JP7018262B2 - Method for producing amidate compound - Google Patents

Description

The present invention relates to a method for producing an amidate compound.

Among the coordinate unsaturated compounds collectively called carbene compounds, heterocyclic carbene compounds (NHCs) have been attracting attention in recent years for their use as catalysts. For example, it can be used as a catalyst for producing a polymer having a polyether structure by ring-opening polymerization of an alkylene oxide such as an epoxy compound (Patent Documents 1 and 2), and a polymerization reaction between an aliphatic diisocyanate and an aliphatic diol. It is known that it is used as a catalyst in (Non-Patent Document 1). However, since carbene compounds are generally unstable to oxygen and water, as compounds that stabilize carbene, for example, compounds in which CO ₂ is added to heterocyclic carbene compounds (hereinafter referred to as carboxylate compounds). () And compounds to which an isocyanate compound is added (hereinafter referred to as amidate compounds) are known (Non-Patent Document 2).

Among these, as a method for producing an amidate compound, for example, 1-methylimidazole is reacted with dimethyl carbonate to produce 1,3-dimethylimidazolium-2-carboxylate, which is a carboxylate compound, and this is isolated. Then, a method of reacting p-chlorophenylisocyanate, which is an isocyanate compound, is known (Non-Patent Document 2). The present inventors reacted 1-butylimidazole with dimethyl carbonate with reference to Non-Patent Document 2 in order to synthesize an amidate compound using 1-butyl-3-methylimidazolium-2-carboxylate as a substrate. An attempt was made to produce -butyl-3-methylimidazolium-2-carboxylate. As a result, in ¹ H-NMR analysis of the reaction solution obtained in the reaction, it was confirmed that 1-butyl-3-methylimidazolium-2-carboxylate was produced, but when the reaction solution was concentrated, 1- Since butyl-3-methylimidazolium-2-carboxylate was decomposed, it was found that 1-butyl-3-methylimidazolium-2-carboxylate could not be isolated (see Comparative Example 1 below). Therefore, the production method described in Non-Patent Document 2 is unsuitable for producing an amidate compound using a carboxylate compound having low stability, which is difficult to isolate, as a substrate, and the carboxylate having low stability. The challenge was to develop a method for producing an amidate compound having high substrate applicability, which can produce an amidate compound of interest even when the compound is used as a substrate.

International Publication No. 2009/0133344 Pamphlet Special Table 2013-526630 Gazette

Polymer Chemistry 2012 Volume 3 pp. 605-608 Organic & Biomolecular Chemistry 2008 Vol. 6, No. 2, pp. 287-295

The present invention has been made in view of the above background techniques, and even when a carboxylate compound having low stability, which is difficult to isolate, is used as a substrate, the desired amidate compound can be produced. It is an object of the present invention to provide a novel method for producing an amidate compound, which can be applied to a substrate and has high substrate applicability.

When the present inventor conducted a diligent study to solve the above problems, the following formula was obtained by reacting the nitrogen-containing compound represented by the following formula (1) with the dialkyl carbonate compound represented by the following formula (2). After obtaining a reaction solution containing the carboxylate compound represented by (3), the carboxylate compound (3) is not isolated from the reaction solution and is reacted with the isocyanate compound represented by the following formula (4). We have found that an amidate compound represented by the following formula (5) can be produced, and have completed the present invention.

That is, the present invention relates to the following [1] to [5].

[1] A reaction solution containing a carboxylate compound represented by the following formula (3) is obtained by reacting a nitrogen-containing compound represented by the following formula (1) with a dialkyl carbonate compound represented by the following formula (2). , A method for producing an amidate compound represented by the following formula (5), which is reacted with an isocyanate compound represented by the following formula (4) without isolating the carboxylate compound represented by the formula (3) from the reaction solution. ..

Equation (1):

（式中、Ｒ^３～Ｒ^５はヘテロ原子を含んでいてもよい炭化水素基であり、一部又は全てが相互に結合して環構造を形成していてもよい。Ｘは窒素原子、酸素原子又は硫黄原子を示す。但し、Ｘが酸素原子又は硫黄原子の場合、Ｒ^５は無い。）

(In the formula, R ³ to R ⁵ are hydrocarbon groups which may contain a hetero atom, and some or all of them may be bonded to each other to form a ring structure. X is a nitrogen atom and oxygen. Indicates an atom or a sulfur atom. However, if X is an oxygen atom or a sulfur atom, there is no ^R5 .)

Equation (2):

（式中、Ｒ^２はヘテロ原子を含んでいてもよい炭化水素基である。）

(In the formula, R ² is a hydrocarbon group that may contain a heteroatom.)

Equation (3):

（式中、Ｒ^２～Ｒ^５及びＸは前記に同じである。）

( ^In the formula, ^R2 to R5 and X are the same as described above.)

Equation (4):

（式中、Ａは置換若しくは無置換の炭化水素基、ｎは１以上の整数である。）

(In the formula, A is a substituted or unsubstituted hydrocarbon group, and n is an integer of 1 or more.)

Equation (5):

（式中、Ａ、ｎ、Ｒ^２～Ｒ^５及びＸは前記に同じである。）

(In the formula, A, n, ^R2 to R5 and X are the ^same as described above.)

[2] The method according to [1], wherein when the nitrogen-containing compound represented by the formula (1) and the dialkyl carbonate compound represented by the formula (2) are reacted in the presence of an alcohol solvent in [1]. A method for producing an amidate compound.

[3] The nitrogen-containing compound represented by the formula (1) is at least one nitrogen-containing compound selected from the group consisting of the following formulas (1-1) to (1-3) [1] or [ 2] The method for producing an amidate compound according to.

Equation (1-1):

（式中、Ｒ^５及びＸは前記に同じ、Ｒ^８及びＲ^９は水素原子又はヘテロ原子を含んでいても良い炭素数１～６の炭化水素基である。）

(In the formula, R ⁵ and X are the same as described above, and R ⁸ and R ⁹ are hydrocarbon groups having 1 to 6 carbon atoms which may contain a hydrogen atom or a hetero atom.)

Equation (1-2):

（式中、Ｒ^５及びＸは前記に同じ、Ｒ^１０及びＲ^１１は水素原子又はヘテロ原子を含んでいても良い炭素数１～６の炭化水素基である。）

(In the formula, R ⁵ and X are the same as described above, and R ¹⁰ and R ¹¹ are hydrocarbon groups having 1 to 6 carbon atoms which may contain a hydrogen atom or a hetero atom.)

