Preparation method of carboxylate compound and preparation method of amidate compound

Abstract

The present invention provides a method for preparing a carboxylate compound represented by the following formula (3a), which is prepared by reacting an imidazolium carboxylate represented by the following formula (1) with a carbonate represented by the following formula (2). Formulas (1), (2) and (3a) are as follows: In the formula, R 1 ~R 7 As defined in the specification.

Description

Technical Field

[0001] The present invention relates to a method for preparing a carboxylate compound and a method for preparing an amidate compound. Background Art

[0002] A carboxylate compound in which carbon dioxide is added to an imidazolium skeleton is known as a stable N-heterocyclic carbene (hereinafter referred to as NHC carbene) precursor, and is used as a catalyst for producing a urethane resin.

[0003] As a conventional method for producing a carboxylate compound, a method of reacting NHC carbene with carbon dioxide is known (Non-Patent Document 1).

[0004] It is known that an amidate compound in which isocyanate is added to the 2-position of an imidazolium skeleton can also be used as a catalyst for preparing a urethane resin. As a method for preparing an amidate compound, a method of reacting a 1,3-dialkylimidazole-2-ylidene group as an NHC carbene with an isocyanate compound is known (Non-Patent Document 2).

[0005] Prior art literature

[0006] Non-patent literature

[0007] Non-patent document 1: Journal of Organic Chemistry, 2009, Vol. 74, pp. 7935-7942

[0008] Non-patent document 2: Struct. Chem. 2013, Vol. 24, pp. 2059-2068 Summary of the invention

[0009] Problems to be solved by the invention

[0010] In the methods described in Non-Patent Documents 1 and 2 for reacting NHC carbenes with carbon dioxide or isocyanate, since NHC carbenes are generally unstable to oxygen or water, they must be prepared under anhydrous and oxygen-free conditions using special equipment such as a glove box, and are therefore not practical methods.

[0011] The present invention is completed in view of the above background technology, and its subject is to provide a method for preparing a carboxylate compound or an amidate compound, which does not require the use of special equipment such as a glove box under anhydrous and oxygen-free conditions.

[0012] Technical solutions to solve problems

[0013] The inventors have conducted careful research to solve the above problems and found that carboxylate compounds can be prepared by reacting imidazolium carboxylates with carbonates such as dialkyl carbonates and alkylene carbonates. In addition, the inventors have found that by reacting imidazolium carboxylates with carbonates such as dialkyl carbonates and alkylene carbonates and then reacting them with nitrogen-containing compounds such as phenyl isocyanate, amidate compounds can be obtained, and the present invention has been completed.

[0014] That is, the present invention includes the following [1] to [9].

[0015] [1] A method for producing a carboxylate compound represented by the following formula (3a), comprising the step of reacting an imidazolium carboxylate represented by the following formula (1) with a carbonate represented by the following formula (2),

[0016] Formula (1):

[0017] [Chemical formula 1]

[0018]

[0019] (Where R 1 and R 4 are the same or different, and represent a hydrocarbon group having 1 to 20 carbon atoms, which may be substituted with a heteroatom or not, R 2 and R 3 are the same or different, and represent a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms which may be substituted with or without a heteroatom, R 2 and R 3 They can also form a ring structure with the carbon atoms to which they are bonded. 5 represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms which may be substituted with a hetero atom or not),

[0020] Formula (2):

[0021] [Chemical formula 2]

[0022]

[0023] (Where R 6 and R 7 are the same or different, and represent a hydrocarbon group having 1 to 6 carbon atoms, R 6 and R 7 together with the oxygen atoms to which they are bonded, form a ring structure or do not form a ring structure),

[0024] Formula (3a):

[0025] [Chemical formula 3]

[0026]

[0027] (Where R 1 , R 2 , R 3 and R 4 as defined above).

[0028] [2] The method for producing a carboxylate compound according to [1], wherein the carbonate represented by formula (2) is dimethyl carbonate.

[0029] [3] The method for preparing a carboxylate compound according to [1] or [2], wherein R 2 and R 3 A hydrogen atom.

[0030] [4] A method for producing an amidate compound represented by the following formula (5), comprising the following steps 1 and 2:

[0031] (Step 1) is a step of reacting an imidazolium carboxylate represented by formula (1) with a carbonate represented by formula (2) to obtain a reactant (A).

[0032] Formula (1):

[0033] [Chemical formula 4]

[0034]

[0035] (Where R 1 and R 4 are the same or different, and represent a hydrocarbon group having 1 to 20 carbon atoms, which may be substituted with a heteroatom or not, R 2 and R 3 are the same or different, and represent a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms which may be substituted with or without a heteroatom, R 2 and R 3 They can also form a ring structure with the carbon atoms to which they are bonded. 5 represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms which may be substituted with a hetero atom or not),

[0036] Formula (2):

[0037] [Chemical formula 5]

[0038]

[0039] (Where R 6 and R 7 are the same or different, and represent a hydrocarbon group having 1 to 6 carbon atoms, R 6 and R 7 together with the oxygen atoms to which they are bonded, form a ring structure or do not form a ring structure),

[0040] (Step 2) is a step of heating the reaction product (A) obtained in step 1 as required, and reacting it with the nitrogen-containing compound represented by formula (4) under heating as required to obtain an amidate compound represented by formula (5).

[0041] Formula (4):

[0042] [Chemical formula 6]

[0043]

[0044] (In the formula, A represents a substituted or unsubstituted hydrocarbon group, Q represents an -NCO group or an -NHCO 2 R 8 , R 8 represents a hydrocarbon group which may be substituted by a heteroatom or not, and n is an integer greater than 1),

[0045] Formula (5):

[0046] [Chemical formula 7]

[0047]

[0048] (In the formula, A, R 1 , R 2 , R 3 , R 4 , n are each as defined above).

[0049] [5] The method for producing an amidate compound according to [4], wherein the reactant (A) comprises a carboxylate compound represented by formula (3a),

[0050] Formula (3a):

[0051] [Chemical formula 8]

[0052]

[0053] (Where R 1 , R 2 , R 3 and R 4 as defined above). [6]

[0055] The method for producing an amidate compound according to [4] or [5], wherein the nitrogen-containing compound represented by formula (4) is a nitrogen-containing compound represented by any one of the following formulas (4-1) to (4-3),

[0056] Formula (4-1):

[0057] [Chemical formula 9]

[0058] R 9 -Q (4-1)

[0059] (wherein, Q is as defined above, R 9 is a hydrocarbon group which may or may not be substituted by a halogen atom or a hydrocarbon group which may or may not be substituted by a heteroatom),

[0060] Formula (4-2):

[0061] [Chemical formula 10]

[0062] QR 10 -Q (4-2)

[0063] (wherein, Q is the same or different and is as defined above, R 10 is a divalent hydrocarbon group which may or may not be substituted by a halogen atom or a divalent hydrocarbon group which may or may not be substituted by a heteroatom),

[0064] Formula (4-3):

[0065] [Chemical formula 11]

[0066]

[0067] (wherein, Q is the same or different and is as defined above, E 1 、E 2 and E 3 Each independently represents a hydrocarbon group which may be substituted by a halogen atom, a hydrocarbon group which may be substituted by a heteroatom, a halogen atom, a dialkylamino group, an alkoxy group, an aryloxy group, a nitro group, a cyano group, a sulfonyl group, a (alkylamino)carbonylamino group, a (dialkylamino)carbonylamino group or an isocyanate group, f and g each independently represent an integer of 0 to 4, a and b each represent 0 or 1, c, d and e each independently represent an integer of 0 to 4, wherein when f is 0, at least one of a or b is 1). [7]

[0069] The method for producing an amidate compound according to any one of [4] to [6], wherein the carbonate represented by formula (2) is dimethyl carbonate. [8]

[0071] The method for producing an amidate compound according to any one of [4] to [7], wherein R 2 and R 3 A hydrogen atom. [9]

[0073] The method for producing an amidate compound according to any one of [6] to [8], wherein R 9is an aromatic hydrocarbon group which may or may not be substituted by a halogen atom or an aromatic hydrocarbon group which may or may not be substituted by a heteroatom, R 10 It is a divalent aromatic hydrocarbon group which may be substituted by a halogen atom or not, or a divalent aromatic hydrocarbon group which may be substituted by a heteroatom or not.

[0074] Effects of the Invention

[0075] According to the present invention, a method for producing a carboxylate compound and a method for producing an amidate compound that do not require special equipment such as a glove box can be provided. DETAILED DESCRIPTION

[0076] Hereinafter, the mode for carrying out the present invention will be described in detail.

[0077] In the present invention, the carboxylate compound represented by formula (3a) (hereinafter referred to as carboxylate compound (3a)) is prepared by reacting the imidazolium carboxylate represented by formula (1) (hereinafter referred to as imidazolium carboxylate (1)) with the carbonate represented by formula (2) (hereinafter referred to as carbonate (2).

[0078] The amidate compound represented by the formula (5) can be produced through the following steps 1 and 2.

[0079] (Step 1) is a step of reacting the imidazolium carboxylate represented by the formula (1) with the carbonate represented by the formula (2) to obtain a reaction product (hereinafter referred to as a reaction product (A)).

[0080] Formula (1):

[0081] [Chemical formula 12]

[0082]

[0083] (Where R 1 and R 4 are the same or different, and represent a hydrocarbon group having 1 to 20 carbon atoms, which may be substituted with a heteroatom or not, R 2 and R 3 are the same or different, and represent a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms which may be substituted with or without a heteroatom, R 2 and R 3 They can also form a ring structure with the carbon atoms to which they are bonded. 5 represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms which may be substituted by a hetero atom or not).

[0084] Formula (2):

[0085] [Chemical formula 13]

[0086]

[0087] (Where R 6 and R 7 represents the same or different hydrocarbon groups having 1 to 6 carbon atoms, R 6 and R 7 They may also form a ring structure together with the oxygen atoms to which they are bonded).

[0088] (Step 2) is a step of heating the reaction product (A) obtained in step 1 as required and reacting it with a nitrogen-containing compound represented by formula (4) (hereinafter referred to as nitrogen-containing compound (4)) under heating as required to obtain an amide compound represented by formula (5) (hereinafter referred to as amide compound (5).

[0089] [Chemical formula 14]

[0090]

[0091] (In the formula, A represents a substituted or unsubstituted hydrocarbon group, Q represents an -NCO group or an -NHCO 2 R 8 , R 8 represents a hydrocarbon group which may be substituted with a heteroatom, and n is an integer greater than 1).

[0092] Formula (5):

[0093] [Chemical formula 15]

[0094]

[0095] (In the formula, A, R 1 , R 2 , R 3 , R 4 , n are each as defined above).

[0096] In a preferred embodiment of the present invention, the reactant (A) comprises a carboxylate compound represented by formula (3a).

[0097] Formula (3a):

[0098] [Chemical formula 16]

[0099]

[0100] (Where R 1 , R 2 , R 3 and R 4 as defined above).

[0101] In formula (1), R1 and R 4 The term "alkyl" refers to a hydrocarbon group having 1 to 20 carbon atoms which may be substituted with a heteroatom or not, and is preferably a hydrocarbon group having 1 to 12 carbon atoms which may be substituted with a heteroatom or not, and is preferably a hydrocarbon group having 1 to 8 carbon atoms which may be substituted with a heteroatom or not. In another embodiment, the hydrocarbon group having 1 to 20 carbon atoms which may be substituted with a heteroatom or not is preferably a primary or secondary alkyl group having 1 to 20 carbon atoms which may be substituted with a heteroatom or not, more preferably a primary or secondary alkyl group having 1 to 12 carbon atoms which may be substituted with a heteroatom or not, and more preferably a primary or secondary alkyl group having 1 to 8 carbon atoms which may be substituted with a heteroatom or not.

