JP7249911B2 - Hexahydrobenzodipyrolium salt and use thereof - Google Patents

Description

The present invention relates to novel hexahydrobenzodipyrolium salts and uses thereof.

Compounds described in Patent Document 1, Patent Document 2, Non-Patent Document 1, and Non-Patent Document 2 have been reported as compounds having a molecular structure similar to the hexahydrobenzodipyrolium salt of the present invention. However, all of them differ from the hexahydrobenzodipyrrolinium salt of the present invention in that they have a spiro structure around the quaternary nitrogen atom. In addition, hexahydrobenzodipyrrolinium salts are used in applications such as ionomer cation sources described in Patent Document 1, for example. However, hexahydrobenzodipyrolium salts suitable as structure-directing agents for zeolite production have not been reported.

U.S. Pat. No. 6,365,705 WO2014/016202 Journal of the Chemical Society, Chemical Communications, 1977, Vol. 15, pp. 525-526 Synthetic Communications, 2005, Vol. 35, pp. 2985-2992

An object of the present invention is to provide a hexahydrobenzodipyrrolinium salt. Another object of the present invention is to provide a method for producing zeolite using hexahydrobenzodipyrolium salt.

In the present invention, a hexahydrobenzodipyrrolinium salt represented by general formula (1) was found. Furthermore, it was found that hexahydrobenzodipyrolium salt (1) functions favorably as a structure-directing agent for zeolite.

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

(Wherein, X is the same or different and represents a hydrogen atom or a halogen atom,
R ¹ , R ² , R ³ and R ⁴ each independently represent an alkyl group having 1 to 10 carbon atoms, a haloalkyl group having 1 to 10 carbon atoms, or an aryl group having 6 to 10 carbon atoms, and these substituted The group is a hydroxyl group, an alkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 10 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an aryloxy group having 6 to 10 carbon atoms, or a dialkylamino group having 2 to 12 carbon atoms. , a monoarylamino group having 6 to 10 carbon atoms and a diarylamino group having 12 to 20 carbon atoms.

Y ^- is the same or different and represents a halide ion, a sulfonate ion represented by R ⁵ SO ₂ O ^- , a carboxylate ion represented by R ⁶ COO ^- or OH ^- (hydroxide ion). ,
R ⁵ represents an alkyl group having 1 to 9 carbon atoms, a fluoroalkyl group having 1 to 9 carbon atoms, or a phenyl group, and the phenyl group is an alkyl group having 1 to 4 carbon atoms, a fluoro may be substituted with one or more substituents selected from the group consisting of an alkyl group, an alkoxy group having 1 to 4 carbon atoms, a fluoroalkoxy group having 1 to 4 carbon atoms, a halogen atom, a cyano group and a nitro group; .

R ⁶ represents an alkyl group having 1 to 6 carbon atoms, a fluoroalkyl group having 1 to 4 carbon atoms, or a phenyl group, and the phenyl group may be substituted with an alkyl group having 1 to 4 carbon atoms. )
[2] ^Y in general formula (1) is chloride ion, bromide ion, iodide ion, benzenesulfonate ion, p-toluenesulfonate ion, methanesulfonate ion, trifluoromethanesulfonate ion or hydroxide The hexahydrobenzodipyrrolinium salt according to [1], which is an ion.
[3] The hexahydrobenzodipyrrolinium salt according to [1] or [2], wherein X in the general formula (1) is a hydrogen atom.
[4] R ¹ , R ² , R ³ and R ⁴ in general formula (1) are each independently an alkyl group having 1 to 6 carbon atoms, an aryloxy group having 6 to 10 carbon atoms, or 2 to 12 carbon atoms; an alkyl group having 1 to 6 carbon atoms optionally substituted with one or more substituents selected from the group consisting of a dialkylamino group and an alkoxy group having 1 to 6 carbon atoms, or an alkyl group having 1 to 6 carbon atoms The hexahydrobenzodipyrrolinium salt according to any one of [1] to [3], which is a phenyl group optionally substituted with a group.
[5] R ¹ , R ² , R ³ and R ⁴ in general formula (1) are each independently a methyl group or an ethyl group, and Y ^- is a chloride ion or a bromide ion [1] to The hexahydrobenzodipyrrolinium salt according to any one of [3].
[6] A crystallization step of crystallizing a composition containing the hexahydrobenzodipyrolium salt represented by the general formula (1) according to [1], a silica source, an alumina source, an alkali source and water. A method for producing zeolite, characterized by:

ADVANTAGE OF THE INVENTION By this invention, a novel hexahydrobenzodipyrolium salt and its manufacturing method can be provided. Furthermore, the present invention can provide a method for producing zeolite using the hexahydrobenzodipyrolium salt.

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

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described below by showing an example of an embodiment.

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

X is the same or different and is a hydrogen atom or a halogen atom, preferably a hydrogen atom, a chlorine atom, a bromine atom or an iodine atom, more preferably a hydrogen atom or a bromine atom, hydrogen Atoms are more preferred.

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

The haloalkyl group having 1 to 10 carbon atoms represented by R ¹ , R ² , R ³ and R ⁴ is not particularly limited as long as it is a linear, branched or cyclic haloalkyl group. is, for example, a trifluoromethyl group, a difluoromethyl group, a perfluoroethyl group, a 2,2,2-trifluoroethyl group, a 1,1-difluoroethyl group, a 2,2-difluoroethyl group, a 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-methyl propyl) group, 2,2,2-trifluoro-1-(trifluoromethyl)ethyl group, perfluorocyclopropyl group, 2,2,3,3-tetrafluorocyclopropyl group, perfluorobutyl group, 2,2, 3,3,4,4,4-heptafluorobutyl group, 3,3,4,4,4-pentafluorobutyl group, 4,4,4-trifluorobutyl group, 1,2,2,3,3 , 3-hexafluoro-1-(trifluoromethyl)propyl group, 1-(trifluoromethyl)propyl group, 1-methyl-3,3,3-trifluoropropyl group, perfluorocyclobutyl group, 2,2, 3,3,4,4-hexafluorocyclobutyl group, perfluoropentyl group, 2,2,3,3,4,4,5,5,5-nonafluoropentyl group, 3,3,4,4,5 , 5,5-heptafluoropentyl group, 4,4,5,5,5-pentafluoropentyl group, 5,5,5-trifluoropentyl group, 1,2,2,3,3,3-hexafluoro -1-(perfluoroethyl)propyl group, 2,2,3,3,3-pentafluoro-1-(perfluoroethyl)propyl group, perfluorocyclopentyl group, perfluorohexyl group, 2,2,3,3,4, 4,5,5,6,6,6-undecafluorohexyl group, 3,3,4,4,5,5,6,6,6-nonafluorohexyl group, 4,4,5,5,6 , 6,6-heptafluorohexyl group, 5,5,6,6,6-pentafluorohexyl group, 6,6,6-trifluorohexyl group, perfluorocyclohexyl group, chloromethyl group, bromomethyl group, iodomethyl group, A 2-chloroethyl group or a 3-bromopropyl group can be exemplified.

Examples of the aryl group having 6 to 10 carbon atoms represented by R ¹ , R ² , R ³ and R ⁴ are not particularly limited, but include a phenyl group, a 2-methylphenyl group and a 3-methylphenyl group. , 4-methylphenyl group, 2,3-dimethylphenyl group, 2,4-dimethylphenyl group, 2,5-dimethylphenyl group, 2,6-dimethylphenyl group, 3,4-dimethylphenyl group, 3,5 -dimethylphenyl group, 2,3,4-trimethylphenyl group, 2,3,5-trimethylphenyl group, 2,3,6-trimethylphenyl group, 2,4,5-trimethylphenyl group, 2,4,6 -trimethylphenyl group, 3,4,5-trimethylphenyl group, 2,3,4,5-tetramethylphenyl group, 2,3,4,6-tetramethylphenyl group, 2,3,5,6-tetra methylphenyl 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, Examples include 4-(2-methylpropyl)phenyl group, 2-cyclobutylphenyl group, 3-cyclobutylphenyl group, 4-cyclobutylphenyl group, 1-naphthyl group and 2-naphthyl group.

The alkyl group having 1 to 10 carbon atoms, the haloalkyl group having 1 to 10 carbon atoms, and the aryl group having 6 to 10 carbon atoms represented by R ¹ , R ² , R ³ and R ⁴ are each as described above. independently a hydroxyl group, an alkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 10 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an aryloxy group having 6 to 10 carbon atoms, and a dialkylamino group having 2 to 12 carbon atoms; group, a monoarylamino group having 6 to 10 carbon atoms, and a diarylamino group having 12 to 20 carbon atoms.

The alkyl group having 1 to 6 carbon atoms is not particularly limited as long as it is a linear, branched or cyclic alkyl group. Examples include methyl group, ethyl group, propyl group, isopropyl group, butyl group, cyclohexylmethyl group, 2-cyclopentylethyl group, 2-methylpropyl group, 2,2-dimethylpropyl group, 3-cyclopropylpropyl group, cyclopropyl group, 2-methylbutyl group, 3-methylbutyl group , 3-methylbutan-2-yl group, tert-butyl group, cyclobutyl group, pentyl group, 2-methylpentyl group, 1-methylbutyl group, 2-methylpentan-2-yl group, 2-ethylpropyl group, cyclopentyl group , hexyl group, 1-methylpentyl group, 2-ethylbutyl group, or cyclohexyl group.

The aryl group having 6 to 10 carbon atoms is not particularly limited, but examples thereof include phenyl group, 2-methylphenyl group, 3-methylphenyl group, 4-methylphenyl group, 2,3-dimethylphenyl group, 2,4-dimethylphenyl group, 2,5-dimethylphenyl group, 2,6-dimethylphenyl group, 3,4-dimethylphenyl group, 3,5-dimethylphenyl group, 2,3,4-trimethylphenyl group, 2,3,5-trimethylphenyl group, 2,3,6-trimethylphenyl group, 2,4,5-trimethylphenyl group, 2,4,6-trimethylphenyl group, 3,4,5-trimethylphenyl group, 2,3,4,5-tetramethylphenyl group, 2,3,4,6-tetramethylphenyl group, 2,3,5,6-tetramethylphenyl group, 2-ethylphenyl group, 3-ethyl phenyl group, 4-ethylphenyl group, 2,3-diethylphenyl group, 2,4-diethylphenyl group, 2,5-diethylphenyl group, 2,6-diethylphenyl group, 3,4-diethylphenyl group, 3 , 5-diethylphenyl group, 2-propylphenyl group, 3-propylphenyl group, 4-propylphenyl group, 2-isopropylphenyl group, 3-isopropylphenyl group, 4-isopropylphenyl group, 2-cyclopropylphenyl group, 3-cyclopropylphenyl group, 4-cyclopropylphenyl group, 2-butylphenyl group, 3-butylphenyl group, 4-butylphenyl group, 2-(1-methylpropyl)phenyl group, 3-(1-methylpropyl) ) phenyl group, 4-(1-methylpropyl)phenyl group, 2-(2-methylpropyl)phenyl group, 3-(2-methylpropyl)phenyl group, 4-(2-methylpropyl)phenyl group, 2- A cyclobutylphenyl group, 3-cyclobutylphenyl group, 4-cyclobutylphenyl group, 1-naphthyl group, or 2-naphthyl group can be exemplified.