Equation (1-3):

（式中、Ｒ^５及びＸは前記に同じ、Ｒ^１２～Ｒ^１５は水素原子又はヘテロ原子を含んでいても良い炭素数１～６の炭化水素基である。）

(In the formula, R ⁵ and X are the same as described above, and R ¹² to R ¹⁵ are hydrocarbon groups having 1 to 6 carbon atoms which may contain a hydrogen atom or a hetero atom.)

[4] The amidate according to any one of [1] to [3], wherein the isocyanate compound represented by the formula (4) is an isocyanate compound represented by the following formulas (4-1) to (4-3). Method for producing a compound.

Equation (4-1):

（式中、Ｒ^６は置換若しくは無置換の炭化水素基である。）

(In the formula, R ⁶ is a substituted or unsubstituted hydrocarbon group.)

Equation (4-2):

（式中、Ｒ^７は置換若しくは無置換の炭化水素基である。）

(In the formula, R ⁷ is a substituted or unsubstituted hydrocarbon group.)

Equation (4-3):

（式中、ｍは０～４の整数である。）

(In the formula, m is an integer from 0 to 4.)

[5] The method for producing an amidate compound according to any one of [1] to [4], wherein X is a nitrogen atom.

According to the present invention, even when a carboxylate compound having low stability, which is difficult to isolate, is used as a substrate, the desired amidate compound can be produced, and the amidate having high substrate applicability can be produced. A novel method for producing a compound can be provided.

Hereinafter, embodiments for carrying out the present invention will be described in detail.

In the formula (1), R ³ to R ⁵ are hydrocarbon groups which may contain heteroatoms, and some or all of them may be bonded to each other to form a ring structure. The hydrocarbon group which may contain a hetero atom includes a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an s-butyl group, a t-butyl group, an n-pentyl group and an n-hexyl group. , N-octyl group, n-decyl group, n-dodecyl group, allyl group, benzyl group, cyclohexyl group, adamantyl group, phenyl group, 2,6-diisopropylphenyl group, 2,4,6-trimethylphenyl group, 2 -Examples include a methoxyethyl group, a 2-ethoxyethyl group, a 2- (dimethylamino) ethyl group and the like. It is preferably a methyl group, an ethyl group, a propyl group, an isopropyl group, a t-butyl group, an n-octyl group, a cyclopentyl group, a cyclohexyl group, a 2,4,6-trimethylphenyl group, and more preferably a methyl group or a methyl group. Ethyl group, isopropyl group, t-butyl group, n-octyl group, phenyl group, particularly preferably methyl group, isopropyl group, t-butyl group, n-octyl group and phenyl group. X is a nitrogen atom, an oxygen atom or a sulfur atom, preferably a nitrogen atom. However, when X is an oxygen atom or a sulfur atom, there is no ^R5 .
In the present invention, from the viewpoint of availability, R ³ and R ⁴ are bonded to each other in the nitrogen-containing compound represented by the formula (1) (hereinafter referred to as nitrogen-containing compound (1)) to form a ring structure. It is preferable to do so. The nitrogen-containing organic compound (1) forming the ring is preferably at least one selected from the group consisting of the nitrogen-containing organic compounds represented by the formulas (1-1) to (1-3). A nitrogen-containing organic compound represented by the formula (1-1) is particularly preferable.

Equation (1-1):

（式中、Ｒ^５及びＸは前記に同じ、Ｒ^８及びＲ^９は水素原子又はヘテロ原子を含んでいても良い炭素数１～６の炭化水素基である。）

(In the formula, R ⁵ and X are the same as described above, and R ⁸ and R ⁹ are hydrocarbon groups having 1 to 6 carbon atoms which may contain a hydrogen atom or a hetero atom.)

Equation (1-2):

（式中、Ｒ^５及びＸは前記に同じ、Ｒ^１０及びＲ^１１は水素原子又はヘテロ原子を含んでいても良い炭素数１～６の炭化水素基である。）

(In the formula, R ⁵ and X are the same as described above, and R ¹⁰ and R ¹¹ are hydrocarbon groups having 1 to 6 carbon atoms which may contain a hydrogen atom or a hetero atom.)

Equation (1-3):

（式中、Ｒ^５及びＸは前記に同じ、Ｒ^１２～Ｒ^１５は水素原子又はヘテロ原子を含んでいても良い炭素数１～６の炭化水素基である。）

(In the formula, R ⁵ and X are the same as described above, and R ¹² to R ¹⁵ are hydrocarbon groups having 1 to 6 carbon atoms which may contain a hydrogen atom or a hetero atom.)

^In formula (1-1), R5 and X are the same as described above. R ⁸ and R ⁹ are hydrocarbon groups having 1 to 6 carbon atoms which may contain a hydrogen atom or a hetero atom, and are preferably hydrogen atoms. Examples of the hydrocarbon group having 1 to 6 carbon atoms which may contain a hetero atom include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an s-butyl group, a t-butyl group and a pentyl group. Examples thereof include a hexyl group, a cyclohexyl group, a phenyl group, a 2-methoxyethyl group, a 2-ethoxyethyl group, a 2- (dimethylamino) ethyl group, and the like, and a methyl group is preferable.

Specific examples of the nitrogen-containing compound represented by the formula (1-1) include 1-methylimidazole, 1-ethyl imidazole, 1-propyl imidazole, 1-isopropyl imidazole, 1-butyl imidazole, 1-t-butyl imidazole. , 1-pentylimidazole, 1-hexylimidazole, 1-heptyl imidazole, 1-octyl imidazole, 1-nonyl imidazole, 1-decyl imidazole, 1-allyl imidazole, 1-benzyl imidazole, 1- (2-methoxyethyl) imidazole , 1- (2-ethoxyethyl) -imidazole, 1- (2-dimethylaminoethyl) imidazole, 1,4,5-trimethylimidazole

Oxazole, 5-methyloxazole, 4,5-dimethyloxazole,

Examples thereof include thiazole, 4-methylthiazole, 5-methylthiazole, 4,5-dimethylthiazole and the like, preferably 1-methylimidazole, 1-ethylimidazole, 1propylimidazole, 1-butylimidazole and 1-octylimidazole. Yes, and particularly preferred are 1-methylimidazole, 1-butylimidazole, and 1-octylimidazole.

