JP7394630B2 - Diammonium salts and their uses - Google Patents

Description

The present invention relates to novel diammonium salts and their uses.

Zeolites are manufactured by crystallizing compositions containing various organic structure directing agents (hereinafter also referred to as "SDA"). To produce zeolite (hereinafter also referred to as "small pore zeolite") whose largest pores are 8-membered rings formed by T (T is silicon, aluminum, phosphorus, gallium, titanium, etc.) atoms and oxygen atoms. Known organic structure directing agents include adamantyl ammonium derivatives, tetraalkylammonium cations, and quinuclidine derivatives (Patent Documents 1 to 3), but diammonium salts such as tricyclo[7.3.0.0 ^3,7 ] There is no example of using dodecane-5,11-diazanium salt as an organic structure directing agent for zeolite production.

US Patent No. 4,544,538 US Patent No. 4,495,303 US Patent No. 4,508,837

An object of the present invention is to provide diammonium salts useful as SDA for zeolites. Another object of the present invention is to provide a method for producing zeolite, preferably small pore zeolite, more preferably AFX type zeolite, using the diammonium salt.

As a result of intensive studies to solve the above problems, the present inventors discovered a novel diammonium salt represented by the following general formula (1), and completed the present invention. Furthermore, it has been found that such a diammonium salt functions suitably as a structure directing agent for zeolite.

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

[In the formula,
R ¹ , R ² , R ³ and R ⁴ each independently represent an alkyl group having 1 to 10 carbon atoms, a haloalkyl group having 1 to 10 carbon atoms, or an aromatic hydrocarbon group having 6 to 10 carbon atoms; Substituents include hydroxyl group, alkyl group having 1 to 6 carbon atoms, aryl group having 6 to 10 carbon atoms, alkoxy group having 1 to 6 carbon atoms, aryloxy group having 6 to 10 carbon atoms, and aryloxy group having 2 to 12 carbon atoms. It may be substituted with one or more substituents selected from the group consisting of a dialkylamino group, a monoarylamino group having 6 to 10 carbon atoms, and a diarylamino group having 12 to 20 carbon atoms.

Y ⁻ is the same or different and represents a halide ion, a sulfonic acid ion represented by R ⁵ SO ₂ O ⁻ , a carboxylic acid ion represented by R ⁶ COO ⁻ , or OH ⁻ (hydroxide ion) .

R ⁵ represents an alkyl group having 1 to 9 carbon atoms, a fluoroalkyl group having 1 to 9 carbon atoms, or a phenyl group; It may be substituted with one or more substituents selected from the group consisting of an alkyl group, 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. .

R ⁶ represents an alkyl group having 1 to 6 carbon atoms, a fluoroalkyl group having 1 to 4 carbon atoms, or a phenyl group, and the phenyl group may be substituted with an alkyl group having 1 to 4 carbon atoms. ]
[2] Y ^- is a chloride ion, bromide ion, iodide ion, benzenesulfonate ion, p-toluenesulfonate ion, methanesulfonate ion, trifluoromethanesulfonate ion or OH ^- (hydroxide ion) The diammonium salt according to [1].
[3] R ¹ , R ² , R ³ and R ⁴ each independently represent an alkyl group having 1 to 10 carbon atoms or an aromatic hydrocarbon group having 6 to 10 carbon atoms; From the group consisting of an alkyl group having 1 to 6 carbon atoms, an aryloxy group having 6 to 10 carbon atoms, a dialkylamino group having 2 to 12 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, and a diarylamino group having 12 to 20 carbon atoms The diammonium salt according to [1] or [2], which may be substituted with one or more selected substituents.
[4] R ¹ , R ² , R ³ and R ⁴ each independently represent an alkyl group having 1 to 6 carbon atoms, an aryloxy group having 6 to 10 carbon atoms, a dialkylamino group having 2 to 12 carbon atoms, or a carbon An alkyl group having 1 to 10 carbon atoms which may be substituted with one or more substituents selected from the group consisting of an alkoxy group having 1 to 6 carbon atoms and a diarylamino group having 12 to 20 carbon atoms [1] The diammonium salt according to [3].
[5] R ¹ , R ² , R ³ and R ⁴ are each independently one or more substituents selected from the group consisting of a dialkylamino group having 2 to 4 carbon atoms and an alkoxy group having 1 to 4 carbon atoms The diammonium salt according to [1] to [4], which is an alkyl group having 1 to 6 carbon atoms which may be substituted with a group.
[6] The diammonium salt according to [1] to [5], wherein R ¹ and R ² are the same substituent, and R ³ and R ⁴ are the same substituent.
[7] R ¹ and R ² are the same and are a methyl group or an ethyl group, R ³ and R ⁴ are the same and are a methyl group or an ethyl group, and Y ^- is a chloride ion, bromide ion or OH ^- (water The diammonium salt according to any one of [1] to [6], which is an oxide ion).
[8] A crystallization step of crystallizing a composition containing a diammonium salt represented by the general formula (1) according to [1], a silica source, an alumina source, an alkali source, and water. A method for producing zeolite.
[9] The method for producing zeolite according to [8] above, wherein the zeolite is a small pore zeolite.
[10] The method for producing zeolite according to [8] or [9] above, wherein the zeolite is an AFX type zeolite.

The present invention can provide a novel diammonium salt. Furthermore, the present invention can provide a method for producing zeolite, preferably small pore zeolite, more preferably AFX type zeolite, using the diammonium salt.

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

Hereinafter, the present invention will be described by showing an example of an embodiment.

First, the definitions of R ¹ , R ² , R ³ , R ⁴ and Y ⁻ in general formula (1) will be explained in detail.

The alkyl group having 1 to 10 carbon atoms represented by R ¹ , R ² , R ³ and R ⁴ may be any linear, branched or cyclic alkyl group, and is not particularly limited. For example, methyl group, ethyl group, propyl group, isopropyl group, butyl group, cyclohexylmethyl group, 2-cyclopentylethyl group, 2-methylpropyl group, 2,2-dimethylpropyl group, 3-cyclopropylpropyl group, Cyclopropyl group, 2-methylbutyl group, 3-methylbutyl group, 3-methylbutan-2-yl group, tert-butyl group, cyclobutyl group, pentyl group, 2-methylpentyl group, 3-ethylpentyl group, 2,4- Dimethylpentyl group, 1-methylbutyl group, 2-methylpentan-2-yl group, 4,4-dimethylpentan-2-yl group, 2-ethylpropyl group, 3-ethylpentan-3-yl group, cyclopentyl group, 2,5-dimethylcyclopentyl group, 3-ethylcyclopentyl group, hexyl group, 2-methylhexyl group, 3,3-dimethylhexyl group, 4-ethylhexyl group, 1-methylpentyl group, 2-methylhexan-2-yl group, 5,5-dimethylhexan-2-yl group, 2-ethylbutyl group, 2,4-dimethylhexan-3-yl group, cyclohexyl group, 4-ethylcyclohexyl group, 4-propylcyclohexyl group, 4,4- Dimethylcyclohexyl group, heptyl group, 1-methylhexyl group, 1-ethylpentyl group, 1-propylbutyl group, bicyclo[2.2.1]heptan-2-yl group, octyl group, 1-methylheptyl group, 1 -ethylhexyl group, 1-propylpentyl group, cyclooctyl group, bicyclo[2.2.2]octan-2-yl group, nonyl group, 1-butylpentyl group, decyl group, 1-methylnonyl group, or 1 -Butylhexyl group is an example.

The haloalkyl group having 1 to 10 carbon atoms represented by R ¹ , R ² , R ³ and R ⁴ may be any linear, branched or cyclic haloalkyl group, and is not particularly limited. However, fluoroalkyl groups are particularly preferred, such as trifluoromethyl group, difluoromethyl group, perfluoroethyl group, 2,2,2-trifluoroethyl group, 1,1-difluoroethyl group, 2,2-difluoroethyl group , perfluoropropyl group, 2,2,3,3,3-pentafluoropropyl group, 2,2,3,3-tetrafluoropropyl group, 3,3,3-trifluoropropyl group, 1,1-difluoropropyl group group, perfluoro(1-methylpropyl) group, 2,2,2-trifluoro-1-(trifluoromethyl)ethyl group, perfluorocyclopropyl group, 2,2,3,3-tetrafluorocyclopropyl group, perfluoro Butyl group, 2,2,3,3,4,4,4-heptafluorobutyl group, 3,3,4,4,4-pentafluorobutyl group, 4,4,4-trifluorobutyl group, 1, 2,2,3,3,3-hexafluoro-1-(trifluoromethyl)propyl group, 1-(trifluoromethyl)propyl group, 1-methyl-3,3,3-trifluoropropyl group, perfluorocyclo Butyl group, 2,2,3,3,4,4-hexafluorocyclobutyl group, perfluoropentyl group, 2,2,3,3,4,4,5,5,5-nonafluoropentyl group, 3, 3,4,4,5,5,5-heptafluoropentyl group, 4,4,5,5,5-pentafluoropentyl group, 5,5,5-trifluoropentyl group, 1,2,2,3 , 3,3-hexafluoro-1-(perfluoroethyl)propyl group, 2,2,3,3,3-pentafluoro-1-(perfluoroethyl)propyl group, perfluorocyclopentyl group, perfluorohexyl group, 2,2 , 3,3,4,4,5,5,6,6,6-undecafluorohexyl group, 3,3,4,4,5,5,6,6,6-nonafluorohexyl group, 4, Examples include 4,5,5,6,6,6-heptafluorohexyl group, 5,5,6,6,6-pentafluorohexyl group, 6,6,6-trifluorohexyl group, perfluorocyclohexyl group, etc. .

The aromatic hydrocarbon group having 6 to 10 carbon atoms represented by R ¹ , R ² , R ³ and R ⁴ is not particularly limited, but includes, for example, phenyl group, 1-naphthyl group, 2-naphthyl group. Examples include groups.

Regarding the alkyl group having 1 to 10 carbon atoms, haloalkyl group having 1 to 10 carbon atoms, and aromatic hydrocarbon group having 6 to 10 carbon atoms represented by R ¹ , R ² , R ³ and R ⁴ , the above-mentioned Each independently represents a hydroxyl group, an alkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 10 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an aryloxy group having 6 to 10 carbon atoms, and a 2 to 12 carbon atoms group. may be substituted with one or more selected from the group consisting of a dialkylamino group, a monoarylamino group having 6 to 10 carbon atoms, and a diarylamino group having 12 to 20 carbon atoms.

The alkyl group having 1 to 6 carbon atoms may be any linear, branched or cyclic alkyl group, and is not particularly limited, but includes, for example, a methyl group, an ethyl group, a propyl group, Isopropyl group, butyl group, cyclohexylmethyl group, 2-cyclopentylethyl group, 2-methylpropyl group, 2,2-dimethylpropyl group, 3-cyclopropylpropyl group, cyclopropyl group, 2-methylbutyl group, 3-methylbutyl group , 3-methylbutan-2-yl group, tert-butyl group, cyclobutyl group, pentyl group, 2-methylpentyl group, 1-methylbutyl group, 2-methylpentan-2-yl group, 2-ethylpropyl group, cyclopentyl group , hexyl group, 1-methylpentyl group, 2-ethylbutyl group, cyclohexyl group, etc.

