JP7065638B2 - Imidazole salt and its manufacturing method - Google Patents

Description

The present invention relates to a novel imidazolium salt and a method for producing the same.

Imidazole salts are used in applications such as ionic liquids, organic electrolytes, and intermediates for pharmaceuticals, and many imidazolium salts have been developed so far. Among the imidazolium salts, the N, N'-di (1-adamantyl) imidazolium salt, which is an imidazolium salt having the same 1-adamantyl group on two nitrogen atoms, has a structure for zeolite production in addition to these uses. It is expected to be applied as a directional agent and a bactericide (Non-Patent Documents 1 and 2).

However, the N, N'-bis (1-adamantyl) imidazolium salt is an imidazolium salt that is difficult to use industrially due to its high production cost.

Journal of the American Chemical Society, 2003, Vol. 125, pp. 113-123 Tetrahedron, 2006, Vol. 62, pp. 8199-8206

An object of the present invention is to provide an imidazolium salt capable of substituting an N, N'-bis (1-adamantyl) imidazolium salt and a method for producing the same. Furthermore, another object of the present invention is to provide a method for producing a zeolite using the imidazolium salt.

As a result of diligent studies to solve the above problems, the present inventors have found a novel imidazolium salt that can replace the N, N'-bis (1-adamantyl) imidazolium salt, and have found the present invention. Has been completed. Furthermore, it has been found that the imidazolium salt functions suitably as a structure-directing agent for zeolite.

That is, the gist of the present invention is as follows.
[1] An imidazolium salt represented by the general formula (1).

(In the formula, R ¹ is a cycloalkyl group having 3 to 12 carbon atoms excluding the 1-adamantyl group, and the cycloalkyl group may be substituted with an alkyl group having 1 to 4 carbon atoms. X ^- is a halogen. It is one of the group consisting of a compound ion, R ² COO ⁻ , R ³ SO ₂ O ⁻ and OH ⁻ . R ² is an alkyl group having 1 to 6 carbon atoms. R ³ is an alkyl group having 1 to 9 carbon atoms. It is one of a group consisting of a group, a fluoroalkyl group having 1 to 9 carbon atoms, and a phenyl group, and the phenyl group is an alkyl group having 1 to 4 carbon atoms and a fluoroalkyl group having 1 to 4 carbon atoms. It may be substituted with one or more substituents selected from the group consisting of an alkoxy group having 1 to 4 carbon atoms, a fluoroalkyl group having 1 to 4 carbon atoms, a halogen atom, a cyano group and a nitro group).
[2] In the general formula (1), X ^- is chloride ion, bromide ion, iodide ion, CH ₃ COO- ^, CH ₃ CH ₂ COO- ^, C ₆ H ₅ SO ₂ ^O- , p-CH ₃ The imidazolium salt according to the above [1], which is C ₆ H ₄ SO ₂ O ⁻ , CH ₃ SO ₂ O ⁻ or OH ⁻ .
[3] The imidazolium salt according to the above [1] or [2], wherein R ¹ is a cycloalkyl group having 5 to 8 carbon atoms in the general formula (1).
[4] The imidazolium salt according to the above [1] or [2], wherein R ¹ is a cycloheptyl group in the general formula (1).
[5] Formaldehyde, glyoxal, 1-adamantylamine, and the general formula R ¹ in the presence of a carboxylic acid represented by the general formula R ² COOH (R ² is an alkyl group having 1 to 6 carbon atoms). It is represented by NH ₂ (R ¹ is a cycloalkyl group having 3 to 12 carbon atoms excluding the 1-adamantyl group, and the cycloalkyl group may be substituted with an alkyl group having 1 to 4 carbon atoms). A method for producing an imidazolium salt represented by the general formula (1), which comprises a step of reacting an amine to obtain an imidazolium salt represented by the general formula (1a).

(In the formula, R ¹ is a cycloalkyl group having 3 to 12 carbon atoms excluding the 1-adamantyl group, and the cycloalkyl group may be substituted with an alkyl group having 1 to 4 carbon atoms. Xa ⁻ is R. It is ² COO ⁻ , and R ² is an alkyl group having 1 to 6 carbon atoms.)

(In the formula, R ¹ is a cycloalkyl group having 3 to 12 carbon atoms excluding the 1-adamantyl group, and the cycloalkyl group may be substituted with an alkyl group having 1 to 4 carbon atoms. X ^- is a halogen. It is one of the group consisting of a compound ion, R ² COO ⁻ , R ³ SO ₂ O ⁻ and OH ⁻ . R ² is an alkyl group having 1 to 6 carbon atoms. R ³ is an alkyl group having 1 to 9 carbon atoms. It is one of a group consisting of a group, a fluoroalkyl group having 1 to 9 carbon atoms, and a phenyl group, and the phenyl group is an alkyl group having 1 to 4 carbon atoms and a fluoroalkyl group having 1 to 4 carbon atoms. It may be substituted with one or more substituents selected from the group consisting of an alkoxy group having 1 to 4 carbon atoms, a fluoroalkyl group having 1 to 4 carbon atoms, a halogen atom, a cyano group and a nitro group).
[6] 1- (1-adamantyl) imidazole and an alkylating agent represented by the general formula R1 ^- Xc (in the formula, R1 is a cycloalkyl group having 3 to 12 carbon atoms excluding the ¹ -adamantyl group. , The cycloalkyl group may be substituted with an alkyl group having 1 to 4 carbon atoms. Xc is either a halogen atom or an R ³ SO ₂ O group, and R ³ is an alkyl group having 1 to 9 carbon atoms. , One of the group consisting of a fluoroalkyl group having 1 to 9 carbon atoms and a phenyl group, the phenyl group being an alkyl group having 1 to 4 carbon atoms, a fluoroalkyl group having 1 to 4 carbon atoms, and carbon. It may be substituted with one or more substituents selected from the group consisting of an alkoxy group having the number 1 to 4, a fluoroalkyl group having 1 to 4 carbon atoms, a halogen atom, a cyano group and a nitro group). A method for producing an imidazolium salt represented by the general formula (1), which comprises a step of obtaining an imidazolium salt represented by the general formula (1c).

(In the formula, R ¹ is a cycloalkyl group having 3 to 12 carbon atoms excluding the 1-adamantyl group, and the cycloalkyl group may be substituted with an alkyl group having 1 to 4 carbon atoms. Xc ⁻ is a halogen. It is a compound ion or R ³ SO ₂ O- ^, and R ³ is one of a group consisting of an alkyl group having 1 to 9 carbon atoms, a fluoroalkyl group having 1 to 9 carbon atoms, and a phenyl group. The phenyl group consists of an alkyl group having 1 to 4 carbon atoms, a fluoroalkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a fluoroalkyl group having 1 to 4 carbon atoms, a halogen atom, a cyano group and a nitro group. It may be substituted with one or more substituents selected from the group.)

(In the formula, R ¹ is a cycloalkyl group having 3 to 12 carbon atoms excluding the 1-adamantyl group, and the cycloalkyl group may be substituted with an alkyl group having 1 to 4 carbon atoms. X ^- is a halogen. It is one of the group consisting of a compound ion, R ² COO ⁻ , R ³ SO ₂ O ⁻ and OH ⁻ , where R ² is an alkyl group having 1 to 6 carbon atoms and R ³ is an alkyl group having 1 to 9 carbon atoms. , A fluoroalkyl group having 1 to 9 carbon atoms, and any one of the group consisting of a phenyl group, wherein the phenyl group is an alkyl group having 1 to 4 carbon atoms, a fluoroalkyl group having 1 to 4 carbon atoms, and carbon. It may be substituted with one or more substituents selected from the group consisting of an alkoxy group having the number 1 to 4, a fluoroalkyl group having 1 to 4 carbon atoms, a halogen atom, a cyano group and a nitro group).
[7] At least one imidazolium salt represented by either the general formula (1a) or the general formula (1c) is used in the general formula Ma-Xb (Ma is at least one of an alkali metal or an alkaline earth metal). It is characterized by having a step of contacting with a metal halide represented by (1b) to obtain an imidazolium salt represented by the general formula (1b). The manufacturing method according to [6].

(In the formula, R ¹ is a cycloalkyl group having 3 to 12 carbon atoms excluding the 1-adamantyl group, and the cycloalkyl group may be substituted with an alkyl group having 1 to 4 carbon atoms. Xb ⁻ is a halogen. It is a compound ion.).
[8] Any of the above [5] to [7], comprising a step of ion-exchange the imidazolium salt represented by the general formula (1b) to obtain an imidazolium salt represented by the general formula (1d). The manufacturing method described in.

(In the formula, R ¹ is a cycloalkyl group having 3 to 12 carbon atoms excluding the 1-adamantyl group, and the cycloalkyl group may be substituted with an alkyl group having 1 to 4 carbon atoms. Xd ⁻ is OH. ^- .).
[9] It has a crystallization step of crystallizing a composition containing a silica source, an alumina source, a structure-directing agent, an alkali source and water, and the composition contains an imidazolium salt represented by the general formula (1). A method for producing a zeolite, which comprises a crystallization step.

(In the formula, R ¹ is a cycloalkyl group having 3 to 12 carbon atoms excluding the 1-adamantyl group, and the cycloalkyl group may be substituted with an alkyl group having 1 to 4 carbon atoms. X ^- is a halogen. It is one of the group consisting of a compound ion, R ² COO ⁻ , R ³ SO ₂ O ⁻ and OH ⁻ . R ² is an alkyl group having 1 to 6 carbon atoms. R ³ is an alkyl group having 1 to 9 carbon atoms. It is one of a group consisting of a group, a fluoroalkyl group having 1 to 9 carbon atoms, and a phenyl group, and the phenyl group is an alkyl group having 1 to 4 carbon atoms, a fluoroalkyl group having 1 to 4 carbon atoms, and a carbon number of carbon atoms. It may be substituted with one or more substituents selected from the group consisting of an alkoxy group of 1 to 4, a fluoroalkyl group having 1 to 4 carbon atoms, a halogen atom, a cyano group or a nitro group).
[10] The production method according to the above [9], wherein the zeolite is an AFX-type zeolite.

INDUSTRIAL APPLICABILITY According to the present invention, it is possible to provide an imidazolium salt that can replace the N, N'-bis (1-adamantyl) imidazolium salt. Furthermore, the present invention can provide such a method for producing an imidazolium salt. In addition to this, the present invention can provide a method for producing a zeolite using such an imidazolium salt.

XRD pattern of AFX type zeolite of Example 2-1 SEM observation image of AFX type zeolite of Example 2-1 SEM observation image of AFX type zeolite of Example 2-4 SEM observation image of AFX type zeolite of Example 2-5

Hereinafter, the imidazolium salt of the present invention will be described.

The present invention relates to an imidazolium salt represented by the following general formula (1) (hereinafter, also referred to as "imidazolium salt of the present invention").

(In the formula, R ¹ is a cycloalkyl group having 3 to 12 carbon atoms excluding the 1-adamantyl group, and the cycloalkyl group may be substituted with an alkyl group having 1 to 4 carbon atoms. X ^- is a halogen. It is one of the group consisting of a compound ion, R ² COO ⁻ , R ³ SO ₂ O ⁻ and OH ⁻ . R ² is an alkyl group having 1 to 6 carbon atoms. R ³ is an alkyl group having 1 to 9 carbon atoms. It is one of a group consisting of a group, a fluoroalkyl group having 1 to 9 carbon atoms, and a phenyl group, and the phenyl group is an alkyl group having 1 to 4 carbon atoms and a fluoroalkyl group having 1 to 4 carbon atoms. It may be substituted with one or more substituents selected from the group consisting of an alkoxy group having 1 to 4 carbon atoms, a fluoroalkyl group having 1 to 4 carbon atoms, a halogen atom, a cyano group and a nitro group).

