical formula] (In the formula (3), R 1 is -CH 3 , -CH 2 -CH 3 . In the formula (3), the formula (4) and the formula (6), R 2 represents a linear alkylene group having 2 to 6 carbon atoms or a cycloalkylene group having 4 to 6 carbon atoms. In the formula (5) and the formula (6), R 3 and R 5 each represent any one of -H, -CH 3 or -CH 2 -CH 3 , and R 4 represents -H. In the formula (5), X represents either a hydrogen atom or an alkali metal atom.)

[0030] (Carbamic acid ester synthesis step) In the carbamic acid ester synthesis step, the dialkyl carbonate represented by the formula (1) used as a raw material is dimethyl carbonate in which both of the two R 1 in the formula (1) are -CH 3 or both of the two R 1 in the formula (1) are -CH 2 -CH 3It is diethyl carbonate, and preferably dimethyl carbonate. When the dialkyl carbonate represented by the formula (1) is dimethyl carbonate, the product that detaches from the raw material along with the synthesis of the hydroxyalkyl carboxamide compound represented by the general formula (6) becomes methanol. Since methanol is a compound with a low boiling point, it is easy to separate from the reaction product, which is preferable.

[0031] In the carbamic acid ester synthesis step, the compound having an amino group and a hydroxy group represented by the formula (2) used as a raw material has R in the formula (2) 2 which is a linear alkylene group having 2 to 6 carbon atoms or a cycloalkylene group having 4 to 6 carbon atoms. As the compound having an amino group and a hydroxy group represented by the formula (2), the hydroxyalkyl carboxamide compound represented by the formula (6) has high versatility, so R 2 is -CH 2 -CH 2 - and ethanolamine, or R 2 is -CH 2 -CH 2 -CH 2 - and 3-amino-1-propanol are preferably used. Also, when R 2 is a cycloalkylene group having 4 to 6 carbon atoms, it is preferably a cyclohexene group.

[0032] In the carbamic acid ester synthesis step, the conditions for reacting the dialkyl carbonate represented by the formula (1) with the compound having an amino group and a hydroxy group represented by the formula (2) can be appropriately determined according to the types of the dialkyl carbonate represented by the formula (1) and the compound represented by the formula (2), and are not particularly limited. For example, when the dialkyl carbonate represented by the formula (1) is dimethyl carbonate and the compound represented by the formula (2) is ethanolamine, it is preferable to carry out the reaction in a sealed container under solvent-free conditions. In this case, the reaction temperature is preferably in the range of 25°C to 150°C, more preferably in the range of 35°C to 120°C, even more preferably in the range of 50°C to 100°C, still more preferably in the range of 60 to 95°C, and particularly preferably in the range of 70°C to 90°C. Also, the reaction time is preferably 0.5 hour to 24 hours, more preferably 1 hour to 12 hours, and even more preferably 2 hours to 6 hours.

[0033] The reaction for synthesizing either one or both of the carbamate represented by formula (3) and the cyclized product represented by formula (4) in the carbamate synthesis step may be carried out in the presence of a catalyst to promote the reaction. As the catalyst, lithium hydride, sodium hydride, potassium hydride, lithium methoxide, sodium methoxide, potassium methoxide, calcium methoxide, lithium tert-butoxide, sodium tert-butoxide, potassium tert-butoxide, triethylamine, diazabicycloundecene, sodium hydroxide, potassium phosphate, sodium phosphate, lithium phosphate, etc. can be used. Among these, in particular, the use of sodium methoxide and sodium tert-butoxide is preferable in terms of reaction yield. The content of the catalyst can be, for example, 0.01 to 0.1 molar equivalent with respect to the compound represented by formula (2).

[0034] In the carbamate synthesis step, either one or both of the carbamate represented by formula (3) and the cyclized product of the carbamate represented by formula (4) are synthesized. In the carbamate synthesis step, only either one of the carbamate represented by formula (3) and the cyclized product of the carbamate represented by formula (4) may be selectively synthesized, or they may be synthesized as a mixture containing them in any ratio.

[0035] (Carboxamide Compound Synthesis Step) The blocking agent containing a pyrazole ring represented by formula (5) used in the carboxamide compound synthesis step is R in formula (5) 3 and R 5 are each -H, -CH 3 , -CH 2 -CH 3 any of these, R 4 represents -H, and X represents either a hydrogen atom or an alkali metal atom. As the blocking agent containing a pyrazole ring represented by formula (5), those in which R 3 and R 5 are -CH 3 are preferred. When R 3 and R 5 are -CH 3 , the produced hydroxyalkyl carboxamide compound represented by formula (6) can easily dissociate the blocking agent upon heating, and the isocyanato group is regenerated, making it highly versatile.

[0036] Also, X in formula (5) may be a hydrogen atom or an alkali metal atom. When X is an alkali metal atom, the compound represented by formula (6) can be obtained in a high yield without using an activator. Examples of the alkali metal when X is an alkali metal atom include lithium, sodium, potassium, etc. Sodium is preferred because it is inexpensive and easily available.