The above-mentioned aryl group having 6 to 10 carbon atoms is not particularly limited, but includes, for example, phenyl group, 2-methylphenyl group, 3-methylphenyl group, 4-methylphenyl group, 2,3-dimethylphenyl group. group, 2,4-dimethylphenyl group, 2,5-dimethylphenyl group, 2,6-dimethylphenyl group, 3,4-dimethylphenyl group, 3,5-dimethylphenyl group, 2,3,4-trimethylphenyl group group, 2,3,5-trimethylphenyl group, 2,3,6-trimethylphenyl group, 2,4,5-trimethylphenyl group, 2,4,6-trimethylphenyl group, 3,4,5-trimethylphenyl group group, 2,3,4,5-tetramethylphenyl group, 2,3,4,6-tetramethylphenyl group, 2,3,5,6-tetramethylphenyl group, 2-ethylphenyl group, 3-ethyl Phenyl group, 4-ethylphenyl group, 2,3-diethylphenyl group, 2,4-diethylphenyl group, 2,5-diethylphenyl group, 2,6-diethylphenyl group, 3,4-diethylphenyl group, 3 , 5-diethylphenyl group, 2-propylphenyl group, 3-propylphenyl group, 4-propylphenyl group, 2-isopropylphenyl group, 3-isopropylphenyl group, 4-isopropylphenyl group, 2-cyclopropylphenyl group, 3-cyclopropylphenyl group, 4-cyclopropylphenyl group, 2-butylphenyl group, 3-butylphenyl group, 4-butylphenyl group, 2-(1-methylpropyl)phenyl group, 3-(1-methylpropyl) ) phenyl group, 4-(1-methylpropyl)phenyl group, 2-(2-methylpropyl)phenyl group, 3-(2-methylpropyl)phenyl group, 4-(2-methylpropyl)phenyl group, 2- Examples include cyclobutylphenyl group, 3-cyclobutylphenyl group, 4-cyclobutylphenyl group, 1-naphthyl group, and 2-naphthyl group.

The alkoxy group having 1 to 6 carbon atoms is not particularly limited, but includes, for example, methoxy group, ethoxy group, propoxy group, isopropoxy group, butoxy group, 2-methylpropoxy group, 2,2-dimethyl Propoxy group, 3-cyclopropylpropoxy group, cyclopropoxy group, 2-methylbutoxy group, 3-methylbutoxy group, tert-butoxy group, cyclobutoxy group, pentyloxy group, 2-methylpentyloxy group, 1-methylbutoxy group Examples include 1,2-dimethylbutoxy group, 1-ethylpropoxy group, cyclopentyloxy group, hexyloxy group, and cyclohexyloxy group.

The above-mentioned aryloxy group having 6 to 10 carbon atoms is not particularly limited, but includes, for example, phenyloxy group, 2-methylphenyloxy group, 3-methylphenyloxy group, 4-methylphenyloxy group, 2-methylphenyloxy group, , 3-dimethylphenyloxy group, 2,4-dimethylphenyloxy group, 2,5-dimethylphenyloxy group, 2,6-dimethylphenyloxy group, 3,4-dimethylphenyloxy group, 3,5-dimethylphenyl Oxy group, 2,3,4-trimethylphenyloxy group, 2,3,5-trimethylphenyloxy group, 2,3,6-trimethylphenyloxy group, 2,4,5-trimethylphenyloxy group, 2,4 , 6-trimethylphenyloxy group, 3,4,5-trimethylphenyloxy group, 2,3,4,5-tetramethylphenyloxy group, 2,3,4,6-tetramethylphenyloxy group, 2,3 , 5,6-tetramethylphenyloxy group, 2-ethylphenyloxy group, 3-ethylphenyloxy group, 4-ethylphenyloxy group, 2,3-diethylphenyloxy group, 2,4-diethylphenyloxy group, 2,5-diethylphenyloxy group, 2,6-diethylphenyloxy group, 3,4-diethylphenyloxy group, 3,5-diethylphenyloxy group, 2-propylphenyloxy group, 3-propylphenyloxy group, 4-propylphenyloxy group, 2-isopropylphenyloxy group, 3-isopropylphenyloxy group, 4-isopropylphenyloxy group, 2-cyclopropylphenyloxy group, 3-cyclopropylphenyloxy group, 4-cyclopropylphenyloxy group, 2-butylphenyloxy group, 3-butylphenyloxy group, 4-butylphenyloxy group, 2-(1-methylpropyl)phenyloxy group, 3-(1-methylpropyl)phenyloxy group, 4-( 1-Methylpropyl)phenyloxy group, 2-(2-methylpropyl)phenyloxy group, 3-(2-methylpropyl)phenyloxy group, 4-(2-methylpropyl)phenyloxy group, 2-cyclobutylphenyl Examples include oxy group, 3-cyclobutylphenyloxy group, 4-cyclobutylphenyloxy group, 1-naphthyloxy group, and 2-naphthyloxy group.

The dialkylamino group having 2 to 12 carbon atoms is not particularly limited, but includes, for example, dimethylamino group, diethylamino group, dipropylamino group, diisopropylamino group, dibutylamino group, bis(2-methylpropyl ) amino group, bis(2,2-dimethylpropyl)amino group, bis(3-cyclopropylpropyl)amino group, dicyclopropylamino group, bis(2-methylbutyl)amino group, bis(3-methylbutyl)amino group , di(tert-butyl)amino group, dicyclobutylamino group, dipentylamino group, bis(2-methylpentyl)amino group, di(1-methylbutyl)amino group, bis(1,2-dimethylbutyl)amino group , di(1-ethylpropyl)amino group, dicyclopentylamino group, dihexylamino group, dicyclohexylamino group, N-ethyl-N-methylamino group, N-methyl-N-propyl group, N-cyclopropyl-N- Methylamino group, N-butyl-N-methylamino group, N-cyclobutyl-N-methylamino group, N-methyl-N-pentyl group, N-cyclopentyl-N-methylamino group, N-hexyl-N-methyl Amino group, N-cyclohexyl-N-methylamino group, N-cycloheptyl-N-methylamino group, N-methyl-N-octylamino group, N-methyl-N-nonylamino group, N-decyl-N-methyl Examples include an amino group and an N-methyl-N-undecylamino group.

The monoarylamino group having 6 to 10 carbon atoms is not particularly limited, but includes, for example, a phenylamino group, a 2-methylphenylamino group, a 3-methylphenylamino group, a 4-methylphenylamino group, 2,3-dimethylphenylamino group, 2,4-dimethylphenylamino group, 2,5-dimethylphenylamino group, 2,6-dimethylphenylamino group, 3,4-dimethylphenylamino group, 3,5-dimethyl Phenylamino group, 2,3,4-trimethylphenylamino group, 2,3,5-trimethylphenylamino group, 2,3,6-trimethylphenylamino group, 2,4,5-trimethylphenylamino group, 2, 4,6-trimethylphenylamino group, 3,4,5-trimethylphenylamino group, 2,3,4,5-tetramethylphenylamino group, 2,3,4,6-tetramethylphenylamino group, 2, 3,5,6-tetramethylphenylamino group, 2-ethylphenylamino group, 3-ethylphenylamino group, 4-ethylphenylamino group, 2,3-diethylphenylamino group, 2,4-diethylphenylamino group , 2,5-diethylphenylamino group, 2,6-diethylphenylamino group, 3,4-diethylphenylamino group, 3,5-diethylphenylamino group, 2-propylphenylamino group, 3-propylphenylamino group , 4-propylphenylamino group, 2-isopropylphenylamino group, 3-isopropylphenylamino group, 4-isopropylphenylamino group, 2-cyclopropylphenylamino group, 3-cyclopropylphenylamino group, 4-cyclopropylphenyl Amino group, 2-butylphenylamino group, 3-butylphenylamino group, 4-butylphenylamino group, 2-(1-methylpropyl)phenylamino group, 3-(1-methylpropyl)phenylamino group, 4- (1-Methylpropyl)phenylamino group, 2-(2-methylpropyl)phenylamino group, 3-(2-methylpropyl)phenylamino group, 4-(2-methylpropyl)phenylamino group, 2-cyclobutyl Examples include phenylamino group, 3-cyclobutylphenylamino group, 4-cyclobutylphenylamino group, 1-naphthylamino group, and 2-naphthylamino group.

The aforementioned diarylamino group having 12 to 20 carbon atoms is not particularly limited, but includes, for example, diphenylamino group, bis(2-methylphenyl)amino group, bis(3-methylphenyl)amino group, bis( 4-methylphenyl)amino group, bis(2,3-dimethylphenyl)amino group, bis(2,4-dimethylphenyl)amino group, bis(2,5-dimethylphenyl)amino group, bis(2,6- dimethylphenyl)amino group, bis(3,4-dimethylphenyl)amino group, bis(3,5-dimethylphenyl)amino group, bis(2,3,4-trimethylphenyl)amino group, bis(2,3, 5-trimethylphenyl)amino group, bis(2,3,6-trimethylphenyl)amino group, bis(2,4,5-trimethylphenyl)amino group, bis(2,4,6-trimethylphenyl)amino group, Bis(3,4,5-trimethylphenyl)amino group, bis(2,3,4,5-tetramethylphenyl)amino group, bis(2,3,4,6-tetramethylphenyl)amino group, bis( 2,3,5,6-tetramethylphenyl)amino group, bis(2-ethylphenyl)amino group, bis(3-ethylphenyl)amino group, bis(4-ethylphenyl)amino group, bis(2,3 -diethylphenyl)amino group, bis(2,4-diethylphenyl)amino group, bis(2,5-diethylphenyl)amino group, bis(2,6-diethylphenyl)amino group, bis(3,4-diethyl) phenyl)amino group, bis(3,5-diethylphenyl)amino group, bis(2-propylphenyl)amino group, bis(3-propylphenyl)amino group, bis(4-propylphenyl)amino group, bis(2-propylphenyl)amino group, -isopropylphenyl) amino group, bis(3-isopropylphenyl) amino group, bis(4-isopropylphenyl) amino group, bis(2-cyclopropylphenyl) amino group, bis(3-cyclopropylphenyl) amino group, bis (4-cyclopropylphenyl) amino group, bis(2-butylphenyl) amino group, bis(3-butylphenyl) amino group, bis(4-butylphenyl) amino group, bis[2-(1-methylpropyl) phenyl]amino group, bis[3-(1-methylpropyl)phenyl]amino group, bis[4-(1-methylpropyl)phenyl]amino group, bis[2-(2-methylpropyl)phenyl]amino group, Bis[3-(2-methylpropyl)phenyl]amino group, bis[4-(2-methylpropyl)phenyl]amino group, bis(2-cyclobutylphenyl)amino group, bis(3-cyclobutylphenyl)amino group group, bis(4-cyclobutylphenyl)amino group, di(1-naphthyl)amino group, di(2-naphthyl)amino group, N-(2-methylphenyl)-N-phenylamino group, N-(3 -Methylphenyl)-N-phenylamino group, N-(4-methylphenyl)-N-phenylamino group, N-(2,3-dimethylphenyl)-N-phenylamino group, N-(2,4- dimethylphenyl)-N-phenylamino group, N-(2,5-dimethylphenyl)-N-phenylamino group, N-(2,6-dimethylphenyl)-N-phenylamino group, N-(3,4 -dimethylphenyl)-N-phenylamino group, N-(3,5-dimethylphenyl)-N-phenylamino group, N-(2,3,4-trimethylphenyl)-N-phenylamino group, N-( 2,3,5-trimethylphenyl)-N-phenylamino group, N-(2,3,6-trimethylphenyl)-N-phenylamino group, N-(2,4,5-trimethylphenyl)-N- Phenylamino group, N-(2,4,6-trimethylphenyl)-N-phenylamino group, N-(3,4,5-trimethylphenyl)-N-phenylamino group, N-(1-naphthyl)- Examples include N-phenylamino group and N-(2-naphthyl)-N-phenylamino group.

