JP2021109856A - Diammonium salt having cyclic structure and use of the same - Google Patents

Abstract

To provide a novel diammonium salt and to provide a method for producing zeolite using a diammonium salt, preferably small-pore zeolite and more preferably AFX-Type zeolite.SOLUTION: There is provided a diammonium salt represented by the general formula (1). [In the formula, two As represent a nitrogen-containing heterocyclic ring having 3 to 20 carbon atoms which may be the same or different and have a crosslinked ring or a condensed ring; Y-s are the same or different and represent a halide ion, a sulfonate ion represented by R1SO2O-, a carboxylate ion represented by R2COO- or OH- (a hydroxide ion); R1 represents an alkyl group having 1 to 9 carbon atoms, a fluoroalkyl group having 1 to 9 carbon atoms or a phenyl group and R2 represents an alkyl group having 1 to 6 carbon atoms, a fluoroalkyl group having 1 to 4 carbon atoms or a phenyl group.]SELECTED DRAWING: None

Description

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

Zeolites are produced by crystallization of compositions containing various organic structure directional agents (hereinafter, also referred to as “SDA”). To produce a zeolite having an 8-membered ring formed of T (T is silicon, aluminum, phosphorus, gallium, titanium, etc.) and oxygen atoms as the maximum pores (hereinafter, also referred to as "small pore zeolite"). As known organic structure-directing agents, adamantylammonium derivatives, tetraalkylammonium cations, quinuclidine derivatives and the like are known (Patent Documents 1 to 3), but tricyclo [7.3.0.0], which is a diammonium salt, is known. ^3,7 ] There is no example of using dodecane-5,11-diazanium salt as an organic structure directing agent for zeolite production.

U.S. Pat. No. 4,544,538 U.S. Pat. No. 4,495,303 U.S. Pat. No. 4,508,837

An object of the present invention is to provide a novel diammonium salt. Furthermore, another object of the present invention is to provide a method for producing a zeolite using a diammonium salt, preferably a small pore zeolite, more preferably an AFX type zeolite.

As a result of diligent studies to solve the above problems, the present inventors have found a diammonium salt represented by the following general formula (1) and have completed the present invention. Furthermore, they have 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] A diammonium salt represented by the general formula (1).

[During the ceremony,
The two A's are the same or different from each other and may have a crosslinked ring or a condensed ring. A nitrogen-containing heterocycle having 3 to 20 carbon atoms (the nitrogen-containing heterocycle is a halogen atom, a hydroxyl group, an oxo group, a hydroxyl group). Alkyl groups having 1 to 6 carbon atoms which may be substituted with, alkyl groups having 1 to 6 carbon atoms which may be substituted with alkoxy groups having 1 to 6 carbon atoms, haloalkyl groups having 1 to 6 carbon atoms, carbons. Alkyl groups with numbers 1 to 6, aryl groups with 6 to 12 carbon atoms, aralkyl groups with 7 to 13 carbon atoms, aryloxy groups with 6 to 10 carbon atoms, alkyloxycarbonyl groups with 1 to 6 carbon atoms, and nitrogen atoms. An acylamino group having 1 to 8 carbon atoms which may be substituted with an alkyl group having 1 to 4 carbon atoms and a nitrogen atom may be substituted with one or more alkyl groups having 1 to 4 carbon atoms. Aminocarbonyl group, alkyloxycarbonyloxy group having 1 to 5 carbon atoms, 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, nitrogen atom A ureido group which 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 diarylamino having 12 to 20 carbon atoms. It may have a group.)
Y ⁻ represents the same or differently, a halide ion, a sulfonic acid ion represented by ^{R 1} SO ₂ O ⁻ , a carboxylic acid ion represented by ^{R 2} COO ^{− , or an 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, It may be substituted with one or more substituents selected from the group of an alkoxy group having 1 to 4 carbon atoms, a fluoroalkyl group having 1 to 4 carbon atoms, a halogen atom, a cyano group and a nitro group). ..
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 may have a crosslinked ring or a condensed ring. A nitrogen-containing heterocycle having 3 to 20 carbon atoms (the nitrogen-containing heterocycle is a halogen atom, a hydroxyl group, or 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. , Aalkyl group with 1 to 6 carbon atoms, aryl group with 6 to 12 carbon atoms, aralkyl group with 7 to 13 carbon atoms, aryloxy group with 6 to 10 carbon atoms, alkyloxycarbonyl group with 1 to 6 carbon atoms, nitrogen The atom may be substituted with an alkyl group having 1 to 4 carbon atoms. The acylamino group having 1 to 8 carbon atoms may be substituted. The nitrogen atom may be substituted with one or more alkyl groups having 1 to 4 carbon atoms. To 9 aminocarbonyl groups, 1 to 5 carbon number alkyloxycarbonyloxy groups, nitrogen atoms may be substituted with 1 to 4 carbon number alkyl groups 1 to 5 carbon number alkyloxycarbonylamino groups, nitrogen A ureido group in which one or more atoms 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, chloride ion, bromide ion, iodide ion, C ₆ H ₅ SO ₂ O ⁻ (benzene sulfonate ion), p-CH ₃ C ₆ H ₄ SO ₂ O. ⁻ (Paratoluene sulfonic acid ion), CH ₃ SO ₂ O ⁻ (methanel sulfonate ion), CF ₃ SO ₂ O ⁻ (trifluoromethane sulfonate ion) or OH ⁻ (hydroxide ion) [1] Or the diammonium salt according to [2].
[4] Two A's are the same and may have a crosslinked ring or a condensed ring. A nitrogen-containing heterocycle having 4 to 20 carbon atoms (the nitrogen-containing heterocycle is an alkoxy having 1 to 6 carbon atoms). Alkyl groups having 1 to 6 carbon atoms, fluoroalkyl groups having 1 to 6 carbon atoms, alkoxy groups having 1 to 6 carbon atoms, aryl groups having 6 to 12 carbon atoms, and 7 to 13 carbon atoms which may be substituted with groups. Aralkyl group, aryloxy group having 6 to 10 carbon atoms, alkyloxycarbonyl group having 1 to 6 carbon atoms, and 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. A group, an aminocarbonyl group having 1 to 9 carbon atoms, a dialkylamino group having 2 to 12 carbon atoms, or a diaryl having 12 to 20 carbon atoms, in which one or more of the nitrogen atoms may be substituted with an alkyl group having 1 to 4 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 may have a crosslinked ring or a condensed ring. A nitrogen-containing heterocycle having 4 to 6 carbon atoms (the nitrogen-containing heterocycle is an alkyl having 1 to 4 carbon atoms). It has a 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 diammonate salt according to any one of [1] to [4].
[6] Two A's are the same, and 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 alkoxy group having 1 to 6 carbon atoms, and carbon. It may have an aryl group of number 6 to 12 or a dialkylamino group of carbon number 2 to 8), and Y ⁻ is the same or different, chloride ion, bromide ion or OH. ^- diammonium salt according to any one of a (hydroxide ion) [1] to [5].
[7] It is characterized by having a crystallization step of crystallizing a composition containing the diammonate salt, silica source, alumina source, alkali source and water according to any one of [1] to [6]. Method for producing zeolite.
[8] The method for producing a zeolite according to [7], wherein the zeolite is a small pore zeolite.
[9] The method for producing a zeolite according to [7] or [8], wherein the zeolite is an AFX-type zeolite.

INDUSTRIAL APPLICABILITY According to the present invention, a novel diammonium salt can be provided. Furthermore, according to the present invention, it is possible to provide a method for producing a zeolite using the diammonium salt, preferably a small pore zeolite, more preferably an AFX type zeolite.

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 with reference to an example of an embodiment.

^{First, the definitions of A and Y −} in the diammonium salt represented by the general formula (1) will be described in detail.

The two A's are the same or different from each other and may have a crosslinked ring or a condensed ring. A nitrogen-containing heterocycle having 3 to 20 carbon atoms (the nitrogen-containing heterocycle is a halogen atom, a hydroxyl group, an oxo group, a hydroxyl group). Alkyl groups having 1 to 6 carbon atoms which may be substituted with, alkyl groups having 1 to 6 carbon atoms which may be substituted with alkoxy groups having 1 to 6 carbon atoms, haloalkyl groups having 1 to 6 carbon atoms, carbons. Alkyl groups with numbers 1 to 6, aryl groups with 6 to 12 carbon atoms, aralkyl groups with 7 to 13 carbon atoms, aryloxy groups with 6 to 10 carbon atoms, alkyloxycarbonyl groups with 1 to 6 carbon atoms, and nitrogen atoms. An acylamino group having 1 to 8 carbon atoms which may be substituted with an alkyl group having 1 to 4 carbon atoms and a nitrogen atom may be substituted with one or more alkyl groups having 1 to 4 carbon atoms. Aminocarbonyl group, alkyloxycarbonyloxy group having 1 to 5 carbon atoms, 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, nitrogen atom A ureido group which 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 diarylamino having 12 to 20 carbon atoms. It may have a group.)