^In formula (1-2), R5 and X are the same as described above. R ¹⁰ and R ¹¹ are hydrocarbon groups having 1 to 6 carbon atoms which may contain a hydrogen atom or a hetero atom, and are preferably hydrogen atoms. Examples of the hydrocarbon group having 1 to 6 carbon atoms which may contain a hetero atom include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an s-butyl group, a t-butyl group and a pentyl group. Examples thereof include a hexyl group, a cyclohexyl group, a phenyl group, a 2-methoxyethyl group, a 2-ethoxyethyl group, a 2- (dimethylamino) ethyl group, and the like, and a methyl group is preferable.

Specific examples of the nitrogen-containing compound represented by the formula (1-2) include 1-methylimidazoline, 1-ethyl imidazoline, 1-propyl imidazoline, 1-isopropyl imidazoline, 1-butyl imidazoline, 1-t-butyl imidazoline. , 1-Pentyl imidazoline, 1-Hexyluimidazoline, 1-Heptyl imidazoline, 1-octyl imidazoline, 1-nonyl imidazoline, 1-decyl imidazoline, 1-allyl imidazoline, 1-benzyl imidazoline, 1- (2-methoxyethyl) imidazoline , 1- (2-ethoxyethyl) imidazoline, 1- (2-dimethylaminoethyl) imidazoline, 1,4,5-trimethylimidazoline

Oxazoline, 5-methyloxazoline, 4,5-dimethyloxazoline,

Examples thereof include thiazolin, 4-methylthiazolin, 5-methylthiazolin, 4,5-dimethylthiazolin, and the like, preferably 1-methylimidazoline, 1-ethylimidazoline, 1-propylimidazoline, 1-butylimidazoline, and particularly preferably. Is 1-methylimidazoline.

^In formula (1-3), R5 and X are the same as described above. R ¹² to R ¹⁵ are hydrocarbon groups having 1 to 6 carbon atoms which may contain a hydrogen atom or a hetero atom, and are preferably hydrogen atoms. Examples of the hydrocarbon group having 1 to 6 carbon atoms which may contain a hetero atom include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an s-butyl group, a t-butyl group and a pentyl group. Examples thereof include a hexyl group, a cyclohexyl group, a phenyl group, a 2-methoxyethyl group, a 2-ethoxyethyl group, a 2- (dimethylamino) ethyl group, and the like, and a methyl group is preferable.

Specific examples of the nitrogen-containing compound represented by the formula (1-3) include 1-methylbenzimidazole, 1-ethylbenzimidazole, 1-propylbenzimidazole, 1-butylbenzimidazole, 1-pentylbenzimidazole, 1 -Hexylbenzimidazole, 1-heptylbenzimidazole, 1-octylbenzimidazole, 1-nonylbenzimidazole, 1-decylbenzimidazole, 1-allylbenzimidazole, 1-benzylbenzoimidazole, 1,6-dimethylbenzoimidazole, 1 -Acetyl-6-methylbenzimidazole, 1,6,7-trimethylbenzimidazole,

Examples thereof include benzoxazole and benzothiazole, preferably 1-methylbenzimidazole, 1-ethyllbenzoimidazole, 1-propylbenzimidazole and 1-butylbenzimidazole, and particularly preferably 1-methylbenzimidazole. be.

In formula (2), R ² is a hydrocarbon group that may contain a heteroatom. The hydrocarbon group which may contain a hetero atom includes a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an s-butyl group, a t-butyl group, an n-pentyl group and an n-hexyl group. , N-octyl group, n-decyl group, n-dodecyl group, allyl group, benzyl group, cyclohexyl group, adamantyl group, phenyl group, 2,6-diisopropylphenyl group, 2,4,6-trimethylphenyl group, 2 -Examples include a methoxyethyl group, a 2-ethoxyethyl group, a 2- (dimethylamino) ethyl group and the like. A methyl group, an ethyl group, a propyl group, an isopropyl group, a t-butyl group, an n-octyl group, a cyclopentyl group, a cyclohexyl group and a phenyl group are preferable, and a methyl group is particularly preferable.

Specific examples of the dialkyl carbonate compound represented by the formula (2) (hereinafter referred to as dialkyl carbonate compound (2)) include dimethyl carbonate, diethyl carbonate, dipropyl carbonate, dibutyl carbonate, dipentyl carbonate, dihexyl carbonate and the like. , Preferably dimethyl carbonate, diethyl carbonate, dipropyl carbonate, dibutyl carbonate, and particularly preferably dimethyl carbonate.

The amount of the dialkyl carbonate compound (2) used is usually 1 mol or more, preferably 1 to 6 mol, with respect to 1 mol of the nitrogen-containing organic compound (1).

Next, a carboxylate compound represented by the formula (3) (hereinafter, referred to as a carboxylate compound (3)) will be described.

In formula ( ³ ), ^R2 to R5 and X are the same as described above. In the carboxylate compound (3), it is preferable that R ³ and R ⁴ are bonded to each other to form a ring structure. The carboxylate compound (3) forming the ring is preferably at least one selected from the group consisting of the carboxylate compounds represented by the formulas (3-1) to (3-3), and is particularly preferable. Is a carboxylate compound represented by the formula (3-1).

Equation (3-1):

（式中、Ｒ^２、Ｒ^５、Ｒ^８、Ｒ^９及びＸは前記に同じである。）

(In the formula, R ² , R ⁵ , R ⁸ , R ⁹ and X are the same as described above.)

Equation (3-2):

（式中、Ｒ^２、Ｒ^５、Ｒ^１０、Ｒ^１１及びＸは前記に同じである。）

(In the formula, R ² , R ⁵ , R ¹⁰ , R ¹¹ and X are the same as described above.)

Equation (3-3):

（式中、Ｒ^２、Ｒ^５、Ｒ^１２～Ｒ^１５及びＸは前記に同じである。）

(In the formula, R ² , R ⁵ , R ¹² to R ¹⁵ and X are the same as described above.)

In formula (3-1), R ² , R ⁵ , R ⁸ , R ⁹ and X are the same as described above.