[0102] Examples of the heteroatom-substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms include methyl, ethyl, propyl, isopropyl, butyl, sec-butyl, tert-butyl, pentyl, hexyl, octyl, 1,1,3,3-tetramethylbutyl, 2-ethylhexyl, decyl, dodecyl, tetradecyl, hexadecyl, octadecyl, allyl, benzyl, cyclohexyl, adamantyl, phenyl, 2,6-diisopropylphenyl, 2,4,6-trimethylphenyl, 2-methoxyethyl, 2-ethoxyethyl, and 2-(dimethylamino)ethyl. Preferred are methyl, ethyl, propyl, isopropyl, butyl, octyl, 1,1,3,3-tetramethylbutyl, dodecyl, cyclopentyl, cyclohexyl, 2-ethylhexyl, benzyl, phenyl, and 2,4,6-trimethylphenyl, and particularly preferred are methyl, ethyl, butyl, octyl, 2-ethylhexyl, 1,1,3,3-tetramethylbutyl, and benzyl.

[0103] In R 1 and R 4 In the case where the hetero atom is substituted by a hetero atom such as an oxygen atom, a nitrogen atom, or a sulfur atom, the hydrocarbon group is, for example, -O-, -N<, -S-, or -SO 2 When the hydrocarbon group is substituted with a heteroatom such as an oxygen atom, a nitrogen atom, a sulfur atom, etc., it is preferred that the hydrocarbon group is substituted with an oxygen atom and the hydrocarbon chain is interrupted by an -O- group.

[0104] R 2 and R 3represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms which may be substituted with a hetero atom, and is preferably a hydrogen atom. In addition, the hydrocarbon group having 1 to 20 carbon atoms which may be substituted with a hetero atom is preferably a hydrocarbon group having 1 to 6 carbon atoms which may be substituted with a hetero atom, and is particularly preferably a hydrocarbon group having 1 to 4 carbon atoms which may be substituted with a hetero atom. Examples of the hydrocarbon group having 1 to 20 carbon atoms which may be substituted with a hetero atom include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a sec-butyl group, a tert-butyl group, a pentyl group, a hexyl group, an octyl group, a 2-ethylhexyl group, a decyl group, a dodecyl group, a tetradecyl group, a hexadecyl group, an octadecyl group, an allyl group, a benzyl group, a cyclohexyl group, an adamantyl group, a phenyl group, a 2,6-diisopropylphenyl group, a 2,4,6-trimethylphenyl group, a 2-methoxyethyl group, a 2-ethoxyethyl group, and a 2-(dimethylamino)ethyl group. Preferred are methyl, ethyl, propyl, isopropyl, butyl, cyclopentyl, cyclohexyl, phenyl, 2-methoxyethyl, 2-ethoxyethyl, and 2-(dimethylamino)ethyl, and particularly preferred are methyl, ethyl, butyl, 2-methoxyethyl, 2-ethoxyethyl, and 2-(dimethylamino)ethyl.

[0105] In R 2 and R 3 In the case where the hetero atom is substituted by a hetero atom such as an oxygen atom, a nitrogen atom, or a sulfur atom, the hydrocarbon group is, for example, -O-, -N<, -S-, or -SO 2 When the hydrocarbon group is substituted with a heteroatom such as an oxygen atom, a nitrogen atom, a sulfur atom, etc., it is preferred that the hydrocarbon group is substituted with an oxygen atom and the hydrocarbon chain is interrupted by an -O- group.

[0106] R 2 and R 3 They can also form a ring structure together with the carbon atom to which they are bonded. 2 and R 3 When they form a ring structure together with the carbon atom to which they are bonded, for example, a benzimidazolium ring structure as shown below can be adopted.

[0107] [Chemical formula 17]

[0108]

[0109] (Where R 1 , R 4 and R 5 As defined above. w , R x , R y and R z Each of them represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms.

[0110] R 5 The hydrocarbon group represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms which may be substituted with a hetero atom or not, and is preferably a hydrocarbon group having 1 to 20 carbon atoms which may be substituted with a hetero atom or not. The hydrocarbon group having 1 to 20 carbon atoms which may be substituted with a hetero atom or not is preferably a hydrocarbon group having 1 to 8 carbon atoms which may be substituted with a hetero atom or not, and is particularly preferably a hydrocarbon group having 1 or 2 carbon atoms which may be substituted with a hetero atom or not. Examples of the hydrocarbon group having 1 to 20 carbon atoms which may be substituted with or without a heteroatom include methyl, ethyl, propyl, isopropyl, butyl, sec-butyl, tert-butyl, pentyl, hexyl, octyl, 2-ethylhexyl, decyl, dodecyl, tetradecyl, hexadecyl, octadecyl, allyl, benzyl, cyclohexyl, adamantyl, phenyl, 2,6-diisopropylphenyl, 2,4,6-trimethylphenyl, 2-methoxyethyl, 2-ethoxyethyl, and 2-(dimethylamino)ethyl. Particularly preferred are methyl, ethyl, propyl, isopropyl, butyl, cyclopentyl, cyclohexyl, 2-ethylhexyl, and phenyl, and methyl and ethyl are preferred.

[0111] In R 5 In the case where the hetero atom is substituted by a hetero atom such as an oxygen atom, a nitrogen atom, or a sulfur atom, the hydrocarbon group is, for example, -O-, -N<, -NH-, -S-, -SO 2 -, and the hydrocarbon chain is interrupted by these groups. When the hydrocarbon group is substituted by a heteroatom such as an oxygen atom, a nitrogen atom, or a sulfur atom, it is preferred that the hydrocarbon group is substituted by an oxygen atom and the hydrocarbon chain is interrupted by an -O- group. In addition, as another embodiment, when the hydrocarbon group is substituted by a heteroatom such as an oxygen atom, a nitrogen atom, or a sulfur atom, a hydrocarbon chain having -OH, -NH 2 Hydrocarbon groups of the same group.

[0112] Examples of the imidazolium carboxylate (1) include 1,3-dimethylimidazolium formate, 1-ethyl-3-methylimidazolium formate, 1-butyl-3-methylimidazolium formate, 1-methyl-3-octylimidazolium formate, 1-methyl-3-(1,1,3,3-tetramethylbutyl)imidazolium formate, 1-methyl-3-(2-ethylhexyl)imidazolium formate, 1-dodecyl-3-methylimidazolium formate, 1-methyl-3-octadecylimidazolium formate, 1-benzyl-3-methylimidazolium formate, 1,3-dibutylimidazolium formate, 1-butyl-3-ethyl Imidazolium formate, 1-butyl-3-octylimidazolium formate, 1-butyl-3-(1,1,3,3-tetramethylbutyl)imidazolium formate, 1-butyl-3-(2-ethylhexyl)imidazolium formate, 1-butyl-3-dodecylimidazolium formate, 1-butyl-3-octadecylimidazolium formate, 1-benzyl-3-butylimidazolium formate, 1,3-dioctylimidazolium formate, 1,3-bis(1,1,3,3-tetramethylbutyl)imidazolium formate, 1-ethyl-3-octylimidazolium formate, 1-ethyl-3-(1,1,3,3-tetramethylbutyl)imidazolium formate imidazolium formate, 1-octyl-3-(2-ethylhexyl)imidazolium formate, 1-(1,1,3,3-tetramethylbutyl)-3-(2-ethylhexyl)imidazolium formate, 1-dodecyl-3-octylimidazolium formate, 1-dodecyl-3-(1,1,3,3-tetramethylbutyl)imidazolium formate, 1-octyl-3-octadecylimidazolium formate, 1-(1,1,3,3-tetramethylbutyl)-3-octadecylimidazolium formate, 1-benzyl-3-octylimidazolium formate, 1-benzyl-3-(1,1,3,3-tetramethylbutyl)imidazolium formate, 1,3-bis( imidazolium formate, 1-ethyl-3-(2-ethylhexyl)imidazolium formate, 1-(2-ethylhexyl)-3-dodecylimidazolium formate, 1-(2-ethylhexyl)-3-octadecylimidazolium formate, 1-benzyl-3-(2-ethylhexyl)imidazolium formate, 1,3-didodecylimidazolium formate, 1-dodecyl-3-octadecylimidazolium formate, 1-benzyl-3-dodecylimidazolium formate, 1,3-dioctadecylimidazolium formate, 1-benzyl-3-octadecylimidazolium formate, 1,3-dibenzylimidazolium formate;

[0113] 1,3-Dimethylimidazolium acetate, 1-ethyl-3-methylimidazolium acetate, 1-butyl-3-methylimidazolium acetate, 1-methyl-3-octylimidazolium acetate, 1-methyl-3-(1,1,3,3-tetramethylbutyl)imidazolium acetate, 1-methyl-3-(2-ethylhexyl)imidazolium acetate, 1-dodecyl-3-methylimidazolium acetate, 1-methyl-3-octadecylimidazolium acetate, 1-benzyl-3-methylimidazolium acetate, 1,3-dibutylimidazolium acetate, 1-butyl-3-ethylimidazolium acetate, 1-butyl-3-octylimidazolium acetate imidazolium acetate, 1-butyl-3-(1,1,3,3-tetramethylbutyl)imidazolium acetate, 1-butyl-3-(2-ethylhexyl)imidazolium acetate, 1-butyl-3-dodecylimidazolium acetate, 1-butyl-3-octadecylimidazolium acetate, 1-benzyl-3-butylimidazolium acetate, 1,3-dioctylimidazolium acetate, 1,3-bis(1,1,3,3-tetramethylbutyl)imidazolium imidazolium acetate, 1-ethyl-3-octylimidazolium acetate, 1-ethyl-3-(1,1,3,3-tetramethylbutyl)imidazolium acetate, 1-octyl-3- (2-ethylhexyl) imidazolium acetate, 1-(1,1,3,3-tetramethylbutyl)-3-(2-ethylhexyl) imidazolium acetate, 1-dodecyl-3-octylimidazolium acetate, 1-dodecyl-3-(1,1,3,3-tetramethylbutyl) imidazolium acetate, 1-octyl-3-octadecyl imidazolium acetate, 1-(1,1,3,3-tetramethylbutyl)-3-octadecyl imidazolium acetate, 1-benzyl-3-octylimidazolium acetate, 1-benzyl-3-(1,1,3,3-tetramethylbutyl) imidazolium acetate, 1,3-bis(2-ethylhexyl) ) imidazolium acetate, 1-ethyl-3-(2-ethylhexyl)imidazolium acetate, 1-(2-ethylhexyl)-3-dodecylimidazolium acetate, 1-(2-ethylhexyl)-3-octadecylimidazolium acetate, 1-benzyl-3-(2-ethylhexyl)imidazolium acetate, 1,3-di(dodecyl)imidazolium acetate, 1-dodecyl-3-octadecylimidazolium acetate, 1-benzyl-3-dodecylimidazolium acetate, 1,3-di(octadecyl)imidazolium acetate, 1-benzyl-3-octadecylimidazolium acetate, 1,3-dibenzylimidazolium acetate;