Regarding the nitrogen-containing heterocycle having a crosslinked ring and having 3 to 20 carbon atoms, the number of carbon atoms in the crosslinked structure is not limited, and for example, a crosslinked structure having 1, 2, or 3 carbon atoms can be exemplified. The carbon number of the crosslinked portion of the nitrogen-containing heterocycle having the crosslinked ring having 3 to 20 carbon atoms shall be a part of the carbon number of the nitrogen-containing heterocycle.

Further, regarding the nitrogen-containing heterocycle having a condensed ring and having 3 to 20 carbon atoms, the number of condensed rings is not limited, and as the nitrogen-containing heterocycle, a bicyclic, tricyclic or tetracyclic ring can be exemplified. The sum of all the carbons of these condensed ring structures corresponds to the above-mentioned carbon number 3 to 20.

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

The nitrogen-containing heterocycle having 3 to 20 carbon atoms which may have a crosslinked ring or a condensed ring is not particularly limited, and is, for example, a pyrrolidine ring, an imidazolidine ring, an indolin ring, an isoindoline ring, and a morpholine. Examples thereof 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, a decahydroquinoline ring, and the like.

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

The alkoxy group having 1 to 6 carbon atoms includes a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, a butoxy group, a 2-methylpropoxy group, a 2,2-dimethylpropoxy group, a 3-cyclopropylpropoxy group and a cyclopropoxy. 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 -Ethylpropoxy group, cyclopentyloxy group, hexyloxy group or cyclohexyloxy group can be exemplified.

As alkyl groups having 1 to 6 carbon atoms, 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-Methylbutane-2-yl group, tert-butyl group, Cyclobutyl group, Pentyl group, 2-Methyl Examples thereof include a pentyl group, a 3-methylpentyl group, a 1-methylbutyl group, a 2-methylpentane-2-yl group, a 2-ethylpropyl group, a cyclopentyl group, a 1-methylpentyl group, a 2-ethylbutyl group or a cyclohexyl group.

The haloalkyl group having 1 to 6 carbon atoms includes a trifluoromethyl group, a difluoromethyl group, a perfluoroethyl group, a 2,2,2-trifluoroethyl group, a 1,1-difluoroethyl group, and a 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, 3,3,4,5,4-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, 2,2,3,3,4,5-hexafluorocyclobutyl group, perfluoropentyl group, 2,2,3,3,4,5,5,5-nonafluoropentyl group, 3, 3,4,5,5,5,5-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 , 3,3,4,5,5,6,6,6-undecafluorohexyl group, 3,3,4,5,5,6,6,6-nonafluorohexyl group, 4, Examples thereof include 4,5,5,6,6,6-heptafluorohexyl group, 5,5,6,6,6-pentafluorohexyl group, 6,6,6-trifluorohexyl group, perfluorocyclohexyl group and the like. ..

Examples of the aryl group having 6 to 12 carbon atoms include a phenyl group, a 2-methylphenyl group, a 3-methylphenyl group, a 4-methylphenyl group, a 2,3-dimethylphenyl group, a 2,4-dimethylphenyl group, and 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, 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 thereof include 4-cyclobutylphenyl group, 1-naphthyl group, 2-naphthyl group, 2-biphenylyl group, 3-biphenylyl group, 4-biphenylyl group and the like.

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

Examples of the aryloxy group having 6 to 10 carbon atoms include a phenyloxy group, a 2-methylphenyloxy group, a 3-methylphenyloxy group, a 4-methylphenyloxy group, a 2,3-dimethylphenyloxy group, and 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, 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 -Cyclobutylphenyloxy group, 1-naphthyloxy group or 2-naphthyloxy group can be exemplified.

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

Alkyl groups in acylamino groups having 1 to 8 carbon atoms in which the nitrogen atom may be substituted with alkyl groups having 1 to 4 carbon atoms include methyl group, ethyl group, propyl group, isopropyl group, butyl group and cyclopropylmethyl group. A group, a 2-methylpropyl group, a cyclopropyl group, a tert-butyl group, or a cyclobutyl group can be exemplified, and the acylamino group thereof can be exemplified by a formylamino group, an acetylamino group or a propanoylamino group.

The nitrogen atom may be substituted with one or more alkyl groups having 1 to 4 carbon atoms. Examples of the alkyl group in the aminocarbonyl group having 1 to 9 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 can be exemplified.

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

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, the alkyl group having 1 to 4 carbon atoms includes a methyl group, an ethyl group, a propyl group, and the like. Examples thereof include isopropyl group, butyl group, cyclopropylmethyl group, 2-methylpropyl group, cyclopropyl group, tert-butyl group or cyclobutyl group, and the alkyl groups having 1 to 5 carbon atoms are methyl group, ethyl group and 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 thereof include methylbutane-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, and a trialkylaminocarbonylamino group. Examples of the alkyl group having 1 to 4 carbon atoms include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a 2-methylpropyl group, a cyclopropyl group, a tert-butyl group or a cyclobutyl group. ..

Examples of the dialkylamino group having 2 to 12 carbon atoms (the two alkyl groups may be bonded to each other to form a ring structure within the above range of the number of carbon atoms) include a dimethylamino group, a diethylamino group, and a 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 a phenylamino group, a 2-methylphenylamino group, a 3-methylphenylamino group, a 4-methylphenylamino group, a 2,3-dimethylphenylamino group, and 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 thereof include 4-cyclobutylphenylamino group, 1-naphthylamino group and 2-naphthylamino group.

The diarylamino group having 12 to 20 carbon atoms includes a diphenylamino group, a bis (2-methylphenyl) amino group, a bis (3-methylphenyl) amino group, a bis (4-methylphenyl) amino group, and a bis (2,2). 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 (2,3,4,5-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-methyl Propyl) 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-phenyl Amino 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, Examples thereof include N- (3,4,5-trimethylphenyl) -N-phenylamino group, N- (1-naphthyl) -N-phenylamino group or N- (2-naphthyl) -N-phenylamino group.

Regarding A, a nitrogen-containing heterocycle having 3 to 20 carbon atoms which is the same and may have a crosslinked ring or a condensed ring (the nitrogen-containing heterocycle is said to be easy to synthesize). , Alkyl groups having 1 to 6 carbon atoms which may be substituted with halogen atoms, hydroxyl groups, oxo groups, hydroxyl groups, alkyl groups having 1 to 6 carbon atoms which may be substituted with alkoxy groups having 1 to 6 carbon atoms, Haloalkyl groups with 1 to 6 carbon atoms, alkoxy groups with 1 to 6 carbon atoms, aryl groups with 6 to 12 carbon atoms, aralkyl groups with 7 to 13 carbon atoms, aryloxy groups with 6 to 10 carbon atoms, from 1 carbon atom Alkyloxycarbonyl group of 6, the 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 the nitrogen atom is substituted with one or more alkyl groups having 1 to 4 carbon atoms. The aminocarbonyl group having 1 to 9 carbon atoms, the alkyloxycarbonyloxy group having 1 to 5 carbon atoms, and the nitrogen atom may be substituted with an alkyl group having 1 to 4 carbon atoms. Alkyloxycarbonylamino group, a ureido group in which one or more nitrogen atoms may be substituted with one or more alkyl groups having 1 to 4 carbon atoms, a dialkylamino group having 2 to 12 carbon atoms, and a monoarylamino having 6 to 10 carbon atoms. It may have a group or a diarylamino group having 12 to 20 carbon atoms.), And the two A's may be the same and have a crosslinked ring or a condensed ring. 4 to 20 nitrogen-containing heterocycles (the nitrogen-containing heterocycle may be substituted with an alkoxy group having 1 to 6 carbon atoms, an alkyl group having 1 to 6 carbon atoms, a fluoroalkyl group having 1 to 6 carbon atoms, 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, and 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 may be substituted, and a nitrogen atom may be substituted with one or more alkyl groups having 1 to 4 carbon atoms. It may have an aminocarbonyl group of 9, a dialkylamino group having 2 to 12 carbon atoms, or a diarylamino group having 12 to 20 carbon atoms)), and the two A's are the same. , A crosslinked ring or a nitrogen-containing heterocycle having 4 to 6 carbon atoms which may have a condensed ring (the nitrogen-containing heterocycle is an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, and carbon. Numbers 6 to 12 It may have a reel group, 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 two A's are the same, and the nitrogen-containing heterocycle has 4 to 6 carbon atoms (the nitrogen-containing heterocycle is an alkyl group having 1 to 4 carbon atoms and 1 to 6 carbon atoms). It 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 crosslinked ring or a 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. Examples thereof include a ring, an 8-azabicyclo [3.2.1] octane ring, a decahydroquinoline ring, and the like.

