JP7394631B2 - Diammonium salt with cyclic structure and its uses - Google Patents

Description

The present invention relates to a novel diammonium salt, a method for producing the same, and uses thereof.

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

The object of the present invention is to provide novel diammonium salts. Another object of the present invention is to provide a method for producing zeolite, preferably small pore zeolite, more preferably AFX type zeolite, using a diammonium salt.

As a result of intensive studies to solve the above problems, the present inventors discovered a diammonium salt represented by the following general formula (1) and completed the present invention. Furthermore, it has been found that this 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,
The two A's are the same or different, and are a nitrogen-containing heterocycle having 3 to 20 carbon atoms, which may have a bridged ring or a condensed ring (the nitrogen-containing heterocycle is a halogen atom, a hydroxyl group, an oxo group, a hydroxyl group) an alkyl group having 1 to 6 carbon atoms which may be substituted with an alkoxy group having 1 to 6 carbon atoms, an alkyl group having 1 to 6 carbon atoms which may be substituted with an alkoxy group having 1 to 6 carbon atoms, a haloalkyl group having 1 to 6 carbon atoms, a carbon An alkoxy group having 1 to 6 carbon atoms, an aryl group having 6 to 12 carbon atoms, an aralkyl group having 7 to 13 carbon atoms, an aryloxy group having 6 to 10 carbon atoms, an alkyloxycarbonyl group having 1 to 6 carbon atoms, a nitrogen atom An acylamino group having 1 to 8 carbon atoms which may be substituted with an alkyl group having 1 to 4 carbon atoms, and an acylamino group having 1 to 9 carbon atoms which may have one or more nitrogen atoms substituted with an alkyl group having 1 to 4 carbon atoms. an aminocarbonyl group having 1 to 5 carbon atoms, an alkyloxycarbonyloxy group having 1 to 5 carbon atoms, an alkyloxycarbonylamino group having 1 to 5 carbon atoms in which the nitrogen atom may be substituted with an alkyl group having 1 to 4 carbon atoms, A ureido group optionally substituted with one or more alkyl groups having 1 to 4 carbon atoms, a dialkylamino group having 2 to 12 carbon atoms, a monoarylamino group having 6 to 10 carbon atoms, or a diarylamino group having 12 to 20 carbon atoms may have a group).
Y ⁻ is the same or different and represents a halide ion, a sulfonic acid ion represented by R ¹ SO ₂ O ⁻ , a carboxylic acid ion represented by R ² COO ⁻ , or OH ⁻ (hydroxide ion) .
R ¹ 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 is an alkyl group having 1 to 4 carbon atoms, a fluoroalkyl group having 1 to 4 carbon atoms, (Optionally substituted with one or more substituents selected from the group consisting of 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 ² represents 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 may be substituted with an alkyl group having 1 to 4 carbon atoms). . ]
[2] Two A's are the same and a nitrogen-containing heterocycle having 3 to 20 carbon atoms that may have a bridged ring or a condensed ring (the nitrogen-containing heterocycle is a halogen atom, a hydroxyl group, an oxo group) , an alkyl group having 1 to 6 carbon atoms which may be substituted with a hydroxyl group, an alkyl group having 1 to 6 carbon atoms which may be substituted with an alkoxy group having 1 to 6 carbon atoms, and a haloalkyl group having 1 to 6 carbon atoms. , alkoxy group having 1 to 6 carbon atoms, aryl group having 6 to 12 carbon atoms, aralkyl group having 7 to 13 carbon atoms, aryloxy group having 6 to 10 carbon atoms, alkyloxycarbonyl group having 1 to 6 carbon atoms, nitrogen Acylamino group having 1 to 8 carbon atoms, the atom of which may be substituted with an alkyl group having 1 to 4 carbon atoms; 1 carbon atom, which may have one or more nitrogen atoms substituted with an alkyl group having 1 to 4 carbon atoms; to 9 aminocarbonyl groups, C1 to C5 alkyloxycarbonyloxy groups, C1 to C5 alkyloxycarbonylamino groups in which the nitrogen atom may be substituted with C1 to C4 alkyl groups, nitrogen A ureido group in which an atom may be substituted with one or more alkyl groups having 1 to 4 carbon atoms, a dialkylamino group having 2 to 12 carbon atoms, a monoarylamino group having 6 to 10 carbon atoms, or a monoarylamino group having 12 to 20 carbon atoms. The diammonium salt according to [1], which may have a diarylamino group.
[3] Y ^- is the same or different, and is a chloride ion, bromide ion, iodide ion, C ₆ H ₅ SO ₂ O ^- (benzenesulfonic acid ion), p-CH ₃ C ₆ H ₄ SO ₂ O ^- (paratoluenesulfonate ion), CH ₃ SO ₂ O ^- (methanelsulfonate ion), CF ₃ SO ₂ O ^- (trifluoromethanesulfonate ion) or OH ^- (hydroxide ion) [1] Or the diammonium salt described in [2].
[4] Two A's are the same and a nitrogen-containing heterocycle having 4 to 20 carbon atoms that may have a bridged ring or a condensed ring (the nitrogen-containing heterocycle is an alkoxy ring having 1 to 6 carbon atoms) Alkyl group having 1 to 6 carbon atoms which may be substituted with a group, fluoroalkyl group having 1 to 6 carbon atoms, alkoxy group having 1 to 6 carbon atoms, aryl group having 6 to 12 carbon atoms, 7 to 13 carbon atoms an aralkyl group having 6 to 10 carbon atoms, an aryloxy group having 6 to 10 carbon atoms, an alkyloxycarbonyl group having 1 to 6 carbon atoms, an acylamino having 1 to 8 carbon atoms in which the nitrogen atom may be substituted with an alkyl group having 1 to 4 carbon atoms; group, an aminocarbonyl group having 1 to 9 carbon atoms in which the nitrogen atom may be substituted with one or more alkyl groups having 1 to 4 carbon atoms, dialkylamino group having 2 to 12 carbon atoms, or diaryl having 12 to 20 carbon atoms The diammonium salt according to any one of [1] to [3], which may have an amino group.
[5] Two A's are the same and a nitrogen-containing heterocycle having 4 to 6 carbon atoms that may have a bridged ring or a condensed ring (the nitrogen-containing heterocycle is an alkyl group having 1 to 4 carbon atoms) group, an alkoxy group having 1 to 6 carbon atoms, an aryl group having 6 to 12 carbon atoms, an aralkyl group having 7 to 13 carbon atoms, an aryloxy group having 6 to 10 carbon atoms, or a dialkylamino group having 2 to 8 carbon atoms. ) The diammonium salt according to any one of [1] to [4].
[6] Two A's are the same nitrogen-containing heterocycle having 4 to 6 carbon atoms (the nitrogen-containing heterocycle is an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a carbon may have an aryl group having 6 to 12 carbon atoms or a dialkylamino group having 2 to 8 carbon atoms), and Y ^- is the same or different and is a chloride ion, bromide ion or OH ^- (hydroxide ion), the diammonium salt according to any one of [1] to [5].
[7] It is characterized by having a crystallization step of crystallizing the composition containing the diammonium salt according to any one of [1] to [6], a silica source, an alumina source, an alkali source, and water. Method of manufacturing zeolite.
[8] The method for producing a zeolite according to [7], wherein the zeolite is a small pore zeolite.
[9] The method for producing zeolite according to [7] or [8], 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 diagram 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 A and Y 2 ⁻ in the diammonium salt represented by the general formula (1) will be explained in detail.

The two A's are the same or different, and are a nitrogen-containing heterocycle having 3 to 20 carbon atoms, which may have a bridged ring or a condensed ring (the nitrogen-containing heterocycle is a halogen atom, a hydroxyl group, an oxo group, a hydroxyl group) an alkyl group having 1 to 6 carbon atoms which may be substituted with an alkoxy group having 1 to 6 carbon atoms, an alkyl group having 1 to 6 carbon atoms which may be substituted with an alkoxy group having 1 to 6 carbon atoms, a haloalkyl group having 1 to 6 carbon atoms, a carbon An alkoxy group having 1 to 6 carbon atoms, an aryl group having 6 to 12 carbon atoms, an aralkyl group having 7 to 13 carbon atoms, an aryloxy group having 6 to 10 carbon atoms, an alkyloxycarbonyl group having 1 to 6 carbon atoms, a nitrogen atom An acylamino group having 1 to 8 carbon atoms which may be substituted with an alkyl group having 1 to 4 carbon atoms, and an acylamino group having 1 to 9 carbon atoms which may have one or more nitrogen atoms substituted with an alkyl group having 1 to 4 carbon atoms. an aminocarbonyl group having 1 to 5 carbon atoms, an alkyloxycarbonyloxy group having 1 to 5 carbon atoms, an alkyloxycarbonylamino group having 1 to 5 carbon atoms in which the nitrogen atom may be substituted with an alkyl group having 1 to 4 carbon atoms, A ureido group optionally substituted with one or more alkyl groups having 1 to 4 carbon atoms, a dialkylamino group having 2 to 12 carbon atoms, a monoarylamino group having 6 to 10 carbon atoms, or a diarylamino group having 12 to 20 carbon atoms may have a group).

Regarding the nitrogen-containing heterocycle having a bridged ring and having 3 to 20 carbon atoms, there is no limitation on the number of carbon atoms in the bridged structure, and for example, a bridged structure having 1, 2, or 3 carbon atoms can be exemplified. The number of carbon atoms in the bridged portion in the nitrogen-containing heterocycle having 3 to 20 carbon atoms having the bridged ring is a part of the number of carbon atoms in the nitrogen-containing heterocycle.

Further, regarding the nitrogen-containing heterocycle having a condensed ring and having 3 to 20 carbon atoms, there is no limitation on the number of condensed rings, and examples of the nitrogen-containing heterocycle include bicyclic, tricyclic, or tetracyclic. The total number of carbon atoms in these condensed ring structures corresponds to the above-mentioned number of carbon atoms of 3 to 20.