The imidazolium salt of the present invention may have resonance structures (1A) and (1B) in which the positions of carbon-nitrogen double bonds of the imidazolium ring are different due to the movement of electrons. It contains a resonance structure. In the present specification, the imidazolium salt of the present invention is expressed as a resonance hybrid represented by the general formula (1).

In the present invention, R ¹ is a cycloalkyl group having 3 to 12 carbon atoms excluding the 1-adamantyl group, and examples of the cycloalkyl group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group and a cycloheptyl group. Cyclooctyl group, cyclononyl group, cyclodecyl group, cycloundecyl group, cyclododecyl group, bicyclo [2.2.1] heptane-2-yl group (norbornan-2-yl group), bicyclo [3.1.1] Any of the group consisting of a heptane-2-yl group, a bicyclo [2.2.2] octane-2-yl group and a bicyclo [3.2.1] octane-2-yl group can be mentioned. When used as a structure-directing agent for zeolite, small pore zeolite, particularly AFX-type zeolite, is easily obtained. Therefore, R ¹ is preferably a cycloalkyl group having 5 to 8 carbon atoms, and is a cycloheptyl group. Is even more preferable.

The cycloalkyl group may be substituted with one or more alkyl groups having 1 to 4 carbon atoms. As the alkyl group, for example, any one of the group consisting of a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a sec-butyl group and a tert-butyl group can be mentioned.

In the present invention, X ⁻ is one of the group consisting of halide ion, R ² COO ⁻ , R ³ SO ₂ O ⁻ and OH ⁻ , and is chloride ion, bromide ion, iodide ion, fluoride ion, CH. ₃ COO- ^, CH ₃ CH ₂ COO- ^, C ₆ H ₅ SO ₂ ^O- , p-CH ₃ C ₆ H ₄ SO ₂ ^O- , CH ₃ SO ₂ O ^{- and} OH-. Preferably, chloride ion, bromide ion, iodide ion, CH ₃ COO ⁻ , CH ₃ CH ₂ COO ⁻ , C ₆ H ₅ SO ₂ O ⁻ , p-CH ₃ C ₆ H ₄ SO ₂ O ⁻ , CH. ₃ It is more preferable to be one of the group consisting of SO ₂ O ⁻ and OH ⁻ .

When X ⁻ is R ² COO ⁻ , R ² is an alkyl group having 1 to 6 carbon atoms, and the alkyl group may be linear or branched, and may be a methyl group, an ethyl group, or a propyl group. It is preferably any one of the group consisting of a group, an isopropyl group, a butyl group, a sec-butyl group, a tert-butyl group, a pentyl group and a hexyl group. Since the yield of the imidazolium salt of the present invention tends to be high, ^R2 is preferably a methyl group.

When X ⁻ is R ³ SO ₂ O ⁻ , R ³ is any of a group consisting of an alkyl group having 1 to 9 carbon atoms, a fluoroalkyl group having 1 to 9 carbon atoms, and a phenyl group. Examples of the alkyl group having 1 to 9 carbon atoms include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a sec-butyl group, a 1-methylbutyl group, a 3-methylbutyl group, and a 1,3-dimethylbutyl group. Any of the group consisting of an octyl group and a nonyl group can be mentioned. Fluoroalkyl groups having 1 to 9 carbon atoms include trifluoromethyl groups, 4,4,4-trifluorobutyl groups and 1,1,2,2,3,3,4,4,4-nonafluorobutyl groups. Can be listed as one of the following groups.

When R ³ is a phenyl group, the phenyl group is an alkyl group having 1 to 4 carbon atoms, a fluoroalkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, and a fluoroalkoxy group having 1 to 4 carbon atoms. , May be substituted with at least one of the group consisting of a halogen atom, a cyano group and a nitro group.

The phenyl group is an alkyl group having 1 to 4 carbon atoms, a fluoroalkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a fluoroalkoxy group having 1 to 4 carbon atoms, a halogen atom, a cyano group and a nitro group. In the case of a phenyl group substituted with at least one of the group consisting of (hereinafter, also referred to as "substituted phenyl group"), the substituted phenyl group includes 2-methylphenyl group, 4-methylphenyl group, 2,5-. Dimethylphenyl group, 2,4,6-trimethylphenyl group, 4-ethylphenyl group, 4-propylphenyl group, 2,4,6-triisopropylphenyl group, 4-tert-butylphenyl group, 2-trifluoromethyl Phenyl group, 3- (trifluoromethyl) phenyl group, 4-trifluoromethylphenyl group, 3,5-bis (trifluoromethyl) phenyl group, 4-methoxyphenyl group, 4- (isopropyloxy) phenyl group, 4 -Trifluoromethoxyphenyl group, 2-fluorophenyl group, 3-fluorophenyl group, 4-fluorophenyl group, 2-chlorophenyl group, 3-chlorophenyl group, 4-chlorophenyl group, 3,5-dichlorophenyl group, 2,6 -Dichlorophenyl group, 2-bromophenyl group, 3-bromophenyl group, 4-bromophenyl group, 2-cyanophenyl group, 3-cyanophenyl group, 4-cyanophenyl group, 2-nitrophenyl group, 3-nitrophenyl Any of the group consisting of a group and a 4-nitrophenyl group can be mentioned.

Since the cost of producing the imidazolium salt of the present invention can be reduced, R ³ is one of the group consisting of a phenyl group, a 4-methyl phenyl group and a methyl group, that is, the R ³ SO ₂ O group is a benzenesulfonyloxy. It is preferably any of a group consisting of a group, a p-toluenesulfonyloxy group and a methanesulfonyloxy group.

When the imidazolium salt of the present invention is used as a structure-directing agent, it becomes easier to direct small pore zeolite and further AFX-type zeolite. Therefore, in the imidazolium salt of the present invention, X ^- is chloride ion, bromide ion, and so on. Group consisting of iodide ion, CH ₃ COO- ^, CH ₃ CH ₂ COO- ^, C ₆ H ₅ SO ₂ ^O- , p-CH ₃ C ₆ H ₄ SO ₂ ^O- , CH ₃ SO ₂ ^{O- and} OH- In addition, R ¹ is preferably a cycloalkyl group having 5 to 8 carbon atoms, and X ⁻ is any one of the group consisting of chloride ion, bromide ion, iodide ion and OH ⁻ . Moreover, it is particularly preferable that R ¹ is a cycloheptyl group.

The present invention also includes a composition containing the imidazolium salt of the present invention. Examples of such a composition include a composition comprising the imidazolium salt of the present invention and another imidazolium salt, the imidazolium salt of the present invention, and N, N'-bis (1-adamantyl). Imidazole salt, N, N'-dicyclopentyl imidazolium salt, N, N'-dicyclohexylimidazolium salt, N, N'-dicycloheptylimidazolium salt, N, N'-dicyclooctylimidazolium salt, N , N'-dicyclododecylimidazolium salt, and N, N'-di [exo-norbornan-2-yl] imidazolium salt, a composition containing at least one imidazolium salt in the group. In the composition, the molar ratio of the imidazolium salt of the present invention to the imidazolium salt is 50 mol% or more, preferably 60 mol% or more.

Next, the method for producing the imidazolium salt of the present invention (hereinafter, also referred to as “the production method of the present invention”) will be described in detail.

The imidazolium salt of the present invention can be obtained by a production method comprising a step of obtaining an imidazolium cation represented by the general formula (1').

(In the formula, R ¹ is a cycloalkyl group having 3 to 12 carbon atoms excluding the 1-adamantyl group, and the cycloalkyl group may be substituted with an alkyl group having 1 to 4 carbon atoms).

As a preferred production method of the present invention, formaldehyde, glyoxal, 1-adamantylamine, and in the presence of a carboxylic acid represented by the general formula ^R2 COOH ( ^R2 is an alkyl group having 1 to 6 carbon atoms). , General formula R ¹ NH ₂ (R ¹ is a cycloalkyl group having 3 to 12 carbon atoms excluding the 1-adamantyl group, and the cycloalkyl group may be substituted with an alkyl group having 1 to 4 carbon atoms. ) Is reacted to obtain an imidazolium salt represented by the general formula (1a) (hereinafter, also referred to as “step-1”), according to the general formula (1). A method for producing the represented imidazolium salt can be mentioned.

(In the formula, R ¹ is a cycloalkyl group having 3 to 12 carbon atoms excluding the 1-adamantyl group, and the cycloalkyl group may be substituted with an alkyl group having 1 to 4 carbon atoms. Xa ⁻ is R. ² COO ⁻ , and R ² is an alkyl group having 1 to 6 carbon atoms.)

(In the formula, R ¹ is a cycloalkyl group having 3 to 12 carbon atoms excluding the 1-adamantyl group, and the cycloalkyl group may be substituted with an alkyl group having 1 to 4 carbon atoms. X ^- is a halogen. It is one of the group consisting of a compound ion, R ² COO ⁻ , R ³ SO ₂ O ⁻ and OH ⁻ , where R ² is an alkyl group having 1 to 6 carbon atoms and R ³ is an alkyl group having 1 to 9 carbon atoms. It is one of a group consisting of a group, a fluoroalkyl group having 1 to 9 carbon atoms, and a phenyl group, and the phenyl group is an alkyl group having 1 to 4 carbon atoms and a fluoroalkyl group having 1 to 4 carbon atoms. It may be substituted with one or more substituents selected from the group consisting of an alkoxy group having 1 to 4 carbon atoms, a fluoroalkyl group having 1 to 4 carbon atoms, a halogen atom, a cyano group and a nitro group).

Step-1 comprises formaldehyde, glyoxal, 1-adamantylamine, and the general formula in the presence of a carboxylic acid represented by the general formula R ² COOH (R ² is an alkyl group having 1 to 6 carbon atoms). Tableed with R ¹ NH ₂ (R ¹ is a cycloalkyl group having 3 to 12 carbon atoms excluding the 1-adamantyl group, and the cycloalkyl group may be substituted with an alkyl group having 1 to 4 carbon atoms). This is a step of reacting the amine to obtain an imidazolium salt represented by the general formula (1a).

(In the formula, R ¹ is a cycloalkyl group having 3 to 12 carbon atoms excluding the 1-adamantyl group, and the cycloalkyl group may be substituted with an alkyl group having 1 to 4 carbon atoms. Xa ⁻ is R. It is ² COO ⁻ , and R ² is an alkyl group having 1 to 6 carbon atoms.)

In step 1, the imidazolium salt represented by the general formula (1a) (hereinafter, also referred to as “imidazolium salt (1a)”) is obtained by the reaction shown below.

(In the formula, R ¹ is a cycloalkyl group having 3 to 12 carbon atoms excluding the 1-adamantyl group, and the cycloalkyl group may be substituted with an alkyl group having 1 to 4 carbon atoms. Xa ⁻ is R. It is ² COO ⁻ , and R ² is an alkyl group having 1 to 6 carbon atoms.)

The formaldehyde used in step 1 may be gaseous formaldehyde, but is preferably supplied from a formaldehyde source. The formaldehyde source may be any as long as it can supply formaldehyde in the presence of a carboxylic acid represented by the general formula R ² COOH (R ² is an alkyl group having 1 to 6 carbon atoms), and formalin, paraformaldehyde and 1 , 3,5-Trioxane, at least one of the group consisting of trioxane. The formaldehyde source is preferably formalin because the yield of the imidazolium salt (1a) tends to be high.

In step-1, formaldehyde, glyoxal and the general formula R ¹ NH ₂ (R ¹ is a cycloalkyl group having 3 to 12 carbon atoms excluding the 1-adamantyl group, and the cycloalkyl group is an alkyl group having 1 to 4 carbon atoms. The ratio of the amine represented by (which may be substituted with) to 1-adamantylamine is 1 to 10 equivalents, preferably 1 to 3 equivalents, respectively. This makes it easier to obtain the imidazolium salt (1a) in a high yield.