Fluoroalkyl groups 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, 2,2,3,3,4,5,4-heptafluorobutyl group, 3,3,4,5,4-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, 2,2,3,3,4,5-hexafluorocyclobutyl group, perfluoropentyl group, 2,2,3,3,4,5,5,5-nonafluoropentyl group, 3 , 3,4,5,4,5,5-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, 2,3,3,4,5,5,6,6,6-undecafluorohexyl group, 3,3,4,4,5,5,6,6-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 and the like. can.

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

Alkyl groups having 1 to 4 carbon atoms include methyl group, ethyl group, propyl group, isopropyl group, butyl group, cyclopropylmethyl group, 2-methylpropyl group, cyclopropyl group, tert-butyl group, or cyclobutyl group. It can be exemplified.

Examples of the dialkylamino group having 2 to 8 carbon atoms (the two alkyl groups may be bonded to each other to form a ring structure within the above range of the number of carbon atoms) include a dimethylamino group, a diethylamino group, and a 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 ⁻ represents the same or differently, a halide ion, a sulfonic acid ion represented by ^{R 1} SO ₂ O ⁻ , a carboxylic acid ion represented by ^{R 2} COO ^{− , or an 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 is a chloride ion, a bromide ion or an iodide ion because it is easy to synthesize. It is preferably present, and more preferably chloride ion or bromide ion.

When Y ⁻ is a sulfonic acid ion represented by ^{R 1} SO ₂ O ^{− , R 1} is selected from the group of alkyl groups having 1 to 9 carbon atoms, fluoroalkyl groups having 1 to 9 carbon atoms and phenyl groups. The phenyl group is an alkyl group having 1 to 4 carbon atoms, a fluoroalkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, and a fluoroalkoxy group having 1 to 4 carbon atoms. , Halogen atom, may be substituted with one or more substituents selected from the group of cyano and nitro groups.

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

The fluoroalkyl group having a carbon number of 1 in R ¹ 9, 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, 3,3,4,5,4-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 Examples include groups, perfluorocyclobutyl groups, 2,2,3,3,4,4-hexafluorocyclobutyl groups or 1,1,2,2,3,3,4,4-nonafluorobutyl groups. can.

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

The fluoroalkyl group having a carbon number of 1 in R ¹ 4, a 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, 3,3,4,5,4-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 Examples thereof include a group, a perfluorocyclobutyl group, a 2,2,3,3,4,4-hexafluorocyclobutyl group and the like.

Examples ^{of the alkoxy group having 1 to 4 carbon atoms in R 1} include a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, a butoxy group, a 2-methylpropoxy group, a cyclopropoxy group, a tert-butoxy group or a cyclobutoxy group. It can be exemplified.

Examples ^{of the fluoroalkoxy group having 1 to 4 carbon atoms in R 1} include a trifluoromethyloxy group, a difluoromethyloxy group, a perfluoroethyloxy group, a 2,2,2-trifluoroethyloxy group, and a 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, 2,2,3,3,4,5,4-heptafluorobutyloxy group, 3,3,4,5,4 4-Pentafluorobutyloxy group, 4,4,4-trifluorobutyloxy group, 1,2,2,3,3,3-hexafluoro-1- (trifluoromethyl) propyloxy group, 1- (tri) Examples thereof 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.

In R ^1, an alkyl group having 1 to 4 carbon atoms, fluoroalkyl group having 1 to 4 carbon atoms, an alkoxy group having from 1 to 4 carbon atoms, fluoroalkoxy group having 1 to 4 carbon atoms, a halogen atom, a cyano group, and nitro 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 and 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 Examples thereof include a group or a 4-nitrophenyl group.

R ¹ is a phenyl group, 4-methylphenyl group, methyl group or trifluoromethyl group in that the raw material is readily available, that is, R ¹ SO ₂ O ⁻ is a benzenesulfonic acid ion, p. -Toluene sulfonic acid ion, methane sulfonic acid ion or trifluoromethane sulfonic acid ion is preferable.

When Y ⁻ is R ² COO ⁻ , R ² is any one selected from the group 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.

Examples of the alkyl group having from 1 carbon atoms for R ² 6, linear, may be a branched or cyclic alkyl group, a methyl group, an ethyl group, a propyl group, an isopropyl group, butyl group, 2-methylpropyl group , 2,2-Dimethylpropyl group, 3-Cyclopropylpropyl group, Cyclopropyl group, 2-Methylbutyl group, 3-Methylbutyl group, 3-Methylbutane-2-yl group, tert-butyl group, Cyclobutyl group, Pentyl group, Examples thereof include 2-methylpentyl group, 1-methylbutyl group, 2-methylpentane-2-yl group, 1-ethylpropyl group, cyclopentyl group, hexyl group, 1-methylpentyl group, 1-ethylbutyl group and cyclohexyl group. ..

The fluoroalkyl group having a carbon number of 1 in the R ² 4, linear, may be a branched or cyclic alkyl group, 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 thereof include propyl group, 1-methyl-3,3,3-trifluoropropyl group, perfluorocyclobutyl group or 2,2,3,3,4,4-hexafluorocyclobutyl group.

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

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

Y ⁻ is the same or different from the above in that it is easy to synthesize, and preferably has a halide ion, a sulfonate ion represented by ^{R 2} SO ₂ O ^{− , or an OH −} (hydroxide ion), and is the same or different. Unlike, chloride ion, bromide ion, iodide ion, C ₆ H ₅ SO ₂ O ⁻ (benzene sulfonate ion), p-CH ₃ C ₆ H ₄ SO ₂ O ⁻ (paratoluene sulfonate ion), CH ₃ SO ₂ O ⁻ (methane sulfonate ion), CF ₃ SO ₂ O ⁻ (trifluoromethane sulfonate ion) or OH ⁻ (hydroxide ion) is more preferable, and the same or different, chloride. , _{bromide, p-CH 3 C 6 H} 4 SO 2 O - ( p-toluenesulfonic acid ion) or OH ^- is more preferably a (hydroxide ion), the same or different, bromide, chloride More preferably, it is a substance 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 the present specification, Me represents a methyl group, Et represents an ethyl group, tBu represents a tert-butyl group, Ph represents a phenyl group, and TsO ⁻ represents a p-toluenesulfonic acid ion.

Among the compounds shown in (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, The compounds represented by 1-65, 1-66, 1-91, 1-92, 1-103, 1-104, 1-276, 1-278 and 1-279 are preferable in terms of good reaction yield.

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

Next, the method for producing the diammonium salt of the present embodiment will be described.

<Embodiment 1 of the 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. Examples thereof include a method for producing a diammonium salt represented by the following general formula (1a) (hereinafter, also referred to as “production method 1”), which comprises a step of reacting with the secondary amine represented.

[In the formula, Ya represents the same or different sulfonyloxy group represented by the ^{halogen atom or R 1} SO _{2 O.} The R ¹ is any one 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, and the phenyl group has 1 to 9 carbon atoms. One selected from the group of an alkyl group of 4, a fluoroalkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a fluoroalkyl group having 1 to 4 carbon atoms, a halogen atom, a cyano group and a nitro group. It may be substituted with 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 crosslinked ring or a condensed ring, and the nitrogen-containing heterocycle is a halogen atom or a hydroxyl group. , An alkyl group having 1 to 6 carbon atoms which may be substituted with an oxo group or 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. Haloalkyl group, alkoxy group with 1 to 6 carbon atoms, aryl group with 6 to 12 carbon atoms, aralkyl group with 7 to 13 carbon atoms, aryloxy group with 6 to 10 carbon atoms, alkyloxycarbonyl with 1 to 6 carbon atoms The group and the nitrogen atom may be substituted with an alkyl group having 1 to 4 carbon atoms. The acylamino group having 1 to 8 carbon atoms and the nitrogen atom may be substituted with one or more alkyl groups having 1 to 4 carbon atoms. Aminocarbonyl groups having 1 to 9 carbon atoms, alkyloxycarbonyloxy groups having 1 to 5 carbon atoms, and alkyloxycarbonylaminos 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 in which one or more groups and nitrogen atoms may be substituted with an alkyl group having 1 to 4 carbon atoms, a dialkylamino group having 2 to 12 carbon atoms, a monoarylamino group 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 described above. Ya ⁻ represents a halide ion or a sulfonic acid ion represented by ^{R 1} SO ₂ O ^−, which is the same or different from the ^{above, and R 1} is the same as described above. It is synonymous.)
The halogen atom of Ya in the general formula (2) is not particularly limited, and examples thereof include a chlorine atom, a bromine atom, and an iodine atom.

