JP7412110B2 - Hexahydrobenzodipyrrole and its manufacturing method - Google Patents

Description

The present invention relates to hexahydrobenzodipyrrole, which is a precursor of hexahydrobenzodipyrolium salt useful as a cation source for ionomers, and a method for producing the same.

Hexahydrobenzodipyrrolium salt is used as a cation source for ionomers and the like (Patent Document 1). However, there is no known example of using hexahydrobenzodipyrolium salt as a structure directing agent for zeolite synthesis.

As a method for synthesizing hexahydrobenzodipyrrolium salt, it is known that hexahydrobenzodipyrrolium salt can be obtained by reacting tetrakis(halomethyl)benzene with a secondary amine (Non-patent Documents 1 and 2). ).

US Patent No. 6,365,705

Helvetica Chimica Acta, 1947, volume 30, pages 2035-2045. Chemische Berichte, 1958, vol. 91, pp. 2485-2495.

An object of the present invention is to provide hexahydrobenzodipyrrole, which is a precursor of hexahydrobenzodipyrrolium salt, which is used as a cation source for ionomers, and a method for producing the same.

As a result of intensive studies to solve the above problems, the present inventors have found that hexahydrobenzodipyrolium salt can be prepared by using hexahydrobenzodipyrole represented by the following general formula (1) as a precursor. They discovered that it can be manufactured efficiently and completed the present invention.

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

[In the formula, X is the same or different and represents a hydrogen atom or a halogen atom.
R ¹ are the same or different, and are an alkyl group having 1 to 10 carbon atoms, a haloalkyl group having 1 to 10 carbon atoms (the above alkyl group having 1 to 10 carbon atoms, and a haloalkyl group having 1 to 10 carbon atoms) 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, 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.) or R ² C(O) (In the formula, R ² represents a haloalkyl group having 1 to 10 carbon atoms.)
However, the two R ¹ 's cannot be methyl groups, propyl groups, butyl groups, cyclohexyl groups, or benzyl groups at the same time. ]
[2] In the general formula (1), R ¹ is the same and is one or more of an ethyl group, an isopropyl group, a cyclopropyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, a cyclobutyl group, An alkyl group having 1 to 4 carbon atoms substituted with a hydroxyl group, an alkyl group having 1 to 4 carbon atoms substituted with one or more alkoxy groups having 1 to 6 carbon atoms, an alkyl group having 5 to 10 carbon atoms, an alkyl group having 5 to 10 carbon atoms; 1 to 10 haloalkyl group (the above alkyl group having 5 to 10 carbon atoms and the above haloalkyl group having 1 to 10 carbon atoms are a hydroxyl group, an alkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 10 carbon atoms, From 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 ) or R ² C(O) (wherein R ² represents a haloalkyl group having 1 to 10 carbon atoms). The hexahydrobenzodipyrrole according to [1], which is an acyl group.
[3] Hexahydrobenzodipyrrole according to [1] or [2], wherein in the general formula (1), X is a hydrogen atom.
[4] In the general formula (1), R ¹ is an alkyl group having 1 to 4 carbon atoms substituted with an ethyl group, an isopropyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, or one or more hydroxyl groups. group, an alkyl group having 1 to 4 carbon atoms substituted with one or more alkoxy groups having 1 to 4 carbon atoms, an alkyl group having 5 to 10 carbon atoms optionally substituted with one or more hydroxyl groups, CF ₃ The hexahydrobenzodipyrrole according to any one of [1] to [3], which is an acyl group represented by C(O) or Cl ₃ CC(O).
[5] In the general formula (1), R ¹ is an ethyl group, a 4-hydroxybutyl group, a 5-hydroxypentyl group, a hexyl group, or an acyl group represented by CF ₃ C(O) [1 ] to hexahydrobenzodipyrrole according to any one of [4].
[6] General formula (2)

[In the formula, X is the same or different and represents a hydrogen atom or a halogen atom.
R ³ is the same or different and is an alkyl group having 1 to 10 carbon atoms or a haloalkyl group having 1 to 10 carbon atoms (the above alkyl group having 1 to 10 carbon atoms and the above haloalkyl group having 1 to 10 carbon atoms are , hydroxyl group, alkyl group having 1 to 6 carbon atoms, aryl group having 6 to 10 carbon atoms, alkoxy group having 1 to 6 carbon atoms, aryloxy group having 6 to 10 carbon atoms, dialkylamino group having 2 to 12 carbon atoms, Represented by a monoarylamino group having 6 to 10 carbon atoms, a diarylamino group having 12 to 20 carbon atoms, and R ^2b C(O) (wherein R ^2b represents an alkyl group having 1 to 4 carbon atoms) may be substituted with one or more substituents selected from the group consisting of acyl groups. ]
General formula (1a) characterized by reacting pyromellitic acid diimide represented by and a reducing agent

[In the formula, X is the same or different and represents a hydrogen atom or a halogen atom.
R ⁴ is the same or different and is an alkyl group having 1 to 10 carbon atoms or a haloalkyl group having 1 to 10 carbon atoms (the above alkyl group having 1 to 10 carbon atoms and the above haloalkyl group having 1 to 10 carbon atoms are , hydroxyl group, alkyl group having 1 to 6 carbon atoms, aryl group having 6 to 10 carbon atoms, alkoxy group having 1 to 6 carbon atoms, aryloxy group having 6 to 10 carbon atoms, dialkylamino group having 2 to 12 carbon atoms, may be substituted with one or more substituents selected from the group consisting of a monoarylamino group having 6 to 10 carbon atoms and a diarylamino group having 12 to 20 carbon atoms. ]
A method for producing hexahydrobenzodipyrrole represented by
[7] In the general formula (2), R ³ is the same and is an alkyl group having 1 to 10 carbon atoms or a haloalkyl group having 1 to 10 carbon atoms (the above alkyl group having 1 to 10 carbon atoms and the above The haloalkyl group having 1 to 10 carbon atoms 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, A dialkylamino group having 2 to 12 carbon atoms, a monoarylamino group having 6 to 10 carbon atoms, a diarylamino group having 12 to 20 carbon atoms, and R ^2b C(O) (wherein R ^2b is a group having 1 to 4 carbon atoms) ), and in the general formula (1a), R ⁴ is the same and an alkyl group having 1 to 10 carbon atoms or a haloalkyl group having 1 to 10 carbon atoms (the above alkyl group having 1 to 10 carbon atoms and the above haloalkyl group having 1 to 10 carbon atoms are a hydroxyl group, a haloalkyl group having 1 to 10 carbon atoms, 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, and dialkylamino groups having 6 to 10 carbon atoms. of the hexahydrobenzodipyrrole according to [6], which may be 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. Production method.
[8] The method for producing hexahydrobenzodipyrrole according to [6] or [7], wherein in the general formulas (1a) and (2), X is a hydrogen atom.
[9] In the general formula (2), R ³ is the same number of carbon atoms substituted with an ethyl group, an isopropyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, or one or more hydroxyl groups. an alkyl group having 1 to 4 carbon atoms, an alkyl group having 1 to 4 carbon atoms substituted with one or more alkoxy groups having 1 to 4 carbon atoms, and an alkyl group having 5 to 10 carbon atoms optionally substituted with one or more hydroxyl groups; an alkyl group or an alkyl group having 1 to 5 carbon atoms substituted with an acyl group represented by R ^2b C(O) (wherein R ^2b represents an alkyl group having 1 to 4 carbon atoms), In the general formula (1a), R ⁴ is the same and has 1 to 4 carbon atoms substituted with an ethyl group, an isopropyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, or one or more hydroxyl groups. an alkyl group having 1 to 4 carbon atoms substituted with one or more alkoxy groups having 1 to 4 carbon atoms, or an alkyl group having 5 to 10 carbon atoms optionally substituted with one or more hydroxyl groups. A method for producing hexahydrobenzodipyrrole according to any one of claims 6 to 8.
[10] In the general formula (2), R ³ is the same and is an ethyl group, 4-acetoxybutyl group, 5-acetoxypentyl group, or hexyl group, and in the general formula (1a), R ⁴ The method for producing hexahydrobenzodipyrrole according to any one of claims 6 to 8, wherein are the same and are an ethyl group, a 4-hydroxybutyl group, a 5-hydroxypentyl group, or a hexyl group.
[11] General formula (3)

(In the formula, X is the same or different and represents a hydrogen atom or a halogen atom.
Y is the same or different and represents a halogen atom or a sulfonyloxy group 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, and the phenyl group is an alkyl group having 1 to 4 carbon atoms, a fluoroalkyl group having 1 to 4 carbon atoms. may be substituted with one or more substituents selected from the group consisting of alkoxy groups having 1 to 4 carbon atoms, fluoroalkoxy groups having 1 to 4 carbon atoms, halogen atoms, cyano groups, and nitro groups. )
An aromatic compound represented by and general formula (4a)

(In the formula, R ^2a represents a haloalkyl group having 1 to 10 carbon atoms.)
An amide compound represented by and the following general formula (4b)

(In the formula, R ^2b represents a haloalkyl group having 1 to 10 carbon atoms.)
General formula (1b) characterized by reacting with an amide compound represented by

(In the formula, X is the same or different and represents a hydrogen atom or a halogen atom.
R ^2a and R ^2b each independently represent a haloalkyl group having 1 to 10 carbon atoms. )
A method for producing hexahydrobenzodipyrrole represented by
[12] The method for producing hexahydrobenzodipyrrole according to [11], wherein in the general formula (3), R ^2a and R ^2b are the same and represent a haloalkyl group having 1 to 10 carbon atoms.
[13] In the general formula (3), Y is the same or different and is a chlorine atom, a bromine atom, an iodine atom, a benzenesulfonyloxy group represented by C ₆ H ₅ SO ₂ O, p-CH ₃ C The method for producing hexahydrobenzodipyrrole according to [11] or [12], which is a p-toluenesulfonyloxy group represented by ₆ H ₄ SO ₂ O or a methanesulfonyloxy group represented by CH ₃ SO ₂ O .
[14] The method for producing hexahydrobenzodipyrrole according to any one of [11] to [13], wherein in the general formulas (3) and (1b), X is a hydrogen atom.
[15] In the general formulas (4) and (1b), R ^2a and R ^2b are the same and are a trifluoromethyl group or a trichloromethyl group, [11] to [14] Any method for producing hexahydrobenzodipyrrole.