[0114] 1,3-Dimethylimidazolium 2-ethylhexanoate, 1-ethyl-3-methylimidazolium 2-ethylhexanoate, 1-butyl-3-methylimidazolium 2-ethylhexanoate, 1-methyl-3-octylimidazolium 2-ethylhexanoate, 1-methyl-3-(1,1,3,3-tetramethylbutyl)imidazolium 2-ethylhexanoate, 1-methyl-3-(2-ethylhexyl)imidazolium 2-ethylhexanoate, 1-dodecyl-3-methylimidazolium 2-ethylhexanoate, 1-methyl-3-octadecylimidazolium 2-ethylhexanoate, 1-benzyl-3-methylimidazolium 2-ethylhexanoate, 1,3-dibutylimidazolium 2-ethylhexanoate, 1-butyl-3-ethylimidazolium 2-ethylhexanoate, 1-butyl- 3-Octyl imidazolium 2-ethylhexanoate, 1-butyl-3-(1,1,3,3-tetramethylbutyl) imidazolium 2-ethylhexanoate, 1-butyl-3-(2-ethylhexyl) imidazolium 2-ethylhexanoate, 1-butyl-3-dodecyl imidazolium 2-ethylhexanoate, 1-butyl-3-octadecyl imidazolium 2-ethylhexanoate, 1-benzyl-3-butyl imidazolium 2-ethylhexanoate, 1,3-dioctyl imidazolium 2-ethylhexanoate, 1,3-bis(1,1,3,3-tetramethylbutyl) imidazolium 2-ethylhexanoate, 1-ethyl-3-octyl imidazolium 2-ethylhexanoate, 1-ethyl-3-(1,1,3,3-tetramethylbutyl) imidazolium 2-ethylhexanoate, 1-octyl- 3-(2-ethylhexyl)imidazolium 2-ethylhexanoate, 1-(1,1,3,3-tetramethylbutyl)-3-(2-ethylhexyl)imidazolium 2-ethylhexanoate, 1-dodecyl-3-octylimidazolium 2-ethylhexanoate, 1-dodecyl-3-(1,1,3,3-tetramethylbutyl)imidazolium 2-ethylhexanoate, 1-octyl-3-octadecylimidazolium 2-ethylhexanoate, 1-(1,1,3,3-tetramethylbutyl)-3-octadecylimidazolium 2-ethylhexanoate, 1-benzyl-3-octylimidazolium 2-ethylhexanoate, 1-benzyl-3-(1,1,3,3-tetramethylbutyl)imidazolium 2-ethylhexanoate, 1,3-bis(2-ethylhexyl)imidazolium 2 -ethylhexanoate, 1-ethyl-3-(2-ethylhexyl)imidazolium 2-ethylhexanoate, 1-(2-ethylhexyl)-3-dodecylimidazolium 2-ethylhexanoate, 1-(2-ethylhexyl)-3-octadecylimidazolium 2-ethylhexanoate, 1-benzyl-3-(2-ethylhexyl)imidazolium 2-ethylhexanoate, 1,3-di(dodecyl)imidazolium 2-ethylhexanoate, 1-dodecyl-3-octadecylimidazolium 2-ethylhexanoate, 1-benzyl-3-dodecylimidazolium 2-ethylhexanoate, 1,3-di(octadecyl)imidazolium 2-ethylhexanoate, 1-benzyl-3-octadecylimidazolium 2-ethylhexanoate, 1,3-dibenzylimidazolium 2-ethylhexanoate;

[0115] 1,3-Dimethylbenzimidazolium formate, 1,3-dimethylbenzimidazolium acetate, 3-dimethylbenzimidazolium-2-ethylhexanoate.

[0116] Preferred imidazolium carboxylates (1) include 1,3-dimethylimidazolium acetate, 1-ethyl-3-methylimidazolium acetate, 1-butyl-3-methylimidazolium acetate, 1-methyl-3-octylimidazolium acetate, 1-methyl-3-(1,1,3,3-tetramethylbutyl)imidazolium acetate, 1-methyl-3-(2-ethylhexyl)imidazolium acetate, 1-dodecyl-3-methylimidazolium acetate, 1-benzyl-3-methylimidazolium acetate, 1,3- Dibutylimidazolium acetate, 1-butyl-3-ethylimidazolium acetate, 1-butyl-3-octylimidazolium acetate, 1-butyl-3-(1,1,3,3-tetramethylbutyl)imidazolium acetate, 1-butyl-3-(2-ethylhexyl)imidazolium acetate, 1-butyl-3-dodecylimidazolium acetate, 1-benzyl-3-butylimidazolium acetate, 1,3-dioctylimidazolium acetate, 1,3-bis(1,1,3,3-tetramethylbutyl)imidazolium acetate , 1-ethyl-3-octylimidazolium acetate, 1-ethyl-3-(1,1,3,3-tetramethylbutyl)imidazolium acetate, 1-octyl-3-(2-ethylhexyl)imidazolium acetate, 1-(1,1,3,3-tetramethylbutyl)-3-(2-ethylhexyl)imidazolium acetate, 1-dodecyl-3-octylimidazolium acetate, 1-dodecyl-3-(1,1,3,3-tetramethylbutyl)imidazolium acetate, 1-benzyl-3-octylimidazolium acetate , 1-benzyl-3-(1,1,3,3-tetramethylbutyl)imidazolium acetate, 1,3-bis(2-ethylhexyl)imidazolium acetate, 1-ethyl-3-(2-ethylhexyl)imidazolium acetate, 1-(2-ethylhexyl)-3-dodecylimidazolium acetate, 1-benzyl-3-(2-ethylhexyl)imidazolium acetate, 1,3-di(dodecyl)imidazolium acetate, 1-benzyl-3-dodecylimidazolium acetate, 1,3-dibenzylimidazolium acetate.

[0117] As the imidazolium carboxylate (1), a commercially available imidazolium carboxylate may be used. As the imidazolium carboxylate (1), an imidazolium carboxylate obtained by a known method may be used. Alternatively, an imidazolium carboxylate obtained by the method described below may be used.

[0118] The carboxylate compound of formula (1) is obtained by reacting a dicarbonyl compound represented by formula (6), a primary amine compound represented by formula (7a), a primary amine compound represented by formula (7b), formaldehyde and a carboxylic acid represented by formula (8).

[0119] Formula (6):

[0120] [Chemical formula 18]

[0121]

[0122] (Where R 2 and R 3 as defined above).

[0123] Formula (7a):

[0124] [Chemical formula 19]

[0125] R 1 -NH 2 (7a)

[0126] (Where R 1 as defined above).

[0127] Formula (7b):

[0128] [Chemical formula 20]

[0129] R 4 -NH 2 (7b)

[0130] (Where R 4 as defined above).

[0131] Formula (8):

[0132] [Chemical formula 21]

[0133]

[0134] In the formula, R 5 As defined above.

[0135] Examples of the dicarbonyl compound represented by formula (6) (hereinafter referred to as dicarbonyl compound (6)) include glyoxal, biacetyl, 3,4-hexanedione, 2,3-pentanedione, 2,3-heptanedione, 5-methyl-2,3-hexanedione, 3-methyl-2,3-cyclopentanedione, 1,2-cyclohexanedione, 1-phenyl-1,2-propanedione, and dibenzoyl. Glyoxal and biacetyl are preferred, and glyoxal is more preferred.

[0136] The primary amine compound represented by formula (7a) (hereinafter referred to as primary amine compound (7a)) and the primary amine compound represented by formula (7b) (hereinafter referred to as primary amine compound (7b)) are selected from methylamine, ethylamine, propylamine, isopropylamine, butylamine, tert-butylamine, hexylamine, octylamine, 1,1,3,3-tetramethylbutylamine, 2-ethylhexylamine, dodecylamine, tetradecylamine, hexadecylamine, octadecylamine, 2-methoxyethylamine, 2-ethoxyethylamine, 3-methoxypropylamine, 3-ethoxypropylamine, 3-propoxypropylamine, At least one primary amine compound selected from the group consisting of amine, 3-isopropoxypropylamine, 3-butoxypropylamine, 3-(2-ethylhexyloxy)propylamine, allylamine, benzylamine, aniline, 2,6-diisopropylaniline, and 2,4,6-trimethylaniline, preferably methylamine, ethylamine, butylamine, hexylamine, octylamine, (1,1,3,3-tetramethylbutyl)amine, 2-ethylhexylamine, dodecylamine, octadecylamine, and benzylamine, and more preferably butylamine, octylamine, 1,1,3,3-tetramethylbutylamine, 2-ethylhexylamine, and benzylamine.

[0137] Examples of the carboxylic acid represented by formula (8) (hereinafter referred to as carboxylic acid (8)) include formic acid, acetic acid, propionic acid, butyric acid, valeric acid, hexanoic acid, heptanoic acid, octanoic acid, 2-ethylhexanoic acid, decanoic acid, lauric acid, tetradecanoic acid, palmitic acid, octadecanoic acid, cyclohexanoic acid, ethoxyacetic acid, propoxyacetic acid, 2-(2-methoxyethoxy)acetic acid, 2-(2-ethoxyethoxy)acetic acid, 2-(2-propoxyethoxy)acetic acid, 3-methoxypropionic acid, 3-ethoxypropionic acid, 3-(2-methoxyethoxy) Carboxylic acids such as propionic acid, 3-(2-ethoxyethoxy)propionic acid, 3-(2-propoxyethoxy)propionic acid, 3-(3-methoxypropoxy)propionic acid, 3-(3-ethoxypropoxy)propionic acid, 3-(3-propoxypropoxy)propionic acid, oleic acid, linoleic acid, sorbic acid, benzoic acid, phthalic acid, isophthalic acid, terephthalic acid, lactic acid, salicylic acid, and trifluoroacetic acid are preferred, and formic acid, acetic acid, propionic acid, butyric acid, valeric acid, hexanoic acid, heptanoic acid, octanoic acid, and 2-ethylhexanoic acid are preferred, and acetic acid is more preferred.

[0138] The dicarbonyl compound (6) may be used directly in the form of an aqueous solution or an alcohol solution such as methanol or butanol.

[0139] The amount of the primary amine compound (7a) and the primary amine compound (7b) (hereinafter, the primary amine compound (7a) and the primary amine compound (7b) are collectively referred to as the amine compound (7)) used is generally 0.1 to 10 mol, preferably 0.5 to 3 mol, relative to 1 mol of the dicarbonyl compound (6). 2 mol of the primary amine compound (7) react to produce 1 mol of the imidazolium carboxylate (1) relative to 1 mol of the dicarbonyl compound (6). For example, when the amount of the primary amine compound (7) is less than 2 mol, in addition to the imidazolium carboxylate (1), a monocarbonyl-monoamino compound obtained by reacting the dicarbonyl compound (6) (raw material) with 1 mol of the amine compound (7) can be obtained as a mixture. When the amount of the primary amine compound (7) exceeds 2 mol relative to 1 mol of the dicarbonyl compound (6), an excess amount of the primary amine compound (7) may be present in addition to the intended imidazolium carboxylate (1). Even when the imidazolium carboxylate (1) is used in the presence of a compound other than the imidazolium carboxylate (1), the carboxylate compound (3a) can be obtained.

[0140] The ratio (molar ratio) of the primary amine compound (7a) to the primary amine compound (7b) is not particularly limited, but is in the range of primary amine compound (7a):primary amine compound (7b)=0:100 to 100:0. When the ratio of primary amine compound (7a):primary amine compound (7b)=0:100 or primary amine compound (7a):primary amine compound (7b)=100:0, R 1 =R 4 Even when the ratio of primary amine compound (7a) to primary amine compound (7b) is 1:1, the compound of formula (1) is still (R 1 , R 1 )、(R 1 , R 4 )、(R 4 , R 4 ) in a mixture of three combinations of primary amine compound (7a):primary amine compound (7b) = 0:100 to 100:0, (R 1 , R 1 )、(R 1 , R 4 )、(R 4 , R 4 ) These three combinations have different ratios. These three combinations are in R 1 With R 4 They may be the same or different and are included in the compound of formula (1).

[0141] Formaldehyde may be used directly in the form of an aqueous solution or an alcohol solution such as methanol or butanol. The amount of formaldehyde used is usually 0.1 to 10 mol, preferably 0.5 to 5.0 mol, per 1 mol of the dicarbonyl compound (6).

[0142] The amount of the carboxylic acid (8) to be used is usually 0.1 to 10 mol, preferably 0.5 to 2 mol, and more preferably 1 to 1.5 mol, based on 1 mol of the dicarbonyl compound (6).

[0143] The reaction temperature varies depending on the optimum temperature of the raw materials, solvent, etc., but is usually -10°C or higher, preferably 0°C to 100°C. The reaction time is usually 0.1 to 24 hours, preferably 1 to 10 hours.