The alkoxy group having 1 to 6 carbon atoms is not particularly limited, and examples thereof include methoxy, ethoxy, propoxy, isopropoxy, butoxy, 2-methylpropoxy and 2,2-dimethyl. propoxy group, 3-cyclopropylpropoxy group, cyclopropoxy group, 2-methylbutoxy group, 3-methylbutoxy group, tert-butoxy group, cyclobutoxy group, pentyloxy group, 2-methylpentyloxy group, 1-methylbutyl group , 1,2-dimethylbutoxy group, 1-ethylpropoxy group, cyclopentyloxy group, hexyl group, or cyclohexyloxy group.

Examples of the aryloxy group having 6 to 10 carbon atoms include, but are not limited to, phenyloxy group, 2-methylphenyloxy group, 3-methylphenyloxy group, 4-methylphenyloxy group, 2 ,3-dimethylphenyloxy group, 2,4-dimethylphenyloxy group, 2,5-dimethylphenyloxy group, 2,6-dimethylphenyloxy group, 3,4-dimethylphenyloxy group, 3,5-dimethylphenyl oxy group, 2,3,4-trimethylphenyloxy group, 2,3,5-trimethylphenyloxy group, 2,3,6-trimethylphenyloxy group, 2,4,5-trimethylphenyloxy group, 2,4 ,6-trimethylphenyloxy group, 3,4,5-trimethylphenyloxy group, 2,3,4,5-tetramethylphenyloxy group, 2,3,4,6-tetramethylphenyloxy group, 2,3 , 5,6-tetramethylphenyloxy group, 2-ethylphenyloxy group, 3-ethylphenyloxy group, 4-ethylphenyloxy group, 2,3-diethylphenyloxy group, 2,4-diethylphenyloxy group, 2,5-diethylphenyloxy group, 2,6-diethylphenyloxy group, 3,4-diethylphenyloxy group, 3,5-diethylphenyloxy group, 2-propylphenyloxy group, 3-propylphenyloxy group, 4-propylphenyloxy group, 2-isopropylphenyloxy group, 3-isopropylphenyloxy group, 4-isopropylphenyloxy group, 2-cyclopropylphenyloxy group, 3-cyclopropylphenyloxy group, 4-cyclopropylphenyloxy group group, 2-butylphenyloxy group, 3-butylphenyloxy group, 4-butylphenyloxy group, 2-(1-methylpropyl)phenyloxy group, 3-(1-methylpropyl)phenyloxy group, 4-( 1-methylpropyl)phenyloxy group, 2-(2-methylpropyl)phenyloxy group, 3-(2-methylpropyl)phenyloxy group, 4-(2-methylpropyl)phenyloxy group, 2-cyclobutylphenyl Examples include oxy group, 3-cyclobutylphenyloxy group, 4-cyclobutylphenyloxy group, 1-naphthyloxy group and 2-naphthyloxy group.

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

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

The diarylamino group having 12 to 20 carbon atoms is not particularly limited, but examples thereof include diphenylamino group, bis(2-methylphenyl)amino group, bis(3-methylphenyl)amino group, bis( 4-methylphenyl)amino group, bis(2,3-dimethylphenyl)amino group, bis(2,4-dimethylphenyl)amino group, bis(2,5-dimethylphenyl)amino group, bis(2,6- dimethylphenyl)amino group, bis(3,4-dimethylphenyl)amino group, bis(3,5-dimethylphenyl)amino group, bis(2,3,4-trimethylphenyl)amino group, bis(2,3, 5-trimethylphenyl)amino group, bis(2,3,6-trimethylphenyl)amino group, bis(2,4,5-trimethylphenyl)amino group, bis(2,4,6-trimethylphenyl)amino group, bis(3,4,5-trimethylphenyl)amino group, bis(2,3,4,5-tetramethylphenyl)amino group, bis(2,3,4,6-tetramethylphenyl)amino group, bis( 2,3,5,6-tetramethylphenyl)amino group, bis(2-ethylphenyl)amino group, bis(3-ethylphenyl)amino group, bis(4-ethylphenyl)amino group, bis(2,3 -diethylphenyl)amino group, bis(2,4-diethylphenyl)amino group, bis(2,5-diethylphenyl)amino group, bis(2,6-diethylphenyl)amino group, bis(3,4-diethyl) phenyl)amino group, bis(3,5-diethylphenyl)amino group, bis(2-propylphenyl)amino group, bis(3-propylphenyl)amino group, bis(4-propylphenyl)amino group, bis(2 -isopropylphenyl)amino group, bis(3-isopropylphenyl)amino group, bis(4-isopropylphenyl)amino group, bis(2-cyclopropylphenyl)amino group, bis(3-cyclopropylphenyl)amino group, bis (4-cyclopropylphenyl)amino group, bis(2-butylphenyl)amino group, bis(3-butylphenyl)amino group, bis(4-butylphenyl)amino group, bis[2-(1-methylpropyl) phenyl]amino group, bis[3-(1-methylpropyl)phenyl]amino group, bis[4-(1-methylpropyl)phenyl]amino group, bis[2-(2-methylpropyl)phenyl]amino group, bis[3-(2-methylpropyl)phenyl]amino group, bis[4-(2-methylpropyl)phenyl]amino group, bis(2-cyclobutylphenyl)amino group, bis(3-cyclobutylphenyl)amino group, bis(4-cyclobutylphenyl)amino group, di(1-naphthyl)amino group, di(2-naphthyl)amino group, N-(2-methylphenyl)-N-phenylamino group, N-(3 -methylphenyl)-N-phenylamino group, N-(4-methylphenyl)-N-phenylamino group, N-(2,3-dimethylphenyl)-N-phenylamino group, N-(2,4- dimethylphenyl)-N-phenylamino group, N-(2,5-dimethylphenyl)-N-phenylamino group, N-(2,6-dimethylphenyl)-N-phenylamino group, N-(3,4 -dimethylphenyl)-N-phenylamino group, N-(3,5-dimethylphenyl)-N-phenylamino group, N-(2,3,4-trimethylphenyl)-N-phenylamino group, N-( 2,3,5-trimethylphenyl)-N-phenylamino group, N-(2,3,6-trimethylphenyl)-N-phenylamino group, N-(2,4,5-trimethylphenyl)-N- phenylamino group, N-(2,4,6-trimethylphenyl)-N-phenylamino group, N-(3,4,5-trimethylphenyl)-N-phenylamino group, N-(1-naphthyl)- N-phenylamino group or N-(2-naphthyl)-N-phenylamino group can be exemplified.

R ¹ , R ² , R ³ and R ⁴ each independently represent an alkyl group having 1 to 6 carbon atoms, an aryloxy group having 6 to 10 carbon atoms, a dialkylamino group having 2 to 12 carbon atoms and a an alkyl group having 1 to 6 carbon atoms optionally substituted by one or more substituents selected from the group consisting of 6 alkoxy groups, or a phenyl optionally substituted by an alkyl group having 1 to 6 carbon atoms each independently an alkyl group having 1 to 6 carbon atoms (the group may be substituted with an alkyl group having 1 to 6 carbon atoms) or a phenyl group (the group is a optionally substituted with alkyl groups of numbers 1 to 6), and each independently a methyl group or an ethyl group is particularly preferred.

When Y ^- is a halide ion, the halide ion is preferably a fluoride ion, a chloride ion, a bromide ion or an iodide ion, preferably a chloride ion, a bromide ion or an iodide ion. more preferred.

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

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

The fluoroalkyl group having 1 to 9 carbon atoms represented by R ⁵ is not particularly limited as long as it is a linear, branched or cyclic fluoroalkyl 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-tetrafluoropropyl group, 3,3,3-trifluoropropyl group, 1,1-difluoropropyl group, perfluoro(1-methylpropyl) group, 2,2,2-trifluoro-1-(trifluoromethyl)ethyl group, perfluorocyclopropyl group, 2,2,3,3-tetrafluorocyclopropyl group, perfluorobutyl group, 2,2,3,3, 4,4,4-heptafluorobutyl group, 3,3,4,4,4-pentafluorobutyl group, 4,4,4-trifluorobutyl group, 1,2,2,3,3,3-hexa fluoro-1-(trifluoromethyl)propyl group, 1-(trifluoromethyl)propyl group, 1-methyl-3,3,3-trifluoropropyl group, perfluorocyclobutyl group, 2,2,3,3, 4,4-hexafluorocyclobutyl group, perfluoropentyl group, 2,2,3,3,4,4,5,5,5-nonafluoropentyl group, 3,3,4,4,5,5,5 -heptafluoropentyl group, 4,4,5,5,5-pentafluoropentyl group, 5,5,5-trifluoropentyl group, 1,2,2,3,3,3-hexafluoro-1-( perfluoroethyl)propyl group, 2,2,3,3,3-pentafluoro-1-(perfluoroethyl)propyl group, perfluorocyclopentyl group, perfluorohexyl group, 2,2,3,3,4,4,5, 5,6,6,6-undecafluorohexyl group, 3,3,4,4,5,5,6,6,6-nonafluorohexyl group, 4,4,5,5,6,6,6 -heptafluorohexyl group, 5,5,6,6,6-pentafluorohexyl group, 6,6,6-trifluorohexyl group, or perfluorocyclohexyl group.

When R ⁵ is a phenyl group, the phenyl group is an alkyl group having 1 to 4 carbon atoms, a fluoroalkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or a fluoroalkoxy group having 1 to 4 carbon atoms. , a halogen atom, and a nitro group such as a cyano group.

The alkyl group having 1 to 4 carbon atoms is not particularly limited as long as it is a linear, branched or cyclic alkyl group. Examples include methyl group, ethyl group, propyl group, Examples include isopropyl group, butyl group, 2-methylpropyl group, cyclopropyl group, tert-butyl group, or cyclobutyl group.

The fluoroalkyl group having 1 to 4 carbon atoms is not particularly limited as long as it is a linear, branched or cyclic fluoroalkyl group. Examples include trifluoromethyl group, difluoromethyl group, perfluoroethyl group, 2,2,2-trifluoroethyl group, 1,1-difluoroethyl group, 2,2-difluoroethyl group, perfluoropropyl group, 2,2,3,3,3-pentafluoropropyl group, 2,2,3,3-tetrafluoropropyl group, 3,3,3-trifluoropropyl group, 1,1-difluoropropyl group, perfluoro(1-methylpropyl) group, 2,2,2-tri fluoro-1-(trifluoromethyl)ethyl group, perfluorocyclopropyl group, 2,2,3,3-tetrafluorocyclopropyl group, perfluorobutyl group, 2,2,3,3,4,4,4-hepta fluorobutyl group, 3,3,4,4,4-pentafluorobutyl group, 4,4,4-trifluorobutyl group, 1,2,2,3,3,3-hexafluoro-1-(trifluoro methyl)propyl group, 1-(trifluoromethyl)propyl group, 1-methyl-3,3,3-trifluoropropyl group, perfluorocyclobutyl group, or 2,2,3,3,4,4-hexafluoro A cyclobutyl group can be exemplified.

The alkoxy group having 1 to 4 carbon atoms is not particularly limited as long as it is a linear, branched or cyclic alkoxy group, and examples thereof include a methoxy group, an ethoxy group, a propoxy group, Examples include isopropoxy, butoxy, 2-methylpropoxy, cyclopropoxy, tert-butoxy, and cyclobutoxy.