Specific examples of the carboxylate compound represented by the formula (3-1) include 1,3-dimethylimidazolium-2-carboxylate, 1-ethyl-3-methylimidazolium-2-carboxylate, and 1-methyl. -3-propylimidazolium-2-carboxylate, 1-methyl-3-isopropylimidazolium-2-carboxylate, 1-butyl-3-methylimidazolium-2-carboxylate, 1-t-butyl-3- Methylimidazolium-2-carboxylate, 1-methyl-3-pentylimidazolium-2-carboxylate, 1-hexyl-3-methylimidazolium-2-carboxylate, 1-heptyl-3-methylimidazolium-2 -Carboxylate, 1-Methyl-3-octylimidazolium-2-carboxylate, 1-methyl-3-nonylimidazolium-2-carboxylate, 1-decyl-3-methylimidazolium-2-carboxylate, 1 -Allyl-3-methylimidazolium-2-carboxylate, 1-benzyl-3-methylimidazolium-2-carboxylate, 1- (2-methoxyethyl) -3-methylimidazolium-2-carboxylate, 1, -(2-ethoxyethyl) -3-methylimidazolium-2-carboxylate, 1- (2-dimethylaminoethyl) -3-methylimidazolium-2-carboxylate,

3-Methyloxazolium-2-carboxylate, 3,5-dimethyloxazolium-2-carboxylate, 3,4,5-trimethyloxazolium-2-carboxylate,

3-Methylthiazolium-2-carboxylate, 3,4-dimethylthiazolium-2-carboxylate, 3,5-dimethylthiazolium-2-carboxylate, 3,4,5-trimethylthiazolium -2-carboxylate, etc., preferably 1,3-dimethylimidazolium-2-carboxylate, 1-ethyl-3-methylimidazolium-2-carboxylate, 1-methyl-3-propylimidazole, etc. Rium-2-carboxylate, 1-butyl-3-methylimidazolium-2-carboxylate, 1-methyl-3-octylimidazolium-2-carboxylate, and particularly preferably 1,3-dimethylimidazolium. -2-carboxylate, 1-butyl-3-methylimidazolium carboxylate, 1-methyl-3-octylimidazolium-2-carboxylate.

In formula (3-2), R ² , R ⁵ , R ⁸ , R ⁹ and X are the same as described above.

Specific examples of the carboxylate compound represented by the formula (3-2) include 1,3-dimethylimidazolinium-2-carboxylate, 1-ethyl-3-methylimidazolinium-2-carboxylate, and 1 -Methyl-3-propylimidazolinium-2-carboxylate, 1-butyl-3-methylimidazolinium-2-carboxylate, 1-methyl-3-pentylimidazolinium-2-carboxylate, 1-hexyl -3-Methylimidazolinium-2-carboxylate, 1-heptyl-3-methylimidazolinium-2-carboxylate, 1-methyl-3-octylimidazolinium-2-carboxylate, 1-methyl-3 -Nonyl imidazolinium-2-carboxylate, 1-decyl-3-methyl imidazolinium-2-carboxylate, 1-allyl-3-methyl imidazolinium-2-carboxylate, 1-benzyl-3-methyl Imidazolinium-2-carboxylate, 1- (2-methoxyethyl) -3-methylimidazolinium-2-carboxylate, 1- (2-ethoxyethyl) -3-methylimidazolinium-2-carboxylate , 1- (2-dimethylaminoethyl) -3-methylimidazolinium-2-carboxylate, 1,3,4,5-tetramethylimidazolinium-2-carboxylate,

3-Methyloxazolinium-2-carboxylate, 3,4-dimethyloxazolinium-2-carboxylate, 3,5-dimethyloxazolinium-2-carboxylate, 3,4,5-trimethyloxazolinium -2-carboxylate,

3-Methylthiazolinium-2-carboxylate, 3,4-dimethylthiazolinium-2-carboxylate, 3,5-dimethylthiazolinium-2-carboxylate, 3,4,5-trimethylthiazolinium -2-carboxylate and the like, preferably 1,3-dimethylimidazolinium-2-carboxylate, 1-ethyl-3-methylimidazolinium-2-carboxylate, 1-methyl-3-propyl. It is imidazolinium-2-carboxylate, 1-butyl-3-methylimidazolinium-2-carboxylate, and particularly preferably 1,3-dimethylimidazolinium-2-carboxylate.

In formula (3-3), R ² , R ⁵ , R ¹² to R ¹⁵ and X are the same as described above.

Specific examples of the carboxylate compound represented by the formula (3-3) include 1,3-dimethylbenzoimidazolium-2-carboxylate, 1-ethyl-3-methylbenzoimidazolium-2-carboxylate, and 1 -Methyl-3-propylbenzoimidazolium-2-carboxylate, 1-butyl-3-methylbenzoimidazolium-2-carboxylate, 1-methyl-3-pentylbenzoimidazolium-2-carboxylate, 1-hexyl -3-Methylbenzoimidazolium-2-carboxylate, 1-heptyl-3-methylbenzoimidazolium-2-carboxylate, 1-methyl-3-octylbenzoimidazolium-2-carboxylate, 1-methyl-3 -Nonylbenzoimidazolium-2-carboxylate, 1-decyl-3-methylbenzoimidazolium-2-carboxylate, 1-allyl-3-methylbenzoimidazolium-2-carboxylate, 1-benzyl-3-methyl Benzoimidazolium-2-carboxylate, 1,3,6-trimethylbenzoimidazolium-2-carboxylate, 1-acetyl-3,6-dimethylbenzoimidazolium-2-carboxylate, 1,3,6,7 -Tetramethylbenzoimidazolium-2-carboxylate, 1,3-dibenzyl-6,7-dimethylbenzoimidazolium-2-carboxylate,

3-Methylbenzoxadiazole-2-carboxylate,

3-Methylbenzothiazolium-2-carboxylate is preferably 1,3-dimethylbenzoimidazolium-2-carboxylate, 1-ethyl-3-methylbenzoimidazolium-2-carboxylate, 1-methyl-3. -Propylbenzoimidazolium-2-carboxylate, 1-butyl-3-methylbenzoimidazolium-2-carboxylate, and particularly preferably 1,3-dimethylbenzoimidazolium-2-carboxylate.

The optimum temperature of the reaction varies depending on the raw materials used, the solvent and the like, but is usually room temperature or higher, preferably 20 to 200 ° C.

The solvent may or may not be used. When a solvent is used, specific examples of the solvent include alcohol solvents such as methanol, ethanol, propanol, butanol, pentanol, hexanol, 1-methoxy-2-propanol and ethoxyethanol, ethylene glycol, propylene glycol and diethylene glycol. Polypropylene solvent, dipropylene glycol mono n-butyl ether, dipropylene glycol monomethyl ether, tripropylene glycol monomethyl ether, propylene glycol mono n-propyl ether, dipropylene glycol mono n-propyl ether, propylene glycol mono n-butyl ether, tripropylene glycol Examples thereof include glycol monoalkyl ether solvents such as mono n-butyl ether, propylene glycol monomethyl ether and diethylene glycol monoethyl ether, preferably a monovalent alcohol solvent, and particularly preferably methanol. The amount of the solvent used is usually 50 parts by weight or less, preferably 10 parts by weight or less, based on 1 part by weight of the nitrogen-containing organic compound (1).