[0037] The ratio of either one or both of the carbamate represented by formula (3) and the cyclized product of the carbamate represented by formula (4) used in the carboxamide compound synthesis step to the blocking agent represented by formula (5) is preferably in the range of 1:1 to 1:10, more preferably in the range of 1:1 to 1:5, in terms of molar ratio (formula (3) (and / or formula (4)): blocking agent), in order to obtain the hydroxyalkyl carboxamide compound represented by formula (6) in a high yield.

[0038] In the carboxamide compound synthesis step, in the presence of a solvent, either one or both of the carbamic acid ester represented by formula (3) and the cyclized form of the carbamic acid ester represented by formula (4) are reacted with a blocking agent. The solvent used in the carboxamide compound synthesis step is preferably a high-boiling polar solvent. Specifically, as the solvent, for example, N,N-dimethylacetamide (DMAc), N,N-dimethylformamide (DMF), N-methyl-2-pyrrolidone (NMP), acetonitrile, formamide, dimethyl sulfoxide (DMSO), hexamethylphosphoric triamide, anisole, dimethoxyethane, diethylene glycol dimethyl ether, etc. can be used. Among these, as the solvent, since the compound represented by formula (6) can be obtained in a high yield, it is preferable to use amide solvents such as N,N-dimethylacetamide, N,N-dimethylformamide, and N-methyl-2-pyrrolidone, and particularly preferably N,N-dimethylformamide.

[0039] The total content of the carbamic acid ester represented by formula (3) and / or the cyclized form of the carbamic acid ester represented by formula (4) and the blocking agent containing a pyrazole ring represented by formula (5) contained in the solvent is preferably in the range of 0.2 mol / L to 4.0 mol / L, and more preferably in the range of 0.5 mol / L to 1.5 mol / L, since the compound represented by formula (6) can be obtained in a high yield.

[0040] In the carboxamide compound synthesis step, the conditions for reacting either one or both of the carbamic acid ester represented by formula (3) and the cyclized form of the carbamic acid ester represented by formula (4) with the blocking agent containing a pyrazole ring represented by formula (5) to synthesize the compound represented by formula (6) can be appropriately determined according to the type of the compound represented by formula (6) as the target product, the type of the solvent used, etc., and are not particularly limited.

[0041] For example, when the hydroxyalkyl carboxamide compound represented by formula (6) has R 2 being -CH 2-CH 2 - is, and R 3 and R 5 is -CH 3 is, and R 4 is -H, it is preferable that the reaction temperature and reaction time are as shown below. That is, the reaction temperature is preferably in the range of 100°C to 200°C, more preferably in the range of 130°C to 160°C, so as to suppress the formation of 2-oxazolidone as a by-product and obtain the compound represented by formula (6) in a high yield.

[0042] The reaction time in the carboxamide compound synthesis step is preferably in the range of 3 hours to 20 hours, more preferably in the range of 4 hours to 10 hours, in order to obtain the compound represented by formula (6) in a high yield. When the reaction time is in the range of 3 hours to 20 hours, the formation of oligomers and / or polymers as by-products can be suppressed, and the productivity is good.

[0043] The reaction in the carboxamide compound synthesis step is preferably carried out in the presence of an activator composed of a base compound in order to promote the above reaction. As the activator composed of a base compound, any one or two or more selected from metal hydrides, alkaline earth metal hydrides, primary to tertiary alkoxides, metal hydroxides, metal phosphates, organic bases, etc. can be used. As the activator, an acidic catalyst such as trifluoromethanesulfonic acid (TfOH) may also be used.

[0044] Specifically, as the activator, lithium hydride, sodium hydride, potassium hydride, lithium methoxide, sodium methoxide, potassium methoxide, calcium methoxide, lithium tert-butoxide, sodium tert-butoxide, potassium tert-butoxide, triethylamine, diazabicycloundecene, sodium hydroxide, potassium phosphate, sodium phosphate, lithium phosphate, etc. can be used. Among these, since the compound represented by formula (6) can be obtained in a high yield, it is preferable to use any one selected from lithium methoxide, sodium methoxide, sodium tert-butoxide, and potassium phosphate as the activator. In particular, since the compound represented by formula (6) can be obtained in a high yield and is easily available, it is preferable to use sodium tert-butoxide.

[0045] The amount of the activator used in the carboxamide compound synthesis step can be appropriately changed according to the types of the carbamate represented by formula (3) and / or the cyclized form of the carbamate represented by formula (4), and the type of the blocking agent containing a pyrazole ring represented by formula (5). For example, when the blocking agent containing a pyrazole ring represented by formula (5) is 3,5-dimethylpyrazole, it is preferable to use the activator in the range of 1 equivalent to 5 equivalents, and more preferably in the range of 1 equivalent to 2 equivalents, based on 1 equivalent of the blocking agent. When the amount of the activator used based on 1 equivalent of the blocking agent is 1 equivalent or more, the reaction promoting effect by using the activator becomes remarkable. Also, when the amount of the activator used based on 1 equivalent of the blocking agent is 5 equivalents or less, it is possible to prevent the solvent from being easily decomposed depending on the type of the solvent used (for example, N,N-dimethylformamide (DMF)).