In step-1, the reaction can be carried out in a solvent. The solvent may be any solvent as long as it does not inhibit the reaction, and specific examples thereof include at least one of alcohol or water, and further, at least one of the group consisting of methanol, ethanol and water. Moreover, you may use these solvents in combination of 2 or more types.

In step 1, the reaction temperature may be any temperature of 0 ° C. or higher and 100 ° C. or lower. Since the yield of the imidazolium salt (1a) tends to be high, the reaction temperature is preferably a temperature of room temperature to 60 ° C. or lower. On the other hand, the reaction time is not particularly limited, and examples thereof include 10 minutes or more and 50 hours or less.

Step-1 may include a step of isolating the obtained imidazolium salt (1a) after the reaction. The isolation method is arbitrary and may include at least one of the group consisting of solvent extraction, column chromatography, preparative thin layer chromatography, preparative liquid chromatography and recrystallization.

In addition, step-1 can also be provided as a method for producing an imidazolium salt (1a).

As another preferable production method of the present invention, 1- (1-adamantyl) imidazole and an alkylating agent represented by the general formula R1 ^- Xc (in the formula, R1 has 3 carbon atoms excluding the ¹ -adamantyl group). To 12 cycloalkyl groups, the cycloalkyl group may be substituted with an alkyl group having 1 to 4 carbon atoms, where Xc is either a halogen atom or an R ³ SO ₂ O group and R ³ is. It is one of a group consisting of an alkyl group having 1 to 9 carbon atoms, a fluoroalkyl group having 1 to 9 carbon atoms, and a phenyl group, and the phenyl group is an alkyl group having 1 to 4 carbon atoms and 1 carbon atom. Substituted with one or more substituents selected from the group consisting of a fluoroalkyl group from 4 to 4, an alkoxy group having 1 to 4 carbon atoms, a fluoroalkyl group having 1 to 4 carbon atoms, a halogen atom, a cyano group and a nitro group. A general formula (hereinafter, also referred to as “step-2”) for obtaining an imidazolium salt represented by the general formula (1c) by reacting with (may be). The method for producing the imidazolium salt represented by 1) can be mentioned.

(In the formula, R ¹ is a cycloalkyl group having 3 to 12 carbon atoms excluding the 1-adamantyl group, and the cycloalkyl group may be substituted with an alkyl group having 1 to 4 carbon atoms. Xc ⁻ is a halogen. It is a compound ion or R ³ SO ₂ O- ^, and R ³ is one of a group consisting of an alkyl group having 1 to 9 carbon atoms, a fluoroalkyl group having 1 to 9 carbon atoms, and a phenyl group. The phenyl group consists of an alkyl group having 1 to 4 carbon atoms, a fluoroalkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a fluoroalkyl group having 1 to 4 carbon atoms, a halogen atom, a cyano group and a nitro group. It may be substituted with one or more substituents selected from the group.)

(In the formula, R ¹ is a cycloalkyl group having 3 to 12 carbon atoms excluding the 1-adamantyl group, and the cycloalkyl group may be substituted with an alkyl group having 1 to 4 carbon atoms. X ^- is a halogen. It is one of the group consisting of a compound ion, R ² COO ⁻ , R ³ SO ₂ O ⁻ and OH ⁻ , where R ² is an alkyl group having 1 to 6 carbon atoms and R ³ is an alkyl group having 1 to 9 carbon atoms. It is one of a group consisting of a group, a fluoroalkyl group having 1 to 9 carbon atoms, and a phenyl group, and the phenyl group is an alkyl group having 1 to 4 carbon atoms and a fluoroalkyl group having 1 to 4 carbon atoms. It may be substituted with one or more substituents selected from the group consisting of an alkoxy group having 1 to 4 carbon atoms, a fluoroalkyl group having 1 to 4 carbon atoms, a halogen atom, a cyano group and a nitro group).

In step-2, 1- (1-adamantyl) imidazole and an alkylating agent represented by the general formula R1 ^- Xc (in the formula, R1 is a cycloalkyl group having 3 to 12 carbon atoms excluding the ¹ -adamantyl group). The cycloalkyl group may be substituted with an alkyl group having 1 to 4 carbon atoms. Xc is either a halogen atom or an R ³ SO ₂ O group, and R ³ has 1 to 9 carbon atoms. It is one of a group consisting of an alkyl group, a fluoroalkyl group having 1 to 9 carbon atoms, and a phenyl group, and the phenyl group is an alkyl group having 1 to 4 carbon atoms and a fluoroalkyl group having 1 to 4 carbon atoms. , It may be substituted with one or more substituents selected from the group consisting of an alkoxy group having 1 to 4 carbon atoms, a fluoroalkyl group having 1 to 4 carbon atoms, a halogen atom, a cyano group and a nitro group.) This is a step of reacting with and to obtain an imidazolium salt represented by the general formula (1c).

In step 2, the imidazolium salt represented by the general formula (1c) (hereinafter, also referred to as “imidazolium salt (1c)”) is obtained by the reaction shown below.

(In the formula, R ¹ is a cycloalkyl group having 3 to 12 carbon atoms excluding the 1-adamantyl group, and the cycloalkyl group may be substituted with an alkyl group having 1 to 4 carbon atoms. Xc ⁻ is a halogen. It is a compound ion or R ³ SO ₂ O- ^, and R ³ is one of a group consisting of an alkyl group having 1 to 9 carbon atoms, a fluoroalkyl group having 1 to 9 carbon atoms, and a phenyl group. The phenyl group consists of an alkyl group having 1 to 4 carbon atoms, a fluoroalkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a fluoroalkyl group having 1 to 4 carbon atoms, a halogen atom, a cyano group and a nitro group. It may be substituted with one or more substituents selected from the group.).

In step 2, 1- (1-adamantyl) imidazole can be obtained by a known production method. As a known production method, for example, the production method disclosed in Journal of the American Chemical Society, 2003, Vol. 125, pp. 113-123 can be mentioned.

On the other hand, 1- (1-adamantyl) imidazole is prepared by a method for producing 1- (1-adamantyl) imidazole by reacting 1-adamantylamine, ammonia, formaldehyde and glyoxal (hereinafter, also referred to as "the present imidazole production method"). It can also be manufactured.

In this imidazole production method, 1- (1-adamantyl) imidazole can be obtained by the following reaction.

In this imidazole production method, formaldehyde is preferably supplied from a formaldehyde source. The formaldehyde source may be any one that can supply formaldehyde, and examples thereof include at least one of the group consisting of formalin, paraformaldehyde and 1,3,5-trioxane. The formaldehyde source is preferably formalin because the yield of 1- (1-adamantyl) imidazole tends to be high.

In this imidazole production method, the reaction can be carried out in a solvent that does not harm the reaction, and examples of the solvent include carboxylic acid solvents such as acetic acid and propionic acid, alcohol solvents such as methanol and ethanol, and water. be able to. Moreover, you may use these solvents in combination of 2 or more types.

In this imidazole production method, it is preferable that ammonia is supplied from an ammonia source. The ammonia source may be any one capable of supplying ammonia, and examples thereof include at least one of the group consisting of ammonia, ammonium acetate, ammonium propionate and ammonium chloride. The ammonia source is preferably ammonium acetate because it is inexpensively available, easy to handle, and tends to yield high yields of 1- (1-adamantyl) imidazole. Ammonium acetate may be obtained from acetic acid and ammonia present in the system.

It can be mentioned that formaldehyde, glyoxal and ammonia in the present imidazole production method have 1 to 10 equivalents, preferably 1 to 3 equivalents, respectively, as a ratio to 1-adamantylamine. This facilitates the acquisition of 1- (1-adamantyl) imidazole in high yield.

In step 2, R ¹ in the general formula R ¹ -Xc is a cycloalkyl group having 3 to 12 carbon atoms excluding the 1-adamantyl group, and the cycloalkyl group is substituted with an alkyl group having 1 to 4 carbon atoms. May be. Further, Xc in the general formula ^R1 -Xc is either a halogen atom or an R ³ SO ₂ O group.

The alkylating agent may be commercially available, or may be obtained by the production method shown below.

When Xc in the general formula ^R1 -Xc is a halogen atom, that is, when the alkylating agent is a haloalkyl, the method for producing the haloalkyl is ^R1 -OH containing ^R1 corresponding to ^R1 of the haloalkyl. In the formula, R ¹ is a cycloalkyl group having 3 to 12 carbon atoms excluding the 1-adamantyl group, and the cycloalkyl group may be substituted with an alkyl group having 1 to 4 carbon atoms) and halogenated. A manufacturing method including a step of reacting with an agent can be mentioned. Examples of the halogenating agent include hydrochloric acid, thionyl chloride, phosgen, triphosgen, phosphorus trichloride, phosphorus pentachloride, phosphorus oxychloride, carbon tetrachloride / triphenylphosphine, hydrobromic acid, thionyl bromide, phosphorus tribromide, and the like. At least one of the group consisting of phosphorus pentabromide, phosphorus oxybromide, carbon tetrabromide / triphenylphosphine, hydroiodic acid, phosphorus triiodide and iodine / triphenylphosphine can be mentioned.

The reaction between R1 ^- OH and the halogenating agent can be carried out in a solvent. The solvent may be any one that does not inhibit the reaction, and specifically, at least one of a group consisting of a halogen-based solvent, an aromatic hydrocarbon-based solvent, an ether-based solvent, an amide-based solvent, a nitrile-based solvent, and a sulfoxide-based solvent. Can be mentioned. The halogen-based solvent is at least one of chloroform or dichloromethane, the aromatic hydrocarbon-based solvent is at least one of the group consisting of toluene, xylene and chlorobenzene, and the ether-based solvent is tetrahydrofuran, 1,2-dimethoxyethane and 1,4-. At least one of the group consisting of dioxane, at least one of N, N-dimethylformamide or N, N-dimethylacetamide as an amide solvent, at least one of acetonitrile or propionitrile as a nitrile solvent, and dimethyl as a sulfoxide solvent. Examples thereof include sulfoxide.

When Xc in the general formula ^R1 -Xc is an R ³ SO ₂ O group, R ³ is any of a group consisting of an alkyl group having 1 to 9 carbon atoms, a fluoroalkyl group having 1 to 9 carbon atoms, and a phenyl group. The phenyl group is an alkyl group having 1 to 4 carbon atoms, a fluoroalkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a fluoroalkoxy group having 1 to 4 carbon atoms, and a halogen atom. , Cyan and nitro groups may be substituted with one or more substituents selected from the group.

When Xc in the general formula ^R1 -Xc is an R ³ SO ₂ O group, that is, when the alkylating agent is a sulfonate represented by R ¹ -OSO ₂ R ³ , the method for producing the sulfonate is a base. In the presence of, R ^{1-OH containing R 1 corresponding to R 1 of} the sulfonate (in the formula, R ¹ is a cycloalkyl group having 3 to 12 carbon atoms excluding the 1-adamantyl group, and the cycloalkyl group is It may be substituted with an alkyl group having 1 to 4 carbon atoms), and a production method having a step of reacting with a sulfonyl chloride can be mentioned. The sulfonyl chloride is, for example, one of a group consisting of R ³ SO ₂ Cl (R ³ is an alkyl group having 1 to 9 carbon atoms, a fluoroalkyl group having 1 to 9 carbon atoms, and a phenyl group. The phenyl group is an alkyl group having 1 to 4 carbon atoms, a fluoroalkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a fluoroalkoxy group having 1 to 4 carbon atoms, a halogen atom, a cyano group and a nitro group. It may be substituted with one or more substituents selected from the group consisting of.). Examples of the base include at least one of the group consisting of organic bases, inorganic bases and alkali metal alkoxides. Specific examples of the organic base include at least one of the group consisting of triethylamine, diisopropylethylamine, 1,4-diazabicyclo [2.2.2] octane, pyridine and 4- (N, N-dimethylamino) pyridine. At least one of the group consisting of sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate and cesium carbonate can be exemplified as the inorganic base, and sodium methoxydo, sodium ethoxydo and potassium-tert-butoxide as alkali metal alkoxides. At least one species in the group can be exemplified.