[0144] The solvent may be used or not. When using a solvent, the solvent used is not particularly limited as long as it does not affect the reaction. As a specific example of the solvent, there can be cited: aromatic hydrocarbon solvents such as toluene, benzene, xylene, hydrocarbon solvents such as methylcyclohexane, cyclohexane, hexane, heptane and octane, halogenated hydrocarbon solvents such as dichloromethane and chloroform, ether solvents such as diethyl ether, tetrahydrofuran and 1,4-dioxane, alcohol solvents such as methanol and ethanol, N, N-dimethylformamide, acetonitrile and water, etc., preferably aromatic hydrocarbon solvents, alcohol solvents and water, particularly preferably toluene and water. The solvent can also be mixed with two or more as needed.

[0145] The amount of the solvent used is usually 50 parts by mass or less, preferably 0.1 to 10 parts by mass, based on 1 part by mass of the dicarbonyl compound (6).

[0146] If necessary, the reaction may be carried out in an inert gas atmosphere such as nitrogen, argon, or helium which does not affect the reaction.

[0147] After the reaction is completed, the imidazolium carboxylate (1) can be isolated by removing impurities (for example, unreacted raw materials) by washing with an organic solvent or by concentrating the reaction solution. It can also be purified by recrystallization or the like as needed.

[0148] The carbonate ester represented by the formula (2) (hereinafter referred to as carbonate ester (2)) is described.

[0149] In formula (2), R 6 and R 7 are the same or different and represent a hydrocarbon group having 1 to 6 carbon atoms, preferably a hydrocarbon group having 1 to 4 carbon atoms, and particularly preferably a methyl group. In another embodiment, the hydrocarbon group having 1 to 6 carbon atoms is preferably an alkyl group having 1 to 6 carbon atoms, and more preferably an alkyl group having 1 to 4 carbon atoms. 6 and R 7 They may also form a ring structure together with the oxygen atom to which they are bonded.

[0150] Specific examples of the carbonate (2) include dialkyl carbonates such as dimethyl carbonate, diethyl carbonate, dipropyl carbonate, dibutyl carbonate, dipentyl carbonate, and dihexyl carbonate; and alkylene carbonates such as ethylene carbonate, propylene carbonate, and butylene carbonate. Preferred are dimethyl carbonate, diethyl carbonate, dipropyl carbonate, and dibutyl carbonate, and particularly preferred is dimethyl carbonate.

[0151] In the preparation of the carboxylate compound (3a) and (step 1), the amount of carbonate (2) used is usually 1 mol or more, preferably 1 to 6 mol, relative to 1 mol of the imidazolium carboxylate (1). In addition, when the imidazolium carboxylate (1) contains excess carboxylic acid or water, these will react with the carbonate (2), so it is preferred to use the carbonate (2) in excess, usually 1 mol or more, preferably 1 to 6 mol, relative to 1 mol of the total of excess carboxylic acid and water in the imidazolium carboxylate (1).

[0152] In the preparation of carboxylate compound (3a) and (step 1), a solvent may or may not be used. When a solvent is used, the solvent used is not particularly limited as long as it does not affect the reaction. Specific examples of solvents include: monohydric alcohol solvents such as methanol, ethanol, propanol, butanol, pentanol, hexanol, 1-methoxy-2-propanol, ethoxyethanol, polyhydric alcohol solvents such as ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol monobutyl ether, dipropylene glycol monomethyl ether, tripropylene glycol monomethyl ether, etc. glycol monoalkyl ether solvents, aromatic hydrocarbon solvents such as toluene, benzene, xylene, aliphatic hydrocarbon solvents such as methylcyclohexane, cyclohexane, hexane, heptane, octane, ester solvents such as ethyl acetate or butyl acetate, ketone solvents such as methyl ethyl ketone, 4-methyl-2-pentanone, etc., preferably a monohydric alcohol solvent, particularly preferably methanol. The amount of solvent used is usually 50 parts by mass or less, preferably 10 parts by mass or less, relative to 1 part by mass of imidazolium carboxylate (1).

[0153] In the preparation of the carboxylate compound (3a) and (step 1), the reaction temperature may vary depending on the raw materials, solvents, etc. used, but is usually above room temperature, preferably 20 to 200° C. The reaction time is usually 0.1 to 48 hours, preferably 1 to 24 hours. In this specification, room temperature usually refers to about 20° C.

[0154] In the preparation of the carboxylate compound (3a) and (step 1), the reaction may be carried out under an inert gas atmosphere which does not affect the reaction, such as nitrogen, argon, helium, etc., as necessary.

[0155] In the preparation of the carboxylate compound (3a), after the reaction is completed, the reaction solution can be concentrated and the solvent can be removed to obtain the carboxylate compound (3a). If necessary, purification such as recrystallization or column fractionation can be performed.

[0156] Alternatively, the carboxylate compound (3a) can be reacted with the nitrogen-containing compound represented by the formula (4) under heating as required to produce the amidate compound represented by the formula (5). When the amidate compound represented by the formula (5) is produced by this method, the same method as that described later in (Step 2) can be used.

[0157] The reactant (A) obtained by (operation 1) can also be used as the reactant (A) of raw material in (operation 2). In addition, in (operation 1), when carbonate (2) or solvent remain in the reactant (A) obtained, it is possible to concentrate the reaction solution and remove carbonate (2) or solvent on the basis of the reaction solution to make the raw material as reactant (A) (operation 2).

[0158] <Process 2>

[0159] The reactant (A) obtained in step 1 is heated as required and reacted with the nitrogen-containing compound represented by formula (4) as required under heating, thereby preparing the amidated compound represented by formula (5). Heating means a temperature from 40° C. to a temperature at which the solvent boils, for example, 40 to 200° C. The reaction in step 2 may be carried out at room temperature or under heating.

[0160] Here, as described above, in a preferred embodiment of the present invention, the reactant (A) contains the carboxylate compound (3a), but the reactant (A) may contain, in addition to the carboxylate compound (3a), compounds represented by the following formulae (3b) to (3f) (hereinafter referred to as compound (3b), compound (3c), compound (3d), compound (3e), and compound (3f), respectively) (Reaction Scheme 1). Compound (3b) is R in Formula (3a). 2 When R is a hydrogen atom, in compound (3c), R 3 When it is a hydrogen atom, it can be included in the reactant (A).

[0161] (Reaction 1)

[0162] [Chemical formula 22]

[0163]

[0164] (Where R 1 ~R 4 , R 6 , R 7 as defined above).

[0165] The compound represented by formula (3d) or / and the compound represented by formula (3e) are produced as intermediates in the reaction of step 1, and the carboxylate compound (3a) or / and the compound represented by formula (3f) are produced from these. In formula (3a), R 2 When a hydrogen atom is present, the compound represented by formula (3c) is 3 When it is a hydrogen atom, it can generate compound (3b) by equilibrium with carboxylate compound (3a).

[0166] Compound (3b) and Compound (3c) are in equilibrium with carboxylate compound (3a). Therefore, if carboxylate compound (3a) is consumed in step 2, the equilibrium is shifted and Compound (3b) and Compound (3c) are converted into carboxylate compound (3a). Therefore, it is estimated that Compound (3b) and Compound (3c) can be treated as equivalent to carboxylate compound (3a).

[0167] Compound (3d) and compound (3e) can react with the compound represented by formula (4a) in the same manner as the carboxylate compound (3a) to prepare an amide compound (5), as shown in the following reaction product 2. Therefore, it can be treated as equivalent to the carboxylate compound (3a). In addition, the compound represented by (4b') or (4b") in the following reaction formula is produced as a by-product. The compound represented by formula (4b') or (4b") is decomposed into the corresponding alcohol compound represented by formula (9a) or (9b) and the isocyanate compound represented by formula (4a) by heat as shown in the following reaction formula. The isocyanate compound represented by formula (4a) produced by decomposition is consumed in the reaction with the carboxylate compound (3a) and compounds (3b) to (3f) contained in the reactant (A). In the following reaction formula 2, the case where Q in formula (4) is an -NCO group is shown, but Q is -NHCO 2 R 8 The situation is the same.

[0168] (Reaction 2)

[0169] [Chemical formula 23]

[0170]

[0171] (Where R 1 ~R 4 , R 6 ~R 7 , A, n are as defined above).

[0172] In addition, among the reactants (A), compound (3f) can be converted into carboxylate compound (3a) by dehydration. This dehydration reaction is believed to be a reaction that can easily occur at normal temperature and pressure. Therefore, it is presumed that it can be treated as equivalent to carboxylate compound (3a).

[0173] The nitrogen-containing compound represented by formula (4) (hereinafter referred to as nitrogen-containing compound (4)) will be described.

[0174] In formula (4), A is a substituted or unsubstituted hydrocarbon group, preferably a substituted or unsubstituted hydrocarbon group having 1 to 100 carbon atoms, more preferably a hydrocarbon group substituted or unsubstituted by halogen atoms or a hydrocarbon group substituted or unsubstituted by hetero atoms, particularly preferably a hydrocarbon group having 1 to 30 carbon atoms substituted or unsubstituted by halogen atoms or a hydrocarbon group having 1 to 30 carbon atoms substituted or unsubstituted by hetero atoms. Examples of the "hydrocarbon group" in the substituted or unsubstituted hydrocarbon group represented by A include aryl groups, alkyl groups, and aralkyl groups. Specifically, examples include linear, branched, or cyclic alkyl groups such as methyl, ethyl, n-propyl, isopropyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-dodecyl, n-octadecyl, and cyclohexyl; aryl groups such as phenyl, 2-methylphenyl, 2,6-dimethylphenyl, 2,4-dimethylphenyl, 2,3-dimethylphenyl, and naphthyl; aralkyl groups such as phenylmethyl, phenylethyl, 1-phenylpropyl, 2-phenylpropyl, 1-phenylbutyl, 2-phenylbutyl, naphthylmethyl, and naphthylethyl; and aralkyl groups formed by appropriate combinations of the above alkyl groups and aryl groups.

[0175] When A is a hydrocarbon group having a substituent, examples of the substituent include: halogen atoms such as fluorine atoms, chlorine atoms, bromine atoms and iodine atoms, dialkylamino groups such as dimethylamino, alkoxy groups such as methoxy and ethoxy, aryloxy groups such as benzyloxy, halogenated alkyl groups such as trifluoromethyl, nitro, cyano, sulfonyl, (alkylamino)carbonylamino, (dialkylamino)carbonylamino or isocyanate groups. In addition, the hydrocarbon group of A may be substituted with heteroatoms such as oxygen atoms, nitrogen atoms and sulfur atoms. When the hydrocarbon group of A is substituted with heteroatoms such as oxygen atoms, nitrogen atoms and sulfur atoms, the hydrocarbon group is, for example, -O-, -N<, -S-, -SO 2 - and other groups, and the hydrocarbon chain is interrupted by these groups.

[0176] Examples of the alkyl moiety of the dialkylamino group, alkoxy group, halogenated alkyl group, (alkylamino)carbonylamino group and (dialkylamino)carbonylamino group include linear or branched alkyl groups having 1 to 6 carbon atoms, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl and n-pentyl. The alkyl group preferably has 1 to 3 carbon atoms, more preferably 1 or 2 carbon atoms.

[0177] Examples of the aryl moiety of the aryloxy group include aryl groups having 6 to 10 carbon atoms, and specific examples include phenyl and naphthyl.

[0178] The number of the substituents can be 1 to 5, preferably 1 to 3, and more preferably 1 or 2.

[0179] In formula (4), n is an integer of 1 or more, preferably 1 to 6, more preferably 1 to 4, and particularly preferably 1 or 2.