[0046] In the manufacturing method of the present embodiment, it is preferable that the carbamic acid ester synthesis step is a step of reacting dimethyl carbonate represented by the following formula (11) with ethanolamine represented by the following formula (12). By this, a carbamic acid ester represented by the following formula (13) may be synthesized, or a cyclic form of a carbamic acid ester represented by the following formula (14) may be synthesized. Further, the carboxamide compound synthesis step can be carried out even when both of the compounds represented by formula (13) and formula (14) are mixed. Therefore, in the carbamic acid ester synthesis step, if it is not particularly necessary to synthesize only one of them, both of the compounds represented by formula (13) and formula (14) may be synthesized simultaneously.

[0047]

Chemical formula

[0048]

Chemical formula

[0049] When synthesizing the carbamic acid ester represented by formula (13) with priority over the cyclic form of the carbamic acid ester represented by formula (14), for example, dialkyl carbonate represented by formula (11) is supplied in an amount of 1.1 times equivalent or more in excess to ethanolamine represented by formula (12), and the reaction is carried out at 50 to 150 ° C for 1 to 10 hours in a closed system so that the alkanol (methanol) does not go out of the system. Then, the heat source is removed, and the excess dialkyl carbonate may be removed under a reduced pressure atmosphere. The excess carbonate may be removed under a reduced pressure atmosphere during the period from the reaction temperature until it is cooled to room temperature (for example, until it is cooled to 100 ° C), or after it is cooled to near room temperature, the excess carbonate may be removed under a reduced pressure atmosphere. Also, when almost selectively synthesizing the cyclic form of the carbamate represented by formula (14), for example, the following method is used. First, 1.0 to 1.3 equivalents of the dialkyl carbonate represented by formula (11) are supplied to the ethanolamine represented by formula (12), and an activator composed of the aforementioned base compound is added, and the reaction is carried out at 70 to 150 °C for 2 to 20 hours in an open system where the generated alkanol is easily distilled off. After the ethanolamine represented by formula (12) has substantially disappeared by the reaction, the remaining dialkyl carbonate represented by formula (11) is distilled off. At the same time, the carbamate represented by formula (13) contained in the reaction system is heated (80 to 150 °C) to promote the dealcoholization reaction (demethanolization reaction) to convert it to the cyclic form represented by formula (14).

[0050] When simultaneously synthesizing both the compounds represented by formula (13) and formula (14), for example, the following method may be used. First, the dialkyl carbonate represented by formula (11) and the ethanolamine represented by formula (12) are reacted in equimolar amounts. After the ethanolamine represented by formula (12) has substantially disappeared by the reaction, it is heated. As a result, a part of the carbamate represented by formula (13) contained in the reaction system undergoes a demethanolization reaction to be converted to the cyclic form represented by formula (14). At this time, the heating conditions for the demethanolization reaction of the carbamate represented by formula (13) are appropriately adjusted so that the mixing ratio of the compound represented by formula (13) and the compound represented by formula (14) falls within a predetermined range. The higher the heating temperature and the longer the heating time, the easier it is for the compound represented by formula (13) to be converted to the cyclic form represented by formula (14).

[0051] In the carbamate synthesis step, when using a compound having an amino group and a hydroxy group represented by the general formula (2) in which R 2 has 2 carbon atoms, the reaction proceeds without using a catalyst, but the reaction rate can be increased by using a catalyst. R 2When using a compound having an amino group and a hydroxy group represented by the general formula (2) with 3 or more carbon atoms, a catalyst is used. When using a catalyst, the mixing ratio of the compound represented by the formula (3) and the compound represented by the formula (4) can be adjusted according to the type and amount of the catalyst used. For example, when using a strong base such as NaOMe or NaOtBu as the catalyst, the compound represented by the formula (4) is more likely to be produced compared to the compound represented by the formula (3). As described above, the compound represented by the formula (13) and the compound represented by the formula (14) can be preferentially synthesized, respectively. In the present embodiment, when ethanolamine represented by the formula (12) is almost converted into the compound represented by the formula (13) and / or the compound represented by the formula (14), the carbamic acid ester synthesis step is terminated, and the carboxamide compound synthesis step is started.

[0052] In the production method of the present embodiment, the carboxamide compound synthesis step preferably includes reacting the carbamic acid ester represented by the formula (13) produced in the carbamic acid ester synthesis step with 3,5-dimethylpyrazole represented by the following formula (15) or the sodium salt of 3,5-dimethylpyrazole represented by the following formula (25). Thereby, as shown by the following formula, a compound represented by the following formula (16) is obtained. Alternatively, the carboxamide compound synthesis step may be a step of reacting 2-oxazolidinone, which is a cyclized product of the carbamic acid ester represented by the formula (14) produced in the carbamic acid ester synthesis step, with 3,5-dimethylpyrazole represented by the formula (15) or the sodium salt of 3,5-dimethylpyrazole represented by the following formula (25). Also in this case, as shown by the following formula, a compound represented by the formula (16) is obtained.

[0053]

Chemical formula

[0054]

Chemical formula

[0055]

Chem.

[0056] The step of synthesizing the carboxamide compound may be a step of reacting the carbamate represented by the formula (13) with 3,5-dimethylpyrazole (and / or the sodium salt of 3,5-dimethylpyrazole) and simultaneously reacting the cyclic form of the carbamate represented by the formula (14) with 3,5-dimethylpyrazole (and / or the sodium salt of 3,5-dimethylpyrazole). That is, in the step of synthesizing the carboxamide compound, a mixture of the carbamate represented by the formula (13) and the cyclic form of the carbamate represented by the formula (14) may be used as a raw material. Even in this case, the compound represented by the formula (16) can be obtained.