The present invention can provide a novel hexahydrobenzodipyrrole and a method for producing the same.

Below, the hexahydrobenzodipyrrole of the present invention will be explained in detail.

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

[In the formula, X is the same or different and represents a hydrogen atom or a halogen atom.
R ¹ is the same or different and is an alkyl group having 1 to 10 carbon atoms or a haloalkyl group having 1 to 10 carbon atoms (the above alkyl group having 1 to 10 carbon atoms and the above haloalkyl group having 1 to 10 carbon atoms are , hydroxyl group, alkyl group having 1 to 6 carbon atoms, aryl group having 6 to 10 carbon atoms, alkoxy group having 1 to 6 carbon atoms, aryloxy group having 6 to 10 carbon atoms, dialkylamino group having 2 to 12 carbon atoms, ) or R ² C(O)( In the formula, R ² represents an acyl group represented by a haloalkyl group having 1 to 10 carbon atoms.
However, the two R ¹ 's cannot be methyl groups, propyl groups, butyl groups, cyclohexyl groups, or benzyl groups at the same time. ]
In the present invention, R ¹ is the same or different, an alkyl group having 1 to 10 carbon atoms, a haloalkyl group having 1 to 10 carbon atoms (the above alkyl group having 1 to 10 carbon atoms and the above mentioned alkyl group having 1 to 10 carbon atoms) The haloalkyl group includes 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 an aryloxy group having 2 to 12 carbon atoms. (optionally substituted with one or more substituents selected from the group consisting of a dialkylamino group, a monoarylamino group having 6 to 10 carbon atoms, and a diarylamino group having 12 to 20 carbon atoms) or R ² C ( O) (wherein, R ² represents a haloalkyl group having 1 to 10 carbon atoms). However, the two R ¹ 's cannot be methyl groups, propyl groups, butyl groups, cyclohexyl groups, or benzyl groups at the same time.

In the present invention, the alkyl group having 1 to 10 carbon atoms represented by R ¹ is not particularly limited, but specifically, it may be a linear, branched or cyclic alkyl group, particularly Although not limited to, specific 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, 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-ethylpentane- 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, 1-butylhexyl group, etc.

In the present invention, the haloalkyl group having 1 to 10 carbon atoms represented by R ¹ is not particularly limited, but specifically, it may be a linear, branched or cyclic haloalkyl group, particularly Although not limited to, specific examples include trifluoromethyl group, difluoromethyl group, perfluoroethyl group, 2,2,2-trifluoroethyl group, 1,1-difluoroethyl group, 2,2-difluoroethyl group. group, perfluoropropyl group, 2,2,3,3,3-pentafluoropropyl group, 2,2,3,3-tetrafluoropropyl group, 3,3,3-trifluoropropyl group, 1,1-difluoro propyl group, perfluoro(1-methylpropyl) group, 2,2,2-trifluoro-1-(trifluoromethyl)ethyl group, perfluorocyclopropyl group, 2,2,3,3-tetrafluorocyclopropyl group, Perfluorobutyl group, 2,2,3,3,4,4,4-heptafluorobutyl group, 3,3,4,4,4-pentafluorobutyl group, 4,4,4-trifluorobutyl group, 1 , 2,2,3,3,3-hexafluoro-1-(trifluoromethyl)propyl group, 1-(trifluoromethyl)propyl group, 1-methyl-3,3,3-trifluoropropyl group, perfluoro Cyclobutyl group, 2,2,3,3,4,4-hexafluorocyclobutyl group, perfluoropentyl group, 2,2,3,3,4,4,5,5,5-nonafluoropentyl group, 3 , 3,4,4,5,5,5-heptafluoropentyl group, 4,4,5,5,5-pentafluoropentyl group, 5,5,5-trifluoropentyl group, 1,2,2, 3,3,3-hexafluoro-1-(perfluoroethyl)propyl group, 2,2,3,3,3-pentafluoro-1-(perfluoroethyl)propyl group, perfluorocyclopentyl group, perfluorohexyl group, 2, 2,3,3,4,4,5,5,6,6,6-undecafluorohexyl group, 3,3,4,4,5,5,6,6,6-nonafluorohexyl group, 4 , 4,5,5,6,6,6-heptafluorohexyl group, 5,5,6,6,6-pentafluorohexyl group, 6,6,6-trifluorohexyl group, perfluorocyclohexyl group, chloromethyl Examples include trichloromethyl group, bromomethyl group, iodomethyl group, 2-chloroethyl group, and 3-bromopropyl group.

In the present invention, the alkyl group having 1 to 10 carbon atoms represented by R ¹ and the haloalkyl group having 1 to 10 carbon atoms may be substituted with one or more hydroxyl groups. Although the alkyl group having 1 to 10 carbon atoms substituted with one or more hydroxyl groups or the haloalkyl group having 1 to 10 carbon atoms substituted with one or more hydroxyl groups is not particularly limited, specifically, , 4-hydroxybutyl group, 5-hydroxypentyl group, 6-hydroxyhexyl group, 4-hydroxycyclohexyl group, 2,3-dihydroxypropyl group, and the like.

In the present invention, the alkyl group having 1 to 10 carbon atoms represented by R ¹ and the haloalkyl group having 1 to 10 carbon atoms may be substituted with one or more alkyl groups having 1 to 6 carbon atoms. The alkyl group having 1 to 6 carbon atoms is not particularly limited, but specifically, it may be a linear, branched, or cyclic alkyl group; Specifically, 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, 2-ethylpropyl group , cyclopentyl group, hexyl group, 1-methylpentyl group, 2-ethylbutyl group, cyclohexyl group, etc.

In the present invention, the alkyl group having 1 to 10 carbon atoms represented by R ¹ and the haloalkyl group having 1 to 10 carbon atoms may be substituted with one or more aryl groups having 6 to 10 carbon atoms. The aryl group having 6 to 10 carbon atoms is not particularly limited, but specifically includes 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, 2,4,6 -Trimethylphenyl group, naphthyl group, etc. can be exemplified.

In the present invention, the alkyl group having 1 to 10 carbon atoms and the haloalkyl group having 1 to 10 carbon atoms represented by R ¹ may be substituted with one or more alkoxy groups having 1 to 6 carbon atoms. The alkoxy group having 1 to 6 carbon atoms is not particularly limited, but specifically includes methoxy group, ethoxy group, propoxy group, isopropoxy group, butoxy group, 2-methylpropoxy group, 2,2 -dimethylpropoxy group, 3-cyclopropylpropoxy group, cyclopropoxy group, 2-methylbutoxy group, 3-methylbutoxy group, tert-butoxy group, cyclobutoxy group, pentyloxy group, 2-methylpentyloxy group, 1- Examples include methylbutyloxy group, 1,2-dimethylbutoxy group, 1-ethylpropoxy group, cyclopentyloxy group, hexyloxy group, and cyclohexyloxy group.

In the present invention, the alkyl group having 1 to 10 carbon atoms and the haloalkyl group having 1 to 10 carbon atoms represented by R ¹ may be substituted with one or more aryloxy groups having 6 to 10 carbon atoms. The aryloxy group having 6 to 10 carbon atoms is not particularly limited, but specifically includes phenyloxy group, 2-methylphenyloxy group, 3-methylphenyloxy group, 4-methylphenyloxy group. , 2,3-dimethylphenyloxy group, 2,4-dimethylphenyloxy group, 2,5-dimethylphenyloxy group, 2,6-dimethylphenyloxy group, 3,4-dimethylphenyloxy group, 3,5- Dimethylphenyloxy group, 2,3,4-trimethylphenyloxy group, 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 group, 2,5-diethylphenyloxy group, 2,6-diethylphenyloxy group, 3,4-diethylphenyloxy group, 3,5-diethylphenyloxy group, 2-propylphenyloxy group, 3-propylphenyloxy group group, 4-propylphenyloxy group, 2-isopropylphenyloxy group, 3-isopropylphenyloxy group, 4-isopropylphenyloxy group, 2-cyclopropylphenyloxy group, 3-cyclopropylphenyloxy group, 4-cyclopropyl Phenyloxy 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-cyclo Examples include butylphenyloxy group, 3-cyclobutylphenyloxy group, 4-cyclobutylphenyloxy group, 1-naphthyloxy group, and 2-naphthyloxy group.

In the present invention, the alkyl group having 1 to 10 carbon atoms and the haloalkyl group having 1 to 10 carbon atoms represented by R ¹ may be substituted with one or more dialkylamino groups having 2 to 12 carbon atoms. The dialkylamino group having 2 to 12 carbon atoms is not particularly limited, but specifically includes 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, bis(1-methylbutyl)amino group, bis(1,2-dimethylbutyl) Amino group, bis(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 Examples include -methylamino group, N-methyl-N-undecylamino group, and the like.

In the present invention, the alkyl group having 1 to 10 carbon atoms and the haloalkyl group having 1 to 10 carbon atoms represented by R ¹ may be substituted with one or more monoarylamino groups having 6 to 10 carbon atoms. . The monoarylamino group having 6 to 10 carbon atoms is not particularly limited, but includes phenylamino group, 2-methylphenylamino group, 3-methylphenylamino group, 4-methylphenylamino group, 2,3 -dimethylphenylamino group, 2,4-dimethylphenylamino group, 2,5-dimethylphenylamino group, 2,6-dimethylphenylamino group, 3,4-dimethylphenylamino group, 3,5-dimethylphenylamino group , 2,3,4-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-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, 4-cyclobutylphenylamino group, 1-naphthylamino group, 2-naphthylamino group, etc.