Further, the nitrogen-containing heterocycle having 3 to 20 carbon atoms may have both a bridged ring and a condensed ring.

The nitrogen-containing heterocycle having 3 to 20 carbon atoms which may have a bridged ring or condensed ring is not particularly limited, but includes, for example, a pyrrolidine ring, an imidazolidine ring, an indoline ring, an isoindoline ring, and a morpholine ring. Examples include a ring, a piperidine ring, a piperazine ring, a tetrahydrotriazine ring, an azepane ring, a morphan ring, an 8-azabicyclo[3.2.1]octane ring, and a decahydroquinoline ring.

Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

Examples of the alkoxy group having 1 to 6 carbon atoms include methoxy group, ethoxy group, propoxy group, isopropoxy group, butoxy group, 2-methylpropoxy group, 2,2-dimethylpropoxy group, 3-cyclopropylpropoxy group, and cyclopropoxy group. group, 2-methylbutoxy group, 3-methylbutoxy group, tert-butoxy group, cyclobutoxy group, pentyloxy group, 2-methylpentyloxy group, 1-methylbutoxy group, 1,2-dimethylbutoxy group, 1 Examples include -ethylpropoxy group, cyclopentyloxy group, hexyloxy group, and cyclohexyloxy group.

Examples of the alkyl group having 1 to 6 carbon atoms include methyl group, ethyl group, propyl group, isopropyl group, butyl group, cyclopentylmethyl group, 2-cyclobutylethyl group, cyclopropylmethyl 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-methyl Examples include pentyl group, 3-methylpentyl group, 1-methylbutyl group, 2-methylpentan-2-yl group, 2-ethylpropyl group, cyclopentyl group, 1-methylpentyl group, 2-ethylbutyl group, and cyclohexyl group.

Examples of the haloalkyl group having 1 to 6 carbon atoms include trifluoromethyl group, difluoromethyl group, perfluoroethyl group, 2,2,2-trifluoroethyl group, 1,1-difluoroethyl group, and 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. .

Examples of the aryl group having 6 to 12 carbon atoms include phenyl group, 2-methylphenyl group, 3-methylphenyl group, 4-methylphenyl group, 2,3-dimethylphenyl 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, 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, 2,3,4,5-tetramethyl Phenyl group, 2,3,4,6-tetramethylphenyl group, 2,3,5,6-tetramethylphenyl group, 2-ethylphenyl group, 3-ethylphenyl 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 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-cyclobutylphenyl group, 3-cyclobutylphenyl group, Examples include 4-cyclobutylphenyl group, 1-naphthyl group, 2-naphthyl group, 2-biphenylyl group, 3-biphenylyl group, and 4-biphenylyl group.

Examples of the aralkyl group having 7 to 13 carbon atoms include benzyl group, phenethyl group, and phenylpropyl group.

Examples of the aryloxy group having 6 to 10 carbon atoms include phenyloxy group, 2-methylphenyloxy group, 3-methylphenyloxy group, 4-methylphenyloxy group, 2,3-dimethylphenyloxy group, 2,4- Dimethylphenyloxy group, 2,5-dimethylphenyloxy group, 2,6-dimethylphenyloxy group, 3,4-dimethylphenyloxy group, 3,5-dimethylphenyloxy group, 2,3,4-trimethylphenyloxy group 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 group, 3-isopropylphenyloxy group, 4-isopropylphenyloxy group, 2-cyclopropylphenyloxy group, 3-cyclopropylphenyloxy group, 4-cyclopropylphenyloxy group, 2-butylphenyloxy group, 3-butyl Phenyloxy 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-cyclobutylphenyloxy group, 3-cyclobutylphenyloxy group, 4 Examples include -cyclobutylphenyloxy group, 1-naphthyloxy group, and 2-naphthyloxy group.

Examples of the alkyl group in the alkyloxycarbonyl group having 1 to 6 carbon atoms include methyl group, ethyl group, propyl group, isopropyl group, butyl group, cyclopentylmethyl group, 2-cyclobutylethyl group, 2-methylpropyl group, 2, Examples include 2-dimethylpropyl group, 3-cyclopropylpropyl group, cyclopropyl group, 2-methylbutyl group, 3-methylbutyl group, 3-methylbutan-2-yl group, tert-butyl group, and cyclobutyl group.

Examples of the alkyl group in the acylamino group having 1 to 8 carbon atoms in which the nitrogen atom may be substituted with an alkyl group having 1 to 4 carbon atoms include methyl group, ethyl group, propyl group, isopropyl group, butyl group, and cyclopropylmethyl. Examples of the acylamino group include a formylamino group, an acetylamino group, and a propanoylamino group.

Examples of the alkyl group in the aminocarbonyl group having 1 to 9 carbon atoms, in which the nitrogen atom may be substituted with one or more alkyl groups having 1 to 4 carbon atoms, include a methyl group, an ethyl group, a propyl group, an isopropyl group, and a butyl group. , cyclopropylmethyl group, 2-methylpropyl group, cyclopropyl group, tert-butyl group, or cyclobutyl group.

Examples of the alkyl group having 1 to 5 carbon atoms in the alkyloxycarbonyloxy group having 1 to 5 carbon atoms include methyl group, ethyl group, propyl group, isopropyl group, butyl group, cyclohexylmethyl group, 2-cyclopentylethyl group, 2- Examples include methylpropyl group, 2,2-dimethylpropyl group, cyclopropyl group, 2-methylbutyl group, 3-methylbutyl group, 3-methylbutan-2-yl group, tert-butyl group, and cyclobutyl group.

Examples of the alkyl group having 1 to 4 carbon atoms in the alkyloxycarbonylamino group having 1 to 5 carbon atoms in which the nitrogen atom may be substituted with an alkyl group having 1 to 4 carbon atoms include a methyl group, an ethyl group, a propyl group, Examples include isopropyl group, butyl group, cyclopropylmethyl group, 2-methylpropyl group, cyclopropyl group, tert-butyl group, and cyclobutyl group, and the alkyl group having 1 to 5 carbon atoms is methyl group, ethyl group, propyl group. group, isopropyl group, butyl group, cyclobutylmethyl group, 2-cyclopropylethyl group, 2-methylpropyl group, 2,2-dimethylpropyl group, cyclopropyl group, 2-methylbutyl group, 3-methylbutyl group, 3- Examples include methylbutan-2-yl group, tert-butyl group, and cyclobutyl group.

Examples of the ureido group in which the nitrogen atom may be substituted with one or more alkyl groups having 1 to 4 carbon atoms include a monoalkylaminocarbonylamino group, a dialkylaminocarbonylamino group, or a trialkylaminocarbonylamino group. Examples of the alkyl group having 1 to 4 carbon atoms include methyl group, ethyl group, propyl group, isopropyl group, butyl group, 2-methylpropyl group, cyclopropyl group, tert-butyl group, and cyclobutyl group. .

Examples of dialkylamino groups having 2 to 12 carbon atoms (two alkyl groups may be bonded together to form a ring structure within the above range of carbon atoms) include dimethylamino group, diethylamino group, dipropylamino group, group, diisopropylamino group, dibutylamino group, bis(2-methylpropyl)amino group, bis(2,2-dimethylpropyl)amino group, bis(3-cyclopropyl)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-methylamino group, N-cyclohexyl-N-methylamino group, N-cycloheptyl-N-methylamino group, N-methyl-N-octylamino group, N -Methyl-N-nonylamino group, N-decyl-N-methylamino group, or N-methyl-N-undecylamino group, azetidyl group, pyrrolidinyl group, piperidino group, azepanyl group, morpholino group or 2-morpholinyl group can be exemplified.

Examples of the monoarylamino group having 6 to 10 carbon atoms include phenylamino group, 2-methylphenylamino group, 3-methylphenylamino group, 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-dimethylphenylamino group, 2,3,4-trimethylphenyl Amino 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-isopropylphenyl Amino group, 3-isopropylphenylamino group, 4-isopropylphenylamino group, 2-cyclopropylphenylamino group, 3-cyclopropylphenylamino group, 4-cyclopropylphenylamino 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-cyclobutylphenylamino group, 3-cyclobutylphenylamino group, Examples include 4-cyclobutylphenylamino group, 1-naphthylamino group, and 2-naphthylamino group.

Examples of the diarylamino group having 12 to 20 carbon atoms include 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-diethylphenyl)amino group, bis(3,5-diethyl) phenyl)amino group, bis(2-propylphenyl)amino group, bis(3-propylphenyl)amino group, bis(4-propylphenyl)amino group, bis(2-isopropylphenyl)amino group, bis(3-isopropyl) phenyl)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, 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)-N-phenylamino group or N-(2-naphthyl) )-N-phenylamino group is an example.