R ¹ , R ² , R ³ and R ⁴ are each independently an alkyl group having 1 to 10 carbon atoms or an aromatic hydrocarbon group having 6 to 10 carbon atoms, and these Substituents include an alkyl group having 1 to 6 carbon atoms, an aryloxy group having 6 to 10 carbon atoms, a dialkylamino group having 2 to 12 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, and a diarylamino group having 12 to 20 carbon atoms. Optionally substituted with one or more substituents selected from the group consisting of groups, each independently an alkyl group having 1 to 6 carbon atoms, an aryloxy group having 6 to 10 carbon atoms; , a carbon that may be substituted with one or more substituents selected from the group consisting of a dialkylamino group having 2 to 12 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, and a diarylamino group having 12 to 20 carbon atoms. More preferably, it is an alkyl group having a number of 1 to 10, each independently having one or more substituents selected from the group consisting of a dialkylamino group having 2 to 4 carbon atoms and an alkoxy group having 1 to 4 carbon atoms. More preferably, it is an optionally substituted alkyl group having 1 to 6 carbon atoms, R ¹ and R ² are the same and are a methyl group or an ethyl group, and R ³ and R ⁴ are the same and are a methyl group or an ethyl group. It is more preferable that R ¹ , R ² , R ³ and R ⁴ are all the same and it is particularly preferable that they are a methyl group or an ethyl group.

Regarding R ¹ , R ² , R ³ and R ⁴ described above, it is preferable that R ¹ and R ² are the same and R ³ and R ⁴ are the same in terms of easy synthesis. , R ¹ , R ² , R ³ and R ⁴ are all the same.

When Y ⁻ is a halide ion, the halide ion is a fluoride ion, a chloride ion, a bromide ion, or an iodide ion, and from the viewpoint of easy synthesis, it is preferable to use a chloride ion, a bromide ion, or an iodide ion. Preferably, it is a chloride ion or a bromide ion.

When Y ^- is a sulfonic acid ion represented by R ⁵ SO ₂ O ^- , R ⁵ is an alkyl group having 1 to 9 carbon atoms, a fluoroalkyl group having 1 to 9 carbon atoms, or 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 fluoroalkoxy group having 1 to 4 carbon atoms, a halogen atom, a cyano group, and a nitro group. (optionally substituted with one or more substituents selected from the group).

The alkyl group having 1 to 9 carbon atoms represented by R ⁵ may be any linear, branched or cyclic alkyl group, and is not particularly limited, but for example, a methyl group. , ethyl group, propyl group, isopropyl group, butyl group, cyclohexylmethyl group, 2-cyclopentylethyl group, 2-methylpropyl group, 2,2-dimethylpropyl group, 3-cyclopropylpropyl group, cyclopropyl group, 2- Methylbutyl group, 3-methylbutyl group, 3-methylbutan-2-yl group, tert-butyl group, cyclobutyl group, pentyl group, 2-methylpentyl group, 3-ethylpentyl group, 2,4-dimethylpentyl group, 1- Methylbutyl group, 2-methylpentan-2-yl group, 4,4-dimethylpentan-2-yl group, 2-ethylpropyl group, 3-ethylpentan-3-yl group, cyclopentyl group, 2,5-dimethylcyclopentyl group group, 3-ethylcyclopentyl group, hexyl group, 2-methylhexyl group, 3,3-dimethylhexyl group, 4-ethylhexyl group, 1-methylpentyl group, 2-methylhexan-2-yl group, 5,5- Dimethylhexan-2-yl group, 2-ethylbutyl group, 2,4-dimethylhexan-3-yl group, cyclohexyl group, 4-ethylcyclohexyl group, 4-propylcyclohexyl group, 4,4-dimethylcyclohexyl group, heptyl group , 1-methylhexyl group, 1-ethylpentyl group, 1-propylbutyl group, bicyclo[2.2.1]heptan-2-yl group, octyl group, 1-methylheptyl group, 1-ethylhexyl group, Examples include 1-propylpentyl group, cyclooctyl group, bicyclo[2.2.2]octan-2-yl group, nonyl group, and 1-butylpentyl group.

The fluoroalkyl group having 1 to 9 carbon atoms represented by R ⁵ may be any linear, branched or cyclic fluoroalkyl group, and is not particularly limited, but for example, Trifluoromethyl group, difluoromethyl group, perfluoroethyl group, 2,2,2-trifluoroethyl group, 1,1-difluoroethyl group, 2,2-difluoroethyl group, perfluoropropyl group, 2,2,3, 3,3-pentafluoropropyl group, 2,2,3,3-tetrafluoropropyl group, 3,3,3-trifluoropropyl group, 1,1-difluoropropyl group, perfluoro(1-methylpropyl) group, 2,2,2-trifluoro-1-(trifluoromethyl)ethyl group, perfluorocyclopropyl group, 2,2,3,3-tetrafluorocyclopropyl group, perfluorobutyl group, 2,2,3,3, 4,4,4-heptafluorobutyl group, 3,3,4,4,4-pentafluorobutyl group, 4,4,4-trifluorobutyl group, 1,2,2,3,3,3-hexa Fluoro-1-(trifluoromethyl)propyl group, 1-(trifluoromethyl)propyl group, 1-methyl-3,3,3-trifluoropropyl group, perfluorocyclobutyl group, 2,2,3,3, 4,4-hexafluorocyclobutyl group, perfluoropentyl group, 2,2,3,3,4,4,5,5,5-nonafluoropentyl group, 3,3,4,4,5,5,5 -heptafluoropentyl group, 4,4,5,5,5-pentafluoropentyl group, 5,5,5-trifluoropentyl group, 1,2,2,3,3,3-hexafluoro-1-( perfluoroethyl)propyl group, 2,2,3,3,3-pentafluoro-1-(perfluoroethyl)propyl group, perfluorocyclopentyl group, perfluorohexyl group, 2,2,3,3,4,4,5, 5,6,6,6-undecafluorohexyl group, 3,3,4,4,5,5,6,6,6-nonafluorohexyl group, 4,4,5,5,6,6,6 Examples include -heptafluorohexyl group, 5,5,6,6,6-pentafluorohexyl group, 6,6,6-trifluorohexyl group, and perfluorocyclohexyl group.

When R ⁵ 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, or a fluoroalkoxy group having 1 to 4 carbon atoms. , a halogen atom, and a nitro group such as a cyano group.

The alkyl group having 1 to 4 carbon atoms may be any linear, branched or cyclic alkyl group, and is not particularly limited, but includes, for example, a methyl group, an ethyl group, a propyl group, Examples include isopropyl group, butyl group, 2-methylpropyl group, cyclopropyl group, tert-butyl group, and cyclobutyl group.

The above-mentioned fluoroalkyl group having 1 to 4 carbon atoms may be any linear, branched or cyclic fluoroalkyl group, and is not particularly limited. For example, trifluoromethyl group, difluoromethyl group, etc. group, perfluoroethyl group, 2,2,2-trifluoroethyl group, 1,1-difluoroethyl group, 2,2-difluoroethyl group, perfluoropropyl group, 2,2,3,3,3-pentafluoropropyl group, 2,2,3,3-tetrafluoropropyl group, 3,3,3-trifluoropropyl group, 1,1-difluoropropyl group, perfluoro(1-methylpropyl) group, 2,2,2-trifluoropropyl group Fluoro-1-(trifluoromethyl)ethyl group, perfluorocyclopropyl group, 2,2,3,3-tetrafluorocyclopropyl group, perfluorobutyl group, 2,2,3,3,4,4,4-hepta Fluorobutyl group, 3,3,4,4,4-pentafluorobutyl group, 4,4,4-trifluorobutyl group, 1,2,2,3,3,3-hexafluoro-1-(trifluorobutyl group) methyl)propyl group, 1-(trifluoromethyl)propyl group, 1-methyl-3,3,3-trifluoropropyl group, perfluorocyclobutyl group, 2,2,3,3,4,4-hexafluorocyclo Examples include butyl group.

The alkoxy group having 1 to 4 carbon atoms may be any linear, branched or cyclic alkoxy group, and is not particularly limited, but includes, for example, a methoxy group, an ethoxy group, a propoxy group, Examples include isopropoxy group, butoxy group, 2-methylpropoxy group, cyclopropoxy group, tert-butoxy group, and cyclobutoxy group.

The above-mentioned fluoroalkoxy group having 1 to 4 carbon atoms may be any linear, branched or cyclic fluoroalkoxy group, and is not particularly limited. For example, trifluoromethyloxy group, difluoromethyloxy group, etc. Methyloxy group, perfluoroethyloxy group, 2,2,2-trifluoroethyloxy group, 1,1-difluoroethyloxy group, 2,2-difluoroethyloxy group, perfluoropropyloxy group, 2,2,3, 3,3-pentafluoropropyloxy group, 2,2,3,3-tetrafluoropropyloxy group, 3,3,3-trifluoropropyloxy group, 1,1-difluoropropyloxy group, perfluoro(1-methyl propyl)oxy group, 2,2,2-trifluoro-1-(trifluoromethyl)ethyloxy group, perfluorocyclopropyloxy group, 2,2,3,3-tetrafluorocyclopropyloxy group, perfluorobutyloxy group, 2,2,3,3,4,4,4-heptafluorobutyloxy group, 3,3,4,4,4-pentafluorobutyloxy group, 4,4,4-trifluorobutyloxy group, 1, 2,2,3,3,3-hexafluoro-1-(trifluoromethyl)propyloxy group, 1-(trifluoromethyl)propyloxy group, 1-methyl-3,3,3-trifluoropropyloxy group , perfluorocyclobutyloxy group, and 2,2,3,3,4,4-hexafluorocyclobutyloxy group.

The halogen atom is not particularly limited, and examples thereof include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

^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 The phenyl group that may be substituted with one or more substituents selected from the group consisting of nitro groups (hereinafter also referred to as "substituted phenyl group") is not particularly limited, but for example, phenyl group, 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-trifluoromethylphenyl group, 3-(trifluoromethyl)phenyl group, 4-trifluoromethylphenyl group, 3,5-bis(trifluoromethyl)phenyl group, 4-methoxyphenyl group, 4-(isopropoxy)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 Examples include 4-cyanophenyl group, 2-nitrophenyl group, 3-nitrophenyl group, and 4-nitrophenyl group.