[0180] In formula (4), Q is -NCO or -NHCO 2 R 8 Base. R 8 The hydrocarbon group may contain a hetero atom, preferably a hydrocarbon group having 1 to 50 carbon atoms which may contain a hetero atom, more preferably a hydrocarbon group having 1 to 30 carbon atoms which may contain a hetero atom, and particularly preferably a hydrocarbon group having 1 to 8 carbon atoms which may contain a hetero atom. Examples of the hydrocarbon group which may contain a hetero atom include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a sec-butyl group, a tert-butyl group, a pentyl group, a hexyl group, an octyl group, a decyl group, a dodecyl group, an allyl group, a benzyl group, a cyclohexyl group, an adamantyl group, a phenyl group, a 2,6-diisopropylphenyl group, a 2,4,6-trimethylphenyl group, a 2-methoxyethyl group, a 2-ethoxyethyl group, and a 2-(dimethylamino)ethyl group. Preferred are a methyl group, an ethyl group, a propyl group, an isopropyl group, a tert-butyl group, an octyl group, a cyclopentyl group, a cyclohexyl group, and a 2,4,6-trimethylphenyl group, more preferably a methyl group, an ethyl group, an isopropyl group, a tert-butyl group, an octyl group, and a phenyl group, and particularly preferably a methyl group, an isopropyl group, a tert-butyl group, an octyl group, and a phenyl group.

[0181] In the present invention, the nitrogen-containing compound (4) is preferably a nitrogen-containing compound represented by any one of formula (4-1), (4-2) and (4-3), and is preferably a nitrogen-containing compound represented by formula (4-1).

[0182] Formula (4-1):

[0183] [Chemical formula 24]

[0184] R 9 -Q (4-1)

[0185] (wherein, Q is as defined above, R 9 is a hydrocarbon group which may or may not be substituted by a halogen atom, or a hydrocarbon group which may or may not be substituted by a heteroatom).

[0186] Formula (4-2):

[0187] [Chemical formula 25]

[0188] QR 10 -Q (4-2)

[0189] (wherein, Q is as defined above, R 10 is a divalent hydrocarbon group which may or may not be substituted by a halogen atom, or a divalent hydrocarbon group which may or may not be substituted by a heteroatom).

[0190] Formula (4-3):

[0191] [Chemical formula 26]

[0192]

[0193] (wherein, Q is the same or different and is as defined above, E 1 、E 2 and E 3 Each independently represents a hydrocarbon group which may be substituted by a halogen atom, a hydrocarbon group which may be substituted by a heteroatom, a halogen atom, a dialkylamino group, an alkoxy group, an aryloxy group, a nitro group, a cyano group, a sulfonyl group, a (alkylamino)carbonylamino group, a (dialkylamino)carbonylamino group or an isocyanate group, f and g each independently represent an integer of 0 to 4, a and b each represent 0 or 1, c, d and e each independently represent an integer of 0 to 4, wherein when f is 0, at least one of a or b is 1).

[0194] When Q is -NCO group, the nitrogen-containing compound (4) is an isocyanate compound represented by the following formula (4a) (hereinafter referred to as isocyanate compound (4a).). When Q is -NHCO 2 R 8 When , it is a carbamate compound represented by the following formula (4b) (hereinafter referred to as a carbamate compound (4b)).

[0195] Formula (4a):

[0196] [Chemical formula 27]

[0197]

[0198] (wherein A and n are as defined above).

[0199] Formula (4b):

[0200] [Chemical formula 28]

[0201]

[0202] (In the formula, A, n, R 8 as defined above).

[0203] In formulas (4-1), (4-2) and (4-3), when Q is a -NCO group, the nitrogen-containing compounds represented by formulas (4-1), (4-2) and (4-3) have structures represented by formulas (4a-1), (4a-2) and (4a-3), respectively.

[0204] Formula (4a-1):

[0205] [Chemical formula 29]

[0206] R 9 -NCO (4a-1)

[0207] (Where R 9 as defined above).

[0208] Formula (4a-2):

[0209] [Chemical formula 30]

[0210] OCN-R 10 -NCO (4a-2)

[0211] (Where R 10 as defined above).

[0212] Formula (4a-3):

[0213] [Chemical formula 31]

[0214]

[0215] (Where, E 1 、E 2 、E 3 , a, b, c, d, e, f, g are as defined above).

[0216] In the present invention, as the isocyanate compound (4a), a polymer such as polymethylene polyphenyl polyisocyanate (polymeric MDI) can be used.

[0217] In formula (4a-1), R 9It is a hydrocarbon group which may or may not be substituted by a halogen atom or a hydrocarbon group which may or may not be substituted by a heteroatom, preferably a hydrocarbon group having 1 to 50 carbon atoms which may or may not be substituted by a halogen atom or a hydrocarbon group having 1 to 50 carbon atoms which may or may not be substituted by a halogen atom, more preferably a hydrocarbon group having 1 to 30 carbon atoms which may or may not be substituted by a halogen atom or a hydrocarbon group having 1 to 30 carbon atoms which may or may not be substituted by a halogen atom, and particularly preferably a hydrocarbon group having 1 to 12 carbon atoms which may or may not be substituted by a halogen atom or a hydrocarbon group having 1 to 12 carbon atoms which may or may not be substituted by a halogen atom. In addition, the hydrocarbon group is preferably an aromatic hydrocarbon group such as an aryl group or an aralkyl group.

[0218] As R 9 The hydrocarbon groups which may or may not be substituted by halogen atoms or the hydrocarbon groups which may or may not be substituted by hetero atoms shown in the above description may specifically include: methyl, ethyl, propyl, isopropyl, butyl, sec-butyl, tert-butyl, pentyl, hexyl, heptyl, decyl, dodecyl, octadecyl, cyclopropyl, cyclopentyl, cyclohexyl, phenyl, chlorophenyl, naphthyl, benzyl, phenethyl, tolyl, allyl and the like, preferably benzyl and phenyl.

[0219] As R 9 Examples of the halogen atom in the hydrocarbon group which may be substituted with a halogen atom or in the hydrocarbon group which may be substituted with a heteroatom include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, and the like. 9 The hydrocarbon group may be substituted by heteroatoms such as oxygen atoms, nitrogen atoms and sulfur atoms. 9 When the hydrocarbon group is substituted with a hetero atom such as an oxygen atom, a nitrogen atom, or a sulfur atom, the hydrocarbon group may be, for example, -O-, -N<, -S-, or -SO 2 - and other groups, and the hydrocarbon chain is interrupted by these groups.

[0220] In formula (4a-2), R 10It is a divalent hydrocarbon group which may or may not be substituted by a halogen atom or a divalent hydrocarbon group which may or may not be substituted by a heteroatom, preferably a divalent hydrocarbon group having 1 to 100 carbon atoms which may or may not be substituted by a halogen atom or a divalent hydrocarbon group having 1 to 100 carbon atoms which may or may not be substituted by a halogen atom, more preferably a divalent hydrocarbon group having 1 to 50 carbon atoms which may or may not be substituted by a halogen atom or a divalent hydrocarbon group having 1 to 50 carbon atoms which may or may not be substituted by a heteroatom, and particularly preferably a divalent hydrocarbon group having 1 to 30 carbon atoms which may or may not be substituted by a halogen atom or a divalent hydrocarbon group having 1 to 30 carbon atoms which may or may not be substituted by a halogen atom. In addition, the hydrocarbon group is preferably a divalent aromatic hydrocarbon group such as an arylene group, an arylalkylene group, or an arylenealkylene group. Specific examples of the divalent hydrocarbon group which may or may not be substituted by a halogen atom or the divalent hydrocarbon group which may or may not be substituted by a hetero atom include: alkylene groups such as methylene, dimethylmethylene, ethylene, n-propylene, n-butylene, n-pentylene, n-hexylene, n-heptylene, n-octylene, n-nonylene, n-decylene, n-dodecylene, n-octadecylene, and cyclohexylene; arylene groups such as phenylene, 2-methylphenylene, 2,6-dimethylphenylene, 2,4-dimethylphenylene, 2,3-dimethylphenylene, and naphthylene; arylalkylene groups such as phenylmethylene, phenylethylene, 1-phenylpropylene, 2-phenylpropylene, 1-phenylbutylene, 2-phenylbutylene, naphthylmethylene, and naphthylethylene; and arylenealkylene groups formed by appropriate combinations of the above alkylene groups and arylene groups. These divalent hydrocarbon groups may be repeated or combined to form one divalent hydrocarbon group.

[0221] In R 10 When the divalent hydrocarbon group shown is substituted by a halogen atom, part or all of the hydrogen atoms bonded to the carbon atoms in the divalent hydrocarbon group may be substituted by a halogen atom. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, and the like. Specifically, examples of the divalent hydrocarbon group substituted by a halogen atom include 1-chloro-3,5-phenylene, 2-chloro-1,4-phenylene, 1-bromo-3,5-phenylene, 1,4-dichloro-3,5-phenylene, 1,2,4,5-tetrachloro-3,6-phenylene, and 1-chloro-4,5-naphthylene. In addition, R 10 The divalent hydrocarbon group may be substituted by heteroatoms such as oxygen atoms, nitrogen atoms and sulfur atoms. 10 When the divalent hydrocarbon group is substituted by a heteroatom such as an oxygen atom, a nitrogen atom, or a sulfur atom, the hydrocarbon group may be, for example, -O-, -N<, -S-, or -SO 2 - and other groups, and the hydrocarbon chain is interrupted by these groups.

[0222] In formula (4a-3), E 1 、E 2 and E 3Each is independently a hydrocarbon group which may be substituted by a halogen atom, a hydrocarbon group which may be substituted by a heteroatom, a halogen atom, a dialkylamino group, an alkoxy group, an aryloxy group, a nitro group, a cyano group, a sulfonyl group, an (alkylamino)carbonylamino group, a (dialkylamino)carbonylamino group or an isocyanate group, preferably a hydrocarbon group which may be substituted by a halogen atom, a hydrocarbon group which may be substituted by a heteroatom, a (alkylamino)carbonylamino group, a (dialkylamino)carbonylamino group or an isocyanate group, more preferably an (alkylamino)carbonylamino group or a (dialkylamino)carbonylamino group.

[0223] As the hydrocarbon group which may or may not be substituted by a halogen atom or the hydrocarbon group which may or may not be substituted by a heteroatom, each independently, a hydrocarbon group having 1 to 50 carbon atoms which may or may not be substituted by a halogen atom or a hydrocarbon group having 1 to 50 carbon atoms which may or may not be substituted by a heteroatom is preferred, a hydrocarbon group having 1 to 30 carbon atoms which may or may not be substituted by a halogen atom or a hydrocarbon group having 1 to 30 carbon atoms which may or may not be substituted by a halogen atom is more preferred, and a hydrocarbon group having 1 to 12 carbon atoms which may or may not be substituted by a halogen atom or a hydrocarbon group having 1 to 12 carbon atoms which may or may not be substituted by a halogen atom or a hydrocarbon group having 1 to 12 carbon atoms which may or may not be substituted by a heteroatom is particularly preferred.

[0224] E 1 、E 2 and E 3 When each of them is independently a halogen atom, examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.

[0225] As E 1 、E 2 or E 3 Examples of the halogen atom of the hydrocarbon group substituted or not substituted by a halogen atom include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, and the like. 1 、E 2 or E 3 The hydrocarbon group may be substituted by heteroatoms such as oxygen atoms, nitrogen atoms, and sulfur atoms. 1 、E 2 or E 3 When the hydrocarbon group is substituted with a hetero atom such as an oxygen atom, a nitrogen atom, or a sulfur atom, the hydrocarbon group may be, for example, -O-, -N<, -S-, or -SO 2 - and other groups, and the hydrocarbon chain is interrupted by these groups.

[0226] Examples of the alkyl moiety of the dialkylamino group, alkoxy group, (alkylamino)carbonylamino group and (dialkylamino)carbonylamino group include linear or branched alkyl groups having 1 to 6 carbon atoms, such as methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group and n-pentyl group. The alkyl group preferably has 1 to 3 carbon atoms, and more preferably has 1 or 2 carbon atoms.