The fluoroalkoxy group having 1 to 4 carbon atoms is not particularly limited as long as it is a linear, branched or cyclic fluoroalkoxy group. methyloxy group, perfluoroethyloxy group, 2,2,2-trifluoroethyloxy group, 1,1-difluoroethyloxy group, 2,2-difluoroethyloxy group, perfluoropropyloxy group, 2,2,3, 3,3-pentafluoropropyloxy group, 2,2,3,3-tetrafluoropropyloxy group, 3,3,3-trifluoropropyloxy group, 1,1-difluoropropyloxy group, perfluoro(1-methyl propyl)oxy group, 2,2,2-trifluoro-1-(trifluoromethyl)ethyloxy group, perfluorocyclopropyloxy group, 2,2,3,3-tetrafluorocyclopropyloxy group, perfluorobutyloxy group, 2,2,3,3,4,4,4-heptafluorobutyloxy group, 3,3,4,4,4-pentafluorobutyloxy group, 4,4,4-trifluorobutyloxy group, 1, 2,2,3,3,3-hexafluoro-1-(trifluoromethyl)propyloxy group, 1-(trifluoromethyl)propyloxy group, 1-methyl-3,3,3-trifluoropropyloxy group , a perfluorocyclobutyloxy group, or a 2,2,3,3,4,4-hexafluorocyclobutyloxy group.

Examples of the halogen atom include, but are not limited to, a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom.

R ⁵ represented by an alkyl group having 1 to 4 carbon atoms, a fluoroalkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a fluoroalkoxy group having 1 to 4 carbon atoms, a halogen atom, a cyano group and A phenyl group optionally substituted with one or more substituents selected from the group consisting of a nitro group (hereinafter also referred to as a "substituted phenyl group") is not particularly limited, but for example, phenyl group, 2-methylphenyl group, 4-methylphenyl group, 2,5-dimethylphenyl group, 2,4,6-trimethylphenyl group, 4-ethylphenyl group, 4-propylphenyl group, 2,4,6- triisopropylphenyl group, 4-tert-butylphenyl group, 2-trifluoromethylphenyl group, 3-(trifluoromethyl)phenyl group, 4-trifluoromethylphenyl group, 3,5-bis(trifluoromethyl)phenyl group, 4-methoxyphenyl group, 4-(isopropoxy)phenyl group, 4-trifluoromethoxyphenyl group, 2-fluorophenyl group, 3-fluorophenyl group, 4-fluorophenyl group, 2-chlorophenyl group, 3- chlorophenyl group, 4-chlorophenyl group, 3,5-dichlorophenyl group, 2,6-dichlorophenyl group, 2-bromophenyl group, 3-bromophenyl group, 4-bromophenyl group, 2-cyanophenyl group, 3-cyanophenyl group, 4-cyanophenyl group, 2-nitrophenyl group, 3-nitrophenyl group or 4-nitrophenyl group.

R ⁵ is preferably a phenyl group, a 4-methylphenyl group, a methyl group or a trifluoromethyl group. That is, the sulfonate ion represented by R ₅ SO ₂ O ^- is the benzenesulfonate ion represented by C ₆ H ₅ SO ₂ O ^- , and the p-CH ₃ C ₆ H ₄ SO ₂ O ^- is represented. Preferred are p-toluenesulfonate ions, methanesulfonate ions represented by CH ₃ SO ₂ ^O-- , and trifluoromethanesulfonate ions represented by CF ₃ SO ₂ ^O-- .

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

The alkyl group having 1 to 6 carbon atoms is not particularly limited as long as it is a linear, branched or cyclic alkyl group. Examples include methyl group, ethyl group, propyl group, isopropyl group, butyl group, 2-methylpropyl group, 2,2-dimethylpropyl group, 3-cyclopropylpropyl group, cyclopropyl group, 2-methylbutyl group, 3-methylbutyl group, 3-methylbutan-2-yl group, tert-butyl group, cyclobutyl group, pentyl group, 2-methylpentyl group, 1-methylbutyl group, 2-methylpentan-2-yl group, 1-ethylpropyl group, cyclopentyl group, hexyl group, 1-methylpentyl group, 1-ethylbutyl A group or a cyclohexyl group can be exemplified.

Although the above fluoroalkyl group having 1 to 4 carbon atoms is not particularly limited, the same groups as the fluoroalkyl groups having 1 to 4 carbon atoms exemplified in the description of R ⁵ can be exemplified.

The above alkyl group having 1 to 4 carbon atoms is not particularly limited, but the same groups as the alkyl groups having 1 to 4 carbon atoms exemplified in the description of R ⁵ can be exemplified.

R ⁶ is preferably either a phenyl group, a 4-methylphenyl group, a methyl group or a trifluoromethyl group. That is, the carboxylate ion represented by R ⁶ COO ^- is the benzoate ion represented by C ₆ H ₅ COO ^- , the 4-methylbenzoate ion represented by 4-CH ₃ C ₆ H ₄ COO ^- , An acetate ion represented by CH ₃ COO ^- or a trifluoroacetate ion represented by CF ₃ COO ^- is preferable.

Y ⁻ is preferably a halide ion, a sulfonate ion represented by R ⁵ SO ₂ O ⁻ or OH ⁻ (hydroxide ion), Cl ⁻ (chloride ion), Br ⁻ (bromide ion), I ⁻ (iodide ion), benzenesulfonate ion represented by C ₆ H ₅ SO ₂ O ⁻ , p-toluenesulfonate ion represented by p—CH ₃ C ₆ H ₄ SO ₂ O ⁻ , a methanesulfonate ion represented by CH ₃ SO ₂ ^O- , a trifluoromethanesulfonate ion represented by CF ₃ SO ₂ ^O- or ^OH- (hydroxide ion), and Br- ⁽ bromide ion), Cl ⁻ (chloride ion) or OH ⁻ (hydroxide ion).

Preferred embodiments of the hexahydrobenzodipyrrolilium salt (1) of the present invention include hexahydrobenzodipyrrolilium salts represented by general formula (1').

In the formula, X, R ¹ , R ² , R ³ , R ⁴ and Y ^— have the same definitions as those in general formula (1), R ¹ and R ² are the same, R ³ and R ⁴ are the same.

A more preferred embodiment is a hexahydrobenzodipyrrolinium salt represented by general formula (1″).

wherein X, R ¹ , R ² , R ³ , R ⁴ and Y ^— have the same definitions as those in general formula (1), and R ¹ , R ² , R ³ and R ⁴ are the same .

A more preferred embodiment is a hexahydrobenzodipyrrolinium salt represented by the general formula (1'').

wherein X represents a hydrogen atom,
R ¹ , R ² , R ³ and R ⁴ , which may be the same or different, represent a methyl group or an ethyl group,
Y ⁻ is the same or different and is chloride ion, bromide ion, iodide ion, benzenesulfonate ion, p-toluenesulfonate ion, methanesulfonate ion, trifluoromethanesulfonate ion or hydroxide ion; Of these, chloride ions, bromide ions and hydroxide ions are particularly preferred.

Specific examples of hexahydrobenzodipyrolium salt (1) include the following (1-1) to (1-978), but the present invention is not limited thereto.

In the present specification, Me is a methyl group, Et is an ethyl group, Pr is a propyl group, iPr is an isopropyl group, Bu is a butyl group, Hex is a hexyl group, Hep is a heptyl group, Oct is an octyl group, and Nony is nonyl. Dec is a decyl group, Dodec is a dodecyl group, Octdec is an octadecyl group, Undec is an undecyl group, Cy is a cyclohexyl group, Ph is a phenyl group, and TsO 2 ^- is a p-toluenesulfonate ion.

Among the compounds represented by (1-1) to (1-978), hexahydrobenzodipyrolium salts of the present invention include 1-2, 1-3, 1-5, 1-26, 1-27, 1-29, 1-38, 1-39, 1-41, 1-62, 1-63, 1-65, 1-74, 1-75, 1-77, 1-110, 1-111, 1- 113, 1-135, 1-136, 1-137, 1-334, 1-335, 1-337, 1-430, 1-431, 1-433, 1-586, 1-587, 1-589, Compounds represented by 1-728, 1-729, 1-731, 1-740, 1-741, 1-743, 1-836, 1-837 and 1-839 are preferred for ease of synthesis.

Next, the method for producing the hexahydrobenzodipyrolium salt (1) of the present invention will be explained.

<Embodiment 1 of manufacturing method>
As a method for producing the hexahydrobenzodipyrolium salt (1) of the present invention, a step of reacting an aromatic compound represented by the general formula (2) with a secondary amine represented by the general formula (3) and a method for producing a hexahydrobenzodipyrrolinium salt represented by the general formula (1a) (hereinafter also referred to as “production method 1”).

X may be the same or different and has the same definition as X in formula (1).

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

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

R ⁷ and R ⁸ are each independently an alkyl group having 1 to 10 carbon atoms, a haloalkyl group having 1 to 10 carbon atoms, or an aryl group having 6 to 10 carbon atoms (these substituents are hydroxyl, to 6 alkyl groups, aryl groups having 6 to 10 carbon atoms, alkoxy groups having 1 to 6 carbon atoms, aryloxy groups having 6 to 10 carbon atoms, dialkylamino groups having 2 to 12 carbon atoms, dialkylamino groups having 6 to 10 carbon atoms, optionally substituted with one or more substituents selected from the group consisting of a monoarylamino group and a diarylamino group having 12 to 20 carbon atoms).

X may be the same or different and has the same definition as X in formula (1).

R ⁷ and R ⁸ are synonymous with R ⁷ and R ⁸ in general formula (3).

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

R ⁵ has the same definition as R ⁵ in formula (2).

Each substituent represented by R ⁷ and R ⁸ above (alkyl group having 1 to 10 carbon atoms, haloalkyl group having 1 to 10 carbon atoms, aryl group having 6 to 10 carbon atoms, alkyl group having 1 to 6 carbon atoms , an aryl group having 6 to 10 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an aryloxy group having 6 to 10 carbon atoms, a dialkylamino group having 2 to 12 carbon atoms, a monoarylamino group having 6 to 10 carbon atoms, diarylamino group having 12 to 20 carbon atoms) has the same meaning as defined for each substituent in R ¹ , R ² , R ³ and R ⁴ .

R ⁷ and R ⁸ are preferably each independently an alkyl group having 1 to 12 carbon atoms or a 2-ethoxyethyl group, and each independently a methyl group, an ethyl group or a 2-ethoxyethyl group. more preferred.

X is preferably a hydrogen atom, a chlorine atom, a bromine atom or an iodine atom, more preferably a hydrogen atom.

Ya represents a halogen atom or an organic sulfonyloxy group represented by R ⁵ SO ₂ O, wherein Ya is a chlorine atom, a bromine atom, an iodine atom, a benzenesulfonyloxy group, a p-toluenesulfonyloxy, a methanesulfonyloxy group; or a trifluoromethylsulfonyloxy group, more preferably a bromine atom, an iodine atom, a p-toluenesulfonyloxy group or a methanesulfonyloxy group.