R ⁵ is preferably a phenyl group, 4-methylphenyl group, methyl group, or trifluoromethyl group because the raw materials are easily available. That is, the sulfonic acid ion represented by R ₅ SO ₂ O ^- , the benzenesulfonic acid ion represented by C _{6 H} 5 SO ₂ O ^- , and the benzenesulfonic acid ion represented by p-CH ₃ C ₆ H ₄ SO ₂ O ^- A p-toluenesulfonate ion, a methanesulfonate ion represented by CH ₃ SO ₂ O ^- , or a trifluoromethanesulfonate ion represented by CF ₃ SO ₂ O ^- is preferable.

When Y ^- is a carboxylic acid ion represented by R ⁶ COO ^- , R ⁶ is an alkyl group having 1 to 6 carbon atoms, a fluoroalkyl group having 1 to 4 carbon atoms, or a phenyl group (the phenyl group is (optionally substituted with an alkyl group having 1 to 4 carbon atoms).

The alkyl group having 1 to 6 carbon atoms may be a linear, branched or cyclic alkyl group, and is not particularly limited, but includes, for example, a methyl group, an ethyl group, a propyl group, an isopropyl group, Butyl group, 2-methylpropyl group, 2,2-dimethylpropyl group, 3-cyclopropylpropyl group, cyclopropyl group, 2-methylbutyl group, 3-methylbutyl group, 3-methylbutan-2-yl group, tert-butyl group group, cyclobutyl group, pentyl group, 2-methylpentyl group, 1-methylbutyl group, 2-methylpentan-2-yl group, 1-ethylpropyl group, cyclopentyl group, hexyl group, 1-methylpentyl group, 1-ethylbutyl group and cyclohexyl group.

The above-mentioned fluoroalkyl group having 1 to 4 carbon atoms is not particularly limited, but the same group as the fluoroalkyl group having 1 to 4 carbon atoms exemplified in the explanation of R ⁵ can be exemplified.

The above-mentioned alkyl group having 1 to 4 carbon atoms is not particularly limited, but may be, for example, the same group as the alkyl group having 1 to 4 carbon atoms exemplified in the explanation of ^R5 .

R ⁶ is preferably a phenyl group, a 4-methylphenyl group, a methyl group, or a trifluoromethyl group because the raw materials are easily available. That is, the carboxylic acid ion represented by R ⁶ COO ^- is a benzoic acid ion represented by C ₆ H ₅ COO ^- , 4-methylbenzoic acid ion represented by 4-CH ₃ C ₆ H ₄ COO ^- , An acetate ion represented by CH ₃ COO ^- or a trifluoroacetate ion represented by CF ₃ COO ^- is preferable.

Note that Y ^- is preferably a halide ion, a sulfonic acid ion represented by R ⁵ SO ₂ O ^- , or OH ^- (hydroxide ion) from the viewpoint of easy synthesis, and Cl ^- (chloride ion). ), Br ^- (bromide ion), I ^- (iodide ion), benzenesulfonic acid ion represented by C ₆ H ₅ SO ₂ O ^- , p-CH ₃ C ₆ H ₄ SO ₂ O ^- It can be p-toluenesulfonate ion, methanesulfonate ion represented by CH ₃ SO ₂ O ^- , trifluoromethanesulfonate ion represented by CF ₃ SO ₂ O ^- or OH ^- (hydroxide ion). More preferably, it is Br ^- (bromide ion), Cl ^- (chloride ion) or OH ^- (hydroxide ion).

Specific examples of the diammonium salt (1) include the following (1-1) to (1-1032), but the present invention is not limited thereto.

In this specification, Me is a methyl group, Et is an ethyl group, Pr is a propyl group, iPr is an isopropyl group, Bu is a butyl group, t-Bu is a tert-butyl group, Cy is a cyclohexyl group, and Ph is a phenyl group. , TsO ^- is p-toluenesulfonic acid ion, C ₆ H ₁₃ is hexyl group, C ₇ H ₁₅ is heptyl group, C ₈ H ₁₇ is octyl group, C ₉ H ₁₉ is nonyl group, C ₁₀ H ₂₁ is Decyl group, C ₁₁ H ₂₃ represents undecyl group, C ₁₂ H ₂₅ represents dodecyl group, and C ₁₈ H ₃₇ represents octadecyl group.

Among the compounds represented by (1-1) to (1-1032), the diammonium salts of the present invention include 1-2, 1-3, 1-5, 1-26, 1-27, 1-29, The compounds represented by 1-38, 1-39, 1-41, 1-62, 1-63, 1-65, 1-590, 1-591 and 1-592 are preferred because they are easy to synthesize.

Next, the method for producing the diammonium salt of the present invention will be explained in detail.

<Embodiment 1 of manufacturing method>
As a method for producing the diammonium salt (1) of the present invention, an aliphatic compound represented by the following general formula (2), a secondary amine represented by the following general formula (3a), and the following general formula (3b) are used. ) A method for producing a diammonium salt represented by general formula (1a) (hereinafter also referred to as "manufacturing method 1") includes a step of reacting with a secondary amine represented by (1a).

Ya are the same or different and represent a halogen atom or an organic sulfonyloxy group represented by R ⁵ SO ₂ O.

R ⁵ has the same meaning as R ⁵ in general formula (1).

R ¹ and R ³ are each independently an alkyl group having 1 to 10 carbon atoms, a haloalkyl group having 1 to 10 carbon atoms, or an aromatic hydrocarbon group having 6 to 10 carbon atoms (these substituents include a hydroxyl group, a carbon Alkyl group having 1 to 6 carbon atoms, aryl group having 6 to 10 carbon atoms, alkoxy group having 1 to 6 carbon atoms, aryloxy group having 6 to 10 carbon atoms, dialkylamino group having 2 to 12 carbon atoms, 6 to 6 carbon atoms 10 monoarylamino groups and diarylamino groups having 12 to 20 carbon atoms, which may be substituted with one or more substituents.

R ² and R ⁴ each independently represent an alkyl group having 1 to 10 carbon atoms, a haloalkyl group having 1 to 10 carbon atoms, or an aromatic hydrocarbon group having 6 to 10 carbon atoms (these substituents include a hydroxyl group, a carbon Alkyl group having 1 to 6 carbon atoms, aryl group having 6 to 10 carbon atoms, alkoxy group having 1 to 6 carbon atoms, aryloxy group having 6 to 10 carbon atoms, dialkylamino group having 2 to 12 carbon atoms, 6 to 6 carbon atoms 10 monoarylamino groups and diarylamino groups having 12 to 20 carbon atoms, which may be substituted with one or more substituents.

R ¹ , R ² , R ³ and R ⁴ have the same meanings as above.

Ya ^- represents a halide ion or a sulfonic acid ion represented by R ⁵ SO ₂ O ^- .

R ⁵ has the same meaning as R ⁵ in general formula (1).

Each substituent represented by R ¹ , R ² , R ³ and R ⁴ above (an alkyl group having 1 to 10 carbon atoms, a haloalkyl group having 1 to 10 carbon atoms, an aromatic hydrocarbon group having 6 to 10 carbon atoms) , alkyl group having 1 to 6 carbon atoms, aryl group having 6 to 10 carbon atoms, alkoxy group having 1 to 6 carbon atoms, aryloxy group having 6 to 10 carbon atoms, dialkylamino group having 2 to 12 carbon atoms, carbon number Regarding the monoarylamino group having 6 to 10 carbon atoms and the diarylamino group having 12 to 20 carbon atoms, the definitions of each substituent in R ¹ , R ² , R ³ and R ⁴ shown in the explanation of general formula (1) are used. are synonymous.

In production method 1, a diammonium salt represented by general formula (1a) is obtained by the reaction shown below.

(In the formula, R ¹ , R ² , R ³ , R ⁴ , Ya and Ya ⁻ are the same as above.)
For the secondary amine (3a) and secondary amine (3b) to be subjected to the reaction in Production Method 1, the same secondary amine may be used, or two different types of secondary amines may be used. , when two different types of secondary amines are used, the asymmetric diammonium salt (1a) of the present invention can be obtained.

In Production Method 1, the secondary amine (3a) and the secondary amine (3b) may be reacted with the aliphatic compound (2) in stages.

As the aliphatic compound (2), secondary amine (3a), and secondary amine (3b) to be subjected to the reaction in Production Method 1, commercially available ones can be used, and known methods for obtaining aliphatic compounds, For example, it can be obtained according to the manufacturing method disclosed in Tetrahedron, Vol. 71, pp. 6944-6955, 2005, Journal of the American Chemical Society, Vol. 129, pp. 13362-13363, 2007, etc.

In the reaction of Production Method 1, the secondary amine (3a) and the secondary amine (3b) are each preferably used in an amount of 1 to 100 molar equivalents, and preferably 1 to 10 molar equivalents each, relative to the aliphatic compound (2). It is more preferable that there be.

In Production Method 1, it is preferable that the aliphatic compound (2), the secondary amine (3a), and the secondary amine (3b) are reacted in the presence of a base. Examples of the base include organic bases and inorganic bases. Examples of the organic base include, but are not limited to, trimethylamine, triethylamine, diisopropylethylamine, pyridine, pyrrolidine, diethylamine, 1,4-diazabicyclo[2.2.2]octane, 1,8-diazabicyclo[5. 4.0] undecene, etc. Examples of the inorganic base include, but are not limited to, sodium hydroxide, potassium hydroxide, sodium hydride, potassium hydride, sodium hydrogen carbonate, potassium hydrogen carbonate, sodium carbonate, Examples include potassium carbonate and cesium carbonate.

The base is preferably diisopropylethylamine, triethylamine, pyridine, pyrrolidine, diethylamine, sodium hydroxide, potassium carbonate or sodium carbonate, and preferably pyrrolidine, diethylamine or sodium hydroxide.

Moreover, the secondary amine (3a) and the secondary amine (3b) can be made to act as the base. For example, the amount of secondary amine (3a) and secondary amine (3b) to be added is excessive, for example, 2 molar equivalents or more, further 5 molar equivalents or more relative to the aliphatic compound (2). The reaction of Production Method 1 can be carried out in the presence of a base.

In the reaction of Production Method 1, the aliphatic compound (2), the secondary amine (3a), and the secondary amine (3b) are preferably reacted in a solvent. The solvent is not limited as long as it does not inhibit the reaction, and examples include aromatic hydrocarbon solvents, ether solvents, ester solvents, halogen solvents, amide solvents, urea solvents, ketone solvents, and nitrile solvents. Examples include solvents, sulfoxide solvents, alcohol solvents and water.