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

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

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

(In the formula, Aa, Ab, Ya and Ya ⁻ are the same as described above.)
As the secondary amine (3a) and the secondary amine (3b) to be subjected to the reaction of the production method 1, the same secondary amine may be used, or two different types of secondary amines may be used. When two different secondary amines are used, it is possible to obtain the asymmetric diammonium salt (1a) of the present invention in which Aa and Ab are different.

In the production method 1, the secondary amine (3a) and the secondary amine (3b) may be reacted stepwise with the aliphatic compound (2).

The aliphatic compound (2) to be subjected to the reaction of the production method 1 is obtained by the production methods described in Reference Examples 1-4 and Reference Examples 1-5 in the present specification, or is obtained by a known production method. Commercially available products can be used, and as known production methods, for example, disclosed in Tetrahedron, Vol. 71, pp. 6944-6955, 2005 and Journal of the American Chemical Society, Vol. 129, pp. 13362-13363, 2007. The above-mentioned manufacturing method can be exemplified.

As the secondary amine (3a) and the secondary amine (3b) to be subjected to the reaction of the production method 1, known ones or commercially available ones can be used.

In the reaction of Production Method 1, the amounts of the secondary amine (3a) and the secondary amine (3b) with respect to the aliphatic compound (2) are preferably 1 to 100 molar equivalents, respectively, and 1 to 10 mol, respectively. Equivalents are more preferred.

In the reaction of Production Method 1, it is preferable that the aliphatic compound (2) and 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 selected from the group of trimethylamine, triethylamine, diisopropylethylamine, 1,4-diazabicyclo [2.2.2] octane and 1,8-diazabicyclo [5.4.0] undecene as organic bases, on the other hand. As the inorganic base, 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 can be exemplified respectively. ..

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

Further, by setting the secondary amine in an excess amount, for example, by setting the amount to 2 equivalents or more, further 5 equivalents or more with respect to the aliphatic compound (2), the reaction of the production method 1 is regarded as a reaction in the presence of a base. May be good.

As the secondary amine (3a) and the secondary amine (3b) to be subjected to the reaction of the production method 1, chemically acceptable salts may be used, and it is preferable to carry out the reaction in the presence of a base.

In the reaction of Production Method 1, the aliphatic compound (2) can be reacted with the secondary amine (3a) and the secondary amine (3b) in a solvent. The solvent is preferably one that does not inhibit the reaction, and for example, an aromatic hydrocarbon solvent, an ether solvent, an ester solvent, a halogen solvent, an amide solvent, a urea solvent, a ketone solvent, a nitrile solvent, and a sulfoxide solvent. , One or more selected from the group of 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 the ester solvent, and one or more selected from the group of chloroform, carbon tetrachloride, and chlorobenzene as the halogen solvent, At least one of N, N-dimethylformamide or N, N-dimethylacetamide as the amide solvent is 1,3-dimethyl-2-imidazolidinone or 1,3-dimethyl-3,4,5 as the urea solvent. , 6-Tetrahydropyrimidine-2 (1H) -one, at least one of acetone or methyl ethyl ketone as the ketone solvent is selected from the group of acetonitrile, propionitrile and benzonitrile as the nitrile solvent 1 One or more can be exemplified by dimethyl sulfoxide as the sulfoxide solvent and one or more selected from the group of methanol, ethanol and propanol as the alcohol solvent.

In the reaction of Production Method 1, one or more selected from the group of ether solvent, alcohol solvent and nitrile solvent are preferable solvents, and one or more selected from the group of tetrahydrofuran, ethanol and acetonitrile are more preferable solvents. , Can be exemplified.

In the reaction of Production Method 1, an arbitrary temperature of 0 ° C. or higher and 200 ° C. or lower is exemplified as a preferable reaction temperature, 20 ° C. or higher and 80 ° C. or lower as a more preferable reaction temperature, and 1 hour or more and 100 hours or less as a preferable reaction time, respectively. can.

The production method 1 is a step of isolating the diammonium salt represented by the general formula (1a) (hereinafter, also referred to as “isolation step”), or ion exchange of this (or the diammonium salt after isolation). It may have at least one of the steps (hereinafter, also referred to as “ion exchange step”).

In the isolation step, the method is arbitrary as long as the diammonium salt represented by the general formula (1a) can be isolated from the reaction mixture, and the isolation methods include solvent extraction, column chromatography, and preparative thin layer chromatography. One or more selected from the group of preparative liquid chromatography and recrystallization can be exemplified.

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

For ion exchange, the diammonium salt represented by the general formula (1a) may be brought into contact with the ion exchange resin. The ion exchange resin ^{may be any ion exchange resin having an exchange group Yb −} , and may be Amberlite IRN-78, Amberlite IRA-400, Amberlite IRA-402, Amberlite IRA-404, Amberlite IRA-900, Amber. One or more selected from the group Light IRA-904, Amber Light IRA-458, Amber Light IRA-958, Amber Light IRA-420, Amber Light IRA-411 and Amber Light IRA-910, preferably Amber Light IRN. -78 or Amberlite IRA-400 can be exemplified.

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 solvent, ester solvent, ketone solvent, nitrile solvent, alcohol solvent and water. As the specific solvent, the same solvent as the specific solvent in the reaction of the above-mentioned production method 1 can be exemplified.

<Embodiment 2 of the 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 sulfonate compound represented by the general formula R 1} SO ₂ Cl (in the formula, R). ¹ is any one 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, and the phenyl group is an alkyl group having 1 to 4 carbon atoms. , A fluoroalkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a fluoroalkoxy group having 1 to 4 carbon atoms, a halogen atom, a cyano group, and one or more substitutions selected from the group of nitro groups. A method for producing a diammonium salt represented by the following general formula (1b) (hereinafter, also referred to as “production method 2”), which comprises a step of reacting with (may be substituted with a group). ).

(In the formula, Z represents the same or different alkylene group having 2 to 11 carbon atoms, and the alkylene group may be substituted with a halogen atom, a hydroxyl group, an oxo group, or a hydroxyl group and has 1 to 6 carbon atoms. Alkyl group, 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, 6 carbon atoms to 12 aryl groups, 7 to 13 carbon atoms of arrukyl groups, 6 to 10 carbon atoms of aryloxy groups, 1 to 6 carbon atoms of alkyloxycarbonyl groups, and nitrogen atoms are substituted with alkyl groups of 1 to 4 carbon atoms. An acylamino group having 1 to 8 carbon atoms, an aminocarbonyl group having 1 to 9 carbon atoms in which one or more nitrogen atoms may be substituted with an alkyl group having 1 to 4 carbon atoms, and an alkyl having 1 to 5 carbon atoms may be substituted. Oxycarbonyloxy 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 one or more alkyl groups having 1 to 4 carbon atoms as the nitrogen atom. One or more selected from the group consisting of optionally substituted ureido groups, dialkylamino groups having 2 to 12 carbon atoms, monoarylamino groups having 6 to 10 carbon atoms and diarylamino groups having 12 to 20 carbon atoms. It may be substituted with a substituent.)

[In the formula, A is a nitrogen-containing heterocycle having 3 to 20 carbon atoms which may have a crosslinked ring or a condensed ring, which is the same or different from the above (the nitrogen-containing heterocycle is a halogen atom, a hydroxyl group, or an oxo group. , Alkyl groups having 1 to 6 carbon atoms which may be substituted with hydroxyl groups, alkyl groups having 1 to 6 carbon atoms which may be substituted with alkoxy groups having 1 to 6 carbon atoms, haloalkyl groups having 1 to 6 carbon atoms. , 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, and nitrogen. The atom may be substituted with an alkyl group having 1 to 4 carbon atoms. The acylamino group having 1 to 8 carbon atoms may be substituted. The nitrogen atom may be substituted with one or more alkyl groups having 1 to 4 carbon atoms. To 9 aminocarbonyl groups, 1 to 5 carbon number alkyloxycarbonyloxy groups, nitrogen atoms may be substituted with 1 to 4 carbon number alkyl groups 1 to 5 carbon number alkyloxycarbonylamino groups, nitrogen A ureido group in which one or more atoms 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. It may have a diarylamino group).