If necessary, the reaction may be carried out in an inert gas atmosphere that does not affect the reaction of nitrogen, argon, helium or the like.

After completion of the reaction, the carboxylate compound (3) is not taken out from the reaction solution, and the reaction solution is used as it is for the reaction with the isocyanate compound represented by the formula (4).

The reaction between the isocyanate compound represented by the formula (4) and the carboxylate compound (3) will be described.

In formula (4), A is a substituted or unsubstituted hydrocarbon group, preferably a substituted or unsubstituted hydrocarbon group having 1 to 100 carbon atoms, and more preferably a substituted or unsubstituted hydrocarbon group having 1 to 50 carbon atoms. A hydrocarbon group, particularly preferably a substituted or unsubstituted hydrocarbon group having 1 to 30 carbon atoms. When A has a substituent, examples of the substituent include a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, an alkylamino group such as a methylamino group, a dialkylamino group such as a dimethylamino group, and methoxy. Examples thereof include an alkoxy group such as a group and an ethoxy group, an aryloxy group such as a benzyloxy group, an alkyl halide group such as a trifluoromethyl group, a nitro group, a cyano group and an isocyanate group. Further, the hydrocarbon group of A may be substituted with a hetero atom such as an oxygen atom, a nitrogen atom or a sulfur atom.

n is an integer of 1 or more, preferably 1 to 6, more preferably 1 to 4, and particularly preferably 1 to 2 from the viewpoint of availability.

The isocyanate compound represented by the formula (4) (hereinafter referred to as the isocyanate compound (4)) is preferably an isocyanate compound represented by the formulas (4-1) to (4-3), and is particularly preferable. It is an isocyanate compound represented by the formula (4-1) or the formula (4-2).

Equation (4-1):

（式中、Ｒ^６は置換若しくは無置換の炭化水素基である。）

(In the formula, R ⁶ is a substituted or unsubstituted hydrocarbon group.)

Equation (4-2):

（式中、Ｒ^７は置換若しくは無置換の炭化水素基である。）

(In the formula, R ⁷ is a substituted or unsubstituted hydrocarbon group.)

Equation (4-3):

（式中、ｍは０～４の整数である。）

(In the formula, m is an integer from 0 to 4.)

In formula (4-1), R ⁶ is a substituted or unsubstituted hydrocarbon group, preferably a substituted or unsubstituted hydrocarbon group having 1 to 100 carbon atoms, and more preferably a substituted or unsubstituted hydrocarbon group having 1 carbon atom. It is a hydrocarbon group of about 50, particularly preferably a substituted or unsubstituted hydrocarbon group having 1 to 30 carbon atoms. When R ⁶ has a substituent, examples of the substituent include a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, an alkylamino group such as a methylamino group, and a dialkylamino group such as a dimethylamino group. Examples thereof include an alkoxy group such as a methoxy group and an ethoxy group, an aryloxy group such as a benzyloxy group, an alkyl halide group such as a trifluoromethyl group, a nitro group, a cyano group and an isocyanate group. Further, the hydrocarbon group of R ⁶ may be substituted with a hetero atom such as an oxygen atom, a nitrogen atom or a sulfur atom.

In formula (4-2), R ⁷ is a substituted or unsubstituted hydrocarbon group, preferably a substituted or unsubstituted hydrocarbon group having 1 to 100 carbon atoms, and more preferably a substituted or unsubstituted hydrocarbon group having 1 carbon atom. It is a hydrocarbon group of about 50, particularly preferably a substituted or unsubstituted hydrocarbon group having 1 to 30 carbon atoms. Specifically, a methylene group, a dimethylmethylene group, an ethylene group, an n-propylene group, an n-butylene group, an n-pentylene group, an n-hexylene group, an n-heptylene group, an n-octylene group, an n-nonylene group, alkylene groups such as n-decylene group, n-dodecylene group, n-octadecylene group, cyclohexylene group, phenylene group, 2-methylphenylene group, 2,6-dimethylphenylene group, 2,4-dimethylphenylene group, 2, 3-dimethylphenylene group, arylene group such as naphthylene group, phenylmethylene group, phenylethylene group, 1-phenylpropylene group, 2-phenylpropylene group, 1-phenylbutylene group, 2-phenylbutylene group, naphthylmethylene group, naphthyl Examples thereof include an arylalkylene group such as an ethylene group, an arylene alkylene group formed by appropriately combining the above-mentioned alkylene group and an arylene group, and the like. These divalent hydrocarbon groups may be repeated or combined to form one divalent hydrocarbon group.

When R ⁷ has a substituent, examples of the substituent include a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, an alkylamino group such as a methylamino group, and a dialkylamino group such as a dimethylamino group. Examples thereof include an alkoxy group such as a methoxy group and an ethoxy group, an aryloxy group such as a benzyloxy group, an alkyl halide group such as a trifluoromethyl group, a nitro group, a cyano group and an isocyanate group. Further, the hydrocarbon group of R ⁷ may be substituted with a hetero atom such as an oxygen atom, a nitrogen atom or a sulfur atom.

In equation (4-3), m is the same as above.

Specific examples of the isocyanate compound (4) are shown below, but the present invention is not limited thereto. In the following specific examples, Et is an ethyl group, Pr is an n-propyl group, and Bu is an n-butyl group.

As the isocyanate compound (4), the formulas (4-1-20), (4-1-30), (4-1-41), (4-1-45), (4-1-46), ( 4-1-48), (4-1-52), (4-1-59), (4-1-88), (4-1-89), (4-1-90), (4- It is a compound represented by 2-20), and particularly preferably a compound represented by the formula (4-1-20).

The amidate compound represented by the formula (5) will be described.

In formula ( ⁵ ), A, ^R2 to R5, X and n are the same as described above. The amidate compound represented by the formula (5) (hereinafter referred to as the amidate compound (5)) is preferably an amidate compound represented by the formulas (5-1) to (5-3).

Equation (5-1):

（式中、Ｒ^２～Ｒ^６、Ｘは前記に同じである。）

( ^In the formula, ^R2 to R6 and X are the same as described above.)

Equation (5-2):

（式中、Ｒ^２～Ｒ^５、Ｒ^７、及びＸは前記に同じである。）

( ^In the formula, ^R2 to R5, ^R7 , and X are the same as described above.)