Specific examples of these solvents include toluene, xylene, and chlorobenzene as aromatic hydrocarbon solvents, tetrahydrofuran, 1,2-dimethoxyethane, and 1,4-dioxane as ether solvents, and ethyl acetate as ester solvents. or butyl acetate, chloroform, carbon tetrachloride, and chlorobenzene as a halogen solvent, N,N-dimethylformamide or N,N-dimethylacetamide as an amide solvent, and 1,3-dimethyl-2 as a urea solvent. -Imidazolidinone or 1,3-dimethyl-3,4,5,6-tetrahydropyrimidin-2(1H)-one, acetone or methyl ethyl ketone as the ketone solvent, acetonitrile, propionitrile and benzodilin as the nitrile solvent Examples of the solvent include nitrile, dimethyl sulfoxide as the sulfoxide solvent, and methanol, ethanol, and propanol as the alcohol solvent.

In Production Method 1, preferred solvents include ether solvents, alcohol solvents, and nitrile solvents, and more preferred solvents include tetrahydrofuran, ethanol, and acetonitrile.

In Production Method 1, the reaction temperature is not particularly limited, but is preferably any temperature from room temperature to 200°C. Since the yield of the diammonium salt tends to be high, the reaction temperature is more preferably from room temperature to 80°C. On the other hand, the reaction time is not particularly limited, and may be, for example, 1 hour or more and 100 hours or less.

In the reaction of Production Method 1, an inorganic salt may be added to activate the aliphatic compound (2). The inorganic salt is not limited as long as it does not inhibit the reaction, and examples thereof include iodide salts such as lithium iodide, sodium iodide, and potassium iodide, and bromide salts such as lithium bromide, sodium bromide, and potassium bromide. and. The inorganic salt is preferably lithium iodide, sodium iodide, or potassium iodide. In the reaction of Production Method 1, the amount of the inorganic salt relative to the aliphatic compound (2) is preferably 0.1 to 100 molar equivalents, more preferably 0.5 to 5 molar equivalents.

Production method 1 includes the step of isolating the diammonium salt represented by general formula (1a) (hereinafter also referred to as "isolation step"), and if necessary, ion-exchanging the diammonium salt after isolation. (hereinafter also referred to as "ion exchange step").

In the isolation step, any method can be used as long as the diammonium salt (1a) can be isolated from the reaction mixture, and general purification methods commonly used by those skilled in the art can also be used as the isolation method. Examples include solvent extraction, column chromatography, preparative thin layer chromatography, preparative liquid chromatography, and recrystallization.

In the ion exchange step, the diammonium salt (1a) is ion exchanged. Thereby, the diammonium salt represented by the general formula (1) of the present invention can be obtained.

As the ion exchange method, for example, a common method used by those skilled in the art for ion exchange of quaternary ammonium salts can be used. For example, the diammonium salt (1a) may be brought into contact with an ion exchange resin. The ion exchange resin may be any ion exchange resin having an exchange group Yb ^- , such as Amberlite IRA-400, Amberlite IRA-402, Amberlite IRA-404, Amberlite IRA-900, Amberlite IRA-904. , Amberlite IRA-458, Amberlite IRA-958, Amberlite IRA-420, Amberlite IRN-78, Amberlite IRA-411 and Amberlite IRA-910, preferably Amberlite IRA-400. .

Ion exchange may be carried out in a solvent that does not inhibit ion exchange. Examples of the solvent include one or more selected from the group of ether solvents, ester solvents, ketone solvents, nitrile solvents, alcohol solvents, and water. Specific examples of the solvents can be the same as those exemplified in the explanation of Production Method 1 above.

<Embodiment 2 of manufacturing method>
As another embodiment of the method for producing a diammonium salt of the present embodiment, a diamine represented by the following general formula (4a), an alkylating agent represented by the following general formula (5a), and the following general formula (5b) are used. ) A method for producing a diammonium salt represented by general formula (1b) (hereinafter also referred to as "manufacturing method 2") is characterized by having a step of reacting with an alkylating agent represented by It will be done.

In the formula, two R ⁷ 's are the same or different and are an alkyl group having 1 to 10 carbon atoms or an aromatic hydrocarbon group having 6 to 10 carbon atoms (these substituents include a hydroxyl group, a Alkyl group, aryl group having 6 to 10 carbon atoms, alkoxy group having 1 to 6 carbon atoms, aryloxy group having 6 to 10 carbon atoms, dialkylamino group having 2 to 12 carbon atoms, monoarylamino group having 6 to 10 carbon atoms (optionally substituted with one or more substituents selected from the group consisting of groups and diarylamino groups having 12 to 20 carbon atoms).

In the formula, R ^8a is an alkyl group having 1 to 10 carbon atoms (these substituents include a hydroxyl group, an alkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 10 carbon atoms, an alkoxy group having 1 to 6 carbon atoms) , one or more selected from the group consisting of an aryloxy group having 6 to 10 carbon atoms, a dialkylamino group having 2 to 12 carbon atoms, a monoarylamino group having 6 to 10 carbon atoms, and a diarylamino group having 12 to 20 carbon atoms. (optionally substituted with a substituent),
Ya represents a halogen atom or an organic sulfonyloxy group represented by R ⁵ SO ₂ O.

R ⁵ has the same meaning as R ⁵ in general formula (1).

In the formula, R ^8b is an alkyl group having 1 to 10 carbon atoms (these substituents include a hydroxyl group, an alkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 10 carbon atoms, an alkoxy group having 1 to 6 carbon atoms) , one or more selected from the group consisting of an aryloxy group having 6 to 10 carbon atoms, a dialkylamino group having 2 to 12 carbon atoms, a monoarylamino group having 6 to 10 carbon atoms, and a diarylamino group having 12 to 20 carbon atoms. (optionally substituted with a substituent),
Ya represents a halogen atom or an organic sulfonyloxy group represented by R ⁵ SO ₂ O.

R ⁵ has the same meaning as R ⁵ in general formula (1).

In the formula, R ⁷ , R ^8a and R ^8b have the same meanings as above.

Ya ^- , which are the same or different, represent a halide ion or a sulfonic acid ion represented by R ⁵ SO ₂ O ^- .

R ⁵ has the same meaning as R ⁵ in general formula (1).

In R ⁷ , an alkyl group having 1 to 10 carbon atoms, an aromatic hydrocarbon group having 6 to 10 carbon atoms, an alkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 10 carbon atoms, an alkoxy group having 1 to 6 carbon atoms There are no particular limitations on the groups, aryloxy groups having 6 to 10 carbon atoms, dialkylamino groups having 2 to 12 carbon atoms, monoarylamino groups having 6 to 10 carbon atoms, and diarylamino groups having 12 to 20 carbon atoms. However, in R ¹ to R ⁴ , an alkyl group having 1 to 10 carbon atoms, an aromatic hydrocarbon group having 6 to 10 carbon atoms, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, Examples include the same as an aryloxy group having 6 to 10 carbon atoms, a dialkylamino group having 2 to 12 carbon atoms, a monoarylamino group having 6 to 10 carbon atoms, and a diarylamino group having 12 to 20 carbon atoms. .

In R ^8a and R ^8b , an alkyl group having 1 to 10 carbon atoms, an alkyl group having 1 to 6 carbon atoms, an aromatic hydrocarbon group having 6 to 10 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, and 6 to 6 carbon atoms The aryloxy group having 10 carbon atoms, the dialkylamino group having 2 to 12 carbon atoms, the monoarylamino group having 6 to 10 carbon atoms, and the diarylamino group having 12 to 20 carbon atoms are not particularly limited, but R ¹ ～R ⁴ , an alkyl group having 1 to 10 carbon atoms, an alkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 10 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an aryloxy group having 6 to 10 carbon atoms , a dialkylamino group having 2 to 12 carbon atoms, a monoarylamino group having 6 to 10 carbon atoms, and a diarylamino group having 12 to 20 carbon atoms.

In production method 2, a diammonium salt represented by general formula (1b) is obtained by the reaction shown below.

(In the formula, R ⁷ , R ^8a , R ^8b , Ya and Ya ⁻ are the same as above.)
As the alkylating agent (5a) and the alkylating agent (5b) used in the reaction of Production Method 2, the same alkylating agent may be used, or two different types of alkylating agents may be used, or two different types of alkylating agents may be used. When using the alkylating agent, the asymmetric diammonium salt (1b) of the present invention can be obtained.

In production method 2, the alkylating agent (5a) and the alkylating agent (5b) may be reacted with the diamine (4a) in stages.

Diamine (4a), alkylating agent (5a), and alkylating agent (5b) to be used in the reaction of Production Method 2 can be obtained commercially, and diamine (4a) can be prepared according to Raw Material Production Method 1 described below. You can also get it.

In the reaction of Production Method 2, the alkylating agent (5a) and the alkylating agent (5b) are each preferably used in an amount of 1 to 100 molar equivalents, more preferably 1 to 10 molar equivalents, relative to the diamine (4a). preferable.

In the reaction of Production Method 2, it is preferable to react the diamine (4a) with the alkylating agent (5a) and the alkylating agent (5b) in a solvent. The solvent is preferably one that does not inhibit the reaction, and the same solvents as those used in the reaction of Production Method 1 can be exemplified.

The specific solvent, preferred solvent, reaction temperature, reaction time, and other conditions in the reaction of Production Method 2 may be the same as those in the reaction of Production Method 1.

Production method 2 includes at least one of the steps of isolating the diammonium salt (1b), or ion-exchanging this (or the diammonium salt represented by the general formula (1b) after isolation). It's okay to stay.

As for the isolation method and other conditions, the same conditions as in the isolation step of Production Method 1 can be exemplified.

A diammonium salt represented by general formula (1c) can be obtained by ion exchange of a diammonium salt represented by general formula (1b).

In the formula, R ⁷ , R ^8a and R ^8b have the same meaning as R ⁷ , R ^8a and R ^8b in general formula (1b), and Y ⁻ is the same or different and represents a halide ion, R ⁵ SO ₂ Represents a sulfonic acid ion represented by O ⁻ , a carboxylic acid ion represented by R ⁶ COO ⁻ , or OH ⁻ (hydroxide ion).

Y ⁻ , R ⁵ and R ⁶ have the same meanings as Y ⁻ , R ⁵ and R ⁶ in general formula (1).

Ion exchange may be carried out by, for example, bringing the diammonium salt (1b) into contact with an ion exchange resin. The ion exchange resin, solvent, and other conditions in the ion exchange may be the same as those in the ion exchange step of Production Method 1.

<Method for producing diamine represented by general formula (4a)>
As an example of an embodiment of the method for producing diamine (4a) to be subjected to production method 2, diamine (4a) is characterized by having a step of reacting a diimide represented by general formula (6a) with a reducing agent. (hereinafter also referred to as "raw material production method 1").

In the formula, two R ⁷ 's may be the same or different, and have the same meaning as R ⁷ in general formula (4a).

In the formula, two R ^7s may be the same or different, and have the same meaning as R ⁷ in general formula (4a).

R ⁷ , preferable or more preferable R ⁷ in raw material production method 1 is the same as in production method 2.