Yb ⁻ represents the same or differently as chloride ion or sulfonic acid ion represented by ^{R 1} SO ₂ O ^{− , and R 1} is the same as described above. ]
The above Z represents an alkylene group having 2 to 11 carbon atoms, which is the same or different from the above, and the alkylene group is an alkyl having 1 to 6 carbon atoms which may be substituted with a halogen atom, a hydroxyl group, an oxo group or a hydroxyl group. A 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, and an alkoxy group having 6 to 12 carbon atoms. Even if the aryl group, the arrukyl group having 7 to 13 carbon atoms, the aryloxy group having 6 to 10 carbon atoms, the alkyloxycarbonyl group having 1 to 6 carbon atoms, and the nitrogen atom are substituted with the alkyl group having 1 to 4 carbon atoms. A good acylamino group having 1 to 8 carbon atoms, an aminocarbonyl group having 1 to 9 carbon atoms in which one or more nitrogen atoms may be substituted with an alkyl group having 1 to 4 carbon atoms, and an alkyloxycarbonyl having 1 to 5 carbon atoms. The oxy group and the nitrogen atom may be substituted with an alkyl group having 1 to 4 carbon atoms. The alkyloxycarbonylamino group having 1 to 5 carbon atoms and the nitrogen atom may be substituted with one or more alkyl groups having 1 to 4 carbon atoms. One or more substituents selected from the group consisting of optionally ureido groups, dialkylamino groups having 2 to 12 carbon atoms, monoarylamino groups having 6 to 10 carbon atoms and diarylamino groups having 12 to 20 carbon atoms. Indicates that it may be replaced with.

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

Other substituents in Z (alkyl groups having 1 to 6 carbon atoms which may be substituted with hydroxyl groups, alkyl groups having 1 to 6 carbon atoms which may be substituted with alkoxy groups having 1 to 6 carbon atoms, carbons Haloalkyl groups with numbers 1 to 6, alkoxy groups with 1 to 6 carbon atoms, aryl groups with 6 to 12 carbon atoms, arrukyl groups with 7 to 13 carbon atoms, aryloxy groups with 6 to 10 carbon atoms, and 1 to 6 carbon atoms. Alkyloxycarbonyl group, the 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 the nitrogen atom being substituted with one or more alkyl groups having 1 to 4 carbon atoms. An aminocarbonyl group having 1 to 9 carbon atoms, an alkyloxycarbonyloxy group having 1 to 5 carbon atoms, and a nitrogen atom having 1 to 5 carbon atoms may be substituted with an alkyl group having 1 to 4 carbon atoms. An alkyloxycarbonylamino group, a ureido group in which one or more nitrogen atoms may be substituted with an alkyl group having 1 to 4 carbon atoms, a dialkylamino group having 2 to 12 carbon atoms, and a monoarylamino group having 6 to 10 carbon atoms. , A diarylamino group having 12 to 20 carbon atoms) is synonymous with the definition of each substituent in ring A above.

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

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

The sulfonated product to be subjected to the reaction of Production Method 2 may be a known or commercially available product.

In the reaction of the production method 2, the amount of the sulfonated product with respect to the diamine (4) is preferably 2 to 10 molar equivalents, more preferably 2 to 5 molar equivalents.

In the reaction of the production method 2, it is preferable that the diamine (4) and the ^{sulfonated product represented by the general formula R 1} SO ₂ Cl are 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. As specific or preferable inorganic bases and inorganic bases, one or more selected from the group of sodium methoxide, sodium ethoxide and potassium tert-butoxide as alkali metal alkoxides, which are the same as the bases in the reaction of Production Method 1, are selected. Each is listed.

In the reaction of the production method 2, the diamine (4) and the sulfonated product can be reacted in a solvent. The solvent preferably does not inhibit the reaction, and is preferably an aromatic hydrocarbon solvent, an ether solvent, an ester solvent, a halogen solvent, an amide solvent, a urea solvent, a ketone solvent, a nitrile solvent and the like. One or more selected from the group of sulfoxide-based solvents can be exemplified.

The specific solvent, preferable solvent, reaction temperature, reaction time and other conditions in the reaction of Production Method 2 can be exemplified by the same conditions as those in the reaction of Production Method 1.

The production method 2 is a step of isolating the diammonium salt represented by the general formula (1b) or a step of ion-exchange this (or the diammonium salt represented by the general formula (1b) after isolation). At least one of them may be included.

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

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

For ion exchange, the diammonium salt represented by the general formula (1b) may be brought into contact with the ion exchange resin. As the ion exchange resin, the solvent and other conditions in the ion exchange, the same conditions as those in the ion exchange step of the production method 1 can be exemplified.

Although the diammonium salt of the present embodiment can be applied to known ammonium salt applications, it is suitable as an organic structure-directing agent (hereinafter, also referred to as “SDA”) in the production of zeolite, and particularly in the production of small pore zeolite. Suitable as SDA in.

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

The method for producing zeolite of the present embodiment is also referred to as a composition containing a diamium salt represented by the general formula (1), a silica source, an alumina source, an alkali source and water (hereinafter, also referred to as a “raw material composition”. ) Is a crystallization step, which is a method for producing a zeolite.

Hereinafter, the crystallization step will be described.

In the method for producing a zeolite of the present embodiment, the obtained zeolite is preferably a small pore zeolite, and 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 IUPAC structure code defined by the Structure Communication of the International Zeolite Association (hereinafter referred to as "IZA"), and is an AFX type structure.

In the present embodiment, the zeolite produced (preferably crystalline aluminosilicate having an AFX structure) uses aluminum (Al) and silicon (Si) as skeleton metals (hereinafter, also referred to as “T atom”) and T. It has a skeletal structure consisting of a three-dimensional network structure in which atoms are bonded via oxygen (O). In the present embodiment, zeolite-related substances such as aluminophosphate and silicoaluminophosphate having a skeletal structure consisting of a network containing phosphorus (P) in the T atom and crystalline aluminosilicate which is a zeolite are different.

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

The silica source is not particularly limited _{, and examples thereof include silica (SiO 2} ) and a silicon compound as a precursor thereof. For example, colloidal silica, atypical silica, sodium silicate, and tetraethyl. At least one selected from the group of orthosilicate, precipitation method silica, fumed silica, crystalline aluminosilicate and aluminosilicate gel can be mentioned, and at least one of crystalline aluminosilicate and aluminosilicate gel is preferable.

The alumina source is not particularly limited, and examples thereof include alumina (Al ₂ O ₃ ) or an aluminum compound as a precursor thereof, and examples thereof include aluminum sulfate, sodium aluminate, and hydroxide. At least one selected from the group of aluminum, aluminum chloride, aluminosilicate gel, crystalline aluminosilicate and metallic aluminum can be mentioned, and among these, at least one of crystalline aluminosilicate and aluminosilicate gel is preferable.

The alkali source is not particularly limited, and examples thereof include hydroxides or halides of alkali metals, which are selected from the group of sodium hydroxide, potassium hydroxide, rubidium hydroxide, and cesium hydroxide. It is preferably at least one kind, and more preferably sodium hydroxide.

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

SiO ₂ / Al ₂ O ₃ : 5 or more, 100 or less,
Preferably 10 or more, 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, 0.60 or less,
More preferably 0.10 or more and 0.40 or less
M / SiO ₂ : 0.06 or more, 1.0 or less,
Preferably 0.08 or more, 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 H ₂ O / SiO ₂ : 5 or more and 60 or less,
Preferably 10 or more, 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 is OH / SiO ₂ , M / SiO ₂ , SDA / SiO _2. And H ₂ O / SiO ₂ are hydroxide ions (mainly derived from an alkaline source), alkali metals (mainly derived from an alkaline source), and SDA (the above general formula (1)) with respect to the silica source in the raw material composition, respectively. (Diammonium salt represented by) or the molar ratio of water.

In addition, 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 the present 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 crystals converted to _{silica (SiO 2 ) to the weight of silicon in the raw material composition converted to silica (SiO 2).} Examples thereof 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 0.5% by weight or more and 3.5% by weight or less.