The reaction between R1 ^- OH and sulfonyl chloride is easily carried out by carrying out the reaction in a solvent. Examples of the solvent include halogen-based solvents, aromatic hydrocarbon-based solvents, ether-based solvents, amide-based solvents, nitrile-based solvents, sulfoxide-based solvents, and water. Specific solvents include, for example, at least one of chloroform or dichloromethane as a halogen-based solvent, at least one of the group consisting of toluene, xylene and chlorobenzene as an aromatic hydrocarbon-based solvent, and tetrahydrofuran and 1,2- as an ether-based solvent. At least one of the group consisting of dimethoxyethane and 1,4-dioxane, at least one of N, N-dimethylformamide or N, N-dimethylacetamide as an amide solvent, and at least one of acetonitrile or propionitrile as a nitrile solvent. Or, as the sulfoxide-based solvent, dimethyl sulfoxide can be mentioned. Moreover, you may use these solvents in combination of 2 or more types.

In step 2, the ratio of the alkylating agent to 1- (1-adamantyl) imidazole may be 1 to 20 equivalents, preferably 1 to 5 equivalents, respectively.

In step-2, the reaction can be carried out in a solvent. The solvent may be any one that does not inhibit the reaction, and specifically includes a halogen-based solvent, an aromatic hydrocarbon-based solvent, an ether-based solvent, an ester-based solvent, a ketone-based solvent, a nitrile-based solvent, and a sulfoxide-based solvent. At least one can be mentioned. The halogen-based solvent is at least one of chloroform or dichloromethane, the aromatic hydrocarbon-based solvent is at least one of the group consisting of toluene, xylene and chlorobenzene, and the ether-based solvent is tetrahydrofuran, 1,2-dimethoxyethane and 1,4-. At least one of the group consisting of dioxane, at least one of ethyl acetate or butyl acetate as the ester solvent, at least one of N, N-dimethylformamide or N, N-dimethylacetamide as the amide solvent, and acetone as the ketone solvent. Alternatively, at least one of methyl ethyl ketone, at least one of acetonitrile or propionitrile as the nitrile solvent, dimethyl sulfoxide and the like as the sulfoxide solvent can be mentioned. Moreover, you may use these solvents in combination of 2 or more types. Preferred solvents in step 2 are aromatic hydrocarbon solvents, ether solvents, amide solvents, nitrile solvents, and more specifically, toluene, tetrahydrofuran, N, N-dimethylformamide, acetonitrile and the like. Can be done.

In step 2, the reaction temperature may be any temperature of 20 ° C. or higher and 150 ° C. or lower. Since the yield of the imidazolium salt (1c) tends to be high, the reaction temperature is preferably 50 ° C. or higher and 120 ° C. or lower. On the other hand, the reaction time is not particularly limited, and examples thereof include 1 hour or more and 100 hours or less.

Step-2 may include a step of isolating the obtained imidazolium salt (1c) after the reaction. The isolation method is arbitrary and may include at least one of the group consisting of solvent extraction, column chromatography, preparative thin layer chromatography, preparative liquid chromatography and recrystallization.

In addition, step-2 can also be provided as a method for producing an imidazolium salt (1c).

In the production method of the present invention, at least one imidazolium salt represented by either the general formula (1a) or the general formula (1c) is used in the general formula (4) Ma-Xb (Ma is an alkali metal or A step of contacting with a metal halide represented by (Xb is a halogen atom), which is at least one of alkaline earth metals, to obtain an imidazolium salt represented by the general formula (1b) (hereinafter, "step-"). 3 ”), is preferable.

(In the formula, R ¹ is a cycloalkyl group having 3 to 12 carbon atoms excluding the 1-adamantyl group, and the cycloalkyl group may be substituted with an alkyl group having 1 to 4 carbon atoms. Xb ⁻ is a halogen. Represents a compound ion.).

In step 3, an imidazolium salt represented by the general formula (1b) (hereinafter, also referred to as “imidazolium salt (1b)”) is obtained by any of the following reactions.

(In the formula, R ¹ is a cycloalkyl group having 3 to 12 carbon atoms excluding the 1-adamantyl group, and the cycloalkyl group may be substituted with an alkyl group having 1 to 4 carbon atoms. Ma is an alkali metal. Alternatively, it is at least one of alkaline earth metals, where Xb is a halogen atom and Xb ⁻ is a halide ion).

The metal halide represented by the general formula Ma-Xb (4) in Step 3 is preferably 1 to 30 equivalents, preferably 1 to 30 equivalents, respectively, with respect to the imidazolium salt represented by the general formula (1a) or (1c). 2 to 10 equivalents can be used. This makes it easier to obtain the imidazolium salt (1b) in a high yield.

In step 3, the reaction can be carried out in a solvent. The solvent may be any one that does not inhibit the reaction, and specifically, at least a group consisting of an ether solvent, an ester solvent, an amide solvent, a ketone solvent, a nitrile solvent, a sulfoxide solvent, an alcohol solvent and water. One type can be mentioned. At least one of the group consisting of tetrahydrofuran, 1,2-dimethoxyethane and 1,4-dioxane as an ether solvent, at least one of ethyl acetate or butyl acetate as an ester solvent, and N, N-dimethylformamide as an amide solvent. Or at least one of N, N-dimethylacetamide, at least one of acetone or methyl ethyl ketone as a ketone solvent, at least one of acetonitrile or propionitrile as a nitrile solvent, dimethylsulfoxide as a sulfoxide solvent, and methanol as an alcohol solvent. Alternatively, at least one of ethanol can be mentioned. From the viewpoint of smooth progress of the reaction, the solvent is preferably a solvent in which a metal halide represented by the general formula Ma-Xb is dissolved, and more preferably acetone, acetonitrile, methanol, ethanol or water.

In step 3, the reaction temperature may be any temperature of 20 ° C. or higher and 150 ° C. or lower. Since the yield of the imidazolium salt (1b) tends to be high, the reaction temperature is preferably in the range of room temperature to 80 ° C. On the other hand, the reaction time is not particularly limited, and examples thereof include 10 minutes or more and 50 hours or less.

Step-3 may include a step of isolating the obtained imidazolium salt (1b) after the reaction. The isolation method is arbitrary and may include at least one of the group consisting of solvent extraction, column chromatography, preparative thin layer chromatography, preparative liquid chromatography and recrystallization.

In addition, step-3 can also be provided as a method for producing an imidazolium salt (1b).

The production method of the present invention is a step of ion-exchange the imidazolium salt represented by the general formula (1b) to obtain an imidazolium salt represented by the general formula (1d) (hereinafter, also referred to as "step-4"). ), It is preferable to have.

In step 4, the imidazolium salt represented by the general formula (1d) (hereinafter, also referred to as “imidazolium salt (1d)”) is obtained by the reaction shown below.

(In the formula, R ¹ is a cycloalkyl group having 3 to 12 carbon atoms excluding the 1-adamantyl group, and the cycloalkyl group may be substituted with an alkyl group having 1 to 4 carbon atoms. Xb ⁻ is a halogen. Represents a compound ion. Xd ^- represents OH- ⁾ .

The ion exchange method in step 4 is arbitrary, but it is preferable to carry out ion exchange by contacting the imidazolium salt (1b) with the ion exchange resin. Examples of the ion exchange resin include amber light IRA-400, amber light IRA-402, amber light IRA-404, amber light IRA-900, amber light IRA-904, amber light IRA-458, amber light IRA-958, and amber. At least one of the group consisting of Light IRA-420, Amber Light IRA-411 and Amber Light IRA-910 can be mentioned. Since the yield of the imidazolium salt (1d) tends to be high, the ion exchange resin is preferably Amberlite IRA-400.

In step-4, ion exchange can be carried out in a solvent. The solvent may be any one that does not inhibit ion exchange, and specifically, at least one of a group consisting of an ether solvent, an ester solvent, an amide solvent, a ketone solvent, a nitrile solvent, an alcohol solvent and water may be used. Can be mentioned. At least one of the group consisting of tetrahydrofuran, 1,2-dimethoxyethane and 1,4-dioxane as an ether solvent, at least one of ethyl acetate or butyl acetate as an ester solvent, and N, N-dimethylformamide as an amide solvent. Alternatively, at least one of N, N-dimethylacetamide, at least one of acetone or methyl ethyl ketone as a ketone solvent, at least one of acetonitrile or propionitrile as a nitrile solvent, and at least one of methanol or ethanol as an alcohol solvent. Can be mentioned.

In step 4, the imidazolium salt (1d) obtained after the ion exchange may contain the raw material imidazolium salt (1b).

In addition, step-4 can also be provided as a method for producing an imidazolium salt (1d).

The imidazolium salt of the present invention can be used in applications in which the imidazolium salt is used, such as ionic liquids, organic electrolytes, pharmaceutical intermediates, and polishing liquids, but in particular, structural oriented agents in the production of zeolites ( Hereinafter, it is preferable to use it as "SDA").

As a method for producing a zeolite using the imidazolium salt of the present invention as SDA (hereinafter, also referred to as "the method for producing a zeolite of the present invention"), a composition containing a silica source, an alumina source, a structure-directing agent, an alkali source and water. A method for producing a zeolite, which comprises a crystallization step of crystallizing the above-mentioned, and wherein the composition contains an imidazolium salt represented by the general formula (1) can be mentioned.

(In the formula, R ¹ is a cycloalkyl group having 3 to 12 carbon atoms excluding the 1-adamantyl group, and the cycloalkyl group may be substituted with an alkyl group having 1 to 4 carbon atoms. X ^- is a halogen. It is one of the group consisting of a compound ion, R ² COO ⁻ , R ³ SO ₂ O ⁻ and OH ⁻ , where R ² is an alkyl group having 1 to 6 carbon atoms and R ³ is an alkyl group having 1 to 9 carbon atoms. It is one of a group consisting of a group, a fluoroalkyl group having 1 to 9 carbon atoms, and a phenyl group, and the phenyl group is an alkyl group having 1 to 4 carbon atoms, a fluoroalkyl group having 1 to 4 carbon atoms, and a carbon number of carbon atoms. It may be substituted with one or more substituents selected from an alkoxy group of 1 to 4, a fluoroalkyl group having 1 to 4 carbon atoms, a halogen atom, a cyano group or a nitro group).

The zeolite obtained by the method for producing a zeolite using the imidazolium salt of the present invention as SDA is a zeolite having pores in which the maximum pores are formed by an oxygen 8-membered ring (hereinafter, also referred to as “small pore zeolite”). It is more preferable that the AFX type zeolite is used.

The zeolite obtained by the method for producing a zeolite using the imidazolium salt of the present invention as SDA is preferably a zeolite containing no phosphoric acid (PO ₄ ) in its skeleton, and preferably aluminosilicate.

Hereinafter, a method for producing a zeolite using the imidazolium salt of the present invention as an SDA will be described by taking AFX-type zeolite as an example of the obtained zeolite.

The AFX-type zeolite is a zeolite having an AFX structure. The AFX structure is an IUPAC structure code defined by the Structure Communication of the International Union of Zeolite Association (hereinafter referred to as "IZA"), and is an AFX type structure.

The zeolite production method of the present invention crystallizes a composition containing a silica source, an alumina source, a structure-directing agent, an alkali source and water (hereinafter, also referred to as “raw material composition”).