In the present invention, the alkyl group having 1 to 10 carbon atoms and the haloalkyl group having 1 to 10 carbon atoms represented by R ¹ may be substituted with one or more diarylamino groups having 12 to 20 carbon atoms, The diarylamino group having 12 to 20 carbon atoms is not particularly limited, but includes 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-diethyl) phenyl)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-diethylphenyl)amino group, bis(2-propylphenyl)amino group, bis(3-propylphenyl)amino group, bis(4-propylphenyl)amino group, bis(2-isopropyl) phenyl)amino group, bis(3-isopropylphenyl)amino group, bis(4-isopropylphenyl)amino group, bis(2-cyclopropylphenyl)amino group, bis(3-cyclopropylphenyl)amino group, bis(4-isopropylphenyl)amino group -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, 4-(1-methylpropyl)phenylamino 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 , N-(2-naphthyl)-N-phenylamino group, etc.

In the present invention, when R ¹ is an acyl group represented by R ² C(O), R ² is a haloalkyl group having 1 to 10 carbon atoms, and the haloalkyl group having 1 to 10 carbon atoms is Any of linear, branched or cyclic haloalkyl groups may be used, and although not particularly limited, specific examples include trifluoromethyl group, difluoromethyl group, perfluoroethyl group, and 2,2,2-trifluoroethyl group. 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 group, 2,2,3,3-tetrafluorocyclopropyl group, perfluorobutyl group, 2,2,3,3,4,4,4-heptafluorobutyl group, 3,3,4,4,4-penta Fluorobutyl 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, trichloromethyl group, bromomethyl group, iodomethyl group, 2-chloroethyl group, 3-bromopropyl group, and the like.

In the present invention, R ¹ is the same in that the hexahydrobenzodipyrrole of the present invention can be obtained in good yield, and is an ethyl group, isopropyl group, cyclopropyl group, isobutyl group, sec-butyl group, tert- Butyl group, cyclobutyl group, alkyl group having 1 to 4 carbon atoms substituted with one or more hydroxyl groups, alkyl group having 1 to 4 carbon atoms substituted with one or more alkoxy groups having 1 to 6 carbon atoms, carbon Alkyl group having 5 to 10 carbon atoms, haloalkyl group having 1 to 10 carbon atoms (the above alkyl group having 5 to 10 carbon atoms and haloalkyl group having 1 to 10 carbon atoms are hydroxyl group, 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 may be substituted with one or more substituents selected from the group consisting of diarylamino groups having 12 to 20 carbon atoms) or ^R2C (O) (wherein ^R2 is a diarylamino group having 1 to 20 carbon atoms) 10 (representing a haloalkyl group), which are the same and are an ethyl group, an isopropyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, or one or more hydroxyl groups. Substituted alkyl group having 1 to 4 carbon atoms, alkyl group having 1 to 4 carbon atoms substituted with one or more alkoxy groups having 1 to 4 carbon atoms, carbon optionally substituted with one or more hydroxyl group Any of an alkyl group of numbers 5 to 10, an acyl group represented by CF ₃ C(O), an acyl group represented by CF ₃ CF ₂ C(O), or an acyl group represented by Cl ₃ CC(O) More preferably, they are the same and are an ethyl group, an isopropyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, an alkyl group having 1 to 4 carbon atoms substituted with one or more hydroxyl groups, An alkyl group having 1 to 4 carbon atoms substituted with one or more alkoxy groups having 1 to 4 carbon atoms, an alkyl group having 5 to 10 carbon atoms, an acyl group represented by CF ₃ C(O) or Cl ₃ CC It is more preferable to be an acyl group represented by (O), which is the same and is represented by an ethyl group, 4-hydroxybutyl group, 5-hydroxypentyl group, hexyl group, or CF ₃ C (O) It is more preferably an acyl group, and particularly preferably any of the same acyl groups represented by ethyl group, 4-hydroxybutyl group, 5-hydroxypentyl group, or CF ₃ C(O). .

Specific examples of the alkyl group having 1 to 4 carbon atoms substituted with one or more hydroxyl groups include hydroxymethyl group, 2-hydroxyethyl group, 3-hydroxypropyl group, and 2,3-dihydroxypropyl group. , 4-hydroxybutyl group, etc.

Specifically, the alkyl group having 1 to 4 carbon atoms substituted with one or more alkoxy groups having 1 to 6 carbon atoms mentioned above includes a methoxymethyl group, an ethoxymethyl group, a propoxymethyl group, a butoxymethyl group, Pentyloxymethyl group, hexyloxymethyl group, 2-methoxyethyl group, 2-ethoxyethyl group, 2-propoxyethyl group, 2-butoxyethyl group, 2-pentyloxyethyl group, 2-hexyloxyethyl group, 3- Methoxypropyl group, ethoxypropyl group, 3-propoxypropyl group, 3-butoxypropyl group, 3-pentyloxypropyl group, 3-hexyloxypropyl group, 4-methoxybutyl group, 4-ethoxybutyl group, 4-propoxybutyl group Examples include 4-butoxybutyl group, 4-pentyloxybutyl group, 4-hexyloxybutyl group, and the like.

Specific examples of the above alkyl group having 5 to 10 carbon atoms include pentyl group, hexyl group, heptyl group, octyl group, nonyl group, and decyl group.

Examples of the alkyl group having 1 to 4 carbon atoms substituted with one or more alkoxy groups having 1 to 4 carbon atoms include methoxymethyl group, ethoxymethyl group, propoxymethyl group, butoxymethyl group, 2-methoxyethyl group, 2-ethoxyethyl group, 2-propoxyethyl group, 2-butoxyethyl group, 3-methoxypropyl group, 3-ethoxypropyl group, 3-propoxypropyl group, 3-butoxypropyl group, 4- Examples include methoxybutyl group, 4-ethoxybutyl group, 4-propoxybutyl group, and 4-butoxybutyl group.

Specific examples of the alkyl group having 5 to 10 carbon atoms which may be substituted with one or more hydroxyl groups include pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, 5- Examples include hydroxypentyl group, 6-hydroxyhexyl group, 7-hydroxyheptyl group, 8-hydroxyoctyl group, 9-hydroxynonyl group, and 10-hydroxydecyl group.

In the present invention, X is the same or different and is a hydrogen atom or a halogen atom, and from the viewpoint of good yield, the same or different X is preferably a hydrogen atom, a chlorine atom, or a bromine atom, and a hydrogen atom It is particularly preferable that

Next, the method for producing hexahydrobenzodipyrrole of the present invention (hereinafter also referred to as "the production method of the present invention") will be described in detail.

A preferred production method of the present invention is a hexahydrobenzodiimide represented by the following general formula (1a), which is characterized by reacting a pyromellitic acid diimide represented by the following general formula (2) with a reducing agent. A method for producing pyrrole (hereinafter also referred to as "Production method-1 of the present invention") can be mentioned.

(In the formula, X is the same or different and represents a hydrogen atom or a halogen atom.
R ³ is the same or different and is an alkyl group having 1 to 10 carbon atoms or a haloalkyl group having 1 to 10 carbon atoms (the above alkyl group having 1 to 10 carbon atoms and the above haloalkyl group having 1 to 10 carbon atoms are , hydroxyl group, alkyl group having 1 to 6 carbon atoms, aryl group having 6 to 10 carbon atoms, alkoxy group having 1 to 6 carbon atoms, aryloxy group having 6 to 10 carbon atoms, dialkylamino group having 2 to 12 carbon atoms, Represented by a monoarylamino group having 6 to 10 carbon atoms, a diarylamino group having 12 to 20 carbon atoms, and R ^2b C(O) (wherein R ^2b represents an alkyl group having 1 to 4 carbon atoms) may be substituted with one or more substituents selected from the group consisting of acyl groups. )
General formula (1a)

(In the formula, X is the same or different and represents a hydrogen atom or a halogen atom.
R ⁴ is the same or different and is an alkyl group having 1 to 10 carbon atoms or a haloalkyl group having 1 to 10 carbon atoms (the above alkyl group having 1 to 10 carbon atoms and the above haloalkyl group having 1 to 10 carbon atoms are , hydroxyl group, alkyl group having 1 to 6 carbon atoms, aryl group having 6 to 10 carbon atoms, alkoxy group having 1 to 6 carbon atoms, aryloxy group having 6 to 10 carbon atoms, dialkylamino group having 2 to 12 carbon atoms, may be substituted with one or more substituents selected from the group consisting of a monoarylamino group having 6 to 10 carbon atoms and a diarylamino group having 12 to 20 carbon atoms. )
In the production method-1 of the present invention, R ³ is the same or different and is an alkyl group having 1 to 10 carbon atoms or a haloalkyl group having 1 to 10 carbon atoms (the above alkyl group having 1 to 10 carbon atoms and the above carbon Haloalkyl groups having numbers 1 to 10 include hydroxyl groups, alkyl groups having 1 to 6 carbon atoms, aryl groups having 6 to 10 carbon atoms, alkoxy groups having 1 to 6 carbon atoms, aryloxy groups having 6 to 10 carbon atoms, and aryloxy groups having 6 to 10 carbon atoms. A dialkylamino group having 2 to 12 carbon atoms, a monoarylamino group having 6 to 10 carbon atoms, a diarylamino group having 12 to 20 carbon atoms, and R ^2b C(O) (wherein R ^2b is an alkyl group having 1 to 4 carbon atoms) (representing a group) may be substituted with one or more substituents selected from the group consisting of acyl groups represented by ().