Commercially available products can be used as the aromatic compound (2) and the secondary amine (3) to be subjected to the reaction in production method 1, and known methods for obtaining aromatic compounds, for example, Tetrahedron, Vol.71, 6944 -6955, 2005, Journal of the American Chemical Society, Vol. 129, pp. 13362-13363, 2007.

In the reaction of production method 1, the secondary amine (3) is preferably 2 to 100 molar equivalents, more preferably 2 to 10 molar equivalents, relative to the aromatic compound (2).

In production method 1, the aromatic compound (2) and the secondary amine (3) are preferably reacted in the presence of a base. Examples of the base include organic bases and inorganic bases. Examples of organic bases include, but are not limited to, trimethylamine, triethylamine, diisopropylethylamine, pyridine, pyrrolidine, diethylamine, 1,4-diazabicyclo[2.2.2]octane, 1,8-diazabicyclo[5. 4.0]undecene and the like, but the inorganic base is not particularly limited, but examples thereof include sodium hydroxide, potassium hydroxide, sodium hydride, potassium hydride, sodium hydrogen carbonate, potassium hydrogen carbonate, sodium carbonate, Potassium carbonate, cesium carbonate and the like can be exemplified, respectively.

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

Also, the secondary amine (3) can act as the aforementioned base. For example, the amount of the secondary amine (3) added is excessive, for example, 2 molar equivalents or more, further 5 molar equivalents or more relative to the aromatic compound (2). The reaction can be carried out in the presence of a base.

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

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

In production method 1, preferred solvents are ether solvents, alcohol solvents and nitrile solvents, and more preferred solvents are tetrahydrofuran, ethanol and acetonitrile.

In Production Method 1, the preferred reaction temperature is any temperature of 0° C. or higher and 200° C. or lower, the more preferred reaction temperature is 20° C. or higher and 80° C. or lower, and the preferred reaction time is 1 hour or longer and 100 hours or shorter.

Production method 1 includes a step of isolating a hexahydrobenzodipyrrolinium salt represented by the general formula (1a) (hereinafter also referred to as an “isolation step”), and, if necessary, hexahydro after isolation. A step of ion-exchanging the benzodipyrrolinium salt (hereinafter, also referred to as an "ion-exchanging step") may be included.

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

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

In the formula, R ⁷ , R ⁸ and X have the same definitions as R ⁷ , R ⁸ and X in general formula (1a), and ^Yb- represents a halide ion or a hydroxide ion.

As the ion exchange method, a general method used for ion exchange of quaternary ammonium salts by those skilled in the art can be used. Just do it. The ion-exchange resin may be any ion-exchange resin having an exchange group ^Yb- . , Amberlite IRA-458, Amberlite IRA-958, Amberlite IRA-420, Amberlite IRN-78, Amberlite IRA-411 and Amberlite IRA-910, preferably Amberlite IRA-400. .

Ion exchange may be carried out in a solvent that does not interfere with ion exchange. The solvent includes one or more selected from the group of ether solvents, ester solvents, ketone solvents, nitrile solvents, alcohol solvents and water. Examples of specific solvents are the same as the specific solvents exemplified in the description of the production method 1 above.

<Embodiment 2 of Manufacturing Method>
As another embodiment of the method for producing a hexahydrobenzodipyrrolium salt of the present embodiment, hexahydrobenzodipyrrole represented by general formula (4a) and an alkylating agent represented by general formula (5a) A method for producing a hexahydrobenzodipyrrolinium salt represented by the general formula (1c) (hereinafter also referred to as “production method 2”), characterized by having a step of reacting.

In the formula, R ⁹ is the same or different and is an alkyl group having 1 to 10 carbon atoms, a haloalkyl group having 1 to 10 carbon atoms, or an aryl group having 6 to 10 carbon atoms (these substituents are hydroxyl group, carbon an alkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 10 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an aryloxy group having 6 to 10 carbon atoms, a dialkylamino group having 2 to 12 carbon atoms, and a dialkylamino group having 2 to 12 carbon atoms; optionally substituted with one or more substituents selected from the group consisting of monoarylamino groups having 10 carbon atoms and diarylamino groups having 12 to 20 carbon atoms).

In the formula, R ¹⁰ is an alkyl group having 1 to 10 carbon atoms or a haloalkyl group having 1 to 10 carbon atoms (these substituents are a hydroxyl group, an alkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 10 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an aryloxy group having 6 to 10 carbon atoms, a dialkylamino group having 2 to 12 carbon atoms, a monoarylamino group having 6 to 10 carbon atoms and a diarylamino group having 12 to 20 carbon atoms. optionally substituted with one or more substituents selected from the group of groups) represents
Ya represents a halogen atom or _an organic sulfonyloxy group represented by ^R5SO2O .

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

In the formula, R ⁹ has the same definition as R ⁹ in general formula (4a).

In the formula, R ¹⁰ has the same definition as R ¹⁰ in general formula (5a).

^Ya- is the same or different and represents a halide ion or a sulfonate ion represented by R ⁵ SO ₂ ^O- .

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

R ⁹ , an alkyl group having 1 to 10 carbon atoms, a haloalkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, an alkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 10 carbon atoms, carbon alkoxy groups having 1 to 6 carbon atoms, aryloxy groups having 6 to 10 carbon atoms, dialkylamino groups having 2 to 12 carbon atoms, monoarylamino groups having 6 to 10 carbon atoms, and diarylamino groups having 12 to 20 carbon atoms is not particularly limited, but in R ¹ to R ⁴ , an alkyl group having 1 to 10 carbon atoms, a haloalkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, an aryl group having 1 to 6 carbon atoms, an alkyl group, an alkoxy group having 1 to 6 carbon atoms, an aryloxy group having 6 to 10 carbon atoms, a dialkylamino group having 2 to 12 carbon atoms, a monoarylamino group having 6 to 10 carbon atoms, and a monoarylamino group having 6 to 10 carbon atoms and 12 to 20 carbon atoms The same as the diarylamino group can be exemplified.

R ¹⁰ , an alkyl group having 1 to 10 carbon atoms, a haloalkyl group having 1 to 10 carbon atoms, an alkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 10 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, and carbon The aryloxy group having 6 to 10 carbon atoms, the dialkylamino group having 2 to 12 carbon atoms, the monoarylamino group having 6 to 10 carbon atoms, and the diarylamino group having 12 to 20 carbon atoms are not particularly limited. , an alkyl group having 1 to 10 carbon atoms, a haloalkyl group having 1 to 10 carbon atoms, an alkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 10 carbon atoms, and an aryl group having 1 to 6 carbon atoms in R ¹ to R ⁴ Examples are the same as alkoxy group, aryloxy group having 6 to 10 carbon atoms, dialkylamino group having 2 to 12 carbon atoms, monoarylamino group having 6 to 10 carbon atoms and diarylamino group having 12 to 20 carbon atoms. be able to.

R ⁹ and R ¹⁰ are each independently selected from an alkyl group having 1 to 6 carbon atoms, an aryloxy group having 6 to 10 carbon atoms, a dialkylamino group having 2 to 12 carbon atoms and an alkoxy group having 1 to 6 carbon atoms. an alkyl group having 1 to 6 carbon atoms optionally substituted by one or more substituents selected from the group consisting of, or a phenyl group optionally substituted by an alkyl group having 1 to 6 carbon atoms Preferably, each independently an alkyl group having 1 to 6 carbon atoms (the group may be substituted with an alkyl group having 1 to 6 carbon atoms) or a phenyl group (the group is optionally substituted with an alkyl group), and each independently a methyl group or an ethyl group is particularly preferred.

Preferred or more preferred Ya is the same as in Production Method 1.

Hexahydrobenzodipyrrole (4a) and alkylating agent (5a), which are subjected to the reaction in production method 2, are commercially available, and hexahydrobenzodipyrrole (4a) can be obtained according to raw material production method 1 described later. can also be obtained.

In the reaction of production method 2, the alkylating agent (5a) is preferably 2 to 100 molar equivalents, more preferably 2 to 10 molar equivalents, relative to hexahydrobenzodipyrrole (4a).

In the reaction of production method 2, it is preferable to react hexahydrobenzodipyrrole (4a) and alkylating agent (5a) in a solvent. The solvent is preferably one that does not inhibit the reaction, and the same solvent as in the reaction of production method 1 can be exemplified.

Specific solvent, preferred solvent, reaction temperature, reaction time and other conditions in the reaction of production method 2 are the same as those in the reaction of production method 1.

Production method 2 is a step of isolating the hexahydrobenzodipyrrolilium salt (1c), or subjecting it (or the isolated hexahydrobenzodipyrroliium salt represented by general formula (1c)) to ion exchange. At least one of the steps may be included.

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

A hexahydrobenzodipyrrolinium salt represented by the general formula (1d) can be obtained by ion exchange of the hexahydrobenzodipyrroliium salt represented by the general formula (1c).

In the formula, R ⁹ and R ¹⁰ have the same definitions as R ⁹ and R ¹⁰ in general formula (1c), and ^Yb- represents a halide ion or a hydroxide ion.

Preferred or more preferred Yb ^— is the same as Yb ^— in production method 1.

Ion exchange can be carried out by bringing the hexahydrobenzodipyrolium salt (1c) into contact with an ion exchange resin. The ion exchange resin, solvent, and other conditions in the ion exchange are the same as those in the ion exchange step of production method 1, for example.

<Method for Producing Hexahydrobenzodipyrrole Represented by General Formula (4a)>
An embodiment of the method for producing hexahydrobenzodipyrrole (4a) to be used in production method 2 is characterized by including a step of reacting pyromellitic diimide represented by general formula (6a) with a reducing agent. A method for producing hexahydrobenzodipyrrole (4a) (hereinafter also referred to as “raw material production method 1”).

In the formula, R ⁹ may be the same or different and has the same definition as R ⁹ in general formula (4a).

In the formula, R ⁹ may be the same or different and has the same definition as R ⁹ in general formula (4a).

R ⁹ , preferred or more preferred R ⁹ in raw material production method 1 is the same as in production method 2.

The reducing agent used in raw material production method 1 includes aluminum hydride, lithium aluminum hydride, sodium bis(2-methoxyethoxy)aluminum hydride, borane-dimethylsulfide complex, borane-tetrahydrofuran complex, borane-pyridine complex, and hydrogen. Sodium borohydride/boron trifluoride-diethyl ether complex can be exemplified, lithium aluminum hydride, sodium bis(2-methoxyethoxy)aluminum hydride, borane-dimethylsulfide complex, and borane-tetrahydrofuran complex are preferred, and hydrogenation Aluminum lithium or borane-dimethylsulfide complexes are more preferred.

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

In raw material production method 1, pyromellitic diimide (6a) and a reducing agent may be reacted in a solvent. The solvent may be one that does not inhibit the reaction, and includes aromatic hydrocarbon solvents such as benzene, toluene, and xylene; ether solvents such as tetrahydrofuran, cyclopentylmethyl ether, diethyl ether, diisopropyl ether, and MTBE; and methanol and ethanol. , isopropyl alcohol, etc., can be exemplified by one or more appropriately selected according to the type of reducing agent. Preferred solvents are aromatic hydrocarbon solvents or ether solvents, and more preferred solvents are toluene or Tetrahydrofuran can be exemplified.