The silica source is silica (SiO ₂ ) or a silicon compound as a precursor thereof, for example, colloidal silica, atypical silica, sodium silicate, tetraethyl orthosilicate, precipitation method silica, fumed silica, crystalline aluminosilicate and aluminosilicate. At least one of the group consisting of silicate gels can be mentioned, preferably at least one of crystalline aluminosilicates and aluminosilicate gels.

The alumina source is alumina (Al ₂ O ₃ ) or an aluminum compound that is a precursor thereof, and is, for example, from aluminum sulfate, sodium aluminate, aluminum hydroxide, aluminum chloride, aluminosilicate gel, crystalline aluminosilicate, and metallic aluminum. At least one of the group can be used, preferably at least one of crystalline aluminosilicates and aluminosilicate gels.

The alkali source may be an alkali metal hydroxide or an alkali metal halide, and is preferably at least one selected from the group consisting of sodium hydroxide, potassium hydroxide, rubidium hydroxide and cesium hydroxide. .. An alkaline component contained in at least one of a silica source and an alumina source can also be regarded as an alkaline source.

The raw material composition comprises a structure oriented agent (SDA). SDA contains an imidazolium salt represented by the general formula (1) (imidazolium salt of the present invention). Since the imidazolium cation contained in the imidazolium salt of the present invention functions as SDA and directs AFX-type zeolite, AFX-type zeolite can be obtained by crystallizing the raw material composition. In the method for producing zeolite of the present invention, for example, X ^- is either a halide ion or a hydroxide ion (OH- ⁾ , and is a group consisting of hydroxide ion, chloride ion, bromide ion and iodide ion. It is preferably either. In the zeolite production method of the present invention, R ¹ in the general formula (1) has a cycloalkyl group having 3 to 12 carbon atoms, a cycloalkyl group having 5 to 10 carbon atoms, and further having 6 to 8 carbon atoms. It is preferably a cycloalkyl group, and more preferably a cycloalkyl group having 7 carbon atoms.

The SDA of the raw material composition may contain the imidazolium salt of the present invention, but may contain the imidazolium salt of the present invention and an imidazolium salt other than the imidazolium salt of the present invention. For example, the raw material composition includes the imidazolium salt of the present invention, as well as N, N'-bis (1-adamantyl) imidazolium salt, N, N'-dicyclopentylimidazolium salt, N, N'-dicyclohexylimidazolium. Salt, N, N'-dicycloheptylimidazolium salt, N, N'-dicyclooctylimidazolium salt, N, N'-dicyclododecylimidazolium salt, and N, N'-di [exo-norbornane -2-Il] It may contain at least one imidazolium salt in the group consisting of imidazolium salts. When the SDA of the raw material composition contains 2 or more imidazolium salts, the molar ratio of the imidazolium salt of the present invention to the SDA in the raw material composition is 40 mol% or more and 100 mol% or less, and 50 mol% or more and 100 mol% or less. It is preferable, and it is more preferable that it is 60 mol% or more and 100 mol% or less.

Since the production cost tends to increase as the amount of SDA increases, the molar ratio of SDA to silica (hereinafter, also referred to as “SDA / SiO ₂ ”) is preferably 2.0 or less, preferably 1.0. Below, it is more preferably 0.50 or less, and further preferably 0.30 or less. When SDA / SiO ₂ is 0.01 or more, further 0.02 or more, and further 0.03 or more, the formation of zeolite having a structure other than AFX type is further suppressed.

The molar ratio of water to silica in the raw material composition (hereinafter referred to as "H ₂ O / SiO ₂ ") is preferably 5 or more and 60 or less, more preferably 10 or more and 45 or less, and 20 or more. It is more preferably 45 or less. When H ₂ O / SiO ₂ is in this range, the mixture has a viscosity that allows appropriate stirring during crystallization.

In order to promote the crystal growth of zeolite, the raw material composition may contain seed crystals. When the seed crystal is contained, the content of the seed crystal in the raw material composition is 0% by weight or more and 10.0% by weight or less, and further 0.5% by weight or more and 5.0% by weight as the weight ratio of the seed crystal to silica. Hereinafter, it may be mentioned that it is 0.5% by weight or more and 3.5% by weight or less.

The seed crystal may be a zeolite having no odd-numbered ring in its crystal structure, and is, for example, a zeolite having a structure of any one of the group consisting of FAU, CHA, AEI, LEV, AFX, ERI, OFF, LTL and GME. Further, a zeolite having a structure of any one of the group consisting of CHA, AEI, LEV, AFX and ERI, and further an AFX type zeolite can be mentioned.

The raw material composition preferably has the following composition. In the following composition, M is an alkali metal, each ratio is a molar ratio, and the seed crystal is a weight ratio.

SiO ₂ / Al ₂ O ₃₅ or more and 100 or less, preferably 10 or more and 50 or less, more preferably 15 or more and 40 or less OH / SiO ₂ 0.06 or more and 1.0 or less, preferably 0.08 or more and 0.60 or less, More preferably 0.10 or more and 0.40 or less M / SiO ₂ 0.06 or more and 1.0 or less, preferably 0.08 or more and 0.60 or less, more preferably 0.10 or more and 0.40 or less SDA / SiO ₂ 0.01 or more and 2.0 or less, preferably 0.02 or more and 1.0 or less, more preferably 0.03 or more and 0.50 or less H ₂ O / SiO ₂₅ or more and 60 or less, preferably
Seed crystal 10.0% by weight or less, preferably 5.0% by weight or less, more preferably 3.5% by weight or less In the crystallization step, the crystallization method of the raw material composition may be appropriately selected. Preferred crystallization methods include hydrothermal treatment of the raw material composition. For hydrothermal treatment, the raw material composition may be placed in a closed pressure-resistant container and heated. The following can be mentioned as the hydrothermal treatment conditions.

Treatment temperature: 80 ° C. or higher and 190 ° C. or lower, preferably 150 ° C. or higher and 190 ° C. or lower Treatment time: 2 hours or more and 500 hours or less Treatment pressure: Self-sustaining pressure Crystallization may be carried out in either a stationary state or a stirring state. Since the composition of the obtained AFX-type zeolite becomes more uniform, it is preferable that the crystallization is performed in a state where the raw material composition is agitated.

The zeolite production method of the present invention may include a washing step and a drying step, or a washing step, a drying step and an SDA removal step after the crystallization step.

In the washing step, the AFX-type zeolite and the liquid phase are solid-liquid separated from the product after the crystallization step. In the washing step, solid-liquid separation may be performed by a known method, and the AFX-type zeolite obtained as a solid phase may be washed with pure water. Specific examples thereof include a method of filtering and washing the product and separating it into a liquid phase and a solid phase to obtain an AFX-type zeolite.

The drying step removes water from the AFX-type zeolite after the crystallization step or the washing step. The conditions of the drying step are arbitrary, but the product after the crystallization step or the AFX-type zeolite obtained after the washing step is treated in the air under the conditions of 100 ° C. or higher and 150 ° C. or lower for 2 hours or longer. Can be exemplified. Examples of the drying method include standing and spraying dryers.

In the SDA removal step, for example, the removal of SDA can be performed by firing or decomposition.

Firing is performed at a temperature of 400 ° C. or higher and 800 ° C. or lower. Further, it is preferable to carry out at a temperature of 700 ° C. or lower. This makes it easy to obtain AFX-type zeolite with less dealuminum. Specific heat treatment conditions include air at 600 ° C. for 1 to 2 hours.

The production method of the present invention may have an ammonium treatment step, if necessary.

The ammonium treatment step is performed to remove the alkali metal contained in the AFX-type zeolite and change the cation type to the ammonium type ₍ hereinafter referred to as “NH4 ⁺ type”). The ammonium treatment step is performed, for example, by bringing an aqueous solution containing ammonium ions into contact with the AFX-type zeolite.

In the case of NH ₄₊ type AFX type zeolite, heat treatment may be performed again ^. By the heat treatment, the cation type becomes a proton type (hereinafter referred to as "H ⁺ type") AFX type zeolite. More specific heat treatment conditions include air at 500 ° C. for 1 to 2 hours.

When the AFX-type zeolite of the present invention contains a transition metal, the production method of the present invention may include a transition metal-containing step of incorporating the transition metal into the AFX-type zeolite.

The transition metal used in the transition metal-containing step is preferably a compound containing one or more transition metals in the group consisting of groups 8, 9, 10 and 11 of the periodic table, and platinum (Pt), A compound containing at least one of the group consisting of palladium (Pd), rhodium (Rh), silver (Ag), iron (Fe), copper (Cu), cobalt (Co), manganese (Mn) and indium (In). It is more preferably present, more preferably a compound containing at least one of iron or copper, and even more preferably a compound containing copper. Examples of the compound containing a transition metal include at least one of the group consisting of nitrates, sulfates, acetates, chlorides, complex salts, oxides and composite oxides of these transition metals.

As a method for containing a transition metal in AFX-type zeolite, for example, at least one of a group consisting of an ion exchange method, an impregnation carrying method, an evaporation dry solid method, a precipitation carrying method, and a physical mixing method can be mentioned.

The AFX-type zeolite obtained by the zeolite production method of the present invention is a catalyst or an adsorbent, and at least one of these substrates, and at least one of a catalyst or an adsorbent exposed to high temperature and high humidity, and It can be used as at least one of a catalyst base material and an adsorbent base material, and is particularly preferable to be used as a catalyst or a catalyst base material. Furthermore, the AFX-type zeolite of the present invention can be used as a nitrogen oxide reduction catalyst, particularly as an SCR catalyst, by containing a transition metal. Furthermore, it can be used as an SCR catalyst for diesel vehicles having a high exhaust gas temperature.

The nitrogen oxide reduction catalyst containing the AFX type zeolite of the present invention can be used in the nitrogen oxide reduction method.

Next, the present invention will be described by way of examples, but the present invention is not limited thereto.
(H1 ^- NMR)
H1 ^- NMR measurements of the sample were performed using Ascend ^TM 400 (400 MHz, manufactured by Bruker) or UltraSchild ^TM Plus 400 (400 MHz, manufactured by Bruker). The measurement data are described in the order of chemical shift, peak multiplicity, coupling constant (Hz), and peak integral value.
(Powder X-ray diffraction)
XRD measurement of the sample was performed using a general X-ray diffractometer (device name: Ultima IV, manufactured by RIGAKU). The measurement conditions are as follows.

Radioactive source: CuKα ray (λ = 1.5405Å)
Measurement mode: Step scan
Scan conditions: 0.01 ° per second
Divergence slit: 1.00 deg
Scattering slit: 1.00 deg
Light receiving slit: 0.30 mm
Measurement time: 1.00 seconds
Measurement range: 2θ = 3.0 ° to 43.0 °
The crystal phase and XRD peak intensity ratio of the sample were confirmed by comparing the obtained XRD pattern with the XRD pattern posted on the home page of IZA's Structure Communication.

(Quantitative quantity of silicon and aluminum)
The composition of the sample was analyzed using a general inductively coupled plasma emission spectrometer (device name: OPTIMA3300DV, manufactured by PERKIN ELMER). The sample was dissolved in a mixed solution of hydrofluoric acid and nitric acid to prepare a measurement solution. The obtained measurement solution was put into an apparatus and the composition of the sample was analyzed. SiO ₂ / Al ₂ O ₃ was calculated from the obtained molar concentrations of silicon (Si) and aluminum (Al).
(Synthesis of imidazolium salt)
Example 1-1

Acetic acid (25 mL, 450 mmol) suspension of 1-adamantylamine (15.1 g, 100 mmol) and cyclopentylamine (9.9 mL, 100 mmol) and formaldehyde (35% aqueous solution, 7.8 mL, 100 mmol) and glyoxal (40%). Aqueous solution, 11.4 mL, 100 mmol) acetic acid (25 mL, 450 mmol) solution was stirred at 40 ° C. for 5 minutes, respectively. At the same temperature, an acetic acid solution of formaldehyde and glyoxal was added to an acetic acid suspension of 1-adamantylamine and cyclopentylamine, and the mixture was further stirred for 15 minutes. After completion of the reaction, the reaction solution was poured into water and the organic layer was extracted with chloroform to obtain a chloroform solution of N- (1-adamantyl) -N'-cyclopentylimidazolium = acetate.