In the production method-1 of the present invention, R ⁴ is the same or different and is an alkyl group having 1 to 10 carbon atoms or a haloalkyl group having 1 to 10 carbon atoms (the above alkyl group having 1 to 10 carbon atoms and the above carbon Haloalkyl groups having numbers 1 to 10 include hydroxyl groups, alkyl groups having 1 to 6 carbon atoms, aryl groups having 6 to 10 carbon atoms, alkoxy groups having 1 to 6 carbon atoms, aryloxy groups having 6 to 10 carbon atoms, and aryloxy groups having 6 to 10 carbon atoms. It may be substituted with one or more substituents selected from the group consisting of 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.) Either.

In the production method-1 of the present invention, the alkyl group having 1 to 10 carbon atoms represented by R ³ and R ⁴ is not particularly limited, but specifically, linear, branched or cyclic alkyl Any group may be used, and there are no particular limitations, but specific 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, 3-ethylpentyl group, 2,4-dimethylpentyl group, 1-methylbutyl group, 2-methylpentan-2-yl group, 4,4-dimethylpentan-2-yl group, 2-ethylpropyl group 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]heptane- 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 Examples include -butylpentyl group, decyl group, 1-methylnonyl group, and 1-butylhexyl group.

In the production method-1 of the present invention, the haloalkyl group having 1 to 10 carbon atoms represented by R ³ and R ⁴ is not particularly limited, but specifically, linear, branched or cyclic haloalkyl Although not particularly limited, specific examples include trifluoromethyl group, difluoromethyl group, perfluoroethyl group, 2,2,2-trifluoroethyl group, and 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 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)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, 2-chloroethyl group, 3-bromopropyl group, and the like.

In the production method-1 of the present invention, the alkyl group having 1 to 10 carbon atoms or the haloalkyl group having 1 to 10 carbon atoms represented by R ³ and R ⁴ may be substituted with one or more hydroxyl groups. The alkyl group having 1 to 10 carbon atoms substituted with a hydroxyl group is not particularly limited, but specifically, 4-hydroxybutyl group, 5-hydroxypentyl group, 6-hydroxyhexyl group, 4-hydroxy Examples include cyclohexyl group and 2,3-dihydroxypropyl group.

In the production method-1 of the present invention, the alkyl group having 1 to 10 carbon atoms or haloalkyl group having 1 to 10 carbon atoms represented by R ³ is one or more R ^2b C(O) (wherein R ^2b is , represents an alkyl group having 1 to 4 carbon atoms.) may be substituted with an acyl group represented by the following. The alkyl group having 1 to 4 carbon atoms is not particularly limited, but specifically includes a methyl group, ethyl group, propyl group, isopropyl group, butyl group, 2-methylpropyl group, and cyclopropyl group. , tert-butyl group, cyclobutyl group, etc. The acyl group represented by R ^2b C(O) (in the formula, R ^2b represents an alkyl group having 1 to 4 carbon atoms) is not particularly limited, but specifically, acetyl Examples include a propionyl group, a propionyl group, a butanoyl group, a pentanoyl group, and the like.

In the production method-1 of the present invention, the alkyl group having 1 to 10 carbon atoms or the haloalkyl group having 1 to 10 carbon atoms represented by R ³ and R ⁴ is substituted with one or more alkyl groups having 1 to 6 carbon atoms. may have been done. The alkyl group having 1 to 6 carbon atoms is not particularly limited, but specifically includes 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, 2-ethylpropyl group, cyclopentyl group, hexyl group, 1-methylpentyl group, 2-ethylbutyl group, cyclohexyl group, etc.

In the production method-1 of the present invention, the alkyl group having 1 to 10 carbon atoms or haloalkyl group having 1 to 10 carbon atoms represented by R ³ and R ⁴ is substituted with one or more aryl group having 6 to 10 carbon atoms. The aryl group having 6 to 10 carbon atoms is not particularly limited, but specifically includes phenyl group, 2-methylphenyl group, 3-methylphenyl group, 4-methylphenyl group. 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, Examples include 2,4,6-trimethylphenyl group and naphthyl group.

In the production method-1 of the present invention, the alkyl group having 1 to 10 carbon atoms or the haloalkyl group having 1 to 10 carbon atoms represented by R ³ and R ⁴ is substituted with one or more alkoxy groups having 1 to 6 carbon atoms. may have been done. The alkoxy group having 1 to 6 carbon atoms is not particularly limited, but specifically includes methoxy group, ethoxy group, propoxy group, isopropoxy group, butoxy group, 2-methylpropoxy group, 2,2 -dimethylpropoxy group, 3-cyclopropylpropoxy group, cyclopropoxy group, 2-methylbutoxy group, 3-methylbutoxy group, tert-butoxy group, cyclobutoxy group, pentyloxy group, 2-methylpentyloxy group, 1- Examples include methylbutyloxy group, 1,2-dimethylbutoxy group, 1-ethylpropoxy group, cyclopentyloxy group, hexyloxy group, and cyclohexyloxy group.

In the production method-1 of the present invention, the alkyl group having 1 to 10 carbon atoms or the haloalkyl group having 1 to 10 carbon atoms represented by R ³ and R ⁴ is one or more aryloxy groups having 6 to 10 carbon atoms. May be replaced. The aryloxy group having 6 to 10 carbon atoms is not particularly limited, but specifically includes phenyloxy group, 2-methylphenyloxy group, 3-methylphenyloxy group, 4-methylphenyloxy group. , 2,3-dimethylphenyloxy group, 2,4-dimethylphenyloxy group, 2,5-dimethylphenyloxy group, 2,6-dimethylphenyloxy group, 3,4-dimethylphenyloxy group, 3,5- Dimethylphenyloxy group, 2,3,4-trimethylphenyloxy group, 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 group, 2,5-diethylphenyloxy group, 2,6-diethylphenyloxy group, 3,4-diethylphenyloxy group, 3,5-diethylphenyloxy group, 2-propylphenyloxy group, 3-propylphenyloxy group group, 4-propylphenyloxy group, 2-isopropylphenyloxy group, 3-isopropylphenyloxy group, 4-isopropylphenyloxy group, 2-cyclopropylphenyloxy group, 3-cyclopropylphenyloxy group, 4-cyclopropyl Phenyloxy 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-cyclo Examples include butylphenyloxy group, 3-cyclobutylphenyloxy group, 4-cyclobutylphenyloxy group, 1-naphthyloxy group, and 2-naphthyloxy group.

In the production method-1 of the present invention, the alkyl group having 1 to 10 carbon atoms or the haloalkyl group having 1 to 10 carbon atoms represented by R ³ and R ⁴ is one or more dialkylamino groups having 2 to 12 carbon atoms. May be replaced. The dialkylamino group having 2 to 12 carbon atoms is not particularly limited, but specifically includes 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, bis(1-methylbutyl)amino group, bis(1,2-dimethylbutyl) Amino group, bis(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 Examples include -methylamino group, N-methyl-N-undecylamino group, and the like.

In the production method-1 of the present invention, the alkyl group having 1 to 10 carbon atoms or the haloalkyl group having 1 to 10 carbon atoms represented by R ³ and R ⁴ is one or more monoarylamino groups having 6 to 10 carbon atoms. may be replaced with . The monoarylamino group having 6 to 10 carbon atoms is not particularly limited, but includes phenylamino group, 2-methylphenylamino group, 3-methylphenylamino group, 4-methylphenylamino group, 2,3 -dimethylphenylamino group, 2,4-dimethylphenylamino group, 2,5-dimethylphenylamino group, 2,6-dimethylphenylamino group, 3,4-dimethylphenylamino group, 3,5-dimethylphenylamino group , 2,3,4-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-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, 4-cyclobutylphenylamino group, 1-naphthylamino group, 2-naphthylamino group, etc.

In the production method-1 of the present invention, the alkyl group having 1 to 10 carbon atoms or the haloalkyl group having 1 to 10 carbon atoms represented by R ³ and R ⁴ is one or more diarylamino groups having 12 to 20 carbon atoms. The diarylamino group having 12 to 20 carbon atoms, which may be substituted, is not particularly limited, but includes 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-trimethyl phenyl)amino group, bis(3,4,5-trimethylphenyl)amino group, bis(2,3,4,5-tetramethylphenyl)amino group, bis(2,3,4,6-tetramethylphenyl) Amino group, bis(2,3,5,6-tetramethylphenyl)amino group, bis(2-ethylphenyl)amino group, bis(3-ethylphenyl)amino group, bis(4-ethylphenyl)amino group, Bis(2,3-diethylphenyl)amino group, bis(2,4-diethylphenyl)amino group, bis(2,5-diethylphenyl)amino group, bis(2,6-diethylphenyl)amino group, bis( 3,4-diethylphenyl) amino group, bis(3,5-diethylphenyl) amino group, bis(2-propylphenyl) amino group, bis(3-propylphenyl) amino group, bis(4-propylphenyl) amino group 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, 4-(1-methylpropyl)phenylamino group, bis[2-(2-methylpropyl)phenyl]amino group 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, N-(2-naphthyl)-N-phenylamino group, etc.

In production method-1 of the present invention, hexahydrobenzodipyrrole represented by general formula (1a) is obtained by the reaction shown below.

(In the formula, R ³ and R ⁴ have the same meanings as above.)
In the production method-1 of the present invention, X in pyromellitic acid diimide (2) is the same or different and is a hydrogen atom or a halogen atom, and the same or Preferably, it is a hydrogen atom, a chlorine atom, or a bromine atom, and a hydrogen atom is more preferable.