Equation (5-3):

（式中、Ｒ^２～Ｒ^５、Ｘ及びｍは前記に同じである。）

(In the formula, R ² to R ⁵ , X and m are the same as described above.)

^In the formula (5-1), ^R2 to R6 and X are the same as described above.

In formula ( ^5-2 ), ^R2 to R5, ^R7 and X are the same as described above.

In formula ( ^5-3 ), ^R2 to R5, X and m are the same as described above.

Specific examples of the amidate compound (5) are shown below, but the present invention is not limited thereto. In the following specific examples, Et is an ethyl group, Pr is an n-propyl group, and Bu is an n-butyl group.

（式（５－３－１ａ）～（３－３－１ｃ）中、ｍは前記に同じ。）

(In the formulas (5-3-1a) to (3-3-1c), m is the same as described above.)

As the amidate compound (5), the formulas (5-1-20a), (5-1-30a), (5-1-41a), (5-1-45a), (5-1-46a), ( 5-1-48a), (5-1-52a), (5-1-59a), (5-1-88a), (5-1-89a), (5-1-90a), (5- 2-20a), (5-1-20b), (5-1-30b), (5-1-41b), (5-1-45b), (5-1-46b), (5-1- 48b), (5-1-52b), (5-1-59b), (5-1-88b), (5-1-89b), (5-1-90b), (5-2-20b). , (5-1-20c), (5-1-30c), (5-1-41c), (5-1-45c), (5-1-46c), (5-1-48c), ( 5-1-52c), (5-1-59c), (5-1-89c), (5-1-90c), (5-1-88c), (5-2-20c), (5- 2-41a), (5-2-48a), (5-2-49a), (5-2-51a), (5-2-41b), (5-2-48b), (5-2-2). 49b), (5-2-51b), (5-2-41c), (5-2-48c), (5-2-49c), (5-2-51c). Particularly preferably, it is a compound represented by the formulas (5-1-20a), (5-1-20b) and (5-1-20c).

When the amidate compound (5) of the present invention has isomers such as optical isomers, stereoisomers, and positional isomers, any mixture of isomers can be used unless it is clearly stated which isomer it is. It is included in the amidate compound (5). For example, when the optical isomer is present in the amidate compound (5), the optical isomer divided from the racemate can also be included in the amidate compound (5). Each of these isomers can be obtained as a single compound by a synthesis method and a separation method (concentration, solvent extraction, column chromatography, recrystallization, etc.) known per se.

Further, the amidate compound (5) is considered to be isomerized by resonance. For example, in the compound represented by the formula (5), when X is a nitrogen atom, it is considered that the following resonance structure can be obtained.

（式中、Ａ、Ｒ^２～Ｒ^５及びｎは前記に同じ。）

(In the formula, A, ^R2 to R5 and n are the ^same as described above.)

In the reaction between the isocyanate compound (4) and the carboxylate compound (3), the carboxylate compound (3) is usually 0.8 mol or more, preferably 1 mol, with respect to 1 mol of the isocyanate group contained in the isocyanate compound (4). The reaction is carried out in an amount of up to 3 mol.

A solvent may or may not be used in the reaction between the isocyanate compound (4) and the carboxylate compound (3). When a solvent is used, the solvent used in the reaction between the nitrogen-containing compound (1) and the dialkyl carbonate (2) can be used as it is as the solvent for this reaction, and a solvent may be added separately. When a solvent is added, the solvent includes, for example, aromatic hydrocarbons such as toluene, benzene and xylene, aliphatic hydrocarbons such as methylcyclohexane, cyclohexane, n-hexane, n-heptane and octane, butyl chloride, 1, Examples thereof include halogenated hydrocarbons such as 2-dichloroethane and halogenated aromatic hydrocarbons such as chlorobenzene and dichlorobenzene, preferably aromatic hydrocarbons and halogenated aromatic hydrocarbons, and particularly preferably toluene and xylene. It is a chlorobenzene. If necessary, two or more kinds of solvents may be mixed and used. The amount of the solvent used is usually 50 parts by weight or less, preferably 0.1 to 35 parts by weight, based on 1 part by weight of the carboxylate compound (4).

The reaction temperature is not particularly limited as long as it is equal to or lower than the boiling point of the solvent, and is usually 10 ° C. or higher, preferably 40 to 200 ° C., and particularly preferably 80 to 150 ° C.

If necessary, the reaction may be carried out in an inert gas atmosphere that does not affect the reaction of nitrogen, argon, helium or the like.

After completion of the reaction, the amidate compound (5) can be obtained by concentrating or filtering the reaction solution. Further, the obtained amidate compound (5) can be purified by a method such as recrystallization.

In the production method of the present invention, the carboxylate compound (3) is reacted with the isocyanate compound (4) from the reaction solution obtained by the reaction of the nitrogen-containing compound (1) and the dialkyl carbonate compound (2) without isolation. .. At this time, in the reaction solution obtained by the reaction of the nitrogen-containing compound (1) and the dialkyl carbonate compound (2), in addition to the carboxylate compound (3), the alcohol compound represented by the formula (b1) which is a by-product Is included.

Equation (b1):

R2 ^- OH (b1)
(In the formula, R ² is the same as above.)

Examples of the alcohol compound represented by the formula (b1) include fatty alcohols such as methanol, ethanol, isopropanol, t-butanol, n-octanol, methoxyethanol and ethoxyethanol, phenols such as phenol, and benzyl alcohol. Aromatic alcohol can be mentioned.

When an alcohol solvent is used in the reaction between the nitrogen-containing compound (1) and the dialkyl carbonate compound (2), the reaction solution contains the alcohol solvent (hereinafter referred to as alcohol compound (b2)).

Since the isocyanate group of the isocyanate compound reacts with the hydroxyl group of the alcohol compound, when the isocyanate compound is reacted with a compound other than the alcohol compound, the reaction is usually not performed in the presence of the alcohol compound. Therefore, normally, the carboxylate compound (3) is isolated from the reaction solution obtained by the reaction of the nitrogen-containing compound (1) and the dialkyl carbonate compound (2), or the alcohol compound is removed from the reaction solution. , React with the isocyanate compound (4). However, in the present invention, even if the alcohol compound (b1) and the alcohol compound (b2) (hereinafter, the alcohol compound (b1) and the alcohol compound (b2) are collectively referred to as the alcohol compound (B)) are present. The desired amidate compound (5) can be obtained. The reason is considered to be to follow the reaction pathway shown in the following reaction formula.