[0057] According to the method for producing the compound of the present embodiment, the compound represented by the formula (6) can be produced without using a halogen-containing compound. The compound represented by the general formula (6) has a structure in which the nitrogen atom of the blocking agent containing the pyrazole ring represented by the general formula (5) is bonded to the carbon atom forming the urethane bond, and the hydroxy group is bonded to the nitrogen atom forming the urethane bond via an alkyl group. Therefore, the compound represented by the general formula (6) can be used as a material for various compounds, as shown below.

[0058] That is, the compound represented by the general formula (6) reacts with various compounds by reacting the hydroxy group in the compound with the functional group of a compound having a functional group such as an isocyanato group, an epoxy group, a carboxy group, or an ester group. Therefore, the compound represented by the general formula (6) has high versatility and can be used as a material for various compounds having multiple functional groups. In addition, the compound represented by the general formula (6) has a blocked isocyanato group and a hydroxy group. Therefore, as shown by the following formula, the compound represented by the general formula (6) can self-polymerize.

[0059] [Chemical formula] (In Formula (27) and Formula (28), R 2 is the same as that in Formula (6).)

[0060] As shown in the above formula, when the compound represented by General Formula (6) is heated, it dissociates the blocking agent represented by General Formula (5) to regenerate the isocyanato group (-NCO). The compound represented by General Formula (27) having the regenerated isocyanato group reacts with the hydroxy group of another molecule (the compound represented by Formula (27)) to form a urethane bond (-NH-CO-O-) and polymerize. As a result, a polymer represented by General Formula (28) (where n in the formula is the number of repetitions) is formed.

[0061] The structure of the compound represented by General Formula (6) produced by the production method of the present embodiment can be confirmed by using known methods such as nuclear magnetic resonance (NMR) spectroscopy, mass spectrometry (MS), infrared spectroscopy (IR), ultraviolet-visible spectroscopy (UV-VIS absorption spectrum), and elemental analysis.

[0062] [Compound] The hydroxyalkyl carboxamide compound of the present embodiment is represented by the following General Formula (60).

[0063] [Chemical formula] (In Formula (60), R 20 represents -CH 2 -CH 2 -CH 2 -. R 30 and R 50 each represent -H, -CH 3 or -CH 2 -CH 3 -, and R 40 represents -H.)

[0064] R in formula (60) 30 and R 50 are each -H, -CH 3 , -CH 2 -CH 3 any of these, and R in formula (6) 3 and R 5 are the same as those. R in formula (60) 30 and R 50 are preferably -CH 3 because, when heated, the blocking agent is easily dissociated and the isocyanato group is regenerated, making it highly versatile. The hydroxyalkyl carboxamide compound of the present embodiment has a blocked isocyanato group and a hydroxy group, is useful as a material for various compounds having multiple functional groups, and has high versatility.

[0065] [Other examples] In the production method of the present embodiment, by performing the carbamate synthesis step, the carbamate represented by formula (3) and / or the cyclized product of the carbamate represented by formula (4) was synthesized. However, the method for synthesizing the carbamate represented by formula (3) and / or the cyclized product of the carbamate represented by formula (4) is not limited to the method described above, and any method may be used. [Examples]

[0066] Hereinafter, the present invention will be described in more detail with reference to examples. Note that the present invention is not limited only to the following examples. "Examples 1 to 11" The compound represented by formula (16) was synthesized by the method shown below.

[0067] (Carbamate synthesis step) 55 g [0.60 mol] of dimethyl carbonate (manufactured by Tokyo Chemical Industry Co., Ltd.) and 31 g [0.50 mol] of ethanolamine (manufactured by Tokyo Chemical Industry Co., Ltd.) were charged into a sealed container (eggplant flask with a glass stopper (200 mL)) and reacted at 80°C for 4 hours under solvent-free conditions. The obtained reaction solution was concentrated under reduced pressure to remove unreacted dimethyl carbonate and analyzed using gas chromatography (GC2014; manufactured by Shimadzu Corporation). As a result, the product in the reaction solution contained 95% by mass of the carbamic acid ester represented by the formula (13) and 5% by mass of the cyclized form of the carbamic acid ester represented by the formula (14). The 55.4 g of the obtained product was used as a raw material as it was in the carboxamide compound synthesis step without purification.

[0068] (Carboxamide Compound Synthesis Step) In the presence of the activator shown in Table 1 and N,N-dimethylformamide (DMF) (manufactured by Tokyo Chemical Industry Co., Ltd.) as a solvent, the product (carbamic acid ester) produced in the carbamic acid ester synthesis step was reacted with 3,5-dimethylpyrazole (manufactured by Tokyo Chemical Industry Co., Ltd.) represented by the formula (15) as a blocking agent at the reaction temperature and reaction time shown in Table 1. As a result, a hydroxyalkyl carboxamide compound represented by the formula (16) was obtained. Table 1 shows the types and amounts of the carbamic acid ester, blocking agent, activator, and solvent used in the carboxamide compound synthesis step, respectively.