The seed crystal is preferably a zeolite having no odd-numbered ring 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. Zeolites are more preferable, zeolites having any structure selected from the group of CHA, AEI, LEV, AFX and ERI are more preferable, and AFX-type zeolites are even more preferable.

In the present embodiment, the raw material composition is crystallized in the crystallization step. Specifically, the raw material composition may be crystallized by hydrothermal treatment. For hydrothermal treatment, the raw material composition may be placed in a closed pressure-resistant container and heated. The following can be mentioned as the hydrothermal treatment conditions.

Treatment temperature: 80 ° C or higher and 190 ° C or lower, preferably 150 ° C or higher and 190 ° C or lower Treatment time: 2 hours or more and 500 hours or less Treatment pressure: Self-sustaining pressure The state of the raw material composition in crystallization is arbitrary, and is left standing or stirred. Any of the following may be used, but it is preferably under stirring.

The zeolite production method of the present embodiment may include a post-treatment step such as a washing step, a drying step, an SDA removal step, or an ammonium treatment step in addition to the above-mentioned crystallization step.

The washing step means a step of washing the zeolite after separation from the liquid phase after the crystallization step. The cleaning method in the cleaning step is arbitrary, but for example, it can be exemplified that the zeolite obtained by solid-liquid separation and recovery of the zeolite and the liquid phase is brought into contact with a sufficient amount of pure water.

The drying step means a step of removing water from the zeolite after the washing step. The drying method in the drying step is arbitrary, and examples thereof include treating zeolite in the air at 100 ° C. or higher and 150 ° C. or lower for 2 hours or longer.

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

Examples of the SDA removal method include treatment in the air at 400 ° C. or higher and 700 ° C. or lower for 1 to 2 hours.

Ammonium treatment step, the removal of alkali metal from the zeolite, and, ammonium cation type type (hereinafter referred to. As "NH ₄ ⁺ type") means the process of the. Examples of the ammonium treatment method include contacting an aqueous solution containing ammonium ions with zeolite. Note that the NH ₄ ⁺ type zeolite, by heat treatment, cation type proton type (hereinafter referred to. As "H ⁺ form") can also be a zeolite. Specific conditions for the heat treatment include, for example, air at 500 ° C. for 1 to 2 hours.

Further, the zeolite production method of the present embodiment may include a modification step of modifying the zeolite using a zeolite containing SDA.

The modification step is a step of modifying the surface or the inside of the zeolite with a metal salt or an organic substance, and the method is arbitrary, and examples thereof include contacting the zeolite with a solution containing the metal salt.

The zeolite obtained by the method for producing zeolite of the present embodiment can be used for 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 incorporating the transition metal into the AFX-type zeolite.

The transition metal used in the transition metal-containing step is preferably a compound containing at least one transition metal in the group consisting of groups 7, 8, 9, 10, 11 and 13 of the periodic table. , Platinum (Pt), Palladium (Pd), Rodium (Rh), Silver (Ag), Iron (Fe), Copper (Cu), Cobalt (Co), Manganese (Mn) and Indium (In). It is more preferably a compound containing more than one species, even more preferably a compound containing at least one of iron or copper, and preferably a compound containing copper. Examples of the compound containing a transition metal include at least one of the group consisting of nitrates, sulfates, acetates, chlorides, complex salts, oxides and composite oxides of these transition metals.

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

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

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

Next, examples of the present invention will be shown. However, the present invention is not limited thereto.
(H ^1- NMR)
Ascend ^TM AVANCE III HD (400MHz, manufactured by Bruker) or UltraShield ^TM Plus AVANCE III (400MHz, manufactured by Bruker) was used to perform ^H 1 -NMR measurements of the sample. As a measurement solvent, heavy chloroform (CDCl ₃₎ or deuterated dimethyl sulfoxide _{-d 6 (DMSO-d 6)} , was measured ^H 1 -NMR sample with tetramethylsilane (TMS) as an internal standard substance. In the case of using heavy water _(D 2 O) as a measurement solvent, it was set solvent signal to 4.70 ppm. The measurement data are described in the order of chemical shift, multiplicity, coupling constant (Hz) and integral value.
(Ion chromatograph)
An anion chromatograph 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 bicarbonate aqueous solution
+ 1.1 mmol / L Sodium carbonate water-soluble group
Flow velocity: 0.8 mL / min
Temperature: 40 ° C
Detection: Electrical conductivity (powder X-ray diffraction)
The XRD measurement of the sample was performed using a general X-ray diffractometer (device name: Ultima IV, manufactured by RIGAKU). The measurement conditions are as follows.

Radioactive source: CuKα ray (λ = 1.5405Å)
Measurement mode: Step scan
Scan width: 0.02 °
Divergence slit: 1.00 deg
Scattering slit: open
Light receiving slit: Open
Measurement time: 1.0 minutes
Measurement range: 2θ = 3.0 ° to 43.0 °
The crystal phase of the sample and the XRD peak intensity ratio were confirmed by comparing the obtained XRD pattern with the XRD pattern posted on the home page of the Structure Communication of IZA.
(Quantitative quantity of silicon and aluminum)
The composition of the sample was analyzed using a general inductively coupled plasma emission spectrometer (device name: OPTIMA3300DV, manufactured by PERKIN ELMER). The sample was dissolved in a mixed solution of hydrofluoric acid and nitric acid to prepare a measurement solution. The obtained measurement solution was put into an apparatus and the composition of the sample was analyzed. _{SiO 2} / Al ₂ O ₃ was calculated from the obtained molar concentrations of silicon (Si) and aluminum (Al).

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-Cyclohexanetetracarboxylic Acid)

1,2,4,5-Cyclohexanetetracarboxylic dianhydride (2.23 g, 9.95 mmol) in an ethanol / toluene (1: 1) mixed solution (20 mL) with p-toluenesulfonic acid position monohydrate (99.0 mg, 0.52 mmol) was added, 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 obtained crude product was purified by column chromatography (eluent: hexane / ethyl acetate) to obtain a colorless oily substance. 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 (400 MHz, 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) in a suspension of lithium aluminum hydride (5.05 g, 133 mmol) and tetrahydrofuran (120 mL). Was added under an ice bath and 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, water (5.8 mL), 1 M 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 obtained crude product was purified by column chromatography (eluent: chloroform / methanol) to form a white solid of 1,2,4,5-tetrakis (hydroxyl). Methyl) cyclohexane (2.98 g, yield 66%) was obtained.

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

Methansulfonyl chloride (0.69 mL, 0.69 mL) in a solution of 1,2,4,5-tetrakis (hydroxymethyl) cyclohexane (401 mg, 1.96 mmol) and triethylamine (1.4 mL, 10.1 mmol) in dichloromethane (5.8 mL). 8.92 mmol) was added under an ice bath and 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 phase was washed with saturated aqueous sodium hydrogen carbonate solution (5 mL), dried over sodium sulfate, and concentrated under reduced pressure to obtain 1,2,4,5-tetrakis (methanesulfonyloxymethyl) as a yellow oil. Cyclohexane (974 mg, 96% yield) was obtained.

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

Example 1-1

1,2,4,5-Tetrakis (methanesulfonyloxymethyl) cyclohexane (974 mg, 1.9 mmol), acetonitrile (7.0 mL) and pyrrolidine (0.65 mL, 7.9 mmol) obtained in Reference Example 1-1 were added. It was put in and stirred in a sealed tube at 85 ° C. for 15 hours. The reaction mixture was allowed to cool to room temperature, 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) for ion exchange. The passed liquid was concentrated and the obtained solid was obtained. By washing with diethyl ether, tetrahydrofuran, ethyl acetate, acetone, dispiro [pyrrolidine-1,2'-(1', 2', 3', 4', 5', 6', 7', 8-decahydro) Benzo [1,2-c: 4, -c'] dipyrrole) -6', 1''-pyrrolidin] -5,11-diium-dichloride (196 mg, 30% yield) was obtained as a white solid. As a result of analyzing the obtained compound with an ion chromatograph, the presence of chloride ions was confirmed.

Dispirol [pyrrolidin-1,2'-(1', 2', 3', 4', 5', 6', 7', 8-decahydrobenzo [1,2-c: 4, -c'] dipyrrole ) -6', 1 ″ -pyrrolidin] -5,11-diium = dichloride NMR spectrum: ^{1 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 to 2.45 (m, 4H), 2.19 to 2.02 (m, 8H), 1.89 to 1.80 (m) , 2H), 1.30 to 1.18 (m, 2H).