Regarding A, from the viewpoint of easy synthesis, two A's are the same nitrogen-containing heterocycle having 3 to 20 carbon atoms that may have a bridged ring or a condensed ring (the nitrogen-containing heterocycle is , a halogen atom, a hydroxyl group, an oxo group, an alkyl group having 1 to 6 carbon atoms which may be substituted with a hydroxyl group, an alkyl group having 1 to 6 carbon atoms which may be substituted with an alkoxy group having 1 to 6 carbon atoms, Haloalkyl group having 1 to 6 carbon atoms, alkoxy group having 1 to 6 carbon atoms, aryl group having 6 to 12 carbon atoms, aralkyl group having 7 to 13 carbon atoms, aryloxy group having 6 to 10 carbon atoms, 1 to 1 carbon atoms 6 alkyloxycarbonyl group, an acylamino group having 1 to 8 carbon atoms which nitrogen atom may be substituted with an alkyl group having 1 to 4 carbon atoms, and one or more nitrogen atoms substituted with an alkyl group having 1 to 4 carbon atoms an aminocarbonyl group having 1 to 9 carbon atoms, which may be substituted with an alkyl group having 1 to 4 carbon atoms, an alkyloxycarbonyloxy group having 1 to 5 carbon atoms, and an alkyl group having 1 to 5 carbon atoms, where the nitrogen atom may be substituted with an alkyl group having 1 to 4 carbon atoms; alkyloxycarbonylamino group of or a diarylamino group having 12 to 20 carbon atoms), and two A's are the same and have a carbon number that may have a bridged ring or a condensed ring. 4 to 20 nitrogen-containing heterocycle (the nitrogen-containing heterocycle is an alkyl group having 1 to 6 carbon atoms which may be substituted with an alkoxy group having 1 to 6 carbon atoms, a fluoroalkyl group having 1 to 6 carbon atoms, Alkoxy group having 1 to 6 carbon atoms, aryl group having 6 to 12 carbon atoms, aralkyl group having 7 to 13 carbon atoms, aryloxy group having 6 to 10 carbon atoms, alkyloxycarbonyl group having 1 to 6 carbon atoms, nitrogen atom is an acylamino group having 1 to 8 carbon atoms which may be substituted with an alkyl group having 1 to 4 carbon atoms, and an acylamino group having 1 to 8 carbon atoms which may be substituted with one or more alkyl groups having 1 to 4 carbon atoms; 9 aminocarbonyl group, a dialkylamino group having 2 to 12 carbon atoms, or a diarylamino group having 12 to 20 carbon atoms), and two A's are the same and , a nitrogen-containing heterocycle having 4 to 6 carbon atoms which may have a bridged ring or a condensed ring (the nitrogen-containing heterocycle includes an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a carbon It may have an aryl group having 6 to 12 carbon atoms, an aralkyl group having 7 to 13 carbon atoms, an aryloxy group having 6 to 10 carbon atoms, or a dialkylamino group having 2 to 8 carbon atoms. ), and two A's are the same and are a nitrogen-containing heterocycle having 4 to 6 carbon atoms (the nitrogen-containing heterocycle is an alkyl group having 1 to 4 carbon atoms, an alkyl group having 1 to 6 carbon atoms, may have an alkoxy group, an aryl group having 6 to 12 carbon atoms, or a dialkylamino group having 2 to 8 carbon atoms).

Examples of the nitrogen-containing heterocycle having 4 to 20 carbon atoms which may have a bridged ring or condensed ring include a pyrrolidine ring, an indoline ring, an isoindoline ring, a morpholine ring, a piperidine ring, a piperazine ring, an azepane ring, and a morphan ring. Examples include a ring, an 8-azabicyclo[3.2.1]octane ring, and a decahydroquinoline ring.

Examples of the fluoroalkyl group having 1 to 6 carbon atoms include trifluoromethyl group, difluoromethyl group, perfluoroethyl group, 2,2,2-trifluoroethyl group, 1,1-difluoroethyl group, and 2,2-difluoroethyl group. group, perfluoropropyl group, 2,2,3,3,3-pentafluoropropyl group, 2,2,3,3-tetrafluoropropyl group, 3,3,3-trifluoropropyl group, 1,1-difluoro propyl 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-hexafluoro-1-(trifluoromethyl)propyl group, 1-(trifluoromethyl)propyl group, 1-methyl-3,3,3-trifluoropropyl group, perfluoro Cyclobutyl 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-heptafluorohexyl group, 5,5,6,6,6-pentafluorohexyl group, 6,6,6-trifluorohexyl group, perfluorocyclohexyl group, etc. can.

Examples of the nitrogen-containing heterocycle having 4 to 6 carbon atoms which may have a bridged ring or condensed ring include a pyrrolidine ring, a piperidine ring, a piperazine ring, and an azepane ring.

Examples of the alkyl group having 1 to 4 carbon atoms include a methyl group, ethyl group, propyl group, isopropyl group, butyl group, cyclopropylmethyl group, 2-methylpropyl group, cyclopropyl group, tert-butyl group, or cyclobutyl group. I can give an example.

Examples of dialkylamino groups having 2 to 8 carbon atoms (two alkyl groups may be bonded together to form a ring structure within the above range of carbon atoms) include dimethylamino group, diethylamino group, dipropylamino group, group, diisopropylamino group, dibutylamino group, bis(2-methylpropyl)amino group, bis(3-cyclopropyl)amino group, dicyclopropylamino group, di(tert-butyl)amino group, dicyclobutylamino group , N-ethyl-N-methylamino group, N-methyl-N-propyl group, N-cyclopropyl-N-methylamino group, azetidyl group, pyrrolidinyl group, piperidino group, azepanyl group, morpholino group or 2-morpholinyl group can be exemplified.

Examples of the nitrogen-containing heterocycle having 4 to 6 carbon atoms include a pyrrolidine ring, a piperidine ring, and an azepane ring.

Y ⁻ is the same or different and represents a halide ion, a sulfonic acid ion represented by R ¹ SO ₂ O ⁻ , a carboxylic acid ion represented by R ² COO ⁻ , or OH ⁻ (hydroxide ion) .

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 ¹ SO ₂ O ^- , R ¹ is selected from the group 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, or a fluoroalkoxy group having 1 to 4 carbon atoms. , a halogen atom, a cyano group, and a nitro group.

Examples of the alkyl group having 1 to 9 carbon atoms in R ¹ include methyl group, ethyl group, propyl group, isopropyl group, butyl group, sec-butyl group, tert-butyl group, cyclobutyl group, 1-methylbutyl group, 3-methylbutyl group. Examples include 1,3-dimethylbutyl group, octyl group, and nonyl group.

Examples of the fluoroalkyl group having 1 to 9 carbon atoms in R ¹ include 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-tetrafluorocyclo Propyl group, perfluorobutyl group, 2,2,3,3,4,4,4-heptafluorobutyl group, 3,3,4,4,4-pentafluorobutyl group, 4,4,4-trifluorobutyl group group, 1,2,2,3,3,3-hexafluoro-1-(trifluoromethyl)propyl group, 1-(trifluoromethyl)propyl group, 1-methyl-3,3,3-trifluoropropyl Examples include perfluorocyclobutyl group, 2,2,3,3,4,4-hexafluorocyclobutyl group, or 1,1,2,2,3,3,4,4,4-nonafluorobutyl group. can.

Examples of the alkyl group having 1 to 4 carbon atoms in R ¹ include methyl group, ethyl group, propyl group, isopropyl group, butyl group, 2-methylpropyl group, cyclopropyl group, tert-butyl group, and cyclobutyl group. .

Examples of the fluoroalkyl group having 1 to 4 carbon atoms in R ¹ include 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-tetrafluorocyclo Propyl group, perfluorobutyl group, 2,2,3,3,4,4,4-heptafluorobutyl group, 3,3,4,4,4-pentafluorobutyl group, 4,4,4-trifluorobutyl group group, 1,2,2,3,3,3-hexafluoro-1-(trifluoromethyl)propyl group, 1-(trifluoromethyl)propyl group, 1-methyl-3,3,3-trifluoropropyl group, perfluorocyclobutyl group, or 2,2,3,3,4,4-hexafluorocyclobutyl group.

Examples of the alkoxy group having 1 to 4 carbon atoms in R ¹ include methoxy group, ethoxy group, propoxy group, isopropoxy group, butoxy group, 2-methylpropoxy group, cyclopropoxy group, tert-butoxy group, or cyclobutoxy group. I can give an example.

Examples of the fluoroalkoxy group having 1 to 4 carbon atoms in R ¹ include trifluoromethyloxy group, difluoromethyloxy group, perfluoroethyloxy group, 2,2,2-trifluoroethyloxy group, and 1,1-difluoroethyloxy group. 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-methylpropyl)oxy group, 2,2,2-trifluoro-1-(trifluoromethyl)ethyloxy group, perfluorocyclopropyloxy group 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-(trifluorobutyloxy group) Examples include fluoromethyl)propyloxy group, 1-methyl-3,3,3-trifluoropropyloxy group, perfluorocyclobutyloxy group, or 2,2,3,3,4,4-hexafluorocyclobutyloxy group. can.

Examples of the halogen atom in R ¹ include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

R ¹ 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. Examples of the phenyl group substituted with one or more substituents selected from the group of groups (hereinafter also referred to as "substituted phenyl group") include 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-(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, 4-cyanophenyl group, 2-nitrophenyl group, 3-nitrophenyl group or 4-nitrophenyl group.

R ¹ is a phenyl group, 4-methylphenyl group, methyl group, or trifluoromethyl group in that the raw materials are easily available, that is, R ¹ SO ₂ O ^- is a benzenesulfonic acid ion, p -Toluenesulfonate ion, methanesulfonate ion or trifluoromethanesulfonate ion is preferred.

When Y ^- is R ² COO ^- , R ² is any one selected from the group consisting of an alkyl group having 1 to 6 carbon atoms, a fluoroalkyl group having 1 to 4 carbon atoms, and a phenyl group; The phenyl group may be substituted with an alkyl group having 1 to 4 carbon atoms.

The alkyl group having 1 to 6 carbon atoms in R ² may be any linear, branched or cyclic alkyl group, including methyl group, ethyl group, propyl group, isopropyl group, butyl group, and 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, Examples include 2-methylpentyl group, 1-methylbutyl group, 2-methylpentan-2-yl group, 1-ethylpropyl group, cyclopentyl group, hexyl group, 1-methylpentyl group, 1-ethylbutyl group, or cyclohexyl group. .

The fluoroalkyl group having 1 to 4 carbon atoms in R ² may be any linear, branched or cyclic alkyl group, including 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-tetrafluoro Propyl 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-hexafluoro-1-(trifluoromethyl)propyl group, 1-(trifluoromethyl) Examples include propyl group, 1-methyl-3,3,3-trifluoropropyl group, perfluorocyclobutyl group, and 2,2,3,3,4,4-hexafluorocyclobutyl group.