In the production method-1 of the present invention, R ³ of pyromellitic acid diimide (2) is the same and is an alkyl group having 1 to 10 carbon atoms or a haloalkyl group having 1 to 10 carbon atoms (the above-mentioned 1 to 10 carbon atoms). The alkyl group and the above-mentioned haloalkyl group having 1 to 10 carbon atoms are hydroxyl group, alkyl group having 1 to 6 carbon atoms, aryl group having 6 to 10 carbon atoms, alkoxy group having 1 to 6 carbon atoms, and 6 to 10 carbon atoms. aryloxy group, dialkylamino group having 2 to 12 carbon atoms, monoarylamino group having 6 to 10 carbon atoms, diarylamino group having 12 to 20 carbon atoms, and R ^2b C(O) (wherein R ^2b is represents an alkyl group having 1 to 4 carbon atoms, and may be substituted with one or more substituents selected from the group consisting of acyl groups represented by R ⁴ of pyrrole (1a) is the same, and is an alkyl group having 1 to 10 carbon atoms or a haloalkyl group having 1 to 10 carbon atoms (the above-mentioned alkyl group having 1 to 10 carbon atoms and the above-mentioned alkyl group having 1 to 10 carbon atoms). The haloalkyl group includes 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 an aryloxy group having 2 to 12 carbon atoms. may be substituted with one or more substituents selected from the group consisting of a dialkylamino group, a monoarylamino group having 6 to 10 carbon atoms, and a diarylamino group having 12 to 20 carbon atoms. preferable.

In the production method-1 of the present invention, R ³ of pyromellitic acid diimide (2) is the same and is an alkyl group having 1 to 10 carbon atoms, or an alkyl group having 1 to 4 carbon atoms substituted with one or more hydroxyl groups. group, an alkyl group having 1 to 4 carbon atoms substituted with one or more alkoxy groups having 1 to 4 carbon atoms, an alkyl group having 5 to 10 carbon atoms optionally substituted with one or more hydroxyl groups, or R ^2b More preferably, it is an alkyl group having 1 to 5 carbon atoms substituted with an acyl group represented by C(O) (in the formula, R ^2b represents an alkyl group having 1 to 4 carbon atoms); R ⁴ of hydrobenzodipyrrole (1a) is the same and is an alkyl group having 1 to 10 carbon atoms, an alkyl group having 1 to 4 carbon atoms substituted with one or more hydroxyl groups, or an alkyl group having 1 to 4 carbon atoms substituted with one or more hydroxyl groups; More preferably, it is an alkyl group having 1 to 4 carbon atoms substituted with an alkoxy group having 1 to 4 carbon atoms, or an alkyl group having 5 to 10 carbon atoms which may be substituted with one or more hydroxyl groups.

In the production method-1 of the present invention, R ³ of pyromellitic acid diimide (2) is the same and is an ethyl group, an isopropyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, or one or more hydroxyl groups. Substituted alkyl group having 1 to 4 carbon atoms, alkyl group having 1 to 4 carbon atoms substituted with one or more alkoxy groups having 1 to 4 carbon atoms, carbon optionally substituted with one or more hydroxyl group A C 1 to 5 alkyl group substituted with an alkyl group having 5 to 10 carbon atoms or an acyl group represented by R ^2b C(O) (in the formula, R ^2b represents an alkyl group having 1 to 4 carbon atoms) More preferably, it is an alkyl group, and R ⁴ of hexahydrobenzodipyrrole (1a) are the same and include an ethyl group, an isopropyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, or one or more An alkyl group having 1 to 4 carbon atoms substituted with a hydroxyl group, an alkyl group having 1 to 4 carbon atoms substituted with one or more alkoxy groups having 1 to 4 carbon atoms, or an alkyl group having 1 to 4 carbon atoms substituted with one or more hydroxyl groups; More preferably, it is an alkyl group having 5 to 10 carbon atoms.

In the production method-1 of the present invention, R ³ of pyromellitic acid diimide (2) is the same and is an ethyl group, 4-acetoxybutyl group, 5-acetoxypentyl group, or hexyl group, and hexahydrobenzodiimide R ⁴ of pyrrole (1a) is the same and is more preferably an ethyl group, 4-hydroxybutyl group, 5-hydroxypentyl group or hexyl group.

The pyromellitic acid diimide (2) used in the production method-1 of the present invention can be obtained by the production method described in Reference Example 1-1 and Reference Example 1-2 herein, or obtained by a known production method. Examples of known manufacturing methods include the manufacturing method disclosed in Tetrahedron, Vol. 56, pp. 6899-6911, 2000.

In the production method-1 of the present invention, the reducing agent is not particularly limited as long as it can supply hydride, and specifically, aluminum hydride, lithium aluminum hydride, bis(2- Examples include sodium methoxyethoxy)aluminum, borane-dimethylsulfide complex, borane-tetrahydrofuran complex, borane-pyridine complex, and sodium borohydride/boron trifluoride-diethyl ether complex. Lithium aluminum hydride, sodium bis(2-methoxyethoxy)aluminum hydride, borane-dimethylsulfide complex, and borane-tetrahydrofuran complex are preferred because they are easily available and have good yields, and lithium aluminum hydride is preferred. , a borane-dimethylsulfide complex is particularly preferred.

In the production method-1 of the present invention, the reducing agent is preferably used in an amount of 2 to 50 equivalents based on pyromellitic acid diimide (2) in order to obtain a good yield of the hexahydrobenzodipyrrole (1a) of the present invention. Particular preference is given to using 4 to 10 equivalents.

Production method-1 of the present invention can be carried out in a solvent. The solvent is not particularly limited as long as it does not inhibit the reaction, but specifically, aromatic hydrocarbon solvents such as toluene, xylene and chlorobenzene, tetrahydrofuran, 1,2-dimethoxyethane and Examples include ether solvents such as 1,4-dioxane, and alcohol solvents such as methanol, ethanol and propanol. Furthermore, two or more of these solvents may be used in combination. Preferred solvents in production method-1 from the viewpoint of good yield of hexahydrobenzodipyrrole (1a) of the present invention are aromatic hydrocarbon solvents and ether solvents, and more specifically, toluene, tetrahydrofuran, etc. Can be done.

In the production method-1 of the present invention, the reaction temperature is not particularly limited, but can be any temperature from 20°C to 150°C. The reaction temperature is preferably 40° C. or higher and 120° C. or lower in terms of a good yield of the hexahydrobenzodipyrrole (1a) of the present invention.

In the production method-1 of the present invention, the reaction time is not particularly limited, and can be, for example, 1 hour or more and 100 hours or less.

Production method-1 of the present invention may include a step of isolating the obtained hexahydrobenzodipyrrole (1a) after the reaction. The isolation method is arbitrary and not particularly limited, but specific examples include solvent extraction, column chromatography, preparative thin layer chromatography, preparative liquid chromatography, and recrystallization. .

Another preferred method of the present invention is to prepare an aromatic compound represented by the following general formula (3), an amide compound represented by the following general formula (4a), and an amide compound represented by the following general formula (4b). A method for producing hexahydrobenzodipyrrole represented by the following general formula (1b) (hereinafter also referred to as "Production method-2 of the present invention"), which is characterized by reacting with:

(In the formula, X is the same or different and represents a hydrogen atom or a halogen atom.
Y is the same or different and represents a halogen atom or a sulfonyloxy group 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, and the phenyl group is an alkyl group having 1 to 4 carbon atoms, a fluoroalkyl group having 1 to 4 carbon atoms. The substituent may be substituted with one or more substituents selected from the group consisting of alkoxy groups having 1 to 4 carbon atoms, fluoroalkoxy groups having 1 to 4 carbon atoms, halogen atoms, cyano groups, and nitro groups. )

(In the formula, R ^2a represents a haloalkyl group having 1 to 10 carbon atoms.)

(In the formula, R ^2b represents a haloalkyl group having 1 to 10 carbon atoms.)

(In the formula, X is the same or different and represents a hydrogen atom or a halogen atom.
R ^2a and R ^2b each independently represent a haloalkyl group having 1 to 10 carbon atoms. )
In production method-2 of the present invention, hexahydrobenzodipyrrole represented by general formula (1b) is obtained by the reaction shown below.

(In the formula, X, Y, R ^2a and R ^2b represent the same meanings as above.)
The amide compound (4a) and amide compound (4b) to be subjected to the reaction of production method-2 of the present invention may be the same compound, or two different types of amide compounds may be used, or two different types of amide compounds may be used. When using the compound, asymmetric hexahydrobenzopyrrole (1b) can be obtained.

In production method-2 of the present invention, the amide compound (4a) and the amide compound (4b) may be reacted with the aromatic compound (3) stepwise or simultaneously.

In production method-2 of the present invention, the aromatic compound represented by general formula (3) may be a commercially available compound, or may be obtained by a known production method. Known manufacturing methods include, for example, the manufacturing methods disclosed in Tetrahedron, Vol. 71, pp. 6944-6955, 2005, Journal of the American Chemical Society, Vol. 129, pp. 13362-13363, 2007, etc. .

In the production method-2 of the present invention, X in the aromatic compound (3) and hexahydrobenzopyrrole (1b) is the same or different and is a hydrogen atom or a halogen atom. The halogen atom is not particularly limited, and examples thereof include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. The X is preferably the same or different and is any one of a hydrogen atom, a chlorine atom, a bromine atom, and an iodine atom, and the same or different A hydrogen atom or a bromine atom is more preferable, and a hydrogen atom is particularly preferable.

In the production method-2 of the present invention, Y in the aromatic compound represented by general formula (3) is the same or different and is either a halogen atom or a sulfonyloxy group represented by R ⁵ SO ₂ O. . Note that R ⁵ is any one of 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 includes 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 of groups.

In the production method-2 of the present invention, when Y is a halogen atom, the halogen atom is not particularly limited, but examples thereof include a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom. .