The reducing agent used in raw material production method 1 is not particularly limited, but includes, for example, aluminum hydride, lithium aluminum hydride, sodium bis(2-methoxyethoxy)aluminum hydride, borane-dimethylsulfide complex, borane-tetrahydrofuran. Complexes, borane-pyridine complexes, and sodium borohydride/boron trifluoride-diethyl ether complexes are examples, and lithium aluminum hydride, sodium bis(2-methoxyethoxy)aluminum hydride, Borane-dimethylsulfide complexes and borane-tetrahydrofuran complexes are preferred, and lithium aluminum hydride or borane-dimethylsulfide complexes are more preferred.

In raw material production method 1, the amount of the reducing agent relative to diimide (6a) is preferably 2 to 50 molar equivalents, more preferably 4 to 10 molar equivalents.

In raw material production method 1, diimide (6a) and a reducing agent may be reacted in a solvent. The solvent may be any solvent as long as it does not inhibit the reaction, and may include aromatic hydrocarbon solvents such as benzene, toluene, and xylene; ether solvents such as tetrahydrofuran, cyclopentyl methyl ether, diethyl ether, diisopropyl ether, and methyl tert-butyl ether; Examples include one or more appropriately selected from the group of alcohol solvents such as methanol, ethanol, and isopropyl alcohol depending on the type of reducing agent, and preferred solvents include aromatic hydrocarbon solvents or ether solvents, and more preferred solvents. Examples include toluene and tetrahydrofuran.

In raw material production method 1, the reaction temperature is not particularly limited, but is preferably any temperature from 20°C to 150°C. From the viewpoint of improving the yield of the diamine compound represented by general formula (2a), the reaction temperature is more preferably 40°C or more and 120°C or less. On the other hand, the reaction time is not particularly limited, and may be, for example, 1 hour or more and 100 hours or less.

Raw material production method 1 may include a step of isolating diamine (4a). As for the isolation method and other conditions, the same conditions as in the isolation step of Production Method 1 can be exemplified.

The diammonium salt (1) of the present invention can be applied to the uses of known ammonium salts, and may also be used as a ligand for transition metal catalysts or as an organic structure directing agent (hereinafter also referred to as "SDA") in the production of zeolite. It is particularly suitable as an SDA for small pore zeolites.

Hereinafter, a method for producing zeolite using the diammonium salt (1) of the present invention as SDA will be described.

The method for producing zeolite of the present embodiment uses a composition (hereinafter also referred to as "raw material composition") containing a diammonium salt represented by general formula (1), a silica source, an alumina source, an alkali source, and water. A method for producing zeolite, comprising a crystallization step of crystallizing the zeolite.

The crystallization process will be explained below. The zeolite obtained by the method for producing zeolite using the diammonium salt of the present invention as SDA is preferably a zeolite that does not contain phosphoric acid (PO ₄ ) in its skeleton, and is preferably an aluminosilicate.

The diammonium salt (1) of the present invention can be used as an SDA directed towards small pore zeolites, especially AFX type zeolites. In the present embodiment, the AFX type zeolite is a zeolite having an AFX structure, and is a crystalline aluminosilicate having an AFX structure.

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

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

In this embodiment, the crystalline aluminosilicate is a three-dimensional structure in which aluminum (Al) and silicon (Si) are used as skeleton metals (hereinafter also referred to as "T atoms"), and the T atoms are bonded via oxygen atoms (O). It has a skeletal structure consisting of a network of

In the zeolite production method of the present invention, a composition (hereinafter also referred to as "raw material composition") containing a silica source, an alumina source, a structure directing agent, an alkali source, and water is crystallized.

The silica source is silica (SiO ₂ ) or a silicon compound that is a precursor thereof, such as colloidal silica, amorphous silica, sodium silicate, tetraethylorthosilicate, precipitated silica, fumed silica, crystalline aluminosilicate, and aluminosilicate. At least one member of the group consisting of silicate gels can be mentioned, and at least one of crystalline aluminosilicate and aluminosilicate gel is preferable.

The alumina source is alumina (Al ₂ O ₃ ) or an aluminum compound that is a precursor thereof, such as aluminum sulfate, sodium aluminate, aluminum hydroxide, aluminum chloride, aluminosilicate gel, crystalline aluminosilicate, and metallic aluminum. At least one of the following groups can be used, and at least one of crystalline aluminosilicate and aluminosilicate gel is preferable.

The alkali source may be contained in the raw material composition as an alkali metal hydroxide or an alkali metal halide, and in particular, it is sufficient if it is contained in the raw material composition as an alkali metal hydroxide exhibiting basicity. . Specifically, at least one member of the group consisting of sodium hydroxide, potassium hydroxide, rubidium hydroxide, and cesium hydroxide, and an alkali component contained in at least one of a silica source and an alumina source are included in the raw material composition. One of the things that can be mentioned is that

The raw material composition contains a diammonium salt represented by general formula (1). Since the diammonium cation contained in the diammonium salt of the present invention functions as SDA and directs to AFX type zeolite, AFX type zeolite can be obtained by crystallizing the raw material composition. In the zeolite production method of the present invention, the type of Y ^- in general formula (1) has almost no effect on the directivity of the zeolite, but for example, Y ^- can be chloride ion, bromide ion, iodide ion, benzene It is preferably sulfonate ion, p-toluenesulfonate ion, methanesulfonate ion, trifluoromethanesulfonate ion or OH ^- (hydroxide ion), chloride ion, bromide ion, iodide ion, and OH ^- (hydroxide ion).

If the amount of SDA increases, the production cost tends to increase, so the raw material composition should have a molar ratio of the diammonium salt of the present invention to silica (hereinafter also referred to as "SDA/SiO ₂ ") of 2.0 or less. It is preferably 1.0 or less, more preferably 0.50 or less, and even more preferably 0.30 or less. When SDA/SiO ₂ is 0.01 or more, further 0.02 or more, or even 0.03 or more, the formation of zeolite having a structure other than the AFX type is further suppressed.

The molar ratio of water to silica (hereinafter referred to as " _H2O / _SiO2 ") in the raw material composition is preferably 5 or more and 60 or less, more preferably 10 or more and 45 or less, and 10 or more. More preferably, it is 30 or less. If H ₂ O/SiO ₂ is within this range, the mixture will have a viscosity that allows for appropriate stirring during crystallization.

The raw material composition may contain seed crystals to promote zeolite crystal growth. When seed crystals are included, the content of seed crystals in the raw material composition is 10.0% by weight or less, further 5.0% by weight or less, or even 3.5% by weight as a weight ratio of seed crystals to silica. The following may be mentioned.

The seed crystal may be any zeolite that does not contain odd-numbered rings in its crystal structure, such as a zeolite having a structure of any one of the group consisting of FAU, CHA, AEI, LEV, AFX, ERI, OFF, LTL, and GME. Further examples include zeolites having a structure of any one of the group consisting of CHA, AEI, LEV, AFX and ERI, and AFX type zeolites.

It is preferable that the raw material composition has the following composition. In addition, M in the following composition is an alkali metal, each ratio is a molar (mol) ratio, and the seed crystal is a weight ratio.

SiO ₂ /Al ₂ O ₃ 5 or more and 100 or less,
Preferably 10 or more and 50 or less,
More preferably 10 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 0.5 or less H ₂ O/SiO ₂ 5 or more and 60 or less,
Preferably 10 or more and 45 or less,
More preferably 10 to 30 Seed crystals 10.0% by weight or less,
Preferably 5.0% by weight or less,
More preferably 3.5% by weight or less In the above composition, SiO ₂ /Al ₂ O ₃ is the molar ratio of silica to alumina in the raw material composition, and OH/SiO ₂ , M/SiO ₂ , SDA/SiO ₂ and _H2O / _SiO2 is the molar ratio of hydroxide ion, alkali metal, SDA, or water, respectively, to silica in the raw material composition. Note that M is an alkali metal; for example, when the alkali metal is sodium, or when the alkali metals are sodium and potassium, M/SiO ₂ is Na/SiO ₂ or (Na+K)/SiO, respectively. It becomes ₂ .

In this embodiment, the raw material composition may contain seed crystals. When seed crystals are included, the content of the seed crystals in the raw material composition is 0% by weight or more as the weight ratio of silicon in the seed crystals calculated as silica to the weight of silicon in the raw material composition converted to silica (SiO ₂ ). The content may be 10.0% by weight or less, more preferably 0.5% by weight or more and 5.0% by weight or less, and even more preferably 0.5% by weight or more and 3.5% by weight or less.

The seed crystal may be any zeolite that does not contain odd-membered rings in its crystal structure, and has, for example, any structure selected from the group of FAU, CHA, AEI, LEV, AFX, ERI, OFF, LTL, and GME. It is preferably a zeolite, more preferably a zeolite having any structure selected from the group of CHA, AEI, LEV, AFX and ERI, and even more preferably an AFX type zeolite.

In the crystallization step, the method for crystallizing the raw material composition may be appropriately selected. A preferred crystallization method includes hydrothermal treatment of the raw material composition. In the hydrothermal treatment, the raw material composition may be placed in a sealed pressure-resistant container and heated. The hydrothermal treatment conditions include the following.

Processing temperature: 80°C or more and 190°C or less, preferably 150°C or more and 190°C or less Processing time: 2 hours or more and 500 hours or less Processing pressure: Autogenous pressure The state of the raw material composition during crystallization is arbitrary, and may be left standing or stirring. Any of the following may be used, but stirring is preferred.

The zeolite manufacturing method of this embodiment may include a post-treatment process such as a washing process, a drying process, an SDA removal process, or an ammonium treatment process.

The washing step described above washes the zeolite. Although the washing method is arbitrary, one example is to contact the zeolite with a sufficient amount of pure water.

The drying step described above removes water from the zeolite. Although the drying method is arbitrary, an example of drying method is to treat the zeolite in the air at a temperature of 100° C. or more and 150° C. or less for 2 hours or more.

The SDA removal step described above removes SDA remaining in the zeolite. A method for removing SDA includes treatment in the air at a temperature of 400° C. or higher and 700° C. or lower for 1 to 2 hours.

The ammonium treatment step described above removes alkali metal from the zeolite and changes the cation type to ammonium type (hereinafter referred to as "NH ₄ ⁺ type"). The ammonium treatment method includes contacting an aqueous solution containing ammonium ions with zeolite. Note that the NH ₄ ⁺ type zeolite may be heat-treated to produce a zeolite whose cation type is a proton type (hereinafter referred to as "H ⁺ type"). Specific heat treatment conditions include, for example, air at 500° C. for 1 to 2 hours.

The zeolite obtained by the zeolite manufacturing method of the present embodiment can be used in known zeolite applications, such as an adsorbent, a catalyst, an adsorbent carrier, or a catalyst carrier.

Crystallization may be performed either standing still or stirring. In order to make the composition of the obtained AFX type zeolite more uniform, it is preferable to perform crystallization while the raw material composition is stirred.

The zeolite manufacturing 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. Specifically, there is a method in which the product is filtered, washed, and separated into a liquid phase and a solid phase to obtain AFX type zeolite.

The drying step removes water from the AFX type zeolite after the crystallization step or the washing step. The conditions for 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 atmosphere at a temperature of 100°C or higher and 150°C or lower for 2 hours or more. This can be exemplified. As a drying method, standing or a spray dryer can be exemplified.