The phenyl group in R ² may be substituted with an alkyl group having 1 to 4 carbon atoms, as described above. The alkyl group having 1 to 4 carbon atoms may be a linear, branched or cyclic alkyl group, and may include a methyl group, ethyl group, propyl group, isopropyl group, cyclopropyl group, butyl group, 2-methylpropyl group. Examples include 3-methylpropyl group, cyclobutyl group, and the like.

R ² is preferably a phenyl group, a 4-methylphenyl group, or a methyl group, since the raw material is easily available.

Y ⁻ is preferably the same or different and is a halide ion, a sulfonic acid ion represented by R ² SO ₂ O ⁻ , or OH ⁻ (hydroxide ion) from the viewpoint of easy synthesis; Differently, chloride ion, bromide ion, iodide ion, C ₆ H ₅ SO ₂ O ⁻ (benzenesulfonate ion), p-CH ₃ C ₆ H ₄ SO ₂ O ⁻ (paratoluenesulfonate ion), More preferably, they are CH ₃ SO ₂ O ^- (methanesulfonate ion), CF ₃ SO ₂ O ^- (trifluoromethanesulfonate ion) or OH ^- (hydroxide ion), and the same or different chloride ion, bromide ion, p-CH ₃ C ₆ H ₄ SO ₂ O ^- (para-toluenesulfonate ion) or OH ^- (hydroxide ion), and the same or different bromide ion, chloride ion More preferably, it is a compound ion or OH ⁻ (hydroxide ion).

Specific examples of the diammonium salt (1) of the present invention include the following (1-1) to (1-330), but the present invention is not limited thereto. In this specification, Me represents a methyl group, Et represents an ethyl group, tBu represents a tert-butyl group, Ph represents a phenyl group, and TsO 2 ⁻ represents a p-toluenesulfonic acid ion.

Among the compounds represented by (1-1) to (1-330), the diammonium salts of the present invention include 1-2, 1-4, 1-50, 1-51, 1-60, 1-64, Compounds represented by 1-65, 1-66, 1-91, 1-92, 1-103, 1-104, 1-276, 1-278 and 1-279 are preferred in terms of good reaction yield.

The present invention relates to a method for producing zeolite using a diammonium salt represented by the above general formula (1).

Next, a method for producing a diammonium salt according to the present embodiment will be explained.

<Embodiment 1 of manufacturing method>
As a method for producing the diammonium salt of the present embodiment, 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 the following general formula (1a) (hereinafter also referred to as "manufacturing method 1"), which includes a step of reacting the diammonium salt with a secondary amine represented by the formula (1a), can be mentioned.

[Wherein, Ya are the same or different and represent a halogen atom or a sulfonyloxy group represented by R ¹ SO ₂ O. The above R ¹ is any one selected from the 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 9 carbon atoms. 4 alkyl group, 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 any of the above substituents. ]

(In the formula, Aa and Ab each independently represent a nitrogen-containing heterocycle having 3 to 20 carbon atoms, which may have a bridged ring or a condensed ring, and the nitrogen-containing heterocycle includes a halogen atom, a hydroxyl group, , an oxo group, an alkyl group having 1 to 6 carbon atoms which may be substituted with a hydroxyl group, an alkyl group having 1 to 6 carbon atoms which may be substituted with an alkoxy group having 1 to 6 carbon atoms, and an alkyl group having 1 to 6 carbon atoms which may be substituted with an alkoxy group having 1 to 6 carbon atoms. haloalkyl group, alkoxy group having 1 to 6 carbon atoms, aryl group having 6 to 12 carbon atoms, aralkyl group having 7 to 13 carbon atoms, aryloxy group having 6 to 10 carbon atoms, alkyloxycarbonyl group having 1 to 6 carbon atoms group, a nitrogen atom may be substituted with an alkyl group having 1 to 4 carbon atoms, an acylamino group having 1 to 8 carbon atoms, and a nitrogen atom may be substituted with one or more alkyl groups having 1 to 4 carbon atoms Aminocarbonyl group having 1 to 9 carbon atoms, alkyloxycarbonyloxy group having 1 to 5 carbon atoms, alkyloxycarbonylamino having 1 to 5 carbon atoms in which the nitrogen atom may be substituted with an alkyl group having 1 to 4 carbon atoms group, a ureido group in which the nitrogen atom may be substituted with one or more alkyl groups having 1 to 4 carbon atoms, dialkylamino groups having 2 to 12 carbon atoms, monoarylamino groups having 6 to 10 carbon atoms, and 12 carbon atoms may be substituted with one or more substituents selected from the group consisting of 20 diarylamino groups.)

(In the formula, Aa and Ab are the same as above. Ya ^- is the same or different and represents a halide ion or a sulfonic acid ion represented by R ¹ SO ₂ O ^- , and R ¹ is the same as above. are synonymous)
The halogen atom of Ya in general formula (2) is not particularly limited, but examples thereof include a chlorine atom, a bromine atom, and an iodine atom.

The definition and specific examples of each substituent shown for R ¹ in general formula (2) are the same as those shown for R ¹ in general formula (1).

The definitions and specific examples of each substituent shown for Aa in general formula (3a) and Ab in general formula (3b) are the same as those shown for A in general formula (1).

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

(In the formula, Aa, Ab, 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, an asymmetric diammonium salt (1a) of the present invention in which Aa and Ab are different 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.

The aliphatic compound (2) to be subjected to the reaction of Production Method 1 is one obtained by the production method described in Reference Example 1-4 and Reference Example 1-5 herein, one obtained by a known production method, or Commercially available products can be used, and known manufacturing methods include those disclosed in Tetrahedron, Vol. 71, pp. 6944-6955, 2005, Journal of the American Chemical Society, Vol. 129, pp. 13362-13363, 2007, etc. An example of this is a manufacturing method.

As the secondary amine (3a) and secondary amine (3b) used in the reaction of Production Method 1, known or commercially available ones can be used.

In the reaction of Production Method 1, the amount of secondary amine (3a) and secondary amine (3b) relative to aliphatic compound (2) is preferably 1 to 100 molar equivalents, and 1 to 10 molar equivalents each. Equivalent amounts are more preferred.

In the reaction of 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. one or more organic bases selected from the group trimethylamine, triethylamine, diisopropylethylamine, 1,4-diazabicyclo[2.2.2]octane and 1,8-diazabicyclo[5.4.0]undecene, on the one hand; Examples of the inorganic base include one or more selected from the group of sodium hydroxide, potassium hydroxide, sodium hydride, potassium hydride, sodium hydrogen carbonate, potassium hydrogen carbonate, sodium carbonate, potassium carbonate, and cesium carbonate. .

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

In addition, by using an excess amount of the secondary amine, for example, 2 equivalents or more, or even 5 equivalents or more relative to the aliphatic compound (2), the reaction of Production Method 1 can be changed to a reaction in the presence of a base. Good too.

For the secondary amine (3a) and secondary amine (3b) used in the reaction of Production Method 1, chemically acceptable salts may be used, and the reaction is preferably 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) can be reacted in a solvent. The solvent is preferably one that does not inhibit the reaction, such as aromatic hydrocarbon solvents, ether solvents, ester solvents, halogen solvents, amide solvents, urea solvents, ketone solvents, nitrile solvents, and sulfoxide solvents. , alcoholic solvents, and water.

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

In the reaction of Production Method 1, one or more preferred solvents are selected from the group of ether solvents, alcoholic solvents, and nitrile solvents, and more preferred solvents are one or more selected from the group of tetrahydrofuran, ethanol, and acetonitrile. , can be exemplified.

In the reaction of Production Method 1, a preferable reaction temperature is any temperature of 0° C. or more and 200° C. or less, a more preferable reaction temperature is 20° C. or more and 80° C., and a preferable reaction time is 1 hour or more and 100 hours or less. can.

Production method 1 involves the step of isolating the diammonium salt represented by general formula (1a) (hereinafter also referred to as "isolation step"), or ion exchange of this (or 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 represented by general formula (1a) can be isolated from the reaction mixture, and isolation methods include solvent extraction, column chromatography, preparative thin layer chromatography, Examples include one or more selected from the group of preparative liquid chromatography and recrystallization.

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

Ion exchange may be carried out by bringing the diammonium salt represented by general formula (1a) 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 IRN-78, Amberlite IRA-400, Amberlite IRA-402, Amberlite IRA-404, Amberlite IRA-900, Amberlite One or more selected from the group of Lite IRA-904, Amberlite IRA-458, Amberlite IRA-958, Amberlite IRA-420, Amberlite IRA-411 and Amberlite IRA-910, preferably Amberlite IRN. -78 or Amberlite IRA-400 are examples.

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. Examples of specific solvents include the same ones as those used in the reaction of Production Method 1 described 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 (4) and a sulfonic acid chloride represented by the general formula R ¹ SO ₂ Cl (in the formula, R ¹ is any one selected from the 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. , one or more substituents selected from the group consisting of 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. A method for producing a diammonium salt represented by the following general formula (1b) (hereinafter also referred to as "Production method 2"), characterized by having a step of reacting with a diammonium salt (which may be substituted with a group). ).