That is, when the isocyanate compound (4) and the carboxylate compound (3) are reacted in the presence of the alcohol compound (B), the isocyanate compound (4) and the alcohol compound (B) first react with each other to form a urethane compound (hereinafter referred to as “urethane compound”). , Urethane compound (C)) is produced. Here, the produced urethane compound (C) reacts with the carboxylate compound (3). Therefore, it is considered that the target amidate compound (5) can be obtained.

Hereinafter, the present invention will be specifically described based on examples, but the present invention is not limited thereto. In the examples, ^{1 1} H-NMR was measured at 400 MHz using AV400 manufactured by Bruker Co., Ltd.

[Production Example 1] Synthesis of 1-butyl-3-methylimidazolium-2-carboxylate

窒素置換した１８０ｍＬのオートクレーブに１－ブチルイミダゾール２５．９ｇ（０．２ｍｏｌ）、炭酸ジメチル２５．０ｇ（０．３ｍｏｌ）、メタノール２６．２ｇを仕込み、１２５℃で１９時間撹拌後、更に１３０℃で４時間撹拌した。得られた反応混合物を２５℃に冷却し、上記式で表される化合物（以下、ＢＭＩｍ－ＣＯ_２と略記する。）のメタノール溶液を７３．０ｇ得た（純分３４．３ｇ、収率９５％）。上記式で表される化合物の^１Ｈ－ＮＭＲ分析結果を以下に示す。

25.9 g (0.2 mol) of 1-butylimidazole, 25.0 g (0.3 mol) of dimethyl carbonate and 26.2 g of methanol were added to a 180 mL autoclave substituted with nitrogen, and the mixture was stirred at 125 ° C. for 19 hours and then further at 130 ° C. The mixture was stirred for 4 hours. The obtained reaction mixture was cooled to 25 ° C. to obtain 73.0 g of a methanol solution of the compound represented by the above formula (hereinafter abbreviated as BMIm-CO ₂ ) (pure content 34.3 g, yield 95). %). The results of ¹ H-NMR analysis of the compound represented by the above formula are shown below.

^{1 1} H-NMR (CD ₃ OD) δ (ppm) = 7.79 (s, 1H), 7.72 (s, 1H), 4.31 (t, J = 7.4Hz, 2H), 4.02 (S, 3H), 1.94-1.88 (m, 2H), 1.44-1.38 (m, 2H), 1.00 (t, J = 7.2Hz, 3H)

[Production Example 2] Synthesis of 1-octyl-3-methyl-2-carboxylate

窒素置換した１８０ｍＬのオートクレーブに１－オクチルイミダゾール２５．０ｇ（１３９ｍｍｏｌ）、炭酸ジメチル１６．７ｇ（１８５ｍｍｏｌ）、メタノール２５．１ｇを仕込み、１２５℃で２９時間撹拌した。室温まで冷却し、炭酸ジメチル８．５ｇ（５４ｍｍｏｌ）を追加し、１３０℃で更に３時間撹拌した。得られた反応混合物を２５℃に冷却し、上記式で表される化合物（以下、ＯＭＩｍ－ＣＯ_２と略記する。）のメタノール溶液を４４．０ｇ得た（純分３３．０ｇ、収率９９％）。上記式で表される化合物の^１Ｈ－ＮＭＲ分析結果を以下に示す。

25.0 g (139 mmol) of 1-octylimidazole, 16.7 g (185 mmol) of dimethyl carbonate and 25.1 g of methanol were charged in a nitrogen-substituted 180 mL autoclave, and the mixture was stirred at 125 ° C. for 29 hours. After cooling to room temperature, 8.5 g (54 mmol) of dimethyl carbonate was added, and the mixture was further stirred at 130 ° C. for 3 hours. The obtained reaction mixture was cooled to 25 ° C. to obtain 44.0 g of a methanol solution of the compound represented by the above formula (hereinafter abbreviated as OMIm-CO ₂ ) (pure content 33.0 g, yield 99). %). The results of ¹ H-NMR analysis of the compound represented by the above formula are shown below.

^{1 1} H-NMR (CD ₃ OD) δ (ppm) = 7.67 (s, 1H), 7.61 (s, 1H), 4.22 (t, J = 7.2Hz, 2H), 3.94 (S, 3H), 1.91-1.84 (m, 2H), 1.32-1.26 (m, 10H), 0.85 (t, J = 7.2Hz, 3H)

[Example 1] Synthesis of BMIm-PI

窒素置換した２００ｍＬ試験管に製造例１で得られたＢＭＩｍ－ＣＯ_２のメタノール溶液を６．０ｇ（ＢＭＩｍ－ＣＯ_２の純分１６ｍｍｏｌ）、フェニルイソシアネート１．９ｇ（１６ｍｍｏｌ）、トルエン１００ｍＬを仕込み、得られた混合物を内温１１０℃で３時間撹拌した。減圧濃縮し、上記式で表される化合物（ＢＭＩｍ－ＰＩ）を４．１ｇ得た（収率９７％）。上記式で表される化合物の^１Ｈ－ＮＭＲ分析結果を以下に示す。

In a nitrogen-substituted 200 mL test tube, 6.0 g (16 mmol of pure BMIm-CO ₂ ), 1.9 g (16 mmol) of phenylisocyanate, and 100 mL of toluene were charged with the methanol solution of BMIm-CO ₂ obtained in Production Example 1. The obtained mixture was stirred at an internal temperature of 110 ° C. for 3 hours. The mixture was concentrated under reduced pressure to obtain 4.1 g of the compound (BMIm-PI) represented by the above formula (yield 97%). The results of ¹ H-NMR analysis of the compound represented by the above formula are shown below.