[0227] Examples of the aryl moiety of the aryloxy group include aryl groups having 6 to 10 carbon atoms, and specific examples include phenyl and naphthyl.

[0228] f and g each independently represent an integer of 0 to 4, a and b each represent 0 or 1, and c, d and e each independently represent an integer of 0 to 4, wherein when f is 0, at least one of a or b is 1.

[0229] Specific examples of the isocyanate compound (4a) are shown below, but the present invention is not limited thereto.

[0230] [Chemical formula 32]

[0231]

[0232] [Chemical formula 33]

[0233]

[0234] [Chemical formula 34]

[0235]

[0236] (wherein m is as defined above).

[0237] As the isocyanate compound (4a), compounds represented by formula (4a-1-1), formula (4a-2-8), formula (4a-2-15) and formula (4a-3-1) are preferred.

[0238] The isocyanate compound (4a) may be used alone or as a mixture of two or more.

[0239] In formula (4-1), (4-2) and (4-3), Q is -NHCO 2 R 8 When the nitrogen-containing compounds represented by formula (4-1), (4-2) and (4-3) become the structures represented by formula (4b-1), (4b-2) and (4b-3), respectively.

[0240] Formula (4b-1):

[0241] [Chemical formula 35]

[0242]

[0243] (Where R 8 , R 9 as defined above).

[0244] Formula (4b-2):

[0245] [Chemical formula 36]

[0246]

[0247] (Where R 8 , R 10 as defined above).

[0248] Formula (4b-3):

[0249] [Chemical formula 37]

[0250]

[0251] (Where R 8 、E 1 、E 2 、E 3 , a, b, c, d, e, f and g are as defined above).

[0252] Specific examples of the carbamate compound (4b) are shown below. However, the present invention is not limited thereto. In the following specific examples, Et represents an ethyl group, Bu represents an n-butyl group, t-Bu represents a tert-butyl group, Oct represents an n-octyl group, and Ph represents a phenyl group.

[0253] [Chemical formula 38]

[0254]

[0255]

[0256] [Chemical formula 39]

[0257]

[0258]

[0259] As the carbamate compound (4b), preferred are compounds represented by formula (4b-1-1) to formula (4b-1-7), formula (4b-2-8) to formula (4b-2-21), and formula (4b-3-1) to formula (4b-3-7), and particularly preferred are compounds represented by (4b-1-1), formula (4b-2-8), and formula (4b-3-1).

[0260] The carbamate compound (4b) used as a raw material may be a commercially available product or may be produced by a known method.

[0261] Next, the amidate compound represented by formula (5) (hereinafter referred to as amidate compound (5)) is described.

[0262] In formula (5), A, R 1 , R 2 , R 3 , R 4 , n are each as defined above.

[0263] The amidate compound (5) is preferably an amidate compound represented by any one of the formula (5-1), formula (5-2) and formula (5-3).

[0264] Formula (5-1):

[0265] [Chemical formula 40]

[0266]

[0267] (Where R 1 , R 2 , R 3 , R 4 and R 9 as defined above).

[0268] Formula (5-2):

[0269] [Chemical formula 41]

[0270]

[0271] (Where R 1 , R 2 , R 3 , R 4 and R 10 as defined above).

[0272] Formula (5-3):

[0273] [Chemical formula 42]

[0274]

[0275] (Where R 1 , R 2 , R 3 , R 4 、E 1 、E 2 、E 3 , a, b, c, d, e, f and g are as defined above).

[0276] In formula (5-1), R 1 , R 2 , R 3 , R 4 and R 9 As defined above.

[0277] In formula (5-2), R 1 , R 2 , R 3 , R 4 and R 10 As defined above.

[0278] In formula (5-3), R 1 , R 2 , R 3 , R 4 、E 1 、E 2 、E 3 , a, b, c, d, e, f and g are as defined above.

[0279] Next, specific examples of the amidate compound (5) are shown. However, the present invention is not limited thereto. In the following specific examples, Et represents an ethyl group, Pr represents an n-propyl group, Bu represents an n-butyl group, Oct represents an n-octyl group, and t-Oct represents a 1,1,3,3-tetramethylbutyl group.

[0280] [Chemical formula 43]

[0281]

[0282]

[0283] [Chemical formula 44]

[0284]

[0285]

[0286] [Chemical formula 45]

[0287]

[0288] The amide compound (5) is preferably a compound represented by formula (5-1-1) to formula (5-1-8), formula (5-2-9) to formula (5-2-24), formula (5-3-1) to formula (5-3-8), and is particularly preferably a compound represented by formula (5-1-4), formula (5-1-5), formula (5-1-8), formula (5-2-13), and formula (5-3-5).

[0289] When the amidated compound (5) has isomers such as optical isomers, stereoisomers, positional isomers, etc., as long as it is not clearly stated which isomer it is, a mixture of any isomers is included in the amidated compound (5). For example, when optical isomers exist in the amidated compound (5), the optical isomers separated from the racemate can also be included in the amidated compound (5). These isomers can be obtained as single compounds by conventionally known separation techniques (concentration, solvent extraction, column chromatography, recrystallization, etc.).

[0290] In step 2, the nitrogen-containing compound (4) is usually used in an amount such that the group represented by Q in the nitrogen-containing compound (4) becomes 0.8 mol or more (preferably 1 to 3 mol) per 1 mol of the total of the carboxylate compound (3a) and the compounds (3b) to (3f) contained in the reactant (A). In this case, the total of the carboxylate compound (3a) and the compounds (3b) to (3f) contained in the reactant (A) may be an amount calculated from the amount of the imidazolium carboxylate (1) used in step 1.

[0291] When the reactant (A) contains a carboxylate compound (3a), the reaction is carried out in an amount such that the group represented by Q in the nitrogen-containing compound (4) becomes 0.8 mol or more (preferably 1 to 3 mol) based on 1 mol of the carboxylate compound (3a).

[0292] In this case, when the reactant (A) contains compounds (3b) to (3f), the amount of the nitrogen-containing compound (4) may be determined by treating the reactant compounds (3b) to (3f) as the carboxylate compound (3a).

[0293] The reaction temperature in step 2 is not particularly limited, but is usually -10°C or higher, preferably 0 to 200°C, more preferably 20 to 150°C. The reaction time is usually 0.1 to 24 hours, preferably 1 to 10 hours.

[0294] When a solvent is used, as a solvent, for example, aromatic hydrocarbon solvents such as toluene, benzene, and xylene, aliphatic hydrocarbon solvents such as methylcyclohexane, cyclohexane, hexane, heptane, and octane, halogenated hydrocarbon solvents such as chlorobutane and 1,2-dichloroethane, halogenated aromatic hydrocarbon solvents such as chlorobenzene, ester solvents such as ethyl acetate or butyl acetate, ketone solvents such as methyl ethyl ketone and 4-methyl-2-pentanone, etc., preferably aromatic hydrocarbon solvents and halogenated aromatic hydrocarbon solvents, ester solvents, ketone solvents, particularly preferably toluene, xylene, chlorobenzene, butyl acetate, 4-methyl-2-pentanone. The solvent can be mixed with two or more as needed. In addition, when the solvent used in step 1 is included in the reactant (A), the solvent can also be used as a solvent in step 2, but the above-mentioned solvent can also be further added. At this time, a solvent different from step 1 can be used.

[0295] When a solvent is used, the amount of the solvent used is usually 50 parts by mass or less, preferably 0.1 parts by mass or more and 35 parts by mass or less, relative to 1 part by mass of the total mass of the carboxylate compound (3a) and the compounds (3b) to (3f). As another embodiment, the amount of the solvent used is preferably usually 50 parts by mass or less, preferably 0.1 parts by mass or more and 35 parts by mass or less, relative to 1 part by mass of the mass of the components other than the solvent in the reactant (A) of step 1.

[0296] Here, the components other than the solvent in the reactant (A) refer to the concentrated residue after removing the solvent from the reaction solution obtained in step 1. The concentrated residue can actually be obtained by distilling off the solvent from the reaction solution by concentration or filtration, and the weight of the concentrated residue can also be obtained by using 1 The weight of the solvent contained in the reaction solution is calculated by H-NMR analysis or GC analysis, and the calculated weight of the solvent is subtracted from the weight of the reaction solution.

[0297] If necessary, the reaction can be carried out in an inert gas atmosphere such as nitrogen, argon, or helium which does not affect the reaction.

[0298] After the reaction is completed, the reaction solution can be concentrated or filtered to remove the solvent to obtain an amide compound (5), and can be purified by recrystallization or column fractionation as needed.

[0299] Example

[0300] Hereinafter, the present invention will be specifically described based on examples, but the present invention is not limited to these. 1 H-NMR was measured at 400 MHz using AV400 manufactured by Bruker Corporation. In the examples, wt% represents mass percentage concentration.

[0301] Preparation Example 1 Synthesis of [DOI][OAc]

[0302] [Chemical formula 46]

[0303]

[0304] Into a 3L 4-mouth reactor replaced with nitrogen, 1049.9g (8.12mol) of octylamine was poured and the temperature was raised to 80°C. After that, a mixture of 366.0g (6.09mol) of acetic acid and 290.4g of 42wt% formalin aqueous solution (pure formaldehyde content 4.06mol) was added dropwise over a period of 1 hour. After the addition, the mixed solution in the reactor was stirred for 30 minutes and cooled to 40°C. To the cooled mixed solution, 581.0g of 41wt% glyoxal aqueous solution (pure glyoxal content 4.06mol) was added dropwise over a period of 30 minutes and stirred for 5 hours. After stirring, the obtained reaction solution was concentrated under reduced pressure to obtain 1582.0g of [DOI][OAc] shown in the above formula. Tetralin was added as an internal standard substance to the obtained [DOI][OAc] and subjected to 1 H-NMR analysis revealed that the product contained 1224.9 g (3.47 mol, yield 85.5%) of [DOI][OAc].

[0305] [DOI][OAc] 1 The results of H-NMR analysis are shown below.

[0306] 1 H-NMR (DMSO-d 6 ) δ (ppm) = 9.32 (s, 1H), 7.80 (s, 2H), 4.17 (t, J = 9.6Hz, 4H), 1.78 (m, 4H), 1.63 (s, 3H), 1.23 (m, 20H), 0.85 (t, J = 6.4Hz, 6H)

[0307] Preparation Example 2 Synthesis of [DBI] [OAc]

[0308] [Chemical formula 47]

[0309]

[0310] Into a 200mL 4-mouth reactor replaced with nitrogen, pour 40g (0.55mol) of butylamine and cool to 0°C. After that, add a mixture of 24.6g (0.41mol) of acetic acid and 20.8g (0.28mol) of 40wt% formalin aqueous solution dropwise over 2 hours. After the addition, stir the mixture in the reactor for 30 minutes. Add 39.6g (0.27mol) of 40wt% glyoxal aqueous solution to the mixture over 30 minutes, and stir for 16 hours after the addition. After stirring, add 100mL of heptane to the obtained reaction solution and separate the liquids. Perform the operation of removing the heptane layer twice to obtain a brown solution. The obtained brown solution is concentrated under reduced pressure to obtain 75.8g (0.27mol, yield 98%) of [DBI][OAc] shown in the above formula. [DBI][OAc] 1 The results of H-NMR analysis are shown below.