A saturated aqueous sodium chloride solution (50 mL) was added to the obtained chloroform solution of N- (1-adamantyl) -N'-cyclopentylimidazolium = acetate, and the mixture was sufficiently stirred, and then the organic layer was separated. The organic layer was dried over anhydrous sodium sulfate and concentrated under reduced pressure. By thoroughly washing the obtained solid with acetone and then drying it, N- (1-adamantyl) -N'-cyclopentyl imidazolium = chloride, N, N'-bis (1-adamantyl) imidazolium = chloride and A white solid (8.21 g, yield 27%) containing N, N'-dicyclopentylimidazolium = chloride was obtained. The white solid contained 90 mol% of N- (1-adamantyl) -N'-cyclopentyl imidazolium = chloride.

NMR spectrum of N- (1-adamantyl) -N'-cyclopentyl imidazolium = chloroform: ¹ H-NMR (400 MHz, CDCl ₃ ): δ11.26 (s, 1H), 7.27 (s, 1H), 7 .18 (s, 1H), 5.42 (quint, J = 7.0Hz, 1H), 2.53 to 2.38 (m, 2H), 2.38 to 2.34 (m, 2H), 2 .32 (s, 3H), 2.254 (s, 3H), 2.246 (s, 3H), 1.93 to 1.80 (m, 4H), 1.79 (s, 6H).

Example 1-2

Acetic acid (2.50 mL, 45.0 mmol) suspension of 1-adamantylamine (1.51 g, 10.0 mmol) and cyclohexylamine (1.14 mL, 10.0 mmol) and formaldehyde (35% aqueous solution, 0.74 mL) , 10.0 mmol) and glyoxal (40% aqueous solution, 1.14 mL, 10.0 mmol) in acetic acid (2.50 mL, 45.0 mmol) were prepared by stirring at 40 ° C. for 5 minutes, respectively. An acetic acid solution of formaldehyde and glyoxal was added to an acetic acid suspension of 1-adamantylamine and cyclohexylamine at 40 ° C., and the mixture was further stirred for 10 minutes. The reaction solution was poured into water and extracted with chloroform to obtain a chloroform solution of N- (1-adamantyl) -N'-cyclohexylimidazolium = acetate.

A saturated aqueous sodium chloride solution (50 mL) was added to the obtained chloroform solution of N- (1-adamantyl) -N'-cyclohexylimidazolium = acetate, and the mixture was sufficiently stirred, and then the organic layer was separated. The organic layer was dried over anhydrous sodium sulfate and concentrated under reduced pressure. The obtained solid was washed with acetone and then dried to cause N- (1-adamantyl) -N'-cyclohexylimidazolium = chloride, N, N'-bis (1-adamantyl) imidazolium = chloride and N, A white solid (2.32 g, yield 55%) containing N'-dicyclohexylimidazolium = chloride was obtained. The white solid contained 68 mol% of N- (1-adamantyl) -N'-cyclohexylimidazolium-chloride.

NMR spectrum of N- (1-adamantyl) -N'-cyclohexylimidazolium = chloroform: ¹ H-NMR (400 MHz, CDCl ₃ ): δ10.93 (s, 1H), 7.38 (s, 1H), 7 .31 (s, 1H), 4.83 (t, J = 12.0Hz, 1H), 2.34 (s, 3H), 2.252 (s, 3H), 2.242 (s, 3H), 2.00 to 1.86 (m, 2H), 1.83 (m, 4H), 1.78 (s, 6H), 1.62 to 1.43 (m, 2H), 1.36 to 1. 19 (m, 2H).

Example 1-3

Acetic acid (25 mL, 450 mmol) suspension of 1-adamantylamine (15.1 g, 100 mmol) and cycloheptylamine (12.7 mL, 100 mmol), formaldehyde (35% aqueous solution, 7.8 mL, 100 mmol) and glyoxal (40). % Aqueous solution, 11.4 mL, 100 mmol) acetic acid (25 mL, 450 mmol) solution was prepared by stirring at 40 ° C. for 5 minutes, respectively. An acetic acid solution of formaldehyde and glyoxal was added to an acetic acid suspension of 1-adamantylamine and cycloheptylamine at 40 ° C., and the mixture was further stirred for 15 minutes. The reaction mixture was poured into water and extracted with chloroform to obtain a chloroform solution of N- (1-adamantyl) -N'-cycloheptylimidazolium = acetate.

A saturated aqueous sodium chloride solution (50 mL) was added to the obtained chloroform solution of N- (1-adamantyl) -N'-cycloheptyl imidazolium = acetate, and the mixture was sufficiently stirred, and then the organic layer was separated. The organic layer was dried over anhydrous sodium sulfate and concentrated under reduced pressure. The obtained solid was washed with acetone and then dried to obtain N- (1-adamantyl) -N'-cycloheptyl imidazolium = chloride, N, N'-bis (1-adamantyl) imidazolium = chloride and N. , N'-Dicycloheptylimidazolium = chloride was obtained as a white solid (4.67 g, yield 14%). The white solid contained 66 mol% of N- (1-adamantyl) -N'-cycloheptylimidazolium-chloride.

NMR spectrum of N- (1-adamantyl) -N'-cycloheptylimidazolium = chloroform: ¹ H-NMR (400 MHz, CDCl ₃ ): δ11.27 (s, 1H), 7.25 (s, 1H), 7.19 (s, 1H), 5.13 (sep, J = 4.5Hz, 1H), 2.31 (s, 3H), 2.24 (s, 3H), 2.23 (s, 3H) , 2.22 to 2.14 (m, 4H), 2.04 to 1.90 (m, 4H), 1.87 to 1.58 (m, 4H), 1.78 (s, 6H).

Example 1-4

Acetic acid (15 mL, 270 mmol) suspension of 1-adamantylamine (9.08 g, 60 mmol) and cyclooctylamine (8.4 mL, 60 mmol), formaldehyde (35% aqueous solution, 5.2 mL, 60 mmol) and glyoxal (40). % Aqueous solution, 6.8 mL, 60 mmol) acetic acid (15 mL, 270 mmol) solution was prepared by stirring at 40 ° C. for 5 minutes, respectively. An acetic acid solution of formaldehyde and glyoxal was added to an acetic acid suspension of 1-adamantylamine and cyclooctylamine at 40 ° C., and the mixture was further stirred for 15 minutes. The reaction mixture was poured into water and extracted with chloroform to obtain a chloroform solution of N- (1-adamantyl) -N'-cyclooctylimidazolium = acetate.

A saturated aqueous sodium chloride solution (50 mL) was added to the obtained chloroform solution of N- (1-adamantyl) -N'-cyclooctylimidazolium = acetate, and the mixture was sufficiently stirred, and then the organic layer was separated. The organic layer was dried over anhydrous sodium sulfate and concentrated under reduced pressure. The obtained solid was washed with acetone and then dried to obtain N- (1-adamantyl) -N'-cyclooctyl imidazolium = chloride, N, N'-bis (1-adamantyl) imidazolium = chloride and N. , N'-Dicyclooctylimidazolium = chloride-containing white solid (4.45 g, yield 21%) was obtained. In addition, the white solid contained 54 mol% of N- (1-adamantyl) -N'-cyclooctylimidazolium = chloride.

NMR spectrum of N- (1-adamantyl) -N'-cyclooctylimidazolium = chloroform: ¹ H-NMR (400 MHz, CDCl ₃ ): δ11.24 (s, 1H), 7.20 (s, 1H), 7.17 (s, 1H), 5.31 (sep, J = 4.7Hz, 1H), 2.32 (s, 3H), 2.24 (s, 3H), 2.23 (s, 3H) , 2.15 to 1.98 (m, 4H), 1.87 to 1.58 (m, 10H), 1.78 (s, 6H).

Example 1-5

Acetic acid (1.25 mL) suspension of 1-adamantylamine (0.76 g, 5.0 mmol) and exo-2-aminonorbornan (0.59 mL, 5.0 mmol) and formaldehyde (35% aqueous solution, 0.37 mL) , 5.0 mmol) and glyoxal (40% aqueous solution, 0.57 mL, 5.0 mmol) in acetic acid (1.25 mL) were prepared by stirring at 40 ° C. for 5 minutes, respectively. An acetic acid solution of formaldehyde and glyoxal was added to an acetic acid suspension of 1-adamantylamine and exo-2-aminonorbornane at 40 ° C. and stirred for an additional 10 minutes. The reaction solution was poured into water and extracted with chloroform to obtain a chloroform solution of N- (1-adamantyl) -N'- [exo-norbornane-2-yl] imidazolium = acetate.

Add a saturated aqueous sodium chloride solution (10 mL) to the obtained chloroform solution of N- (1-adamantyl) -N'-[exo-norbornane-2-yl] imidazolium = acetate, stir well, and then separate the organic layer. Liquid. The organic layer was dried over anhydrous sodium sulfate and concentrated under reduced pressure. The obtained solid was washed with acetone and then dried to obtain N- (1-adamantyl) -N'-[exo-norbornane-2-yl] imidazolium-chloride, N, N'-bis (1-adamantyl). A white solid (0.10 g, yield 6%) containing imidazolium = chloride and N, N'-di [exo-norbornane-2-yl] imidazolium = chloride was obtained. In addition, the white solid contained 65 mol% of N- (1-adamantyl) -N'-cyclooctylimidazolium = chloride.

N- (1-adamantyl) -N'-[exo-norbornane-2-yl] NMR spectrum of imidazolium-chloride: ¹ H-NMR (400 MHz, CDCl ₃ ): δ11.17 (s, 1H), 7. 33 (d, J = 1.5Hz, 1H), 7.22 (d, J = 1.5Hz, 1H), 4.97 (dd, J = 4.4,8.6Hz, 1H), 2.65 (S, 1H), 2.51 (s, 1H), 2.31 (s, 3H), 2.26 (s, 3H), 2.25 (s, 3H), 2.18 (m, 1H) , 1.91 to 1.73 (m, 1H), 1.78 (s, 6H), 1.73 to 1.63 (m, 1H), 1.63 to 1.50 (m, 3H), 1 .40 (m, 1H), 1.28 (m, 1H).

Example 1-6

Acetic acid (2.6 mL) suspension of 1-adamantylamine (9.08 g, 10 mmol) and cyclododecylamine (1.83 g, 10 mmol), formaldehyde (35% aqueous solution, 0.75 mL, 10 mmol) and glyoxal (40). % Aqueous solution, 1.14 mL, 10 mmol) acetic acid (2.6 mL) solution was prepared by stirring at 40 ° C. for 5 minutes, respectively. An acetic acid solution of formaldehyde and glyoxal was added to an acetic acid suspension of 1-adamantylamine and cyclododecylamine at 40 ° C., and the mixture was further stirred for 30 minutes. The reaction mixture was poured into water and extracted with chloroform to obtain a chloroform solution of N- (1-adamantyl) -N'-cyclododecylimidazolium = acetate.

A saturated aqueous sodium chloride solution (50 mL) was added to the obtained chloroform solution of N- (1-adamantyl) -N'-cyclododecylimidazolium = acetate, and the mixture was sufficiently stirred, and then the organic layer was separated. The organic layer was dried over anhydrous sodium sulfate and concentrated under reduced pressure. The obtained solid was washed with acetone and then dried to obtain N- (1-adamantyl) -N'-cyclododecylimidazolium = chloride, N, N'-bis (1-adamantyl) imidazolium = chloride and N. , N'-Dicyclododecylimidazolium = chloride was obtained as a white solid (2.10 g, yield 49%). In addition, the white solid contained 44 mol% of N- (1-adamantyl) -N'-cyclododecylimidazolium = chloride.