^{1 1} H-NMR (CD ₃ OD) δ (ppm) = 7.53 (s, 1H), 7.47 (s, 1H), 7.33-7.25 (m, 4H), 7.00 (t) , J = 7.2Hz, 1H), 4.38 (t, J = 7.4Hz, 2H), 3.98 (s, 3H), 1.89 (quint, J = 7.6Hz, 2H), 1 .39 (sext, J = 7.4Hz, 2H), 0.97 (t, J = 7.2Hz, 3H)

[Example 2] Synthesis of OMIm-PI

窒素置換した２００ｍＬ試験管に製造例２で得られたＯＭＩｍ－ＣＯ_２のメタノール溶液４．０ｇ（ＯＭＩｍ－ＣＯ_２の純分１３ｍｍｏｌ）、フェニルイソシアネート１．５ｇ（１３ｍｍｏｌ）、トルエン１００ｍＬを仕込み、得られた混合物を内温１１０℃で３時間撹拌した。減圧濃縮し、上記式で表される化合物（ＯＭＩｍ－ＰＩ）を３．３ｇ得た（収率８４％）。上記式で表される化合物の^１Ｈ－ＮＭＲ分析結果を以下に示す。

A nitrogen-substituted 200 mL test tube was charged with 4.0 g of the methanol solution of OMIm-CO ₂ obtained in Production Example 2 (pure content of OMIm-CO ₂ 13 mmol), 1.5 g of phenyl isocyanate (13 mmol), and 100 mL of toluene. The resulting mixture was stirred at an internal temperature of 110 ° C. for 3 hours. Concentration under reduced pressure gave 3.3 g of the compound represented by the above formula (OMIm-PI) (yield 84%). The results of ¹ H-NMR analysis of the compound represented by the above formula are shown below.

^{1 1} H-NMR (CD ₃ OD) δ (ppm) = 7.51 (s, 1H), 7.45-7.33 (m, 6H), 4.37 (t, J = 7.4Hz, 2H) 3.97 (s, 3H), 1.91-1.86 (m, 2H), 1.35-1.27 (m, 10H), 0.88 (t, J = 6.8Hz, 3H)

[Comparative Example 1] Synthesis of 1-Butyl-3-methylimidazolium-2-carboxylate 20.0 g (0.2 mol) of 1-butyl imidazole and 19.3 g (0.2 mol) of dimethyl carbonate in a 180 mL autoclave substituted with nitrogen. ), 20.0 g of methanol was charged, and the mixture was stirred at 120 ° C. for 22.5 hours. The obtained reaction solution was analyzed by ¹ H-NMR, and it was confirmed that 71% of BMIm-PI was produced. Then, when the reaction solution was concentrated under reduced pressure at 60 ° C., all the compounds represented by the above formula were decomposed into impurities, and 1-butyl-3-methylimidazolium-2-carboxylate could be obtained. There wasn't.

[Comparative Example 2] Synthesis of 1-butyl-3-methylimidazolium-2-carboxylate 90.0 g (0.7 mol) of 1-butyl imidazole and 87.0 g (1.0 mol) of dimethyl carbonate in a 500 mL autoclave substituted with nitrogen. ), 89.5 g of methanol was charged, and the mixture was stirred at 130 ° C. for 23 hours to obtain 256.8 g of a reaction solution. The obtained reaction solution was analyzed by ¹ H-NMR, and it was confirmed that 1-butyl-3-methylimidazolium-2-carboxylate was obtained in a pure content of 118.4 g (yield 89%).
Next, 100.0 g of butyl cellosolve was added to 199.9 g of the reaction solution (92.2 g of pure 1-butyl-3-methylimidazolium-2-carboxylate and 79.8 g of pure methanol), and the temperature was 40 ° C. Methanol was distilled off to obtain 199.6 g of a butyl cellosolve solution of BMIm-PI. When the obtained butyl cellosolve solution of 1-butyl-3-methylimidazolium-2-carboxylate was analyzed by ¹ H-NMR, the pure content of 1-butyl-3-methylimidazolium-2-carboxylate was 78.2 g. , The pure content of methanol was 3.2 g, and the pure content of 1-butyl-3-methylimidazolium-2-carboxylate was reduced by about 15%, and impurities were produced instead.

Claims (5)

The nitrogen-containing compound represented by the following formula (1) is reacted with the dialkyl carbonate compound represented by the following formula (2) to obtain a reaction solution containing the carboxylate compound represented by the following formula (3), and the above reaction is obtained. A method for producing an amidate compound represented by the following formula (5), which is reacted with an isocyanate compound represented by the following formula (4) without isolating the carboxylate compound represented by the formula (3) from the liquid. , The nitrogen-containing compound represented by the following formula (1) is the nitrogen-containing compound represented by the following formula (1-1) or the following formula (1-3). Production method.
Equation (1):

(In the formula, R ³ to R ⁵ are hydrocarbon groups which may contain a hetero atom, and some or all of them may be bonded to each other to form a ring structure. X is a nitrogen atom and oxygen. Indicates an atom or a sulfur atom. However, if X is an oxygen atom or a sulfur atom, there is no ^R5 .)
Equation (2):

(In the formula, R ² is a hydrocarbon group that may contain a heteroatom.)
Equation (3):

( ^In the formula, ^R2 to R5 and X are the same as described above.)
Equation (4):

(In the formula, A is a substituted or unsubstituted hydrocarbon group, and n is an integer of 1 or more.)
Equation (5):

(In the formula, A, n, ^R2 to R5 and X are the ^same as described above.)
Equation (1-1):

(In the formula, R ⁵ and X are the same as described above, and R ⁸ and R ⁹ are hydrocarbon groups having 1 to 6 carbon atoms which may contain a hydrogen atom or a hetero atom.)
Equation (1-3):

(In the formula, R ⁵ and X are the same as described above, and R ¹² to R ¹⁵ are hydrocarbon groups having 1 to 6 carbon atoms which may contain a hydrogen atom or a hetero atom.) In claim 1, the reaction solution obtained by reacting the nitrogen-containing compound represented by the formula (1) with the dialkyl carbonate compound represented by the formula (2) is further the alcohol compound represented by the following formula (b1). The method for producing an amidate compound according to claim 1, wherein the reaction solution contains an alcohol compound represented by the following formula (b1) and is reacted with an isocyanate compound represented by the formula (4).
Equation (b1):
R ² -OH (b1)
(In the formula, R ² Is the same as above. ) According to claim 1 or 2 , when the nitrogen-containing compound represented by the formula (1) is reacted with the dialkyl carbonate compound represented by the formula (2), the reaction is carried out in the presence of an alcohol solvent. A method for producing an amidate compound. The method for producing an amidate compound according to any one of claims 1 to 3, wherein the isocyanate compound represented by the formula (4) is an isocyanate compound represented by the following formulas (4-1) to (4-3).
Equation (4-1):

(In the formula, R ⁶ is a substituted or unsubstituted hydrocarbon group.)
Equation (4-2):

(In the formula, R ⁷ is a substituted or unsubstituted hydrocarbon group.)
Equation (4-3):

(In the formula, m is an integer from 0 to 4.) The method for producing an amidate compound according to any one of claims 1 to 4, wherein X is a nitrogen atom.