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

Add 5-amino-1-butanol (6.5 mL, 70 mmol) to a suspension of 1,2,4,5-cyclohexanetetracarboxylic dianhydride (6.99 g, 31.2 mmol) acetic acid (63 mL). , Stirred for 19 hours under heating and reflux. 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 is washed with saturated aqueous sodium hydrogen carbonate solution (250 mL × 2), dried over sodium sulfate, and concentrated to concentrate 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 1} H-NMR (400 MHz, CDCl ₃ ) δ (ppm): 4.05 (t) , J = 5.7Hz, 4H), 3.51 (t, J = 6.7Hz, 4H), 2.98-2.86 (m, 4H), 2.71-2.57 (m, 2H) , 2.03 (s, 6H), 1.69 to 1.39 (m, 4H).
(Synthesis of 5,11-bis (4-acetoxybutyl) -5,11-diazatricyclo [7.3.0.0 ^3,7 ] dodecane)

N, N'-bis (4-acetoxybutyl) -1,2,4,5-cyclohexanetetracarboxylic acid diimide (8.) in a suspension of lithium hydride (4.53 g, 119 mmol) and tetrahydrofuran (150 mL). A 94 g, 19.8 mmol) solution of tetrahydrofuran (70 mL) was added under an ice bath and stirred at 60 ° C. for 14 hours. After the reaction, the reaction solution was cooled in an ice bath, water (4.6 mL), a 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 off, the solid was washed with tetrahydrofuran and ethyl acetate, and the solvent was distilled off from the filtrate under reduced pressure to obtain a yellow oil of 5,11-bis (4-acetoxybutyl)-. 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 1} H-NMR (400 MHz, CDCl ₃ ) δ (ppm): 3 .60 to 3.52 (m, 4H), 2.92 to 2.79 (m, 4H), 2.46 to 2.36 (m, 4H), 2.20 to 2.05 (m, 8H) , 1.72 to 1.51 (m, 12H), 1.30 to 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 ( P-Toluenesulfonyl chloride (9.27 g, 48) in a solution of 8.0 mL, 57.4 mmol) and 1,4-diazabicyclo [2.2.2] octane (0.27 g, 2.37 mmol) in dichloromethane (220 mL). .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. By filtering the reaction mixture, concentrating the filtrate, and washing the resulting solid with acetone, the white solid dispiro [pyrrolidine-1,2'-{1', 2', 3', 4', 5', 5 ', 6', 7', 8-decahydrobenzo [1,2-c: 4, -c'] dipyrrole} -6', 1''-pyrrolidine] -5,11-diium-dichloride (4.18 g) , Yield 55%) was obtained. As a result of analyzing the obtained compound by ion chromatography, the presence of chloride ions was confirmed.

Dispirol [pyrrolidin-1,2'-{1', 2', 3', 4', 5', 6', 7', 8-decahydrobenzo [1,2-c: 4, -c'] dipyrrole } -6', 1''-pyrrolidin] -5,11-diium = dichloride NMR spectrum: ^{1 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 to 2.45 (m, 4H), 2.19 to 2.02 (m, 8H), 1.89 to 1.80 (m) , 2H), 1.30 to 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) and toluene (0.36 mL) obtained in Reference Example 1-1 were added, and the mixture was stirred under an ice bath. Pyridine (0.40 mL, 5.0 mmol) and thionyl chloride (0.36 mL, 4.99 mmol) were added, and the mixture was heated at 70 ° C. for 6 hours and then cooled in an ice bath. The solid precipitated in the reaction solution was filtered off, the filtrate was concentrated, and then hexane was added to suspend the solid. The solid was filtered again, the filtrate was concentrated, and the resulting crude product was purified by column chromatography (eluent: hexane-ethyl acetate) to give 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, 7.8 Hz, 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, ethanol: tetrahydrofuran (1: 1) mixture (1.0 mL), sodium iodide (114 mg, 0.76 mmol) and 3- (diethylamino) pyrrolidine (0.50 mL, 3.17 mmol) were added, and the mixture was 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 by 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, 2-c: 4, -c ' ] dipyrrole) -6', 1 '' - pyrrolidin] 5,11 Jiiumu = dichloride of NMR _{^{spectra: 1 H-NMR (400MHz,}} D 2 O) δ (ppm): 4.00 to 3.87 (m, 4H), 3.87 to 3.52 (m, 10H), 3.44 to 3.13 (m, 4H), 2.74 to 2.54 (m, 12H) ), 2.53 to 2.35 (m, 2H), 2.23 to 2.09 (m, 2H), 2.03 to 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 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, 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%) white Obtained as a solid. As a result of analyzing the obtained compound by 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 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 to 2.54 (m, 4H), 1.99 to 1.81 (m, 10H), 1.73 to 1.63 (m) , 4H), 1.36 to 1.24 (m, 2H).

Example 1-5

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) are added and sealed. The mixture was stirred in a tube at 90 ° C. for 16 hours. After allowing the reaction solution to cool to room temperature, it is ice-cooled, and the solid precipitated by adding ice-cooled acetone is collected by filtration to obtain dyspiro [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-bismethanesulfonate (105 mg, 30% yield) 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-methyl piperidine] 5,11 Jiiumu = NMR spectrum of bis _{^{methanesulfonate: 1 H-NMR (400MHz,}} 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 to 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 1-6

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-bismethanesulfonate (105 mg, 0.20 mmol) was dissolved in methanol and amberlite IRA-400 Cl ^- type (1. 8 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 [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, 86% yield) Was obtained as a white solid. As a result of analyzing the obtained compound by 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-methyl piperidine] 5,11 Jiiumu = dichloride of NMR _{^{spectra: 1 H-NMR (400MHz,}} D 2 O) δ (ppm): 4.17~4 .09 (m, 2H), 3.75 to 3.65 (m, 2H), 3.50 to 3.35 (m, 4H), 3.28 to 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 added and 90 in a sealed tube. The mixture was stirred at ° C. for 16 hours. The reaction mixture was allowed to cool to room temperature, cooled, and ice-cooled acetone was added to remove the precipitated solid 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-phenyl-piperidine] 5,11 Jiiumu = NMR spectrum of bis _{^{methanesulfonate: 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 to 3.37 (m, 2H), 3.35 to 3.16 (m, 4H), 2.97 to 2.80 (m, 4H), 2.71 (s, 6H), 2.67 ~ 2.48 (m, 4H), 2.11 to 1.95 (m, 8H), 1.94 to 1.88 (m, 2H), 1.35 to 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-bismethanesulfonate (85.2 mg, 0.13 mmol) was dissolved in methanol and amberlite IRA-400 Cl ^- type (85.2 mg, 0.13 mmol) was dissolved. 2.2 cm ³ ) was added, and the mixture was 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 by 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-phenyl-piperidine] 5,11 Jiiumu = dichloride of NMR _{^{spectra: 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

Dispirol [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) is filled ^{with an anion exchange resin (Amberlite IRN78 OH-} type, 7.9 cm ^3). Dispirolidine [pyrrolidine-1,2'-{1', 2', 3', 4', 5', 6', 7', 8-decahydrobenzo [1,2-c: 4, An aqueous solution (10 mL) of −c'] dipyrrole} -6', 1''-pyrrolidine] -5,11-diium-dihydroxyde was obtained. This was diluted with ion-exchanged water, titrated with 0.010 M hydrochloric acid, and the ion exchange rate was measured. As a result, the ion exchange rate was 67%.

Dispirol [pyrrolidine-1,2'-{1', 2', 3', 4', 5', 6', 7', 8-decahydrobenzo [1,2-c: 4, -c'] dipyrrole } -6 ', 1''- pyrrolidin] 5,11 Jiiumu = NMR spectra of aqueous solutions of _{^{dihydroxide: 1 H-NMR (400MHz,}} 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 to 2.45 (m, 4H), 2.18 to 2.02 (m, 8H), 1.88 to 1. 79 (m, 2H), 1.29 to 1.18 (m, 2H).