[0069]

Table 1

[0070] The following were used as the activators shown in Table 1. MeOLi: Lithium methoxide (manufactured by SIGMA-ALDRICH) MeONa: Sodium methoxide (manufactured by Tokyo Chemical Industry Co., Ltd.) MeOK: Potassium methoxide (manufactured by SIGMA-ALDRICH) (MeO) 2 Ca: Calcium methoxide (manufactured by SIGMA-ALDRICH) tBuOLi: Lithium tert-butoxide (manufactured by SIGMA-ALDRICH) tBuONa: Sodium tert-butoxide (manufactured by FUJIFILM Wako Pure Chemical Corporation) tBuOK: Potassium tert-butoxide (manufactured by Tokyo Chemical Industry Co., Ltd.) Triethylamine: (manufactured by Fujifilm Wako Pure Chemical Corporation) 1,8-Diazabicyclo[5.4.0]undec-7-ene: (manufactured by Tokyo Chemical Industry Co., Ltd.) NaOH: Sodium hydroxide (manufactured by Fujifilm Wako Pure Chemical Corporation) K 3 PO 4 : Potassium phosphate (manufactured by Fujifilm Wako Pure Chemical Corporation)

[0071] For the hydroxyalkyl carboxamide compounds obtained by the production methods of Examples 1 to 11, using biphenyl as an internal standard substance, they were analyzed by gas chromatography (GC2014; manufactured by Shimadzu Corporation), and the yield was calculated according to the following calculation formula. The results are shown in Table 1. Yield (%) = (amount of target compound produced (mol) / amount of carbamate used (mol)) × 100

[0072] For the hydroxyalkyl carboxamide compounds obtained by the production methods of Examples 1 to 11, using an NMR (nuclear magnetic resonance) apparatus (Bruker AvanceIII) respectively, 1 1H-NMR and 13 13C-NMR measurements were performed, and the structure was identified based on the following results. Figure 1 is the 1 1H-NMR measurement chart of Example 1. Figure 2 is the 13 13C-NMR measurement chart of Example 1. As a result, it was confirmed that the hydroxyalkyl carboxamide compounds obtained by the production methods of Examples 1 to 11 were all hydroxyalkyl carboxamide compounds represented by the formula (16).

[0073] 1 1H-NMR (600 MHz, CDCl 3 , 300 K) δ (ppm): 2.21 (s, 3H, Me), 2.22 (s, 3H, Me), 3.70 (q, J = 5.7, 2H, -CH 2 -), 4.09 (t, J = 5.6, 2H, -CH 2-), 5.81 (s, 1H, CH), 6.54 (s, 1H, OH), 8.17 (s, 1H, NH) 13 C{ 1 H}-NMR (125 MHz, CDCl 3 , 300 K) δ (ppm): 10.9 (s), 13.2 (s), 37.8 (s), 46.9 (s), 105.5 (s), 140.1 (s), 147.8 (s), 161.4 (s)

[0074] As shown in Table 1, in Examples 1 to 11 using the activators shown in Table 1, hydroxyalkyl carboxamide compounds represented by formula (16) were obtained in all cases. In particular, in Example 1 using lithium methoxide as the activator, Example 2 using sodium methoxide, Example 6 using sodium tert-butoxide, and Example 11 using potassium phosphate, the compounds represented by formula (16) were obtained in high yields of 40% or more.

[0075] "Examples 12 to 22" (Carbamate synthesis step) The carbamate synthesis step was carried out in the same manner as in Example 1.

[0076] (Carboxamide compound synthesis step) In the presence of sodium tert-butoxide as the activator, in N,N-dimethylformamide (DMF) as the solvent, the product (carbamate) produced in the carbamate synthesis step and 3,5-dimethylpyrazole represented by formula (15) as the blocking agent were reacted at the reaction temperatures and reaction times shown in Table 2. As a result, the compound represented by formula (16) was obtained. Table 2 shows the types and amounts of carbamate, blocking agent, activator, and solvent used in the carboxamide compound synthesis step, respectively.

[0077]

Table 2

[0078] For the hydroxyalkyl carboxamide compounds obtained by the production methods of Examples 12 to 22, the yields were calculated in the same manner as in Example 1. The results are shown in Table 2.

[0079] Also, for the hydroxyalkyl carboxamide compounds obtained by the production methods of Examples 12 to 22, the structures were specified in the same manner as in Example 1. As a result, it was confirmed that all of the hydroxyalkyl carboxamide compounds obtained by the production methods of Examples 12 to 22 were hydroxyalkyl carboxamide compounds represented by the formula (16).

[0080] As shown in Table 2, in Examples 12 to 22, hydroxyalkyl carboxamide compounds represented by the formula (16) were obtained in all cases. In Example 12 where the amount of the activator used was 1.5 equivalents relative to 1 equivalent of the blocking agent, a higher yield was obtained as compared with Example 14 where the amount of the activator was 2.0 equivalents and Example 13 where the amount of the activator used was 1.0 equivalent.