In the production method-2 of the present invention, when Y is a sulfonyloxy group 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 phenyl 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, It may be substituted with one or more substituents selected from the group of cyano groups and nitro groups.

When R ⁵ is an alkyl group having 1 to 9 carbon atoms, the alkyl group having 1 to 9 carbon atoms is not particularly limited, but examples include methyl group, ethyl group, propyl group, isopropyl group, butyl group. Examples include a sec-butyl group, a 1-methylbutyl group, a 3-methylbutyl group, a 1,3-dimethylbutyl group, an octyl group, and a nonyl group.

When R ⁵ is a fluoroalkyl group having 1 to 9 carbon atoms, the alkyl group having 1 to 9 carbon atoms is not particularly limited; for example, trifluoromethyl group, 4,4,4-trifluoromethyl group, etc. Examples include fluorobutyl group and 1,1,2,2,3,3,4,4,4-nonafluorobutyl 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. The group may be substituted with one or more substituents selected from the group consisting of halogen atoms, cyano groups, and nitro groups.

R ⁵ is an alkyl group having 1 to 4 carbon atoms, a fluoroalkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a fluoroalkoxy group having 1 to 4 carbon atoms, a halogen atom, a cyano group, and a nitro group In the case of a phenyl group substituted with at least one member of the group consisting of: 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, Examples include 2-nitrophenyl group, 3-nitrophenyl group, and 4-nitrophenyl group.

In the production method-2 of the present invention, Y in the aromatic compound (3) may be the same or different and represented by a chlorine atom, a bromine atom, an iodine atom, or a C ₆ H ₅ SO ₂ O in order to improve the yield. benzenesulfonyloxy group represented by p-CH ₃ C ₆ H ₄ SO ₂ O, methanesulfonyloxy group represented by CH ₃ SO ₂ O or CF ₃ SO ₂ O The same or different trifluoromethanesulfonyloxy group is preferably a trifluoromethanesulfonyloxy group represented by a chlorine atom, a bromine atom, an iodine atom, a benzenesulfonyloxy group represented by C ₆ H ₅ SO ₂ O, p-CH ₃ C ₆ More preferably, it is a p-toluenesulfonyloxy group represented by H ₄ SO ₂ O or a methanesulfonyloxy group represented by CH ₃ SO ₂ O.

In production method-2 of the present invention, R ^2a in the amide compound (4a) and R ^2b in the amide compound (4b) are the same or different and are a haloalkyl group having 1 to 10 carbon atoms. The haloalkyl group having 1 to 10 carbon atoms is not particularly limited, but specifically, it may be a linear, branched, or cyclic haloalkyl group. 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) ) 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, 2 Examples include -chloroethyl group and 3-bromopropyl group.

The R ² is preferably the same and a haloalkyl group having 1 to 10 carbon atoms, and is the same and is preferably a haloalkyl group having 1 to 10 carbon atoms, and CF ₃ (trifluoromethyl group), CF ₃ CF ₂ (pentafluoroethyl group) or CCl ₃ (trichloromethyl group), and they are the same and preferably CF ₃ (trifluoromethyl group) or CCl ₃ (trichloromethyl group). More preferred.

In the production method-2 of the present invention, the amount of the amide compound represented by the amide compound (4a) and the amide compound (4b) is 2 to 50 equivalents with respect to the aromatic compound represented by the general formula (3). The amount is preferably 2 to 5 equivalents, more preferably 2 to 5 equivalents.

In production method-2 of the present invention, the yield can be improved by carrying out the reaction in the presence of a base. Examples of the base include organic bases and inorganic bases. Specific organic bases include, but are not particularly limited to, trimethylamine, triethylamine, diisopropylethylamine, 1,4-diazabicyclo[2.2.2]octane, 1,8-diazabicyclo[5.4.0 ] Undecene, etc. can be exemplified, and examples of the inorganic base include, but are not particularly limited to, sodium hydride, potassium hydride, sodium carbonate, potassium carbonate, cesium carbonate, and the like. The base is preferably one of diisopropylethylamine, 1,8-diazabicyclo[5.4.0]undecene, sodium hydride, and potassium hydride, and sodium hydride is preferable from the viewpoint of improving the yield. This is particularly preferred.

In production method-2 of the present invention, the reaction can be carried out in a solvent. The solvent is not particularly limited as long as it does not inhibit the reaction, but examples include aromatic hydrocarbon solvents such as toluene, xylene, and chlorobenzene, tetrahydrofuran, 1,2-dimethoxyethane, and 1,4-dimethoxyethane. Ether solvents such as dioxane, ester solvents such as ethyl acetate and butyl acetate, amide solvents such as N,N-dimethylformamide and N,N-dimethylacetamide, 1,3-dimethyl-2-imidazolidinone, 1 , 3-dimethyl-3,4,5,6-tetrahydropyrimidin-2(1H)-one and other urea solvents, acetone, methyl ethyl ketone and other ketone solvents, acetonitrile, propionitrile, benzonitrile and other nitrile solvents Alternatively, sulfoxide solvents such as dimethyl sulfoxide can be exemplified. Further, two or more of these solvents may be used in combination. Preferred solvents in production method 2 of the present invention include ether solvents, amide solvents, and nitrile solvents in terms of good yield, and more preferred solvents include tetrahydrofuran, N,N-dimethylformamide, acetonitrile, etc. can be mentioned.

In production method-2 of the present invention, the reaction temperature is not particularly limited, but can be any temperature from room temperature to 200°C. Since the yield of hexahydrobenzodipyrrole (1b) tends to be high, the reaction temperature is preferably at least room temperature and at most 80°C.

In production method-2 of the present invention, the reaction time is not particularly limited, and can be, for example, 1 hour or more and 100 hours or less.

Production method-2 of the present invention may include a step of isolating the obtained hexahydrobenzodipyrrole after the reaction. Isolation methods are arbitrary and are not particularly limited, but examples include solvent extraction, column chromatography, preparative thin layer chromatography, preparative liquid chromatography, and recrystallization.

Next, the present invention will be explained by examples, but the present invention is not limited thereto.
(H ¹ -NMR)
H ¹ -NMR measurements of the samples were performed using Ascend ^TM AVANCE III HD (400 MHz, manufactured by Bruker) or UltraShield ^TM Plus AVANCE III (400 MHz, manufactured by Bruker). H ¹ -NMR analysis of the sample was performed using deuterium chloroform (CDCl ₃ ), deuterium acetone (Acetone-d ₆ ) or deuterium dimethyl sulfide (DMSO-d ₆ ) as the measurement solvent and tetramethylsilane (TMS) as the internal standard substance. was measured. Furthermore, when heavy water (D ₂ O) was used as the measurement solvent, the solvent signal was set to 4.70 ppm. The measurement data was described in the order of chemical shift, multiplicity, coupling constant (Hz), and integral value.
(ion chromatograph)
Anion chromatography was measured using an ion chromatograph device IC-2001 (manufactured by Tosoh). The measurement conditions are as follows.

Column: TSKgel SuperIC-AZ
Eluent: 7.5 mmol/L sodium hydrogen carbonate aqueous solution
+1.1 mmol/L sodium carbonate water-soluble group
Flow rate: 0.8mL/min
Temperature: 40℃
Detection: Electrical conductivity Reference example 1-1

5-aminopentanol (4.80 mL, 44.0 mmol) was added to a suspension of pyromellitic anhydride (4.36 g, 20.0 mmol) and acetic acid (40 mL), and the mixture was stirred under reflux for 19 hours. . After the reaction, the reaction solution was allowed to cool to room temperature, water (120 mL) was added, and the aqueous layer was extracted with ethyl acetate (120 mL x 3). The combined organic layers were washed with a saturated aqueous sodium bicarbonate solution (100 mL) and concentrated to give N,N'-bis(5-acetoxypentyl)pyromellitic acid diimide (8.88 g, yield 94) as a pale yellow solid. %) was obtained. This product was used in the next reaction without further purification.

NMR spectrum of N,N'-bis(5-acetoxypentyl)pyromellitic acid diimide: ¹ H-NMR (400 MHz, DMSO-d ₆ ) δ (ppm): 8.18 (s, 2H), 3.98 ( t, J=6.6Hz, 4H), 3.62 (t, J=7.3Hz, 4H), 1.98 (s, 6H), 1.70 to 1.54 (m, 8H), 1. 40-1.27 (m, 4H).

Reference example 1-2

4-Aminobutanol (4.10 mL, 44.0 mmol) was added to a suspension of pyromellitic anhydride (4.36 g, 20.0 mmol) and acetic acid (40 mL), and the mixture was stirred under reflux for 19 hours. After the reaction, the reaction solution was allowed to cool to room temperature, water (120 mL) was added, and the aqueous layer was extracted with ethyl acetate (120 mL x 3). The combined organic layers were washed with a saturated aqueous sodium bicarbonate solution (100 mL x 2) and concentrated to give N,N'-bis(4-acetoxybutyl)pyromellitic acid diimide (8.72 g, yield 98) as a pale yellow solid. %) was obtained. This product was used in the next reaction without further purification.

NMR spectrum of N,N'-bis(4-acetoxybutyl)pyromellitic acid diimide: ¹ H-NMR (400 MHz, DMSO-d ₆ ) δ (ppm): 8.19 (s, 2H), 4.02 ( t, J = 6.0Hz, 4H), 3.65 (t, J = 6.6Hz, 4H), 1.99 (s, 6H), 1.73 to 1.55 (m, 8H).