In the raw material production method 1, the preferred reaction temperature is any temperature of 20° C. or higher and 150° C. or lower, the more preferred reaction temperature is 40° C. or higher and 120° C. or lower, and the preferred reaction time is 1 hour or longer and 100 hours or shorter. .

Raw material production method 1 may include a step of isolating hexahydrobenzodipyrrole (4a).

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

<Embodiment 3 of manufacturing method>
As another embodiment of the method for producing hexahydrobenzodipyrrolium salt (1) of the present embodiment, hexahydrobenzodipyrrole represented by general formula (4b) and alkyl represented by general formula (5a) A method for producing a hexahydrobenzodipyrolium salt represented by the general formula (1f) (hereinafter also referred to as “production method 3”), characterized by comprising a step of reacting with an agent can.

wherein X is the same or different and represents a hydrogen atom or a halogen atom;
R ¹¹ are the same or different and represent a hydrogen atom or an acyl group represented by R ¹² C(O),
R ¹² represents a haloalkyl group having 1 to 10 carbon atoms.

The alkylating agent (5a) used in production method 3 has the same definition as the alkylating agent (5a) in production method 2.

In the formula, R ¹⁰ has the same definition as R ¹⁰ in general formula (4b).

In the formula, X has the same definition as X in general formula (4b).

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

Preferred or more preferred X and preferred Ya are the same as in Production Method 1, respectively.

R ¹² is a haloalkyl group having 1 to 10 carbon atoms, and can be exemplified by the same haloalkyl group having 1 to 10 carbon atoms for R ¹ , R ² , R ³ and R ⁴ , although it is not particularly limited. A preferable haloalkyl group having 1 to 10 carbon atoms represented by R ¹² is preferably a trifluoromethyl group, a pentafluoroethyl group, or a trichloromethyl group, and is preferably a trifluoromethyl group or a trichloromethyl group. more preferred.

Although R ¹¹ is not particularly limited, it is preferably a hydrogen atom, a trifluoroacetyl group, a pentafluoroethylcarbonyl group or a trichloromethylcarbonyl group, and is a hydrogen atom, a trifluoroacetyl group or a trichloromethylcarbonyl group. is more preferable.

In production method 3, R ¹⁰ and preferred R ¹⁰ are the same as R ¹⁰ and preferred R ¹⁰ in production method 2.

In production method 3, Ya and preferred or more preferred Ya are the same as Ya and preferred or more preferred Ya in production method 1.

The hexahydrobenzodipyrrole and the alkylating agent to be subjected to the reaction of Production Method 3 may be known or commercially available.

In production method 3, the amount of the alkylating agent (5a) used relative to hexahydrobenzodipyrrole (4b) is preferably 4 to 100 molar equivalents, more preferably 4 to 10 molar equivalents.

In production method 3, it is preferable to react hexahydrobenzodipyrrole (4b) with the alkylating agent (5a) in the presence of a base. The base can be exemplified by the same base as in the reaction of Production Method 1, and is preferably one or more selected from the group of sodium hydroxide, potassium hydroxide, sodium methoxide and sodium ethoxide. is more preferable.

In production method 3, hexahydrobenzodipyrrole (4b) and the alkylating agent (5a) are preferably reacted in a solvent. The solvent is preferably one that does not inhibit the reaction, and is not particularly limited.

Specific solvent, preferred solvent, reaction temperature, reaction time and other conditions in production method 3 are the same as those in the reaction of production method 1 described above.

Production method 3 is a step of isolating the hexahydrobenzodipyrrolilium salt (1f), or subjecting it (or the isolated hexahydrobenzodipyrrolilium salt represented by general formula (1f)) to ion exchange. At least one of the steps may be performed.

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

The hexahydrobenzodipyrrolinium salt (1f) is ion-exchanged by ion exchange to obtain the hexahydrobenzodipyrrolilium salt represented by the general formula (1g).

In the formula, R ¹⁰ has the same definition as R ¹⁰ in general formula (1f), and Yb ^- represents a halide ion or OH ^- .

Ion exchange can be carried out by bringing the hexahydrobenzodipyrrolinium salt represented by the general formula (1f) into contact with an ion exchange resin.

The ion exchange resin, solvent and other conditions in the ion exchange of the hexahydrobenzodipyrolium salt represented by the general formula (1f) are the same as those in the ion exchange step of production method 1.

<Method for Producing Hexahydrobenzodipyrrole Represented by General Formula (4c)>
As an embodiment of the method for producing hexahydrobenzodipyrrole represented by general formula (4c) to be subjected to production method 3, an aromatic compound (2) is reacted with an amide compound represented by general formula (3b). A method for producing hexahydrobenzodipyrrole represented by the general formula (4c) (hereinafter also referred to as “raw material production method 2”), characterized by having a step of allowing.

(Wherein, X and Ya have the same meanings as above.)

In the formula, R ¹² has the same definition as R ¹² in general formula (4b).

In the formula, X is the same as X in general formula (2).

In the formula, R ¹² is the same as R ¹² in general formula (3b).

Preferred X and Ya have the same meanings as preferred X and Ya in Production Method 1, and ^R12 has the same meaning as ^R12 in the reaction in Production Method 3.

The aromatic compound (2) and the amide compound (3b) to be subjected to the reaction of the raw material production method 2 may be commercially available products and can be obtained according to known synthetic methods well known to those skilled in the art.

In the raw material production method 2, the amide compound (3b) is preferably 2 to 50 molar equivalents, more preferably 2 to 5 molar equivalents, relative to the aromatic compound (2).

In the raw material production method 2, it is preferable to react the aromatic compound (2) and the amide compound (3b) in the presence of a base. The base can be exemplified by the same base as in the reaction of Production Method 1, and is preferably diisopropylethylamine, 1,8-diazabicyclo[5.4.0]undecene, sodium hydride or potassium hydride, Sodium hydride is more preferred.

In the raw material production method 2, the reaction can be carried out in a solvent. The solvent is preferably one that does not inhibit the reaction, and includes aromatic hydrocarbon solvents, ether solvents, ester solvents, halogen solvents, amide solvents, urea solvents, ketone solvents, nitrile solvents and sulfoxide solvents. One or more selected from the group. Examples of specific solvents are the same as the specific solvents in the reaction of production method 1, respectively.

Preferred solvents include one or more selected from the group of ether solvents, amide solvents and nitrile solvents, and more preferred solvents are one or more selected from the group of tetrahydrofuran, N,N-dimethylformamide and acetonitrile. can be exemplified.

The reaction temperature, reaction time, and other conditions in the reaction of the raw material production method 2 are the same conditions as those in the reaction of the production method 1 can be exemplified.

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

A method for producing a zeolite using the hexahydrobenzodipyrolium salt (1) of the present invention as SDA will be described below.

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

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

The AFX structure is an IUPAC structure code determined by the Structure Commission of the International Zeolite Association (hereinafter referred to as "IZA"), and is a structure of AFX type.

In the present embodiment, the crystalline aluminosilicate uses aluminum (Al) and silicon (Si) as skeleton metals (hereinafter also referred to as “T atoms”), and the T atoms are three-dimensionally bonded through oxygen atoms (O). It has a skeletal structure consisting of a network of

The silica source is silica (SiO ₂ ) or its precursor silicon compound, such as colloidal silica, amorphous silica, sodium silicate, tetraethylorthosilicate, precipitated silica, fumed silica, crystalline aluminosilicate and aluminosilicate. It includes at least one selected from the group of silicate gels, preferably at least one of crystalline aluminosilicate and aluminosilicate gel.

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

The alkali source includes at least one of alkali metal hydroxides and halides, and is preferably at least one selected from the group consisting of sodium hydroxide, potassium hydroxide, rubidium hydroxide and cesium hydroxide.

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

_SiO2 / _Al2O3 : 5 or more and 100 or less _,
preferably 10 or more and 50 or less,
More preferably 15 or more and 40 or less OH/SiO ₂ : 0.06 or more and 1.0 or less,
preferably 0.08 or more and 0.60 or less,
More preferably 0.10 or more and 0.40 or less M/SiO ₂ : 0.06 or more and 1.0 or less,
preferably 0.08 or more and 0.60 or less,
More preferably 0.10 or more and 0.40 or less SDA/SiO ₂ : 0.01 or more and 2.0 or less
Preferably 0.02 or more and 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 and 50 or less,
More preferably 15 or more _and 40 _or less In the above composition, SiO ₂ /Al ₂ O ₃ is _the molar ratio of silica to alumina in the raw material composition, ₂ O/SiO ₂ is the molar ratio of hydroxide ion, alkali metal, SDA or water, respectively, to silica in the feed composition. 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 respectively Na/SiO ₂ or (Na+K)/SiO ₂ .

In the present embodiment, the raw material composition may contain seed crystals. When seed crystals are included, the content of the seed crystals in the raw material composition is 0% by weight or more as a weight ratio of silicon in the seed crystals converted to silica with respect to the weight of silicon in the raw material composition converted to silica (SiO ₂ ). 10.0% by weight or less, further 0.5% by weight or more and 5.0% by weight or less, or further 0.5% by weight or more and 3.5% by weight or less.

The seed crystal may be any zeolite that does not contain an odd-numbered ring in the crystal structure, and has any structure selected from the group of FAU, CHA, AEI, LEV, AFX, ERI, OFF, LTL and GME, for example. Zeolite is preferred, zeolite having any one structure selected from the group of CHA, AEI, LEV, AFX and ERI is more preferred, and AFX-type zeolite is even more preferred.

In the present embodiment, the raw material composition is crystallized in the crystallization step, and the raw material composition may be crystallized by subjecting the raw material composition to hydrothermal treatment. The hydrothermal treatment can be carried out by placing the raw material composition in a sealed pressure-resistant container and heating it. Hydrothermal treatment conditions include the following.

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: Autogenous pressure The state of the raw material composition during crystallization is arbitrary, and can be left still or stirred. Any of the following methods may be used, but stirring is preferred.

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.

The washing step washes the zeolite. Any washing method can be used, but one example is contacting the zeolite with a sufficient amount of pure water.

The drying step removes water from the zeolite. Although the drying method is arbitrary, zeolite may be treated in air at 100° C. or higher and 150° C. or lower for 2 hours or longer.

The SDA removal step removes SDA remaining in the zeolite. As a method for removing SDA, a treatment at 400° C. or higher and 700° C. or lower in the air for 1 to 2 hours can be mentioned.

The ammonium treatment step removes the alkali metal from the zeolite and changes the cation type to the ammonium type (hereinafter referred to as "NH ₄ ⁺ type"). The ammonium treatment method includes contacting an aqueous solution containing ammonium ions with zeolite. The NH ₄ ⁺ -type zeolite may be heat-treated to obtain a proton-type zeolite (hereinafter referred to as "H ⁺ -type") cation type. As specific heat treatment conditions, 500° C. in air for 1 to 2 hours can be exemplified.

The zeolite obtained by the zeolite production method of the present embodiment can be used for known zeolite applications such as adsorbents, catalysts, adsorbent carriers, and catalyst carriers.