[0081] As shown in Table 2, in Example 18 where the amount of the solvent used was 4.0 ml, a higher yield was obtained as compared with Example 12 where the amount of the solvent used was 0.5 ml, Example 16 where the amount of the solvent used was 1.0 ml, and Example 17 where the amount of the solvent used was 2.0 ml. As shown in Table 2, in Example 12 where the reaction time was 5 hours, a higher yield was obtained as compared with Example 14 where the reaction time was 4 hours. Also, in Example 17 where the reaction time was 5 hours, a higher yield was obtained as compared with Example 19 where the reaction time was 17 hours.

[0082] "Examples 23 to 26" (Carbamic acid ester synthesis step) The carbamic acid ester synthesis step was carried out in the same manner as in Example 1.

[0083] (Carboxamide compound synthesis step) In the presence of sodium tert-butoxide as an activator, in the solvent shown in Table 3, the product (carbamic acid ester) produced in the carbamic acid ester synthesis step was reacted with 3,5-dimethylpyrazole represented by the formula (15) as a blocking agent at the reaction temperature and reaction time shown in Table 3. As a result, the compound represented by the formula (16) was obtained. Table 3 shows the carbamic acid ester, blocking agent, activator, types and amounts of solvents used in the carboxamide compound synthesis step, respectively.

[0084]

Table 3

[0085] As the solvents shown in Table 3, the following were used. DMF: N,N-dimethylformamide (manufactured by Tokyo Chemical Industry Co., Ltd.) DMAc: N,N-dimethylacetamide (manufactured by Fujifilm Wako Pure Chemical Corporation) NMP: N-methyl-2-pyrrolidone (manufactured by Fujifilm Wako Pure Chemical Corporation) Acetonitrile: (manufactured by Fujifilm Wako Pure Chemical Corporation) DMSO: Dimethyl sulfoxide (manufactured by Fujifilm Wako Pure Chemical Corporation)

[0086] For the hydroxyalkyl carboxamide compounds obtained by the production methods of Examples 23 to 26, the yields were calculated in the same manner as in Example 1. The results are shown in Table 3. For comparison, the results of Example 13 shown in Table 2 are also shown in Table 3.

[0087] In addition, for the hydroxyalkyl carboxamide compounds obtained by the production methods of Examples 23 to 26, the structures were specified in the same manner as in Example 1, respectively. As a result, it was confirmed that all of the hydroxyalkyl carboxamide compounds obtained by the production methods of Examples 23 to 26 were hydroxyalkyl carboxamide compounds represented by the formula (16).

[0088] As shown in Table 3, in Examples 23 to 26, hydroxyalkyl carboxamide compounds represented by formula (16) were obtained in all cases. In particular, in Example 13 where N,N-dimethylformamide (DMF) was used as the solvent, the compound represented by formula (16) was obtained in a high yield.

[0089] "Example 27" (Carbamate synthesis step) The carbamate synthesis step was carried out in the same manner as in Example 1.

[0090] (Carboxamide compound synthesis step) Without using an activator, in the solvent shown in Table 4, the product (carbamate) produced in the carbamate synthesis step and the sodium salt of 3,5-dimethylpyrazole represented by formula (25) as a blocking agent were reacted at the reaction temperature and reaction time shown in Table 4. As a result, the compound represented by formula (16) was obtained.

[0091] The sodium salt of 3,5-dimethylpyrazole as a blocking agent was synthesized by the following method. 1.9 g (20 mmol) of 3,5-dimethylpyrazole (manufactured by Tokyo Chemical Industry Co., Ltd.) was dissolved in 2 mL of tetrahydrofuran (THF), 1.1 g (20 mmol) of sodium methoxide (manufactured by Tokyo Chemical Industry Co., Ltd.) was added, and the mixture was refluxed for 1 hour. Then, by concentrating under reduced pressure, 2.3 g of the sodium salt of 3,5-dimethylpyrazole was obtained as white crystals.

[0092] Table 4 shows the carbamate, blocking agent, types and amounts of solvents used in the carboxamide compound synthesis step.

[0093]

Table 4

[0094] For the hydroxyalkyl carboxamide compound obtained by the production method of Example 27, the yield was calculated in the same manner as in Example 1. The results are shown in Table 4. Also, for the hydroxyalkyl carboxamide compound obtained by the production method of Example 27, the structure was specified in the same manner as in Example 1. As a result, it was confirmed that the hydroxyalkyl carboxamide compound obtained by the production method of Example 27 is a hydroxyalkyl carboxamide compound represented by the formula (16).

[0095] As shown in Table 4, in Example 27 using the sodium salt of 3,5-dimethylpyrazole represented by the formula (25) as the blocking agent, the hydroxyalkyl carboxamide compound represented by the formula (16) was obtained in a high yield of 50% or more without using an activator.

[0096] "Example 28" A hydroxyalkyl carboxamide compound was produced in the same manner as in Example 21, except that pyrazole (manufactured by Tokyo Chemical Industry Co., Ltd.) was used instead of 3,5-dimethylpyrazole represented by the formula (15) as the blocking agent. Table 4 shows the carbamate ester, blocking agent, activator, types and amounts of solvents used in the carboxamide compound synthesis step, reaction temperature, and reaction time. For the hydroxyalkyl carboxamide compound obtained by the production method of Example 28, the yield was calculated in the same manner as in Example 1. The results are shown in Table 4.