NMR spectrum of N- (1-adamantyl) -N'-cyclododecylimidazolium = chloroform: ¹ H-NMR (400 MHz, CDCl ₃ ): δ11.17 (s, 1H), 7.31 (t, J = 1) .8Hz, 1H), 7.21 (t, J = 1.8Hz, 1H), 4.99 (tt, J = 5.5,7.5Hz, 1H), 2.33 (s, 3H), 2 .28 (s, 3H), 2.27 (s, 3H), 2.23-1.98 (m, 2H), 1.93 to 1.65 (m, 8H), 1.65 to 1.13 (M, 18H).

Example 1-7

Cyclopentyl methanesulfonate (0.168 g, 1.0 mmol) was added to a solution of 1- (1-adamantyl) imidazole (0.202 g, 1.0 mmol) in acetonitrile (2.0 mL), and the mixture was heated under reflux for 24 hours. After the reaction, the solvent was distilled off from the reaction solution under reduced pressure, the obtained solid was washed with saturated aqueous sodium hydrogen carbonate solution, extracted with chloroform, and N- (1-adamantyl) -N'-cyclopentylimidazolium = A chloroform solution of methanesulfonate was obtained.

A saturated aqueous sodium chloride solution (10 mL) was added to the obtained chloroform solution of N- (1-adamantyl) -N'-cyclopentylimidazolium = methanesulfonate, and the mixture was sufficiently stirred, and then the organic layer was separated. The organic layer was dried over anhydrous sodium sulfate and concentrated under reduced pressure. The obtained solid was washed with acetone and then dried to obtain a white solid of N- (1-adamantyl) -N'-cyclopentylimidazolium-chloride (0.035 g, yield 12%).

NMR spectrum of N- (1-adamantyl) -N'-cyclopentyl imidazolium = chloroform: ¹ H-NMR (400 MHz, CDCl ₃ ): δ11.26 (s, 1H), 7.27 (s, 1H), 7 .18 (s, 1H), 5.42 (quint, J = 7.0Hz, 1H), 2.53 to 2.38 (m, 2H), 2.38 to 2.34 (m, 2H), 2 .32 (s, 3H), 2.254 (s, 3H), 2.246 (s, 3H), 1.93 to 1.80 (m, 6H), 1.79 (s, 4H).

Example 1-8

Bromocyclohexane (120 μL, 1.0 mmol) was added to a solution of 1- (1-adamantyl) imidazole (202 mg, 1.0 mmol) in chlorobenzene (2.0 mL), and the mixture was heated under reflux for 24 hours. After allowing to cool, the solvent was distilled off from the reaction solution under reduced pressure, and the obtained solid was washed with saturated aqueous sodium hydrogen carbonate solution and extracted with chloroform. The organic layer is dried over anhydrous sodium sulfate, the solvent is distilled off from the organic layer, and then the obtained solid is washed with acetone and dried to obtain N- (1-adamantyl) -N'-cyclohexylimidazolium =. A white solid of bromide (11 mg, yield 3.3%) was obtained.

NMR spectrum of N- (1-adamantyl) -N'-cyclohexylimidazolium = bromide: ¹ H-NMR (400 MHz, CDCl ₃ ): δ11.04 (s, 1H), 7.40 (s, 1H), 7 .34 (s, 1H), 4.84 (t, J = 12.0Hz, 1H), 2.34 (s, 3H), 2.252 (s, 3H), 2.242 (s, 3H), 2.00 to 1.86 (m, 2H), 1.83 (m, 4H), 1.78 (s, 6H), 1.62 to 1.43 (m, 2H), 1.36 to 1. 19 (m, 2H).

Example 1-9

Cycloheptyl p-toluenesulfonate (2.79 g, 10 mmol) was added to a solution of 1- (1-adamantyl) imidazole (2.09 g, 10 mmol) in acetonitrile (11 mL), and the mixture was heated under reflux for 18 hours. After the reaction, the solvent was distilled off from the reaction solution under reduced pressure, and the obtained solid was washed with saturated aqueous sodium hydrogen carbonate solution and extracted with chloroform. After drying the organic layer with anhydrous sodium sulfate, the solvent was distilled off from the organic layer to obtain a yellow solid of N- (1-adamantyl) -N'-cycloheptylimidazolium = p-toluenesulfonate.

Lithium chloride (1.33 g, 31 mmol) was added to the obtained solution of N- (1-adamantyl) -N'-cycloheptylimidazolium = p-toluenesulfonate in acetone (22 mL), and the mixture was stirred at 50 ° C. for 2 hours. .. After the reaction, the solvent was distilled off from the reaction solution under reduced pressure, and after washing with chloroform, the solvent was distilled off from the filtrate under reduced pressure, and the solid was washed with acetone to obtain N- (1-adamantyl) -N'-. A white solid (1.09 g, yield 31%) of cycloheptyl imidazolium = chloroform was obtained.

NMR spectrum of N- (1-adamantyl) -N'-cycloheptylimidazolium = chloroform: ¹ H-NMR (400 MHz, CDCl ₃ ): δ11.27 (s, 1H), 7.25 (s, 1H), 7.19 (s, 1H), 5.13 (sep, J = 4.5Hz, 1H), 2.31 (s, 3H), 2.24 (s, 3H), 2.23 (s, 3H) , 2.22 to 2.14 (m, 4H), 2.04 to 1.90 (m, 4H), 1.87 to 1.58 (m, 4H), 1.78 (s, 6H).

Example 1-10

Cycloheptyl methanesulfonate (13.8 g, 72 mmol) was added to a solution of 1- (1-adamantyl) imidazole (12.1 g, 60 mmol) in acetonitrile (120 mL), and the mixture was heated under reflux for 15 hours. After the reaction, the solvent was distilled off from the reaction solution under reduced pressure, the obtained solid was washed with saturated aqueous sodium hydrogen carbonate solution, extracted with chloroform, and N- (1-adamantyl) -N'-cycloheptyl imidazolium. = A chloroform solution of methanesulfonate was obtained.

A saturated aqueous sodium chloride solution (100 mL) was added to the obtained chloroform solution of N- (1-adamantyl) -N'-cycloheptyl imidazolium = methanesulfonate, and the mixture was sufficiently stirred, and then the organic layer was separated. The organic layer was dried over anhydrous sodium sulfate and concentrated under reduced pressure. The obtained solid was washed with acetone and then dried to obtain a white solid of N- (1-adamantyl) -N'-cycloheptylimidazolium-chloride (7.68 g, yield 38%).

Reference example 1-1

Acetic acid (15.0 mL, 270 mmol) suspension of 1-adamantylamine (9.07 g, 60 mmol) and ammonium acetate (4.62 g, 60 mmol), formaldehyde (35% aqueous solution, 4.4 mL, 60 mmol) and glyoxal ( A 40% aqueous solution, 6.8 mL, 60 mmol) acetic acid (15.0 mL, 270 mmol) solution was stirred at 40 ° C. for 5 minutes, respectively. An acetic acid solution of formaldehyde and glyoxal was added to an acetic acid suspension of 1-adamantylamine and ammonium acetate at 90 ° C., and the mixture was further stirred for 5 hours. The reaction solution was poured into an aqueous sodium hydroxide solution under ice-cooling, and the organic layer was extracted with chloroform. The organic layer was dried over anhydrous sodium sulfate and concentrated under reduced pressure. The obtained solid was sublimated (210 ° C./0.6 mmHg) to obtain a white solid of 1- (1-adamantyl) imidazole (1.80 g, yield 14%).

NMR spectrum of 1- (1-adamantyl) imidazole: ¹ H-NMR (400 MHz, CDCl ₃ ): δ7.64 (s, 1H), 7.07 (t, J = 1.3 Hz, 1H), 7.06 (D, J = 3.7Hz, 1H), 2.23 (s, 3H), 2.09 (s, 3H), 2.08 (s, 3H), 1.78 (t, J = 12.6Hz) , 3H), 1.76 (t, J = 12.6Hz, 3H).

Reference example 1-2

Triethylamine (4.6 mL, 33 mmol) and 1,4-diazabicyclo in a solution of cycloheptanol (3.9 mL, 33 mmol) and p-toluenesulfonic acid chloride (5.72 g, 30 mmol) in tetrahydrofuran (100 mL) under an ice bath. [2.2.2] Octane (0.34 g, 3.0 mmol) was added slowly in sequence, and then the mixture was stirred at room temperature for 24 hours. After completion of the reaction, the reaction solution was poured into a saturated aqueous sodium hydrogen carbonate solution under ice-cooling and extracted with ethyl acetate. The organic layer was dried over anhydrous sodium sulfate, and the solvent was distilled off from the organic layer to obtain a crude product. This was purified by silica chromatography (hexane: ethyl acetate = 8: 1) to obtain a pale yellow oily cycloheptyl p-toluenesulfonic acid (5.11 g, yield 63%).

NMR spectrum of cycloheptyl p-toluenesulfonic acid: ¹ H-NMR (400 MHz, CDCl ₃ ): δ7.88 (d, J = 8.1 Hz, 2H), 7.33 (d, J = 8.1 Hz, 2H) ), 4.87 (tt, J = 4.8, 7.8 Hz, 1H), 2.44 (s, 3H), 1.93 to 1.70 (m, 4H), 1.69 to 1.58. (M, 2H), 1.54 to 1.45 (m, 4H), 1.42 to 1.28 (m, 2H).

Reference example 1-3

Methanesulfonic acid chloride (8.12 mL, 105 mmol) is slowly added to a solution of cycloheptanol (11.9 mL, 100 mmol) and triethylamine (16.7 mL, 120 mmol) in dichloromethane (250 mL) under an ice bath, and then at room temperature. Was stirred for 1 hour. After completion of the reaction, the reaction solution was poured into water and extracted with chloroform. After drying the organic layer with anhydrous sodium sulfate, the solvent was distilled off from the organic layer to obtain a pale yellow oily cycloheptyl methanesulfonate (18.9 g, yield 98%).

NMR spectrum of cycloheptyl methanesulfonate: ¹ H-NMR (400 MHz, CDCl ₃ ): δ4.87 (tt, J = 4.6, 8.0 Hz, 1H), 2.99 (s, 3H), 2. 12 to 1.97 (m, 2H), 1.95 to 1.82 (m, 2H), 1.77 to 1.63 (m, 2H), 1.62 to 1.52 (m, 4H), 1.52 to 1.38 (m, 2H).

(Synthesis of AFX type zeolite)
Example 2-1
Composition containing N- (1-adamantyl) -N'-cycloheptyl imidazolium chloride obtained in Example 1-3 (N- (1-adamantyl) -N'-cycloheptyl imidazolium chloride content = 66 mol %), 48% NaOH and aluminosilicate gel (SiO ₂ / Al ₂ O ₃ = 22.8) were mixed to obtain a composition. The composition of the obtained composition is shown.
SiO ₂ / Al ₂ O ₃ = 22.8
OH / SiO ₂ = 0.15
Na / SiO ₂ = 0.15
SDA / SiO ₂ = 0.033
H ₂ O / SiO ₂ = 40

After adding AFX-type zeolite to the composition so that the seed crystal content of the composition was 3.0% by weight, the mixture was sufficiently stirred.
The stirred composition was sealed in a stainless steel autoclave and heated at 180 ° C. for 48 hours while rotating the autoclave to obtain a product.

The product was filtered, washed and dried in air at 110 ° C. overnight. The product was a single phase of AFX-type zeolite, and SiO ₂ / Al ₂ O ₃ was 23.3.

The XRD pattern of the AFX type zeolite of this example is shown in FIG.