In the SDA removal step, SDA can be removed, for example, by firing or decomposition. Firing is performed at a temperature of 400°C or higher and 800°C or lower. Furthermore, it is preferable to carry out at a temperature of 700°C or lower. This makes it easier to obtain AFX type zeolite with less dealumination. Specific heat treatment conditions include air at 600° C. for 1 to 2 hours.

The manufacturing method of the present invention may include 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 ammonium type (hereinafter referred to as "NH ₄ ⁺ type"). The ammonium treatment step is performed, for example, by bringing an aqueous solution containing ammonium ions into contact with AFX type zeolite.

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

Moreover, the zeolite manufacturing method of this embodiment may include a modification step of modifying the zeolite using the zeolite containing SDA.

The above modification step is a step of modifying the surface or interior of the zeolite with a metal salt or an organic substance, and the method may be arbitrary, but an example may be bringing the zeolite into contact with a solution containing a metal salt.

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 causing the AFX-type zeolite to contain a transition metal.

The transition metal used in the transition metal-containing step is preferably a compound containing one or more transition metals from the group consisting of Groups 7, 8, 9, 10, 11, and 13 of the periodic table. , platinum (Pt), palladium (Pd), rhodium (Rh), silver (Ag), iron (Fe), copper (Cu), cobalt (Co), manganese (Mn) and indium (In). It is more preferable that it is a compound containing at least one species, it is even more preferable that it is a compound containing at least one of iron or copper, and it is preferable that it is a compound containing copper. Examples of compounds containing transition metals include at least one member of the group consisting of nitrates, sulfates, acetates, chlorides, complex salts, oxides, and composite oxides of these transition metals.

Examples of the method for incorporating a transition metal into AFX type zeolite include at least one of the group consisting of an ion exchange method, an impregnation support method, an evaporation drying method, a precipitation support method, and a physical mixing method.

The AFX type zeolite obtained by the zeolite production method of the present invention can be used as a catalyst or an adsorbent, as well as at least one of these base materials, and further as a catalyst or an adsorbent that is exposed to high temperature and high humidity, and It can be used as at least either a catalyst base material or an adsorbent base material, and is particularly preferably 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 with high exhaust gas temperatures.

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

Next, the present invention will be explained by examples, but the present invention is not limited thereto.
(H ¹ -NMR)
H ¹ -NMR measurements of the samples were performed using Ascend ^TM 400 (400 MHz, manufactured by Bruker) or UltraShield ^TM Plus 400 (400 MHz, manufactured by Bruker). Measure H ¹ -NMR of the sample using deuterated chloroform (CDCl ₃ ), deuterated dimethyl sulfoxide (DMSO-d ₆ ), or heavy water (D ₂ O) as the measurement solvent and tetramethylsilane (TMS) as the internal standard substance. did. The measurement data was described in the order of chemical shift, multiplicity, coupling constant (Hz), and integral value.
(ion chromatograph)
Anion chromatography was measured using an ion chromatograph device IC-2001 (manufactured by Tosoh). The measurement conditions are as follows.

Column: TSKgel SuperIC-AZ
Eluent: 7.5 mmol/L sodium hydrogen carbonate aqueous solution
+1.1 mmol/L sodium carbonate water-soluble group
Flow rate: 0.8mL/min
Temperature: 40℃
Detection: Electrical conductivity (powder X-ray diffraction)
The sample was subjected to XRD measurement using a general X-ray diffraction device (device name: Ultima IV, manufactured by RIGAKU). The measurement conditions are as follows.

Radiation source: CuKα radiation (λ=1.5405Å)
Measurement mode: Step scan
Scan width: 0.02°
Divergence slit: 1.00deg
Scattering slit: open
Light receiving slit: open
Measurement time: 1.0 minutes
Measurement range: 2θ=3.0°~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 IZA Structure Commission home page.
(Quantification 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). A measurement solution was prepared by dissolving the sample in a mixed solution of hydrofluoric acid and nitric acid. The obtained measurement solution was put into the 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 diammonium salt)
Example 1-1

To a suspension of lithium aluminum hydride (1.67 g, 43.9 mmol) and tetrahydrofuran (73 mL) was added N,N'-diethylcyclohexanetetracarboxydiimide (2.04 g, 7.31 mmol) under an ice bath. The mixture was stirred at 60°C for 9 hours. After the reaction, the reaction solution was cooled in an ice bath, and water (1.7 mL), 15% aqueous sodium hydroxide solution (1.7 mL), and water (5.1 mL) were sequentially added and stirred. The solid precipitated from the reaction solution was filtered, washed with tetrahydrofuran and ethyl acetate, and the solvent was distilled off from the filtrate under reduced pressure to obtain 5,11-diethyl-5,11-diazatricyclo[7.3 .0.0 ^3,7 ] dodecane crude product (1.79 g) was obtained.

NMR spectrum of crude product of 5,11-diethyl-5,11-diazatricyclo[7.3.0.0 ^3,7 ]dodecane: ¹ H-NMR (400 MHz, CDCl ₃ ) δ (ppm): 3.04 ~2.87 (m, 4H), 2.40 (q, J=7.2Hz, 4H), 2.21 ~ 2.06 (m, 4H), 1.94 ~ 1.83 (m, 4H) , 1.66 to 1.55 (m, 2H), 1.20 to 1.03 (m, 2H), 1.10 (t, J = 7.2Hz, 6H).

Bromoethane (1 mL/1.26 mL) was added to a solution of the crude product (1.79 g) of 5,11-diethyl-5,11-diazatricyclo[7.3.0.0 ^3,7 ]dodecane in tetrahydrofuran/ethanol (1 mL/1.26 mL). .78 mL, 24.0 mmol) was added thereto, and the mixture was stirred at room temperature for 18 hours, and then at 60°C for 30 hours. After cooling the reaction solution to room temperature, the precipitated solid was collected by filtration and washed with a tetrahydrofuran/ethanol mixture (1:1) to obtain a white solid of 5,5,11,11-tetraethyltricyclo[7. 3.0.0 ^3,7 ]dodecane-5,11-diazanium dibromide (3.47 g, 40% total yield over two steps) was obtained. As a result of analyzing the obtained compound using ion chromatography, the presence of bromide ions was confirmed.

NMR spectrum of 5,5,11,11-tetraethyltricyclo[7.3.0.0 ^3,7 ]dodecane-5,11-diazanium dibromide: ¹ H-NMR (400 MHz, D ₂ O) δ (ppm ): 4.00-3.86 (m, 4H), 3.45-3.30 (m, 8H), 3.14-2.99 (m, 4H), 2.70-2.53 (m , 4H), 2.00 to 1.89 (m, 2H), 1.40 to 1.23 (m, 14H).

(Synthesis of tetraethyl 1,2,4,5-cyclohexanetetracarboxylate)
Reference example 1-1

P-toluenesulfonic acid positional monohydrate was added to an ethanol/toluene (1:1) mixed solution (20 mL) of 1,2,4,5-cyclohexanetetracarboxylic dianhydride (2.23 g, 9.95 mmol). (99.0 mg, 0.52 mmol) was added and stirred under heating and reflux for 16 hours. After the reaction, the reaction solution was allowed to cool to room temperature, the solvent was distilled off under reduced pressure, and the resulting crude product was purified by column chromatography (eluent: hexane/ethyl acetate) to obtain a colorless oil. Tetraethyl 1,2,4,5-cyclohexanetetracarboxylate (3.51 g, yield 95%) was obtained.

NMR spectrum of tetraethyl 1,2,4,5-cyclohexanetetracarboxylate: ¹ H-NMR (400MHz, DMSO-d ₆ ) δ (ppm): 4.08 to 3.89 (m, 8H), 2.93 ~2.77 (m, 4H), 2.40 ~ 2.27 (m, 2H), 2.17 ~ 2.06 (m, 2H), 1.14 (t, J = 7.0Hz, 12H) .
(Synthesis of 1,2,4,5-tetraxy(hydroxymethyl)cyclohexane)

A solution of tetraethyl 1,2,4,5-cyclohexanetetracarboxylate (8.24 g, 22.1 mmol) in tetrahydrofuran (115 mL) was added to a suspension of lithium aluminum hydride (5.05 g, 133 mmol) and tetrahydrofuran (120 mL). was added under an ice bath, and the mixture was stirred at 65° C. for 3 hours and at room temperature for 15 hours. After the reaction, the reaction solution was cooled in an ice bath, and water (5.8 mL), 1M aqueous sodium hydroxide solution (22 mL), and water (17 mL) were sequentially added and stirred. The solid precipitated from the reaction solution was filtered off, and the solid was washed with tetrahydrofuran and ethyl acetate. The solvent was distilled off from the filtrate under reduced pressure, and the resulting crude product was purified by column chromatography (eluent: chloroform/methanol) to obtain 1,2,4,5-tetrakis (hydroxy) as a white solid. Methyl)cyclohexane (2.98 g, yield 66%) was obtained.

NMR spectrum of 1,2,4,5-tetrakis(hydroxymethyl)cyclohexane: ¹ H-NMR (400 MHz, DMSO-d ₆ ) δ (ppm): 4.43 (t, J = 4.9 Hz, 4H), 3.47-3.36 (m, 4H), 3.28-3.18 (m, 4H), 1.52-1.40 (m, 2H), 1.40-1.30 (m, 2H) ).
(Synthesis of 1,2,4,5-tetrakis(methanesulfonyloxymethyl)cyclohexane)

Methanesulfonyl chloride (0.69 mL, 8.92 mmol) was added under an ice bath, and the mixture was stirred at 0°C for 21.5 hours. Water (5 mL) was added to the reaction mixture, and after liquid separation, the aqueous layer was extracted with chloroform (5 mL x 3). The combined organic phases were washed with saturated aqueous sodium bicarbonate (5 mL), dried over sodium sulfate, and concentrated under reduced pressure to give 1,2,4,5-tetrakis(methanesulfonyloxymethyl) as a yellow oil. Cyclohexane (974 mg, yield 96%) was obtained.

NMR spectrum of 1,2,4,5-tetrakis(methanesulfonyloxymethyl)cyclohexane: ¹ H-NMR (400MHz, DMSO-d ₆ ) δ (ppm): 4.31 to 4.20 (m, 4H), 4.14-4.03 (m, 4H), 3.21 (s, 12H), 2.30-2.09 (m, 4H), 1.75-1.58 (m, 4H).

Example 1-2

To a solution of 1,2,4,5-tetrakis(methanesulfonyloxymethyl)cyclohexane (400 mg, 0.77 mmol) in acetonitrile (1.0 mL) was added bis(2-ethoxyethyl)amine (0.59 mL, 3.23 mmol). and stirred in a sealed tube at 90°C for 16 hours. The reaction solution was allowed to cool to room temperature and then concentrated. The obtained crude product was dissolved in methanol, an anion exchange resin (Amberlite IRA-400 Cl ^- type, 12 cm ³ ) was added, and the mixture was stirred at room temperature for 3 hours. The anion exchange resin was removed by filtration and concentrated. Chloroform was added to the obtained crude product, the precipitated solid was filtered off, and the filtrate was concentrated. By adding ice-cooled acetone thereto and collecting the precipitated solid by filtration, 5,5,11,11-tetrakis(ethoxyethyl)-tricyclo[7.3.0.0 ^3.7 ]dodecane-5, 11-Diazanium dichloride (112 mg, yield 28%) was obtained as a white solid. As a result of analyzing the obtained compound using ion chromatography, the presence of chloride ions was confirmed.