(In the formula, Z is the same or different and represents an alkylene group having 2 to 11 carbon atoms, and the alkylene group has 1 to 6 carbon atoms, which may be substituted with a halogen atom, a hydroxyl group, an oxo group, or a hydroxyl group. an alkyl group having 1 to 6 carbon atoms, an alkyl group having 1 to 6 carbon atoms which may be substituted with an alkoxy group having 1 to 6 carbon atoms, a haloalkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, and an alkyl group having 6 to 6 carbon atoms. 12 aryl group, an alkyl group having 7 to 13 carbon atoms, an aryloxy group having 6 to 10 carbon atoms, an alkyloxycarbonyl group having 1 to 6 carbon atoms, and a nitrogen atom substituted with an alkyl group having 1 to 4 carbon atoms. Acylamino group having 1 to 8 carbon atoms which may be optionally substituted, an aminocarbonyl group having 1 to 9 carbon atoms which may have the nitrogen atom substituted with one or more alkyl groups having 1 to 4 carbon atoms, and an alkyl group having 1 to 5 carbon atoms. Oxycarbonyloxy group, alkyloxycarbonylamino group having 1 to 5 carbon atoms which may be substituted with an alkyl group having 1 to 4 nitrogen atoms, one or more alkyl groups having 1 to 4 nitrogen atoms; One or more selected from the group consisting of an optionally substituted ureido group, 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. (May be substituted with a substituent.)

[In the formula, A is the same or different, and is a nitrogen-containing heterocycle having 3 to 20 carbon atoms, which may have a bridged ring or a condensed ring (the nitrogen-containing heterocycle is a halogen atom, a hydroxyl group, an oxo group) , an alkyl group having 1 to 6 carbon atoms which may be substituted with a hydroxyl group, an alkyl group having 1 to 6 carbon atoms which may be substituted with an alkoxy group having 1 to 6 carbon atoms, and a haloalkyl group having 1 to 6 carbon atoms. , alkoxy group having 1 to 6 carbon atoms, aryl group having 6 to 12 carbon atoms, aralkyl group having 7 to 13 carbon atoms, aryloxy group having 6 to 10 carbon atoms, alkyloxycarbonyl group having 1 to 6 carbon atoms, nitrogen Acylamino group having 1 to 8 carbon atoms, the atom of which may be substituted with an alkyl group having 1 to 4 carbon atoms; 1 carbon atom, which may have one or more nitrogen atoms substituted with an alkyl group having 1 to 4 carbon atoms; to 9 aminocarbonyl groups, C1 to C5 alkyloxycarbonyloxy groups, C1 to C5 alkyloxycarbonylamino groups in which the nitrogen atom may be substituted with C1 to C4 alkyl groups, nitrogen A ureido group in which an atom may be substituted with one or more alkyl groups having 1 to 4 carbon atoms, a dialkylamino group having 2 to 12 carbon atoms, a monoarylamino group having 6 to 10 carbon atoms, or a monoarylamino group having 12 to 20 carbon atoms. may have a diarylamino group).

Yb ^- is the same or different and represents a chloride ion or a sulfonic acid ion represented by R ¹ SO ₂ O ^- , and R ¹ is the same as above. ]
The above Z's are the same or different and represent an alkylene group having 2 to 11 carbon atoms, and the alkylene group is an alkyl group having 1 to 6 carbon atoms which may be substituted with a halogen atom, a hydroxyl group, an oxo group, or a hydroxyl group. group, an alkyl group having 1 to 6 carbon atoms which may be substituted with an alkoxy group having 1 to 6 carbon atoms, a haloalkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an alkoxy group having 6 to 6 carbon atoms, Aryl group, alkyl group having 7 to 13 carbon atoms, aryloxy group having 6 to 10 carbon atoms, alkyloxycarbonyl group having 1 to 6 carbon atoms, even if the nitrogen atom is substituted with an alkyl group having 1 to 4 carbon atoms. Acylamino group having 1 to 8 carbon atoms, aminocarbonyl group having 1 to 9 carbon atoms optionally having the nitrogen atom substituted with one or more alkyl groups having 1 to 4 carbon atoms, alkyloxycarbonyl having 1 to 5 carbon atoms An oxy group, an alkyloxycarbonylamino group having 1 to 5 carbon atoms, in which the nitrogen atom may be substituted with an alkyl group having 1 to 4 carbon atoms, and an alkyloxycarbonylamino group having one or more carbon atoms having 1 to 4 carbon atoms; one or more substituents selected from the group consisting of an optionally substituted ureido group, 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; may be substituted with.

The above alkylene group having 2 to 11 carbon atoms is not particularly limited, but includes, for example, ethylene group, 1,3-propylene group, 1,4-butene group, 1,5-pentene group, or 1, It can represent a 6-hexene group, etc.

Other substituents in Z (alkyl group having 1 to 6 carbon atoms which may be substituted with a hydroxyl group, alkyl group having 1 to 6 carbon atoms which may be substituted with an alkoxy group having 1 to 6 carbon atoms, carbon Haloalkyl group having 1 to 6 carbon atoms, alkoxy group having 1 to 6 carbon atoms, aryl group having 6 to 12 carbon atoms, aralkyl group having 7 to 13 carbon atoms, aryloxy group having 6 to 10 carbon atoms, 1 to 6 carbon atoms an alkyloxycarbonyl group, an acylamino group having 1 to 8 carbon atoms, the nitrogen atom of which may be substituted with an alkyl group having 1 to 4 carbon atoms, and an acylamino group having one or more carbon atoms having one or more carbon atoms, an aminocarbonyl group having 1 to 9 carbon atoms which may be substituted with an alkyl group having 1 to 5 carbon atoms; an alkyloxycarbonyloxy group having 1 to 5 carbon atoms which may be substituted with an alkyl group having 1 to 4 carbon atoms; Alkyloxycarbonylamino group, ureido group in which the nitrogen atom may be substituted with one or more alkyl groups having 1 to 4 carbon atoms, dialkylamino group having 2 to 12 carbon atoms, monoarylamino group having 6 to 10 carbon atoms , a diarylamino group having 12 to 20 carbon atoms) is the same as the definition of each substituent in ring A above.

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

(In the formula, Z, R ¹ , A and Yb ⁻ are the same as above.)
The diamine (4) to be subjected to the reaction in Production Method 2 can be obtained by the production method described in Reference Example 1-2 and Reference Example 1-3 in this specification, a diamine obtained by a known production method, or a commercially available diamine. Examples of known manufacturing methods include those disclosed in Tetrahedron, Vol. 74, pp. 1144-1150, 2018 and Synthesis, Vol. 1, pp. 79-86, 2008. can.

The sulfonic acid chloride used in the reaction of Production Method 2 may be any known or commercially available one.

In the reaction of Production Method 2, the amount of the sulfonic acid chloride relative to diamine (4) is preferably 2 to 10 molar equivalents, more preferably 2 to 5 molar equivalents.

In the reaction of Production Method 2, the diamine (4) and the sulfonic acid chloride represented by the general formula R ¹ SO ₂ Cl are preferably reacted in the presence of a base. Examples of the base include one or more selected from the group of organic bases, inorganic bases, and alkali metal alkoxides. Specific or preferred inorganic bases, the same as the bases in the reaction of Production Method 1, as the alkali metal alkoxides, one or more selected from the group of sodium methoxide, sodium ethoxide and potassium tert-butoxide, Each can be mentioned.

In the reaction of Production Method 2, the diamine (4) and the sulfonic acid chloride can be reacted in a solvent. The solvent is preferably one that does not inhibit the reaction, and includes aromatic hydrocarbon solvents, ether solvents, ester solvents, halogen solvents, amide solvents, urea solvents, ketone solvents, nitrile solvents, and Examples include one or more selected from the group of sulfoxide solvents.

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 a step of isolating a diammonium salt represented by general formula (1b), or a step of ion-exchanging this (or a diammonium salt represented by general formula (1b) after isolation). It may contain at least one of the following.

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 represented by the above general formula (1) can be obtained by ion exchange of the diammonium salt represented by the general formula (1b).

Ion exchange can be carried out by bringing the diammonium salt represented by general formula (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.

The diammonium salt of this embodiment can be applied to the uses of known ammonium salts, but is also suitable as an organic structure directing agent (hereinafter also referred to as "SDA") in the production of zeolite, and is particularly suitable for the production of small pore zeolite. Suitable as SDA in

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 the general formula (1), a silica source, an alumina source, an alkali source, and water. ) is a method for producing zeolite, characterized by comprising a crystallization step of crystallizing the zeolite.

The above crystallization step will be explained below.

In the method for producing zeolite of the present embodiment, the zeolite obtained is preferably a small pore zeolite, more preferably an AFX type zeolite. In the present embodiment, the AFX type zeolite is a zeolite having an AFX structure, and is a crystalline aluminosilicate 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 produced zeolite (preferably a crystalline aluminosilicate having an AFX structure) has aluminum (Al) and silicon (Si) as skeleton metals (hereinafter also referred to as "T atoms"), and T It has a skeletal structure consisting of a three-dimensional network structure in which atoms are bonded via oxygen (O). In this embodiment, zeolite analogs such as aluminophosphate and silicoaluminophosphate, which have a skeleton structure consisting of a network containing phosphorus (P) in the T atom, are different from crystalline aluminosilicate, which is a zeolite.

The diammonium salt represented by the general formula (1) above can be used as an SDA directed toward small pore zeolites, particularly AFX type zeolites.

The silica source is not particularly limited, but examples include silica (SiO ₂ ) or silicon compounds serving as its precursors, such as colloidal silica, amorphous silica, sodium silicate, and tetraethyl silica. At least one selected from the group of orthosilicate, precipitated silica, fumed silica, crystalline aluminosilicate, and aluminosilicate gel, and preferably at least one of crystalline aluminosilicate and aluminosilicate gel.

The alumina source is not particularly limited, but examples include alumina (Al ₂ O ₃ ) or aluminum compounds that are precursors thereof, such as aluminum sulfate, sodium aluminate, hydroxide, etc. At least one selected from the group of aluminum, aluminum chloride, aluminosilicate gel, crystalline aluminosilicate, and metal aluminum is mentioned, and among these, at least one of crystalline aluminosilicate and aluminosilicate gel is preferable.

The alkali source is not particularly limited, but includes, for example, alkali metal hydroxides or halides, selected from the group of sodium hydroxide, potassium hydroxide, rubidium hydroxide, and cesium hydroxide. It is preferably at least one type, and more preferably sodium hydroxide.