[0097] For the hydroxyalkyl carboxamide compound obtained by the production method of Example 28, using an NMR (nuclear magnetic resonance) apparatus (Bruker AvanceIII), 1 1H-NMR and 13 13C-NMR measurements were performed, and the structure was specified based on the following results. Figure 3 is the 1 1H-NMR measurement chart of Example 28. Figure 4 is the 13 13C-NMR measurement chart of Example 28. As a result, it was confirmed that the hydroxyalkyl carboxamide compound obtained by the production method of Example 28 was a hydroxyalkyl carboxamide compound represented by the formula (16).

[0098] 1 H-NMR (600 MHz, CDCl 3 , 300 K) δ (ppm): 3.78 (dd, J = 11, 5.7 Hz, 2H, -CH 2 -), 4.32 (t, J = 5.7 Hz, 2H, -CH 2 -), 6.30 (t, J = 2.1 Hz, 1H, CH), 7.42 (d, J = 2.1 Hz, 1H, CH), 7.57 (d, J = 2.1 Hz, 1H, CH), 8.18 (S, 1H, NH) 13 C{ 1 H}-NMR (125 MHz, CDCl 3 , 300 K) δ (ppm): 38.3 (S), 50.7 (S), 106.0 (S), 130.5 (S), 139.4 (S), 161.3 (S)

[0099] As shown in Table 4, in Example 28 using pyrazole as the blocking agent, a hydroxyalkyl carboxamide compound represented by the formula (16) was obtained in a high yield of 60% or more.

[0100] "Example 29" A hydroxyalkyl carboxamide compound was produced in the same manner as in Example 21, except that 3-amino-1-propanol (manufactured by Tokyo Chemical Industry Co., Ltd.) was used instead of ethanolamine as the compound having an amino group and a hydroxy group. Table 4 shows the carbamic acid ester, blocking agent, activator, types and amounts of solvents used in the carboxamide compound synthesis step, reaction temperature, and reaction time. The yield of the hydroxyalkyl carboxamide compound obtained by the production method of Example 29 was calculated in the same manner as in Example 1. The results are shown in Table 4.

[0101] Regarding the hydroxyalkyl carboxamide compound obtained by the production method of Example 29, using an NMR (nuclear magnetic resonance) apparatus (Bruker AvanceIII), 1 1H-NMR and 13 13C-NMR measurements were performed, and the structure was identified based on the following results. Figure 5 is the 1 1H-NMR measurement chart of Example 29. Figure 6 is the 13 13C-NMR measurement chart of Example 29. As a result, the hydroxyalkyl carboxamide compound obtained by the production method of Example 29 was found to be a hydroxyalkyl carboxamide compound represented by the formula (60) (in the formula (60), R 20 represents -CH 2 -CH 2 -CH 2 -. R 30 and R 50 each represent -CH 3 , and R 40 represents -H.).

[0102] 1 1H-NMR (600 MHz, CD 3 3OD, 300 K) δ (ppm): 1.96 (quint, J = 7.1 Hz, 2H, -CH 2 -), 2.16 (s, 3H, CH 3 ), 2.24 (s, 3H, CH 3 ), 3.20 (t, J = 7.1 Hz, 2H, -CH 2 -), 5.83 (s, 1H, CH), 8.05 (s, 1H, NH) 13 13C{ 1 1H}-NMR (125 MHz, CD 3 3OD, 300 K) δ (ppm): 10.8 (S), 13.2 (S), 30.9 (S), 36.3 (S), 46.7 (S), 106.1 (S), 141.1 (S), 148.7 (S), 163.9 (S)

[0103] As shown in Table 4, in Example 29 using 3-amino-1-propanol as the compound having an amino group and a hydroxy group, the hydroxyalkyl carboxamide compound represented by the formula (60) was obtained in a high yield of 39%.

[0104] "Example 30" A hydroxyalkyl carboxamide compound was produced in the same manner as in Example 13, except that the reaction was carried out at the reaction temperature shown in Table 5. Table 5 shows the carbamic acid ester, blocking agent, activator, types and amounts of solvents used in the carboxamide compound synthesis step, reaction temperature, and reaction time. For the hydroxyalkyl carboxamide compound obtained by the production method of Example 30, the yield was calculated in the same manner as in Example 1. The results are shown in Table 5. For comparison, the results of Example 13 shown in Table 2 are also shown in Table 5.

[0105]

Table 5

[0106] For the hydroxyalkyl carboxamide compound obtained by the production method of Example 30, the structure was specified in the same manner as in Example 1. As a result, it was confirmed that the hydroxyalkyl carboxamide compound obtained by the production method of Example 30 was the hydroxyalkyl carboxamide compound represented by the formula (16).

[0107] As shown in Table 5, in Example 13 where the reaction temperature was 150 °C, the hydroxyalkyl carboxamide compound represented by the formula (16) was obtained in a higher yield compared to Example 30 where the reaction temperature was 130 °C.