Next, examples of the present disclosure are shown. However, the present disclosure is not limited to these.
(H ¹ -NMR)
H ¹ -NMR spectra of samples were measured using Ascend ^™ 400 (400 MHz, Bruker) or UltraShield ^™ Plus 400 (400 MHz, Bruker). Deuterated chloroform (CDCl ₃ ), deuterated dimethylsulfoxide- _{d 6} (DMSO-d ₆ ), deuterated acetone (Acetone-d ₆ ), or deuterated water (D ₂ O) was used as the measurement solvent, and tetramethylsilane (TMS) was used as the internal standard substance. ) was used to measure the H ¹ -NMR spectrum of the sample. The measured data are listed in order of chemical shift, multiplicity, coupling constant (Hz) and integral value.
(Powder X-ray diffraction)
A general X-ray diffraction device (Device name: Ultima IV, manufactured by RIGAKU) was used to measure the XRD of the sample. The measurement conditions are as follows.

Radiation source: CuKα ray (λ = 1.5405 Å)
Measurement mode: step scan
Scan width: 0.02°
Divergence slit: 1.00deg
Scattering slit: open
Receiving slit: open
Measurement time: 1.0 minutes
Measurement range: 2θ = 3.0° to 43.0°
The crystalline phase and XRD peak intensity ratio of the sample were confirmed by comparing the obtained XRD pattern with the XRD pattern posted on the home page of IZA's Structure Commission.
(quantification of silicon and aluminum)
A composition analysis of the sample was performed using a general inductively coupled plasma emission spectrometer (device name: OPTIMA3300DV, manufactured by PERKIN ELMER). A 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 the apparatus and the composition of the sample was analyzed. SiO ₂ /Al ₂ O ₃ was calculated from the obtained molar concentrations of silicon (Si) and aluminum (Al).
(Synthesis of hexahydrobenzodipyrolium salt)
Example 1-1

To a solution of 1,2,4,5-tetrakis(bromomethyl)benzene (1.80 g, 4.00 mmol) in ethanol (8.0 mL) was added a 2.0 M tetrahydrofuran solution of dimethylamine (8.40 mL, 16.8 mmol). The mixture was added and stirred at 70°C for 5 hours. After the reaction, the precipitated solid was collected by filtration and washed with a mixed solution of ethanol/tetrahydrofuran (1:1) to give a white solid of 2,2,6,6-tetramethyl-1,2,3,5,6, 7-Hexahydrobenzo[1,2-c:4,5-c′]dipyrrolilium dibromide (1.40 g, 92% yield) was obtained.

NMR spectrum of 2,2,6,6-tetramethyl-1,2,3,5,6,7-hexahydrobenzo[1,2-c:4,5-c′]dipyrolium dibromide: ¹ H- NMR (400 MHz, _D2O ): ? 7.46 (s, 2H), 4.92 (s, 8H), 3.37 (s, 12H).

Example 1-2

N-ethyl-N-methylamine (1.44 mL, 16 .8 mmol) was added and stirred at 70° C. for 2 hours. After the reaction, the solvent was distilled off from the reaction solution under reduced pressure, and the resulting solid was washed with acetone to give a white solid of 2,6-diethyl-2,6-dimethyl-1,2,3,5,6. ,7-hexahydrobenzo[1,2-c:4,5-c′]dipyrrolinium dibromide (1.10 g, 68% yield).

NMR spectrum of 2,6-diethyl-2,6-dimethyl-1,2,3,5,6,7-hexahydrobenzo[1,2-c:4,5-c′]dipyrolium dibromide: ¹ H - NMR (400 MHz, D ₂ O): δ 7.40 (s, 2H), 4.89 (d, J = 14.5 Hz, 4H), 4.78 (d, J = 14.5 Hz, 4H), 3 .64 (q, J=7.2 Hz, 4H), 3.17 (s, 6H), 1.38 (t, J=7.2 Hz, 6H).

Example 1-3

Diethylamine (12.2 mL, 118 mmol) was added to a solution of 1,2,4,5-tetrakis(bromomethyl)benzene (12.6 g, 28.0 mmol) in ethanol/tetrahydrofuran (1:1, 90 mL) at 70°C for 4 hours. Stirred for an hour. After the reaction, the precipitated solid was collected by filtration and washed with a mixed solution of ethanol/tetrahydrofuran (1:1) to obtain 2,2,6,6-tetraethyl-1,2,3,5,6,7 as a white solid. -Hexahydrobenzo[1,2-c:4,5-c′]dipyrrolilium dibromide (9.87 g, 81% yield).

NMR spectrum of 2,2,6,6-tetraethyl-1,2,3,5,6,7-hexahydrobenzo[1,2-c:4,5-c′]dipyrolium dibromide: ¹ H-NMR (400 MHz, DMSO- _d6 ) δ 7.33 (s, 2H), 4.82 (s, 8H), 3.53 (q, J = 7.2 Hz, 8H), 1.27 (q, J = 7 .2Hz, 12H).

Examples 1-4

To a solution of 1,2,4,5-tetrakis(bromomethyl)benzene (1.44 g, 3.20 mmol) in ethanol/tetrahydrofuran (1:1, 10 mL) was added N-ethyl-N-isopropylamine (1.62 mL, 13. 4 mmol) was added and stirred at 70° C. for 5 hours. After cooling the reaction solution to room temperature, the precipitated solid was collected by filtration and washed with a mixed solution of ethanol/tetrahydrofuran (1:1) to give 2,6-diethyl-2,6-diisopropyl-1,2 as a white solid. ,3,5,6,7-hexahydrobenzo[1,2-c:4,5-c′]dipyrrolilium dibromide (0.873 g, 59% yield).

NMR spectrum of 2,6-diethyl-2,6-diisopropyl-1,2,3,5,6,7-hexahydrobenzo[1,2-c:4,5-c′]dipyrrolilium dibromide: ¹ H - NMR (400 MHz, D ₂ O) δ 7.24 (s, 2H), 4.94 (d, J = 15.2 Hz, 4H), 4.78 (d, J = 15.2 Hz, 4H), 3. 99-3.90 (m, 2H), 3.57-3.48 (m, 4H), 1.34-1.31 (m, 12H), 1.11-1.06 (m, 6H).

Examples 1-5

To a solution of 1,2,4,5-tetrakis(bromomethyl)benzene (1.80 g, 4.00 mmol) in ethanol/tetrahydrofuran (1:1, 13 mL) was added N-tert-butyl-N-ethylisopropylamine (2.33 mL). , 16.8 mmol) was added and stirred at 70° C. for 7 hours. After cooling the reaction solution to room temperature, the precipitated solid was collected by filtration and washed with a mixed solution of ethanol/tetrahydrofuran (1:1) to give a white solid of 2,6-di(tert-butyl)-2,6- Diethyl-1,2,3,5,6,7-hexahydrobenzo[1,2-c:4,5-c′]dipyrolium dibromide (1.15 g, 53% yield) was obtained.

2,6-di(tert-butyl)-2,6-diethyl-1,2,3,5,6,7-hexahydrobenzo[1,2-c:4,5-c′]dipyrrolinium of dibromide NMR spectrum: ¹ H-NMR (400 MHz, D ₂ O) δ 7.24 (s, 2H), 5.18-5.12 (m, 4H), 4.64 (d, J = 16.3Hz, 4H) , 3.61 (d, J=7.0 Hz, 4H), 1.49 (s, 18H), 0.96-0.89 (m, 6H).

Examples 1-6

Diisopropylamine (1.88 mL, 13.4 mmol) was added to a solution of 1,2,4,5-tetrakis(bromomethyl)benzene (1.44 g, 3.20 mmol) in ethanol/tetrahydrofuran (1:1, 10 mL). C. for 5 hours. After cooling the reaction solution to room temperature, the solvent was distilled off from the reaction solution, and the resulting solid was washed with chloroform to give a white solid of 2,2,6,6-tetraisopropyl-1,2,3, 5,6,7-Hexahydrobenzo[1,2-c:4,5-c′]dipyrolium dibromide (1.05 g, 67% yield) was obtained.

NMR spectrum of 2,2,6,6-tetraisopropyl-1,2,3,5,6,7-hexahydrobenzo[1,2-c:4,5-c′]dipyrolium dibromide: ¹ H- NMR (400 MHz, _D2O ) δ 7.22 (s, 2H), 4.82 (s, 8H), 3.98 (sept, J = 6.4 Hz, 4H), 1.26 (d, J = 6 .4Hz, 24H).

Examples 1-7

To a solution of 1,2,4,5-tetrakis(bromomethyl)benzene (1.12 g, 2.50 mmol) in ethanol/tetrahydrofuran (1:1, 10 mL) was added didodecylamine (3.71 g, 10.5 mmol), Stir at 70° C. for 18 hours. After cooling the reaction solution to room temperature, the precipitated solid was filtered off. The solvent was distilled off from the filtrate under reduced pressure, and the obtained solid was washed with ethyl acetate to give 2,2,6,6-tetradodecyl-1,2,3,5,6,7-tetradodecyl-1,2,3,5,6,7- Hexahydrobenzo[1,2-c:4,5-c′]dipyrrolilium dibromide (2.19 g, 88% yield) was obtained.

NMR spectrum of 2,2,6,6-tetradodecyl-1,2,3,5,6,7-hexahydrobenzo[1,2-c:4,5-c′]dipyrolium dibromide: ¹ H— NMR (400 MHz, CDCl ₃ ) δ 7.67 (s, 2H), 5.27 (s, 8H), 3.78-3.53 (m, 8H), 1.83-1.65 (m, 8H) , 1.45-1.17 (m, 72H), 0.88 (t, J=6.7Hz, 12H).

Examples 1-8

Bis(2-ethoxyethyl)amine (1.87 mL, 10.3 mmol) was added to a solution of 1,2,4,5-tetrakis(bromomethyl)benzene (1.12 g, 2.50 mmol) in tetrahydrofuran (10 mL). C. for 2 hours. After cooling the reaction solution to room temperature, the precipitated solid was collected by filtration and washed with tetrahydrofuran to give a white solid of 2,2,6,6-tetrakis(2-ethoxyethyl)-1,2,3, 5,6,7-Hexahydrobenzo[1,2-c:4,5-c′]dipyrrolinium dibromide (2.19 g, 88% yield) was obtained.

NMR of 2,2,6,6-tetrakis(2-ethoxyethyl)-1,2,3,5,6,7-hexahydrobenzo[1,2-c:4,5-c′]dipyrolium dibromide Spectrum: ¹ H-NMR (400 MHz, D ₂ O) δ 7.47 (s, 2H), 5.10 (s, 8H), 3.94-3.86 (m, 16H), 3.46 (q, J=7.1 Hz, 8H), 1.17 (t, J=7.1 Hz, 12H).

Examples 1-9

To a solution of bis[(2-diisopropylamino)ethyl]amine (1.64 mL, 5.13 mmol) in chloroform (12 mL) was added 1,2,4,5-tetrakis(bromomethyl)benzene (1.12 g, 2.50 mmol). chloroform (25 mL) solution was added in an ice bath, and the mixture was stirred at 50° C. for 17 hours. After cooling the reaction solution to room temperature, the solvent was distilled off. The resulting viscous liquid was diluted with ethanol, added with 30% aqueous sodium hydroxide solution (2.00 mL, 15.2 mmol) and stirred for 20 minutes. The solvent was distilled off from the solution under reduced pressure to obtain a viscous liquid. Acetone was added to this liquid, the precipitated solid was separated by filtration, and the solvent was distilled off from the filtrate. Ethyl acetate was added to the resulting viscous liquid, and the precipitated solid was collected by filtration and washed with ethyl acetate to give 2,2,6,6-tetrakis[bis(2-diisopropylamino)ethyl as a white solid. ]-1,2,3,5,6,7-hexahydrobenzo[1,2-c:4,5-c′]dipyrrolinium dibromide (0.940 g, 45% yield).