In this embodiment, the raw material composition preferably has any combination of molar composition ratios shown below.

_SiO2 / _Al2O3 : 5 or more, 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/ _SiO2 : 0.06 or more, 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 0.50 or less
More preferably 0.03 or more and 0.30 or less _H2O / _SiO2 : 5 or more and 60 or less,
Preferably 10 or more and 50 or less,
More preferably 15 or more and 40 or less In the above composition, SiO ₂ /Al ₂ O ₃ is the molar ratio of the silica source to the alumina source in the raw material composition, and OH/SiO ₂ , M/SiO ₂ , SDA/SiO ₂ and H ₂ O/SiO ₂ are hydroxide ions (mainly derived from an alkali source), alkali metals (mainly derived from an alkali source), and SDA (general formula (1)) relative to the silica source in the raw material composition, respectively. diammonium salt) or water.

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 seed crystals in the raw material composition is the weight ratio of the weight of silicon in the seed crystal converted to silica (SiO ₂ ) to the weight of silicon in the raw material composition converted to silica (SiO ₂ ). Examples of the content include 0% by weight or more and 10.0% by weight or less, further 0.5% by weight or more and 5.0% by weight or less, and further still 0.5% by weight or more and 3.5% by weight or less.

The seed crystal is preferably a zeolite that does not contain odd-numbered 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 more preferably a zeolite, more preferably a zeolite having any structure selected from the group of CHA, AEI, LEV, AFX and ERI, even more preferably an AFX type zeolite.

In this embodiment, the raw material composition is crystallized in the crystallization step, and specifically, the raw material composition may be crystallized by hydrothermal treatment. 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 the present embodiment may include a post-treatment process such as a washing process, a drying process, an SDA removal process, or an ammonium treatment process in addition to the crystallization process described above.

The above-mentioned washing step means a step of washing the zeolite after it has been separated from the liquid phase after the above-mentioned crystallization step. Although the cleaning method in the cleaning step is arbitrary, for example, the zeolite obtained by solid-liquid separation and recovery of the zeolite and the liquid phase may be brought into contact with a sufficient amount of pure water.

The drying step described above refers to a step of removing water from the zeolite after the washing step. Although the drying method in the drying step is arbitrary, for example, the zeolite may be treated in the atmosphere at 100° C. or more and 150° C. or less for 2 hours or more.

The SDA removal step means a step of removing SDA remaining in the zeolite.

As a method for removing SDA, for example, treatment may be carried out 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 means a step of removing alkali metal from the zeolite and changing the cation type to ammonium type (hereinafter referred to as "NH ₄ ⁺ type"). An example of the ammonium treatment method is to bring an aqueous solution containing ammonium ions into contact with zeolite. Note that the NH ₄ ⁺ type zeolite can also be made into a zeolite whose cation type is a proton type (hereinafter referred to as "H ⁺ type") by heat treatment. Specific conditions for the heat treatment include, for example, 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.

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.

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, 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, examples of the present invention will be shown. However, the present invention is not limited thereto.
(H ¹ -NMR)
H ¹ -NMR measurements of the samples were performed using Ascend ^TM AVANCE III HD (400 MHz, manufactured by Bruker) or UltraShield ^TM Plus AVANCE III (400 MHz, manufactured by Bruker). H ¹ -NMR of the sample was measured using deuterated chloroform (CDCl ₃ ) or deuterated dimethyl sulfoxide- _{d 6} (DMSO-d ₆ ) as a measurement solvent and tetramethylsilane (TMS) as an internal standard substance. Furthermore, when heavy water (D ₂ O) was used as the measurement solvent, the solvent signal was set to 4.70 ppm. 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).

In the formula, Me group represents a methyl group, Et represents an ethyl group, Ph represents a phenyl group, and Ms represents a methanesulfonyl group.

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

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 thereto, and the mixture was 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 1-1

1,2,4,5-tetrakis(methanesulfonyloxymethyl)cyclohexane (974 mg, 1.9 mmol) obtained in Reference Example 1-1, acetonitrile (7.0 mL) and pyrrolidine (0.65 mL, 7.9 mmol). and stirred at 85° C. for 15 hours in a sealed tube. The reaction solution was allowed to cool to room temperature, and then concentrated. Acetone was added to the obtained crude product, and the precipitated solid was collected by filtration. The obtained solid was washed with ethyl acetate, diethyl ether, and tetrahydrofuran. The obtained solid was passed through an anion exchange resin (Amberlite IRA-400 Cl ^- type (16 cm ³ , eluent: methanol) to perform ion exchange. The passed liquid was concentrated, and the obtained solid By washing with diethyl ether, tetrahydrofuran, ethyl acetate, and acetone, dispiro[pyrrolidine-1,2'-(1',2',3',4',5',6',7',8-decahydro Benzo[1,2-c:4,-c']dipyrrole)-6',1''-pyrrolidine]-5,11-diium dichloride (196 mg, yield 30%) was obtained as a white solid. As a result of analyzing the resulting compound using ion chromatography, the presence of chloride ions was confirmed.

Dispiro[pyrrolidine-1,2'-(1',2',3',4',5',6',7',8-decahydrobenzo[1,2-c:4,-c']dipyrrole )-6',1''-pyrrolidine]-5,11-diium dichloride NMR spectrum: ¹ H-NMR (400 MHz, D ₂ O) δ (ppm): 3.74 (dd, J = 11.8 , 7.7Hz, 4H), 3.51 (dd, J = 7.3, 7.1Hz, 4H), 3.40 (ddd, J = 7.3, 7.1Hz, 4H), 3.14 ( brdd, J=11.8, 10.4Hz, 4H), 2.64-2.45 (m, 4H), 2.19-2.02 (m, 8H), 1.89-1.80 (m , 2H), 1.30-1.18 (m, 2H).

Reference example 1-2
(Synthesis of N,N'-bis(4-acetoxybutyl)-1,2,4,5-cyclohexanetetracarboxylic acid diimide)

To a suspension of 1,2,4,5-cyclohexanetetracarboxylic dianhydride (6.99 g, 31.2 mmol) and acetic acid (63 mL), 5-amino-1-butanol (6.5 mL, 70 mmol) was added. The mixture was stirred under heating and reflux for 19 hours. After the reaction, the reaction solution was allowed to cool to room temperature, water (180 mL) was added, and the aqueous layer was extracted with ethyl acetate (340 mL). The organic layer was washed with a saturated aqueous sodium bicarbonate solution (250 mL x 2), dried over sodium sulfate, and concentrated to give N,N'-bis(4-acetoxybutyl)-1,2,4 as a pale yellow solid. , 5-cyclohexanetetracarboxylic acid diimide (8.94 g, yield 64%) was obtained.

NMR spectrum of N,N'-bis(4-acetoxybutyl)-1,2,4,5-cyclohexanetetracarboxylic acid diimide: ¹ H-NMR (400 MHz, CDCl ₃ ) δ (ppm): 4.05 (t , J=5.7Hz, 4H), 3.51 (t, J=6.7Hz, 4H), 2.98 to 2.86 (m, 4H), 2.71 to 2.57 (m, 2H) , 2.03 (s, 6H), 1.69-1.39 (m, 4H).
(Synthesis of 5,11-bis(4-acetoxybutyl)-5,11-diazatricyclo[7.3.0.0 ^3,7 ]dodecane)

To a suspension of lithium hydride (4.53 g, 119 mmol) and tetrahydrofuran (150 mL) was added N,N'-bis(4-acetoxybutyl)-1,2,4,5-cyclohexanetetracarboxylic acid diimide (8. A solution of 94 g, 19.8 mmol) in tetrahydrofuran (70 mL) was added under an ice bath, and the mixture was stirred at 60° C. for 14 hours. After the reaction, the reaction solution was cooled in an ice bath, and water (4.6 mL), 15% aqueous sodium hydroxide solution (4.6 mL), and water (13.3 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-bis(4-acetoxybutyl)- as a yellow oil. 5,11-diazatricyclo[7.3.0.0 ^3,7 ]dodecane (6.84 g, yield >99%) was obtained.
NMR spectrum of 5,11-bis(4-acetoxybutyl)-5,11-diazatricyclo[7.3.0.0 ^3,7 ]dodecane: ¹ H-NMR (400 MHz, CDCl ₃ ) δ (ppm): 3 .60-3.52 (m, 4H), 2.92-2.79 (m, 4H), 2.46-2.36 (m, 4H), 2.20-2.05 (m, 8H) , 1.72-1.51 (m, 12H), 1.30-1.13 (m, 2H).

Example 1-2

5,11-bis(4-acetoxybutyl)-5,11-diazatricyclo[7.3.0.0 ^3,7 ]dodecane (6.84 g, 22.0 mmol) obtained in Reference Example 1-2, triethylamine ( 8.0 mL, 57.4 mmol) and 1,4-diazabicyclo[2.2.2]octane (0.27 g, 2.37 mmol) in dichloromethane (220 mL), p-toluenesulfonyl chloride (9.27 g, 48 .6 mmol) was added under ice cooling. After stirring at room temperature for 14.5 hours, the precipitated solid was collected by filtration and washed with chloroform to obtain a white solid. The obtained solid was dissolved in methanol (100 mL), an anion exchange resin (Amberlite IRA-400 ^Cl type, 250 cm ³ ) was added, and the mixture was stirred at room temperature for 115 hours. The reaction mixture was filtered, the filtrate was concentrated, and the resulting solid was washed with acetone to obtain a white solid dispiro[pyrrolidine-1,2'-{1',2',3',4',5 ',6',7',8-decahydrobenzo[1,2-c:4,-c']dipyrrole}-6',1''-pyrrolidine]-5,11-diium dichloride (4.18 g , yield 55%). As a result of analyzing the obtained compound using ion chromatography, the presence of chloride ions was confirmed.