Example 2-2
The product was obtained in the same manner as in Example 2-1 except that the composition having the following composition was used, and the product was filtered, washed and dried.
SiO ₂ / Al ₂ O ₃ = 22.8
OH / SiO ₂ = 0.20
Na / SiO ₂ = 0.20
SDA / SiO ₂ = 0.033
H ₂ O / SiO ₂ = 40
Seed crystal content = 3.0% by weight

The product was a single phase of AFX-type zeolite with SiO ₂ / Al ₂ O ₃ of 22.2.

Example 2-3
The product was obtained in the same manner as in Example 2-1 except that the composition having the following composition was used, and the product was filtered, washed and dried.
SiO ₂ / Al ₂ O ₃ = 22.8
OH / SiO ₂ = 0.20
Na / SiO ₂ = 0.20
SDA / SiO ₂ = 0.066
H ₂ O / SiO ₂ = 40
Seed crystal content = 3.0% by weight

The product was a single phase of AFX-type zeolite with SiO ₂ / Al ₂ O ₃ of 22.6.

Example 2-4
Y-type zeolite (trade name: HSZ-350HUA, manufactured by Tosoh), which was stirred overnight at room temperature in a 0.44 mol / L sulfuric acid aqueous solution, water, and N- (1-adamantyl) obtained in Example 1-3. -N'-Cycloheptylimidazolium chloride (content = 66 mol%) and 48% NaOH were mixed to obtain a composition having the following composition.
SiO ₂ / Al ₂ O ₃ = 24.9
OH / SiO ₂ = 0.35
Na / SiO ₂ = 0.35
SDA / SiO ₂ = 0.066
H ₂ O / SiO ₂ = 25

After adding AFX-type zeolite to the composition so that the seed crystal content of the composition was 3.0% by weight, the mixture was sufficiently stirred.

The product was obtained in the same manner as in Example 2-1 except that the obtained composition was heated at 150 ° C. for 89 hours, which was filtered, washed and dried.

The product was a single phase of AFX-type zeolite, and SiO ₂ / Al ₂ O ₃ was 17.5.

Example 2-5
Y-zeolite and water treated in the same manner as in Example 2-4, N- (1-adamantyl) -N'-cycloheptyl imidazolium chloride (content> 99 mol%) obtained in Example 1-9. And 48% NaOH were mixed to obtain a composition having the following composition.
SiO ₂ / Al ₂ O ₃ = 24.9
OH / SiO ₂ = 0.35
Na / SiO ₂ = 0.35
SDA / SiO ₂ = 0.10
H ₂ O / SiO ₂ = 25

After adding AFX-type zeolite to the composition so that the seed crystal content of the composition was 3.0% by weight, the mixture was sufficiently stirred.

The product was obtained in the same manner as in Example 2-1 except that the obtained composition was heated at 150 ° C. for 90 hours, which was filtered, washed and dried.

The product was a single phase of AFX-type zeolite, and SiO ₂ / Al ₂ O ₃ was 17.8.

The imidazolium salt of the present invention can be used in the same manner as the known imidazolium salt, but can be used as a substitute for the N, N'-bis (1-adamantyl) imidazolium salt, particularly zeolite. Can be used as a structure-directing agent.

Claims (10)

An imidazolium salt represented by the general formula (1).

(In the formula, R ¹ is a cycloalkyl group having 3 to 12 carbon atoms excluding the 1-adamantyl group, and the cycloalkyl group may be substituted with an alkyl group having 1 to 4 carbon atoms. X ^- is a halogen. It is one of the group consisting of a compound ion, R ² COO ⁻ , R ³ SO ₂ O ⁻ and OH ⁻ . R ² is an alkyl group having 1 to 6 carbon atoms. R ³ is an alkyl group having 1 to 9 carbon atoms. It is one or more substituents selected from the group consisting of a group, a fluoroalkyl group having 1 to 9 carbon atoms, and a phenyl group, and the phenyl group is an alkyl group having 1 to 4 carbon atoms and 1 to 4 carbon atoms. Is substituted with one or more substituents selected from the group consisting of a fluoroalkyl group, an alkoxy group having 1 to 4 carbon atoms, a fluoroalkyl group having 1 to 4 carbon atoms, a halogen atom, a cyano group and a nitro group. May be good.) In the general formula (1), X ^- is chloride ion, bromide ion, iodide ion, CH ₃ COO- ^, CH ₃ CH ₂ COO- ^, C ₆ H ₅ SO ₂ ^O- , p-CH ₃ C ₆ H. ₄ The imidazolium salt according to claim 1, which is SO ₂ O ⁻ , CH ₃ SO ₂ O ⁻ or OH ⁻ . The imidazolium salt according to claim 1 or 2, wherein in the general formula (1), R ¹ is a cycloalkyl group having 5 to 8 carbon atoms. The imidazolium salt according to claim 1 or 2, wherein R ¹ is a cycloheptyl group in the general formula (1). In the presence of a carboxylic acid represented by the general formula R ² COOH (R ² is an alkyl group having 1 to 6 carbon atoms), formaldehyde, glyoxal, 1-adamantylamine, and the general formula R ¹ NH ₂ ( R ¹ is a cycloalkyl group having 3 to 12 carbon atoms excluding the 1-adamantyl group, and the cycloalkyl group may be substituted with an alkyl group having 1 to 4 carbon atoms.) Reacts with an amine represented by. A method for producing an imidazolium salt represented by the general formula (1), which comprises a step of obtaining an imidazolium salt represented by the general formula (1a).

(In the formula, R ¹ is a cycloalkyl group having 3 to 12 carbon atoms excluding the 1-adamantyl group, and the cycloalkyl group may be substituted with an alkyl group having 1 to 4 carbon atoms. Xa ⁻ is R. ² COO ⁻ , and R ² is an alkyl group having 1 to 6 carbon atoms.)

(In the formula, R ¹ is a cycloalkyl group having 3 to 12 carbon atoms excluding the 1-adamantyl group, and the cycloalkyl group may be substituted with an alkyl group having 1 to 4 carbon atoms. X ^- is a halogen. It is one of the group consisting of a compound ion, R ² COO ⁻ , R ³ SO ₂ O ⁻ and OH ⁻ . R ² is an alkyl group having 1 to 6 carbon atoms. R ³ is an alkyl group having 1 to 9 carbon atoms. It is one of a group consisting of a group, a fluoroalkyl group having 1 to 9 carbon atoms, and a phenyl group, and the phenyl group is an alkyl group having 1 to 4 carbon atoms and a fluoroalkyl group having 1 to 4 carbon atoms. It may be substituted with one or more substituents selected from the group consisting of an alkoxy group having 1 to 4 carbon atoms, a fluoroalkyl group having 1 to 4 carbon atoms, a halogen atom, a cyano group and a nitro group.) 1- (1-adamantyl) imidazole and an alkylating agent represented by the general formula R1 ^- Xc (in the formula, R1 is a cycloalkyl group having 3 to 12 carbon atoms excluding the ¹ -adamantyl group, and the cyclo. The alkyl group may be substituted with an alkyl group having 1 to 4 carbon atoms. Xc is either a halogen atom or an R ³ SO ₂ O group, and R ³ is an alkyl group having 1 to 9 carbon atoms and an number of carbon atoms. It is one of the group consisting of 1 to 9 fluoroalkyl groups and phenyl groups, and the phenyl groups are alkyl groups having 1 to 4 carbon atoms, fluoroalkyl groups having 1 to 4 carbon atoms, and 1 carbon atoms. It may be substituted with one or more substituents selected from the group consisting of an alkoxy group of 4 and a fluoroalkyl group having 1 to 4 carbon atoms, a halogen atom, a cyano group and a nitro group). , A method for producing an imidazolium salt represented by the general formula (1), which comprises a step of obtaining an imidazolium salt represented by the general formula (1c).

(In the formula, R ¹ is a cycloalkyl group having 3 to 12 carbon atoms excluding the 1-adamantyl group, and the cycloalkyl group may be substituted with an alkyl group having 1 to 4 carbon atoms. Xc ⁻ is a halogen. It is a compound ion or R ³ SO ₂ O- ^, and R ³ is one of a group consisting of an alkyl group having 1 to 9 carbon atoms, a fluoroalkyl group having 1 to 9 carbon atoms, and a phenyl group. The phenyl group consists of an alkyl group having 1 to 4 carbon atoms, a fluoroalkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a fluoroalkyl group having 1 to 4 carbon atoms, a halogen atom, a cyano group and a nitro group. It may be substituted with one or more substituents selected from the group of

(In the formula, R ¹ is a cycloalkyl group having 3 to 12 carbon atoms excluding the 1-adamantyl group, and the cycloalkyl group may be substituted with an alkyl group having 1 to 4 carbon atoms. X ^- is a halogen. It is one of the group consisting of a compound ion, R ² COO ⁻ , R ³ SO ₂ O ⁻ and OH ⁻ , where R ² is an alkyl group having 1 to 6 carbon atoms and R ³ is an alkyl group having 1 to 9 carbon atoms. , A fluoroalkyl group having 1 to 9 carbon atoms, and any one of the group consisting of a phenyl group, wherein the phenyl group is an alkyl group having 1 to 4 carbon atoms, a fluoroalkyl group having 1 to 4 carbon atoms, and carbon. It may be substituted with one or more substituents selected from the group consisting of an alkoxy group having the number 1 to 4, a fluoroalkyl group having 1 to 4 carbon atoms, a halogen atom, a cyano group and a nitro group.) The at least one imidazolium salt represented by either the general formula (1a) or the general formula (1c) is used in the general formula Ma-Xb (Ma is at least one of an alkali metal or an alkaline earth metal. 5. The step of claim 5 or claim 6 is characterized by comprising a step of contacting with a metal halide represented by the halogen atom () to obtain an imidazolium salt represented by the general formula (1b). The manufacturing method described.

(In the formula, R ¹ is a cycloalkyl group having 3 to 12 carbon atoms excluding the 1-adamantyl group, and the cycloalkyl group may be substituted with an alkyl group having 1 to 4 carbon atoms. Xb ⁻ is a halogen. It is a compound ion.) The production method according to claim 7 , further comprising a step of ion-exchange the imidazolium salt represented by the general formula (1b) to obtain an imidazolium salt represented by the general formula (1d).

(In the formula, R ¹ is a cycloalkyl group having 3 to 12 carbon atoms excluding the 1-adamantyl group, and the cycloalkyl group may be substituted with an alkyl group having 1 to 4 carbon atoms. Xd ⁻ is OH. ^- .) It has a crystallization step of crystallizing a composition containing a silica source, an alumina source, a structure-directing agent, an alkali source and water, and the composition is a crystallization step containing an imidazolium salt represented by the general formula (1). A method for producing a zeolite, which comprises.

(In the formula, R ¹ is a cycloalkyl group having 3 to 12 carbon atoms excluding the 1-adamantyl group, and the cycloalkyl group may be substituted with an alkyl group having 1 to 4 carbon atoms. X ^- is a halogen. It is one of the group consisting of a compound ion, R ² COO ⁻ , R ³ SO ₂ O ⁻ and OH ⁻ . R ² is an alkyl group having 1 to 6 carbon atoms. R ³ is an alkyl group having 1 to 9 carbon atoms. It is one of a group consisting of a group, a fluoroalkyl group having 1 to 9 carbon atoms, and a phenyl group, and the phenyl group is an alkyl group having 1 to 4 carbon atoms, a fluoroalkyl group having 1 to 4 carbon atoms, and a carbon number of carbon atoms. It may be substituted with one or more substituents selected from the group consisting of an alkoxy group of 1 to 4, a fluoroalkyl group having 1 to 4 carbon atoms, a halogen atom, a cyano group or a nitro group.) The production method according to claim 9, wherein the zeolite is an AFX-type zeolite.

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