2,2,6,6-tetrakis[bis(2-diisopropylamino)ethyl]-1,2,3,5,6,7-hexahydrobenzo[1,2-c:4,5-c′]dipyrrolinium = NMR spectrum of dibromide: ¹ H-NMR (400 MHz, DMSO-d ₆ ) δ 7.53 (s, 2H), 5.09 (s, 8H), 3.53 (t, J = 6.8 Hz, 8H) , 2.98 (sept, J=6.5 Hz, 8 H), 2.77 (t, J=6.8 Hz, 8 H), 0.97 (d, J=6.5 Hz, 48 H).

Examples 1-10

N-methylaniline (1.10 mL, 10.0 mmol) was added to a solution of 1,2,4,5-tetrakis(bromomethyl)benzene (1.12 g, 2.50 mmol) in tetrahydrofuran (10 mL) and stirred at room temperature for 24 hours. bottom. After the reaction, the solvent was distilled off from the reaction mixture under reduced pressure, and the obtained solid was washed with chloroform and then with acetone to give a white solid of 2,6-dimethyl-2,6-diphenyl-1,2,3, 5,6,7-Hexahydrobenzo[1,2-c:4,5-c′]dipyrolium dibromide (0.250 g, 20% yield) was obtained.

NMR spectrum of 2,6-dimethyl-2,6-diphenyl-1,2,3,5,6,7-hexahydrobenzo[1,2-c:4,5-c′]dipyrolium dibromide: ¹ H - NMR (400 MHz, D ₂ O) δ 7.82-7.73 (m, 4H), 7.71-7.54 (m, 8H), 5.56-5.43 (m, 8H), 3. 54 (s, 3H), 3.53 (s, 3H).

Examples 1-11

N-methyl-p-toluidine (1.30 mL, 10.3 mmol) was added to a solution of 1,2,4,5-tetrakis(bromomethyl)benzene (1.12 g, 2.50 mmol) in tetrahydrofuran (10 mL), and the mixture was stirred at room temperature. Stirred for 6 hours. After the reaction, the solvent was distilled off from the reaction mixture under reduced pressure, and the obtained solid was washed with chloroform and then with acetone to obtain 2,6-dimethyl-2,6-di(p-tolyl)-1 as a white solid. ,2,3,5,6,7-hexahydrobenzo[1,2-c:4,5-c′]dipyrrolilium dibromide (0.213 g, 16% yield).

2,6-dimethyl-2,6-di(p-tolyl)-1,2,3,5,6,7-hexahydrobenzo[1,2-c:4,5-c′]dipyrrolinium of dibromide NMR spectrum: ¹ H-NMR (400 MHz, D ₂ O) δ 7.62 (s, 2H), 7.61 (d, J = 8.5 Hz, 4H), 7.42 (d, J = 8.5 Hz, 4H), 5.44 (s, 8H), 3.50 (s, 6H), 2.34 (s, 6H).

Examples 1-12

A solution of 1,2,4,5-tetrakis(bromomethyl)benzene (1.80 g, 4.00 mmol) in tetrahydrofuran (16 mL) was added with 30% aqueous sodium hydroxide solution (1.15 mL, 8.80 mmol), bis(2-ethoxy Ethyl)amine (1.45 mL, 8.00 mmol) was added sequentially and stirred under reflux for 2 hours. After the reaction solution was cooled to room temperature, it was diluted with chloroform and dried over magnesium sulfate. The magnesium sulfate was filtered off from the solution and the solvent was concentrated from the filtrate under reduced pressure. Acetone was added to the resulting viscous liquid, and the precipitated solid was collected by filtration and washed with acetone to obtain 2,2,6,6-tetrakis(2-ethoxyethyl)-1,2,3 as a white solid. ,5,6,7-hexahydrobenzo[1,2-c:4,5-c′]dipyrrolinium dibromide (1.63 g, 68% yield).

Examples 1-13

2,2,6,6-tetraethyl-1,2,3,5,6,7-hexahydrobenzo[1,2-c:4,5-c′]dipyrrolilium dibromide (5.61 g, 12.9 mmol ) was passed through a column packed with an anion exchange resin (Amberlite IRA-900 Cl ⁻ type, 250 cm ³ ), and methanol was distilled off from the solution. The obtained solid was washed with acetone and collected by filtration to obtain 2,2,6,6-tetraethyl-1,2,3,5,6,7-hexahydrobenzo[1, 2-c:4,5-c′]dipyrrolium dichloride (4.42 g, >99% yield) was obtained.

NMR spectrum of 2,2,6,6-tetraethyl-1,2,3,5,6,7-hexahydrobenzo[1,2-c:4,5-c′]dipyrrolilium dichloride: ¹ H-NMR (400 MHz, D ₂ O) δ 7.33 (s, 2H), 4.82 (s, 8H), 3.53 (q, J=7.2Hz, 8H), 1.27 (q, J=7. 2Hz, 12H).

Examples 1-14

To a suspension of lithium aluminum hydride (3.04 g, 80.0 mmol) and tetrahydrofuran (100 mL), N,N'-diethylpyromellitic diimide (5.45 g, 20.0 mmol) was added under an ice bath, Stir at 60° C. for 18 hours. After the reaction, the reaction solution was cooled in an ice bath, water (3.0 mL), 15% aqueous sodium hydroxide solution (3.0 mL) and water (9.0 mL) were sequentially added and stirred. The solid precipitated from the reaction mixture was separated by filtration, washed with tetrahydrofuran and ethyl acetate, and the solvent was distilled off from the filtrate under reduced pressure to obtain 2,6-diethyl-1,2,3,5,6. ,7-hexahydrobenzo[1,2-c:4,5-c′]dipyrrole crude product (4.10 g) was obtained.

NMR spectrum of the crude product of 2,6-diethyl-1,2,3,5,6,7-hexahydrobenzo[1,2-c:4,5-c′]dipyrrole: ¹ H-NMR (400 MHz , CDCl ₃ ) δ 7.01 (s, 2H), 3.88 (s, 8H), 2.77 (q, J = 7.2 Hz, 8H), 1.19 (q, J = 7.2 Hz, 12H ).

2,6-diethyl-1,2,3,5,6,7-hexahydrobenzo[1,2-c:4,5-c′]dipyrrole crude product (4.10 g) in acetonitrile (40 mL) Bromoethane (4.48 mL, 60.0 mmol) was added to the solution. After stirring at room temperature for 13 hours, the solvent was distilled off from the reaction solution under reduced pressure. The obtained solid was washed with acetone and collected by filtration to obtain 2,2,6,6-tetraethyl-1,2,3,5,6,7-hexahydrobenzo[1, 2-c:4,5-c′]dipyrrolilium dibromide (3.47 g, 40% overall yield over two steps) was obtained.

NMR spectrum of 2,2,6,6-tetraethyl-1,2,3,5,6,7-hexahydrobenzo[1,2-c:4,5-c′]dipyrolium dibromide: ¹ H-NMR (400 MHz, DMSO- _d6 ) δ 7.33 (s, 2H), 4.82 (s, 8H), 3.53 (q, J = 7.2 Hz, 8H), 1.27 (q, J = 7 .2Hz, 12H).

Examples 1-15
(Synthesis of 2,6-dihexyl-1,2,3,5,6,7-hexahydrobenzo[1,2-c:4,5-c′]dipyrrole)

To a suspension of lithium aluminum hydride (3.42 g, 90.0 mmol) and tetrahydrofuran (150 mL), N,N'-dihexylpyromellitic diimide (6.19 g, 15.0 mmol) was added under an ice bath, Stir at 60° C. for 7 hours. After the reaction, the reaction solution was cooled in an ice bath, water (3.5 mL), 15% aqueous sodium hydroxide solution (3.5 mL) and water (10.5 mL) were sequentially added and stirred. A solid precipitated from the reaction solution was filtered off, and the solid was washed with tetrahydrofuran and ethyl acetate. Diethyl ether was added to the viscous liquid obtained by distilling off the solvent from the filtrate under reduced pressure, and the precipitated solid was collected by filtration to give a white solid of 2,6-dihexyl-1,2,3, 5,6,7-Hexahydrobenzo[1,2-c:4,5-c′]dipyrrole (2.15 g, 44% yield) was obtained.

NMR spectrum of 2,6-dihexyl-1,2,3,5,6,7-hexahydrobenzo[1,2-c:4,5-c′]dipyrrole: ¹ H-NMR (400 MHz, CDCl ₃ ) δ7.00 (s, 2H), 3.86 (s, 8H), 2.68 (t, J = 7.7Hz, 4H), 1.57 (dt, J = 6.9, 7.7Hz, 4H ), 1.44-1.23 (m, 12H), 0.90 (t, J=6.9Hz, 6H).
(Synthesis of 2,2,6,6-tetrahexyl-1,2,3,5,6,7-hexahydrobenzo[1,2-c:4,5-c′]dipyrrolilium=dibromide)

2,6-dihexyl-1,2,3,5,6,7-hexahydrobenzo[1,2-c:4,5-c′]dipyrrole (1.78 g, 5.43 mmol) in acetonitrile/toluene ( 1:1, 10 mL) solution, 1-bromohexane (1.54 mL, 11.0 mmol) was added. Stir at 100° C. for 12 hours. Chloroform was added to the resulting viscous liquid, and the precipitated solid was collected by filtration to give 2,2,6,6-tetrahexyl-1,2,3,5,6,7-hexahydro as a white solid. Benzo[1,2-c:4,5-c′]dipyrrolilium dibromide (3.36 g, 94% yield) was obtained.

NMR spectrum of 2,2,6,6-tetrahexyl-1,2,3,5,6,7-hexahydrobenzo[1,2-c:4,5-c′]dipyrrolilium dibromide: ¹ H— NMR (400 MHz, DMSO-d ₆ ) δ 7.39 (s, 2H), 4.95 (s, 8H), 3.59-3.41 (m, 8H), 1.72-1.49 (m, 8H), 1.37-1.18 (m, 24H), 0.87 (t, J=6.7Hz, 12H).

Examples 1-16
(Synthesis of 2,6-bis(trifluoroacetyl)-1,2,3,5,6,7-hexahydrobenzo[1,2-c:4,5-c′]dipyrrole)

A suspension of sodium hydride (1.09 g, 25.0 mmol) in N,N-dimethylformamide (25 mL) and a solution of trifluoroacetamide (2.83 g, 25.0 mmol) in N,N-dimethylformamide (25 mL) was added dropwise and stirred at room temperature for 1 hour, then 1,2,4,5-tetrakis(bromomethyl)benzene (2.24 g, 5.00 mmol) was added. After stirring at room temperature for 24 hours, the reaction was poured into 2M hydrochloric acid and stirred for 15 minutes. The solid precipitated from the mixed solution was collected by filtration and washed with ethyl acetate to give 2,6-bis(trifluoroacetyl)-1,2,3,5,6,7-hexahydrobenzo[1 as a yellow solid. ,2-c:4,5-c′]dipyrrole (0.690 g, 39% yield) was obtained.