Dispiro[pyrrolidine-1,2'-{1',2',3',4',5',6',7',8-decahydrobenzo[1,2-c:4,-c']dipyrrole }-6',1''-pyrrolidine]-5,11-dium dichloride NMR spectrum: ¹ H-NMR (400 MHz, D ₂ O) δ (ppm): 3.74 (dd, J = 11.8 , 7.7Hz, 4H), 3.51 (dd, J = 7.3, 7.1Hz, 4H), 3.40 (ddd, J = 7.3, 7.1Hz, 4H), 3.14 ( brdd, J=11.8, 10.4Hz, 4H), 2.64-2.45 (m, 4H), 2.19-2.02 (m, 8H), 1.89-1.80 (m , 2H), 1.30-1.18 (m, 2H).

Reference example 1-3
(Synthesis of 1,2,4,5-tetrakis(chloromethyl)cyclohexane)

1,2,4,5-tetrakis(hydroxymethyl)cyclohexane (0.21 g, 1.0 mmol) obtained in Reference Example 1-1 and toluene (0.36 mL) were added, and the mixture was stirred in an ice bath. Pyridine (0.40 mL, 5.0 mmol) and thionyl chloride (0.36 mL, 4.99 mmol) were added, heated at 70° C. for 6 hours, and then cooled in an ice bath. The solid precipitated in the reaction solution was filtered off, and the filtrate was concentrated and then suspended in hexane. The solid was filtered off again, the filtrate was concentrated, and the resulting crude product was purified by column chromatography (eluent: hexane-ethyl acetate) to produce 1,2,4,5-tetrakis (chloromethyl ) Cyclohexane (55.8 mg, 20%) was obtained as a white solid.

NMR spectrum of 1,2,4,5-tetrakis(chloromethyl)cyclohexane: ¹ H-NMR (400 MHz, CDCl ₃ ) δ (ppm): 3.63 (dd, J = 11.2, 6.7 Hz, 4H ), 3.45 (dd, J=11.3, 7.8Hz, 4H), 2.30 to 2.18 (m, 4H), 1.86 to 1.71 (m, 4H).

Example 1-3

1,2,4,5-tetrakis(chloromethyl)cyclohexane (210 mg, 0.76 mmol) obtained in Reference Example 1-3, a mixture of ethanol:tetrahydrofuran (1:1) (1.0 mL), sodium iodide (114 mg, 0.76 mmol) and 3-(diethylamino)pyrrolidine (0.50 mL, 3.17 mmol) were added and stirred in a sealed tube at 70° C. for 16 hours. The reaction solution was allowed to cool to room temperature and then concentrated. Chloroform was added to the residue, the precipitated solid was filtered off, and the filtrate was concentrated. Ice-cooled acetone was added to the obtained crude product, and the precipitated solid was collected by filtration and washed with acetonitrile. The obtained solid was dissolved in methanol, an anion exchange resin (Amberlite IRA-400 Cl ^- type, 3.2 cm ³ ) was added, and the mixture was stirred at room temperature for 3 hours. By removing the anion exchange resin by filtration and concentrating the filtrate under reduced pressure, 3,3''-bis(diethylamino)dispiro[pyrrolidine-1,2'-(1',2',3',4',5',6',7',8'-decahydrobenzo[1,2-c:4,-c']dipyrrole)-6',1''-pyrrolidine]-5,11-diium dichloride ( 18.2 mg, yield 5%) was obtained as a white solid. As a result of analyzing the obtained compound using ion chromatography, the presence of chloride ions was confirmed.

3,3''-bis(diethylamino)dispiro[pyrrolidine-1,2'-(1',2',3',4',5',6',7',8'-decahydrobenzo[1, NMR spectrum of 2-c:4,-c']dipyrrole)-6',1''-pyrrolidine]-5,11-diium dichloride: ¹ H-NMR (400 MHz, D ₂ O) δ (ppm): 4.00-3.87 (m, 4H), 3.87-3.52 (m, 10H), 3.44-3.13 (m, 4H), 2.74-2.54 (m, 12H) ), 2.53-2.35 (m, 2H), 2.23-2.09 (m, 2H), 2.03-1.90 (m, 2H), 1.41-1.26 (m , 2H), 0.94 (t, J = 7.2Hz, 12H).

Example 1-4

1,2,4,5-tetrakis(chloromethyl)cyclohexane (168 mg, 0.60 mmol), ethanol:tetrahydrofuran (1:1) mixture (1.0 mL), sodium iodide (90.3 mg, 0.60 mmol) and piperidine (0.25 mL, 2.52 mmol) were added, and the mixture was stirred at 70° C. for 16 hours in a sealed tube. The reaction solution was allowed to cool to room temperature and then concentrated. Chloroform was added to the residue, and the precipitated solid was collected by filtration and washed with acetonitrile. The obtained crude product was dissolved in methanol, an anion exchange resin (Amberlite IRA-400 Cl ^- type, 3.7 cm ³ ) was added, and the mixture was stirred at room temperature for 3 hours. By filtering the reaction mixture and concentrating the filtrate under reduced pressure, dispiro[piperidine-1,2'-{1',2',3',4',5',6',7', 8-decahydrobenzo[1,2-c:4,-c']dipyrrole}-6',1''-piperidine]-5,11-diium dichloride (48.2 mg, yield 21%) in white Obtained as a solid. As a result of analyzing the obtained compound using ion chromatography, the presence of chloride ions was confirmed.

Dispiro[piperidine-1,2'-(1',2',3',4',5',6',7',8-decahydrobenzo[1,2-c:4,-c']dipyrrole )-6',1''-piperidine]-5,11-diium dichloride NMR spectrum: ¹ H-NMR (400 MHz, D ₂ O) δ (ppm): 4.04 (dd, J = 12,2 , 7.2Hz, 4H), 3.41 (dd, J = 5.7, 5.7Hz, 4H), 3.36 (dd, J = 5.7, 5.7Hz, 4H), 3.05 ( dd, J=12.2, 11.8Hz, 4H), 2.69-2.54 (m, 4H), 1.99-1.81 (m, 10H), 1.73-1.63 (m , 4H), 1.36-1.24 (m, 2H).

Example 1-5

Add 1,2,4,5-tetrakis(methanesulfonyloxymethyl)cyclohexane (337 mg, 0.66 mmol), acetonitrile (1.0 mL), and 4-methylpiperidine (0.34 mL, 2.77 mmol), and seal. The mixture was stirred in the tube at 90°C for 16 hours. After cooling the reaction solution to room temperature, ice-cooling and adding ice-cooled acetone to collect the precipitated solid by filtration gave dispiro[4-methylpiperidine-1,2'-(1',2', 3',4',5',6',7',8-decahydrobenzo[1,2-c:4,-c']dipyrrole)-6',1''-4-methylpiperidine]-5 , 11-diium bismethane sulfonate (105 mg, yield 30%) was obtained as a white solid.

Dispiro[4-methylpiperidine-1,2'-(1',2',3',4',5',6',7',8-decahydrobenzo[1,2-c:4,-c ']dipyrrole)-6',1''-4-methylpiperidine]-5,11-diium bismethane sulfonate NMR spectrum: ¹ H-NMR (400 MHz, D ₂ O) δ (ppm): 4.17 ~4.09 (m, 2H), 3.75 ~ 3.65 (m, 2H), 3.50 ~ 3.35 (m, 4H), 3.28 ~ 3.20 (m, 2H), 3 .15 to 3.03 (m, 4H), 2.79 (dd, J=10.4, 10.4Hz, 2H), 2.70 (s, 6H), 2.60 to 2.40 (m, 4H), 1.88-1.73 (m, 6H), 1.72-1.58 (m, 2H), 1.56-1.37 (m, 4H), 1.26-1.10 ( m, 2H), 0.90 (d, J=6.5Hz, 6H).

Example 1-6

Dispiro[4-methylpiperidine-1,2'-(1',2',3',4',5',6',7',8-decahydrobenzo[1,2-c:4,-c ']Dipyrrole)-6',1''-4-methylpiperidine]-5,11-diium bismethane sulfonate (105 mg, 0.20 mmol) was dissolved in methanol, and Amberlite IRA-400 Cl ^- type (1. 8 cm ³ ) and stirred at room temperature for 3 hours. By filtering the reaction mixture and concentrating the filtrate under reduced pressure, dispiro[4-methylpiperidine-1,2'-(1',2',3',4',5',6',7',8 -decahydrobenzo[1,2-c:4,-c']dipyrrole)-6',1''-4-methylpiperidine]-5,11-diium dichloride (80.2 mg, yield 86%) was obtained as a white solid. As a result of analyzing the obtained compound using ion chromatography, the presence of chloride ions was confirmed.

Dispiro[4-methylpiperidine-1,2'-(1',2',3',4',5',6',7',8-decahydrobenzo[1,2-c:4,-c ']dipyrrole)-6',1''-4-methylpiperidine]-5,11-diium dichloride NMR spectrum: ¹ H-NMR (400MHz, D ₂ O) δ (ppm): 4.17 to 4 .09 (m, 2H), 3.75-3.65 (m, 2H), 3.50-3.35 (m, 4H), 3.28-3.20 (m, 2H), 3.15 ~3.03 (m, 4H), 2.79 (dd, J=11.1, 11.1Hz, 2H), 2.60 ~ 2.40 (m, 4H), 1.88 ~ 1.73 ( m, 6H), 1.72 to 1.58 (m, 2H), 1.56 to 1.37 (m, 4H), 1.26 to 1.10 (m, 2H), 0.90 (d, J=6.5Hz, 6H).