Example 1-1

N,N'-bis(5-acetoxypentyl)pyromellitic acid diimide (7.09 g, 15.0 mmol) was added to a suspension of lithium aluminum hydride (3.41 g, 90.0 mmol) and tetrahydrofuran (150 mL). The mixture was added under an ice bath and stirred at 60°C for 5 hours. After the reaction, the reaction solution was cooled in an ice bath, and water (3.40 mL), 15% aqueous sodium hydroxide solution (3.40 mL), and water (10.2 mL) were sequentially added and stirred. The solid precipitated from the reaction solution was filtered off, and the solid was washed with tetrahydrofuran and ethyl acetate. The solvent was distilled off from the filtrate under reduced pressure, and the resulting liquid was purified by silica column chromatography to obtain 2,6-bis(5-hydroxypentyl)-1,2,3,5,6 as a yellow oil. ,7-hexahydrobenzo[1,2-c:4,5-c']dipyrrole (2.26 g, yield: 45%) was obtained.

NMR spectrum of 2,6-bis(5-hydroxypentyl)-1,2,3,5,6,7-hexahydrobenzo[1,2-c:4,5-c']dipyrrole: ¹ H-NMR (400MHz, CDCl ₃ ) δ (ppm): 7.00 (s, 2H), 3.87 (s, 8H), 3.64 (t, J=6.5Hz, 4H), 2.71 (t, J=7.3Hz, 4H), 1.67 to 1.54 (m, 8H), 1.52 to 1.41 (m, 4H) (no peak derived from hydroxyl group could be observed).

Example 1-2

N,N'-bis(4-acetoxybutyl)pyromellitic acid diimide (8.00 g, 18.0 mmol) was added to a suspension of lithium aluminum hydride (4.10 g, 108 mmol) and tetrahydrofuran (180 mL) in an ice bath. The mixture was added at the bottom and stirred at 60°C for 5 hours. After the reaction, the reaction solution was cooled in an ice bath, and water (4.10 mL), 15% aqueous sodium hydroxide solution (4.10 mL), and water (12.3 mL) were sequentially added and stirred. The solid precipitated from the reaction solution was filtered off, and the solid was washed with tetrahydrofuran and ethyl acetate. The solvent was distilled off from the filtrate under reduced pressure, and the resulting liquid was purified by silica column chromatography to obtain 2,6-bis(4-hydroxybutyl)-1,2,3,5,6 as a yellow oil. ,7-hexahydrobenzo[1,2-c:4,5-c']dipyrrole (1.75 g, yield: 32%) was obtained.

NMR spectrum of 2,6-bis(4-hydroxybutyl)-1,2,3,5,6,7-hexahydrobenzo[1,2-c:4,5-c']dipyrrole: ¹ H-NMR (400MHz, CDCl ₃ ) δ (ppm): 7.00 (s, 2H), 3.88 (s, 8H), 3.65 (t, J=6.5Hz, 4H), 2.70 (t, J=7.4Hz, 4H), 1.62 to 1.52 (m, 4H), 1.51 to 1.39 (m, 4H) (no peak derived from hydroxyl group could be observed).

Example 1-3

A solution of trifluoroacetamide (2.83 g, 25.0 mmol) in N,N-dimethylformamide (25 mL) was added to a suspension of sodium hydride (1.09 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 solution was poured into 2M hydrochloric acid and stirred for 15 minutes. The solid precipitated from the mixture was collected by filtration and washed with ethyl acetate to obtain a yellow solid of 2,6-bis(trifluoroacetyl)-1,2,3,5,6,7-hexahydrobenzo[1 ,2-c:4,5-c']dipyrrole (0.690 g, yield 39%) 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 ( 400MHz, Acetone-d ₆ ) δ (ppm): 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).

Reference example 1-3

2,6-bis(5-hydroxypentyl)-1,2,3,5,6,7-hexahydrobenzo[1,2-c:4,5-c']dipyrrole synthesized in Example 1-1 (3.32 g, 10.0 mmol), triethylamine (3.62 mL, 26.0 mmol) and 1,4-diazabicyclo[2.2.2]octane (0.112 g, 1.00 mmol) in dichloromethane (100 mL). , p-toluenesulfonyl chloride (4.19 g, 22.0 mmol) was added under an ice bath. After stirring at room temperature for 12 hours, the precipitated solid was collected by filtration and washed with chloroform to obtain a white solid. Next, the methanol solution of the obtained solid was passed through a column packed with an anion exchange resin (Amberlite IRA-400 Cl ^-type , 250 cm ³ ), and then methanol was distilled off from the solution. By washing the obtained solid with acetone and collecting the solid by filtration, dispiro[piperidine-1,2'-(1',2',3',5',6',7'-hexahydrobenzo [1,2-c:4,5-c']dipyrrolium)-6',1''-piperidine]=dichloride (3.30 g, 90% total yield over two steps) was obtained. As a result of analyzing the obtained compound using ion chromatography, the presence of chloride ions was confirmed.

Dispiro[piperidine-1,2'-(1',2',3',5',6',7'-hexahydrobenzo[1,2-c:4,5-c']dipyrrolium)-6' , 1''-piperidine] = dichloride NMR spectrum: ¹ H-NMR (400 MHz, D ₂ O) δ (ppm): 7.37 (s, 2H), 4.85 (s, 8H), 3.55 ~3.51 (m, 8H), 1.94 ~ 1.85 (m, 8H), 1.72 ~ 1.62 (m, 4H).

Reference example 1-4

2,6-bis(4-hydroxybutyl)-1,2,3,5,6,7-hexahydrobenzo[1,2-c:4,5-c']dipyrrole synthesized in Example 1-2 (1.25 g, 4.10 mmol), triethylamine (1.49 mL, 10.7 mmol) and 1,4-diazabicyclo[2.2.2]octane (45.9 mg, 0.410 mmol) in dichloromethane (41 mL). , p-toluenesulfonyl chloride (1.72 g, 9.00 mmol) was added under an ice bath. After stirring at room temperature for 12 hours, the precipitated solid was collected by filtration and washed with chloroform to obtain a white solid. Next, the methanol solution of the obtained solid was passed through a column packed with an anion exchange resin (Amberlite IRA-400 Cl ^-type , 250 cm ³ ), and then methanol was distilled off from the solution. By washing the obtained solid with acetone and collecting the solid by filtration, dispiro[pyrrolidine-1,2'-(1',2',3',5',6',7'-hexahydrobenzo [1,2-c:4,5-c']dipyrrolium)-6',1''-pyrrolidine]=dichloride (1.25 g, 89% total yield over two steps) was obtained. As a result of analyzing the obtained compound using ion chromatography, the presence of chloride ions was confirmed.

Dispiro[pyrrolidine-1,2'-(1',2',3',5',6',7'-hexahydrobenzo[1,2-c:4,5-c']dipyrrolium)-6' , 1''-pyrrolidine] = dichloride NMR spectrum: ¹ H-NMR (400 MHz, D ₂ O) δ (ppm): 7.37 (s, 2H), 4.84 (s, 8H), 3.73 ~3.60 (m, 8H), 2.30 ~ 2.18 (m, 8H).

Reference example 1-5

2,6-bis(trifluoroacetyl)-1,2,3,5,6,7-hexahydrobenzo[1,2-c:4,5-c']dipyrrole ( Bromoethane (0.630 mL, 8.40 mmol) and 30% aqueous sodium hydroxide solution (1.32 mL, 10.0 mmol) were added to a solution of 0.704 g, 2.00 mmol) in ethanol/tetrahydrofuran (1:1, 6.8 mL). ) and stirred at 70°C for 18 hours in a sealed container. 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, which was dried using molecular sieve 4A, and after filtering off the solid, ethanol was distilled off from the filtrate. The obtained solid was washed with acetone and collected by filtration to obtain a white solid of 2,2,6,6-tetraethyl-1,2,3,5,6,7-hexahydrobenzo[1,2-c :4,5-c']dipyrrolium dibromide (0.659 g, yield 76%) was obtained. As a result of analyzing the obtained compound using ion chromatography, the presence of bromide ions was confirmed.

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

Reference example 1-6

2,6-bis(trifluoroacetyl)-1,2,3,5,6,7-hexahydrobenzo[1,2-c:4,5-c']dipyrrole ( 0.704 g, 2.00 mmol) in ethanol/tetrahydrofuran (1:1, 6.8 mL), 1,4-dibromobutane (0.500 mL, 4.20 mmol), and 30% aqueous sodium hydroxide solution (1. 32 mL, 10.0 mmol) was added thereto, and the mixture was stirred at 70°C for 20 hours. After the reaction, the reaction solution was cooled to room temperature, and the solvent was distilled off under reduced pressure. After adding ethanol to the obtained residue and filtering off the solid, ethanol was distilled off from the filtrate. The obtained solid was washed with acetone and collected by filtration to obtain a white solid dispiro[pyrrolidine-1,2'-(1',2',3',5',6',7'-hexahydrobenzo [1,2-c:4,5-c']dipyrrolium)-6',1''-pyrrolidine]=dibromide (0.803 g, yield 94%) was obtained. As a result of analyzing the obtained compound using ion chromatography, the presence of bromide ions was confirmed.

Dispiro[pyrrolidine-1,2'-(1',2',3',5',6',7'-hexahydrobenzo[1,2-c:4,5-c']dipyrrolium)-6' , 1''-pyrrolidine] = dibromide NMR spectrum: ¹ H-NMR (400 MHz, D ₂ O) δ (ppm): 7.37 (s, 2H), 4.84 (s, 8H), 3.73 ~3.60 (m, 8H), 2.30 ~ 2.18 (m, 8H).

Example 1-4

N,N'-diethylpyromellitic acid diimide (5.45 g, 20.0 mmol) was added to a suspension of lithium aluminum hydride (3.04 g, 80.0 mmol) and tetrahydrofuran (100 mL) under an ice bath. Stirred at 60°C for 18 hours. After the reaction, the reaction solution was cooled in an ice bath, and 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 solution was filtered, and the solid was washed with tetrahydrofuran and ethyl acetate, and then 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 2,6-diethyl-1,2,3,5,6,7-hexahydrobenzo[1,2-c:4,5-c']dipyrrole (crude product): ¹ H-NMR ( 400MHz, CDCl ₃ ) δ (ppm): 7.01 (s, 2H), 3.88 (s, 8H), 2.77 (q, J = 7.2Hz, 4H), 1.19 (q, J =7.2Hz, 6H).