Example 1-10

Add 1,2,4,5-tetrakis (methanesulfonyloxymethyl) cyclohexane (336 mg), acetonitrile (1.0 mL) and methyl 4-piperidin carboxylate (0.36 mL, 2.6 mmol) in a sealed tube at 90 ° C. Was stirred for 17 hours. The reaction mixture was allowed to cool to room temperature, concentrated, the obtained crude product was dissolved in methanol, an anion exchange resin (Amberlite IRA400 Cl ⁻ type, 16 cm ³ ) was added, and the mixture was stirred at room temperature for 3 hours. The anion exchange resin was removed by filtration, the filtrate was concentrated under reduced pressure, acetone was added to the residue, and the precipitated solid was collected by filtration. The obtained solid was washed with ethyl acetate, dissolved in methanol, and washed with activated charcoal to obtain 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 by 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, 2-c: 4, -c ' ] dipyrrole} -6', 1 '' piperidine] 5,11 Jiiumu = dichloride of NMR _{^{spectra: 1 H-NMR (400MHz,}} D 2 O) δ (ppm): 4 .18 (m, 1H), 3.91 (m, 1H), 3.78 to 3.69 (m, 8H), 3.66 to 3.37 (m, 6H), 3.35 to 3.16 (M, 2H), 3.13 to 2.94 (m, 4H), 2.89 to 2.74 (m, 2H), 2.70 to 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 in a sealed tube at 70 ° C. for 18 hours. 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, dyspiro [azepan-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, 4% yield) white Obtained as a solid. As a result of analyzing the obtained compound by ion chromatography, the presence of chloride ions was confirmed.

Dispirol [Azepan-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 1} H-NMR (400 MHz, D ₂ O) δ (ppm): 3.98 (dd, J = 12.2) , 7.1Hz, 4H), 3.58-3.48 (m, 4H), 3.48-3.43 (m, 4H), 3.07 (dd, J = 11.4, 10.4Hz, 4H), 2.69 to 2.52 (m, 4H), 1.98 to 1.79 (m, 10H), 1.78 to 1.63 (m, 8H), 1.36 to 1.23 ( m, 2H).

(Synthesis of AFX type zeolite)
Example 2-1
The dispiro [pyrrolidine-1,2'-(1', 2', 3', 5', 6', 7'-hexahydrobenzo] [1,2-c: 4,5] obtained in Example 1-2. -C'] Dipyrrolium) -6', 1''-Pyrrolidine] = 48% NaOH and Y-type zeolite (trade name: HSZ-350HUA, manufactured by Toso, silica and alkali source) using dichloride as a structure-directing agent (SDA). Was mixed to obtain a composition. The composition of the obtained composition is shown.

SiO ₂ / Al ₂ O ₃ = 11.1
OH / SiO ₂ = 0.35
Na / SiO ₂ = 0.35
SDA / SiO ₂ = 0.10
H ₂ O / SiO ₂ = 25
After adding the seed crystal AFX type zeolite to the composition so that the seed crystal content of the composition was 3.0% by weight, the mixture was sufficiently stirred.
The stirred composition was sealed in a stainless steel autoclave and heated at 180 ° C. for 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 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 (9)

A diammonium salt represented by the general formula (1).

[During the ceremony,
The two A's are the same or different from each other and may have a crosslinked ring or a condensed ring. A nitrogen-containing heterocycle having 3 to 20 carbon atoms (the nitrogen-containing heterocycle is a halogen atom, a hydroxyl group, an oxo group, a hydroxyl group). Alkyl groups having 1 to 6 carbon atoms which may be substituted with, alkyl groups having 1 to 6 carbon atoms which may be substituted with alkoxy groups having 1 to 6 carbon atoms, haloalkyl groups having 1 to 6 carbon atoms, carbons. Alkyl groups with numbers 1 to 6, aryl groups with 6 to 12 carbon atoms, aralkyl groups with 7 to 13 carbon atoms, aryloxy groups with 6 to 10 carbon atoms, alkyloxycarbonyl groups with 1 to 6 carbon atoms, and nitrogen atoms. An acylamino group having 1 to 8 carbon atoms which may be substituted with an alkyl group having 1 to 4 carbon atoms and a nitrogen atom may be substituted with one or more alkyl groups having 1 to 4 carbon atoms. Aminocarbonyl group, alkyloxycarbonyloxy group having 1 to 5 carbon atoms, 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, nitrogen atom A ureido group which 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 diarylamino having 12 to 20 carbon atoms. It may have a group.)
Y ⁻ represents the same or differently, a halide ion, a sulfonic acid ion represented by ^{R 1} SO ₂ O ⁻ , a carboxylic acid ion represented by ^{R 2} COO ^{− , or an 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, It may be substituted with one or more substituents selected from the group of an alkoxy group having 1 to 4 carbon atoms, a fluoroalkyl group having 1 to 4 carbon atoms, a halogen atom, a cyano group and a nitro group). ..
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). .. ] Two A's are the same and may have a crosslinked ring or a condensed ring. A nitrogen-containing heterocycle having 3 to 20 carbon atoms (the nitrogen-containing heterocycle is a halogen atom, a hydroxyl group, an oxo group, or a hydroxyl group. Alkyl groups having 1 to 6 carbon atoms which may be substituted, alkyl groups having 1 to 6 carbon atoms which may be substituted by alkoxy groups having 1 to 6 carbon atoms, haloalkyl groups having 1 to 6 carbon atoms, carbon atoms 1 to 6 alkoxy groups, 6 to 12 carbon number aryl groups, 7 to 13 carbon number aralkyl groups, 6 to 10 carbon number aryloxy groups, 1 to 6 carbon number alkyloxycarbonyl groups, nitrogen atoms are carbon An acylamino group having 1 to 8 carbon atoms which may be substituted with an alkyl group of numbers 1 to 4, 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. Aminocarbonyl group, alkyloxycarbonyloxy group having 1 to 5 carbon atoms, 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, nitrogen atom is carbon A ureido group which may be substituted with one or more alkyl groups of numbers 1 to 4, 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. The diammonium salt according to claim 1. Y ⁻ is the same or different, chloride ion, bromide ion, iodide ion, C ₆ H ₅ SO ₂ O ⁻ (benzene sulfonate ion), p-CH ₃ C ₆ H ₄ SO ₂ O ⁻ (para) Tollin sulfonic acid ion), CH ₃ SO ₂ O ⁻ (methanel sulfonic acid ion), CF ₃ SO ₂ O ⁻ (trifluoromethanesulfonic acid ion) or OH ⁻ (hydroxide ion) according to claim 1 or 2. The diammonium salt described. Two A's are the same and may have a crosslinked ring or a condensed ring. A nitrogen-containing heterocycle having 4 to 20 carbon atoms (the nitrogen-containing heterocycle is substituted with an alkoxy group having 1 to 6 carbon atoms. Alkyl groups having 1 to 6 carbon atoms, fluoroalkyl groups having 1 to 6 carbon atoms, alkoxy groups having 1 to 6 carbon atoms, aryl groups having 6 to 12 carbon atoms, and aralkyl groups having 7 to 13 carbon atoms. , An aryloxy group having 6 to 10 carbon atoms, an alkyloxycarbonyl group having 1 to 6 carbon atoms, an 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, nitrogen. An aminocarbonyl group having 1 to 9 carbon atoms, a dialkylamino group having 2 to 12 carbon atoms, or a diarylamino group having 12 to 20 carbon atoms, in which the atom may be substituted with one or more alkyl groups having 1 to 4 carbon atoms. The diammonate salt according to any one of claims 1 to 3 which may have). Two A's are the same and may have a crosslinked ring or a condensed ring. A nitrogen-containing heterocycle having 4 to 6 carbon atoms (the nitrogen-containing heterocycle is an alkyl group having 1 to 4 carbon atoms and carbon. It has an alkoxy group of numbers 1 to 6, an aryl group of 6 to 12 carbon atoms, an aralkyl group of 7 to 13 carbon atoms, an aryloxy group of 6 to 10 carbon atoms or a dialkylamino group of 2 to 8 carbon atoms. The diammonium salt according to any one of claims 1 to 4. Two A's are the same and have a nitrogen-containing heterocycle having 4 to 6 carbon atoms (the nitrogen-containing heterocycle has an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, and 6 carbon atoms. It may have 12 aryl groups or dialkylamino groups having 2 to 8 carbon atoms), and Y ⁻ is the same or different, chloride ion, bromide ion or OH ⁻ (water). The diammonium salt according to any one of claims 1 to 5, which is an oxide ion). A method for producing a zeolite, which comprises a crystallization step of crystallizing a composition containing the diammonate salt, the silica source, the alumina source, the alkali source and water according to any one of claims 1 to 6. The method for producing a zeolite according to claim 7, wherein the zeolite is a small pore zeolite. The method for producing a zeolite according to claim 7 or 8, wherein the zeolite is an AFX type zeolite.

Images