Example 1-7

1,2,4,5-tetrakis(methanesulfonyloxymethyl)cyclohexane (318 mg, 0.62 mmol), acetonitrile (1.0 mL), and 4-phenylpiperidine (451 mg, 2.80 mmol) were placed in a sealed tube. Stirred at ℃ for 16 hours. After the reaction solution was allowed to cool to room temperature, ice-cooled acetone was added thereto, and the precipitated solid was collected by filtration. By washing the obtained solid with diethyl ether, dispiro[4-phenylpiperidine-1,2'-(1',2',3',4',5',6',7',8-deca Hydrobenzo[1,2-c:4,-c']dipyrrole)-6',1''-4-phenylpiperidine]-5,11-diium bismethanesulfonate (85.2 mg, yield 21%) was obtained as a white solid.

Dispiro[4-phenylpiperidine-1,2'-(1',2',3',4',5',6',7',8-decahydrobenzo[1,2-c:4,-c ']dipyrrole)-6',1''-4-phenylpiperidine]-5,11-diium bismethane sulfonate NMR spectrum: ¹ H-NMR (400 MHz, D ₂ O) δ (ppm): 7.37 ~7.20 (m, 10H), 4.40 ~ 4.28 (m, 2H), 3.86 ~ 3.75 (m, 2H), 3.71 ~ 3.57 (m, 4H), 3 .48-3.37 (m, 2H), 3.35-3.16 (m, 4H), 2.97-2.80 (m, 4H), 2.71 (s, 6H), 2.67 ~2.48 (m, 4H), 2.11 ~ 1.95 (m, 8H), 1.94 ~ 1.88 (m, 2H), 1.35 ~ 1.18 (m, 2H).

Example 1-8

Dispiro[4-phenylpiperidine-1,2'-(1',2',3',4',5',6',7',8-decahydrobenzo[1,2-c:4,-c ']Dipyrrole)-6',1''-4-phenylpiperidine]-5,11-diium bismethane sulfonate (85.2 mg, 0.13 mmol) was dissolved in methanol, and Amberlite IRA-400 Cl ^- type ( 2.2 cm ³ ) and stirred at room temperature for 3 hours. The reaction mixture was filtered, and the filtrate was concentrated under reduced pressure. By washing the obtained solid with chloroform, dispiro[4-phenylpiperidine-1,2'-(1',2',3',4',5',6',7',8-decahydro benzo[1,2-c:4,-c']dipyrrole)-6',1''-4-phenylpiperidine]-5,11-diium dichloride (40.0 mg, yield 12%) as a white solid. obtained as. As a result of analyzing the obtained compound using ion chromatography, the presence of chloride ions was confirmed.

Dispiro[4-phenylpiperidine-1,2'-(1',2',3',4',5',6',7',8-decahydrobenzo[1,2-c:4,-c ']dipyrrole)-6',1''-4-phenylpiperidine]-5,11-diium dichloride NMR spectrum: ¹ H-NMR (400MHz, D ₂ O) δ (ppm): 7.37-7 .20 (m, 10H), 4.40-4.28 (m, 2H), 3.86-3.75 (m, 2H), 3.71-3.57 (m, 4H), 3.48 -3.37 (m, 2H), 3.35-3.16 (m, 4H), 2.97-2.80 (m, 4H), 2.67-2.48 (m, 4H), 2 .11-1.95 (m, 8H), 1.94-1.88 (m, 2H), 1.35-1.18 (m, 2H).

Example 1-9

Dispiro[pyrrolidine-1,2'-{1',2',3',4',5',6',7',8-decahydrobenzo[1,2-c:4,-c']dipyrrole }-6',1''-pyrrolidine]-5,11-diium dichloride (54.8 mg, 0.156 mmol) was filled in an anion exchange resin (Amberlite IRN78 OH ^- type, 7.9 cm ³ ). Dispiro[pyrrolidine-1,2'-{1',2',3',4',5',6',7',8-decahydrobenzo[1,2-c:4, -c']dipyrrole}-6',1''-pyrrolidine]-5,11-diium dihydroxide 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%.

Dispiro[pyrrolidine-1,2'-{1',2',3',4',5',6',7',8-decahydrobenzo[1,2-c:4,-c']dipyrrole NMR spectrum of aqueous solution of }-6',1''-pyrrolidine]-5,11-dium dihydroxide: ¹ H-NMR (400 MHz, D ₂ O) δ (ppm): 3.74 (dd, J= 11.8, 7.7Hz, 4H), 3.51 (dd, J=7.2, 7.2Hz, 4H), 3.40 (dd, J=7.2, 7.2Hz, 4H), 3 .14 (dd, J=11.8, 10.4Hz, 4H), 2.62-2.45 (m, 4H), 2.18-2.02 (m, 8H), 1.88-1. 79 (m, 2H), 1.29-1.18 (m, 2H).

Example 1-10

1,2,4,5-tetrakis(methanesulfonyloxymethyl)cyclohexane (336 mg), acetonitrile (1.0 mL) and methyl 4-piperidinecarboxylate (0.36 mL, 2.6 mmol) were added, and the mixture was heated at 90°C in a sealed tube. The mixture was stirred 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. After washing the obtained solid with ethyl acetate, dissolving it in methanol and washing with activated carbon, 4,4''-bis(methoxycarbonyl)dispiro[piperidine-1,2'-{1',2',3 ',4',5',6',7',8-decahydrobenzo[1,2-c:4,-c']dipyrrole}-6',1''piperidine]-5,11-diium= Dichloride (174 mg, 56% yield) was obtained as a white solid. As a result of analyzing the obtained compound using ion chromatography, the presence of chloride ions was confirmed.

4,4''-bis(methoxycarbonyl)dispiro[piperidine-1,2'-{1',2',3',4',5',6',7',8-decahydrobenzo[1, NMR spectrum of 2-c:4,-c']dipyrrole}-6',1''piperidine]-5,11-diium dichloride: ¹ H-NMR (400 MHz, D ₂ O) δ (ppm): 4 .18 (m, 1H), 3.91 (m, 1H), 3.78-3.69 (m, 8H), 3.66-3.37 (m, 6H), 3.35-3.16 (m, 2H), 3.13-2.94 (m, 4H), 2.89-2.74 (m, 2H), 2.70-2.54 (m, 2H), 2.27-1 .80 (m, 13H), 1.30 (m, 1H).

Example 1-11

1,2,4,5-tetrakis(chloromethyl)cyclohexane (83.0 mg, 0.30 mmol), ethanol:tetrahydrofuran mixed solution (0.50 mL, 1:1), sodium iodide (45.0 mg, 0.30 mmol) ) and hexamethyleneimine (0.14 mL, 1.24 mmol) were added, and the mixture was stirred at 70° C. for 18 hours in a sealed tube. The reaction solution was allowed to cool to room temperature and then concentrated. Chloroform was added to the residue, and the precipitated solid was collected by filtration. The obtained solid was dissolved in methanol, an anion exchange resin (Amberlite IRA-400 Cl ^- type, 1.5 cm ³ ) was added, and the mixture was stirred at room temperature for 3 hours. By removing the anion exchange resin by filtration and concentrating the filtrate under reduced pressure, dispiro[azepane-1,2'-{1',2',3',4',5',6',7', 8-decahydrobenzo[1,2-c:4,-c']dipyrrole}-6',1''-azepane]-5,11-diium dichloride (5.3 mg, yield 4%) in white Obtained as a solid. As a result of analyzing the obtained compound using ion chromatography, the presence of chloride ions was confirmed.

Dispiro[azepane-1,2'-{1',2',3',4',5',6',7',8-decahydrobenzo[1,2-c:4,-c']dipyrrole }-6',1''-azepane]-5,11-diium dichloride NMR spectrum: ¹ H-NMR (400 MHz, D ₂ O) δ (ppm): 3.98 (dd, J = 12.2 , 7.1Hz, 4H), 3.58 to 3.48 (m, 4H), 3.48 to 3.43 (m, 4H), 3.07 (dd, J=11.4, 10.4Hz, 4H), 2.69-2.52 (m, 4H), 1.98-1.79 (m, 10H), 1.78-1.63 (m, 8H), 1.36-1.23 ( m, 2H).

(Synthesis of AFX type zeolite)
Example 2-1
Dispiro[pyrrolidine-1,2'-(1',2',3',5',6',7'-hexahydrobenzo[1,2-c:4,5 -c']dipyrrolium)-6',1''-pyrrolidine]=dichloride as a structure directing agent (SDA), 48% NaOH and Y-type zeolite (trade name: HSZ-350HUA, manufactured by Tosoh, silica and alkali source) were mixed 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 = 0.10
_H2O / _SiO2 = 25
A seed crystal AFX type zeolite was added to the composition so that the seed crystal content of the composition was 3.0% by weight, and then the mixture 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, and the SiO ₂ /Al ₂ O ₃ was 10.9.

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,
The two A's are the same or different, and are a nitrogen-containing heterocycle having 3 to 5 carbon atoms that may have a bridged ring or a condensed ring (the nitrogen-containing heterocycle has a halogen atom or a hydroxyl group) ).
Y ⁻ is the same or different and represents a halide ion or OH ⁻ (hydroxide ion). ] The diammonium salt according to claim 1, wherein Y ^- is the same or different and is a chloride ion, bromide ion, iodide ion or OH ^- (hydroxide ion). The diammonium salt according to claim 1 or 2 , wherein the two A's are the same and are nitrogen-containing heterocycles having 4 to 5 carbon atoms which may have a bridged ring or a condensed ring. Two A's are the same and are nitrogen- containing heterocycles having 4 to 5 carbon atoms, and Y ^- is the same or different and is a chloride ion, bromide ion, or OH ^- (hydroxide ion) ) The diammonium salt according to any one of claims 1 to 3 . A method for producing zeolite, comprising a crystallization step of crystallizing a composition containing a diammonium salt according to any one of claims 1 to 3 , a silica source, an alumina source, an alkali source, and water. The method for producing zeolite according to claim 5 , wherein the zeolite is an AFX type zeolite.