Reference example 1-7

The crude product containing 2,6-diethyl-1,2,3,5,6,7-hexahydrobenzo[1,2-c:4,5-c']dipyrrole synthesized in Example 1-4 ( Bromoethane (4.48 mL, 60.0 mmol) was added to a solution of 4.10 g) in acetonitrile (40 mL). After stirring at room temperature for 13 hours, the solvent was distilled off from the reaction solution under reduced pressure. By washing the obtained solid with acetone and collecting the solid by filtration, a white solid of 2,2,6,6-tetraethyl-1,2,3,5,6,7-hexahydrobenzo[1, 2-c:4,5-c']dipyrrolium dibromide (3.47 g, 40% total yield over two steps) was obtained. As a result of analyzing the obtained compound using ion chromatography, the presence of bromide ions was confirmed.

Example 1-5

N,N'-dihexylpyromellitic acid diimide (6.19 g, 15.0 mmol) was added to a suspension of lithium aluminum hydride (3.42 g, 90.0 mmol) and tetrahydrofuran (150 mL) under an ice bath. The mixture was stirred at 60°C for 7 hours. After the reaction, the reaction solution was cooled in an ice bath, and water (3.5 mL), 15% aqueous sodium hydroxide solution (3.5 mL), and water (10.5 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. Diethyl ether was added to the viscous liquid obtained by distilling the solvent off from the filtrate under reduced pressure, and the precipitated solid was collected by filtration to obtain a white solid of 2,6-dihexyl-1,2,3, 5,6,7-hexahydrobenzo[1,2-c:4,5-c']dipyrrole (2.15 g, yield 44%) 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 ) δ (ppm): 7.00 (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).

Reference example 1-8

2,6-dihexyl-1,2,3,5,6,7-hexahydrobenzo[1,2-c:4,5-c']dipyrrole (1.78 g, 5 1-bromohexane (1.54 mL, 11.0 mmol) was added to a solution of .43 mmol) in acetonitrile/toluene (1:1, 10 mL). The mixture was stirred at 100°C for 12 hours. By adding chloroform to the obtained viscous liquid and filtering the precipitated solid, a white solid of 2,2,6,6-tetrahexyl-1,2,3,5,6,7-hexahydro Benzo[1,2-c:4,5-c']dipyrrolium dibromide (3.36 g, yield 94%) was obtained. As a result of analyzing the obtained compound using ion chromatography, the presence of bromide ions was confirmed.

NMR spectrum of 2,2,6,6-tetrahexyl-1,2,3,5,6,7-hexahydrobenzo[1,2-c:4,5-c']dipyrrolium dibromide: ¹ H- NMR (400MHz, DMSO-d ₆ ) δδ (ppm): 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).

Reference example 2-1
(Synthesis of AFX type zeolite)
Example 1-2 was carried out, and then dispiro[pyrrolidine-1,2'-(1',2',3',5',6',7'-hexahydro Benzo[1,2-c:4,5-c']dipyrrolium)-6',1''-pyrrolidine]=dichloride was used as the structure directing agent (SDA), and 48% NaOH and Y-type zeolite (trade name: HSZ) were added. -350HUA, manufactured by Tosoh, silica and alkali source) were mixed to obtain a composition. The molar composition of the resulting composition is shown.

SiO ₂ /Al ₂ O ₃ = 11.1
OH/ _SiO2 = 0.35
Na/ _SiO2 = 0.35
SDA/ _SiO2 = 0.10
_H2O / _SiO2 = 25
After adding the _{seed crystal} AFX type zeolite to the composition, enough The mixture was stirred.
The stirred composition was sealed in a stainless steel autoclave, and heated at 180° C. for 162 hours while rotating the autoclave to obtain a product.

The product was filtered, washed and dried in air at 110° C. overnight. When the product was analyzed using a powder X-ray diffraction device (device name: Ultima IV, manufactured by RIGAKU), the product was found to be a single phase of AFX type zeolite. Further, when the composition of the sample was analyzed using an inductively coupled plasma emission spectrometer (device name: OPTIMA3300DV, manufactured by PERKIN ELMER), the SiO ₂ /Al ₂ O ₃ ratio was 10.1.

Claims (14)

Hexahydrobenzodipyrrole represented by general formula (1).
[In the formula, X is the same or different and represents a hydrogen atom or a halogen atom.
R ¹ is the same or different and is a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms, a linear, branched or cyclic haloalkyl group having 1 to 10 carbon atoms (the above-mentioned 10 linear, branched or cyclic alkyl groups and the above linear, branched or cyclic haloalkyl groups having 1 to 10 carbon atoms are hydroxyl groups and linear, branched or cyclic alkyl groups having 1 to 6 carbon atoms. ) or R ² C(O) (wherein R ² represents a linear, branched or cyclic haloalkyl group having 1 to 10 carbon atoms) ) represents an acyl group. However, the two R ^1s cannot be a methyl group, a propyl group, a butyl group, a cyclohexyl group, and a benzyl group at the same time. ]. In the general formula (1), R ¹ is the same, and ethyl group, isopropyl group, cyclopropyl group, isobutyl group, sec-butyl group, tert-butyl group, cyclobutyl group, 4-hydroxybutyl group, 5 -Hydroxypentyl group, hexyl group, linear, branched or cyclic haloalkyl group having 1 to 10 carbon atoms (the above linear, branched or cyclic haloalkyl group having 1 to 10 carbon atoms is substituted with a hydroxyl group) ) or R ² C(O) (wherein R ² represents a linear, branched or cyclic haloalkyl group having 1 to 10 carbon atoms). Hexahydrobenzodipyrrole according to 1. The hexahydrobenzodipyrrole according to claim 1 or 2, wherein in the general formula (1), X is a hydrogen atom. The hexahydrobenzodipyrrole according to any one of claims 1 to 3, wherein in the general formula (1), R ¹ is an ethyl group, an isopropyl group, an isobutyl group, a sec-butyl group, or a tert-butyl group. The hexahydrobenzodipyrrole according to any one of claims 1 to 4, wherein in the general formula (1), R ¹ is an ethyl group. General formula (2)
[In the formula, X is the same or different and represents a hydrogen atom or a halogen atom.
R ³ is the same or different and is a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms or a linear, branched or cyclic haloalkyl group having 1 to 10 carbon atoms (the above-mentioned 1 to 10 carbon atoms); 10 linear, branched or cyclic alkyl groups and the above-mentioned linear, branched or cyclic haloalkyl groups having 1 to 10 carbon atoms may be substituted with a hydroxyl group. ]
General formula (1a) characterized by reacting pyromellitic acid diimide represented by and a reducing agent
[In the formula, X is the same or different and represents a hydrogen atom or a halogen atom.
R ⁴ is the same or different and is a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms or a linear, branched or cyclic haloalkyl group having 1 to 10 carbon atoms (the above-mentioned 1 to 10 carbon atoms); 10 linear, branched or cyclic alkyl groups and the above-mentioned linear, branched or cyclic haloalkyl groups having 1 to 10 carbon atoms may be substituted with a hydroxyl group. ]
A method for producing hexahydrobenzodipyrrole represented by The method for producing hexahydrobenzodipyrrole according to claim 6, wherein in the general formulas (1a) and (2), X is a hydrogen atom. In the general formula (2), R ³ are the same and are an ethyl group, isopropyl group, isobutyl group, sec-butyl group or tert-butyl group, and in the general formula (1a), R ⁴ are the same The method for producing hexahydrobenzodipyrrole according to claim 6 or 7, wherein the hexahydrobenzodipyrrole is an ethyl group, isopropyl group, isobutyl group, sec-butyl group or tert-butyl group. The hexane compound according to claims 6 to 8, wherein in the general formula (2), R ³ are the same and are an ethyl group, and in the general formula (1a), R ⁴ are the same and are an ethyl group. Method for producing hydrobenzodipyrrole. General formula (3)
(In the formula, X is the same or different and represents a hydrogen atom or a halogen atom.
Y represents a halogen atom . )
An aromatic compound represented by and general formula (4a)
(In the formula, R ^2a represents a linear, branched or cyclic haloalkyl group having 1 to 10 carbon atoms.)
An amide compound represented by and the following general formula (4b)
(In the formula, R ^2b represents a linear, branched, or cyclic haloalkyl group having 1 to 10 carbon atoms.)
General formula (1b) characterized by reacting with an amide compound represented by
(In the formula, X is the same or different and represents a hydrogen atom or a halogen atom.
R ^2a and R ^2b each independently represent a linear, branched or cyclic haloalkyl group having 1 to 10 carbon atoms. )
A method for producing hexahydrobenzodipyrrole represented by The hexahydrobenzodipyrrole according to claim 10, wherein in the general formula (3), R ^2a and R ^2b are the same and are a linear, branched or cyclic haloalkyl group having 1 to 10 carbon atoms. Production method. The method for producing hexahydrobenzodipyrrole according to claim 10 or 11, wherein in the general formula (3), Y is the same or different and is a chlorine atom, a bromine atom, or an iodine atom. The method for producing hexahydrobenzodipyrrole according to any one of claims 10 to 12, wherein in the general formulas (3) and (1b), X is a hydrogen atom. In the general formulas (4) and (1b), R ^2a and R ^2b are the same and are a trifluoromethyl group or a trichloromethyl group, according to any one of claims 10 to 13. Method for producing hexahydrobenzodipyrrole.