[0311] 1 H-NMR (DMSO-d 6 )δ (ppm) = 9.53 (s, 1H), 7.82 (s, 2H), 4.19 (t, J = 6.8Hz, 4H), 1.81 (m, 4H), 1.68 (s, 4.5H), 1.29 (m, 4H), 0.91 (t, J = 7.2Hz, 6H)

[0312] Preparation Example 3 Synthesis of [D2EHI][OAc]

[0313] [Chemical formula 48]

[0314]

[0315] Into a 2L 4-mouth reactor replaced with nitrogen, 750.0 g (5.80 mol) of 2-ethylhexylamine was poured, and a mixture of 261.3 g (4.35 mol) of acetic acid and 217.8 g (2.90 mol) of a 40 wt% formalin aqueous solution was added dropwise over a period of 1 hour and 30 minutes. After the addition, the mixture in the reactor was stirred for 30 minutes. 421.0 g (2.90 mol) of a 40 wt% glyoxal aqueous solution was added dropwise to the mixture over a period of 20 minutes, and then stirred for 5 hours after the addition. The obtained reaction solution was concentrated under reduced pressure to obtain 1219.1 g (2.89 mol, yield 99%) of [D2EHI][OAc] shown in the above formula. 1 The results of H-NMR analysis are shown below.

[0316] 1 H-NMR (DMSO-d 6) δ (ppm) = 9.35 (s, 1H), 7.82 (s, 2H), 4.15 (d, J = 7.2Hz, 4H), 1.84 (m, 2H), 1.71 (s, 3H), 1.25 (m, 16H), 0.87 (t, J = 7.2Hz, 12H)

[0317] Preparation Example 4 Synthesis of [DtOctI][OAc]

[0318] [Chemical formula 49]

[0319]

[0320] Into a 100mL 3-necked reactor substituted with nitrogen, pour 6.97g (0.116mol) of acetic acid, 5.80g (0.077mol of pure formaldehyde) of 40wt% formalin aqueous solution, and 11.2g (0.077mol of pure glyoxal) of 40wt% glyoxal aqueous solution, and heat to 50°C. Then, add 20.00g (0.154mol) of 1,1,3,3-tetramethylbutylamine to the mixed solution in the reactor dropwise over a period of 2 hours, and stir for 2 hours. After stirring, the obtained reaction solution is concentrated under reduced pressure to obtain 24.83g (0.069mol, 90% yield) of [DtOctI][OAc] shown in the above formula. 1 The results of H-NMR analysis are shown below.

[0321] 1 H-NMR (CDCl 3 )δ (ppm) = 10.63 (s, 1H), 7.34 (s, 2H), 2.04 (s, 3H), 2.04 (s, 4H), 1.83 (s, 12H), 0.87 (s, 18H)

[0322] Example 1 Synthesis of DOIm_PI

[0323] [Chemical formula 50]

[0324]

[0325] (Step 1) Preparation of 1,3-di-n-octylimidazolium-2-carboxylate

[0326] Into a 5L pressure-resistant container, 1070.1g of [DOI][OAc] obtained in Preparation Example 1 (pure mass of DOI][OAc: 828.6g (2.35mol)), 1069.5g of toluene, and 756.0g of dimethyl carbonate (8.39mol) were added, and nitrogen substitution was performed. Thereafter, the mixed solution was stirred at 120°C for 15 hours. After stirring, the obtained reaction mixture was cooled. The cooled reaction mixture was concentrated under reduced pressure to 1043.5g, and the excess dimethyl carbonate and by-produced methyl acetate were removed, and toluene was added to make 2058.6g. The obtained toluene solution was subjected to HPLC-MS / MS using dimethyl sulfoxide as an internal standard substance. 1 H-NMR analysis showed that 339.3 g (1.01 mol, 42.8% yield) of 1,3-di-n-octylimidazolium-2-carboxylate was obtained. In addition, it was known that the obtained toluene solution contained 128.0 g (0.38 mol, 16.2% yield) of 1,3-di-n-octylimidazolium-4-carboxylate and 211.7 g (0.57 mol, 24.4% yield) of 1,3-di-n-octylimidazolium methyl carbonate.

[0327] The 1H-NMR analysis results of 1,3-di-n-octylimidazolium-2-carboxylate are shown below.

[0328] 1 H-NMR (CDCl 3 )δ (ppm) = 7.21 (s, 2H), 4.55 (t, J = 7.6Hz, 4H), 1.78 (m, 4H), 1.31 (m, 20H), 0.88 (t, J = 6.4Hz, 6H)

[0329] 1,3-di-n-octylimidazolium-4-carboxylate 1 The results of H-NMR analysis are shown below.

[0330] 1 H-NMR (CDCl 3 ) δ (ppm) = 7.49 (s, 1H), 4.73 (t, J = 7.2Hz, 2H), 4.26 (t, J = 7.2Hz, 2H), 1.78 (m, 4H), 1.31 (m, 20H), 0.88 (t, J = 6.4Hz, 6H)

[0331] 1,3-Di-n-octylimidazolium methyl carbonate 1 The results of H-NMR analysis are shown below.

[0332] 1 H-NMR (CDCl 3)δ (ppm) = 7.44 (s, 2H), 4.32 (t, J = 7.2Hz, 4H), 3.39 (s, 3H), 1.78 (m, 4H), 1.31 (m, 20H), 0.88 (t, J = 6.4Hz, 6H)

[0333] (Process 2)

[0334] Into a 3L 4-mouth reactor purged with nitrogen, 1700.2 g of the toluene solution obtained in step 1 and 807.4 g of toluene were poured and heated to reflux. While heating to reflux, 229.7 g (1.93 mol) of phenyl isocyanate was added dropwise over 2 hours, and the mixture was stirred for 10 hours. After stirring, 761.0 g of heptane was added and heated to 50°C until the obtained reaction mixture was concentrated to 1433.1 g, and all solids were dissolved to prepare a heptane solution. The heptane solution was cooled from 50°C to 30°C to precipitate crystals, and after stirring at 30°C for 1 hour, the heptane solution was cooled to 10°C at 10°C per hour for 2 hours, and stirred at 10°C for another 1 hour to obtain a slurry. By filtering the obtained slurry, 426.8 g (1.04 mol, 62.2% yield from step 1) of the compound represented by the above formula was obtained as a slightly yellow solid.

[0335] DOIm_PI 1 The results of H-NMR analysis are shown below.

[0336] 1 H-NMR (DMSO-d 6 ) δ (ppm) = 9.32 (s, 1H), 7.80 (s, 2H), 4.17 (t, J = 9.6Hz, 4H), 1.78 (m, 4H), 1.63 (s, 3H), 1.23 (m, 20H), 0.85 (t, J = 6.4Hz, 6H)

[0337] Example 2 Synthesis of DBIm_PI

[0338] [Chemical formula 51]

[0339]

[0340] (Process 1)

[0341] In a 180 mL pressure-resistant container, 30.0 g (pure weight 0.11 mol) of [DBI][OAc] obtained in Preparation Example 2, 44.8 g (0.50 mol) of dimethyl carbonate, and 30.0 g of toluene were added and replaced with nitrogen. The mixture was then stirred at 120° C. for 7 hours. After stirring, the reaction mixture was concentrated under reduced pressure to obtain 25.2 g of a brown liquid. The brown liquid was purified by evaporation. 1 H-NMR analysis and calculation by integral ratio showed that 9.8 g (0.04 mol, yield 39.2%) of 1,3-di-n-butylimidazolium-2-carboxylate was obtained. In addition, it was known that the obtained toluene solution contained 1.8 g (0.008 mol, yield 7.4%) of 1,3-di-n-butylimidazolium-4-carboxylate and 13.8 g (0.05 mol, yield 48.5%) of 1,3-di-n-butylimidazolium methyl carbonate. 25.2 g of chlorobenzene was added to the obtained brown liquid to prepare a chlorobenzene solution.

[0342] 1,3-di-n-butylimidazolium-2-carboxylate 1 The results of H-NMR analysis are shown below.

[0343] 1 H-NMR (DMSO-d 6 )δ (ppm) = 7.71 (s, 2H), 4.45 (t, J = 7.2Hz, 4H), 1.81 (m, 4H), 1.28 (m, 4H), 0.89 (m, 6H)

[0344] 1,3-di-n-butylimidazolium-4-carboxylate 1 The results of H-NMR analysis are shown below.

[0345] 1 H-NMR (DMSO-d 6 )δ (ppm) = 9.45 (s, 1H), 7.60 (s, 1H), 4.59 (t, J = 7.2Hz, 2H), 4.15 (t, J = 7.2Hz, 2H), 1.81 (m, 4H), 1.28 (m, 4H), 0.89 (m, 6H)

[0346] 1,3-di-n-butylimidazolium methyl carbonate 1 The results of H-NMR analysis are shown below.

[0347] 1 H-NMR (DMSO-d 6)δ (ppm) = 9.73 (s, 1H), 7.89 (s, 2H), 4.22 (t, J = 7.2Hz, 4H), 3.17 (s, 3H), 1.81 (m, 4H), 1.28 (m, 4H), 0.89 (m, 6H)

[0348] (Process 2)

[0349] Into a nitrogen-substituted 180mL 3-mouth reactor, 40.0g of the chlorobenzene solution obtained in step 1, 40.0g of chlorobenzene, and 13.4g (0.10mol) of methyl N-phenylamine formate were poured, and the mixture was heated to reflux for 5 hours. After heating to reflux, the reaction mixture was concentrated under reduced pressure to obtain 26.8g of a dry residue. Next, 17.1g of butyl acetate was added to the dry residue, the temperature was raised to 60°C, and the solid was completely dissolved, and then cooled to room temperature to obtain 5.8g (19.4mmol, 21.8% yield from step 1) of the compound represented by the above formula (DBIm_PI). 1 The results of H-NMR analysis are shown below.

[0350] 1 H-NMR (DMSO-d 6 )δ (ppm) = 7.60 (s, 2H), 7.42 (d, J = 8.4Hz, 2H), 7.14 (d, J = 7.6Hz, 2H), 6.80 (t, J = 7 .6Hz, 1H), 4.48 (t, J=7.6Hz, 4H), 1.80 (m, 4H), 1.30 (m, 4H), 0.91 (t, J=7.6Hz, 6H)

[0351] Example 3 Synthesis of D2HIm_PI

[0352] [Chemical formula 52]

[0353]

[0354] (Process 1)

[0355] In a 5L pressure-resistant container, 1104.2g (pure weight 3.07mol) of [D2EHI][OAc] obtained in Preparation Example 3, 744.9g (8.27mol) of dimethyl carbonate, and 1104.2g of toluene were added and replaced with nitrogen. Then, the mixed solution was heated to 120°C and stirred for 12 hours. After stirring, the obtained reaction mixture was concentrated under reduced pressure to obtain 1095.8g of brown liquid. The obtained brown liquid was subjected to 1H-NMR analysis and calculation by integral ratio showed that 526.8 g (1.49 mol, 46.6% yield) of 1,3-di-2-ethylhexyl imidazolium-2-carboxylate was obtained. In addition, it was known that the obtained toluene solution contained 142.4 g (0.423 mol, 13.8% yield) of 1,3-di-2-ethylhexyl imidazolium-4-carboxylate and 466.6 g (1.27 mol, 41.2% yield) of 1,3-di-2-ethylhexyl imidazolium methyl carbonate.

[0356] 1,3-di-2-ethylhexyl imidazolium-2-carboxylate 1 The results of H-NMR analysis are shown below.

[0357] 1 H-NMR (DMSO-d 6 )δ (ppm) = 7.70 (s, 2H), 4.38 (t, J = 6.0Hz, 4H), 1.84 (m, 2H), 1.25 (m, 16H), 0.87 (m, 12H)

[0358] 1,3-di-2-ethylhexyl imidazolium-4-carboxylate 1 The results of H-NMR analysis are shown below.

[0359] 1 H-NMR (DMSO-d 6 ) δ (ppm) = 9.18 (s, 1H), 7.64 (s, 1H), 4.53 (t, J = 6.0Hz, 2H), 4.05 (t, J = 6.0Hz, 2H), 1.84 (m, 2H), 1.25 (m, 16H), 0.87 (m, 12H)

[0360] 1,3-di-2-ethylhexyl imidazolium carbonate methyl ester 1 The results of H-NMR analysis are shown below.