NMR spectrum of 5,5,11,11-tetrakis(ethoxyethyl)-tricyclo[7.3.0.0 ^3.7 ]dodecane-5,11-diazanium dichloride: ¹ H-NMR (400 MHz, D ₂ O ) δ (ppm): 4.06 (dd, J=12.3, 6.6Hz, 4H), 3.80 (brs, 8H), 3.61 (brdd, J=5.0, 4.1Hz, 4H), 3.54-3.46 (m, 12H), 3.07 (dd, J=10.7, 10.7Hz, 4H), 2.60-2.44 (m, 4H), 1. 85 (brd, J=13.4, 2H), 1.27 to 1.13 (m, 2H), 1.10 (t, J=7.1Hz, 6H), 1.09 (t, J=7 .1Hz, 6H).

Example 1-3

A solution of 11% dimethylamine (1.6 mL, 3.20 mmol) in ethanol was added to a solution of 1,2,4,5-tetrakis(methanesulfonyloxymethyl)cyclohexane (350 mg, 0.68 mmol) in acetonitrile (1.0 mL). and stirred at 90° C. for 19 hours in a sealed tube. The reaction solution was allowed to cool to room temperature and then concentrated. The obtained crude product was dissolved in methanol, an anion exchange resin (Amberlite IRA400 Cl ^- type, 8.3 cm ³ ) was added, and the mixture was stirred at room temperature for 4 hours. The anion exchange resin was removed by filtration and concentrated. By adding chloroform to the obtained crude product and collecting the precipitated solid by filtration, 5,5,11,11-tetramethyltricyclo[7.3.0.0 ^3.7 ]dodecane-5,11 -Diazanium dichloride (13.1 mg, yield 7%) was obtained as a white solid. As a result of analyzing the obtained compound using ion chromatography, the presence of chloride ions was confirmed.

NMR spectrum of 5,5,11,11-tetramethyltricyclo[7.3.0.0 ^3.7 ]dodecane-5,11-diazanium dichloride: ¹ H-NMR (400 MHz, D ₂ O) δ( ppm): 3.76 (dd, J=12.6, 7.7Hz, 4H), 3.13 (brs, 6H), 3.16 to 3.07 (m, 4H), 3.03 (brs, 6H), 2.68-2.52 (m, 4H), 1.85 (dt, J=13.1, 4.7Hz, 2H), 1.30-1.15 (m, 2H).

Example 1-4

Add N-ethylmethylamine (0.27 mL, 3.15 mmol) to a solution of 1,2,4,5-tetrakis(methanesulfonyloxymethyl)cyclohexane (372 mg, 0.72 mmol) in acetonitrile (1.0 mL), The mixture was stirred in a sealed tube at 90°C for 16 hours. The reaction solution was allowed to cool to room temperature and then concentrated. The obtained crude product was dissolved in methanol, an anion exchange resin (Amberlite IRA400 Cl ^- type, 8.3 cm ³ ) was added, and the mixture was stirred at room temperature for 3 hours. The anion exchange resin was removed by filtration and concentrated. Add ice-cooled acetone to the obtained crude product, then add chloroform, and collect the precipitated solid by filtration to obtain 5,11-diethyl-5,11-dimethyltricyclo[7.3.0.0 ^3.7 ] Dodecane-5,11-diazanium dichloride (21.2 mg, yield 9%) was obtained as a white solid. As a result of analyzing the obtained compound using ion chromatography, the presence of chloride ions was confirmed.

NMR spectrum of 5,11-diethyl-5,11-dimethyltricyclo[7.3.0.0 ^3.7 ]dodecane-5,11-diazanium dichloride: ¹ H-NMR (400 MHz, D ₂ O) δ (ppm): 3.89-3.68 (m, 4H), 3.41-3.22 (m, 4H), 3.08-2.98 (m, 4H), 3.10-2.89 (m, 10H), 2.66-2.44 (m, 4H), 1.88-1.78 (m, 2H), 1.34-1.12 (m, 8H).

Example 1-5

1,2,4,5-tetrakis(methanesulfonyloxymethyl)cyclohexane (1.06 g, 2.1 mmol), acetonitrile (7.0 mL) and diethylamine (0.83 mL, 8.0 mmol) were placed in a sealed tube. Stirred at ℃ for 17 hours. The reaction solution was allowed to cool to room temperature and then concentrated. The obtained crude product was dissolved in methanol, an anion exchange resin (Amberlite IRA400 Cl ^- type, 16 cm ³ ) was added, and the mixture was stirred at room temperature for 3 hours. The anion exchange resin was removed by filtration, the filtrate was concentrated under reduced pressure, acetone was added to the residue, and the precipitated solid was collected by filtration. By washing the obtained solid with chloroform, 5,5,11,11-tetraethyl-5,11-diazatricyclo[7.3.0.0 ^3.7 ]dodecanium dichloride (54.8 mg, yield 8 %) as a white solid. As a result of analyzing the obtained compound using ion chromatography, the presence of chloride ions was confirmed.

NMR spectrum of 5,5,11,11-tetraethyl-5,11-diazatricyclo[7.3.0.0 ^3.7 ]dodecanium dichloride: ¹ H-NMR (400 MHz, D ₂ O) δ (ppm): 3.99-3.85 (m, 4H), 3.44-3.28 (m, 8H), 3.11-2.97 (m, 4H), 2.68-2.51 (m, 4H) ), 1.98 to 1.86 (m, 2H), 1.39 to 1.21 (m, 14H).

Example 1-6

An aqueous solution of 5,5,11,11-tetraethyl-5,11-diazatricyclo[7.3.0.0 ^3.7 ]dodecanium dichloride (54.8 mg, 0.156 mmol) was mixed with an anion exchange resin (Amberlite IRN). ^5,5,11,11 -tetraethyl-5,11-diazatricyclo[ ^{7.3.0.0 3.7 ]} dodecanium dihydroxide. An aqueous solution (10 mL) was obtained. This was diluted with ion-exchanged water, titrated with 0.010M hydrochloric acid, and the ion-exchange rate was measured, and the ion-exchange rate was 67%.

NMR spectrum of aqueous solution of 5,5,11,11-tetraethyl-5,11-diazatricyclo[7.3.0.0 ^3.7 ]dodecanium dihydroxide: ¹ H-NMR (400 MHz, D ₂ O) δ( ppm): 3.99-3.85 (m, 4H), 3.44-3.28 (m, 8H), 3.11-2.97 (m, 4H), 2.68-2.51 ( m, 4H), 1.98 to 1.86 (m, 2H), 1.39 to 1.21 (m, 14H).

Example 1-7

Add 1,2,4,5-tetrakis(methanesulfonyloxymethyl)cyclohexane (320 mg), acetonitrile (1.0 mL) and N,N-diethyl-N'-methylethylenediamine (0.34 mL, 2.7 mmol), The mixture was stirred in a sealed tube at 90°C for 17 hours. The reaction solution was allowed to cool to room temperature and then concentrated. The obtained crude product was dissolved in methanol, an anion exchange resin (Amberlite IRA400 Cl ^- type, 16 cm ³ ) was added, and the mixture was stirred at room temperature for 3 hours. The anion exchange resin was removed by filtration, the filtrate was concentrated under reduced pressure, acetone was added to the residue, and the precipitated solid was collected by filtration. The obtained solid was dissolved in methanol and washed with activated carbon to obtain 5,11-N,N-diethylaminoethyl-5,11-dimethyl-5,11-diazatricyclo[7.3.0.0 ^3.7 ] Dodecanium dichloride (90.2 mg, yield 27%) was obtained as a white solid. NMR spectrum of 5,11-N,N-diethylaminoethyl-5,11-dimethyl-5,11-diazatricyclo[7.3.0.0 ^3.7 ]dodecanium dichloride: ¹ H-NMR (400 MHz, D ₂ O) δ (ppm): 4.03-3.86 (m, 4H), 3.58-3.36 (m, 4H), 3.27-3.14 (m, 6H), 3.14- 3.05 (m, 4H), 3.04-2.94 (m, 4H), 2.76-2.54 (m, 12H), 2.00-1.89 (m, 2H), 1. 40-1.22 (m, 2H), 1.04 (t, J=7.3Hz, 12H).

(Synthesis of AFX type zeolite)
Example 2-1
5,5,11,11-tetraethyltricyclo[7.3.0.0 ^3,7 ]dodecane-5,11-diazanium dibromide obtained in Example 1-1, 48% NaOH and Y-type zeolite ( (trade name: HSZ-350HUA, manufactured by Tosoh) to obtain a composition. The composition of the obtained composition is shown.

SiO ₂ /Al ₂ O ₃ = 11.1
OH/ _SiO2 = 0.35
Na/ _SiO2 = 0.35
SDA/ _SiO2 = 0.08
_H2O / _SiO2 = 25
After adding AFX type zeolite to the composition so that the seed crystal content of the composition was 3.0% by weight, it was sufficiently stirred.

The stirred composition was sealed in a stainless steel autoclave, and heated at 180° C. for 168 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, with a SiO ₂ /Al ₂ O ₃ of 9.8.

The XRD pattern of the AFX type zeolite of this example is shown in FIG. 1, and the SEM image is shown in FIG.

Claims (6)

Diammonium salt represented by general formula (1).
[In the formula,
R ¹ , R ² , R ³ and R ⁴ each independently represent a methyl group, an ethyl group, a propyl group, or an isopropyl group, and these substituents may be substituted with a hydroxyl group .
Y ⁻ is the same or different and represents a halide ion, a sulfonic acid ion represented by R ⁵ SO ₂ O ⁻ , a carboxylic acid ion represented by R ⁶ COO ⁻ , or OH ⁻ (hydroxide ion) .
R ⁵ represents a methyl group, an ethyl group, a propyl group, or an isopropyl group .
R ⁶ represents a methyl group, an ethyl group, a propyl group, or an isopropyl group. ] The diammonium salt according to claim 1, wherein Y ^- is a chloride ion, bromide ion, iodide ion or OH ^- (hydroxide ion). The diammonium salt according to claim 1 or 2 ^, wherein R ¹ and R 2 are the same substituent, and R ³ and R ⁴ are the same substituent. R ¹ and R ² are the same and are a methyl group or ethyl group, R ³ and R ⁴ are the same and are a methyl group or an ethyl group, and Y ^- is a chloride ion, bromide ion, or OH ^- (hydroxide ion) ) The diammonium salt according to any one of claims 1 to 3 . A zeolite comprising a crystallization step of crystallizing a composition containing a diammonium salt represented by the general formula (1) according to claim 1, a silica source, an alumina source, an alkali source, and water. Production method. The method for producing zeolite according to claim 5 , wherein the zeolite is an AFX type zeolite.