NMR spectrum of 2,6-bis(trifluoroacetyl)-1,2,3,5,6,7-hexahydrobenzo[1,2-c:4,5-c′]dipyrrole: ¹ H-NMR ( 400 MHz, Acetone-d ₆ ) δ 7.51-7.43 (m, 2H), 5.14 (s, 4H), 4.91 (s, 4H). ¹⁹ F-NMR (376 MHz, Acetone-d ₆ ) δ -73.4 (s, 6F).
(Synthesis of 2,2,6,6-tetraethyl-1,2,3,5,6,7-hexahydrobenzo[1,2-c:4,5-c′]dipyrolium=dibromide)

2,6-bis(trifluoroacetyl)-1,2,3,5,6,7-hexahydrobenzo[1,2-c:4,5-c′]dipyrrole (0.704 g, 2.00 mmol) of ethanol/tetrahydrofuran (1:1, 6.8 mL) solution, bromoethane (0.630 mL, 8.40 mmol), 30% aqueous sodium hydroxide solution (1.32 mL, 10.0 mmol) were added, and the mixture was kept in a sealed container at 70°C. and stirred for 18 hours. After the reaction, the reaction solution was cooled to room temperature and the solvent was distilled off under reduced pressure. Ethanol was added to the obtained residue, and the residue was dried with molecular sieve 4A. After the solid was separated by filtration, the ethanol was distilled off from the filtrate. The resulting solid was washed with acetone and filtered to give 2,2,6,6-tetraethyl-1,2,3,5,6,7-hexahydrobenzo[1,2-c as a white solid. : 4,5-c′]dipyrrolinium dibromide (0.659 g, 76% yield) was obtained.

Examples 1-17

of 2,2,6,6-tetraethyl-1,2,3,5,6,7-hexahydrobenzo[1,2-c:4,5-c′]dipyrrolinium dibromide (216 mg, 0.497 mmol) After the methanol solution was passed through a column packed with an anion exchange resin (Amberlite IRN-78 OH ^- type, 30 cm ³ ), methanol was distilled off from the solution to give 2,2,6,6-tetraethyl-1,2 ,3,5,6,7-hexahydrobenzo[1,2-c:4,5-c′]dipyrrolinium dihydroxide (5 mL) was obtained. This was diluted with ion-exchanged water, titrated with 0.010 M hydrochloric acid, and the ion exchange rate was measured to be 91%.

NMR spectrum of an aqueous solution of 2,2,6,6-tetraethyl-1,2,3,5,6,7-hexahydrobenzo[1,2-c:4,5-c′]dipyrrolinium dihydroxide: ¹ H-NMR (400 MHz, D _O ) δ 7.29 (s, 2H), 4.79 (s, 8H), 3.50 (q, J = 7.3 Hz, 8H), 1.24 (q, J = 7.3Hz, 12H).

Reference example 1-18

Silver methanesulfonate (408 mg, 2.00 mmol) was added to a solution of 1,2,4,5-tetrakis(bromomethyl)benzene (225 mg, 0.499 mmol) in acetonitrile (11 mL), and the mixture was stirred at 85° C. for 2 hours. After cooling the reaction solution to room temperature, the solid was filtered off, and the filtrate was concentrated to give 1,2,4,5-tetrakis(methanesulfonyloxy)methylbenzene (255 mg, yield >99) as a white solid. %) was obtained.

NMR spectrum of 1,2,4,5-tetrakis(methanesulfonyloxy)methylbenzene: ¹ H-NMR (400 MHz, D ₂ O) δ 7.63 (s, 2H), 5.36 (s, 8H), 3 .06(s, 12H).

Reference example 1-19

Silver p-toluenesulfonate (1.18, 4.22 mmol) was added to a solution of 1,2,4,5-tetrakis(bromomethyl)benzene (453 g, 1.01 mmol) in acetonitrile (22 mL), and the mixture was stirred at 85°C for 2 hours. Stirred. After cooling the reaction solution to room temperature, the solid was removed by filtration, and the filtrate was concentrated to give 1,2,4,5-tetrakis(p-toluenesulfonyloxy)benzene (848 g, yield > 1,2,4,5-tetrakis(p-toluenesulfonyloxy)benzene as a white solid. 99%) was obtained.

NMR spectrum of 1,2,4,5-tetrakis(p-toluenesulfonyloxy)benzene: ¹ H-NMR (400 MHz, D ₂ O) δ 7.72 (brd, J=8.3 Hz, 8H), 7.33 (brd, J = 8.3 Hz, 8H), 7.09 (s, 2H), 4.94 (s, 8H), 2.45 (s, 12H).

Example 1-20

Diethylamine (0.10 mL) was added to an ethanol/tetrahydrofuran (1:1, 0.76 mL) solution of 1,2,4,5-tetrakis(methanesulfonyloxy)benzene (119 mg, 0.233 mmol) obtained in Reference Example 1-1. , 0.96 mmol) was added and stirred at 70° C. for 16 hours. After cooling the reaction solution to room temperature, the precipitated solid was collected by filtration and washed with a mixed solution of ethanol/tetrahydrofuran (1:1) to give 2,2,6,6-tetraethyl-1,2,3 as a white solid. ,5,6,7-hexahydrobenzo[1,2-c:4,5-c′]dipyrrolinium bis(methanesulfonate) (71.7 mg, 66% yield).

NMR spectrum of 2,2,6,6-tetraethyl-1,2,3,5,6,7-hexahydrobenzo[1,2-c:4,5-c′]dipyrrolithium bis(methanesulfonate): ¹ H-NMR (400 MHz, D ₂ O) δ 7.30 (s, 2H), 4.80 (s, 8H), 3.51 (q, J = 7.1 Hz, 8H), 1.25 (t, J=7.1Hz, 12H).

Example 1-21

Diethylamine (0 .14 mL, 1.35 mmol) was added and stirred at 75° C. for 13 hours. After cooling the reaction solution to room temperature, the precipitated solid was collected by filtration and washed with a mixed solution of ethanol/tetrahydrofuran (1:1) to give 2,2,6,6-tetraethyl-1,2,3 as a white solid. ,5,6,7-hexahydrobenzo[1,2-c:4,5-c′]dipyrrolinium bis(p-toluenesulfonate) (123 mg, 61% yield).

NMR of 2,2,6,6-tetraethyl-1,2,3,5,6,7-hexahydrobenzo[1,2-c:4,5-c′]dipyrolium bis(p-toluenesulfonate) Spectrum: ¹ H-NMR (400 MHz, D ₂ O) δ 7.59 (brd, J = 8.3 Hz, 4H), 7.29 (s, 2H), 7.28 (brd, J = 8.3 Hz, 4H ), 4.80 (s, 8H), 3.50 (q, J=7.2 Hz, 8H), 1.24 (t, J=7.1 Hz, 12H).

(Synthesis of AFX-type zeolite)
Example 2-1
2,2,6,6-tetraethyl-1,2,3,5,6,7-hexahydrobenzo[1,2-c:4,5-c′]dipyrrolinium obtained in Example 1-3 = Using dibromide as a structure-directing agent (SDA), 48% NaOH and Y-type zeolite (trade name: HSZ-350HUA, manufactured by Tosoh Corporation, silica and alkalinity source) were mixed to obtain a composition. The composition of the resulting composition is shown.

_SiO2 / _Al2O3 = _11.1
OH/ _SiO2 = 0.35
Na/ _SiO2 = 0.35
SDA/ _SiO2 = 0.10
_H2O / _SiO2 = 25
After the seed crystal AFX zeolite was added to the composition, the composition was sufficiently stirred so that the seed crystal content of the composition was 3.0% by weight. The stirred composition was sealed in a stainless steel autoclave and heated at 180° C. for 184 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 observation diagram is shown in FIG.

Example 2-2
2,2,6,6-tetraethyl-1,2,3,5,6,7-hexahydrobenzo[1,2-c:4,5-c′]dipyrrolinium obtained in Example 1-13= The product was obtained by filtration, washing and drying in the same manner as in Example 2-1, except that a dichloride was used as the structure-directing agent (SDA).

The product was a single-phase AFX-type zeolite with a SiO ₂ /Al ₂ O ₃ of 9.8.

The XRD pattern of the AFX-type zeolite of this example is shown in FIG. 3, and the SEM observation diagram is shown in FIG.

Claims (6)

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

(Wherein, X is the same or different and represents a hydrogen atom or a halogen atom,
R ¹ , R ² , R ³ and R ⁴ each independently represent an alkyl group having 1 to 10 carbon atoms, a haloalkyl group having 1 to 10 carbon atoms, or an aryl group having 6 to 10 carbon atoms, and these substituted The group is a hydroxyl group, an alkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 10 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an aryloxy group having 6 to 10 carbon atoms, or a dialkylamino group having 2 to 12 carbon atoms. , a monoarylamino group having 6 to 10 carbon atoms and a diarylamino group having 12 to 20 carbon atoms.
Y ^- is the same or different and represents a halide ion, a sulfonate ion represented by R ⁵ SO ₂ O ^- , a carboxylate ion represented by R ⁶ COO ^- or OH ^- (hydroxide ion). ,
R ⁵ represents an alkyl group having 1 to 9 carbon atoms, a fluoroalkyl group having 1 to 9 carbon atoms, or a phenyl group, and the phenyl group is an alkyl group having 1 to 4 carbon atoms, a fluoro may be substituted with one or more substituents selected from the group consisting of an alkyl group, an alkoxy group having 1 to 4 carbon atoms, a fluoroalkoxy group having 1 to 4 carbon atoms, a halogen atom, a cyano group and a nitro group; .
R ⁶ represents an alkyl group having 1 to 6 carbon atoms, a fluoroalkyl group having 1 to 4 carbon atoms, or a phenyl group, and the phenyl group may be substituted with an alkyl group having 1 to 4 carbon atoms. ) Y ^- in the general formula (1) is chloride ion, bromide ion, iodide ion, benzenesulfonate ion, p-toluenesulfonate ion, methanesulfonate ion, trifluoromethanesulfonate ion or hydroxide ion. A hexahydrobenzodipyrrolinium salt according to claim 1. 3. The hexahydrobenzodipyrrolinium salt according to claim 1 or 2, wherein X in the general formula (1) is a hydrogen atom. R ¹ , R ² , R ³ and R ⁴ in the general formula (1) are each independently an alkyl group having 1 to 6 carbon atoms, an aryloxy group having 6 to 10 carbon atoms, or a dialkyl group having 2 to 12 carbon atoms. an alkyl group having 1 to 6 carbon atoms optionally substituted with one or more substituents selected from the group consisting of an amino group and an alkoxy group having 1 to 6 carbon atoms, or an alkyl group having 1 to 6 carbon atoms; The hexahydrobenzodipyrrolinium salt according to any one of claims 1 to 3, which is an optionally substituted phenyl group. R ¹ , R ² , R ³ and R ⁴ in the general formula (1) are each independently a methyl group or an ethyl group, and Y ^- is a chloride ion or a bromide ion. A hexahydrobenzodipyrrolinium salt according to any one of claims. A crystallization step of crystallizing a composition containing the hexahydrobenzodipyrolium salt represented by the general formula (1) according to claim 1, a silica source, an alumina source, an alkali source and water. A method for producing a zeolite.

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