[0361] 1 H-NMR (DMSO-d 6 )δ (ppm) = 9.51 (s, 1H), 7.89 (s, 2H), 4.24 (t, J = 7.6Hz, 4H), 3.18 (s, 3H), 1.84 (m, 2H), 1.25 (m, 16H), 0.87 (m, 12H)

[0362] (Process 2)

[0363] Into a 5L 4-mouth reactor substituted with nitrogen, 882.7g of the brown liquid obtained in step 1 (1,3-di-2-ethylhexyl imidazolium-2-carboxylate and their equivalents, 1,3-di-2-ethylhexyl imidazolium-4-carboxylate and 1,3-di-2-ethylhexyl imidazolium methyl carbonate, totaling 2.56 mol) and 2487.8g of toluene were added, and the mixture was heated to reflux. Thereafter, 292.3g (2.45 mol) of phenyl isocyanate was dripped into the liquid in the reactor over a period of 2 hours. After the dripping, the mixture was reacted for 13 hours and 30 minutes while refluxing. After the reaction, the reaction mixture obtained was concentrated under reduced pressure to obtain 1078.6g of the compound (D2HIm_PI) represented by the above formula. Tetralin was added to the obtained D2HIm_PI as an internal standard substance and the mixture was subjected to reflux. 1 The results of 1H-NMR analysis showed that D2HIm_PI contained 990.9 g (2.41 mol, yield 93.8%). The results of 1H-NMR analysis of D2Him_PI are shown below.

[0364] 1 H-NMR (DMSO-d 6 ) δ (ppm) = 7.59 (s, 2H), 7.39 (d, J = 8.4Hz, 2H), 7.12 (t, J = 8.4Hz, 2H), 6.76 (t, J=8.4Hz, 1H), 4.44(t, J=6.8Hz, 4H), 1.86(m, 2H), 1.25(m, 16H), 0.82(m, 12H)

[0365] Example 4D2 Synthesis of Him_crMDI

[0366] [Chemical formula 53]

[0367]

[0368] (Process 1)

[0369] In a 180 mL pressure-resistant container, 40.0 g (pure weight 99.5 mmol) of [D2EHI][OAc] and 26.9 g (299 mmol) of dimethyl carbonate prepared by the same preparation method as in Preparation Example 3 were added and replaced with nitrogen. Thereafter, the mixed solution in the pressure-resistant container was stirred at 120° C. for 6 hours. After stirring, the obtained reaction mixture was concentrated under reduced pressure to obtain 35.3 g of brown liquid. Dimethyl sulfone was added to the obtained brown liquid as an internal standard substance and the mixture was concentrated under reduced pressure to obtain 35.3 g of brown liquid. 1H-NMR internal standard analysis showed that 7.5 g (0.02 mol, yield 22.3%) of 1,3-di-2-ethylhexyl imidazolium-2-carboxylate was obtained. In addition, it was known that the obtained brown liquid contained 5.7 g (0.02 mol, yield 17.1%) of 1,3-di-2-ethylhexyl imidazolium-4-carboxylate and 18.3 g (0.05 mol, yield 50.0%) of 1,3-di-2-ethylhexyl imidazolium methyl carbonate.

[0370] (Process 2)

[0371] 30.2 g of toluene was added to a 200 mL 4-mouth reactor purged with nitrogen and refluxed. While refluxing the toluene, a mixed solution of 30.1 g of the brown liquid obtained in step 1 (1,3-di-2-ethylhexyl imidazolium-2-carboxylate and 1,3-di-2-ethylhexyl imidazolium-4-carboxylate and 1,3-di-2-ethylhexyl imidazolium methyl carbonate salt, total: 75.7 mmol) and 30.4 g of toluene was added dropwise to the reactor over 2 hours. In addition, a mixed solution of 10.6 g (NCO content: 83.1 mmol) of polymethylene polyphenyl polyisocyanate (Desmodur 44V20L manufactured by Sumika Covestro Urethane Co., Ltd., NCO content: 7.86 mmol / g) and 30.5 g of toluene was added dropwise to the reactor over 2 hours, and stirred for 1 hour while refluxed. After stirring, the obtained reaction mixture was concentrated under reduced pressure to obtain 37.4 g of a reaction product (D2HIm_crMDI) containing the compound represented by the above formula. 1 The results of H-NMR analysis are shown below.

[0372] 1 H-NMR (CDCl 3 )δ(ppm)=7.51-6.91(m), 4.52-4.37(m), 4.01-3.66(m), 1.88(br), 1.34-1.26(m), 0.89-0.82(m)

[0373] Example 5D2 Synthesis of Him_TDI

[0374] [Chemical formula 54]

[0375]

[0376] In a 180 mL pressure-resistant container, 70.1 g (pure weight 0.17 mol) of [D2EHI][OAc] and 53.9 g (0.60 mol) of dimethyl carbonate prepared by the same preparation method as in Preparation Example 3 were added and nitrogen purged. Thereafter, the mixed solution in the pressure-resistant container was stirred at 120° C. for 6 hours. After stirring, the obtained reaction mixture was concentrated under reduced pressure to obtain 67.7 g of a brown liquid. Dimethyl sulfone was added to the obtained brown liquid as an internal standard substance and the mixture was concentrated under reduced pressure to obtain 67.7 g of a brown liquid. 1 H-NMR internal standard analysis showed that 5.3 g (0.02 mol, yield 9.3%) of 1,3-di-2-ethylhexyl imidazolium-2-carboxylate was obtained. In addition, the brown liquid obtained contained 10.3 g (0.03 mol, yield 18.1%) of 1,3-di-2-ethylhexyl imidazolium-4-carboxylate, which is the equivalent of 1,3-di-2-ethylhexyl imidazolium-2-carboxylate, and 41.8 g (0.11 mol, yield 66.8%) of 1,3-di-2-ethylhexyl imidazolium methyl carbonate.

[0377] (Process 2)

[0378] 30.3 g of toluene was added to a 200 mL 4-mouth reactor purged with nitrogen and refluxed. Then, while refluxing the toluene, a mixed solution of 30.0 g of the brown liquid obtained in step 1 (1,3-di-2-ethylhexyl imidazolium-2-carboxylate and 1,3-di-2-ethylhexyl imidazolium-4-carboxylate and 1,3-di-2-ethylhexyl imidazolium methyl carbonate in total: 70.0 mmol) and 30.2 g of toluene was added dropwise to the reactor over 2 hours. In addition, a mixed solution of 6.7 g (38.4 mmol) of toluene diisocyanate (manufactured by Tokyo Chemical Industry Co., Ltd., about 80% of 2,4-toluene diisocyanate, about 20% of 2,6-toluene diisocyanate) and 30.5 g of toluene was added dropwise to the reactor over 2 hours, and stirred for 1 hour while refluxed. After stirring, the obtained reaction mixture was concentrated under reduced pressure to obtain 31.2 g of a reaction product (D2Him_TDI) containing the compound represented by the above formula. 1 The results of H-NMR analysis are shown below.

[0379] 1 H-NMR (CDCl 3 )δ(ppm)=7.28-6.88(m, 5H), 4.59-4.43(m, 8H), 2.24-2.17(m, 3H), 1.92(m, 4H), 1.37-1.27(m, 32H), 0.9-0.83(m, 24H)

[0380] Example 6 Synthesis of DtOctIm_PI

[0381] [Chemical formula 55]

[0382]

[0383] (Process 1)

[0384] In a 180 mL pressure vessel, 24.8 g (0.069 mol) of [DtOctI][OAc] obtained in Preparation Example 4, 27.0 g (0.297 mol) of dimethyl carbonate, and 30.0 g of toluene were added and replaced with nitrogen. Then, the mixed solution in the pressure vessel was stirred at 120° C. for 6 hours. After stirring, the obtained reaction mixture was concentrated under reduced pressure to obtain a reactant (A).

[0385] (Process 2)

[0386] Into a 100mL 3-necked reactor substituted with nitrogen, half of the reactant (A) obtained in step 1 and 40.0 g of chlorobenzene were poured, and the mixture was heated to reflux. The mixture after heating to reflux was cooled to 60°C, and a mixture of 3.9 g (0.032 mol) of phenyl isocyanate and 12.2 g of chlorobenzene was added dropwise thereto over 10 minutes, and then stirred at 60°C for 1 hour. After stirring, the obtained reaction mixture was cooled to room temperature, 50.0 g of heptane was added thereto, and the mixture was filtered. The residue was washed with 50.0 g of heptane to obtain 7.55 g (0.014 mmol, 40.0% yield from step 1) of the compound represented by the above formula. 1 The results of H-NMR analysis are shown below.

[0387] 1 H-NMR (CDCl 3 ) δ (ppm) = 7.59 (d, J = 9.2Hz, 2H), 7.30 (t, J = 7.6Hz, 2H), 7.08 (s, 2H) 6.93 (t, J = 7.2Hz, 1H), 2.40 (m, 4H), 1.87 (m, 12H), 0.99 (s, 18H).

Claims

1. A method for preparing a carboxylate compound, wherein the carboxylate compound is represented by the following formula (3a), the method comprising reacting an imidazolium carboxylate represented by the following formula (1) with a carbonate represented by the following formula (2), Formula (1): ， In formula (1), R 1 and R 4 The same or different, representing a hydrocarbon group having 1 to 12 carbon atoms; R 2 and R 3 Both represent hydrogen atoms; R 5 represents methyl, Formula (2): ， In formula (2), R 6 and R 7 All are methyl, Formula (3a): ， In formula (3a), R 1 , R 2 , R 3 and R 4 As defined above.

2. A method for preparing an amide compound, wherein the amide compound is represented by the following formula (5), and the method for preparing the amide compound comprises the following steps 1 and 2: Step 1 is a step of reacting an imidazolium carboxylate represented by formula (1) with a carbonate represented by formula (2) to obtain a reaction product containing a carboxylate compound represented by the following formula (3a). Formula (1): ， In formula (1), R 1 and R 4 The same or different, representing a hydrocarbon group having 1 to 12 carbon atoms; R 2 and R 3 Both represent hydrogen atoms; R 5 represents methyl, Formula (2): ， In formula (2), R 6 and R 7 All are methyl, Formula (3a): ， In formula (3a), R 1 , R 2 , R 3 and R 4 As defined above, Step 2 is a step of heating the reactant containing the carboxylate compound represented by the above formula (3a) obtained in step 1 as required, and reacting it with the nitrogen-containing compound represented by the formula (4) under heating as required to obtain the amidate compound represented by the formula (5). Formula (4): ， In formula (4), A is an aromatic group, and Q represents -NCO or -NHCO2R 8 , R 8 is a methyl group, n is an integer greater than 1, Formula (5): ， In formula (5), A, R 1 , R 2 , R 3 , R 4 , n are each as defined above.

3. The method for preparing an amidate compound according to claim 2, wherein: The nitrogen-containing compound represented by formula (4) is a nitrogen-containing compound represented by any one of the following formulas (4-1) to (4-3), Formula (4-1): ， In formula (4-1), Q is as defined above, R 9 is phenyl, Formula (4-2): ， In formula (4-2), Q is the same or different and is as defined above; R 10 is phenylene, Formula (4-3): ， In formula (4-3), Q is the same or different and is as defined above; E 1 、E 2 and E 3 Each independently represents a hydrocarbon group which may be substituted by a halogen atom, a hydrocarbon group which may be substituted by a heteroatom, a halogen atom, a dialkylamino group, an alkoxy group, an aryloxy group, a nitro group, a cyano group, a sulfonyl group, a (alkylamino)carbonylamino group, a (dialkylamino)carbonylamino group, or an isocyanate group; f is an integer of 1 to 4, g is 0, a and b are each 1, and c, d and e are all 0.

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