[0108] "Example 31" A hydroxyalkyl carboxamide compound was produced in the same manner as in Example 12, except that the reaction was carried out at the reaction temperature shown in Table 5. Table 5 shows the carbamate esters, blocking agents, activators, types and amounts of solvents used in the carboxamide compound synthesis step, reaction temperature, and reaction time. For the hydroxyalkyl carboxamide compound obtained by the production method of Example 31, the yield was calculated in the same manner as in Example 1. The results are shown in Table 5. For comparison, the results of Example 12 shown in Table 2 are also shown in Table 5.

[0109] The structure of the hydroxyalkyl carboxamide compound obtained by the production method of Example 31 was specified in the same manner as in Example 1. As a result, it was confirmed that the hydroxyalkyl carboxamide compound obtained by the production method of Example 31 was a hydroxyalkyl carboxamide compound represented by the formula (16).

[0110] As shown in Table 5, in Example 12 where the reaction temperature was 150 °C, the hydroxyalkyl carboxamide compound represented by the formula (16) was obtained in a higher yield compared to Example 31 where the reaction temperature was 100 °C.

[0111] "Example 32" A hydroxyalkyl carboxamide compound was produced in the same manner as in Example 12, except that trifluoromethanesulfonic acid (TfOH) (manufactured by Tokyo Chemical Industry Co., Ltd.) was used as the activator. Table 5 shows the carbamate esters, blocking agents, activators, types and amounts of solvents used in the carboxamide compound synthesis step, reaction temperature, and reaction time. For the hydroxyalkyl carboxamide compound obtained by the production method of Example 32, the yield was calculated in the same manner as in Example 1. The results are shown in Table 5.

[0112] The structure of the hydroxyalkyl carboxamide compound obtained by the production method of Example 32 was specified in the same manner as in Example 1. As a result, it was confirmed that the hydroxyalkyl carboxamide compound obtained by the production method of Example 32 was a hydroxyalkyl carboxamide compound represented by the formula (16).

Industrial Applicability

[0113] The present invention can be used as a material for various compounds having polyfunctional groups and a method for producing the same.

Claims

1. A method for producing a hydroxyalkyl carboxamide compound represented by the following general formula (6), comprising a first step of synthesizing a compound represented by the following general formula (6) by reacting, in the presence of a solvent, either one or both of a carbamic acid ester represented by the following general formula (3) and a cyclic form of a carbamic acid ester represented by the following general formula (4) with a blocking agent containing a pyrazole ring represented by the following general formula (5). 【Chemical 1】 (In formula (3), R １ represents -CH ３ , -CH ２ -CH ３ . In formula (3), formula (4) and formula (6), R ２ represents a linear alkylene group having 2 to 6 carbon atoms or a cycloalkylene group having 4 to 6 carbon atoms. In formula (5) and formula (6), R ３ and R ５ each represent any one of -H, -CH ３ or -CH ２ -CH ３ , and R ４ represents -H. In formula (5), X represents either a hydrogen atom or an alkali metal atom.) 2. Before the first step, A second step of synthesizing either one or both of a carbamic acid ester represented by the following general formula (3) and a cyclic form of a carbamic acid ester represented by the following general formula (4) by reacting a dialkyl carbonate represented by the following general formula (1) with a compound having an amino group and a hydroxy group represented by the following general formula (2). The method for producing a hydroxyalkyl carboxamide compound according to claim 1, characterized in that the second step is carried out. [Chemical 2] (In Formula (1) and Formula (3), R １ represents -CH ３ , -CH ２ -CH ３ . Two Rs １ in Formula (1) are the same. In Formula (2) to Formula (4), R2 represents a linear alkylene group having 2 to 6 carbon atoms or a cycloalkylene group having 4 to 6 carbon atoms.) 3. In formula (3), R １ represents -CH ３ , and in formula (3), formula (4), and formula (6), R ２ represents -CH ２ -CH ２ -. In formula (5) and formula (6), R ３ and R ５ represent -CH ３ , R ４ represents -H. A method for producing a hydroxyalkyl carboxamide compound according to claim 1 or claim 2, characterized by the above.

4. In the first step, the method for producing a hydroxyalkyl carboxamide compound according to any one of claims 1 to 3, characterized in that either one or both of the carbamic acid ester and the cyclic form are reacted with the blocking agent in the presence of an activator composed of a base compound.

5. The method for producing a hydroxyalkyl carboxamide compound according to claim 4, characterized in that the activator is any one or two or more selected from hydrides of alkali metals, hydrides of alkaline earth metals, primary to tertiary alkoxides, hydroxides of alkali metals, and phosphates of alkali metals.

6. The method for producing a hydroxyalkyl carboxamide compound according to claim 4, characterized in that the activator is any one selected from lithium methoxide, sodium methoxide, and sodium tert-butoxide.

7. In the first step, the method for producing a hydroxyalkyl carboxamide compound according to any one of claims 1 to 6, characterized in that either one or both of the carbamic acid ester and the cyclic form are reacted with the blocking agent in an amide-based solvent.

8. The method for producing a hydroxyalkyl carboxamide compound according to claim 7, wherein the amide solvent is N,N-dimethylformamide.

9. A hydroxyalkyl carboxamide compound represented by the following general formula (60). [Chemical 3] (In formula (60), R ２０ represents -CH ２ -CH ２ -CH ２ -. R ３０ and R ５０ each represent -H, -CH ３ or -CH ２ -CH ３ of any one, and R ４０ represents -H.)

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